JP2015108098A - Active energy ray-polymerizable resin composition and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new active energy ray-polymerizable resin composition that has antistatic property and excellent heat resistance and the like and can be suitably used for optical purposes, and to provide a laminate, particularly, a laminate for an optical element, which is excellent in punching processability and moisture heat durability compared to the prior arts.SOLUTION: A laminate for an optical element having the following properties can be obtained by using an adhesive and/or a coating agent using an active energy ray-polymerizable resin composition in lamination of various optical films. The laminate for an optical element achieves easy and firm adhesion and a tight contact regardless of types of various optical films, has excellent polymerization curability at a low exposure dose, contains substantially no organic solvent, and has high durability.

Description

  The present invention relates to an active energy ray-polymerizable resin composition having novel antistatic performance, and a laminate using the resin composition, particularly a laminate suitable for use in an optical element.

 The active energy ray-polymerizable resin composition has a high polymerization rate and generally can be used in the absence of a solvent. Therefore, the active energy ray-polymerizable resin composition has excellent workability and has extremely low energy required for polymerization. The active energy ray polymerizable resin composition typically contains a resin component that can be polymerized by active energy rays and a monomer component having an α, β-unsaturated double bond group. Examples of the resin component include oligomers having a low molecular weight and an α, β-unsaturated double bond group at the molecular end, such as polyester resins, polyurethane resins, polyepoxy resins, and polyacrylic resins. It's being used. The monomer component is polymerized together with the resin component by irradiation with active energy rays, but can function as a solvent until the polymerization is completed. Therefore, the active energy ray polymerizable resin does not require a separate solvent, and thus has an advantage that the solvent does not volatilize when the coating film is formed.

  From the above viewpoints, the use of the active energy ray-polymerizable resin composition can reduce environmental pollution in order to improve recent environmental pollution problems. Therefore, active energy ray polymerizable resin compositions are used in various fields including building materials, packaging materials, printing materials, display device materials such as displays, and electric and electronic component materials such as optical devices. The field of use is expanding.

 On the other hand, in recent years, the development and generalization of information communication devices including displays has been remarkable, and in the field of display devices, further improvements in the performance and productivity of materials such as coating agents, adhesives, and sealing agents are required. . And various embodiment which uses the said active energy ray polymeric resin composition as a material of a display apparatus is proposed.

  In display devices, various films are usually used depending on the application, such as an antireflection film for preventing reflection from an external light source, and a protective film (protection film) for preventing scratches on the surface of the display device. ing. For example, as a liquid crystal cell member constituting a liquid crystal display (LCD), a polarizing film or a retardation film is laminated.

  Further, the flat panel display (FPD) is not only used as a display device, but also provided with a touch panel function on the surface thereof, and may be used as an input device. Also in the touch panel, films such as a protective film, an antireflection film, and an ITO vapor deposition resin film are used.

  The film is typically applied to a display device in the form of a laminate as an optical element member. For example, the above-described film is applied to a display device in a form in which a coating layer made of a coating agent is provided on the surface layer for preventing scratches, preventing fingerprint adhesion, preventing charging, or facilitating adhesion. In another form, the said film is applied to a display apparatus with the form stuck on adherends, such as an optical element, via the adhesive agent and the pressure sensitive adhesive. The coating agent, adhesive, or pressure-sensitive adhesive used in the above-described form is required to have characteristics such as transparency or heat resistance. In response to such a demand, in this technical field, generally, a solvent-containing two-component thermosetting type or active energy ray polymerizable type adhesive or pressure sensitive adhesive mainly composed of a polyacrylic resin is used. It is used.

 Of the various films described above, the polarizing film generally has a three-layer structure in which both surfaces of a polyvinyl alcohol-based polarizer are sandwiched between triacetylcellulose-based, cycloolefin-based, or acrylic protective films. For this reason, in a polarizing film, since the dimensional change characteristic of the material which comprises each layer differs, it is easy to produce the warp by the dimensional change accompanying the change of temperature or humidity.

On the other hand, for example, in an inspection process for a laminate in which a polarizing film is attached to a glass surface for a liquid crystal cell in an LCD manufacturing process, the polarizing film or the like is peeled off when there is air or dust entrainment during lamination. A new polarizing film or the like is reapplied. This re-pasting is also called “rework”.
However, the laminate after sticking the polarizing film with a pressure-sensitive adhesive is generally inspected after being stored for a certain period of time at a high temperature in order to improve the adhesiveness. In addition to being difficult to peel off, the re-peelability of the polarizing film was lowered, and after peeling, the glass surface was sometimes contaminated with adhesive residue or cloudiness.

In the film laminated with the pressure-sensitive adhesive, the release film is bonded to the adhesive layer for the purpose of protecting the adhesive layer, and in use, the release film is peeled off and attached to the adherend. However, there has been a problem that the pressure-sensitive adhesive sheet is charged by static electricity when the release film is peeled off, and dust and dirt are attached to cause appearance defects. Further, for example, in the LCD manufacturing process, rework is also performed as described above.
However, there are cases where troubles occur in liquid crystals and electronic circuits due to static electricity generated during rework. Further, it has been pointed out that the same trouble occurs when the polarizing film is charged and adhered to the glass surface for a liquid crystal cell due to static electricity generated when the release film is peeled off as described above. Furthermore, the presence of static electricity has a problem of sucking dust and debris and causing defects due to foreign matters, and an early solution has been desired.

On the other hand, various pressure-sensitive adhesives have been proposed.
For example, in order to impart antistatic performance to a laminated member, the resin is often treated with an antistatic agent such as conductive fine particles or a surfactant.

  For example, examples of the conductive fine particles include metal powder, metal oxide fine particles such as ITO and ATO, and further carbon (Patent Documents 1 to 3). However, there was a problem that a considerable amount had to be added and transparency was lost.

  For example, surfactants include anionic, cationic, and nonionic surfactants, which are inexpensive and are used in various applications (Patent Document 4). However, they also have a problem that they cause bleeding from the surface of the adhesive layer and contaminate others. In addition, the anionic system lacks compatibility with the resin, is difficult to disperse uniformly, and has low heat resistance. There were problems such as low compatibility with polymers.

  As described above, pressure-sensitive adhesives containing these surfactants are easily affected by humidity. Under high humidity, the cohesive force decreases due to the influence of moisture, and an adhesive layer is formed on the adherend during rework. There is a problem that it is easy to remain (so-called “glue residue”). Furthermore, these pressure-sensitive adhesives having surfactants and conductive fine particles have poor compatibility, and thus the transparency of the coating film is impaired or coloring is observed. Further, there is a problem that the surfactant or the conductive fine particles migrate to the adherend interface (so-called “bleed”) and the original performance of the pressure-sensitive adhesive such as adhesive force is lowered.

  In addition, an antistatic pressure-sensitive adhesive containing an alkali metal salt as an antistatic agent in an acrylic resin is disclosed, which is used in tape applications for electronics, protective film applications, and polarizing film fixing applications, respectively. (Patent Documents 5 to 7). However, the use of antistatic pressure-sensitive adhesives containing metal ions for materials used in electrical products and electronic components has the potential for contamination associated with metal ion bleeding, and as a pressure-sensitive adhesive film. The heat-and-moisture resistance decreases.

  Thus, there is still no pressure-sensitive adhesive that can satisfy both the antistatic performance and the adherend contamination suppression performance during reworking by containing the antistatic agent in the pressure-sensitive adhesive.

In view of such circumstances, pressure-sensitive adhesive properties and optical properties can be prevented from lowering, and can be used from film label applications to electrical and optical applications. Rather than imparting an antistatic function to the adhesive, it is desirable to impart that function to the active energy ray polymerizable resin composition used on one or both sides of the laminated film such as the polarizing film described above. I came.
Furthermore, in the field of display devices, in addition to conventional advantages, development of an active energy ray polymerizable resin composition excellent in various properties required for optical applications and excellent in antistatic properties is desired. . More specifically, it is an active energy ray-polymerizable resin composition that can be suitably used as a coating agent or an adhesive that constitutes a laminate for an optical element, substantially containing no organic solvent, and having adhesion and Resin composition with excellent dimensional stability during curing and excellent optical properties such as refractive index, total light transmittance, and haze, and durability in harsh environments at high humidity and high temperature Things are sought.

Japanese Unexamined Patent Publication No. 01-222141 Japanese Patent Laid-Open No. 05-070760 JP 2005-330409 A JP 04-007350 A Japanese National Patent Publication No. 10-511726 JP 2006-199873 A Japanese Patent Laid-Open No. 06-128539

  In view of the above situation, the present invention has antistatic properties, is excellent in heat resistance, moist heat resistance, thermal dimensional stability, weather resistance, etc., can be suitably used in optical applications, and substantially uses an organic solvent. It is an object of the present invention to provide a novel active energy ray polymerizable resin composition useful as a coating agent or an adhesive that is not included in the above and is easy to handle. Further, the present invention is a laminate having a resin layer formed by using the resin composition on at least one main surface of various transparent films, particularly various optical films, regardless of the type of the various optical films. The present invention provides a laminate, particularly an optical element laminate, in which the resin layer can be easily or firmly adhered or coated to the optical film, and is excellent in punching workability and wet heat durability as compared with conventional ones. Objective.

 As a result of intensive studies to solve the above problems, the present inventors have found that the above-mentioned target can be achieved by the active energy ray polymerizable composition and adhesive shown below, and have completed the present invention.

〔一般式（１）中Ｒ¹〜Ｒ⁸は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアリール基、又は、置換基を有してもよい複素環基を表し、Ｒ⁵〜Ｒ⁸は、隣り合う置換基同士で環を形成してもよい。〕
一般式（２）

〔一般式（２）中Ｒ¹〜Ｒ⁴は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアリール基、又は、置換基を有してもよい複素環基を表し、Ａ⁺は、アルカリ金属イオンを表す。〕
一般式（３）

〔一般式（３）中Ｒ⁵〜Ｒ⁸は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアリール基、又は、置換基を有してもよい複素環基を表し、隣り合う置換基同士で環を形成してもよい。
Ｒ⁹は、置換基を有してもよいアルキレン結合基、置換基と二重結合を有してもよいアルキレン結合基、置換基と三重結合を有してもよいアルキレン結合基、置換基を有してもよいアリーレン結合基、置換基を有してもよい複素環結合基、又は、エーテル結合基、エステル結合基、チオエーテル結合基、ジチオール結合基、カルボニル結合基、スルフィニル結合基、スルホニル結合基、ホスホニル結合基、アミノ結合基、イミノ結合基、もしくはシリル結合基を表す。
Ｒ¹⁰は、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、又は、ハロゲン基を表す。
Ｒ¹¹は、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、又は、−Ｒ⁹Ｒ¹⁰を表す。〕 That is, the present invention provides an ionic compound (A) represented by any one of the following general formulas (1) to (3):
an α, β-ethylenically unsaturated double bond group-containing compound (B);
The present invention relates to an active energy ray-polymerizable resin composition comprising an active energy ray polymerization initiator (E).
General formula (1)

[In General Formula (1), R ^{1 to} R ⁸ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. Represents a good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and R ^{5 to} R ⁸ may form a ring with adjacent substituents; Good. ]
General formula (2)

[In General Formula (2), R ^{1 to} R ⁴ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. A good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and A ⁺ represents an alkali metal ion. ]
General formula (3)

[In General Formula (3), R ^{5 to} R ⁸ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. It represents a good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and adjacent substituents may form a ring.
R ⁹ represents an alkylene bonding group that may have a substituent, an alkylene bonding group that may have a substituent and a double bond, an alkylene bonding group that may have a substituent and a triple bond, or a substituent. Arylene bond group which may have, heterocyclic bond group which may have substituent, or ether bond group, ester bond group, thioether bond group, dithiol bond group, carbonyl bond group, sulfinyl bond group, sulfonyl bond Represents a group, a phosphonyl linking group, an amino linking group, an imino linking group, or a silyl linking group.
R ¹⁰ represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a halogen group.
R ¹¹ represents a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or —R ⁹ R ¹⁰ . ]

Furthermore, the present invention provides a total amount of the active energy ray polymerizable resin composition,
0.01 to 10% by weight of compound (A),
1 to 99% by weight of compound (B),
The active energy ray-polymerizable resin composition is characterized by containing 0.01 to 20% by weight of the active energy ray polymerization initiator (E).

 Furthermore, the present invention relates to the above active energy ray-polymerizable resin composition, wherein the compound (B) contains an α, β-ethylenically unsaturated double bond group-containing compound (b1) having a hydroxyl group.

 Furthermore, the present invention is characterized in that the compound (B) includes an α, β-ethylenically unsaturated double bond group-containing compound (b2) having one or more cyclic structures and having no hydroxyl group. The present invention relates to an active energy ray polymerizable resin composition.

  Furthermore, this invention relates to the laminated body which has a base material (G) and the resin layer which consists of the said resin composition provided in the at least one main surface of this base material (G).

  Furthermore, this invention relates to the said laminated body characterized by the base material (G) being a transparent film (H).

  Further, in the present invention, the transparent film (H) is a polyacetyl cellulose film, a polynorbornene film, a polypropylene film, a polyacryl film, a polycarbonate film, a polyester film, a polyvinyl alcohol film, and a polyimide. It is at least 1 sort (s) selected from the group which consists of a system film, It is related with the said laminated body characterized by the above-mentioned.

  Furthermore, this invention relates to the laminated body for optical elements which has an optical film and the resin layer which consists of the said resin composition provided in the at least one main surface of this optical film.

 ADVANTAGE OF THE INVENTION According to this invention, the active energy ray polymeric resin composition which can superpose | polymerize with low illumination intensity and has antistatic property can be provided. In addition, according to the present invention, by using the resin composition as an adhesive or a coating agent, the optical film can be easily and firmly adhered or adhered to the optical film, and excellent in punching workability, heat resistance, and moist heat resistance. A laminate, particularly a laminate for an optical element having excellent antistatic properties can be provided.

〔一般式（１）中Ｒ¹〜Ｒ⁸は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアリール基、又は、置換基を有してもよい複素環基を表し、Ｒ⁵〜Ｒ⁸は、隣り合う置換基同士で環を形成してもよい。〕
一般式（２）

〔一般式（２）中Ｒ¹〜Ｒ⁴は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアリール基、又は、置換基を有してもよい複素環基を表し、Ａ⁺は、アルカリ金属イオンを表す。〕
一般式（３）

〔一般式（３）中Ｒ⁵〜Ｒ⁸は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアリール基、又は、置換基を有してもよい複素環基を表し、隣り合う置換基同士で環を形成してもよい。
Ｒ⁹は、置換基を有してもよいアルキレン結合基、置換基を有してもよいアルケニル結合基、置換基を有してもよいアルキニレン結合基、置換基を有してもよいアリーレン結合基、置換基を有してもよい複素環結合基、又は、エーテル結合基、エステル結合基、チオエーテル結合基、ジチオール結合基、カルボニル結合基、スルフィニル結合基、スルホニル結合基、ホスホニル結合基、アミノ結合基、イミノ結合基、もしくはシリル結合基を表す。
Ｒ¹⁰は、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、又は、ハロゲン基を表す。
Ｒ¹¹は、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、又は、−Ｒ⁹Ｒ¹⁰を表す。〕 Hereinafter, embodiments of the present invention will be described.
<Active energy ray polymerizable resin composition>
The active energy ray polymerizable resin composition of the present invention includes an ionic compound (A) represented by any one of the following general formulas (1) to (3) and an α, β-ethylenically unsaturated double bond group. It is an active energy ray polymerizable resin composition characterized by including a compound (B) and an active energy ray polymerization initiator (E).

General formula (1)

[In General Formula (1), R ^{1 to} R ⁸ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. Represents a good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and R ^{5 to} R ⁸ may form a ring with adjacent substituents; Good. ]
General formula (2)

[In General Formula (2), R ^{1 to} R ⁴ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. A good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and A ⁺ represents an alkali metal ion. ]
General formula (3)

[In General Formula (3), R ^{5 to} R ⁸ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. It represents a good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and adjacent substituents may form a ring.
R ⁹ represents an alkylene bond group that may have a substituent, an alkenyl bond group that may have a substituent, an alkynylene bond group that may have a substituent, or an arylene bond that may have a substituent. Group, heterocyclic group which may have a substituent, or ether bond group, ester bond group, thioether bond group, dithiol bond group, carbonyl bond group, sulfinyl bond group, sulfonyl bond group, phosphonyl bond group, amino A linking group, an imino linking group, or a silyl linking group is represented.
R ¹⁰ represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a halogen group.
R ¹¹ represents a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or —R ⁹ R ¹⁰ . ]

 Here, the “active energy ray” means an energy ray in a broad sense that can provide energy necessary for activation for causing a chemical reaction, including ultraviolet rays, visible rays, infrared rays, electron beams, and radiation. . The active energy ray polymerizable resin composition of the present invention (hereinafter referred to as “resin composition”) undergoes a polymerization reaction upon irradiation with the active energy ray to form a cured product. Although it does not specifically limit, In one Embodiment of this invention, it is preferable that the said active energy ray is light energy containing an ultraviolet-ray.

Hereinafter, the constituent components of the resin composition will be specifically described.
(A) component:
In the resin composition of the present invention, an ionic compound (A), an ammonium salt compound (a1) represented by the following general formula (1), and an alkali metal salt system represented by the following general formula (2) The compound (a2) and the ammonium salt compound (a3) represented by the following general formula (3) will be described.

General formula (1)

[In General Formula (1), R ^{1 to} R ⁸ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. Represents a good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and R ^{5 to} R ⁸ may form a ring with adjacent substituents; Good. ]

General formula (2)

[In General Formula (2), R ^{1 to} R ⁴ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. A good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and A ⁺ represents an alkali metal ion. ]

General formula (3)

〔一般式（３）中Ｒ⁵〜Ｒ⁸は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアリール基、又は、置換基を有してもよい複素環基を表し、隣り合う置換基同士で環を形成してもよい。
Ｒ⁹は、置換基を有してもよいアルキレン結合基、置換基を有してもよいアルケニル結合基、置換基を有してもよいアルキニレン結合基、置換基を有してもよいアリーレン結合基、置換基を有してもよい複素環結合基、又は、エーテル結合基、エステル結合基、チオエーテル結合基、ジチオール結合基、カルボニル結合基、スルフィニル結合基、スルホニル結合基、ホスホニル結合基、アミノ結合基、イミノ結合基、もしくはシリル結合基を表す。
Ｒ¹⁰は、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、又は、ハロゲン基を表す。
Ｒ¹¹は、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、又は、−Ｒ⁹Ｒ¹⁰を表す。〕

[In General Formula (3), R ^{5 to} R ⁸ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. It represents a good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and adjacent substituents may form a ring.
R ⁹ represents an alkylene bond group that may have a substituent, an alkenyl bond group that may have a substituent, an alkynylene bond group that may have a substituent, or an arylene bond that may have a substituent. Group, heterocyclic group which may have a substituent, or ether bond group, ester bond group, thioether bond group, dithiol bond group, carbonyl bond group, sulfinyl bond group, sulfonyl bond group, phosphonyl bond group, amino A linking group, an imino linking group, or a silyl linking group is represented.
R ¹⁰ represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a halogen group.
R ¹¹ represents a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or —R ⁹ R ¹⁰ . ]

In the ammonium salt compound (a1) or (a3), the cation part is N ⁺ R ⁵ R ⁶ R ⁷ R ⁸ , and all the constituent parts including the anion part are organic. It is characterized by high compatibility with things. In addition, when the ammonium salt compound (a1) or (a3) is used, the antistatic performance is hardly affected by environmental humidity.

  In addition, the alkali metal salt compound (a2) has a feature that the cation part is an alkali metal ion, so that the production process can be shortened and can be produced at low cost. However, when an alkali metal salt compound (a2) is used, there is a possibility that electronic components such as an internal circuit, a transistor, an IC, and a CPU may be contaminated. The Further, when the alkali metal salt compound (a2) is used, if the adherend is aluminum or the like, the floating is likely to occur in a high temperature and high humidity environment. Furthermore, when the alkali metal salt compound (a2) is used, the antistatic performance is easily affected by environmental humidity.

  Therefore, in the present invention, it is more preferable to use the ammonium salt compound (a1) or (a3) represented by the general formula (1) or (3).

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group. , Octadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl Group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group 4-methylphenacyl group, 2-methylphenacyl group 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3- Torofenashiru group, and the like.

  As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferable, and a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o- , M-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, Phenalenyl, fluorenyl, anthryl, bianthracenyl, teranthraceni Group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexa Examples thereof include a phenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an oberenyl group.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H- Quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group Nyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

  Examples of the halogen group include halogen groups such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The alkylene linking group which may have a substituent is preferably an alkylene group having 1 to 30 carbon atoms, such as a methylene linking group, an ethylene linking group, a propylene linking group, a butylene linking group, a hexylene linking group, or an octylene linking group. Group, decylene bond group, dodecylene bond group, okdadecylene bond group, isopropylene bond group, isobutylene bond group, sec-butylene bond group, tert-butylene bond group, 1-ethylpentylene bond group, cyclopentylene bond group, cyclohexene Silene bond group, trifluoromethylene bond group, 2-ethylhexylylene bond group, phenacylene bond group, 1-naphthoylmethylene bond group, 2-naphthoylmethylene bond group, 4-methylsulfanylphenacylene bond group, 4-phenylsulfanyl Phenacylene linking group, 4-dimethylaminophen Nacylene bond group, 4-cyanophenacylene bond group 4-methylphenacylene bond group, 2-methylphenacylene bond group, 3-fluorophenacylene bond group, 3-trifluoromethylphenacylene bond group, 3-nitrophenacylene Examples include a linking group.

  Examples of the alkylene linking group which may have a substituent and a double bond include C2-C10 alkylene linking groups having one or more double bonds.

  Examples of the alkylene linking group which may have a substituent and a triple bond include C 2-10 alkylene linking groups having one or more triple bonds.

  The arylene linking group which may have a substituent is preferably an arylene linking group having 6 to 30 carbon atoms, such as a phenylene linking group, a biphenylene linking group, a naphthylene linking group, a 9-anthrylene linking group, a phenanthrylene linking group, or a pyrenyllene linking group. Group, naphthacenylene bond group, indenylene bond group, azulylene bond group, fluorenylene bond group, terphenylene bond group, quarterphenylene bond group, tolylene bond group, xylylene bond group, cumenylene bond group, mesitylene bond group, pentalenylene bond group, binaphthalylene bond group Group, Turnaphthalenylene bond group, Quarter Naphthalenylene bond group, Heptalenylene bond group, Biphenylenylene bond group, Indasenylene bond group, Fluoranthenylene bond group, Acenaphthyleneylene bond group, Aseantrirenylene bond group Phenalylene bond group, fluorenylene bond group, anthrylene bond group, bianthracenylene bond group, teranthracenylene bond group, quarter anthracenylene bond group, anthraquinolylene bond group, phenanthrylene bond group, triphenylenylene bond group, pyrenylene Bonding group, chrysenylene bonding group, naphthacenylene bonding group, preadenylene bonding group, picenylene bonding group, peryleneylene bonding group, pentaphenylene bonding group, pentacenylene bonding group, tetraphenylenyl group, hexaphenylene bonding group, hexasenylene bonding group, rubisenylene bonding A group, a coronenylene linking group, a trinaphthyleneylene linking group, a heptaphenylene linking group, a heptasenylene linking group, a pyrantrenylene linking group, an oberenylene linking group and the like.

  The heterocyclic linking group which may have a substituent is preferably an aromatic or aliphatic heterocyclic linking group containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. For example, thienylene bond group, benzo [b] thienylene bond group, naphtho [2,3-b] thienylene bond group, thiantrenylylene bond group, furylylene bond group, pyranylene bond group, isobenzofuranylene bond group, chromenylene bond group , Xanthenylene bond group, phenoxathiinylylene bond group, 2H-pyrrolylylene bond group, pyrrolylylene bond group, imidazolylene bond group, pyrazolylene bond group, pyridylylene bond group, pyrazinylylene bond group, pyrimidinylylene bond group, pyridazinylylene bond group, indolinylylene bond group Group, isoindoleylene linking group, 3H-indoleylene linking group, indoleylene linking group, 1H-indazolylene linking group, purinylylene linking group, 4H-quinolidinylylene linking group, isoquinolylene linking group, quinolylene linking group, lid Dinylylene linking group, naphthyridinylylene linking group, quinoxanylylene linking group, quinazolinylylene linking group, cinnolinylylene linking group, pteridinylylene linking group, 4aH-carbazolylene linking group, carbazolylline linking group, β-carbolinylylene linking group, phenanthridinylylene linking group Linking group, perimidinylylene linking group, phenanthrolinylylene linking group, phenazinylylene linking group, phenalsadinylylene linking group, isothiazolylylene linking group, phenothiazinylylene linking group, isoxazolylylene linking group, flazanyrrylene linking group, phenoxa Dilinylene bond group, isochromanirylene bond group, chromanylylene bond group, pyrrolidinylylene bond group, pyrrolinylylene bond group, imidazolidinylylene bond group, imidazolinylylene bond group, pyrazolid Examples include a nylylene linking group, a pyrazolinylylene linking group, a piperidylylene linking group, a piperazinylylene linking group, an indolinylylene linking group, an isoindolinylylene linking group, a quinuclidinylylene linking group, a morpholinylylene linking group, and a thioxanthryllylene linking group.

  Other bonding groups include ether bonding groups, ester bonding groups, thioether bonding groups, dithiol bonding groups, carbonyl bonding groups, sulfinyl bonding groups, sulfonyl bonding groups, phosphonyl bonding groups, amino bonding groups, imino bonding groups, or silyls. A linking group or the like represents a linking group containing an oxygen atom, a nitrogen atom, a phosphorus atom, or a sulfur atom.

  Furthermore, the alkyl group which may have a substituent mentioned above, or an alkylene bond group, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a substituent and a double bond. An alkylene bond group which may have a substituent and a triple bond, an aryl group which may have a substituent, or an arylene bond group and a heterocyclic group which may have a substituent Alternatively, the hydrogen atom of the heterocyclic bond group may be further substituted with another substituent.

  Examples of such substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, trifluoromethyl group, perfluoroethyl group, perfluoroalkyl group, trichloromethyl group, perchloroalkyl group, and tribromomethyl. Halogenated alkyl groups such as methoxy groups, alkoxy groups such as methoxy groups, ethoxy groups, tert-butoxy groups, aryloxy groups such as phenoxy groups, p-tolyloxy groups, methoxycarbonyl groups, butoxycarbonyl groups, phenoxycarbonyl groups, vinyloxy Alkoxycarbonyl groups such as carbonyl groups, aryloxycarbonyl groups, acyloxy groups such as acetoxy groups, propionyloxy groups, benzoyloxy groups, acetyl groups, benzoyl groups, isobutyryl groups, acryloyl groups, methacryloyl groups, methoxa groups An acyl group such as a methyl group, an alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group, an arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group, an alkylamino group such as a methylamino group and a cyclohexylamino group, Dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group, arylamino groups such as phenylamino group and p-tolylamino group, alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group, Aryl group such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, etc., hydroxyl group, carboxyl group, sulfonamide group, formyl group, mercapto group, sulfo group, mesyl group Group, p-tolue Sulfonyl, amino, nitro, nitroso, cyano, trifluoromethyl, trichloromethyl, trimethylsilyl, phosphinico, phosphono, alkylsulfonyl, arylsulfonyl, trialkylammonium, dimethylsulfonyl Group, triphenylphenacylphosphoniumyl group and the like.

  Among such substituents, a preferred substituent is an electron-withdrawing substituent. When the electron-withdrawing substituent is substituted, the ionic compound is generally easily dissociated and the antistatic performance is improved.

  Such electron-attracting substituents are generic names for substituents that attract electrons from the other party by resonance effects and induced effects, and many of them have a positive value for the substituent constant σ in Hammett's rule. It is. These substituents are not particularly limited, and specific examples thereof include Chemical Review Vol. 91, Nos. 165 to 195, published in 1991, with a σp greater than 0. More specifically, halogen groups, cyano groups, carboxyl groups, nitro groups, nitroso groups, acyl groups, alkyloxycarbonyls Group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, amide group, perfluoroalkyl group, perfluoroalkylthio group, perfluoroalkylcarbonyl group, sulfonamide group, 4-cyanophenyl group and the like.

  Further, like the above-described substituents, examples of a preferable linking group include an electron-withdrawing linking group. The presence of an electron-withdrawing linking group is preferable because the ionic compound is easily dissociated and the antistatic performance is improved. As such a linking group, a carbonyl linking group, a sulfonyl linking group or the like is preferably used.

R ^{1 to} R ⁴ are preferably an alkyl group which may have a substituent or an aryl group which may have a substituent, more preferably a substituent, in view of the stability of the compound. It is an aryl group that may have.

R ^{5 to} R ⁸ are preferably an alkyl group which may have a substituent in consideration of the stability of the compound.

In view of the stability of the compound, R ⁹ is preferably a sulfonyl bond group, and R ¹⁰ is preferably a halogen group. R ¹¹ is preferably a combination of a sulfonyl bond group and a halogen group or a halogenated alkyl group, as in R ⁹ and R ¹⁰ .

  Representative examples of the ammonium salt compound (a1) represented by the general formula (1) in the present invention are shown in the following Tables 1 to 6 as exemplified compounds (a1-1) to (a1-92), Representative examples of the alkali metal salt compound (a2) represented by the formula (2) are shown in the following Table 7 as exemplified compounds (a2-1) to (a2-10), and also represented by the general formula (3). Representative examples of the ammonium salt compound (a3) to be prepared are specifically exemplified in the following Tables 8 to 14 as exemplified compounds (a3-1) to (a3-106), but are not limited thereto. is not. In the exemplified compounds, Me is a methyl group, Et is an ethyl group, Bu is a normal butyl group, Pr is a normal propyl group, i-Pr is an isopropyl group, Hex is a hexyl group, Oct is an octyl group, and c-Hex is cyclohexyl. Group, Dec represents a decyl group, Cet represents a cetyl (also referred to as hexadecyl) group, and Ph represents a phenyl group.

  The resin composition of the present invention uses other antistatic agents in combination with the ammonium salt compound (a1), alkali metal salt compound (a2), or ammonium salt compound (a3). May be. Although it does not specifically limit as a compound to use together, Well-known surfactant and organic salt of an alkali metal are mentioned, These can use these individually or in combination.

  In addition, the resin composition of the present invention comprises 100 parts by weight of the active energy ray-polymerizable resin composition based on the ionic compound (A) which is the alkali metal salt compound (a2) or the ammonium salt compound (a3). %, Preferably 0.01 to 10 parts by weight, more preferably 0.01 to 10% by weight. If the amount is less than 0.01% by weight, sufficient antistatic performance may not be obtained, and even when added by 10% by weight or more, it may be difficult to obtain further antistatic performance, and further heat resistance May result in defects.

(B) component:
In one embodiment of the resin composition of the present invention, it is important that the resin composition contains an α, β-ethylenically unsaturated double bond group-containing compound (B) in addition to the essential components described above. . In particular, any compound containing one or more α, β-unsaturated double bond groups can be used without limitation, but α, β-ethylenic compounds having one or more hydroxyl groups in the structure thereof can be used. It is preferable to contain an unsaturated double bond group containing compound (b1). The compound (b1) is divided into a compound (b1-1) having a hydroxyl group and not having a cyclic structure and a compound (b1-2) having a hydroxyl group and having a cyclic structure, both of which have a hydroxyl group. By this, a big effect is shown by the adhesive improvement with the below-mentioned base material (G).
Furthermore, it contains an α, β-ethylenically unsaturated double bond group-containing compound (b2) having at least one cyclic structure and no hydroxyl group in terms of improving durability such as heat resistance or heat and humidity resistance. It is preferable. Moreover, (alpha), (beta) -ethylenically unsaturated double bond group containing compound (b3) other than (b1) and (b2) can also be contained.

 When the resin composition contains the compound (b1), it is easy to improve the solubility of the ionic compound (A). Further, the viscosity of the resin composition can be easily reduced, and the workability during coating can be easily improved. Although it does not specifically limit, The following is mentioned as a compound which can be used as a component (B).

 Among the compounds (b1), the compound (b1-1) having a hydroxyl group and not having a cyclic structure is not particularly limited as long as it has a hydroxyl group in the structure but does not have a cyclic structure. For example, 2-hydroxyethyl (meth) acrylate [2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are collectively referred to as “2-hydroxyethyl (meth) acrylate”. The same applies below. ], 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 2-hydroxy (meth) acrylate Butyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, cyclohexanedimethanol mono (meth) acryl Acid ester, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, ethyl (meth) acrylate-α- (hydroxymethyl), monofunctional (meth) acrylate glycerol, or (meth) Glycidyl acrylate, ( T) Fatty acid ester-based (meth) acrylic acid ester such as glycidyl acrylate acrylate, glycidyl stearate (meth) acrylate, or the above hydroxyl group such as 2- (acryloyloxy) ethyl 6-hydroxyhexanonate A (meth) acrylic acid ester having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone lactone to the α, β-ethylenically unsaturated double bond group-containing compound, or the hydroxyl group-containing α, β-ethylenically unsaturated group Hydroxyl-containing aliphatic (meth) acrylates such as alkylene oxide-added (meth) acrylates in which alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide are repeatedly added to a double bond group-containing compound;

 For example, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyoctyl vinyl ether, hydroxydecyl vinyl ether, hydroxydodecyl vinyl ether, hydroxyoctadecyl vinyl ether, glyceryl vinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, triethylene glycol Hydroxyl-containing aliphatic vinyl ethers such as methylolpropane monovinyl ether, pentaerythritol monovinyl ether, or alkylene oxide-added vinyl ether having a hydroxyl group at the terminal where alkylene oxide such as ethylene oxide or propylene oxide is repeatedly added;

 For example, (meth) allyl alcohol [allyl alcohol and methallyl alcohol are collectively referred to as “(meth) allyl alcohol”. The same applies below. ], Isopropenyl alcohol, dimethyl (meth) allyl alcohol, hydroxyethyl (meth) allyl ether, hydroxypropyl (meth) allyl ether, hydroxybutyl (meth) allyl ether, hydroxyhexyl (meth) allyl ether, hydroxyoctyl (meth) Allyl ether, hydroxydecyl (meth) allyl ether, hydroxydodecyl (meth) allyl ether, hydroxyoctadecyl (meth) allyl ether, glyceryl (meth) allyl ether, or an alkylene oxide such as ethylene oxide or propylene oxide repeatedly added to the terminal Hydroxyl group-containing aliphatic (meth) allyl alcohols or (meth) allylate such as alkylene oxide addition system (meth) allyl ether having a hydroxyl group Kind;

For example, α, β-ethylenically unsaturated double bond group-containing compounds having a plurality of hydroxyl groups such as propenediol, butenediol, heptenediol, octenediol, and glycerol di (meth) acrylate;
For example, N-hydroxyethyl (meth) acrylamide [N-hydroxyethyl acrylamide and N-hydroxyethyl methacrylamide are collectively referred to as “N-hydroxyethyl (meth) acrylamide”. The same applies below. ], Hydroxyl-containing (meth) acrylamides such as N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyoctyl (meth) acrylamide;

Examples thereof include monomers having a hydroxyl group and an ethenyl group such as vinyl alcohol, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.
As the compound (B), 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid 2 in terms of the solubility of the above-mentioned ionic compound (A) and the adhesion to the substrate (G) described later. Α, β-ethylenically unsaturated double bonds having 2 to 18 carbon atoms such as hydroxypropyl, 4-hydroxybutyl (meth) acrylate, 1 to 2 mol of ε-caprolactone and 2-hydroxyethyl (meth) acrylate Group-containing compounds are particularly preferred.

Among the compounds (b1), the compound (b1-2) having a hydroxyl group and having a cyclic structure can be used without particular limitation as long as it has both of the cyclic structures. Since the compound (b1-2) has one or more ring structures in the molecule, it is preferable from the viewpoint of water resistance in addition to durability such as heat resistance and moist heat resistance even if it has a hydroxyl group. .
The compound (b1-2) is not particularly limited as long as it has both a hydroxyl group and a cyclic structure in its structure. For example, (meth) acrylic acid 1,2-cyclohexanedimethanol, (meth) acrylic acid 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol (meth) acrylate, 2-hydroxy-3-phenoxymethyl (meth) acrylate, 2-hydroxy-3-phenoxyethyl (meth) acrylate, ( 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-phenoxybutyl (meth) acrylate, 2-hydroxy-3-phenoxydecyl (meth) acrylate, 2-hydroxy- (meth) acrylate 3-phenoxyoctadecyl, (meth) acrylic acid monohydroxyethyl phthalate, (meth ) Having a cyclic structure other than a hydroxyl group and a hetero ring such as acrylic acid 2- (4-benzoyl-3-hydroxyphenoxy) ethyl (meth) acrylate;

 For example, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone [2-hydroxy-4- {2-acryloyloxy} ethoxybenzophenone and 2-hydroxy-4- {2-methacryloyloxy} ethoxybenzophenone Are also expressed as “2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone”. The same applies below. ], 2-hydroxy-4- {2- (meth) acryloyloxy} butoxybenzophenone, 2,2′-dihydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- Hydroxyl-containing benzophenone-based (meth) acrylic esters such as (meth) acryloyloxy} ethoxy-4 ′-(2-hydroxyethoxy) benzophenone;

  For example, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -5-chloro -2H-benzotriazole, 2- (2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, and 2- (2'-hydroxy -3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-ben Hydroxyl group-containing benzotriazole-based triazole (meth) acrylic acid esters;

  For example, 2,4-diphenyl-6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methylphenyl) -6- [2- Hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy }]-S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis ( 2-Ethoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2- Hydroxy-4- {2- Meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S- Hydroxyl-containing triazines such as triazine and 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy})]-S-triazine (meta ) Acrylic acid esters and the like, and these may be used alone or in combination of two or more.

 As the compound (b1-2), in view of compatibility with the compound (A) and durability such as heat resistance and water resistance, 1,2-cyclohexanedimethanol acrylate, 1,3-cyclohexanedimethanol acrylate Particularly preferred are 1,4-cyclohexanedimethanol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and the like.

 The α, β-ethylenically unsaturated double bond group-containing compound (b2) having one or more cyclic structures and no hydroxyl group is an α, β-ethylenic compound having a ring structure containing no hetero atom in the molecule. There is an unsaturated double bond group-containing compound (b2-1) and an α, β-ethylenically unsaturated double bond group-containing compound (b2-2) having a ring structure containing a hetero atom in the molecule, From the viewpoint of modification, (b2-1) is preferable.

The compound (b2-1) is not particularly limited as long as it has a ring structure other than a heterocyclic ring in its structure. For example, cyclohexyl (meth) acrylate, 1-methyl-1- (meth) acrylate Cyclopentyl, 1-ethyl-1-cyclopentyl (meth) acrylate, 1-isopropyl-1-cyclopentyl (meth) acrylate, 1-methyl-1-cyclohexyl (meth) acrylate, 1-ethyl (meth) acrylate 1-cyclohexyl, 1-isopropyl-1-cyclohexyl (meth) acrylate, 1-ethyl-1-cyclooctyl (meth) acrylate, benzyl (meth) acrylate, iso-bornyl (meth) acrylate, (meth) Phenyl acrylate, 2-methoxyethyl (meth) acrylate, 2-oxo-1, (meth) acrylate, -Phenylethyl, 2-oxo-1,2-diphenylethyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, 1-naphthylmethyl (meth) acrylate, (meth ) 1-anthryl acrylate, 2-anthryl (meth) acrylate, 9-anthryl (meth) acrylate, 9-anthrylmethyl (meth) acrylate, 2-methyladamantyl-2-yl (meth) acrylate, (Meth) acrylic acid dicyclopentanyl, (meth) acrylic acid dicyclopentenyl, (meth) acrylic acid dicyclopentenyloxyethyl, (meth) acrylic acid 2-ethyladamantyl-2-yl, (meth) acrylic acid 2 -N-propyladamantyl-2-yl, 2-isopropyladamantyl-2-yl (meth) acrylate, 1- (adamantan-1-yl) -1-methylethyl (meth) acrylate, 1- (adamantan-1-yl) -1-ethylethyl (meth) acrylate, 1- (adamantan-1-(meth) acrylic acid Yl) -1-methylpropyl, 1- (adamantan-1-yl) -1-ethylpropyl (meth) acrylate, (meth) acrylic acid-5-oxo-4-oxa-tricyclo [4.2.1. 0 ^3,7 ] non-2-yl, (meth) acrylic acid-5-oxo-4-oxa-tricyclo [5.2.1.0 ^3,8 ] dec-2-yl, (meth) acrylic acid dihydro -Α-Turpinyl, (meth) acrylic acid-6-oxo-7-oxa-bicyclo [3.2.1] oct-2-yl, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [3 3.1] Oct-2-yl 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyloxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate 2- (meth) acryloyloxydecyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, (meth) acrylic (3,4-epoxycyclohexyl) methyl, (meth) acrylic acid-o-2-propenylphenyl, (Meth) acrylic acid cyclic esters such as (meth) acrylic acid cyclohexyl glycidyl ether and (meth) acrylic acid phenylglycidyl ether;

 For example, N- (4-carbamoylphenyl) (meth) acrylamide, β- (2-furyl) (meth) acrylamide, 2,3-bis (2-furyl) acrylamide, N- (9H-fluoren-2-yl) (Meth) acrylamide, N-[(R) -1-phenylethyl] (meth) acrylamide, N-[(S) -1-phenylethyl] (meth) acrylamide, (Z) -N-methyl-3- ( Phenyl) (meth) acrylamide, (Z) -3- (phenyl) (meth) acrylamide, N, N-diethyl-3-phenyl (meth) acrylamide, (Z) -N, N-dimethyl-3- (phenyl) (Meth) acrylamides containing cyclic structures such as (meth) acrylamide

  For example, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyl Oxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4-isopropenylbenzenecarboxylic acid, Carboxylic acids such as cinnamic acid, 7-amino-3-vinyl-3-cephem-4-carboxylic acid and the like, and carboxylic acids containing alicyclic and aromatic rings containing aromatic groups and aromatic rings, and acid anhydrides thereof Kind;

  For example, (meth) acrylic acid cyclic esters containing a sulfonyl group, such as (meth) acrylic acid sulfophenoxyethyl, (meth) acrylic acid sulfocyclohexyl, (meth) acrylic acid sulfobenzyl;

 For example, (meth) acryloyloxyethyldimethylbenzylammonium-p-toluenesulfonate, (meth) acryloyloxyethyltrimethylammonium-p-toluenesulfonate, (meth) acryloylaminopropyltrimethylammonium-p-toluenesulfonate, phenyl-2- ( Metal salts and ammonium salts of (meth) acrylic acid cyclic esters containing a sulfonyl group such as (meth) acryloyloxyethyl phosphate;

 For example, di (meth) acrylic acid tricyclodecane dihydroxymethyl, di (meth) acrylic acid tricyclodecane dihydroxymethyl dicaprolactonate, di (meth) acrylic acid 1,2-adamantanediol, di (meth) acrylic acid 1 , 3-adamantanediol, 1,4-adamantanediol di (meth) acrylate, tricyclodecanyl dimethylol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, di (meth) acrylate di Cyclopentenyl, dicyclopentenyloxyethyl di (meth) acrylate, 1,4-bis (2-hydroxypropyl) benzene di (meth) acrylate, 1,3-bis (2-hydroxy) di (meth) acrylate Propyl) benzene, di (meth) acrylic acid-2,2-bis (hydroxyphenyl) Tetraethylene oxide adduct of lopan, tetraethylene oxide adduct of 2,2-bis (hydroxyphenyl) methane di (meth) acrylate, tetraethylene oxide of di (meth) acrylic acid-4,4′-sulfonyldiphenol Adduct, Tetraethylene oxide adduct of di (meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) propane, Tetra of di (meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) methane Ethylene oxide adduct, di (meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) propane, di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxyphenyl) methane, di (meta ) Tetraethylene oxide adduct of acrylic acid-2,2-bis (hydroxyphenyl) propane-dicap Bifunctional (meth) acrylic acid cyclic esters such as lolactonate, tetraethylene oxide adduct of di (meth) acrylic acid-2,2-bis (hydroxyphenyl) methane-dicaprolactonate;

 For example, 5-vinylbicyclo [2.2.1] hept-2-ene, 2,5-bis (allyloxy) norbornane, 5-vinyl-2,3-oxirane norbornane, 2- (2-propenyl) bicyclo [2 2.1] heptane, 5-vinylbicyclo [2.2.1] hept-2-ene, 2-ethenylideneadamantane, 1-allyladamantane, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinyl Cyclic compounds containing alkenyl groups such as benzoic acid, 4-isopropenylbenzenecarboxylic acid, cinnamic acid, 7-amino-3-vinyl-3-cephem-4-carboxylic acid, cyclohexyl vinyl ether, cyclohexylmaleimide, vinylcyclohexene monooxirane ;

  For example, vinyl benzoylformate, vinyl benzoyl acetate, vinyl benzoylpropionate, vinyl benzoylbutyrate, vinyl benzoylvalerate, vinyl benzoylhexanoate, vinyl benzoyldodecanoate, 1-naphthoylvinyl acetate, 1-naphthoylpropionate, 1- Naphthoyl vinyl butyrate, 1-naphthoyl vinyl valerate, 1-naphtho vinyl hexanoate, 2-naphtho vinyl acetate, 2-naphtho vinyl propionate, 2-naphtho vinyl butyrate, 2-naphtho vinyl butyrate, 2- Vinyl naphthoyl hexanoate, vinyl nicotinoyl acetate, vinyl nicotinoyl propionate, vinyl nicotinoyl butyrate, vinyl nicotinoyl valerate, vinyl nicotinoyl hexanoate, vinyl nicotinoyl decanoate, nicotine Vinyl dodecanoate, vinyl isonicotinoyl acetate, vinyl isonicotinoyl propionate, vinyl isonicotinoyl butyrate, vinyl isonicotinoyl valerate, vinyl isonicotinoyl hexanoate, vinyl isonicotinoyl decanoate, vinyl isonicotinoyl dodecanoate, 2-furoyl Vinyl acetate, vinyl 2-furoylpropionate, vinyl 2-furoylbutyrate, vinyl 2-furoylvalerate, vinyl 2-furoylhexanoate, vinyl 2-furoyldecanoate, vinyl 2-furoyldodecanoate, 3-furoyl Vinyl acetate, vinyl 3-furoylpropionate, vinyl 3-furoylbutyrate, vinyl 3-furoylvalerate, vinyl 3-furoylhexanoate, vinyl 3-furoyldecanoate, vinyl 3-furoyldodecanoate, vinyl anthraniloyl acetate , Vinyl anthraniloyl propionate, vinyl anthraniloyl butyrate, vinyl anthraniloyl valerate, vinyl anthraniloyl hexanoate, vinyl anthraniloyl decanoate, vinyl anthraniloyl decanoate, 4- (2-t-ethoxycarbonylethyl) Aromatic vinyl compounds having an acyl group such as oxy) styrene, 4- (2-t-butoxycarbonylethyloxy) styrene, 4- (2-t-butoxycarbonylpropyloxy) styrene;

 For example, benzoyl formate (meth) allyl, benzoyl acetate (meth) allyl, benzoylpropionate (meth) allyl, benzoylbutyrate (meth) allyl, benzoylvalerate (meth) allyl, benzoylhexanoic acid (meth) allyl, benzoyldodecanoic acid (Meth) allyl, 1-naphthoylacetic acid (meth) allyl, 1-naphthoylpropionic acid (meth) allyl, 1-naphthoylbutyric acid (meth) allyl, 1-naphthoylvaleric acid (meth) allyl, 1-naphthoylhexane Acid (meth) allyl, 2-naphthoylacetic acid (meth) allyl, 2-naphthoylpropionic acid (meth) allyl, 2-naphthoylbutyric acid (meth) allyl, 2-naphthoylvaleric acid (meth) allyl, 2-naphthoyl Aromatic (meth) allyl having an acyl group such as hexanoic acid (meth) allyl Ethylenically unsaturated cyclic monomers containing carbonyl groups of compounds, and the like;

 For example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4-t-butoxystyrene, 4-t- Butoxy-α-methylstyrene, 4- (2-ethyl-2-propoxy) styrene, 4- (2-ethyl-2-propoxy) -α-methylstyrene, 4- (1-ethoxyethoxy) styrene, 4- ( Aromatic vinyl monomers such as 1-ethoxyethoxy) -α-methylstyrene, 1-butylstyrene, 1-chloro-4-isopropenylbenzene;

 For example, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, cyclohexyl ethyl vinyl ether, menthyl vinyl ether, tetrahydrofurfuryl vinyl ether, norbornenyl vinyl ether, 1-adamantyl vinyl ether, 2-adamantyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, 1-naphthyl vinyl ether, 2- Cyclic vinyl ethers such as naphthyl vinyl ether;

 For example, vinyl phenyl pentyl ether, vinyl phenyl hexyl ether, vinyl phenyl heptyl ether, vinyl phenyl octyl ether, vinyl phenyl nonyl ether, vinyl phenyl decyl ether, vinyl phenyl undecyl ether, vinyl phenyl dodecyl ether, vinyl phenyl tridecyl ether, vinyl Phenyl tetradecyl ether, vinyl phenyl pentadecyl ether, vinyl phenyl hexadecyl ether, vinyl phenyl heptadecyl ether, vinyl phenyl octadecyl ether, vinyl phenyl nonadecyl ether, vinyl phenyl eicosyl ether, vinyl phenyl henecosyl ether, vinyl phenyl doco Sil ether, vinyl phenyl methyl butyl ether, vinyl phenyl Rupentyl ether, vinyl phenyl methyl hexyl ether, vinyl phenyl methyl heptyl ether, vinyl phenyl methyl octyl ether, vinyl phenyl methyl nonyl ether, vinyl phenyl methyl decyl ether, vinyl phenyl methyl undecyl ether, vinyl phenyl methyl dodecyl ether, vinyl phenyl methyl Tridecyl ether, vinyl phenylmethyl tetradecyl ether, vinyl phenyl methyl pentadecyl ether, vinyl phenyl methyl hexadecyl ether, vinyl phenyl methyl heptadecyl ether, vinyl phenyl methyl octadecyl ether, vinyl phenyl methyl nonadecyl ether, vinyl phenyl methyl eicosyl Ether, vinyl phenyl methyl henecosyl ether, vinyl Aromatic vinyl ether-based monomers having a long-chain alkyl groups such as E methylpropenylmethyl docosyl ether;

 Hexyl 4-vinylbenzoate, octyl 4-vinylbenzoate, nonyl 4-vinylbenzoate, decyl 4-vinylbenzoate, dodecyl 4-vinylbenzoate, tetradecyl 4-vinylbenzoate, hexadecyl 4-vinylbenzoate, 4 -Octadecyl vinylbenzoate, eicosyl 4-vinylbenzoate, docosyl 4-vinylbenzoate, hexyl 4-isopropenylbenzoate, octyl 4-isopropenylbenzoate, nonyl 4-isopropenylbenzoate, 4-isopropenylbenzoic acid Decyl, dodecyl 4-isopropenylbenzoate, tetradecyl 4-isopropenylbenzoate, hexadecyl 4-isopropenylbenzoate, octadecyl 4-isopropenylbenzoate, eicosyl 4-isopropenylbenzoate, docosyl 4-isopropenylbenzoate, etc. Head of Vinyl benzoate ester or isopropenyl benzoic acid ester monomers having alkyl group;

 For example, tetra (ethylene oxide) vinyl phenyl ether, methyl tetra (ethylene oxide) vinyl phenyl ether, ethyl tetra (ethylene oxide) vinyl phenyl ether, propyl tetra (ethylene oxide) vinyl phenyl ether, n-butyl tetra (ethylene oxide) vinyl phenyl ether , N-pentyltetra (ethylene oxide) vinyl phenyl ether, tetra (propylene oxide) vinyl phenyl ether, methyl tetra (propylene oxide) vinyl phenyl ether, ethyl tetra (propylene oxide) vinyl phenyl ether, propoxy tetra (propylene oxide) vinyl phenyl ether N-butyltetra (propylene oxide) vinyl phenyl ether, n Pentaxytetra (propylene oxide) vinyl phenyl ether, poly (ethylene oxide) vinyl phenyl ether, methyl poly (ethylene oxide) vinyl phenyl ether, ethyl poly (ethylene oxide) vinyl phenyl ether, poly (propylene oxide) vinyl phenyl ether, methyl poly (propene Oxide) vinyl phenyl ether, ethyl poly (propylene oxide) ethenyl phenyl ether, poly (ethylene oxide) vinyl benzyl ether, methyl poly (ethylene oxide) vinyl benzyl ether, ethyl poly (ethylene oxide) ethenyl benzyl ether, poly (propylene oxide) vinyl Benzyl ether, methyl vinyl poly (propylene oxide) vinyl benzyl Ether, ethyl poly (propylene oxide) vinyl benzyl ether, poly (ethylene oxide) vinyl phenyl ethyl ether, methyl poly (ethylene oxide) vinyl phenyl ethyl ether, ethyl poly (ethylene oxide) vinyl phenyl ethyl ether, poly (oxypropylene) vinyl phenyl ethyl ether Vinyl phenyl ether monomers having a long-chain polyalkylene oxide moiety such as methyl poly (propylene oxide) vinyl phenyl ethyl ether, ethyl poly (propylene oxide) vinyl phenyl ethyl ether;

 For example, isopropenyl phenylmethyl butyl ether, isopropenyl phenyl methyl pentyl ether, isopropenyl phenyl methyl hexyl ether, isopropenyl phenyl methyl heptyl ether, isopropenyl phenyl methyl octyl ether, isopropenyl phenyl methyl nonyl ether, isopropenyl phenyl methyl decyl ether, Isopropenyl phenylmethyl undecyl ether, isopropenyl phenyl methyl dodecyl ether, isopropenyl phenyl methyl tridecyl ether, isopropenyl phenyl methyl tetradecyl ether, isopropenyl phenyl methyl pentadecyl ether, isopropenyl phenyl methyl hexadecyl ether, isopropenyl phenyl Methyl heptadecyl ether, Isopropenyl phenyl having a long chain alkyl group such as isopropenyl phenyl methyl octadecyl ether, isopropenyl phenyl methyl nonadecyl ether, isopropenyl phenyl methyl eicosyl ether, isopropenyl phenyl methyl heneicosyl ether, isopropenyl phenyl methyl docosyl ether Type monomers;

 For example, poly (ethylene oxide) isopropenyl phenyl ether, methyl poly (ethylene oxide) isopropenyl phenyl ether, ethyl poly (ethylene oxide) isopropenyl phenyl ether, poly (propylene oxide) isopropenyl phenyl ether, methyl poly (propylene oxide) isopropenyl phenyl Ether, ethyl poly (propene oxide) isopropenyl phenyl ether, poly (ethylene oxide) isopropenyl benzyl ether, methyl poly (ethylene oxide) isopropenyl benzyl ether, ethyl poly (ethylene oxide) isopropenyl benzyl ether, poly (propylene oxide) isopropenyl benzyl Ether, methyl poly (propylene oxide) Isopropenyl-based monomers having a polyalkylene oxide moiety, such as propenyl benzyl ether;

 For example, mono-long-chain alkyl ester cyclic monomers of dicarboxylic acid such as vinyl phenylnonyl succinate, vinyl phenyl methyl decyl hexahydrophthalate, vinyl phenyl ethyl dodecyl terephthalate;

For example, monopolyalkylene oxide esters of dicarboxylic acids such as vinyl phenyl poly (ethylene oxide) succinate, vinyl phenyl methyl poly (ethylene oxide) hexahydrophthalate, vinyl phenyl ethyl poly (ethylene oxide) terephthalate;
Polyalkylene oxides such as methyl 4-vinylbenzoate poly (ethylene oxide), ethyl polyvinylbenzoate poly (ethylene oxide), methyl 4-isopropenylbenzoate poly (propylene oxide), ethyl polyisopropylenylbenzoate poly (propylene oxide) Vinyl benzoate or isopropenyl benzoate monomers having a moiety;

 For example, alkenyl group-containing cyclic sulfonic acids such as styrenesulfonic acid, 2-propenyloxybenzenesulfonic acid, 2-methyl-2-propenyloxybenzenesulfonic acid;

For example, ammonium styrene sulfonate, monomethyl ammonium styrene sulfonate, dimethyl ammonium styrene sulfonate, trimethyl ammonium styrene sulfonate, tetramethyl ammonium styrene sulfonate, ethyl ammonium styrene sulfonate, diethyl ammonium styrene sulfonate, triethyl styrene sulfonate Styrenesulfonic acid such as ammonium, tetraethylammonium styrenesulfonate, propylammonium styrenesulfonate, dipropylammonium styrenesulfonate, tripropylammonium styrenesulfonate, butylammonium styrenesulfonate, pentylammonium styrenesulfonate or hexylammonium styrenesulfonate Ammonium salts of
Metal salts of styrene sulfonic acid such as sodium styrene sulfonate, potassium styrene sulfonate, lithium styrene sulfonate, magnesium styrene sulfonate, zinc styrene sulfonate, iron styrene sulfonate;
Metal salts and ammonium salts of alkenyl group-containing vinyloxybenzenesulfonic acid such as ammonium vinyloxybenzenesulfonate, sodium vinyloxybenzenesulfonate, potassium vinyloxybenzenesulfonate, etc .;
2-methyl-2-propenyloxybenzenesulfonate ammonium, 2-methyl-2-propenyloxybenzenesulfonate sodium, 2-methyl-2-propenyloxybenzenesulfonate potassium and the like 2-methyl-2-propenyloxybenzenesulfonate Examples include acid metal salts and ammonium salts.

  In addition, for example, o-di (meth) allylbisphenol A, hydrogenated bisphenol A in which an aromatic ring structure is hydrogenated, and the like have an α, β-unsaturated double bond group, compound (b2-1) included. These may use only 1 type or may use multiple types together.

 As the compound (b2-1), from the viewpoint of durability such as heat resistance and water resistance, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-phenoxyethyl acrylate, iso-bornyl acrylate, diacrylate acrylate Particularly preferred are cyclopentanyl, dicyclopentanyl diacrylate, dicyclopentenyl acrylate, dicyclopentenyl diacrylate, and 2-ethyladamantyl-2-yl acrylate.

 The compound (b2-2) is not particularly limited as long as it has a heterocyclic structure in its structure. For example, pentamethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, Heterocyclic (meth) acrylic acid esters containing a nitrogen atom such as 4- (pyrimidin-2-yl) piperazin-1-yl (meth) acrylate;

For example, 1-vinylpyrrole, 1-vinyl-2-imidazoline, 1-vinyl-2-methyl-2-imidazoline, 1-vinylimidazole, 2-vinylpyrrole, 2-methyl-5-vinyl-1H-pyrrole, 2 -Vinyl-2-imidazoline, 4,5-dihydro-2-vinyl-1H-imidazole, 2-vinyl-1H-imidazole, 1-vinyl-1H-pyrazole, 1-vinyl-3,5-dimethyl-1H-pyrazole 3-methyl-5-phenyl-1-vinylpyrazole, 1-vinylindole, 1-vinyl-2-methyl-1H-indole, 1-vinylisoindole, 1-vinyl-1H-benzimidazole, 1-vinylindazole 1-vinylquinoline, 1-vinylisoxaline, 1-vinylquinazoline, 1-vinylcinnoline, Nilcarbazole, 1,1′-divinyl-2,2′-bi (1H-imidazole), N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, 1-vinylpyridin-2 (1H) -one, Vinyl group-containing compounds having a nitrogen atom-containing heterocycle such as 1-vinyl-2 (1H) -pyridinethione;

 For example, 1- (meth) allyl-1H-imidazole, 1- (meth) allyl-2-methyl-1H-imidazole, 1- (meth) allyl-3-methyl-1H-imidazol-3-ium, 1- ( (Meth) allyl-3-ethyl-1H-imidazol-3-ium, 5-bromo-1- (meth) allyl-1H-pyrazole, 1- (meth) allylpiperazine, 1- (meth) allyl-5,5- Diethylpyrimidine, N- (meth) allyl-s-triazine-2,4,6-triamine, N- (meth) allyl-4,6-dichloro-1,3-5-triazine-2-amine, 2-vinyl Piperazine, 4-vinylpiperazine, 1-benzyl-2-vinylpiperazine, 1-benzyl-3-vinylpiperazine, 1,4-dimethyl-3-vinylpiperazine, 2-vinylpyridine, -Vinylpyridine, 4-vinylpyridine, 6-methyl-2-ethenylpyridine, 2-vinylpyrazine, 2-methyl-5-vinylpyrazine, 2-methyl-6-vinylpyrazine, 2,5-dimethyl-3- Vinylpyrazine, 2-vinylpyrimidine, 2-vinylpyridazine, 2-vinyl-4,6-diamino-1,3,5-triazine, 6-vinyl-1,3,5-dimethyl-2,4-diamine, 3 -Vinyl group-containing compounds having a nitrogen atom-containing six-membered ring such as vinyl-1,2,4,5-tetrazine;

 For example, 2-vinyl-1H-benzimidazole, 2-vinyl-5,6-dimethyl-1H-benzimidazole, 2-vinylindazole, 2-vinylquinoline, 4-vinylquinoline, 2-vinylisoquinoline, 2-vinyliso Xaline, 2-vinylquinoxaline, 2-vinylquinazoline, 2-vinylcinnoline, 1- (meth) allyl-1H-benzimidazole, 1- (meth) allyl-3-methyl-1H-indazole, 1- (meta ) Nitrogen atoms such as allyl-4-methyl-1H-indazole, N- (meth) allylquinolin-4-amine, di (meth) allylquinoline, 1,2-di (meth) allyl-1,2-dihydroisoquinoline Containing heteropolycyclic vinyl group-containing compounds;

 For example, 1-methyl-4,5-divinyl-1H-imidazole, 2,3-divinylpyridine, 2,4-divinylpyridine, 2,5-divinylpyridine, 2,6-divinylpyridine and the like containing nitrogen atoms Compounds having a ring structure and two or more vinyl groups;

 For example, 4- (meth) allyl-3,5-dimethyl-1H-pyrazole, 5- (1-methylpropyl) -5- (meth) allylpyrimidine, 5- (meth) allyl-5-isopropylpyrimidine, 2- (Meth) allylpyridine-containing compounds having a nitrogen atom-containing heterocyclic structure, such as (meth) allylpyridine, 4- (meth) allylpyridine, 3,6-dihydro-3- (meth) allylpyridine;

 For example, 2- (meth) allyl-1H-indole, 3- (meth) allyl-1H-indole, 2- (meth) allylindazole, 3-phenyl-4- (meth) allylisoquinoline, 9- (meth) allyl (Meth) allyl group-containing compounds having a heteropolycyclic structure containing a nitrogen atom, such as -9H-carbazole;

 For example, imide (meth) acrylate, 2- (4-oxazolin-3-yl) ethyl (meth) acrylate, di (meth) acrylic acid ethoxylated isocyanuric acid, tri (meth) acrylic acid ethoxylated isocyanuric acid, ε-caprolactone Heterocyclic structures containing oxygen atoms in addition to nitrogen atoms such as modified tris- (2-acryloyloxyethyl) isocyanurate, di (meth) acrylic acid isocyanuric acid ethylene oxide modification, tri (meth) acrylic acid isocyanuric acid ethylene oxide modification (Meth) acrylic acid esters having;

 For example, 4-acryloylmorpholine, N- [2- (1H-imidazol-5-yl) ethyl] (meth) acrylamide, N- (oxetane-3-ylmethoxymethyl) (meth) acrylamide, N- (oxetane-2 -Heterocyclic acrylamides such as (ylmethoxymethyl) (meth) acrylamide;

 For example, maleimide derivatives having both nitrogen and oxygen atoms such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide;

 For example, 2-vinyl oxazole, 2-phenyl-4-vinyl oxazole, 2-phenyl-5-vinyl oxazole, 5-ethoxy-2-vinyl oxazole, 3-vinyl-5-nitrosoxazole, 2-vinyl-4,5 -It has a heterocyclic structure containing an oxygen atom in addition to a nitrogen atom such as diphenyloxazole, 2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazolin-5-one, 2-vinylbenzoxazole Vinyl group-containing compounds;

 For example, glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ( (Meth) acrylic acid-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-methyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-ethyl-2-oxotetrahydropyran -4-yl, (meth) acrylic acid-4-propyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2,2- Dimethyl-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-5-oxoteto Hydrofuran-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5, 5-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-3 , 3-Dimethyl-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-2-ylmethyl, and the like. ;

 For example, glycidyl group-containing vinyl esters such as glycidyl cinnamate, allyl glycidyl ether, 1,3-butadiene monooxirane;

 For example, 2-vinylthiazol, 4-methyl-5-vinylthiazole, 2-vinylbenzothiazole, 2- [2- (1-naphthyl) vinyl] benzothiazole, 2- [2- (dimethylamino) vinyl] benzo Examples include ethenyl group-containing compounds having a heterocyclic structure containing a sulfur atom in addition to a nitrogen atom such as thiazole, and these may be used alone or in combination.

 As the compound (b2-2), glycidyl acrylate, glycidyl methacrylate, methacrylic acid (3,4-epoxy) from the viewpoint of the solubility of the ionic compound (A) described above and durability such as heat resistance and water resistance. (Cyclohexyl) methyl, 4-acryloylmorpholine, 1-vinylimidazole, N-vinyl-ε-caprolactam, 1-vinylpyridin-2 (1H) -one, di (meth) acrylic acid ethoxylated isocyanuric acid, tri (meth) acrylic Acid ethoxylated isocyanuric acid is particularly preferred.

 The compound (b3) other than (b1) or (b2) is not particularly limited as long as it has an α, β-ethylenically unsaturated double bond group in its structure. ) Monomethylaminoethyl acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, monoethylaminopropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid-mono or di-alkylamino esters such as diethylaminoethyl, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate;

 For example, methyl (meth) acrylate, ethyl (meth) acrylate, 1-propyl (meth) acrylate, 2-propyl (meth) acrylate, n-butyl (meth) acrylate, sec- (meth) acrylic acid sec- Butyl, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate, iso-amyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, n-nonyl (meth) acrylate, (meth) acryl iso-nonyl, decyl (meth) acrylate, (meth) ) Dodecyl acrylate, octadecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate Of (meth) acrylic acid alkyl esters;

 For example, (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, (meth ) Acrylic acid dimer, maleic acid; fumaric acid, monomethylmaleic acid, monomethylfumaric acid, aconitic acid, sorbic acid, cinnamic acid, α-chlorosorbic acid, glutaconic acid, citraconic acid, mesaconic acid, itaconic acid, tiglic acid, Angelic acid, senetic acid, crotonic acid, isococrotonic acid, mucobromic acid, mucochloric acid, sorbic acid, muconic acid, aconitic acid, penicillic acid, gellanic acid, citronellic acid, 4-acrylamidobutanoic acid, 6-acrylamidohexanoic acid, 2- (Meth) acryloyloxyethyl succine , Mono (meth) acrylic acid ω-carboxy polycaprolactone ester, etc., repeating polylactone-based (meth) acrylic acid ester, ethylene oxide, propylene oxide and other alkylene oxides having a carboxyl group at the terminal by ring-opening addition of a lactone ring Carboxyl group-containing aliphatic α, β-unsaturated double bond group-containing carboxylic acids such as esters of adducted alkylene oxide-added succinic acid having a carboxyl group at the terminal and (meth) acrylic acid And acid anhydrides thereof;

 For example, (meth) acrylic acid (meth) allyl, (meth) acrylic acid 1-butenyl, (meth) acrylic acid 2-butenyl, (meth) acrylic acid 3-butenyl, (meth) acrylic acid 1,3-methyl- 3-butenyl, (meth) acrylic acid 2-chloro-2-propenyl, (meth) acrylic acid 3-chloro-2-propenyl, (meth) acrylic acid 2- (2-propenyloxy) ethyl, (meth) acrylic acid 2- Propenyl lactyl, 3,7-dimethyloct-6-en-1-yl (meth) acrylate, (meth) acrylic acid (E) -3,7-dimethyloct-2,6-dien-1-yl, (Meth) acrylic acid esters further containing an unsaturated group such as rosinyl (meth) acrylate, cinnamyl (meth) acrylate, vinyl (meth) acrylate;

  For example, perfluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluorooctyl (meth) acrylate, (meth) Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-par (meth) acrylate Fluoromethyl-2-perfluoroethylmethyl, triperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate , (Meth) acrylic propenoic acid 2-perf Orodeshiruechiru, (meth) (meth) acrylic acid perfluoroalkyl esters such as 2-perfluoro-hexadecyl acrylate;

 For example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 3-propoxyethyl (meth) acrylate, 2-butoxy (meth) acrylate Alkoxy group-containing (meth) acrylic acid esters such as ethyl, 3-butoxyethyl (meth) acrylate, 4-butoxyethyl (meth) acrylate;

  For example, alkylene oxide-containing (meth) acrylic acid derivatives such as an alkylene oxide adduct of (meth) acrylic acid;

 For example, (meth) acrylic acid (methoxycarbonyl) methyl, (meth) acrylic acid (methoxycarbonyl) ethyl, (meth) acrylic acid (methoxycarbonyl) propyl, (meth) acrylic acid (methoxycarbonyl) butyl, (meth) acrylic Acid (methoxycarbonyl) decyl, (meth) acrylic acid (ethoxycarbonyl) methyl, (meth) acrylic acid (ethoxycarbonyl) ethyl, (meth) acrylic acid (ethoxycarbonyl) propyl, (meth) acrylic acid (ethoxycarbonyl) butyl , (Meth) acrylic acid (ethoxycarbonyl) hexyl, (meth) acrylic acid (ethoxycarbonyl) octyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) ethyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) propyl , (Meth) acrylic acid 2- (ethoxyca (Rubonyloxy) butyl, 2- (ethoxycarbonyloxy) hexyl (meth) acrylate, 2- (ethoxycarbonyloxy) octyl (meth) acrylate, 2- (propoxycarbonyloxy) ethyl (meth) acrylate, (meth) 2- (Butoxycarbonyloxy) ethyl acrylate, 2- (butoxycarbonyloxy) butyl (meth) acrylate, 2- (octyloxycarbonyloxy) ethyl (meth) acrylate, 2- (octyloxy) (meth) acrylate Aliphatic (meth) acrylic acid esters having one carbonyl group such as carbonyloxy) butyl;

 For example, 2-oxobutanoylethyl (meth) acrylate, 2-oxobutanoylpropyl (meth) acrylate, 2-oxobutanoylbutyl (meth) acrylate, 2-oxobutanoylhexyl (meth) acrylate, (Meth) acrylic acid 2-oxobutanoyloctyl, (meth) acrylic acid 2-oxobutanoyldecyl, (meth) acrylic acid 2-oxobutanoyldodecyl, (meth) acrylic acid 3-oxobutanoylethyl, ) 3-oxobutanoylpropyl acrylate, 3-oxobutanoylbutyl (meth) acrylate, 3-oxobutanoylhexyl (meth) acrylate, 3-oxobutanoyloctyl (meth) acrylate, (meth) acrylic 3-oxobutanoyldecyl acid, 3-oxobutanoyldodecyl (meth) acrylate (Meth) acrylic acid 4-cyanooxobutanoylethyl, (meth) acrylic acid 4-cyanooxobutanoylpropyl, (meth) acrylic acid 4-cyanooxobutanoylbutyl, (meth) acrylic acid 4-cyanooxobutanoyl Ruhexyl, 4-cyanooxobutanoyloctyl (meth) acrylate, 2,3-di (oxobutanoyl) propyl (meth) acrylate, 2,3-di (oxobutanoyl) butyl (meth) acrylate, ( Aliphatic (meth) acrylic acid esters having two carbonyl groups such as 2,3-di (oxobutanoyl) hexyl (meth) acrylate and 2,3-di (oxobutanoyl) octyl (meth) acrylate Kind;

 For example, sulfomethyl (meth) acrylate, 2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, 3-sulfopropyl (meth) acrylate, 2-sulfobutyl (meth) acrylate, (meth) 4-sulfobutyl acrylate, 2-sulfobutyl (meth) acrylate, 6-sulfohexyl (meth) acrylate, sulfooctyl (meth) acrylate, sulfodecyl (meth) acrylate, sulfolauryl (meth) acrylate, (meth ) (Meth) acrylic acid alkyl esters containing a sulfonyl group such as sulfostearyl acrylate;

 For example, (meth) acrylic acid phosphooxyethyl, (meth) acrylic acid phosphooxypropyl, (meth) acrylic acid phosphooxybutyl, (meth) acrylic acid-3-chloro-2-acid phosphooxyethyl, ( (Meth) acrylic acid-3-chloro-2-acid phosphooxypropyl, (meth) acrylic acid-3-chloro-2-acid phosphooxybutyl, (meth) acrylic acid phosphooxyethylene oxide (ethylene oxide addition moles: 4-10), (meth) acrylic acid phosphooxypropylene oxide (propylene oxide addition moles: 4-10) and other phosphonic acid group-containing (meth) acrylic acid esters;

 Monomethylaminoethyl (meth) acrylamide, monoethylaminoethyl (meth) acrylamide, monomethylaminopropyl (meth) acrylamide, monoethylaminopropyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethyl Mono- or di-alkylaminoalkyl (meth) acrylamides such as aminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide;

For example, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltripropoxysilane, 3- (meth) acryloyloxypropyltributoxysilane 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropylbutyldimethoxysilane, 3- (meth) acryloyloxypropylethyldipropoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropyltrime Kishishiran, 3- (meth) acryloyloxy propyl triethoxysilane, 3- (meth) acryloyl alkoxysilyl group-containing (meth) acrylic acid esters such as propyl tripropoxysilane;

 For example, metal salts and ammonium of (meth) acrylic acid esters containing sulfonyl groups such as (meth) acryloyloxydimethylethylammonium ethyl sulfate, (meth) acryloylaminopropyltrimethylammonium sulfate, (meth) acryloylaminopropyltriethylammonium sulfate salt;

 For example, di (meth) acrylic acid ethylene oxide, di (meth) acrylic acid triethylene oxide, di (meth) acrylic acid tetraethylene oxide, di (meth) acrylic acid polyethylene oxide, di (meth) acrylic acid propylene oxide, di (Meth) acrylic acid dipropylene oxide, di (meth) acrylic acid tripropylene oxide, di (meth) acrylic acid polypropylene oxide, di (meth) acrylic acid butene oxide, di (meth) acrylic acid pentane oxide, di (meth) 2,2-dimethylpropyl acrylate, hydroxypivalylhydroxypivalate di (meth) acrylate, hydroxypivalylhydroxypivalate hydroxypivalate dicaprolactonate, 1,6-hexane di (meth) acrylate Gio Di (meth) acrylic acid 1,2-hexanediol, di (meth) acrylic acid 1,5-hexanediol, di (meth) acrylic acid 2,5-hexanediol, di (meth) acrylic acid 1,7- Heptanediol, 1,8-octanediol di (meth) acrylic acid, 1,2-octanediol di (meth) acrylic acid, 1,9-nonanediol di (meth) acrylic acid, 1, di (meth) acrylic acid 1, 10-decanediol, di (meth) acrylic acid 1,2-decanediol, di (meth) acrylic acid 1,12-dodecanediol, di (meth) acrylic acid 1,2-dodecanediol, di (meth) acrylic acid 1,14-tetradecanediol, 1,2-tetradecanediol di (meth) acrylate, 1,16-hexadecanediol di (meth) acrylate, di ( A) 1,2-hexadecanediol acrylate, 2-methyl-2,4-pentanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, di (meth) acryl Acid 2-methyl-2-propyl-1,3-propanediol, di (meth) acrylate 2,4-dimethyl-2,4-pentanediol, di (meth) acrylate 2,2-diethyl-1,3 -Propanediol, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate, 2-ethyl-1,3-hexane di (meth) acrylate Diol, Di (meth) acrylic acid 2,5-dimethyl-2,5-hexanediol, Di (meth) acrylic acid 2-methyl-1,8-octanediol, Di (meth) acrylic 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, 2-methyl-2-propyl-1, di (meth) acrylate, Bifunctional (meth) acrylic acid esters such as 3-propanediol, di (meth) acrylic acid 2,4-dimethyl-2,4-pentanediol, di (meth) acrylic acid 1,1,1-trishydroxymethylethane Kind;

 For example, 1,2,3-propanetriol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate Tricaprolactonate, 2,2-dimethylpropane-1,3-diol tri (meth) acrylate, trimethylolhexane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, tri (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol, 1,1,1-trishydroxymethylethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate, Trifunctional (meth) acrylic esters such as pentaerythritol tri (meth) acrylate;

 For example, tetra (meth) acrylic acid pentaerythritol, tetra (meth) acrylic acid ethoxylated pentaerythritol, tetra (meth) acrylic acid ditrimethylolpropane, hexa (meth) acrylic acid dipentaerythritol, tetra (meth) acrylic acid 2, 2-bis (hydroxymethyl) 1,3-propanediol, tetra (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol tetracaprolactonate, tetra (meth) acrylic acid di1, 2,3-propanetriol, tetra (meth) acrylate di-2-methylpentane-2,4-diol, tetra (meth) acrylate di-2-methylpentane-2,4-diol tetracaprolactonate, tetra ( (Meth) acrylic acid di-2,2-dimethylpropane-1,3- All, tetra (meth) acrylate ditrimethylolbutane, tetra (meth) acrylate ditrimethylolhexane, tetra (meth) acrylate ditrimethyloloctane, tetra (meth) acrylate di-2,2-bis (hydroxymethyl) 1, 3-propanediol, hexa (meth) acrylate di-2,2-bis (hydroxymethyl) 1,3-propanediol, hexa (meth) acrylate tri-2,2-bis (hydroxymethyl) 1,3-propanediol , Hepta (meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, octa (meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, hepta (meta ) Di2,2-bis (hydroxymethyl) 1,3-propanediol acrylate Polyfunctional (meth) acrylic acid esters such as real sharp emission oxide;

  For example, vinyl esters of carboxylic acids such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatate, vinyl pivalate, vinyl palmitate, vinyl stearate;

 For example, vinyl acetoacetate, vinyl acetopropionate, vinyl acetoisobutyrate, vinyl acetobutyrate, vinyl acetovalerate, vinyl acetohexanoate, vinyl aceto-2-ethylhexanoate, vinyl aceto-n-octanoate, vinyl acetodecanoate, acetodecane Vinyl acid, vinyl acetooctadecanoate, vinyl acetopivalate, vinyl acetocaprate, vinyl acetocrotonate, vinyl acetosorbate, vinyl propanoyl acetate, vinyl butyryl acetate, vinyl isobutyryl acetate, vinyl palmitoyl acetate, vinyl stearoyl acetate, vinyl pyroyl acetate , Vinyl propanoyl valerate, vinyl butyryl valerate, vinyl isobutyryl valerate, palmitoyl vinyl valerate, stearoyl valerate, pyrvoyl Vinyl Rerin acid, 2-acetoacetoxyethyl vinyl ether, 2-acetoacetoxyethyl butyl vinyl ether, 2-acetoacetoxyethyl hexyl vinyl ether, aliphatic vinyl compounds of having an acyl group such as 2-acetoacetoxyethyl octyl vinyl ether;

  For example, methyl vinyl ether, ethyl vinyl ether, 2-chlorovinyl ether, n-propyl vinyl ether, allyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, tert -Pentyl vinyl ether, n-hexyl vinyl ether, isohexyl vinyl ether, 2-ethylbutyl vinyl ether, 2-ethylhexyl vinyl ether, n-heptyl vinyl ether, n-octyl vinyl ether, isooctyl vinyl ether, nonyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, hexanedecyl vinyl ether , Octa Sil vinyl ether, ethoxymethyl vinyl ether, 2-methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, 2-butoxyethyl vinyl ether, acetoxymethyl vinyl ether, 2-acetoxyethyl vinyl ether, 3-acetoxypropyl vinyl ether, 4-acetoxybutyl vinyl ether, 4-ethoxy Butyl vinyl ether, 2- (2-methoxyethoxy) ethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, diethylene glycol methyl vinyl ether, diethylene glycol ethyl vinyl ether, diethylene glycol butyl vinyl ether, etc. The aliphatic Vinyl ether compounds;

  For example, ethylene glycol divinyl ether, diethylene glycol divinyl ether (DEGVE), triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, polypropylene glycol Divinyl ether, butanediol divinyl ether, neopentyl glycol divinyl ether, hexanediol divinyl ether, nonanediol divinyl ether, hydroquinone divinyl ether, 1,4-cyclohexanediol divinyl ether (CHODVE), 1,4-cyclohexanedimethanol divinyl ether ( HDVE), trimethylolpropane trivinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether (TMPEOTVE), epentaerythritol tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ditrimethylolpropane tetravinyl ether, dipentaerythritol hexavinyl ether, etc. Vinyl ethers of

 For example, fluorine-containing vinyl compounds such as perfluorovinyl, perfluoropropene, perfluoro (propyl vinyl ether), vinylidene fluoride;

  For example, (meth) allylchlorosilane, (meth) allyltrimethoxysilane, (meth) allyltriethoxysilane, (meth) allylaminotrimethylsilane, diethoxyethylvinylsilane, trichlorovinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, tripropoxy Alkoxysilyl group-containing α, β-unsaturated double bond group-containing compounds such as vinylsilane and vinyltris (2-methoxyethoxy) silane;

 For example, alkenyl group-containing sulfonic acids such as vinyl sulfonic acid, 2-propenyl sulfonic acid, 2-methyl-2-propenyl sulfonic acid, and vinyl sulfuric acid;

For example, metal salts and ammonium salts such as ammonium vinyl sulfonate, sodium vinyl sulfonate, potassium vinyl sulfonate, sodium vinyl alkyl sulfosuccinate;
Metal salts and ammonium salts of 2-methyl-2-propenylsulfonic acid such as ammonium 2-methyl-2-propenylsulfonate, sodium 2-methyl-2-propenylsulfonate, and potassium 2-methyl-2-propenylsulfonate;

  For example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-propyl (Meth) acrylamide, N-tert-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-nonyl (meth) acrylamide, N-tricosyl (meth) acrylamide, N-nonadecyl (Meth) acrylamide, N-docosyl (meth) acrylamide, N-methylene (meth) acrylamide, N-tridecyl (meth) acrylamide, N- (5,5-dimethylhexyl) (meth) acrylamide, crotonamide, maleami , Fumaramide, mesaconamide, citraconic amide, itaconic amide, 2-methylprop-2-enoylamine, N, N-dimethyl (meth) acrylamide, N, N-diethyl- (meth) acrylamide, N- [3- (N ′, N Aliphatic (meth) acrylamides such as' -dimethylamino) propyl]-(meth) acrylamide, N- (dibutylaminomethyl) (meth) acrylamide, N-vinylmethanamide, N-vinylacetamide;

 For example, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N-methoxyhexyl (meth) acrylamide, N-methoxy Octyl (meth) acrylamide, N-methoxydecyl (meth) acrylamide, N-methoxydodecyl (meth) acrylamide, N-methoxyoctadecyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide N-ethoxypropyl (meth) acrylamide, N-ethoxybutyl (meth) acrylamide, N-ethoxyhexyl (meth) acrylamide, N-ethoxyoctyl (meth) acrylamide, N-iso Roxymethyl (meth) acrylamide, N-isopropoxyethyl (meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-isopropoxybutyl (meth) acrylamide, N-isopropoxyhexyl (meth) acrylamide, N-isopropoxy Octyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide, N-butoxypropyl (meth) acrylamide, N-butoxybutyl (meth) acrylamide, N-butoxyhexyl (meth) acrylamide N-butoxyoctyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-isobutoxyethyl (meth) acrylamide, N-isobutoxypropyl (meth) Acrylamide, N-isobutoxybutyl (meth) acrylamide, N-isobutoxyhexyl (meth) acrylamide, N-isobutoxyoctyl (meth) acrylamide, N- (pentoxymethyl) (meth) acrylamide, N-1-methyl- N-alkoxy group-containing (meth) acrylamides such as 2-methoxyethyl (meth) acrylamide, N, N-di (methoxymethyl) meth) acrylamide, N, N-di (ethoxymethyl) (meth) acrylamide;

  For example, N- (2-oxobutanoylethyl) (meth) acrylamide, N- (2-oxobutanoylpropyl) (meth) acrylamide, N- (2-oxobutanoylbutyl) (meth) acrylamide, N- ( (Meth) acrylamides having a carbonyl group such as 2-oxobutanoylhexyl) (meth) acrylamide, N- (2-oxobutanoyloctyl) (meth) acrylamide, diacetone (meth) acrylamide;

For example, (meth) acrylamides containing sulfonic acids such as (meth) acrylamide sulfonic acid, tert-butyl- (meth) acrylamide sulfonic acid, (meth) acrylamide-2-methyl-1-propanesulfonic acid;
For example, nitrile group-containing α, such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinnitrile, fumaronitrile, mesaconnitrile, citraconnitrile, itacononitrile, 2-propenenitrile, 2-methacrylic acid (meth) acrylate, etc. β-unsaturated double bond group-containing compounds;

  For example, saturated carboxylic acids such as (meth) allyl acetate, (meth) allyl propionate, (meth) allyl butyrate (meth) allyl caprate, (meth) allyl laurate, allyl octylate, coconut oil fatty acid, vinyl pivalate, etc. (Meth) allyl esters of acids;

 For example, acetoacetic acid (meth) allyl, acetopropionic acid (meth) allyl, acetoisobutyric acid (meth) allyl, acetobutyric acid (meth) allyl, acetovaleric acid (meth) allyl, acetohexanoic acid (meth) allyl, aceto-2- Ethylhexanoic acid (meth) allyl, aceto-n-octanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetooctadecanoic acid (meth) allyl, acetopivalic acid (meth) allyl, acetocaprin Acid (meth) allyl, acetocrotonic acid (meth) allyl, acetosorbic acid (meth) allyl, propanoyl acetate (meth) allyl, butyryl acetate (meth) allyl, isobutyryl acetate (meth) allyl, palmitoyl acetate (meth) allyl, Stearoyl acetate (meth) allyl, (meth) allyl Aliphatic (meth) allyl compounds having an acyl group such as hydrin;

  For example, vinyl halides such as vinyl chloride, vinylidene chloride and allyl chloride;

  For example, dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;

  For example, cis-diallyl succinate, diallyl 2-methylidene succinate, vinyl (E) -but-2-enoate, (Z) -octadeca-9-enoate, (9Z, 12Z, 15Z) -octadeca-9, Α, β-unsaturated double bond group-containing compounds containing polyfunctional unsaturated bonds such as vinyl 12,15-trienoate;

  For example, ethylene, propylene, 1-butene, 2-butene, 2-methylpropene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene 1-docosene, 1-tetracocene, 1-hexacocene, 1-octacocene, 1-triacontene, 1-dotriacontene, 1-tetratoacontene, 1-hexatriacontene, 1-octatriacontene, 1-tetraconten And alkenes such as polybutene-1, polypentene-1, poly-4-methylpentene-1, and the like. In particular, it is not limited to these. These may use only 1 type or may use multiple types together.

 As the other α, β-ethylenically unsaturated double bond group-containing compound (b3), a compound having a (meth) acryloyl group is preferable from the viewpoint of reactivity, and the resin composition of the present invention is subjected to active energy ray polymerization. When used as a reactive adhesive or an active energy ray polymerizable coating agent, it is preferable that bifunctional or higher (meth) acrylic acid esters are included from the viewpoint of the active energy ray polymerization rate.

  In the α, β-ethylenically unsaturated double bond group-containing compound (B) having no B atom in the molecule of the present invention, polymerization curability by irradiation with active energy rays, adhesion to the substrate (G) described later In addition, the superiority of the compound (B) in terms of durability such as heat resistance, moist heat resistance and water resistance is as follows: (b1-2)> (b1-1) ≧ (b2-1)> (b2-2) Although it is> (b3), it can be set as a favorable resin composition by mix | blending timely so that both a hydroxyl group and cyclic structure may contain.

As a preferred ratio of the components constituting the α, β-ethylenically unsaturated double bond group-containing compound (B) of the present invention, compound (b1) is 1 to 45 parts by weight in 100 parts by weight of compound (B). Parts, compound (b2) is 1 to 45 parts by weight, and compound (b3) is 10 to 98 parts by weight.
When the amount of the compound (b1) is less than 1 part by weight, not only the solubility of the ionic compound (A) described above is lowered, but also the adhesion with the substrate (G) described later is lowered. When the amount of the compound (b1) is more than 45 parts by weight, the water resistance is inferior, which is not preferable. When the compound (b2) is less than 1 part by weight, the heat resistance and moist heat resistance of the coating film are lowered. When the amount of the compound (b2) is more than 45 parts by weight, the flexibility of the coating film is lost and the coating becomes brittle.

Ingredient (E):
The resin composition of the present invention can be cured by a polymerization reaction that proceeds by irradiation with various activation energy rays. However, the resin composition needs to contain an active energy ray polymerization initiator (E) in addition to the essential components (A) and (B). By using the active energy ray polymerization initiator (E), the polymerization reaction can be promoted. In one embodiment of the present invention, the activation energy is preferably ultraviolet light.

In the present invention, as the component (E), a compound arbitrarily selected from known compounds as an active energy ray polymerization initiator can be used.
Specific examples include the following. 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthofluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl Dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4-thioxanthone, camphorquinone, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and the like.
Moreover, as a commercial item, the following is mentioned, for example. Irgacure 184,907,651,1700,1800,819,369, 261 (BASF), DAROCUR-TPO (BASF, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide), Darocur-1173 (Merck), Ezacure KIP150, and TZT (Nihon Shibel Hegner), Kayacure BMS, Kayacure DMBI (Nippon Kayaku) and the like.
Moreover, the photoinitiator which has at least 1 (meth) acryloyl group in a molecule | numerator can also be used.
Further, as the α, β-ethylenically unsaturated double bond group-containing compound (b2-2) having a heterocyclic structure, glycidyl (meth) acrylate, 4- (glycidyloxy) butyl (meth) acrylate, (meth) Heterocycle-containing (meth) acrylic acid esters having a 3-membered or 4-membered oxygen atom such as (3-methyl-3-oxetanyl) methyl acrylate and (meth) acrylic acid-3,4-epoxycyclohexylmethyl When a cationically polymerizable compound (E) described below is used, it is preferable to contain a known photoacid generator as an active energy ray polymerization initiator as necessary. Examples of the photoacid generator include sulfonium salts such as UVACURE 1590 (manufactured by Daicel Cytec), CPI-110P (manufactured by Sun Apro), IRGACURE 250 (manufactured by Ciba Specialty Chemicals), and WPI-113 (Wako Pure Chemical). ), Rp-2074 (made by Rhodia Japan), and other examples such as iodonium salts are mentioned. By using in combination, cross-linking progresses and an adhesive layer with excellent durability against heat and humidity is formed. Therefore, it is preferable.
Moreover, the active energy ray polymerization initiator which has at least 1 (meth) acryloyl group in a molecule | numerator can also be used.
In the present invention, as the component (E), the above-mentioned compounds can be used alone or in combination of two or more. In the present invention, as the component (E), the above-mentioned compounds can be used alone or in combination of two or more.

The resin composition of the present invention does not substantially contain an organic solvent. The resin composition preferably contains no organic solvent, but the active energy ray polymerization initiator (E) is often poorly soluble in the polymerizable component. Therefore, a small amount of an organic solvent may be included to dissolve the active energy ray polymerization initiator (E). The content of the organic solvent in the resin composition is preferably within 5% by weight.

  Furthermore, in order to improve the performance of the active energy ray polymerization initiator (E), an active energy ray sensitizer may be used in combination. Representative examples of the active energy ray sensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles or other nitrogen-containing compounds. Of these, anthracene or benzophenone, thioxanthone or perylene, phenothiazine, and rose bengal are preferably used.

 From the viewpoint of reactivity, the blending ratio of the component (E) is preferably 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, with the total amount of the resin composition being 100 parts by weight. It is a range.

The resin composition in the present invention comprises 100 weights of the ionic compound (A), the α, β-ethylenically unsaturated double bond group-containing compound (B), and the active energy ray polymerization initiator (E). %, Compound (A) 0.01 to 10% by weight, compound (B) 1 to 99% by weight, active energy ray polymerization initiator (E) 0.01 to 20% by weight. The compound (A) is contained in a ratio of 0.1 to 8% by weight, the compound (B) is 20 to 82% by weight, and the active energy ray polymerization initiator (E) is contained in a ratio of 0.5 to 10% by weight. Is more preferable.
When the compound (A) is 0.01% by weight or more, sufficient antistatic properties can be easily obtained, and when it is 10% by weight or less, it can be expected to suppress a decrease in adhesiveness, heat resistance, and moist heat resistance. .

Component (C):
In one embodiment of the resin composition of the present invention, the resin composition may contain an oligomer (C) in addition to the essential components. By using the oligomer (C), when the resin composition is used as a coating agent or an adhesive, adhesion and adhesion to the substrate (G) described later can be further improved. Moreover, it becomes easy to improve the heat resistance or heat-and-moisture resistance of the resin layer.

 The oligomer (C) is a compound obtained by adding an α, β-unsaturated double bond group to a polymer of monomers and / or various compounds having at least an α, β-unsaturated double bond group. , One or more α, β-unsaturated double bond groups in the molecule. The oligomer may have various functional groups in addition to the α, β-unsaturated double bond group. In one embodiment of the present invention, the oligomer (C) is selected from the group consisting of a polyester oligomer (c1), a polyurethane oligomer (c2), a polyepoxy oligomer (c3), and a polyacrylic oligomer (c4). Including at least one kind, these can be used without any particular limitation.

(C1) Polyester oligomer As the polyester oligomer (c1), the terminal of the polyester obtained by polycondensation of a polybasic acid and a polyhydric alcohol on the main chain skeleton or a hydroxyl group in the polyester chain and (meth) acrylic acid, maleic A compound obtained by esterification with an α, β-ethylenically unsaturated double bond group-containing compound having one or more carboxyl groups in the molecule such as an acid, or a carboxyl group in the terminal or polyester chain of the polyester ( It is a compound obtained by esterification with the aforementioned compound (X) such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. In addition, a polyester oligomer obtained from an acid anhydride, glycidyl (meth) acrylate, and a compound having at least one hydroxyl group can also be used as the polyester oligomer (c1).

 Examples of the polybasic acid include aliphatic, alicyclic, and aromatic acids, and each can be used without any particular limitation. More specifically, examples of the aliphatic polybasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, chloromaleic acid, fumaric acid, and dodecanedioic acid. Examples thereof include acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, succinic anhydride, maleic anhydride, and the like, and these aliphatic dicarboxylic acids and anhydrides thereof can be used. Derivatives of succinic anhydride (methyl succinic anhydride, 2,2-dimethyl succinic anhydride, butyl succinic anhydride, isobutyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride, phenyl anhydride Succinic acid, etc.), glutaric anhydride derivatives (glutaric anhydride, 3-allyl glutaric anhydride, 2,4-dimethyl glutaric anhydride, 2,4-diethyl glutaric anhydride, butyl glutaric anhydride, hexyl glutaric anhydride, etc. ), Maleic anhydride derivatives (2-methylmaleic anhydride, 2,3-dimethylmaleic anhydride, butylmaleic anhydride, pentylmaleic anhydride, hexylmaleic anhydride, octylmaleic anhydride, decylmaleic anhydride, dodecyl Maleic anhydride, 2,3-dichloromaleic anhydride, phenyl maleic anhydride Phosphate, also anhydride derivative of 2,3-diphenyl maleic anhydride, etc.) and the like can be used. .

 More specifically, as the alicyclic polybasic acid, for example, as the alicyclic dicarboxylic acid, for example, dimer acid, cyclopropane-1α, 2α-dicarboxylic acid, cyclopropane-1α, 2β-dicarboxylic acid , Cyclopropane-1β, 2α-dicarboxylic acid, cyclobutane-1,2-dicarboxylic acid, cyclobutane-1α, 2β-dicarboxylic acid, cyclobutane-1α, 3β-dicarboxylic acid, cyclobutane-1α, 3α-dicarboxylic acid, (1R) -Cyclopentane-1β, 2α-dicarboxylic acid, trans-cyclopentane-1,3-dicarboxylic acid, (1β, 2β) -cyclopentane-1,3-dicarboxylic acid, (1β, 3β) -cyclopentane-1, 3-dicarboxylic acid, (1S, 2S) -1,2-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, , 3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,1-cycloheptanedicarboxylic acid, cubane-1,4-dicarboxylic acid, 2,3-norbornanedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid , Saturated alicyclic dicarboxylic acids such as hexahydrophthalic acid and tetrahydrophthalic acid, 1-cyclobutene-1,2-dicarboxylic acid, 3-cyclobutene-1,2-dicarboxylic acid, 1-cyclopentene-1,2-dicarboxylic acid Acid, 4-cyclopentene-1,3-dicarboxylic acid, 1-cyclohexene-1,2-dicarboxylic acid, 2-cyclohexene-1,2-dicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene- 1,3-dicarboxylic acid, 2,5-hexadiene-1α, 4α-dicar Unsaturated double bond in such phosphate rings include one or two unsaturated alicyclic dicarboxylic acid having, like these alicyclic dicarboxylic acids and anhydrides thereof can be used.

 Further, derivatives of hexahydrophthalic anhydride (3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride), derivatives of tetrahydrophthalic anhydride (1,2,3,6-tetrahydrophthalic anhydride, 3- Methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, methylbutenyl-1,2,3,6-tetrahydrophthalic anhydride, etc.) Hydrogenated phthalic anhydride derivatives can also be used as alicyclic dicarboxylic acid anhydrides.

 More specifically, examples of the aromatic polybasic acid include, for example, o-phthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, 2,5-dimethylterephthalic acid, 2 , 2'-biphenyldicarboxylic acid, 4,4-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, norbornene dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, phenylindanedicarboxylic acid 1,2-azulene dicarboxylic acid, 1,3-azulene dicarboxylic acid, 4,5-azulene dicarboxylic acid, (−)-1,3-acenaphthene dicarboxylic acid, 1,4-anthracene dicarboxylic acid, 1,5- Anthracene dicarboxylic acid, 1,8-anthracene dicarboxylic acid, 2,3-anthracenedical Acids, 1,2-phenanthrene dicarboxylic acids, 4,5-phenanthrene dicarboxylic acids, aromatic dicarboxylic acids such as 3,9-perylene dicarboxylic acid, and aromatic dicarboxylic acids such as phthalic anhydride and 4-methylphthalic anhydride An anhydride is mentioned, These aromatic dicarboxylic acid and its anhydride etc. can be utilized.

 Furthermore, chlorendic anhydride, het anhydride, biphenyldicarboxylic anhydride, hymic anhydride, endomethylene-1,2,3,6-tetrahydrophthalic anhydride, methyl-3,6-endomethylene-1,2,3 , 6-tetrahydrophthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, octahydro- Acid anhydrides such as 1,3-dioxo-4,5-isobenzofurandicarboxylic acid anhydride can also be used as the polybasic acid.

 Polyhydric alcohols include relatively low molecular weight polyols having a number average molecular weight (Mn) of about 50 to 500 and relatively high molecular weight polyols having a number average molecular weight (Mn) of 500 to 30,000. Each can be used without any particular limitation.

 More specific examples of relatively low molecular weight polyols include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2, 4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3′-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol (Addition mole number 10 or less), polyoxypropylene glycol (addition mole number 10 or less), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol 1,9-nonanediol, neopentyl glycol, Aliphatic or alicyclic diols such as octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecane dimethanol, cyclopentadiene dimethanol, and dimer diol ;

 1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4′-methylenediphenol, 4, 4 ′-(2-norbornylidene) diphenol, 4,4′-dihydroxybiphenol, o-, m- and p-dihydroxybenzene, 4,4′-isopropylidenephenol, addition-type bisphenol obtained by adding alkylene oxide to bisphenol Aromatic diols and the like.

Examples of the raw material bisphenol of addition-type bisphenol include bisphenol A and bisphenol F, and examples of the raw material alkylene oxide include ethylene oxide and propylene oxide.
More specific examples of the relatively high molecular weight polyols include high molecular weight polyester polyols, high molecular weight polyamide polyols, high molecular weight polycarbonate polyols, and high molecular weight polyurethane polyols. The high molecular weight polycarbonate polyol is obtained by reacting the above-mentioned relatively low molecular weight diol with a carbonate or phosgene.

As a commercial item of the said high molecular weight polyester polyol, the Byron series by Toyobo Co., Ltd., the Kuraray polyol P series by Kuraray, and the Kyowapol series by Kyowa Hakko Chemical Co., Ltd. are mentioned, for example.
As a commercial product of the high molecular weight polyamide polyol, TPAE617 manufactured by Fuji Kasei Kogyo Co., Ltd. can be used.
Examples of commercially available high molecular weight polycarbonate polyols include Oxymer N112 manufactured by Perstorp, PCDL series manufactured by Asahi Kasei Chemicals, Kuraray polyol PMHC series, and Kuraray polyol C series manufactured by Kuraray.

Examples of commercially available high molecular weight polyurethane polyols include Byron UR series manufactured by Toyobo Co., Ltd., Takelac E158 (hydroxyl value = 20, acid value <3) manufactured by Mitsui Chemicals Polyurethane, Takelac E551T (hydroxyl value = 30, Acid value <3), Takelac Y2789 (hydroxyl value = 10, acid value <2) and the like.
In addition, polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone diol, poly (β-methyl-γ-valerolactone) diol, and polyvalerolactone diol can also be used as the high molecular weight polyol. Included in polyols.

(C2) Polyurethane-based oligomer The polyurethane-based oligomer (c2) is a compound obtained by reacting at least one isocyanate group with the compound (b1), or a compound having at least one isocyanate group and the above-mentioned compound. A compound obtained by reacting the compound (b1) with a urethane prepolymer having a terminal isocyanate group obtained by reacting with a polyhydric alcohol, or a compound having at least one isocyanate group and a polyhydric alcohol. It is obtained by reacting the compound (b1) with a urethane prepolymer having a terminal isocyanate group obtained by reacting a urethane prepolymer having a terminal isocyanate group obtained further with a compound having at least one amino group. A compound. Moreover, what contains the urea bond group obtained by making an isocyanate group and an amino group react is also contained in a polyurethane-type oligomer (d2).

 Examples of the compound having at least one isocyanate group include monofunctional polyisocyanates and polyfunctional isocyanates, and aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, etc., respectively. Can be mentioned. More specifically, as monofunctional polyisocyanate, for example, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octyl isocyanate, decyl isocyanate, octadecyl isocyanate, stearyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, benzyl isocyanate, p-chlorophenyl Isocyanate, p-nitrophenyl isocyanate, 2-chloroethyl isocyanate, 2,4-dichlorophenyl isocyanate, 3-chloro-4-methylphenyl isocyanate, trichloroacetyl isocyanate, chlorosulfonyl isocyanate, (R)-(+)-α-methyl Benzyl isocyanate, (S)-(−)-α-methylbenzyl isocyan Nate, (R)-(-)-1- (1-naphthyl) ethyl isocyanate, (R)-(+)-1-phenylethyl isocyanate, (S)-(-)-1-phenylethyl isocyanate, p- And toluenesulfonyl isocyanate.

 Among polyfunctional isocyanates, the aromatic polyisocyanate is more specifically, for example, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate ( Alias: 4,4'-MDI), 2,4-tolylene diisocyanate (alias: 2,4-TDI), 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-tri Examples include isocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4′-diphenyl ether diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, and the like.

Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodeca Examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.
Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, , 4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

 As alicyclic polyisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Examples thereof include methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane and the like.

 Moreover, as a part of (c2) component, the above-mentioned 2-methylpentane-2,4-diol adduct of polyisocyanate, trimer having an isocyanurate ring, and the like can be used in combination. Polyphenylmethane polyisocyanate (also known as PAPI), naphthylene diisocyanate, modified polyisocyanate thereof, and the like can be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretonimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups can be used. A reaction product of a polyol and a diisocyanate can also be used as a compound having at least two isocyanate groups.

 More specifically, as amines having an amino group, for example, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2 , 4-trimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2-hydroxyethylethylenediamine, hexamethylenediamine 2-hydroxyethylethylenediamine, N- (2-hydroxyethyl) propylenediamine, (2-hydroxyethyl Propylene) diamine, (di-2-hydroxyethylethylene) diamine, (di-2-hydroxyethylpropylene) diamine, (2-hydroxypropylethylene) diamine, (di 2-hydroxypropyl ethylene) diamine, aliphatic such as piperazine polyamine;

Cycloaliphatic polyamines such as isophoronediamine and dicyclohexylmethane-4,4′-diamine;
Phenylenediamine, xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltoluenediamine, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 4,4′-bis- ( sec-butyl) aromatic diamines such as diphenylmethane;
Silylamines having a monofunctional silylamino group such as trimethylsilyldimethylamine;
Silylamines having a bifunctional silylamino group such as 1,1,3,3-tetramethyldisilazane can be used.

(C3) Polyepoxy oligomer The polyepoxy oligomer (c3) is a compound having a glycidyl group and one or more hydroxyl groups or carboxyl groups in a molecule such as hydroxyethyl (meth) acrylate, (meth) acrylic acid, and maleic acid. A compound obtained by a reaction with an α, β-unsaturated double bond group-containing compound having a compound, substantially having no glycidyl group and having an α, β-unsaturated double bond group-containing compound It is. Representative examples include bisphenol type, epoxidized oil type, phenol novolac type, and alicyclic type. As the bisphenol type polyepoxy oligomer, α, β-unsaturation having one or more carboxyl groups in the molecule such as bisphenol type diglycidyl ether obtained by reacting bisphenols and epichlorohydrin and (meth) acrylic acid It is obtained by reacting with a double bond group-containing compound.

 The epoxidized oil polyepoxy oligomer has at least one hydroxyl group or carboxyl group in the molecule such as epoxidized oil such as soybean oil and hydroxyethyl (meth) acrylate, (meth) acrylic acid, maleic acid, etc. Those obtained by reaction with an α, β-unsaturated double bond group-containing compound can be used. As the novolak type polyepoxy oligomer, α, β-unsaturation having novolak type epoxy resin and one or more hydroxyl groups or carboxyl groups in the molecule such as hydroxyethyl (meth) acrylate, (meth) acrylic acid, maleic acid, etc. What is obtained by reaction with a double bond group containing compound can be used. Examples of the alicyclic polyepoxy oligomer include α, β- having one or more hydroxyl groups or carboxyl groups in the molecule such as alicyclic epoxy resin and hydroxyethyl (meth) acrylate, (meth) acrylic acid, maleic acid and the like. What was synthesize | combined by reaction with an unsaturated double bond group containing compound can be used.

(C4) Polyacrylic oligomer In the present invention, an acrylic oligomer (c4) can also be used as the oligomer (C). Specific examples of usable compounds include modified polyethers having α, β-unsaturated double bond groups, amine-modified α, β-unsaturated double bond group-containing compounds, alkyd resins, and spiroacetal resins. Selected from the group consisting of a modified α, β-unsaturated double bond group-containing compound obtained by adding an α, β-unsaturated double bond group to various compounds such as polybutadiene resin, polythiol polyene resin and polyhydric alcohol. Oligomers or prepolymers of one or more compounds can be used.

In addition to the aggregation density, the weight average molecular weight of the oligomer (C) (below) from the viewpoint of obtaining excellent properties in terms of compatibility with other components that form a coating film by polymerization, and durability such as heat resistance and moist heat resistance. , Mw.) Is preferably in the range of 300 to 50,000 in terms of compatibility of the polymer coating film, good durability (heat resistance, moist heat resistance) and agglomeration density, and 400 to 30,000. It is preferable that it is the range of these. By using an oligomer having Mw of 50,000 or less, it is possible to easily provide a resin composition having excellent fluidity and compatibility with the components (A) and (B). Along with this, it is possible to easily suppress problems such as a decrease in coating properties of the resin composition, a decrease in coating film durability such as adhesion, and a whitening of the coating film. On the other hand, by using an oligomer having an Mw of 300 or more, cohesive failure in the adhesive layer is less likely to occur when the film base and the adherend are pasted using the resin composition as an adhesive. .
In addition, the measuring method of a number average molecular weight (Mn), a weight average molecular weight (Mw), an acid value (AV), and a hydroxyl value (OHV) is mentioned later.

 Although it does not specifically limit, In preferable one Embodiment of this invention, it is preferable that the said oligomer (C) contains a polyurethane-type oligomer (c2) at least. When using the said resin composition for uses, such as an adhesive agent, there exists a tendency for the elasticity and softness | flexibility of a contact bonding layer to change depending on the coupling group in the said oligomer (C). When the bonding group is an ester or ether group, it is easy to obtain excellent flexibility. However, it tends to have low elasticity and low hydrolysis resistance. On the other hand, when the component (c2) is used, it is easy to balance elasticity and flexibility based on the urethane bond. Moreover, since the said component (c2) also has favorable hydrolysis resistance, it can improve water resistance and heat-and-moisture resistance easily. Furthermore, generally, when a corona treatment or the like is performed on a film-like substrate, a carbonyl group is present on the film surface. For such a carbonyl group, the urethane bond is easy to form a counter electrode bond (acid-base interaction) at a basic site caused by a nitrogen atom, and therefore has good adhesion and adhesion to a film-like substrate. It can be improved easily. On the other hand, when the linking group is an ester or ether, the interaction with the carbonyl group on the film-like substrate occurs between the oxygen atom and a relatively weak bond compared to the case where the linking group is urethane. Become. Actually, in the resin composition prepared at the same blending ratio, when the component (c2) is used as the oligomer (C) and when other components are used, the former is different in various characteristics. Tends to give superior results. However, even when an oligomer component other than the component (c2) is used in the present invention, desired characteristics can be easily obtained by appropriately blending other constituent components.

 In one embodiment of the resin composition of the present invention, the total amount of components (A), (B), and (E) is 100 parts by weight, and the amount of oligomer (C) is 1 to 250 parts by weight. preferable. More preferably, it is the range of 1-100 weight part. By setting the oligomer (C) to 1 part by weight or more, deficiency in cohesive force can be improved, and characteristics such as heat resistance and moist heat resistance can be easily improved. On the other hand, by setting the oligomer (C) to 250 parts by weight or less, when the resin composition is used as a coating agent or an adhesive, it becomes easy to obtain excellent adhesion or adhesion to the substrate.

Component (D):
In one embodiment of the resin composition of the present invention, the resin composition may contain a cationically polymerizable compound (D) in addition to the essential components. By using the cationic polymerizable compound (D), when the resin composition is used as a coating agent or an adhesive, different types of polymerization curing by active energy ray irradiation is possible, so that the cured coating film forms a phase separation structure. Moreover, since it is easy to control elasticity, stress relaxation property and creep property, it is possible to further improve the adhesion and adhesion to the substrate (G). Moreover, it becomes easy to improve the heat resistance or heat-and-moisture resistance of the resin layer.

The cationically polymerizable compound (D) contains at least one functional group that is cationically polymerized by an acid catalyst, and these can be used without any particular limitation.
The cationic polymerizable compound (D) is preferably a cyclic hetero compound or a vinyl ether exemplified in the above-mentioned compound (B) from the viewpoint of reactivity by active energy rays. Among the cyclic hetero compounds, a 3-membered cyclic ether group is preferred. An oxirane compound (d1) having one or more of them is particularly preferably used.
Examples of the three-membered cyclic ether group include oxirane, methyloxirane, phenyloxirane, 1,2-diphenyloxirane, methylideneoxirane, oxiranylmethyl, oxiranylmethanol, oxiranecarboxylic acid, (chloromethyl) oxirane. , Aliphatic cyclic ether groups such as (bromomethyl) oxirane and oxiranyl acetonitrile;
For example, 3,4-oxiranecyclohexylmethyl 3,4-oxiranecyclohexanecarboxylate, 3,4-oxirane-6-methylcyclohexylmethyl 3,4-oxirane-6-methylcyclohexanecarboxylate, ethylenebis (3,4-oxirane Cyclohexanecarboxylate), bis (3,4-oxiranecyclohexylmethyl) adipate, bis (3,4-oxirane-6-methylcyclohexylmethyl) adipate, diethylene glycol bis (3,4-oxiranecyclohexyl methyl ether), ethylene glycol bis ( 3,4-oxiranecyclohexyl methyl ether), 2,3,4,15-dioxirane-7,11,18,21-tetraoxatrispiro- [5.2.2.5.2.2] heny Sun (also a compound which can be named 3,4-oxiranecyclohexanespiro-2 ′, 6′-dioxanespiro-3 ″, 5 ″ -dioxanespiro-3 ′ ″, 4 ′ ″-oxiranecyclohexane), 4- (3,4-oxiranecyclohexyl) -2,6-dioxa-8,9-oxiranespiro [5.5] undecane, 4-vinylcyclohexene dioxide, bis-2,3-oxiranecyclopentyl ether, and dicyclo Examples thereof include a three-membered cyclic ether group bonded to an alicyclic ring such as pentadiene dioxide. A compound in which one or more hydrogen atoms in the three-membered cyclic ether group-containing compound are bonded to another chemical structure can be an oxirane compound (d1).
The oxirane compounds exemplified here may be used alone or in combination with a plurality of oxirane compounds.

 The oxirane equivalent of the oxirane compound (d1) is usually 30 to 3000 g / eq, preferably 50 to 1500 g / eq. When the oxirane equivalent is 30 g / eq or more, the flexibility of the coating film after polymerization and curing is excellent, and the adhesion to the substrate (G) is improved. On the other hand, it is preferable that it is 3000 g / eq or less because of excellent compatibility with other components.

 The oxirane compound (d1) is more preferably an oxirane compound (d1-1) having an aromatic ring substituent in order to improve heat resistance and moist heat resistance.

  More specifically, examples of the aromatic ring substituent include phenyl, phenylene, tolyl, tolreno, benzyl, benzylidene, benzylidine, xylyl, xylylene, phthalylidene, isophthalylidene, terephthalylidene, phenethylidene, phenethylidine, styryl, styrylidene, as-pseudocumyl. , V-pseudocumyl, s-pseudocumyl, mesityl, cumenyl, α-cumyl, hydrocinnamyl, cinnamyl, cinnamylidene, cinnamilidine, duryl, jurylene, thymyl, carbacrylyl, cuminyl, cuminylidene, neophyll, xenyl, benzhydryl, benzhydrylidene, trityl, etc. The representative substituents include benzene, toluene, xylene, styrene, hemimeritene, pseudocumene, mesitylene, cumene, Ningu, isodurene, durene, cymene, an aromatic ring can be mentioned one or more forms of group obtained by removing a hydrogen atom in the benzene derivatives such as Meriten can bind to other chemical structures.

  In addition, for example, cycloalkenes such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclobutadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene;

  For example, [4n + 2] annulene having a carbon number other than benzene and having 3 or more carbon atoms constituting the ring;

  For example, aromatic polycyclic compounds such as biphenyl and triphenylmethane;

 For example, pentalene, indene, indane, ninhydrin, naphthalene, tetralin, decalin, sapotalene, cadalene, eudarene, naphthol, menadiol, gossypol, naphthoquinone, lauson, juglone, menadione, plumbagin, futhiocol, echinochrome A, alkanenin, shikonin, acetonaphthone Carbon condensed bicyclic compounds such as acid, naphthoyl, naphthalic acid, naphthalate, acetomenaphton, naphthionic acid, naphthionate, naphthionyl, dansyl, crocenic acid, flavianic acid, chromotropic acid, neocuperone, azulene, camazulene, guaiazulene, heptalene, octalene, purprogaline ;

 For example, as-indacene, s-indacene, as-hydroindacene, s-hydroindacene, biphenylene, acenaphthylene, acenaphthene, acenaphthoquinone, fluorene, phenalene, perinaphthene, phenanthrene, phenanthryl, phenanthryllium, phenanthryllidene, Phenanthrylene, phenanthrol, molhole, phenanthrone, phenanthraquinone, pimantrene, reten, anthracene, anthryl, anthryllium, anthrylidene, anthrylene, anthrol, anthranol, anthrobin, anthraline, ditranol, anthroyl, anthrone, bianthrone, anthraquinone , Anthraquinonyl, anthraquinonylene, alizarin, quinizarin, anthralphine, chrysazine, anthragalo Le, purpurin, flavonol pull pudding, Anne tiger pull pudding, quinalizarin, Tekutokinon, chrysophanol, chrysolite fan acid, emodin, rain, Kermes acid, carmine acid, Jiantorimido, Antorimido, Kurisanmin acid, carbon fused tricyclic ring such as colchicine;

  For example, trindene, trindane, fluoranthene, acephenanthrylene, acephenanthrene, acanthrylene, aceanthrene, triphenylene, pyrene, chrysene, tetraphen, tetracene, naphthacene, rubrene, tetracycline, chlortetracycline, oxytetracycline, pleiadene, benzo Carbon-fused tetracyclic compounds such as anthrone;

  For example, carbon condensed pentacyclic compounds such as picene, perylene, pentaphen, pentacene, tetraphenylene, coranthrylene, coranthrene;

For example, corannulene, fluorene, anthanthrene, zetrene, hexahelicene, hexaphen, hexacene, rubicene, coronene, trinaphthylene, heptaphene, heptacene, pyranthrene, octaphene, octacene, terylene, naphthathenonaphthacene, nonaphene, nonacene, violanthrene, violanthrene, iso Carbon condensed ring compounds having 6 or more rings such as violanthrene, isoviolanthrone, ovarene, decaphen, decacene, decacyclene, pentasenopentacene, quaterrylene, hexasenohexacene, etc .;
Examples thereof include aromatic rings in which a group in the form of removing one or more hydrogen atoms in a cyclic compound such as can be bonded to other chemical structures.

 As the oxirane compound (d1) having an aromatic ring, glycidyl ether of bisphenol A, glycidyl ether of bisphenol F, and 1,3-phenylenebis (methylene) bis (7-oxabicyclo [4.1. 0] heptane-3-carboxylate), 1,4-phenylenebis (methylene) bis (7-oxabicyclo [4.1.0] heptane-3-carboxylate), 1,3-{(7-oxabicyclo) [4.1.0] Heptan-3-ylmethoxy) methyl} benzene and 1,4-{(7-oxabicyclo [4.1.0] heptan-3-ylmethoxy) methyl} benzene are particularly preferred compounds.

  Among the cyclic hetero compounds, the cyclic hetero compounds other than the oxirane compounds include a 4-membered ether oxetanyl group-containing compound (d2), a 5-membered or higher cyclic ether compound (d3), two or more oxygens or oxygen other than oxygen. There is a compound (d4) having a hetero group.

 Examples of the oxetanyl group-containing compound (d2) include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, di (1-ethyl-3- Oxetanyl) methyl ether, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, phenol novolac oxetane, 3-ethyl-{(3-triethoxysilylpropoxy) Methyl} oxetane and the like. The oxetanyl group-containing compound (d2) may be used alone or in combination of two or more.

  Examples of the cyclic ether compound (d3) having 5 or more members include 2-methyltetrahydrofuran, 2,5-diethoxytetrahydrofuran, tetrahydrofuran-2,2-dimethanol 3-methyl-2,4 (3H, 5H)- Frangion, 2,4-dioxotetrahydrofuran-3-carboxylate, 1,5-di (tetrahydrofuran-2-yl) pentan-3-yl propanoate, 4- (2,5-dioxotetrahydrofuran-3-yl) ) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, methoxytetrahydropyran, 2- (propadienyloxy) tetrahydro-2H-pyran, 2- (tetrahydrofurfuryloxy) tetrahydropyran N- (2,6-Dioxotetrahydro-2H-pyran-3-yl) phthal Luimide, 3- [3-hydroxypropyl] oxy] oxepane, (2R, 3R) -2-methyl-3- (benzyloxymethyl) oxepane-3-ol, 5-chloro-2- (2-phenylethyl) oxepane Etc. may be used alone or in combination of two or more.

Examples of the compound (d4) having two or more oxygen or hetero groups other than oxygen include a cyclic ester compound, a cyclic formal compound, a cyclic carbonate compound, and a fluorine-containing cyclic compound. The cyclic ester compound is preferably a lactone. More preferably, the cyclic formal compound is a compound selected from dioxolanes, dioxanes and trioxanes.
Industrially, propiolactone, butyrolactone, valerolactone, caprolactone, 1,3-dioxolane, 1,2-dioxane, 1,3-dioxane, 1,4-dioxane, 1,3,5-trioxane, ethylene carbonate , Propylene carbonate, glycerin carbonate and the like are preferably used in terms of reactivity.

 Among the cationically polymerizable compounds (D), vinyl ethers can be selected and used from the above-mentioned compound (B) in a timely manner.

Examples of the cationically polymerizable compound (D) include (d1), (d2), (d3), (d4) and vinyl ethers, and are not particularly limited, but a saturated heterocyclic 3-membered cyclic oxirane compound ( d1) is preferred. The oxirane compound (d1) has a large steric distortion and tends to cause a nucleophilic ring-opening reaction. Therefore, interaction with the below-mentioned base material (G) is large, and it is industrially preferable. These may be used alone or in combination of two or more depending on the purpose of use.
As described above, by using the cationic polymerizable compound (D) in combination with the resin composition of the present invention, it is easy to suppress the curing shrinkage of the coating film that is polymerized and cured by irradiating active energy rays, so that the curing shrinkage is large. It becomes possible to improve the appearance defect of the laminated body resulting from this.

 In one embodiment of the resin composition of the present invention, the total amount of components (A), (B), and (E) is 100 parts by weight, and the cationic polymerizable compound (D) is used in an amount of 1 to 350 parts by weight. Preferably there is. More preferably, it is the range of 1-150 weight part. By setting the cationic polymerizable compound (D) to 1 part by weight or more, deficiency of cohesive force can be improved, and improvement of characteristics such as heat resistance and moist heat resistance is facilitated. On the other hand, by setting the cationic polymerizable compound (D) to 350 parts by weight or less, when the resin composition is used as a coating agent or an adhesive, it is easy to obtain excellent adhesion or adhesion to the substrate. Become.

Other components (F):
If the resin composition of this invention is a range which does not impair the effect by this invention, it is also possible to mix | blend various additives suitably. For example, organic or inorganic fillers from the viewpoints of polymerization curing shrinkage reduction, thermal expansion coefficient reduction, dimensional stability improvement, elastic modulus improvement, viscosity adjustment, thermal conductivity improvement, strength improvement, toughness improvement, coloring improvement, etc. Can be blended. Such fillers may be composed of materials such as polymers, ceramics, metals, metal oxides, metal salts, and dyes and pigments. Moreover, about the shape, it is not specifically limited, For example, a particulate form, fibrous form, etc. may be sufficient. When blending the above polymer materials, silane coupling agents, flexibility imparting agents, plasticizers, flame retardants, storage stabilizers, antioxidants, ultraviolet absorbers, thixotropy imparting agents, dispersion stability It is also possible to dissolve, semi-dissolve, or micro-disperse in the resin composition as a polymer blend or polymer alloy, not as independent fillers, such as agents, fluidity imparting agents, and antifoaming agents.

  The resin composition of the present invention can be prepared by uniformly mixing the above-described components according to a method well known in the art. The resin composition can be applied to various uses in any form of liquid, paste, and film. In one Embodiment of this invention, Preferably, the said resin composition is used for the use of a coating agent or an adhesive agent.

  It is preferable that the viscosity of the resin composition of the present invention is appropriately adjusted according to the usage form. The resin composition of the present invention preferably contains substantially no organic solvent, but a solvent may be used as needed to adjust the viscosity. For example, organic solvents such as methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene, xylene, and other hydrocarbon solvents, or water can be used as the solvent. . By using such a solvent, the viscosity of the resin composition can be easily adjusted. Moreover, a viscosity can also be reduced by heating a resin composition, without using a solvent.

  In one embodiment of the present invention, a resin layer typically having a film thickness of 0.1 to 6 μm is formed using a resin composition. Therefore, from the viewpoint of coating film formation, the viscosity of the resin composition is at least in the range of 1-1,500 mPa · s, preferably in the range of 10-1,300 mPa · s, and more preferably in the range of 20-1,000 mPa · s. It is desirable that When the viscosity is 1,500 mPa · s or less, a thin film having a thickness of 0.1 to 6 μm can be easily formed on the substrate by coating, and optical characteristics such as transmittance can be easily improved. On the other hand, when the viscosity is 1 mPa · s or more, it is easy to control the thickness of the resin layer formed from the resin composition.

  Moreover, in another embodiment, the resin layer which has a film thickness of 6-300 micrometers is formed using a resin composition. In this case, the viscosity of the resin composition is at least in the range of 1,500 to 100,000 mPa · s, and preferably in the range of 3,000 to 50,000 mPa · s. Adjustment of the viscosity and coating of the resin composition according to the above embodiment can be easily performed by adding a solvent to the resin composition as necessary.

  The resin composition of the present invention is preferably used for a coating agent or an adhesive. Typically, the resin composition is applied to one side or both sides of a substrate by an appropriate method according to a conventional method, and then cured to form a resin layer. Therefore, one embodiment of the present invention relates to a laminate having a base material (G) described later and a resin layer made of a resin composition provided on at least one main surface of the base material (G). . In this embodiment, the film thickness of the resin layer is set according to the use of the laminate.

  For example, when using the said resin composition for the use of the laminated bodies for optical elements, such as the below-mentioned hard coat film or a polarizing film, the said resin composition is thin-film coated. The thickness of the resin layer formed by coating is preferably from 0.1 to 6 μm, and more preferably from 0.1 to 3 μm. By setting the thickness of the resin layer to 0.1 μm or more, it is easy to obtain sufficient adhesion or adhesive force when the resin composition is used as a coating agent or an adhesive. On the other hand, when the thickness of the resin layer exceeds 6 μm, there is often no change in properties such as adhesion or adhesive strength.

  Moreover, when using the said resin composition for the uses of laminated bodies for optical elements, such as the below-mentioned decorating film (meaning the filling sheet for touchscreens), the said resin composition is thick-coated. The thickness of the resin layer formed by coating is preferably 6 to 300 μm, and more preferably 20 μm to 250 μm. By making the thickness of the resin layer 6 μm or more, it is easy to obtain sufficient stress relaxation and creep characteristics in addition to the filling function of the touch panel when the resin composition is used as a coating agent or an adhesive. is there. On the other hand, by setting the thickness of the resin composition layer to 300 μm or less, it is easy to suppress a decrease in coating properties such as streaking.

  There is no restriction | limiting in particular in the coating method of the said resin composition. For example, various well-known methods such as Meyer bar, applicator, brush, spray, roller, gravure coater, die coater, micro gravure coater, lip coater, comma coater, curtain coater, knife coater, reverse coater, spin coater, etc. Can be applied. Moreover, it can select without particular restriction | limiting also about forms, such as thin film coating or thick film coating.

  The resin composition of the present invention can be applied onto a substrate by a known and usual method, and then has an α, β-unsaturated bonding group by irradiating the formed coating layer with active energy rays. The polymerization reaction of the compound proceeds to form a cured product. In one embodiment of the present invention, it is preferable that the active energy ray is mainly composed of light energy in the wavelength range of 150 to 550 nm including ultraviolet rays. Suitable light sources for providing such light energy include, for example, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, LED lamps, xenon lamps, and metal halide lamps. Is mentioned. In addition, in another embodiment of the present invention, a laser beam, an electron beam, or the like can be used as an active energy ray for exposure.

The irradiation intensity of the active energy ray is preferably 10 to 500 mW / cm ² . When the light irradiation intensity is less than 10 mW / cm ² , it takes a long time for curing, and when it exceeds 500 mW / cm ² , the substrate may be deteriorated in various substrates due to heat radiated from the lamp. Therefore, it is not preferable. The integrated dose expressed as a product of irradiation intensity and irradiation time is preferably 50 to 5,000 mJ / cm ² . When the integrated irradiation amount is less than 50 mJ / cm ² , it takes a long time for polymerization and curing, and when it is larger than 5,000 mJ / cm ² , the irradiation time becomes very long and the productivity is inferior. A typical active energy ray polymerizable resin composition generally requires an integrated dose of 1,000 mJ / cm ² or more. However, the above resin composition according to the present invention is favorably polymerized even at a low integrated dose of less than 1,000 mJ / cm ² .

  In the laminate of the present invention, the resin layer on the substrate is formed by polymerization and curing of the resin composition by irradiation with active energy rays, and has a glass transition temperature of approximately −80 ° C. to 150 ° C. ( Hereinafter referred to as Tg). From the viewpoint of the punchability of the laminate, the Tg of the resin layer is more preferably in the range of −40 to 120 ° C., and further preferably in the range of 0 to 120 ° C.

  From the above viewpoints, in one embodiment of the present invention, the resin composition has an ionic compound (A) and α, so that the Tg of the resin layer (polymerized cured product of the resin composition) is within the above range. The β-ethylenically unsaturated double bond group-containing compound (B) and the polymerization initiator (E) are essential components, and if necessary, an oligomer (C), a cationic polymerizable compound component (D), and It is preferable that additional components such as other additives (F) are appropriately selected and configured. In such an embodiment, it is preferable to use a compound having a (meth) acryloyl group as the α, β-unsaturated double bond group of the components (B) and (C), and a compound having an acryloyl group. More preferably, is used.

  In one embodiment of the present invention, the resin composition is used as an active energy ray polymerizable coating agent (hereinafter referred to as a coating agent), and the resin composition forms a coating layer covering one side or both sides of the substrate. In such an embodiment, the base material may be a wood, a metal plate, a plastic plate, a film-like base material, a glass plate, a processed paper product, or the like, and these can be used without particular limitation.

  On the other hand, in another embodiment of the present invention, the resin composition is used as an active energy ray polymerizable adhesive (hereinafter referred to as an adhesive), and the resin composition bonds two or more substrates (G). An adhesive layer is formed. In such an embodiment, the base material (G) needs to be made of a material that easily transmits active energy rays in order to advance the polymerization reaction by irradiation with active energy rays. As the substrate (G), it is particularly preferable to use a transparent film (H) or a transparent glass plate. However, if a transparent film (H) or a transparent glass plate is used as one of the substrates, the other substrate is difficult to transmit active energy rays, such as wood, metal plates, plastic plates, and processed paper products. It is also possible to use a base material made of such a material. In this case, the resin composition can be polymerized and cured by irradiating active energy rays from the transparent film (H) or the transparent glass plate side.

  In the laminated body of this invention, it is preferable to use a film-form base material as a base material (G). Specific examples of the film-like substrate include cellophane, various plastic films, and paper. Of these, the use of various transparent plastic films is preferred. Moreover, as a film-like base material, as long as the film is transparent, it may have a single layer structure, or may have a multilayer structure formed by laminating a plurality of base materials. Even if it has a film, it can be used conveniently. When constituting the laminated body of this invention, it is preferable to form the resin layer which consists of the resin composition of this invention in the at least one surface of a transparent film (H).

  Hereinafter, more specific embodiments of the laminate of the present invention will be described by taking a case where a transparent film is used as a base material as an example. That is, the following description relates to a laminate having a resin layer, such as a coat layer or an adhesive layer, formed of the resin composition of the present invention on at least one main surface of the transparent film (H).

  A laminate constituted by using the resin composition of the present invention as a coating agent is typically a sheet-like film having a structure of transparent film / coat layer or coat layer / transparent film / coat layer. . Such a laminate can be obtained by applying a resin composition to at least one main surface of the transparent film (H), polymerizing and curing the resin composition, and forming a coat layer.

  On the other hand, a laminate constituted by using the resin composition of the present invention as an adhesive is typically transparent film / adhesive layer / transparent film, or transparent film / adhesive layer / transparent film / adhesive layer / transparent film. The sheet-like multilayer film obtained by laminating a plurality of transparent films. In another embodiment, the laminate is a sheet-like multilayer film such as transparent film / adhesive layer / transparent film / adhesive layer / transparent film / adhesive layer / transparent film, and other optical members such as glass or optical molded bodies. It may have a fixed configuration. The laminate can be obtained by curing the adhesive layer by polymerizing and curing the approximate resin composition from one side or both sides of the film with active energy rays.

  When the resin composition is used as a coating agent or an adhesive, the polymerization and curing of the resin composition is carried out by applying active energy rays to the coating layer at the time of coating the resin composition, at the time of laminating or after laminating the film-like substrate. It is implemented by irradiating. Although it does not specifically limit, it is preferable that the said irradiation is implemented after lamination | stacking, such as a film-form base material.

  As above-mentioned, when a transparent film (H) is used as a base material (G), the said laminated body can be used suitably for an optical use. From the viewpoint of obtaining good optical properties, the transparent film (H) used in the laminate is, for example, heat excellent in optical properties such as transparency, mechanical strength, thermal stability, moisture barrier properties, and isotropic properties. It is preferable that it is various transparent films (H) comprised from a plastic resin. Such various transparent films are also referred to as various plastic films or plastic sheets. Specific examples include, for example, polyvinyl alcohol films, polytriacetyl cellulose films, polyolefin films such as polypropylene, polyethylene, polycycloolefin, and ethylene-vinyl acetate copolymers, polyester films such as polyethylene terephthalate and polybutylene terephthalate, Examples include polycarbonate films, polynorbornene films, polyarylate films, polyacrylic films, polyphenylene sulfide films, polystyrene films, polyvinyl films, polyamide films, polyimide films, and polyoxirane films.

  In the laminate of the present invention, when a multilayer film is formed by laminating a plurality of transparent films (H), the transparent films (H) to be used may be the same or different. For example, a polyacrylic film may be laminated on a polycycloolefin film via an adhesive layer.

  Although the thickness of a transparent film can be determined suitably, generally, it is 1-500 micrometers from viewpoints of workability | operativity, such as intensity | strength or a handleability, and thin-layer property, etc., 1-300 micrometers is preferable, 5- 200 μm is more preferable. In the optical application, the thickness of the transparent film is particularly preferably in the range of 5 to 150 μm.

  In one embodiment of the optical element laminate according to the present invention, it is preferable to use the optical film (I) mainly used in optical applications as the transparent film (H). Here, the optical film (I) is a film obtained by subjecting the transparent film (H) itself to a special treatment and has optical functions such as light transmission light diffusion, light collection, refraction, scattering, and HAZE. Intended for things. Such optical film (I) can be used alone or in combination of several kinds. In one Embodiment of this invention, the laminated body for optical elements can be comprised by forming the resin layer which consists of the said resin composition in at least one main surface of the said optical film (I).

  Specific examples of the optical element laminate include, for example, a hard coat film, an antistatic coat film, an antiglare coat film, a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, a light diffusion film, a brightness enhancement film, Examples include a prism film (also referred to as a prism sheet), a decorative film (meaning a filling sheet for a touch panel), a light guide film (also referred to as a light guide plate), and the like. You may stick the said laminated body for optical elements to glass plates, such as a liquid crystal display device, a PDP module, a touch panel module, and an organic EL module, using the resin composition of this invention as an adhesive agent. As another form, the resin composition of the present invention may be used as an adhesive, and the optical element laminate may be adhered to the various optical films (I).

  Hereinafter, a polarizing film is mentioned as an example of the laminated body for optical elements, and the embodiment of the laminated body will be described more specifically. The polarizing film is also called a polarizing plate, and is an optical film (I) having a multilayer structure in which a polarizer is sandwiched between two film-like substrates. When the transparent film (H) is provided on both sides of the polarizer in the polarizing film, the transparent film (H) made of the same polymer material is used on the front and back surfaces, or the transparent film (H) made of a different polymer material is used. It may be used. The polarizing film has a structure in which, for example, both surfaces of a polyvinyl alcohol-based polarizer are sandwiched between two polytriacetylcellulose-based protective films (hereinafter referred to as “TAC films”) that are polyacetylcellulose-based films. As another example, the polarizing film has one or both sides of a polyvinyl alcohol polarizer sandwiched between films such as polycycloolefin film, polyacrylic film, polycarbonate film, and polyester film that are polynorbornene films. It has a structure.

Although it does not specifically limit, For example, the said polarizing plate (polarizing film) can be manufactured as follows.
(I) The resin composition of the present invention is applied as an adhesive to one main surface of the first transparent film (first protective film) to form a first polymerizable adhesive layer. Moreover, the resin composition of this invention is apply | coated to one main surface of a 2nd transparent film (2nd protective film) as an adhesive agent, and a 2nd polymeric contact bonding layer is formed. Next, the first polymerizable adhesive layer and the second polymerizable adhesive layer are simultaneously and / or sequentially overlapped on both main surfaces of the polyvinyl alcohol polarizer. Next, the obtained laminate is irradiated with active energy rays to polymerize and cure the first and second adhesive layers.

  (II) The resin composition of the present invention is applied as an adhesive to one main surface of the polyvinyl alcohol-based polarizer to form a first polymerizable adhesive layer, and the surface of the first polymerizable adhesive layer Is covered with a first transparent film (first protective film). Next, the other main surface of the polyvinyl alcohol-based polarizer is coated with the resin composition of the present invention as an adhesive to form a second polymerizable adhesive layer, and the surface of the second polymerizable adhesive layer is Cover with a second protective film. Next, the obtained laminate is irradiated with active energy rays to polymerize and cure the first and second polymerizable adhesive layers.

  (III) The end portion of the first transparent film (first protective film) overlaid with one main surface of the polyvinyl alcohol polarizer, and the second protective film overlaid on the other surface of the polyvinyl alcohol polarizer. The resin composition of the present invention is dropped as an adhesive on each end, and the laminate is passed between rolls to spread the adhesive between the layers. Next, the active energy ray is irradiated to the laminate to polymerize and cure the active energy ray-polymerizable adhesive.

  The polarizing film has been described as an example as an embodiment of the optical element laminate. However, the laminate is characterized by using the resin composition of the present invention as a coating agent or adhesive for various substrates. Therefore, it is not limited to the polarizing film, and it should be easily understood that a laminated body that can be suitably used for optical applications can be configured in other embodiments using other various substrates.

The polarizing film obtained as described above is further formed by laminating a peelable film on the upper layer to first form the pressure-sensitive adhesive film. It is common.
The pressure sensitive adhesive film is
(A) A pressure-sensitive adhesive is applied to the release treatment surface of the peelable film, dried, and a film-like optical member is laminated on the surface of the adhesive layer.
(A) A film-like optical member can be obtained by directly applying a pressure-sensitive adhesive and drying, and laminating the release-treated surface of the peelable film on the surface of the adhesive layer.
The pressure-sensitive adhesive is obtained by reacting a pressure-sensitive adhesive resin and a crosslinking agent. This reaction is performed when the pressure-sensitive adhesive group is dried and on the surface of the pressure-sensitive adhesive layer. It progresses when and after laminating a peelable film.
The pressure-sensitive adhesive film for academic use is not limited to the above embodiment, and pressure-sensitive adhesive layers may be provided on both surfaces of the optical member.
Moreover, it is not always necessary to use a peelable film.
And it can use as a laminated body which can be used for an optical use by peeling the peelable film which has covered the surface of the adhesive layer of a pressure-sensitive-type adhesive film, and sticking it on a film member or a glass member.
In particular, a polarizing film is obtained by sticking a pressure-sensitive adhesive film obtained by laminating a pressure-sensitive adhesive on a polarizing film formed using the active energy ray polymerizable resin composition of the present invention to a glass member for a liquid crystal cell. What obtained the optical glass laminated body of the structure of / pressure-sensitive adhesive layer / glass member is called optical element laminated body.

 Hereinafter, the present invention will be described with reference to specific examples. However, the present invention is not limited to the following examples. Further, “parts” and “%” described in the following Examples and Comparative Examples represent “parts by weight” and “% by weight”, respectively.

Manufacture of pressure sensitive adhesive resin:
(Synthesis Example 1)
A reaction vessel, a stirrer, a thermometer, a reflux condenser, a reaction vessel of a polymerization reaction apparatus equipped with an air introduction tube, the following, α, β-ethylenically unsaturated double bond group-containing compound, catalyst and organic solvent are respectively shown below. The ratio was charged.

[Reaction tank]
Butyl acrylate 79 parts 2-hydroxyethyl acrylate 20 parts 4-hydroxybutyl acrylate 1 part Ethyl acetate 54 parts 2,2'-azobisisobutyronitrile 0.05 part

  After replacing the air in the reaction tank with nitrogen gas, the temperature was raised to 80 ° C. in an air atmosphere while stirring, and the reaction was conducted for 6 hours with stirring. Then, 179 parts of ethyl acetate was added and cooled to room temperature. About 30% of a transparent pressure-sensitive adhesive resin solution was obtained. The results are shown in Table 15.

(Synthesis Example 2)
The reaction was conducted in the same manner as in Synthesis Example 1 except that the α, β-ethylenically unsaturated double bond group-containing compound used in Synthesis Example 1 was changed as shown in Table 15, and the nonvolatile content concentration was about 30. % To obtain a clear solution. The results are shown in Table 15.

The detail of each component described in Table 1 is as follows. In Table 1, the symbol “-” means no formulation.
· Α, β-ethylenically unsaturated double bond group-containing compound BA: butyl acrylate, MA: methyl acrylate, 2HEA: 2-hydroxyethyl acrylate, 4HBA: 2-hydroxyethyl acrylate, AA: acrylic acid

  The appearance observation, nonvolatile content concentration, viscosity, and weight average molecular weight (Mw) shown in Table 15 used in each synthesis example are values determined according to the following methods.

"appearance"
The appearance of the pressure-sensitive adhesive resin obtained in each synthesis example was observed and visually evaluated.

<Measurement of nonvolatile content concentration (NV)>
About 1 g of the solution of each synthesis example was weighed in a metal container, dried in an oven at 150 ° C. for 20 minutes, the residue was weighed, and the remaining rate was calculated to obtain a non-volatile content concentration (%).

"viscosity"
The solution of the pressure-sensitive adhesive resin obtained in each synthesis example was rotated at 12 rpm for 1 minute using a # 3 rotor in a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) in an atmosphere of 23 ° C. The solution viscosity (mPa · s) was measured under the conditions.

"yield"
The charged quantity and finished quantity of the pressure-sensitive adhesive resin obtained in each synthesis example were weighed, and the yield was calculated by the following calculation method and displayed in%.
Yield (%) = 100x finished quantity (g) / prepared quantity (g)

《Molecular weight》
The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured using Showa Denko GPC (gel permeation chromatography) “Shodex GPC System-21”. GPC is a liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in molecular size. Tetrohydrofuran is used as a solvent, and the number average molecular weight (Mn) and weight average molecular weight (Mn) are determined in terms of polystyrene. It was.

<Active energy ray polymerizable resin composition>
[Composition Examples 1 to 234]
An ionic compound (A), an α, β-ethylenically unsaturated double bond group-containing compound (B), an oligomer (C), a cation are placed in a light-shielded 300 ml mayonnaise bottle substituted with an oxygen concentration of 10% or less. The polymerizable compound (D), the active energy ray polymerization initiator (E), and the various additives (F) were charged in the ratios shown in Table 16, sufficiently stirred with an air motor, and sufficiently defoamed. Then, the active energy ray polymeric resin composition shown to the compounding example was obtained.

  About the active energy ray polymeric resin composition of the compounding example shown in Table 16, the solution external appearance and the viscosity were calculated | required according to the following method, and the result was shown in Table 17. Moreover, the measuring method of an acid value, a hydroxyl value, and a glass transition temperature was also shown below.

The details of the active energy ray polymerizable resin composition described in Table 16 are as follows. In Table 2, the symbol “-” means no formulation.
・ Ingredient (a)
MLCO: Niken “MLCO 0603-105” manufactured by Daiken Chemical Co., Ltd., GA-703: Graphite dispersion “GA-703” manufactured by Hitachi Chemical Co., Ltd., Nanotech ITO: “Nanotech ITO Slurry” manufactured by CI Kasei Co., Ltd., PEL-20A: Japan Carlit lithium perchlorate-containing poly (ethylene glycol / propylene oxide) copolymer, a1 to a3: Tables 1 to 14 listed and component (b1-1)
4HBA: 4-hydroxybutyl acrylate, 2HEA: 2-hydroxyethyl acrylate, component (b1-2)
CHDMA: 1,4-cyclohexanedimethanol acrylic acid, HPPA: 2-hydroxy-3-phenoxypropyl acrylate, component (b2-1)
IBXA: isobornyl acrylate, DCPA: dicyclopentanyl acrylate, ADCP: dicyclopentanyl diacrylate-component (b2-2)
ACMO: 4-acryloylmorpholine, GMA: glycidyl mesylate / component (b3)
NPGDA: neopentyl glycol diacrylate, BA: butyl acrylate, component (c1)
Ebecryl 885: manufactured by Daicel Cytec Co., Ltd., polyester acrylate / component (c2)
Purple light UV3000B: Polyurethane oligomer (urethane acrylate) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
・ Ingredient (d1-1)
CEP01: 1,3-phenylenebis (methylene) bis (7-oxabicyclo [4.1.0] heptane-3-carboxylate), JER828: Bisphenol A type oxirane resin (manufactured by Mitsubishi Chemical Corporation)
・ Ingredient (d1)
2021P: 3,4-oxiranecyclohexylmethyl-3,4-oxiranecyclohexanecarboxylate (manufactured by Daicel Chemical Industries)
・ Ingredient (d2)
DOME: Di (1-ethyl-3-oxetanyl) methyl ether component (d3)
GC: Glycerin carbonate, component (E)
TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF, DAROCUR TPO), CPI-110P: p-phenylthiophenyldiphenylsulfonium PF ₆ salt In the present invention, the above components are limited. The active energy ray polymerizable resin composition excellent in various characteristics can be provided.

"appearance"
The appearance of the resin composition obtained in each formulation example was observed and visually evaluated.

"viscosity"
About 1.2 ml of the resin composition obtained in each blending example was measured with an E-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.) under an atmosphere of 23 ° C., and a rotation speed of 0.5 to The solution viscosity (mPa · s) was measured at 100 rpm for 1 minute.

<< Hydroxyl value (OHV) >>
About 1 g of a sample is accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. Further, 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for about 1 hour. To this, phenolphthalein reagent is added as an indicator and lasts for 30 seconds. Thereafter, the solution is titrated with a 0.1N alcoholic potassium hydroxide solution until the solution becomes light red.
The hydroxyl value was determined by the following formula. The hydroxyl value was a numerical value in the dry state of the resin (unit: mgKOH / g).
Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (Non-volatile content concentration / 100) + D
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Consumption of 0.1N alcoholic potassium hydroxide solution in the empty experiment (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution
D: Acid value (mgKOH / g)

《Acid value (AV)》
About 1 g of a sample was precisely weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. To this was added a phenolphthalein test solution as an indicator, which was held for 30 seconds, and then titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned light red.
The acid value (mgKOH / g) was determined by the following equation as the value of the resin in the dry state.
Acid value (mgKOH / g) = {(5.611 × a × F) / S} / (Nonvolatile content concentration / 100)
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution

<< Glass transition temperature (Tg) >>
An “SSC5200 disk station” (manufactured by Seiko Instruments Inc.) was connected to a robot DSC (differential scanning calorimeter, “RDC220” manufactured by Seiko Instruments Inc.) and used for measurement.
About 10 mg of a sample is put in an aluminum pan, weighed and set in a differential scanning calorimeter, and heated for 5 minutes at a temperature of 100 ° C. using the same type of aluminum pan without a sample as a reference. Rapid cooling was performed to 120 ° C. Thereafter, the temperature was raised at 10 ° C./min, and the glass transition temperature (Tg, unit: ° C.) was determined from the DSC chart obtained during the temperature elevation.

 Using the active energy ray polymerizable resin composition blended at the ratio shown in Table 16, laminates were prepared by the following methods, respectively.

<Example of production of laminate A (polarizing plate)>
[Examples 1 to 237] [Comparative Examples 1 to 13]
The following laminates were prepared using the resin compositions shown in Tables 16 and 17 as active energy ray polymerizable adhesives.
As a protective film (1) which is a transparent film (H), a polynorbornene-based film containing no UV absorber manufactured by Nippon Zeon Co., Ltd .: trade name “ZF-14” (thickness: 100 μm) is used. Made of Mitsubishi Rayon Co., Ltd. Polyacrylic film containing no UV absorber: The product name “HDB-002” (thickness 50 μm) is used, and the surface is corona-treated with a discharge amount of 300 W · min / m ² , respectively. Within 1 hour after the treatment, the adhesive shown in the formulation example was applied using a wire bar coater so as to have a film thickness of 4 μm, an adhesive layer was formed, and the above polyvinyl alcohol polarizer between the adhesive layer Then, a laminate comprising protective film (1) / adhesive layer / PVA polarizer / adhesive layer / protective film (2) was obtained.
Four sides of this laminate were fixed with cellophane tape so that the protective film (1) was in contact with the tin plate, and was fixed to the tin plate.
A polarizing plate was produced by irradiating ultraviolet rays having a maximum illuminance of 300 mW / cm ² and an integrated light amount of 300 mJ / cm 2 from the protective film (2) side with an active energy ray irradiation device (high pressure mercury lamp manufactured by Toshiba Corporation).

 With respect to the obtained laminate (polarizing plate) itself, peel strength, gel fraction, punching workability, shrinkage rate, heat resistance and heat-and-moisture resistance were determined according to the following methods, and the results are shown in Table 18.

<Peel strength>
The adhesive strength was measured in accordance with JIS K6 854-4 Adhesive-Peel Adhesion Strength Test Method-Part 4: Floating Roller Method.
That is, the obtained polarizing plate was cut into a size of 25 mm × 150 mm using a cutter to obtain a measurement sample. The sample was affixed on a metal plate using a double-sided adhesive tape (DF8712S manufactured by Toyochem Co., Ltd.) using a laminator to obtain a laminate for measurement of the polarizing plate and the metal plate. The polarizing plate of the laminate for measurement is provided with a peeling flicker between the protective film and the polarizer in advance, and the laminate for measurement is 300 mm / min under the conditions of 23 ° C. and 50% relative humidity. It peeled at the speed | rate of and was set as peeling force. Under the present circumstances, the peeling force of both a polyvinyl alcohol-type polarizer and a protective film (1) and a polyvinyl alcohol-type polarizer and a protective film (2) was measured. This peeling force was evaluated as an adhesive force in four stages. In the case of “△” evaluation or higher, there is no problem in actual use.
(Evaluation criteria)
A: Unpeelable or polarizing plate breakage O: Peeling force is 2.0 (N / 25 mm) or more to less than 5.0 (N / 25 mm).
(Triangle | delta): Peeling force is 1.0 (N / 25mm) or more-less than 2.0 (N / 25mm).
X: Peeling force is less than 1.0 (N / 25 mm).

<Gel fraction>
A non-corona-treated polynorbornene-based film (trade name “Zeonor ZF-14: 100 μm”) with an active energy ray-polymerizable adhesive and a wire bar coater to a film thickness of 20 to 25 μm. Then, an active energy ray-polymerizable adhesive layer was formed, and Zeonor ZF-14 not subjected to corona treatment was laminated on the active energy ray-polymerizable adhesive layer to obtain a laminate composed of three layers. Then, the active energy ray polymerizable adhesive layer was polymerized and cured by irradiating with an active energy ray irradiation device (a high-pressure mercury lamp manufactured by Toshiba Corporation) with an active energy ray having a maximum illuminance of 300 mW / cm ² and an integrated light amount of 300 mJ / cm ^2. The laminate Zeonor ZF-14 was peeled off to obtain an adhesive layer.
After the weight of the adhesive layer was measured (weight 1) was sandwiched between metal meshes so that the adhesive layers did not overlap each other, and refluxed in methyl ethyl ketone (MEK) for 3 hours. The film was further dried at 80 ° C. for 30 minutes, and the weight of the adhesive layer was measured (weight 2). The gel fraction was calculated from the following formula and evaluated in three stages. In the case of “△” evaluation or higher, there is no problem in actual use.
Gel fraction (%) = {1− (weight 1−weight 2) / weight 1)} × 100
(Evaluation criteria)
○: Gel fraction is 90% or more Δ: Gel fraction is 80% to less than 90% ×: Gel fraction is less than 80%

<Punching workability>
The produced polarizing plate was punched out from the protective film (1) side using a 100 mm × 100 mm blade manufactured by Dumbbell.
The peripheral peeling distance of the punched polarizing plate was measured with a ruler and evaluated according to the following four levels. In the case of “△” evaluation or higher, there is no problem in actual use.
(Evaluation criteria)
A: 0 mm
○: 1mm or less △: 1-3mm
×: 3 mm or more

"Shrinkage factor"
The polarizing plate pieces are left in a constant temperature and humidity chamber of 60 ° C.-dry and 60 ° C.-90 RH%, the amount of shrinkage in the stretching direction after 60 hours is measured, and the ratio of the amount of shrinkage to the original length (100 mm) Was determined as the shrinkage rate and evaluated in the following three stages.
Note that “dry” is a test condition when only the temperature is controlled and humidity is not controlled in an oven with a humidity adjusting function. In the case of “△” evaluation or higher, there is no problem in actual use.
(Evaluation criteria)
○: Shrinkage rate is 0.2% or less Δ: Shrinkage rate is greater than 0.2% and 0.4% or less ×: Shrinkage rate exceeds 0.4%

"Heat-resistant"
The polarizing plate obtained in each Example and Comparative Example was cut into a size of 50 mm × 40 mm and exposed for 1000 hours under the conditions of 80 ° C.-dry and 100 ° C. dry. After exposure, the presence or absence of peeling at the end of the polarizing plate was visually evaluated in the following three stages. In the case of “△” evaluation or higher, there is no problem in actual use.
(Evaluation criteria)
A: No peeling at all even under the condition of 100 ° C.-dry.
○: No peeling at all at 80 ° C.-dry condition.
(Triangle | delta): There exists peeling less than 1 mm on 80 degreeC-dry conditions.
X: 1 mm or more peeled off at 80 ° C.-dry condition.

《Moisture and heat resistance》
The polarizing plates obtained in each Example and Comparative Example were cut into a size of 50 mm × 40 mm and exposed for 1000 hours under conditions of 60 ° C.-90% RH and 85 ° C.-85% RH. After exposure, the presence or absence of peeling at the end of the polarizing plate was visually evaluated in the following three stages. In the case of “△” evaluation or higher, there is no problem in actual use.
(Evaluation criteria)
A: No peeling at all at 85 ° C. to 85% RH.
○: No peeling at all at 60 ° C.-90% RH.
(Triangle | delta): There exists peeling of less than 1 mm on the conditions of 60 degreeC-90% RH.
X: There is peeling of 1 mm or more under the condition of 60 ° C.-90% RH.

<Example of production of laminate B (pressure-sensitive adhesive film)>
[Examples 1 to 237] [Comparative Examples 8 to 13]
Next, 5 parts of TDI / TMP (trimethylolpropane adduct body of tolylene diisocyanate) is added as a cross-linking agent to 100 parts of the pressure-sensitive adhesive resin solution obtained in the synthesis example and stirred well. Thus, a pressure sensitive adhesive was obtained.
This was coated on a peeled polyester film (hereinafter referred to as “peelable film”) so that the thickness after drying was 25 μm, and dried at 100 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. did.
After drying, the pressure-sensitive adhesive layer was bonded to one side of the polarizing film prepared above to obtain a laminated film having a configuration of “peelable film / pressure-sensitive adhesive layer / polarizing plate”.
Subsequently, the obtained laminated film was aged (dark reaction) for 1 week under the condition of a temperature of 23 ° C. and a relative humidity of 50%, and the reaction of the pressure-sensitive adhesive layer was advanced to obtain a pressure-sensitive adhesive film.

[Comparative Examples 1 to 7]
For 100 parts of the pressure-sensitive adhesive resin solution obtained in the synthesis example, 5 parts of TDI / TMP (trimethylolpropane adduct of tolylene diisocyanate) and 0.5 antistatic agent are used as a crosslinking agent. Part was added and stirred well to obtain a pressure sensitive adhesive. [Examples 1 to 237] In the same manner as in [Comparative Examples 8 to 13], pressure-sensitive adhesive films were obtained.

The symbols shown in Table 18 are as follows.
Antistatic agent MLCO: Niken “MLCO 0603-105” manufactured by Daiken Chemical Co., Ltd. GA-703: Graphite dispersion “GA-703” manufactured by Hitachi Chemical Co., Ltd. Nanotech ITO: “Nanotech ITO slurry” manufactured by CI Kasei Co., Ltd., PEL -20A: manufactured by Nippon Carlit Co., Ltd., lithium perchlorate-containing poly (ethylene glycol / propylene oxide) copolymer, a1-4, a3-1: Tables 1 to 14 and crosslinking agent TDI / TMP: Tolylene diisocyanate 2-methyl-2- (hydroxymethyl) propane-1,3-diol adduct / protective film ZF-14: Polynorbornene film manufactured by ZEON Corporation, HBD-002: acrylic film manufactured by Mitsubishi Rayon Corporation.

 For the obtained laminate (pressure-sensitive adhesive film), re-peelability (reworkability), durability (heat resistance, moist heat resistance), and antistatic properties (surface resistance value, peeling withstand voltage) are determined according to the following methods. The results are also shown in Table 18.

<Evaluation method of removability (reworkability)>
The pressure-sensitive adhesive film obtained in each Example and Comparative Example was cut into a size of 25 mm × 150 mm, the peelable film was peeled off, and attached to a float glass plate having a thickness of 1.1 mm using a laminator, 50 It was kept in an autoclave at 5 ° C. for 20 minutes at a temperature to obtain a laminate of a polarizing film and a glass plate.
The laminate was allowed to stand at 23 ° C. and a relative humidity of 50% for 1 week, and then peeled off at a speed of 300 mm / min in the direction of 180 °. The haze on the glass surface after peeling was visually observed and evaluated in three stages. In the case of “△” evaluation or higher, there is no problem in actual use.
(Evaluation criteria)
○: No fogging, no problem in practical use, very good.
Δ: Some fogging is observed, but no problem in practical use and good.
X: Transfer of the pressure-sensitive adhesive is recognized over the entire surface, and is not practical.

《Durability (heat resistance, wet heat resistance) evaluation method》
The pressure-sensitive adhesive film obtained in each Example and Comparative Example was cut into a size of 150 mm × 80 mm, the peelable film was peeled off, and the polarizing film was placed on both sides of a 1.1 mm thick float glass plate. A laminator was used to stick so that the absorption axes were orthogonal. Subsequently, the glass plate on which the polarizing film was attached was held in an autoclave at 50 ° C. and 5 atm for 20 minutes to obtain a laminated body for an optical element of a laminated body of the polarizing film and the glass plate.
As evaluation of heat resistance, floating peeling after leaving the laminate at 95 ° C. for 1000 hours, and light leakage (white spots) when light was transmitted through the laminate were visually observed.
In addition, as an evaluation of the heat and moisture resistance, the above laminate was floated after being left for 1000 hours at 80 ° C. and a relative humidity of 90%, and light leakage (white spots) when light was transmitted through the laminate was visually observed. did.
The heat resistance and moist heat resistance were evaluated based on the following four-stage evaluation criteria. In the case of “△” evaluation or higher, there is no problem in actual use.
(Evaluation criteria)
A: No floating peeling, foaming, whitening, or displacement was observed, and there was no problem in practical use.
○: No floating peeling, foaming, or whitening was observed, and the deviation was less than 0.2 mm.
△: Slightly floating peeling, foaming, and whitening are recognized, but the deviation is less than 0.2 to 0.5 mm, and there is no problem in practical use. ×: Fully floating peeling, foaming, whitening It is impractical.

<Evaluation method of antistatic performance (surface resistance value: SR)>
The peel-off film of the pressure-sensitive adhesive film is peeled off, and the surface resistance value of the exposed adhesive layer surface is measured under the conditions of 23 ° C.-35, 45, 55% RH (manufactured by Mitsubishi Chemical Corporation). : MCT-HT450) (unit: Ω / □), and the antistatic performance evaluation of the initial value and the time-lapse value was made.
(Initial value evaluation)
A peelable film is coated with a comma coater at a speed of 2 m / min, dried in a 100 ° C. oven to form a pressure-sensitive adhesive layer having a thickness of 25 μm, and a polyester film having a thickness of 50 μm on the surface of the adhesive layer. Were bonded together to prepare a pressure-sensitive adhesive film. After aging for one week under the conditions of a temperature of 23 ° C. and a relative humidity of 50%, the antistatic performance was evaluated by the above method and set as an initial value.
(Evaluation over time)
The pressure-sensitive adhesive film aged for 1 week is allowed to stand for 7 days under conditions of a temperature of 60 ° C. and a relative humidity of 95%, and then for 24 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50%. The antistatic performance was evaluated by the above method, and the time-dependent value was obtained. In the case of “△” evaluation or higher, there is no problem in actual use.
(Evaluation criteria)
○: “Surface resistance value is less than 1.0 × 10 ¹⁰ ”
Δ: “Surface resistance value is 1.0 × 10 ¹⁰ or more and less than 1.0 × 10 ¹¹ ”
×: “Surface resistance value is 2.0 × 10 ¹¹ or more.”

<< Evaluation method of antistatic performance (peeling withstand voltage: EV) >>
The release film of the pressure-sensitive adhesive film is peeled off, and the exposed adhesive layer is attached to a Teflon (registered trademark) sheet (thickness 1 mm) under the conditions of a temperature of 23 ° C. and a relative humidity of 50%, and crimped with a hand roll did. After 24 hours from the press bonding, after static electricity was removed on a glass plate with a static eliminator (“SJ-F010” manufactured by Keyence Corporation), the pressure-sensitive adhesive film was peeled from the Teflon (registered trademark) sheet, and Teflon ( The static electricity on the sheet surface of (registered trademark) was measured at 10 locations with a static electricity measuring instrument (“STATION DZ3” manufactured by Sishido static electricity Co., Ltd.), and the value having the maximum absolute value was defined as peeling charge (unit: kV). In the case of “△” evaluation or higher, there is no problem in actual use.
(Evaluation criteria)
○: “Peeling withstand voltage is less than ± 0.1 kV”
Δ: “Peeling withstand voltage is ± 0.1 kV or more and less than ± 0.5 kV”
×: “Peeling withstand voltage is ± 0.5 kV or more.”

  When the active energy ray polymerizable resin composition of the present invention was used as a bonding adhesive for polarizing plates having antistatic properties, as shown in Table 18, in Examples 6 to 237, the polarizing plate adhesives There is no particular problem with the pressure-sensitive adhesive layer using a layer or a pressure-sensitive adhesive. Moreover, in Examples 1-5, although levels, such as adhesiveness, heat resistance, and heat-and-moisture resistance, are low, it can be used. On the other hand, in Comparative Examples 1 to 7, the polarizing plate withstands practical use, but since the pressure sensitive adhesive contains an antistatic agent, the pressure sensitive adhesive layer of the pressure sensitive adhesive film is particularly It turns out that it becomes easy to receive the influence of a heat | fever and a water | moisture content, and the re-peelability and durability of a pressure sensitive adhesive become especially low. Moreover, it turns out that antistatic performance is also inferior from such alteration of the pressure-sensitive adhesive layer. Moreover, since the comparative example 8 does not contain an antistatic agent in both the adhesive for bonding of the polarizing plate and the pressure sensitive adhesive, it can be seen that the antistatic performance is not exhibited. Furthermore, in Comparative Examples 9 to 13, it is possible to maintain the performance of the pressure-sensitive adhesive by including a general-purpose antistatic agent in the bonding adhesive for polarizing plates, but a commercially available antistatic agent When the polarizing film is bonded to each other, the adhesion, shrinkage rate, or durability is inferior. Moreover, it turns out that the antistatic property of a pressure-sensitive-type adhesive layer cannot be ensured only by containing a commercially available antistatic agent in the bonding adhesive of a polarizing plate.

Claims (8)

An ionic compound (A) represented by any one of the following general formulas (1) to (3);
an α, β-ethylenically unsaturated double bond group-containing compound (B);
An active energy ray-polymerizable resin composition comprising an active energy ray polymerization initiator (E).

General formula (1)

[In General Formula (1), R ^{1 to} R ⁸ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. Represents a good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and R ^{5 to} R ⁸ may form a ring with adjacent substituents; Good. ]
General formula (2)

[In General Formula (2), R ^{1 to} R ⁴ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. A good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and A ⁺ represents an alkali metal ion. ]
General formula (3)

[In General Formula (3), R ^{5 to} R ⁸ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. It represents a good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and adjacent substituents may form a ring.
R ⁹ represents an alkylene bond group that may have a substituent, an alkenyl bond group that may have a substituent, an alkynylene bond group that may have a substituent, or an arylene bond that may have a substituent. Group, heterocyclic group which may have a substituent, or ether bond group, ester bond group, thioether bond group, dithiol bond group, carbonyl bond group, sulfinyl bond group, sulfonyl bond group, phosphonyl bond group, amino A linking group, an imino linking group, or a silyl linking group is represented.
R ¹⁰ represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a halogen group.
R ¹¹ represents a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or —R ⁹ R ¹⁰ . ] In the total amount of the active energy ray polymerizable resin composition,
0.01 to 10% by weight of compound (A),
1 to 99% by weight of compound (B),
The active energy ray-polymerizable resin composition according to claim 1, comprising 0.01 to 20% by weight of the active energy ray polymerization initiator (E).  The active energy ray polymerizable resin composition according to claim 1 or 2, wherein the compound (B) contains an α, β-ethylenically unsaturated double bond group-containing compound (b1) having a hydroxyl group.  The compound (B) comprises an α, β-ethylenically unsaturated double bond group-containing compound (b2) having one or more cyclic structures and no hydroxyl group. The active energy ray polymerizable resin composition described.   The laminated body which has a base material (G) and the resin layer which consists of a resin composition in any one of Claims 1-4 provided in the at least one main surface of this base material (G).   The laminate according to claim 5, wherein the substrate (G) is a transparent film (H).   The transparent film (H) is selected from the group consisting of a polyacetylcellulose film, a polynorbornene film, a polypropylene film, a polyacryl film, a polycarbonate film, a polyester film, a polyvinyl alcohol film, and a polyimide film. The laminate according to claim 6, wherein the laminate is at least one selected.   The laminated body for optical elements which has an optical film and the resin layer which consists of a resin composition in any one of Claims 1-4 provided in the at least one main surface of this optical film.