TWI498401B - Pressure sensitive adhesive for optical member and optical member - Google Patents

Description

Adhesive for optical members and optical members

The present invention relates to an adhesive, an adhesive for an optical member, an optical member containing the adhesive layer therewith, and an adhesive for temporary surface protection.

More specifically, the present invention relates to an adhesive for an optical member for a glass substrate of an optical laminate and a liquid crystal cell, and an adhesive layer formed with an adhesive layer composed of an adhesive for the optical member. The optical member, particularly the polarizing plate with an adhesive layer, is suitable for an image display device such as a liquid crystal display device, an organic EL (electroluminescence) display device, or a PDP (plasma display panel). For example, an optical film (a polarizing film, a retardation film, an optical compensation film, a brightness enhancement film, or the like) is coated with a protective film such as a cellulose triacetate film.

In the prior art, a polarizing plate is laminated on a surface of a liquid crystal cell in which an aligned liquid crystal component is sandwiched between two glass plates to form a liquid crystal display panel, and the polarizing plate is a polarizing film, for example, polarized. The both sides of the polyvinyl alcohol-based film or the like are coated with a cellulose film, for example, a cellulose triacetate film, and the layer formed on the surface of the liquid crystal cell is usually abutted by the adhesive layer provided on the surface of the polarizing plate. The liquid crystal cell is pressed on the surface of the liquid crystal cell.

Further, an adhesive layer provided on the surface of the optical member such as the polarizing plate is provided with a separator to prevent damage or contamination, or a surface protective film is provided to prevent damage or contamination during processing and transportation. However, when it is bonded to a liquid crystal cell or the like, such a separator or a surface protective film is not required, and it is removed and removed. Static electricity is generated when the separator or the surface protective film is peeled off from the optical member, and there is a problem that the static electricity is caused by adhesion of dust to the optical member, or abnormal display due to disorder of liquid crystal alignment, or causing peripheral circuits. Electrostatic breakdown of components, etc.

Further, when the optical member provided with the pressure-sensitive adhesive layer is bonded to the liquid crystal cell, when foreign matter is mixed or damaged, and then an error or the like occurs, the film is peeled off and then bonded, but in the peeling process, In the same situation, static electricity is generated, causing a bad situation.

In this way, for example, in an adhesive composition for an optical member, an ionic liquid is formulated in a base polymer (for example, see Patent Document 1).

Patent Document 1: Japanese Patent Laid-Open No. 2006-11365

However, in the technique disclosed in the above Patent Document 1, although the effect of the antistatic property is confirmed, it depends only on the antistatic property of the ionic liquid, and thus the antistatic property is also insufficient. Further, the base polymer itself generally does not have antistatic properties, and therefore has low compatibility with the formulated ionic liquid, and the ionic liquid may bleed out over time. Moreover, the durability and light leakage prevention performance which are important in the use of optical members, especially polarizing plates, are not considered at all.

Furthermore, the liquid crystal display panel of the polarizing plate is widely used as a display device such as a computer, a liquid crystal television, or a car navigation, and the use environment is also very demanding, and it is required to have excellent durability even when used in such a harsh environment, for example. It is required that foaming or peeling between the adhesive layer and the glass plate does not occur even in a harsh environment of high temperature and high humidity, and it is required that there is no so-called light leakage in a high-temperature, high-humidity environment. That is, the polarizing film shrinks and the adhesive layer cannot follow the shrinkage, causing light to leak from the peripheral portion of the liquid crystal display panel.

Therefore, in the above background, an object of the present invention is to provide an antistatic property which is excellent in adhesion between an optical laminate, in particular, a polarizing plate and a glass substrate under high temperature and high humidity conditions, and an adhesive layer and a glass substrate. The adhesive for an optical member excellent in durability, such as a light leakage phenomenon caused by shrinkage of the polarizing film, and an optical member to which the adhesive layer is attached, are not generated between the foaming and the peeling.

Further, an object of the present invention is to provide an adhesive for temporary surface protection, which is used to solve the problem that, in order to protect a surface and impart functionality, various displays such as a word processor, a computer, a mobile phone, and a television are polarized. An optical member such as a laminate or a laminate thereof, a transparent surface protection sheet such as polyethylene, polyester, or polypropylene laminated on the surface of an electronic substrate or the like by an adhesive, but a surface protective adhesive sheet laminated with an adhesive After the assembly of the liquid crystal display or the like is completed, for example, the surface protection effect is terminated, and most of the material is peeled off. At this time, the surface is protected from static electricity when the surface is adhered to the adhesive sheet, and the surrounding dust is caught; or the adhesive sheet is removed by the peeling surface. The peeling of static electricity generated during the material causes damage to the liquid crystal substrate and the electronic circuit.

However, the inventors of the present invention have made intensive studies in view of the above circumstances, and as a result, it has been found that, in the acrylic resin constituting the main component of the adhesive, a hydroxyl group-containing monomer having a conventionally used amount is used as a polymerization component thereof. The present invention can be completed by obtaining an adhesive for an optical member excellent in antistatic properties of an acrylic resin itself and having excellent antistatic properties.

That is, the gist of the present invention is shown below.

(1) An adhesive comprising a resin composition [I] containing an acrylic resin (A) as a main component, and the acrylic resin (A) containing 15% by weight or more of a hydroxyl group. The polymerization component of the monomer is polymerized.

(2) The adhesive according to (1), wherein the acrylic resin (A) has a weight average molecular weight of from 100,000 to 3,000,000, and further has a degree of dispersion of 7 or less.

(3) The adhesive according to (1) or (2), wherein the resin composition [I] contains the unsaturated group-containing compound (B) and the polymerization initiator (C), and is activated by an active energy ray and heat At least one of them is cross-linked.

(4) The adhesive according to any one of (1) to (3) wherein the resin composition [I] contains a crosslinking agent (D) and is crosslinked by a crosslinking agent.

(5) The adhesive according to any one of (1) to (4), wherein the resin composition [I] further contains a decane coupling agent (E).

(6) The adhesive according to any one of (1) to (5), wherein the resin composition [I] further contains an antistatic agent (F).

(7) An adhesive for an optical member, which comprises the adhesive according to any one of (1) to (6).

(8) The adhesive for an optical member according to (7), wherein the optical member is a polarizing plate.

(9) An optical member with an adhesive layer characterized by having an adhesive layer containing an adhesive for an optical member as in (7) or (8).

(10) An adhesive for temporary surface protection comprising the adhesive according to any one of (1) to (4) or (6).

The adhesive of the present invention has an excellent effect on antistatic properties, and has an effect that it is excellent in adhesion between an optical laminate and a glass substrate even under conditions of high temperature and high humidity, and an adhesive and A liquid crystal display panel which does not cause foaming or peeling between glass substrates, and which can suppress light leakage caused by shrinkage of an optical film.

Hereinafter, the present invention will be described in detail.

Further, in the present invention, the (meth)acryl group means a propenyl group or a methacryl group, and the (meth)acryloyl group means an acryl group or a methacryl group, and the so-called (meth) group Acrylate means acrylate or methacrylate.

The acrylic resin (A) used in the present invention is obtained by separately polymerizing or copolymerizing other copolymerized components by containing a hydroxyl group-containing monomer as a polymerization component as an essential component.

The hydroxyl group-containing monomer (a1) of the present invention may, for example, be 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate or 5-hydroxypentyl (meth)acrylate. 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate, etc. Hydroxyalkyl (meth)acrylate, caprolactone modified caprolactone modified monomer such as 2-hydroxyethyl (meth)acrylate, 2-propenyloxyethyl phthalate-2-hydroxyethyl Monomer-containing monomer such as ester, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, etc.; 2-hydroxypropyl (meth) acrylate, (methyl) 2-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-(meth)acrylate a monomer having a secondary hydroxyl group such as phenoxypropyl ester; a monomer having a tertiary hydroxyl group such as 2,2-dimethyl-2-hydroxyethyl (meth)acrylate.

Further, a polypropylene glycol derivative such as diethylene glycol mono(meth)acrylate or polyethylene glycol mono(meth)acrylate or polypropylene glycol mono(meth)acrylate may be used. , polyethylene glycol-polypropylene glycol mono(meth)acrylate, poly(ethylene glycol-butanediol) mono(meth)acrylate, poly(propylene glycol-butanediol) mono(meth)acrylic acid Ester iso-oxyalkylene modified monomer.

In the hydroxyl group-containing monomer (a1), in terms of excellent reactivity with a crosslinking agent, a monomer having a primary hydroxyl group is preferred, and further impurities such as di(meth)acrylate are less. In terms of ease of manufacture, it is particularly preferred to use 2-hydroxyethyl (meth)acrylate.

Further, as the hydroxyl group-containing monomer (a1) used in the present invention, it is also preferred to use a content of the di(meth)acrylate which is an impurity of 0.5% or less, and more preferably 0.2% or less. Those who use the best are 0.1% or less.

Examples of the other copolymer component other than the hydroxyl group-containing monomer (a1) include a (meth)acrylate monomer (a2), and a functional group other than the hydroxyl group-containing monomer (a1). Monomer (a3) or other copolymerizable monomer (a4).

The (meth)acrylate monomer (a2) may, for example, be an alkyl methacrylate or a phenyl (meth)acrylate.

With respect to the alkyl (meth)acrylate, the carbon number of the alkyl group is usually preferably from 1 to 12, particularly preferably from 1 to 8, more preferably from 4 to 8. Specific examples thereof include methyl (meth)acrylate and (methyl). Ethyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-propyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, cetyl (meth)acrylate, Octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid Ester and the like. Further, examples of the phenyl (meth)acrylate include benzyl (meth)acrylate and phenoxyethyl (meth)acrylate.

Examples of the other (meth) acrylate-based monomer include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and 3-methoxy (meth)acrylate. Butyl ester, 2-butoxyethyl (meth)acrylate, 2-butoxy diethylene glycol (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy Triethylene glycol (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, methoxy dipropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate , octyloxy polyethylene glycol-polypropylene glycol-mono (meth) acrylate, dodecyloxy polyethylene glycol mono (meth) acrylate, octadecyloxy polyethylene glycol mono (methyl An aliphatic (meth) acrylate such as acrylate or tetrahydrofurfuryl (meth) acrylate. These may be used alone or in combination of two or more.

In the (meth) acrylate monomer (a2), n-butyl (meth) acrylate or (methyl) is preferably used in terms of copolymerizability, adhesiveness, ease of handling, and easy availability of a raw material. Ethyl 2-ethylhexyl acrylate is more preferably n-butyl (meth) acrylate in terms of excellent antistatic properties.

Examples of the functional group-containing monomer (a3) include a carboxyl group-containing monomer, a glycidyl group-containing monomer, a guanamine group-containing monomer, an amine group-containing monomer, and a nitrogen-containing monomer. Further, a phosphate group-containing monomer, a sulfonic acid group-containing monomer, or the like may be used alone or in combination of two or more.

Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, and acrylamide N-ethanol. Michael, an adduct of acid, cinnamic acid, or (meth)acrylic acid (for example, acrylic acid dimer, methacrylic acid dimer, acrylic acid terpolymer, methacrylic acid terpolymer, acrylic acid tetramer) , tetramethylene methacrylate, etc.), di-2-(methyl)propenyloxyethyl dicarboxylate (for example, succinic acid mono-2-propenyloxyethyl ester, succinic acid mono-2-methyl Propylene methoxyethyl ester, phthalic acid mono-2-propenyloxyethyl ester, phthalic acid mono-2-methylpropenyloxyethyl ester, hexahydrophthalic acid mono-2-propenyloxy Ethyl ester, hexahydrophthalic acid mono-2-methylpropenyloxyethyl ester, etc.).

Examples of the glycidyl group-containing monomer include glycidyl (meth)acrylate and allyl glycidyl ether.

Examples of the above-mentioned mercapto group-containing monomer include acrylamide, methacrylamide, N-(n-butoxyalkyl)propenylamine, and N-(n-butoxyalkyl)methyl. Acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)propene Guanamine, acrylamide-3-methylbutylmethylamine, dimethylaminoalkyl acrylamide, dimethylaminoalkylmethacrylamide, and the like.

Examples of the amino group-containing monomer include dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.

Examples of the above nitrogen-containing monomer include an acrylonitrile group. Porphyrin and the like.

Examples of the phosphoric acid group-containing monomer include 2-(methyl)propenyloxyethyl phosphate and bis(2-(methyl)propenyloxyethyl) phosphate.

Examples of the sulfonic acid group-containing monomer include an olefin sulfonic acid such as ethylenesulfonic acid, allylsulfonic acid or methallylsulfonic acid, and 2-propenylamine-2-methylpropanesulfonic acid. Acid, styrene sulfonic acid or a salt thereof and the like.

In the functional group-containing monomer (a3), a carboxyl group-containing monomer, a glycidyl group-containing monomer, a mercapto group-containing monomer, and a nitrogen-containing monomer are further used, and further, the exfoliating property is excellent, and In terms of durability, it is also preferable to use a carboxyl group-containing monomer.

Examples of the other copolymerizable monomer (a4) include acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl octadecanoate, and vinyl chloride. , vinylidene chloride, alkyl vinyl ether, vinyl toluene, vinyl pyridine, vinyl pyrrolidone, dialkyl itaconate, dialkyl fumarate, allyl alcohol, propylene chloride, A A monomer such as a vinyl ketone, N-propylene guanamine methyl trimethyl ammonium chloride, allyl trimethyl ammonium chloride, or dimethyl allyl vinyl ketone.

In the case of a high molecular weight, the following compounds having two or more ethylenically unsaturated groups, that is, ethylene glycol di(meth)acrylate or diethylene glycol di(methyl) may be used in combination. Acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, divinylbenzene, and the like.

Further, in the present invention, in order to further improve the antistatic property of the acrylic resin (A), it is preferred to further copolymerize a compound having an antistatic property as a copolymerizable monomer.

The compound having an antistatic property may have a structural portion exhibiting hydrophilicity, and examples of the hydrophilic group include a compound having an ionic group. Examples of the compound having an ionic group include an ionic liquid having a polymerizable group such as a quaternary compound such as dimethylaminoethyl (meth)acrylate or a (meth) acrylate such as an imidazolium salt, and an ionic solid. A polymerizable compound containing an ionic group such as a (meth)acrylic acid urethane compound having a quaternary ammonium salt group.

Among these, polyethylene glycol (meth) acrylate, imidazolium salt-containing ionic liquid containing (meth) acrylonitrile, and amino acid (meth) acrylate containing quaternary ammonium salt can be used. Ethyl formate or ethylene glycol is a polyethylene glycol having a repeating unit of 5 to 50 or ethyl methacrylate using a single terminal methyl group, an ethyl group, an allyl group or the like as a raw material.

Further, a compound having antistatic properties can be introduced into the side chain of the acrylic resin (A) produced by temporary copolymerization by a graft reaction. In this case, for example, a compound having a hydroxyl group is selected from the compound having a hydrophilic structural moiety, and reacted with a polyisocyanate compound to form a urethane prepolymer, and then reacted with a hydroxyl group of the acrylic resin (A). By this, you can import it.

In the present invention, the acrylic resin (A) is produced by polymerizing the monomer components (a1) to (a4), and when the polymerization is carried out, radical polymerization, suspension polymerization, or bulk formation by solution Polymerization, emulsion polymerization, and the like are carried out by a conventionally known method. For example, the above hydroxyl group-containing monomer (a1), (meth) acrylate monomer (a2), other functional group-containing monomer (a3), and other copolymerizable single monomers are mixed or added dropwise in an organic solvent. a polymerization monomer such as a body (a4), a polymerization initiator (azobisisobutyronitrile, azobisisovaleronitrile, benzammonium peroxide, etc.), and polymerized in a reflux state or at 50 to 90 ° C for 2 to 20 hours. .

It is necessary to contain 15% by weight or more of the hydroxyl group-containing monomer (a1) as a copolymerization component of the acrylic resin (A) with respect to the entire copolymerization component, and if it is too small, sufficient antistatic property cannot be obtained. The content of the hydroxyl group-containing monomer (a1) is preferably from 15 to 90% by weight, more preferably from 20 to 70% by weight, particularly preferably from 25 to 50% by weight. When the content of the hydroxyl group-containing monomer (a1) is too large, the storage stability of the acrylic resin tends to be lowered, and if it is too small, the antistatic property tends to be insufficient.

Further, the content ratio of the polymerization component other than the hydroxyl group-containing monomer (a1) is preferably from 0 to 85% by weight, particularly preferably from 10 to 85% by weight, more preferably from 10 to 85% by weight. 30 to 80% by weight; the functional group-containing monomer (a3) other than the (meth)acrylic monomer (a1) is preferably 0 to 40% by weight, particularly preferably 0 to 30% by weight, more preferably 0 to 30% by weight. 20% by weight; the other copolymerized monomer (a4) is preferably 0 to 50% by weight, particularly preferably 0 to 40% by weight, more preferably 0 to 30% by weight.

The weight average molecular weight of the acrylic resin (A) thus obtained is usually from 100,000 to 3,000,000, preferably from 300,000 to 2,500,000, and particularly preferably from 600,000 to 2,000,000. When the weight average molecular weight is too small, there is a tendency that sufficient cohesive force cannot be obtained even by crosslinking treatment of at least one of active energy ray irradiation and heat; if it is too large, a large amount of solvent is required to be applied, or coating property or The tendency to be inferior in terms of cost.

Further, the degree of dispersion (weight average molecular weight/number average molecular weight) of the acrylic resin (A) is not particularly limited, but is preferably 7 or less, particularly preferably 5.5 or less, more preferably 4.5 or less, and particularly preferably 3.5 or less. When the degree of dispersion is too high, the durability of the pressure-sensitive adhesive layer such as moist heat resistance or light leakage tends to be deteriorated. Furthermore, the lower limit of the dispersion is usually 1.1 in terms of the limit of manufacture.

Further, the glass transition temperature of the acrylic resin (A) is not uniform, but is preferably -80 to -20 ° C, particularly preferably -75 to -25 ° C, more preferably -60 to -30 ° C, if the glass is transferred If the temperature is too high, the viscosity tends to be insufficient, and if it is too low, the heat resistance tends to be deteriorated.

Further, the above weight average molecular weight is obtained by converting the molecular weight of the standard polystyrene by a high performance liquid chromatography ("Waters 2695 (body)" and "Waters 2414 (detector) manufactured by Waters Corporation, Japan). ")") used three columns in series: Shodex GPC KF-806L (rejection limit molecular weight: 2 × 10 ⁷ , separation range: 100 ~ 2 × 10 ⁷ , theoretical number of stages: 10,000 segments / root, filler material: The styrene-divinylbenzene copolymer and the filler particle diameter: 10 μm were measured, and the degree of dispersion was determined based on the weight average molecular weight and the number average molecular weight. Further, the glass transition temperature was calculated based on the Fox formula.

Furthermore, in the present invention, the resin composition [I] contains the acrylic resin (A) as a main component. Here, the term "containing as a main component" means that the acrylic resin (A) is usually contained in an amount of 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more based on the total amount of the resin composition [I]. ). Further, the upper limit is usually 99.9% by weight.

In the present invention, an adhesive is formed by crosslinking the resin composition [I] containing the acrylic resin (A) as a main component.

The method of crosslinking the above resin composition [I] includes [α] a compound (B) containing an unsaturated group and a polymerization initiator (C), and at least one of an active energy ray and heat. And a method of crosslinking; [β] a method of crosslinking using a crosslinking agent (D). Further, regarding the degree of crosslinking, sufficient crosslinking can be obtained by using only the above [α] method or [β] method, and if possible, the crosslinking of the adhesive is made closer and the light leakage prevention property is improved. In other words, each of the above methods [α] and [β] is used in combination.

First, the above [α] method, that is, the compound (B) containing an unsaturated group and the polymerization initiator (C), at least one of an active energy ray and heat (at least one of active energy ray irradiation and heating) The method of crosslinking the resin composition [I] will be described.

In the case where the crosslinking is carried out by at least one of the active energy ray and the heat (at least one of the active energy ray irradiation and the heating), the resin composition [I] is used in addition to the acrylic resin (A). A resin composition [I] containing a compound (B) containing an unsaturated group and a polymerization initiator (C). Thus, by adjusting the hardening containing the unsaturated group-containing compound (B), it is possible to achieve an adhesive property suitable for use in an optical member. Further, by containing the polymerization initiator (C), the reaction at the time of irradiation with the active energy ray and/or at the time of heating can be stabilized.

In the case of the above cross-linking, the unsaturated group-containing compound (B) is polymerized (polymerized) by at least one of an active energy ray and heat to carry out crosslinking (physical crosslinking) with the acrylic resin (A). ). When the acrylic resin (A) contains an unsaturated group in the side chain, not only the unsaturated group-containing compound (B) is crosslinked by polymerization of at least one of an active energy ray and heat, but also Crosslinking is also caused by the polymerization of the saturated acrylic resin (A) and the unsaturated group-containing compound (B).

The unsaturated group-containing compound (B) used in the present invention may be a monofunctional unsaturated group-containing compound having one unsaturated group in one molecule, or may have two in one molecule. The polyunsaturated unsaturated group-containing compound having an unsaturated group is preferably a compound having two or more unsaturated groups and having an unsaturated group in terms of hardenability upon irradiation with an active energy ray, and more preferably has a compound having two or more unsaturated groups. A compound containing an unsaturated group of three or more unsaturated groups.

As the structure of the unsaturated group-containing compound (B), for example, a (meth)acrylic acid ethyl methacrylate compound, a (meth)acrylic acid epoxy ester compound, or a polyester (meth) acrylate can be used. A compound or an ethylenically unsaturated monomer having one or more ethylenically unsaturated groups in one molecule, for example, a monofunctional monomer, a difunctional monomer, a trifunctional or higher monomer, or the like. Among these, the (meth)acrylic acid ethyl ester-based compound (b1) and the ethylenically unsaturated monomer (b2) are preferably used from the viewpoint of excellent curing speed and stability to physical properties.

Further, as the unsaturated group-containing compound (B), it is more preferable that the antistatic property contains a structure in which an alkyl group, an hydroxy group or an acid-base ion pair and/or a betaine structure exhibits hydrophilicity. The compound at the site.

The (meth)acrylic acid urethane-based compound (b1) is a (meth) acrylate-based compound having a urethane bond in the molecule, and can be made of a hydroxyl group-containing (meth)acrylic compound. The valence isocyanate compound is produced by reaction.

The (meth)acrylic compound containing a hydroxyl group is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 2. - hydroxybutyl ester, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 2-(methyl)propenyloxyethyl-2-hydroxypropyl phthalate, 2-Hydroxy-3-(methyl)propenyloxypropyl (meth)acrylate, caprolactone modified 2-hydroxyethyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (Meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate The ester or ethylene oxide is modified with pentaerythritol tri(meth)acrylate, and among them, a hydroxyl group-containing (meth)acrylic compound having three or more acrylonitrile groups is preferably used. Further, these may be used alone or in combination of two or more.

The polyvalent isocyanate compound is not particularly limited, and examples thereof include polyisocyanates such as aromatic, aliphatic, and alicyclic resins, and examples thereof include toluene diisocyanate, diphenylmethane diisocyanate, and hydrogenated diphenyl. Methane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, hydrogenated dimethyl diisocyanate, benzodimethyl diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene Diisocyanate, tetramethylphenyldimethyl diisocyanate, isophorone diisocyanate, lower Polyisocyanate such as ene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, phenyl diisocyanate, leucine diisocyanate, triisocyanate, naphthalene diisocyanate or the like or polyisocyanates Terpolymer compound or polymer compound, biuret type polyisocyanate, water-dispersible polyisocyanate (for example, "Aquanate 100", "Aquanate 110", "Aquanate 200" manufactured by NIPPON POLYURETHANE INDUSTRY "Aquanate 210" or the like, or a reaction product of the polyisocyanate and a polyhydric alcohol. Among them, isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate or the trimer compound or polymer compound are preferably used.

The polyhydric alcohol is not particularly limited, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, and butylene glycol. An alkanediol compound such as polybutylene glycol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone, trimethylolethane, trishydroxyl Polyhydric alcohols such as propane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerin, polyglycerol, polytetramethylene glycol; polyethylene oxide, polypropylene oxide, epoxy a polyether polyol of at least one structure of ethane-propylene oxide block or random copolymerization; belonging to the polyol or polyether polyol and maleic anhydride, maleic acid, antibutene Polyester polyols of condensates of diacids, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid and the like; polycaprolactones such as caprolactone modified polytetramethylene polyols An alcohol, a polyolefin-based polyol, a polybutadiene-based polyol such as a hydrogenated polybutadiene polyol, or the like. Among these, polyethylene glycol derivatives are preferably used, and polyethylene glycol and polyethylene glycol monomethyl ether are particularly preferably used.

Further, examples of the polyhydric alcohol include 2,2-bis(hydroxymethyl)butyric acid, tartaric acid, 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, and 2,2-double. (hydroxymethyl)propionic acid, 2,2-bis(hydroxyethyl)propionic acid, 2,2-bis(hydroxypropyl)propionic acid, dihydroxymethylacetic acid, bis(4-hydroxyphenyl)acetic acid, A sulfonic acid group-containing or sulfonate-based polyol such as a carboxyl group-containing polyol such as 4,4-bis(4-hydroxyphenyl)pentanoic acid or uronic acid or a sodium 1,4-butanediol sulfonate.

In the case of using a reaction product of a polyisocyanate and a polyhydric alcohol, for example, a polyisocyanate containing an isocyanate group at the terminal obtained by reacting the above polyhydric alcohol with the above polyisocyanate may be used. In the reaction of the above polyisocyanate with a polyhydric alcohol, in order to promote the reaction, it is also preferred to use a metal catalyst such as dibutyltin of bis(dodecanoic acid) or a 1,8-diazabicyclo[5.4.0] The amine of monoene-7 is a catalyst or the like.

Further, as the above-mentioned (meth)acrylic acid ethyl methacrylate-based compound (b1), it is preferred to use an alkyl group having an alkyl group having an oxyalkylene group in terms of excellent antistatic properties. Ethyl carbamate compound.

The (meth)acrylic acid ethyl methacrylate-based compound containing an oxyalkylene chain is also obtained by using an alkanediol-based compound as the above-mentioned polyol, and as the (oxy) alkyl group-containing chain (meth) The structure of the ethyl acrylate-based compound is hardened by irradiation with an active energy ray, and the degree of freedom of the alkyl group of the oxyalkyl group is large and the ion transport is likely to occur, so that the antistatic property is excellent. Preferably, one of the terminal hydroxyl groups of the alkanediol-based compound is reacted with an isocyanate group, and the other is an ethyl methacrylate having an oxyalkylene chain structure remaining in the form of a hydroxyl group.

Further, the (meth)acrylic acid urethane-based compound having an alkylene group-containing alkyl chain may be an alkanediol-based compound having only one hydroxyl group instead of the above-mentioned polyol-based alkane having a plurality of hydroxyl groups. An alcohol-based compound. Examples of the alkanediol-based compound having only one hydroxyl group include polyethylene glycol monomethyl ether, polyethylene glycol monoallyl ether, polyethylene glycol lauryl ether, and polyethylene glycol. Alkane ether, polyethylene glycol stearyl ether, polyethylene glycol decyl phenyl ether, polyethylene glycol tridecyl ether, polyethylene glycol oleyl ether, polyethylene glycol octyl phenyl ether, polyethylene oxide oil An alkyl group-containing polyalkylene glycol derivative such as a polyethylene glycol derivative such as hexadecyl ether or a polypropylene glycol derivative such as polypropylene glycol monomethyl ether.

The method for producing the (meth)acrylic acid urethane-based compound is not particularly limited, and examples thereof include a method in which a hydroxyl group-containing (meth)acrylic compound and a polyvalent isocyanate compound are mixed at 30. The reaction was carried out at -80 ° C for 2 to 10 hours. In the reaction, it is preferred to use ethyl octylate, di(n-dodecyl) di-n-butyltin, lead octoate, potassium octylate, potassium acetate, stannous octoate, triethylenediamine or the like. Media.

The weight average molecular weight of the above (meth)acrylic acid urethane-based compound is preferably from 300 to 4,000, more preferably from 400 to 3,000, particularly preferably from 500 to 2,000. In other words, when the weight average molecular weight is too small, the cohesive strength after curing tends to be insufficient, and if it is too large, the viscosity tends to be too high and it tends to be difficult to manufacture.

Moreover, as the (meth)acrylic acid ethyl methacrylate-based compound of the present invention, a (meth)acrylic acid urethane-based compound having a quaternary ammonium salt structure or an imidazolium salt in the molecule is preferably used. Further, in order to make the network containing the unsaturated group and the acrylic resin tight, and the durability is improved, it is preferable to form a (meth)acrylic acid urethane-based compound to intentionally remain. It has a structure of isocyanate groups.

As the ethylenically unsaturated monomer (b2) used in the present invention, a monofunctional monomer, a difunctional monomer, a trifunctional or higher monomer, or the like can be used.

The monofunctional monomer may be a monomer containing one ethylenically unsaturated group, and examples thereof include styrene, vinyl toluene, chlorostyrene, α-methylstyrene, and (meth)acrylic acid. Methyl ester, ethyl (meth)acrylate, acrylonitrile, vinyl acetate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate , phenoxyethyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, (methyl) 3-Chloro-2-hydroxypropyl acrylate, mono (meth) acrylate, glycidyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, (a) Acrylic Ester, tricyclodecyl (meth)acrylate, dicyclopentenyl (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (a) Octyl acrylate, decyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-octadecane (meth) acrylate Ester, benzyl (meth) acrylate, phenol oxirane modified (meth) acrylate, nonyl phenol propylene oxide modified (meth) acrylate, 2-(methyl) propylene phthalate A half ester (meth) acrylate of a phthalic acid derivative such as a nonyloxy-2-hydroxypropyl ester, an oxime (meth) acrylate, a carbitol (meth) acrylate, or a benzyl (meth) acrylate Ester, butoxyethyl (meth)acrylate, allyl (meth)acrylate, acryloyl porphyrin, 2-hydroxyethyl acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, mono-2-(meth)acryloxyethyl phosphate, and the like.

Examples of the ethylenically unsaturated monomer include, in addition to the above, a methacrylic acid addition product or a dicarboxylic acid mono-2-propenyloxyethyl ester, and examples of the above-mentioned acrylic acid addition product include: Acrylic acid dimer, methacrylic acid dimer, acrylic acid terpolymer, methacrylic acid terpolymer, acrylic acid tetramer, methacrylic acid tetramer, and the like. Further, examples of the above-mentioned dicarboxylic acid mono-2-propenyloxyethyl ester which is a carboxylic acid having a specific substituent include succinic acid mono-2-propenyloxyethyl ester and succinic acid mono 2-methyl. Propylene methoxyethyl ester, phthalic acid mono-2-propenyloxyethyl ester, phthalic acid mono-2-methylpropenyloxyethyl ester, hexahydrophthalic acid mono-2-propene oxime Ethyl ethyl ester, hexahydrophthalic acid mono-2-methylpropenyloxyethyl ester, and the like. Further, an oligoester acrylate can also be mentioned.

The difunctional monomer may be a monomer containing two ethylenically unsaturated groups, and examples thereof include ethylene glycol di(meth)acrylate and diethylene glycol di(meth)acrylate. Tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(methyl) Acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified bisphenol A type di(meth)acrylate, propylene oxide modified double Phenol A type di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,6-hexanediol ethylene oxide modified di(meth)acrylate, glycerin II Methyl) acrylate, pentaerythritol di(meth) acrylate, ethylene glycol diglycidyl ether di(meth) acrylate, diethylene glycol diglycidyl ether di(meth) acrylate, phthalic acid Diglycidyl ester di(meth)acrylate, hydroxypivalic acid modified neopentyl glycol di(meth)acrylate, iso-cyanuric acid ethylene oxide modified diacrylate, phosphoric acid double (2- (Meth) propylene oxiranyl ethyl ester).

The trifunctional or higher monomer may be a monomer containing three or more ethylenically unsaturated groups, and examples thereof include trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylic acid. Ester, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate , tris(meth)propylene methoxy ethoxy trimethylolpropane, glycerol polyglycidyl ether poly(meth) acrylate, iso-cyanuric acid oxirane modified tri(meth) acrylate Ethylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, epoxy Ethyl is modified with pentaerythritol tetra(meth)acrylate, succinic acid modified pentaerythritol tri(meth)acrylate, and the like.

In the ethylenically unsaturated monomer (b2), a compound containing an oxyalkylene chain is preferably used, and the ethylenically unsaturated monomer having the oxyalkylene chain is not particularly limited, and examples thereof include, for example, The monofunctional ethylenically unsaturated monomer having an oxyalkylene group, a difunctional ethylenically unsaturated monomer, and a trifunctional or higher ethylenically unsaturated monomer described below.

The monofunctional ethylenically unsaturated monomer of the above-mentioned oxygen-containing alkylene chain may, for example, be a monofunctional ethylenically unsaturated monomer having an oxyalkylene chain represented by the following formula (1).

(wherein X is an alkylene group, n is an integer of 1 or more, A is a (meth)propenyl group or an alkenyl group, and B is a hydrogen atom, an alkyl group, a phenyl group or a fluorenyl group.)

X in the above formula (1) is an alkylene group, and among them, an alkylene group having a carbon number of 1 to 10 is preferred, and a carbon number of 1 to 4 such as a particularly extended ethyl group, a propyl group or a butyl group is preferably 1-4. alkyl. Further, when n is a polyoxyalkylene group having 2 or more, the alkyl group may be a homopolymer of the same alkyl group, or may be a copolymer of a different alkyl group to form a random or block.

In the above formula (1), A is a (meth) acrylonitrile group or an alkenyl group, and as the alkenyl group, a carbon number of 2 to 6 is usually used, and for example, a vinyl group or an allyl group is used. Among these, a methacryl fluorenyl group, an acryl fluorenyl group, an allyl group, a particularly preferred methacryl fluorenyl group, and an acryl fluorenyl group are preferable.

B in the above formula (1) is a hydrogen atom, an alkyl group, a phenyl group or a fluorenyl group, and as the alkyl group, those having a carbon number of 1 to 20, preferably 1 to 10 are usually used. Among these, a hydrogen atom, a methyl group, and an ethyl group are preferable.

n in the above formula (1) is an integer of 1 or more, preferably 1 to 500, particularly preferably 2 to 100, more preferably 3 to 50. When the value of n is too small, the antistatic performance tends to be insufficient, and if it is too large, the durability tends to be insufficient.

Specific examples of the monofunctional monomer of the above oxygen-containing alkylene chain,

[A: Case of (meth)acrylonitrile group]

For example, a polyethylene glycol derivative such as polyethylene glycol mono(meth)acrylate, a polypropylene glycol derivative such as polypropylene glycol mono(meth)acrylate, or polyethylene glycol-polypropylene glycol-mono (methyl group) Acrylate, poly(ethylene glycol-butanediol) mono(meth)acrylate, poly(propylene glycol-butanediol) mono(meth)acrylate, alkoxy polyethylene glycol (meth)acrylic acid Ester and the like.

[A: Alkenyl case]

For example, a polyethylene glycol derivative such as polyethylene glycol monoallyl ether, a polypropylene glycol derivative such as polypropylene glycol monoallyl ether, or polyethylene glycol-polypropylene glycol-monoallyl ether can be mentioned.

Among the above, a polyethylene glycol derivative is preferred. From the viewpoint of balance between antistatic property and durability, the ethylene oxide addition molar number n is preferably from 5 to 500, particularly preferably from 5 to 100. More preferably 6 to 30. When the ethylene oxide addition molar number n is too small, the antistatic property tends to be deteriorated, and if it is too large, the durability tends to be deteriorated. Further, from the viewpoint of the influence on the hardenability, the system A is preferably a (meth) acrylonitrile group.

Further, the weight average molecular weight of the monofunctional ethylenically unsaturated monomer having an alkylene group represented by the above formula (1) is usually preferably from 100 to 20,000, particularly preferably from 200 to 10,000, more preferably 300. ~1000. When the weight average molecular weight is too small, the antistatic property tends to be deteriorated, and if it is too large, the moist heat resistance tends to be lowered.

Examples of the difunctional ethylenically unsaturated monomer of the above-mentioned oxygen-containing alkylene chain include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and tetraethylene glycol. Di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butyl Diol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate, propylene oxide modified bisphenol A type II (Meth)acrylate, 1,6-hexanediol ethylene oxide modified di(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol II Glycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl diglycidyl di(meth)acrylate, hydroxypivalic acid modified new Pentandiol di(meth)acrylate, iso-cyanuric acid ethylene oxide modified diacrylate, and the like.

Examples of the trifunctional or higher ethylenically unsaturated monomer of the above-mentioned oxygen-containing alkylene chain include, for example, iso-cyanuric acid ethylene oxide-modified triacrylate, and ethylene oxide-modified dipentaerythritol. Acrylate, ethylene oxide modified dipentaerythritol hexa(meth) acrylate, ethylene oxide modified pentaerythritol tri(meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate Wait.

In the above unsaturated group-containing compound (B), it is preferred to use an alkyl group-containing (meth)acrylic acid urethane compound (b1) in terms of excellent antistatic properties. Or an ethylenically unsaturated monomer (b2) having an alkylene chain. Further, from the viewpoint of improving durability, a compound containing three or more unsaturated groups is preferred. Further, it is preferred to have a cyclic structure in the molecule.

Further, in terms of further improving the antistatic property, it is preferred to use an acid-base ion pair and/or a betaine-structured (meth)acrylate compound as a compound containing an unsaturated group. (B).

Further, examples of the method for producing a (meth) acrylate compound containing an acid-base ion pair and/or a betaine structure in a molecule include potassium hydroxide and a carboxyl group-containing polyfunctional (meth)acrylic acid. The method of reacting the ester monomer is not limited thereto. Specifically, a (meth)acrylic acid neutralizer such as potassium (meth)acrylate or a potassium hydroxide neutralizer of M-510 manufactured by Toagosei Co., Ltd., or the like is preferably used.

Further, an ionic liquid containing a polymerizable unsaturated group may be used as the unsaturated group-containing compound (B), and examples thereof include an ionic liquid containing 1-(2-(methyl)acryloxyl b (3-(2-(methyl) propylene oxyethyl)-3-octyl chloroimidazolium and the like (meth) propylene decyloxyalkyl-3 a halogen salt of an alkylimidazolium, 1-(2-(methyl)acryloxyethyl)-3-octyl imidazolium trifluoromethane iminoide or 1-(2-(methyl)propene Fluorinated salt of (meth) propylene oxyalkyl-3-alkylimidazolium, such as methoxyethyl)-3-octyl imidazolium tetrafluoroborate, 1-(2-(methyl) propylene oxime Oxyethyl)-3-ethyl-2-methylimidazolium dicyanamide or 1-(2-(methyl)propenyloxyethyl)-3-ethyl-2-methylimidazolium sulfonate (meth)acrylic acid imidazolium compound such as cyanic acid or the like (meth) propylene oxyalkyl-alkylimidazolium cyano group-containing salt, 1-butyl-3-vinylimidazolium tetrafluoroboric acid ( 1B3VIBF4), 1-butyl-3-vinylimidazolium trifluoromethaneimine (1B3VITFSI) and other vinylimidazolium compounds, trimethylaminoethyl (meth)acrylate ethyl dicyanamide Quaternary ammonium salt-based compound.

Further, the ionic liquid system of the present invention refers to an ionic substance composed of a cationic component and an anionic component which are maintained at a fixed temperature in the range of 0 to 100 °C.

These unsaturated group-containing compounds (B) may be used singly or in combination of two or more.

The content of the unsaturated group-containing compound (B) is preferably 5 to 99 parts by weight based on 100 parts by weight of the acrylic resin (A). More preferably, it is 7 to 50 parts by weight, and particularly preferably 10 to 30 parts by weight. When the content of the unsaturated group-containing compound (B) is too large, the compatibility with the resin is deteriorated, and the coating film tends to be whitened. If the content is too small, the crosslinking density of the adhesive is insufficient, and the light leakage prevention property or The tendency to reduce durability.

Further, in the present invention, the content of the unsaturated group as the entire resin composition [I] is usually preferably from 10 to 360 mmol/100 g, particularly preferably from 30 to 30, in terms of balance between durability and light leakage prevention performance. 240 mmol/100 g, more preferably 50 to 180 mmol/100 g. When the content of the unsaturated group is too small, there is a tendency that it is difficult to obtain a balance between durability and light leakage prevention performance due to insufficient cohesive force. If the amount is too large, the adhesive strength tends to be too low and the durability tends to be adversely affected.

As the polymerization initiator (C), for example, various polymerization initiators such as a photopolymerization initiator (c1) and a thermal polymerization initiator (c2) can be used, but active energy such as ultraviolet rays can be used for a short period of time. In terms of crosslinking by wire irradiation (hardening), a photopolymerization initiator (c1) is particularly preferred.

Further, when the photopolymerization initiator (c1) is used, the resin composition [I] is crosslinked by irradiation with an active energy ray, and when the thermal polymerization initiator (c2) is used, the resin composition is heated by heating. [I] Crosslinking, but it is preferred to use both together as needed.

The photopolymerization initiator (c1) is not particularly limited, and examples thereof include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and benzyldiyl group. Methyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- Phytyl (4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone, 2-hydroxy-2- Acetophenones such as methyl-1-[4-(1-methylvinyl)phenyl]acetone oligomers; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. Diphenyl ketone, methyl ortho-benzoylbenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyl-diphenyl sulfide, 3,3', 4, 4'-tetrakis(t-butylperoxycarbonyl)diphenyl ketone, 2,4,6-trimethyldiphenyl ketone, 4-benzylidene-N,N-dimethyl-N- a diphenyl ketone such as [2-(1-oxo-2-propenyloxy)ethyl]benzylammonium bromide or (4-benzylidenebenzyl)trimethylammonium chloride; Isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one thioxanthone such as meso chloride; 2,4,6- Trimethyl benzhydryl-diphenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide, bis(2,4, 6-trimethylbenzylidene)- A fluorenylphosphine oxide such as phenylphosphine oxide. In addition, these photopolymerization initiators (c1) may be used alone or in combination of two or more.

Further, as such an auxiliary agent, the following may be used in combination: triethanolamine, triisopropanolamine, 4,4'-dimethylaminodiphenyl ketone (micilenone), 4,4'- Diethylaminodiphenyl ketone, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (n-butoxy) Ester, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropyl Thioxanthone and the like.

Among these, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzhydryl isopropyl ether, 4-(2-hydroxyethoxy)-phenyl (2) are preferably used. -Hydroxy-2-propyl)one, 2-hydroxy-2-methyl-1-phenylpropan-1-one.

Further, examples of the thermal polymerization initiator (c2) include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate acetate, and peroxide B. Indole acetate, 1,1-bis(trihexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(trihexylperoxy)-cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane 1,1-bis(t-butylperoxy)-cyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 1,1-bis (t-butyl) Oxy) butane, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, hydrogen peroxide to menthane, diisopropylbenzene hydrogen peroxide, 1,1,3 , 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, third hexyl hydroperoxide, tert-butyl hydroperoxide, α,α'-bis(t-butylperoxy) Cumene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, tributyl cumene peroxide, peroxide Tributyl, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, Isobutyl hydrazine, 3,5,5-trimethylhexyl peroxide, octyl peroxide, dodecane decoxide, octadecyl oxyhydroxide, butyl hydrazine peroxide, m-toluene peroxide Benzoe, benzammonium peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, peroxydicarbonate (2-ethoxyethyl) ester, di(2-ethoxyhexyl)peroxydicarbonate, bis(3-methoxybutyl)peroxydicarbonate, second dibutyl peroxydicarbonate Ester, bis(3-methyl-3-methoxybutyl)peroxydicarbonate, α,α'-bis(indenylperoxy)diisopropylbenzene, isopropyl peroxynonanoate Phenyl ester, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, trihexyl peroxy neodecanoate, Oxidation of tert-butyl neodecanoate, third hexyl peroxypivalate, tert-butyl peroxypivalate, 1,2-,3,3-tetramethyl peroxy-2-ethylhexanoate Ester, 2,5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexanoate, 1-ethylhexyl-1-ylperoxy-2-ethylhexanoate Ethyl ethyl ester, third hexyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, mono-trihexyl isopropyl carbonate, isobutyric acid peroxide Tributyl ester, peroxybutyl maleate, third tert-butyl ester, perylene-3,5,5-methylhexanoic acid, tert-butyl ester, tert-butyl peroxydodecanoate, isopropoxide Carbonic acid mono-tert-butyl ester, peroxy-2-ethylhexyl carbonate mono-t-butyl ester, third-butyl peroxyacetate, tert-butyl-tolyl-benzoic acid benzoate, third benzoic acid peroxide Butyl ester, bis(t-butylperoxy)isophthalate, 2,5-dimethyl-2,5-bis(m-tolylperyloxy)hexane, benzoic acid benzoic acid Trihexyl ester, 2,5-dimethyl-2,5-bis(benzimidylperoxy)hexane, peroxyallyl monocarbonate monobutyl ester, tert-butyl trimethyl peroxide Organic peroxidation such as mercapto, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)diphenyl ketone, 2,3-dimethyl-2,3-diphenylbutane Activator; 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl)azo]formamidine Amine, 1,1'-azo double ( Cyclohexane-1-carbonitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4 - dimethyl valeronitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis(2-methyl-N-phenylpropanthene) Dihydrochloride, 2,2'-azobis[N-(4-chlorophenyl)-2-methylpropionamidine dihydrochloride, 2,2'-azobis[N-(4- Hydrogen phenyl)-2-methylpropionamidine dihydrochloride, 2,2'-azobis[2-methyl-N-(phenylmethyl)propanthene] dihydrochloride, 2,2 '-Azobis[2-methyl-N-(2-propenyl)propanthene] dihydrochloride, 2,2'-azobis[N-(2-hydroxyethyl)-2-methyl Propionate] dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis [ 2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazepine Indole-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane]dihydrochloride, 2, 2'-Azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-[1 -(2-hydroxyethyl)-2-imidazolin-2-yl]propane]dihydrochloride, 2,2'-azobis[2-(2- Oxazolin-2-yl)propane], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propanamide], 2 , 2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propanamide], 2,2'-azobis[2-methyl-N- (2-hydroxyethyl)propanamide], 2,2'-azobis(2-methylpropionamide), 2,2'-azobis(2,4,4-trimethylpentane ), 2,2'-azobis(2-methylpropane), dimethyl-2,2-azobis(2-methylpropionate), 4,4'-azobis (4- An azo initiator such as cyanovaleric acid or 2,2'-azobis[2-(hydroxymethyl)propanenitrile. In addition, these thermal polymerization initiators may be used alone or in combination of two or more.

The content of the above polymerization initiator (C) is preferably 0.01 to 10 parts by weight, particularly preferably 0.1 to 7 parts by weight, more preferably 0.3 to 3 parts by weight based on 100 parts by weight of the above acrylic resin (A). When the content of the polymerization initiator (C) is too small, the curing property tends to be unstable, and the physical properties tend to be unstable. If the amount is too large, the above effects tend not to be obtained.

When the active energy ray is irradiated, an electron beam, a proton beam, a neutron beam, or the like may be used in addition to light such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays, and electromagnetic waves such as X-rays and gamma rays. The hardening by ultraviolet irradiation is advantageous in terms of the ease of the irradiation device, the price, and the like. Further, when electron beam irradiation is performed, the photopolymerization initiator (c1) can be hardened without using the photopolymerization initiator (c1).

Further, as the light source for performing the above ultraviolet irradiation, a high pressure mercury lamp, an electrodeless lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, a black light lamp or the like can be used. In the case of using the above high-pressure mercury lamp, it is carried out, for example, at 5 to 3000 mJ/cm ² , preferably 10 to 1000 mJ/cm ² . Further, in the case of using the above electrodeless lamp, it is carried out, for example, at 2 to 1500 mJ/cm ² , preferably 5 to 500 mJ/cm ² . Further, the irradiation time varies depending on the type of the light source, the distance between the light source and the coated surface, the coating thickness, and other conditions, and is usually from several seconds to several tens of seconds, and may be a fraction of a second depending on the case. On the other hand, in the case of irradiation with the above-described electron beam, for example, an electron beam having an energy in the range of 50 to 1000 Kev is used, and the irradiation amount is set to 2 to 50 Mrad.

Further, when a thermal polymerization initiator (c2) is used as the polymerization initiator (C), the polymerization reaction is started by heating. The treatment temperature and the treatment time at the time of crosslinking by heating vary depending on the type of the thermal polymerization initiator (c2) to be used, and are usually calculated based on the half life of the initiator, and the treatment temperature is usually preferably 70 ° C. ～170 ° C, the treatment time is usually preferably 0.2 to 20 minutes, particularly preferably 0.5 to 10 minutes.

Next, a method of crosslinking using the above-mentioned [β] using a crosslinking agent (D) will be described.

When the crosslinking agent (D) is used for the crosslinking, the resin composition [I] containing the crosslinking agent (D) in addition to the acrylic resin (A) is used as the resin composition [I].

When the above-mentioned crosslinking agent (D) is used, it is preferred that the acrylic resin (A) has a functional group, and crosslinking (chemical crosslinking) is carried out by reacting the functional group with a crosslinking agent.

The crosslinking agent (D) may be a compound having a functional group reactive with the functional group contained in the acrylic resin (A), and examples thereof include an isocyanate compound, an epoxy compound, and nitrogen. A propidium compound, a melamine compound, an aldehyde compound, an amine compound, or a metal chelate compound. Among these, an isocyanate compound is preferably used from the viewpoint of improving the adhesion to the substrate or the reactivity with the base polymer.

Examples of the isocyanate compound include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hydrogenated toluene diisocyanate, 1,3-benzenedimethyl diisocyanate, and 1,4-benzyldimethyl group. Diisocyanate, hexamethylene diisocyanate, diphenylmethane-4,4-diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, tetramethylbenzene Dimethyl diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, and an adduct of the polyisocyanate compound and a polyol compound such as trimethylolpropane, and a condensation of the polyisocyanate compound Urea or isocyanurate body.

Examples of the epoxy compound include bisphenol A-epichlorohydrin epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol diglycidyl ether, and glycerol triglycidyl. Ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerin polyglycidyl Ether, etc.

Examples of the aziridine-based compound include tetramethylolmethane-tris-β-aziridine propionate, trimethylolpropane-tri-β-aziridine propionate, and N. N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), N,N'-hexamethylene-1,6-bis(1-aziridinecarboxamide) Wait.

Examples of the melamine-based compound include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl melamine, hexapentoxymethyl melamine, and six. Hexyloxymethyl melamine, melamine resin, and the like.

Examples of the aldehyde compound include glyoxal, malondialdehyde, succinaldehyde, maleic aldehyde, glutaraldehyde, formaldehyde, acetaldehyde, and benzaldehyde.

Examples of the amine-based compound include hexamethylenediamine, triethylenediamine, polyethyleneimine, hexamethyleneamine, diethylidenetriamine, triethyltetramine, isophoronediamine, and amine resin. , polyamine, etc.

Examples of the metal chelate compound include acetylacetone or acetamidine complex compounds of a polymetallic such as aluminum, iron, copper, zinc, tin, titanium, nickel, lanthanum, magnesium, vanadium, chromium, or zirconium. Wait.

Further, these crosslinking agents (D) may be used singly or in combination of two or more.

The content of the above-mentioned crosslinking agent (D) can be appropriately selected depending on the amount of the functional group contained in the acrylic resin (A), the molecular weight of the acrylic resin (A), and the purpose of use, and is usually relative to 100 parts by weight. The acrylic resin (A) is preferably 0.1 to 15 parts by weight, more preferably 0.2 to 12 parts by weight, particularly preferably 1.5 to 10 parts by weight. When the amount of the crosslinking agent (D) is too small, cohesive force is insufficient, and sufficient durability tends not to be obtained. When the amount is too large, flexibility and adhesion are lowered, durability is deteriorated, and peeling is likely to occur, and it is difficult to optically The tendency of components to fit.

Further, in the present invention, in order to further improve the antistatic property of the adhesive obtained by crosslinking the resin composition [I], it is preferred to introduce a structure having antistatic properties into a part of the crosslinking agent (D). Crosslinker at the site.

As a method of introducing a structural site having antistatic properties into the crosslinking agent, for example, when a polyisocyanate compound is used as a crosslinking agent, a compound having a hydroxyl group in its structure can be used as a compound having antistatic properties. By reacting the above hydroxyl group with an isocyanate group, a crosslinking agent having a structure having an antistatic property introduced therein can be produced.

Further, in order to introduce a structural portion having antistatic properties into the crosslinking agent, a structural portion having antistatic properties may be introduced into the crosslinking agent in advance, and then it may be mixed with the acrylic resin (A), or When the acrylic resin (A) is mixed with the crosslinking agent (D), a compound having antistatic properties is simultaneously formulated to react with the crosslinking agent (D).

In the present invention, it is sufficient to carry out crosslinking by using at least one of active energy ray and heat (at least one of active energy ray irradiation and heating), but it is preferable to use [β] in combination. By cross-linking with a crosslinking agent, the crosslinking density of the adhesive can be increased, and the cohesive force can be improved to prevent light leakage and durability.

Further, in the present invention, the resin composition [I] as the adhesive forming material preferably further contains a decane coupling agent (E) from the viewpoint of improving the adhesion of the optical member. The content of the decane coupling agent (E) is usually 0.001 to 10 parts by weight, more preferably 0.01 to 1 part by weight, particularly preferably 0.03 to 0.8 part by weight, per 100 parts by weight of the acrylic resin (A). When the content of the decane coupling agent (E) is too small, the mixing effect tends not to be obtained, and if it is too large, the compatibility with the acrylic resin (A) is deteriorated, and the adhesion or cohesive force tends not to be obtained.

Examples of the decane coupling agent (E) include an epoxy decane coupling agent, an acrylic decane coupling agent, a decyl decane coupling agent, a hydroxy decane coupling agent, a carboxy decane coupling agent, and an amine decane coupling agent. A guanamine-based decane coupling agent, an isocyanate-based decane coupling agent, or the like. These may be used alone or in combination of two or more. Among these, an epoxy decane coupling agent or a fluorenyl decane coupling agent is preferably used, and it is preferred to use an epoxy decane coupling agent in combination with an improvement in wet heat durability and an excessive increase in adhesion. A mercapto decane coupling agent.

Specific examples of the epoxy decane coupling agent include γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, and γ-glycidoxypropyl propyl. Methyldiethoxydecane, γ-glycidoxypropylmethyldimethoxydecane, methyltris(glycidyl)decane, β-(3,4-epoxycyclohexyl)ethyl Trimethoxy decane, etc., among which γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, γ-glycidoxypropylmethyldiethyl, and γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane Oxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane.

Specific examples of the above fluorenyl decane coupling agent include γ-mercaptopropyltrimethoxydecane, γ-mercaptopropyltriethoxydecane, and γ-mercaptopropyldimethoxymethylnonane.

The resin composition [I] of the present invention preferably further contains an antistatic agent (F). As the antistatic agent, a conventionally known antistatic agent (a compound having an ionic group) can be used, and for example, an alkali metal salt, an alkaline earth metal salt, a quaternary ammonium salt, an imidazolium salt, a cyano group-containing salt can be used. , an aliphatic sulfonate, a higher alcohol sulfate salt, a higher alcohol alkylene oxide adduct sulfate salt, a higher alcohol phosphate salt, a higher alcohol alkylene oxide adduct phosphate salt, an alkyl betaine compound, an alkane A base imidazoline compound, an alkylalanine compound, a polyvinylbenzyl type cationic compound, a polyacrylic acid type cationic compound, or the like.

Among these, an alkali metal salt, an alkaline earth metal salt, a quaternary ammonium salt, an imidazolium salt, and a cyano group-containing salt are preferably used, and an alkali metal salt and an imidazolium salt are particularly preferably used.

As the above alkali metal salt, for example, a cation selected from Li ⁺ , Na ⁺ , K ⁺ and a group selected from Cl ^- , Br ^- , I ^- , BF ₄ ^- , PF ₆ ^- , SCN ^- , ClO _{4 are} preferably used. _{^{-, CF 3 SO 3 -,}} (CF- 3 SO 2) 2 N -, (CF 3 SO 2) 3 C - anion of the metal salt thereof. Among these, a lithium salt is preferred because it is excellent in ion conductivity and excellent in antistatic function, and specifically, LiBr, LiI, LiBF ₄ , LiPF ₆ , LiSCN, LiClO ₄ , LiCF are preferably used. ₃ lithium salt such as SO ₃ , Li(CF ₃ SO ₂ ) 2N, Li(CF ₃ SO ₂ ) ₃ C, particularly preferably LiCF ₃ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N, LiI, LiClO ₄ , More preferably, LiCF ₃ SO ₃ or Li(CF ₃ SO ₂ ) ₂ N is used, and LiCF ₃ SO _{3 is} preferably used, and the alkali metal salt can be dissolved in a polyether polyol.

Examples of the alkaline earth metal salt include a calcium salt, a magnesium salt, and the like.

As the quaternary ammonium salt, for example, a tetraalkylammonium salt such as an alkyltrimethylammonium salt or a dialkyldimethylammonium salt, a trialkylbenzylammonium salt or an alkylpyridinium salt is preferably used. Poly)oxyalkylalkyltrialkylammonium salt.

Examples of the imidazolium salt include an imidazolium salt having an alkylimidazolium cation such as a monoalkylimidazolium cation, a dialkylimidazolium cation, or a trialkylimidazolium cation, and specifically, 1,3-di Methylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methyl Imidazolium cation, 1-octyl-3-methylimidazolium cation, 1-mercapto-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-fourteen Alkyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2, An imidazolium salt of 3-dimethylimidazolium cation, 1-hexyl-2,3-dimethylimidazolium cation or the like.

As the cyano group-containing salt, an ionic compound having a known cyano group-containing anion can be used, and an ionic compound having a cyano group-containing anion represented by the following formula (2) is particularly preferably used.

(wherein X represents any one selected from the group consisting of boron, carbon, nitrogen, aluminum, ruthenium, phosphorus, arsenic, and selenium. Y represents a hydrogen atom, an alkyl group, or a trifluoromethyl group. L ₁ and L ₂ denotes an organic linking group which may be the same or different. a is an integer of 1 or more, and b, c and d are integers of 0 or more.)

X in the above formula (2) is at least one element selected from the group consisting of boron, carbon, nitrogen, sulfur, aluminum, lanthanum, phosphorus, arsenic, and selenium, and among them, boron, carbon, and the like are preferable. Nitrogen, sulfur.

In the above formula (2), Y represents a hydrogen atom, an alkyl group or a trifluoromethyl group, and as the alkyl group, a carbon number of 1 to 10 is preferred, and a carbon number of 1 to 4 is preferred as the alkyl group. Specific examples thereof include a methyl group and an ethyl group. Y is preferably a hydrogen atom, a methyl group or a trifluoromethyl group.

L ₁ and L ₂ in the above formula (2) are an organic linking group, and preferably -S-, -O-, -SO ₂ -, -CO-, particularly preferably -SO ₂ -, -CO-. The L ₁ and L ₂ may be the same or different.

In the above formula (2), a is an integer of 1 or more, and b, c and d are integers of 0 or more, and the valence of the anion is -1, so when the valence of the element X is x, x-1 is satisfied. The relationship between (a + d) determines the values of a and c.

Specific examples of the cyano group-containing anion represented by the above formula (2) include S ^- (CN), N ^- (CN) ₂ , N ^- (-SO ₂ -CN) ₂ , and C-(CN). ₃ , B ^- (CN) _4, etc., among these, S ^- (CN), N ^- (CN) ₂ are preferably used.

Further, the molecular weight of the cyano group-containing anion is usually from 30 to 300, preferably from 50 to 250.

The cation component of the cyano group-containing ionic compound is not particularly limited, and examples thereof include metal cations such as an alkali metal, an alkaline earth metal, a transition metal, and a rare earth metal, or a cation of a heterocyclic compound, and a quaternary ammonium salt. A cation, a quaternary phosphonium cation or the like is preferred, and among these, a cation or a quaternary ammonium cation of a heterocyclic compound is preferably used.

Further, the cation of the heterocyclic compound is preferably a cation of a heterocyclic compound of 1 to 6 membered rings having 1 to 5 hetero atoms, and particularly preferably a nitrogen atom as a hetero atom. A cation of a heterocyclic compound of 1 to 5 membered rings of 5 hetero atoms, preferably an imidazolium salt.

Specific examples of the ionic compound having a cyano group-containing anion represented by the above formula (2) include 1,3-dimethylimidazolium dicyanamide and 1-ethyl-3-methylimidazole.鎓Cyanamide, 1-methyl-3-propylimidazolium dicyanamide, 1-butyl-3-methylimidazolium dicyanamide, 1-methyl-3-pentyl imidazolium dicyanamide, 1-hexyl-3-methylimidazolium dicyanamide, 1-heptyl-3-methylimidazolium dicyanamide, 1-methyl-3-octyl imidazolium dicyanamide, 1-mercapto-3 -methylimidazolium dicyanamide, 1-dodecyl-3-methylimidazolium dicyanamide, 1-ethyl-3-propylimidazolium dicyanamide, 1-butyl-3-ethyl Dialkylimidazolium dicyanamide such as imidazolium dicyanamide, 3-ethyl-1,2-dimethylimidazolium dicyanamide, 1,2-dimethyl-3-propylimidazolium dicyanamide , 1-butyl-2,3-dimethylimidazolium dicyanamide, 1,2-dimethyl-3-hexyl imidazolium dicyanamide, 1,2-dimethyl-3-octyl imidazolium Trialkylimidazolium dicyanamide such as dicyandiamide, 1-ethyl-3,4-dimethylimidazolium dicyanamide, 1-isopropyl-2,3-dimethylimidazolium dicyanamide, 1,3-dimethylimidazolium thiocyanate, 1-ethyl-3-methylimidazolium sulfonate Acid salt, 1-methyl-3-propylimidazolium thiocyanate, 1-butyl-3-methylimidazolium thiocyanate, 1-methyl-3-pentylimidazolium thiocyanate , 1-hexyl-3-methylimidazolium thiocyanate, 1-heptyl-3-methylimidazolium thiocyanate, 1-methyl-3-octyl imidazolium thiocyanate, 1- Mercapto-3-methylimidazolium, oxazolidine thiocyanate, 1-dodecyl-3-methylimidazolium thiocyanate, 1-ethyl-3-propylimidazolium thiocyanate, Dialkylimidazolium thiocyanate such as 1-butyl-3-ethylimidazolium thiocyanate 3-ethyl-1,2-dimethylimidazolium thiocyanate, 1,2-dimethyl 3-propylimidazolium thiocyanate, 1-butyl-2,3-dimethylimidazolium thiocyanate, 1,2-dimethyl-3-hexylimidazolium thiocyanate, 1,2-dimethyl-3-octyl imidazolium thiocyanate, 1-ethyl-3,4-dimethylimidazolium thiocyanate, 1-isopropyl-2,3-dimethyl Trialkylimidazolium thiocyanate such as imidazolium thiocyanate.

Among these, it is preferable to use a solid imidazolium salt from the viewpoint of easily preparing a high-purity ionic compound by recrystallization by purification, and it is preferable to use 1-b. Base-2,3-dimethylimidazolium dicyanamide, 1-ethyl-2,3-dimethylimidazolium thiocyanate.

Further, as the antistatic agent (F), a so-called ionic liquid is preferably used in the ionic compound. The ionic liquid system of the present invention represents an ionic substance composed of a cationic component and an anionic component which are maintained at a fixed temperature in the range of 0 to 100 °C.

The cation component is not particularly limited, and a cation used in a usual ionic liquid can be used. Examples of the cations include cations of a heterocyclic compound, particularly a cation of a heterocyclic compound of 1 to 5 membered rings having 1 to 5 hetero atoms, and particularly containing a nitrogen atom as a hetero atom. The cations and the like of the heterocyclic compound of the 5- to 5-membered ring of the five hetero atoms are preferably an imidazolium cation, a pyrrolidinium cation, a piperidinium cation, a pyridinium cation or the like. Further, a chain-like quaternary ammonium cation or a quaternary phosphonium cation is preferably used. Among these, an imidazolium cation, a pyridinium cation, a quaternary ammonium cation, and a quaternary phosphonium cation are preferable, and an imidazolium cation is particularly preferable from the viewpoint of a low viscosity.

On the other hand, the anion component is not particularly limited, and for example, C1 ^- , Br ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , C10 ₄ ^- , NO ₃ ^- , CH can be used. ₃ COO ^- , CF ₃ COO ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₃ C ^- , AsF ₆ ^- , SbF ₆ ^- , NbF ₆ ^- , TaF ₆ ^- , F(HF) _n ^- , (CN) ₂ N ^- , C ₄ F ₉ SO ₃ ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- , C ₃ F ₇ COO ^- , (CF ₃ SO ₂ )(CF ₃ CO)N ^{- an} anion used in a usual ionic liquid.

The content of the antistatic agent (F) is usually 0.001 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, particularly preferably 0.02 to 5 parts by weight, per 100 parts by weight of the acrylic resin (A). When the content of the antistatic agent (F) is too small, the preparation effect tends not to be obtained, and if it is too large, the durability may be deteriorated or the antistatic agent may bleed out.

In the present invention, in the resin composition [I] of the adhesive forming material, the following substances may be further blended in the range of not impairing the effects of the present invention: other acrylic adhesives, other adhesives, and urethane Ester resin, rosin, rosin ester, hydrogenated rosin ester, phenol resin, aromatic modified terpene resin, aliphatic petroleum resin, alicyclic petroleum resin, styrene resin, xylene resin, polyol, etc. A known additive such as an adhesive, a colorant, a filler, an anti-aging agent, an ultraviolet absorber, a functional dye, or a compound which causes coloration or discoloration by irradiation with ultraviolet rays or radiation.

In addition to the above-mentioned additives, impurities and the like contained in a raw material for production of a constituent component of the resin composition [I] may be contained in a small amount.

In the present invention, an adhesive for an optical member obtained by crosslinking the above resin composition [I] can be obtained, and by providing the adhesive on an optical member (optical laminate), an adhesive layer can be obtained. Optical member.

In the optical member with the adhesive layer, it is preferable to provide a release sheet on the surface of the adhesive layer opposite to the optical member.

The method for producing the optical member to which the adhesive layer is attached is not particularly limited, and can be produced by (1) applying a resin composition [I] to an optical member, and drying the bonded sheet after bonding. Or (2) coating the resin composition [I] on the release sheet, and bonding it to the optical member after drying, in terms of the possibility of deterioration of the substrate due to the dilution of the solvent, it is preferred ( 2) A method of producing a resin composition [I] coated on a release sheet.

Moreover, when it is used for practical use, the release sheet is peeled and used, and it is more preferable that the release sheet is a release sheet of a bismuth system.

Further, when the resin composition [I] is crosslinked by at least one of irradiation with an active energy ray and heating, it can be produced by the following method: [1] coating a resin composition on an optical member [I] After drying, the release sheet is bonded and treated by at least one of active energy ray irradiation and heating; [2] the resin composition [I] is coated on the release sheet, and the optical member is bonded after drying, by active At least one of energy line irradiation and heating is processed; [3] coating the resin composition [I] on the optical member, drying, and further treating by at least one of active energy ray irradiation and heating, and then laminating the mold [4] The resin composition [I] is applied onto the release sheet, dried, and further processed by at least one of active energy ray irradiation and heating, and then the optical member is bonded. Among these, from the viewpoint of not impairing the substrate, handling property, and stable production, the method of [2] is preferred, and only the active energy ray irradiation is performed.

When the coating is carried out, it is preferably diluted with a solvent and then applied as a dilution concentration, preferably 10 to 50% by weight, particularly preferably 11 to 25% by weight. The solvent is not particularly limited as long as it dissolves the resin composition [I], and for example, an ester solvent such as methyl acetate, ethyl acetate, methyl acetate or ethyl acetate can be used. A ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone, or an aromatic solvent such as toluene or xylene. Among these, ethyl acetate and methyl ethyl ketone are preferably used from the viewpoints of solubility, drying property, and price.

The gel fraction of the pressure-sensitive adhesive layer produced by the above method is preferably 80% or more, and particularly preferably 90% or more in terms of durability and light leakage prevention performance. If the gel fraction is too low, there is a tendency that the durability is insufficient or the light leakage phenomenon is deteriorated due to insufficient cohesive force. Further, the upper limit of the gel fraction is usually 100%.

In addition, when the gel fraction of the optical member adhesive agent is adjusted to the above range, for example, it can be achieved by adjusting the irradiation amount or the irradiation intensity of the active energy ray, and adjusting the type of the unsaturated group-containing compound and The amount, the type of the polymerization initiator and the ratio of the combination thereof are adjusted, the amount of the polymerization initiator is adjusted, and the kind and amount of the crosslinking agent are adjusted. Further, since the gelation rate changes due to the interaction between the irradiation amount of the active energy ray, the irradiation intensity, the composition ratio of the polymerization initiator, and the blending amount, it is necessary to obtain a balance therebetween.

Further, the above gel ratio is a standard of the degree of crosslinking, and can be calculated by the following method.

That is, the adhesive sheet obtained as follows (without a separator) was wrapped with a 200 mesh SUS wire mesh, and immersed in toluene at 23 ° C for 24 hours to leave the wire mesh. The weight percentage of the insoluble adhesive component is taken as the gel fraction. The weight of the substrate is previously subtracted.

Further, the thickness of the pressure-sensitive adhesive layer in the optical member to which the pressure-sensitive adhesive layer is applied is not particularly limited, but is preferably 5 to 300 μm, particularly preferably 10 to 50 μm, and more preferably 12 to 30 μm. If the thickness of the adhesive layer is too thin, the adhesive property tends to be difficult to stabilize, and if it is too thick, the thickness of the entire optical member tends to increase excessively.

The optical member with an adhesive layer obtained in the present invention can be directly used for, for example, a liquid crystal display panel, or when it is a release sheet, after the release sheet is peeled off, the adhesive layer is bonded to the glass. The substrate is then used, for example, for a liquid crystal display panel.

The initial adhesive force of the adhesive layer of the present invention is appropriately determined depending on the material of the adherend or the like. For example, in the case of adhering to an alkali-free glass plate, it is preferred to have an adhesive force of 0.01 N/25 mm to 50 N/25 mm. Further, even in the case of permanent adhesion, if static electricity is generated during secondary processing (re-adhesion), there is also adhesion of dust or the like, and therefore it is required to have antistatic properties.

The above initial adhesion is calculated in the following manner. The optical member to which the adhesive layer was prepared was cut into a width of 25 mm, the release film was peeled off, and the adhesive layer side was pressed against an alkali-free glass plate ("Corning 1737" manufactured by Corning). The optical member is bonded to the glass plate. Thereafter, autoclaving treatment (50 ° C, 0.5 MPa, 20 minutes) was carried out, and after 24 hours, a peeling test was performed at 180 ° C.

The optical member of the present invention is not particularly limited, and examples thereof include an optical film which is applied to an image display device such as a liquid crystal display device, an organic EL display device, or a PDP, for example, a polarizing plate, a phase difference plate, an elliptically polarizing plate, and optical compensation. A film, a brightness enhancement film, and a laminate of these, etc., among which a polarizing plate is particularly effective in the present invention.

The polarizing plate used in the present invention is generally obtained by laminating a cellulose triacetate film as a protective film on both surfaces of a polarizing film, and the polarizing film is used in an average degree of polymerization of 1,500 to 10,000 and a degree of saponification. a film formed of 85 to 100 mol% of a polyvinyl alcohol-based resin as an original film, and a uniaxially stretched film dyed by an aqueous solution of iodine-potassium iodide or a dichroic dye (2 to 10 times, preferably 3 to 7) The extension ratio of the magnification is about).

The polyvinyl alcohol-based resin is usually produced by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate, and may contain a small amount of an unsaturated carboxylic acid (including a salt, an ester, a guanamine, a nitrile, etc.), an olefin, or the like. A component which can be copolymerized with vinyl acetate, such as a vinyl ether or an unsaturated sulfonate. Further, examples thereof include a polyvinyl acetal resin such as a polyvinyl butyral resin or a polyethylene formaldehyde resin, and a polyvinyl alcohol derivative, which is obtained by reacting polyvinyl alcohol with an aldehyde in the presence of an acid.

Furthermore, the above description has been given of the case where the adhesive of the present invention is used for the use of an optical member, and the adhesive of the present invention is preferably temporarily provided in terms of antistatic property and high-speed peelability depending on the case. The surface protection application is used as an adhesive for temporary surface protection. Therefore, the following description of the use of the adhesive of the present invention for temporary surface protection use is disclosed.

When it is used as a temporary surface protective adhesive, it is preferable to contain an unsaturated group-containing compound (B), a polymerization initiator (C), and a crosslinking agent in addition to the acrylic resin (A) component. (D) and at least one resin composition [I] of the antistatic agent (F) component, which is used as a resin composition [1] to form an adhesive after crosslinking, and particularly preferably contains acrylic acid. The resin composition (A), the unsaturated group-containing compound (B), and the polymerization initiator (C) component, and further, the resin composition [I] containing the antistatic agent (F) is crosslinked to form an adhesive. .

The acrylic resin (A) used as the temporary surface protective adhesive can be the same as the acrylic resin (A).

As the unsaturated group-containing compound (B) used as the temporary surface protective adhesive, the same as the above unsaturated group-containing compound (B) can be used, and in order to increase the crosslinking density of the adhesive, it is preferred. A polyfunctional, that is, an unsaturated group-containing compound having two or more unsaturated groups is used, and a compound having an unsaturated group having three or more unsaturated groups is particularly preferred.

Further, from the viewpoint of excellent antistatic performance, it is preferred to use an alkyl methacrylate-based compound (b1) or an ethylenically unsaturated monomer (b2) containing an alkanediol chain. Particularly preferred is an ethyl (meth) acrylate-based compound containing an alkylene glycol chain and containing three or more unsaturated groups.

The content of the unsaturated group-containing compound (B) is preferably 200 parts by weight or less, more preferably 5 to 150 parts by weight, particularly preferably 10 to 100 parts by weight, per 100 parts by weight of the acrylic resin (A). It is preferably 20 to 80 parts by weight. When the content of the unsaturated group-containing compound (B) is too small, the crosslinking becomes insufficient, and the cohesive force is lowered to cause contamination by the adherend. If the content is too large, the adhesive strength tends to decrease.

The polymerization initiator (C) used as the temporary surface protective adhesive can be the same as the above polymerization initiator (C).

As the crosslinking agent (D) used as the temporary surface protective adhesive, the same as the above-mentioned crosslinking agent (D) can be used.

As the antistatic agent (F) used as the temporary surface protective adhesive, the same antistatic agent (F) as described above can be used, and among them, an alkali metal salt, an alkaline earth metal salt, and a quaternary ammonium salt are preferably used. It is particularly preferred to use an alkali metal salt.

The temporary surface protective adhesive which cured the resin composition [I] can be effectively used as a temporary surface protective adhesive sheet by laminating on a substrate.

Furthermore, the "sheet" of the present invention also encompasses the meaning of a film.

The substrate to which the above resin composition [I] is provided is not particularly limited, and examples thereof include polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, and polybutylene. Polyester resin such as ethylene phthalate/ethylene isophthalate copolymer, polyolefin resin such as polyethylene, polypropylene or polymethylpentene, polyvinyl fluoride, polyvinylidene fluoride, poly Polyvinyl fluoride resin such as vinyl fluoride, nylon 6, nylon 6,6 and other polyamines, polyvinyl chloride, polyvinyl chloride/vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, poly Ethylene polymer such as vinyl alcohol or vinylon, cellulose resin such as cellulose triacetate or celecin, acrylic acid such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate or polybutyl acrylate. Synthetic resin film or sheet of resin, polystyrene, polycarbonate, polyarylate, polyimine, etc.; metal foil of aluminum, copper, iron; paper such as Daolin paper, cellophane; glass fiber, natural fiber, A woven or non-woven fabric composed of synthetic fibers or the like. These base materials can be used as a single layer or as a laminate having two or more layers.

Among these substrates, a synthetic resin film or sheet such as polyethylene terephthalate, polyethylene or polypropylene is preferably used in consideration of the price.

Moreover, in order to improve the adhesion of the adhesive to the substrate, the substrate may be subjected to corona discharge treatment, plasma treatment, primer coating, degreasing treatment, surface roughening treatment, etc., to improve the easy adhesion treatment, and further Set the antistatic layer to resist static electricity.

The thickness of the substrate is not particularly limited, and is usually a thickness of usually 500 μm or less, preferably 5 to 300 μm, more preferably 10 to 200 μm.

The thickness of the resin composition [I] provided on the substrate is not particularly limited, and after drying, it is usually a thickness of about 1 to 100 μm, preferably about 2 to 50 μm. When the adhesive sheet for temporary surface protection is peeled off from the adherend, the adhesive paste tends to remain on the surface of the adherend, and if it is too thin, there is a tendency that the adhesive force is adhered to the adherend. When the adhesive sheet for temporary surface protection is bonded to the adherend, and the adherend sheet for the adherend and the temporary surface protection is exposed to a high temperature, the adhesive sheet for temporary surface protection is peeled off.

Before the adhesive sheet for temporary surface protection is bonded to the adherend, the film may be separated from the surface layer of the adhesive in order to protect the adhesive from contamination. As the separator, a substrate obtained by subjecting a base material such as a synthetic resin film or sheet exemplified above, paper, cloth, or nonwoven fabric to a release treatment can be used.

When the resin composition [I] is provided on the above substrate, it is usually prepared as a solution of the resin composition [I], and in particular, it is applied to a substrate after being adjusted to a viscosity suitable for coating with a solvent, and dried. . The coating method includes a direct coating method in which a solution-like resin composition [I] is directly applied to a substrate, and a solution-like resin composition [I] is applied onto a separator, and then with a base. A transfer coating method such as a material bonding.

In the direct coating method, a resin composition [I] is applied onto a substrate, heated and dried, and then irradiated with an active energy ray, followed by laminating a separator; and a resin is coated on the substrate. After the composition [I] was dried by heating, the separator was attached, and then the active energy ray was irradiated thereto. The coating can be carried out by a method such as roll coating, die coating, gravure coating, blade coating, screen printing or the like.

On the other hand, in the transfer coating method, a resin composition [I] is applied onto a separator and heated and dried, and then an active energy ray is applied thereto, and then the substrate is bonded thereto; The resin composition [I] is applied onto the film, heated and dried, and then bonded to the substrate, and then irradiated with an active energy ray. Regarding the coating method, the same method as the direct coating can be used.

The type of the adherend to which the temporary surface protective adhesive sheet is adhered is not particularly limited. For example, in addition to the synthetic resin film or sheet, metal foil, paper, woven fabric or non-woven fabric exemplified in the above substrate, glass may be cited. Board, synthetic resin board, metal board.

The initial adhesive force of the temporary surface protective adhesive sheet is appropriately determined depending on the adherend material or the like. For example, when adhered to a SUS304BA board, it preferably has an adhesive force of 0.01 N/25 mm to 50 N/25 mm, and is used for temporary protection (for surface protection, shielding), preferably 0.01 N/25 mm to 5 N/ 25mm adhesion.

The above adhesion is calculated in the following manner. First, the obtained adhesive sheet is cut into 25 mm × 100 mm, and then rubbed 2 times with a 2 kg rubber roller in an environment of 23 ° C and a relative humidity of 50%, and the adhesive sheet is crimped to be viscous. Test pieces were prepared on a stainless steel plate (SUS304BA plate) or an acrylic plate (PMMA plate). After the test piece was allowed to stand in the same environment for 30 minutes, a 180-degree peeling test was performed at a peeling speed of 0.3 m/min, and the measured adhesive force (N/25 mm) was taken as the initial adhesive force.

Moreover, the high-speed peeling adhesive force of the temporary surface-protecting adhesive sheet is usually 6 times or less of the initial adhesive strength, preferably 4 times or less, more preferably 2 times or less. This high speed peel adhesion is calculated in the following manner. The test piece prepared by the same method as the above initial adhesion was allowed to stand in an environment of 23 ° C and a relative humidity of 50% for 30 minutes. Thereafter, in this environment, a 180-degree peeling test was performed at a high speed of a peeling speed of 30 m/min, and the measured adhesive force (N/25 mm) was taken as a high-speed peeling adhesive force.

(Example)

Hereinafter, the present invention will be specifically described by way of examples, and the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

In addition, the "parts" and "%" in the examples indicate the weight basis unless otherwise specified.

(Example of adhesive for optical member) [Preparation of hydroxyl group-containing acrylic resin (A)] (refer to Table 1.) [Acrylic resin (A-1)]

100 parts of ethyl acetate was placed in a four-necked round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet, and a thermometer, and 0.05 part of azobisisobutyronitrile (AIBN) was added as a polymerization initiator while stirring. The mixture was heated at a reflux temperature, and a mixture of 20 parts of 2-hydroxyethyl acrylate (a1), 79 parts of butyl acrylate (a2), and 1 part of acrylic acid (a3) was added dropwise over 2 hours. A polymerization initiator liquid obtained by dissolving 0.05 part of AIBN in 10 parts of ethyl acetate was added to the polymerization process, and the mixture was polymerized at the reflux temperature of ethyl acetate for 3.5 hours, and then diluted to obtain an acrylic acid system. Resin (A-1) solution (weight average molecular weight (Mw) was 870,000, dispersion (Mw/Mn) was 4.9, glass transition temperature was -47 ° C, solid content was 35%, and viscosity was 7,000 mPa ‧ S (25 °C)).

[Acrylic resin (A-2)]

100 parts of ethyl acetate was placed in a four-necked round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet, and a thermometer, and 0.05 part of azobisisobutyronitrile (AIBN) was added as a polymerization initiator while stirring. The mixture was heated at a reflux temperature, and a mixture of 30 parts of 2-hydroxyethyl acrylate (a1), 69 parts of butyl acrylate (a2), and 1 part of acrylic acid (a3) was added dropwise over 2 hours. A polymerization initiator liquid obtained by dissolving 0.05 part of AIBN in 10 parts of ethyl acetate was added to the polymerization process, and it was polymerized at the reflux temperature of ethyl acetate for 3.5 hours, and then diluted to obtain an acrylic resin. (A-2) solution (weight average molecular weight (Mw) was 850,000, dispersion (Mw/Mn) was 4.5, glass transition temperature was -43 ° C, solid form was 35%, viscosity was 7,000 mPa ‧ (25 ° C )).

[Acrylic resin (A-3)]

120 parts of ethyl acetate was placed in a four-necked round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet, and a thermometer, and 0.05 part of azobisisobutyronitrile (AIBN) was added as a polymerization initiator while stirring. The mixture was heated at a reflux temperature, and a mixture of 50 parts of 2-hydroxyethyl acrylate (a1), 49 parts of butyl acrylate (a2), and 1 part of acrylic acid (a3) was added dropwise over 2 hours. A polymerization initiator liquid obtained by dissolving 0.05 part of AIBN in 10 parts of ethyl acetate was added to the polymerization process, and it was polymerized at the reflux temperature of ethyl acetate for 3.5 hours, and then diluted to obtain an acrylic resin. (A-3) solution (weight average molecular weight (Mw) was 760,000, degree of dispersion (Mw/Mn) was 4.4, glass transition temperature was -35 ° C, solid form was 27%, viscosity was 3,000 mPa ‧ (25 ° C )).

[Acrylic resin (A-4)]

100 parts of ethyl acetate was placed in a four-necked round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet, and a thermometer, and 0.05 part of azobisisobutyronitrile (AIBN) was added as a polymerization initiator while stirring. The temperature was raised, and 30 parts of 2-hydroxyethyl acrylate (a1), 30 parts of 2-methoxyethyl acrylate (a2), 39 parts of butyl acrylate (a2), and 1 part of acrylic acid were added dropwise at reflux temperature for 2 hours. a mixture of (a3). A polymerization initiator liquid obtained by dissolving 0.05 part of AIBN in 10 parts of ethyl acetate was added to the polymerization process, and it was polymerized at the reflux temperature of ethyl acetate for 3.5 hours, and then diluted to obtain an acrylic resin. (A-4) solution (weight average molecular weight (Mw) was 980,000, degree of dispersion (Mw/Mn) was 4.3, glass transition temperature was -42 ° C, solid form was 32%, viscosity was 7,000 mPa ‧ (25 ° C )).

[Acrylic resin (A-5)]

100 parts of ethyl acetate was placed in a four-necked round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet, and a thermometer, and 0.05 part of azobisisobutyronitrile (AIBN) was added as a polymerization initiator while stirring. The mixture was heated at a reflux temperature, and a mixture of 30 parts of 2-hydroxyethyl acrylate (a1) and 70 parts of butyl acrylate (a2) was added dropwise over 2 hours. A polymerization initiator liquid obtained by dissolving 0.05 part of AIBN in 10 parts of ethyl acetate was added to the polymerization process, and it was polymerized at the reflux temperature of ethyl acetate for 3.5 hours, and then diluted to obtain an acrylic resin. (A-5) solution (weight average molecular weight (Mw) was 850,000, dispersion (Mw/Mn) was 4.4, glass transition temperature was -43 ° C, solid form was 35%, and viscosity was 5,500 mPa·s (25 ° C )).

[Acrylic resin (A-6)]

100 parts of ethyl acetate was placed in a four-necked round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet, and a thermometer, and 0.05 part of azobisisobutyronitrile (AIBN) was added as a polymerization initiator while stirring. The mixture was heated at a reflux temperature, and a mixture of 30 parts of 4-hydroxybutyl acrylate (a1), 69 parts of butyl acrylate (a2), and 1 part of acrylic acid (a3) was added dropwise over 2 hours. A polymerization initiator liquid obtained by dissolving 0.05 part of AIBN in 10 parts of ethyl acetate was added to the polymerization process, and it was polymerized at the reflux temperature of ethyl acetate for 3.5 hours, and then diluted to obtain an acrylic resin. (A-6) solution (weight average molecular weight (Mw) was 680,000, dispersion (Mw/Mn) was 4.9, glass transition temperature was -44 ° C, solid form was 29%, viscosity was 1,900 mPa.s (25 ° C )).

[Acrylic resin (A-7)]

70 parts of ethyl acetate was placed in a four-necked round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet, and a thermometer, and 0.05 part of azobisisobutyronitrile (AIBN) was added as a polymerization initiator while stirring. The mixture was heated at a reflux temperature, and a mixture of 30 parts of 2-hydroxyethyl acrylate (a1), 69 parts of 2-ethylhexyl acrylate (a2), and 1 part of acrylic acid (a3) was added dropwise over 2 hours. A polymerization initiator liquid obtained by dissolving 0.05 part of AIBN in 10 parts of ethyl acetate was added to the polymerization process, and it was polymerized at the reflux temperature of ethyl acetate for 3.5 hours, and then diluted to obtain an acrylic resin. (A-7) solution (weight average molecular weight (Mw) was 940,000, degree of dispersion (Mw/Mn) was 5.4, glass transition temperature was -56 ° C, solid form was 28%, and viscosity was 9,200 mPa.s (25 °C)).

[Acrylic resin (A-8)]

1.5 parts of 2-hydroxyethyl acrylate (a1), 98 parts of butyl acrylate (a2), 0.5 parts of acrylic acid (a3), and a four-neck round bottom flask equipped with a reflux cooler, a stirrer, a nitrogen gas inlet, and a thermometer. After 75 parts of ethyl acetate and 45 parts of acetone were heated and refluxed, 0.03 parts of azobisisobutyronitrile (AIBN) was added as a polymerization initiator, and the mixture was reacted at reflux temperature for 3 hours, and then ethyl acetate was used. Dilute to obtain an acrylic resin (A-8) solution (weight average molecular weight (Mw) of 2 million, dispersion degree (Mw/Mn) of 3.1, glass transition temperature of -54 ° C, solid content of 16%, viscosity of 8,000 mPa.s (25 ° C)).

[Acrylic resin (A-9)]

12 parts of 2-hydroxyethyl acrylate (a1), 87.5 parts of butyl acrylate (a2), 0.5 part of acrylic acid (a3), and a four-neck round bottom flask equipped with a reflux cooler, a stirrer, a nitrogen gas inlet, and a thermometer. After 100 parts of ethyl acetate and 45 parts of acetone were heated and refluxed, 0.03 parts of azobisisobutyronitrile (AIBN) was added as a polymerization initiator, and after reacting for 3 hours at the reflux temperature of ethyl acetate, 100 parts of acetic acid was used. The ester was diluted with 100 parts of toluene and further reacted at 80 ° C for 3 hours. Thereafter, the mixture was diluted with ethyl acetate to obtain a solution of an acrylic resin (A-9) having a weight average molecular weight (Mw) of 1.35 million, a degree of dispersion (Mw/Mn) of 11, and a glass transition temperature of -50 ° C. The solid shape is divided into 20% and the viscosity is 4800 mPa‧S (25 ° C)).

[Manufacture of Unsaturated Group-Containing Compound (B-1)]

19.2 parts of isophorone diisocyanate, 0.05 part of di-tert-butylhydroxyphenol, and 0.02 part of di(dodecanoic acid) were placed in a four-necked round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet, and a thermometer. Dibutyltin, at 50 ° C or less, 80.8 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Light AcryLate PE-3A manufactured by Kyoeisha Chemical Co., Ltd., hydroxyl value 120 mgKOH/g), and then continued at 70 ° C The reaction is carried out to obtain an unsaturated group-containing compound (B-1).

[Photopolymerization initiator (C-1)]

The following was prepared as a photopolymerization initiator (C-1).

‧ Mixture of benzophenone and 1-hydroxycyclohexyl phenyl ketone in a mass ratio of 1:1 (Ciba Specialty Chemicals, "Irgacure 500")

[Crosslinking agent (D-1)]

The following was prepared as the crosslinking agent (D-1).

‧ 55% ethyl acetate solution of toluene diisocyanate adduct of trimethylolpropane (manufactured by NIPPON POLYURETHANE INDUSTRY, "Coronate L-55E")

[decane compound (E-1)]

The following was prepared as the decane-based compound (E-1).

‧γ-glycidoxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM403")

[antistatic agent (F)]

The following were prepared as an antistatic agent (F-1).

‧ 1-Ethyl-2,3-dimethylimidazolium dicyanamide The following were prepared as an antistatic agent (F-2).

‧ 1-Ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) sulfoximine salt The following were prepared as an antistatic agent (F-3).

‧ Lithium Perchlorate (manufactured by Japan Carlit) prepares the following as an antistatic agent (F-4).

‧Lithane trifluoromethanesulfonate (LiCF ₃ SO ₃ ) (manufactured by Sanko Chemical Co., Sankonol EAc-30T)

(Examples 1 to 7, Comparative Examples 1, 2)

In the obtained acrylic resin (A-1 to A-9), 2.5 parts of a crosslinking agent (D-1) was blended with respect to 100 parts of the acrylic resin, and the viscosity was diluted with ethyl acetate to prepare a coatable layer ( A resin composition of 1000-5000 mPa ‧ / 25 ° C). The resin composition was applied onto a polyester release sheet so that the thickness after drying became 25 μm, and after drying at 90 ° C for 3 minutes, the resin composition layer side was transferred to polyethylene terephthalate. The diester film (thickness: 38 μm) was aged at 23 ° C and 65% RH for 14 days to obtain a sample of the adhesive.

(surface resistivity)

After the obtained sample of the adhesive was cut into 40×40 mm, the sample was conditioned for 3 hours at 23° C. and 65% RH, and then the peeled sheet was peeled off, and the adhesive layer was used for 10 to 20 seconds. The surface resistivity was measured by a resistivity meter "Hiresta-UP" manufactured by Chemical Corporation. Furthermore, the smaller the surface resistance value, the better the antistatic property.

It is understood that a monomer having only a hydroxyl group of 1.5 or 12% by weight is used as compared with the surface resistance of an adhesive using an acrylic resin (A-1 to 7) containing 15% by weight or more of a hydroxyl group-containing monomer. The adhesive of the acrylic resin (A-8) or (A-9) has a large surface resistivity, and the adhesive using the acrylic resin (A-8) or (A-9) has poor antistatic properties.

(Example 8)

The composition [I] solution (diluted to a viscosity (1000-10000 mPa‧s/25 ° C) by ethyl acetate) was prepared using the compounding composition as shown in Table 3. The obtained composition [I] solution was applied onto a polyester release sheet so that the thickness after drying became 25 μm, and after drying at 90 ° C for 3 minutes, the composition [I] layer was transferred. onto a polarizing plate (thickness 190 m), using an electrodeless lamp [LH6UV lamps H Bulb] Fusion of manufacturing companies to 600 mW / cm ² of the peak irradiance, 240mJ / cm ² cumulative exposure amount of ultraviolet irradiation, so that The laminate was aged at 23 ° C and 65% RH for 14 days to obtain a polarizing plate with an adhesive layer.

Further, the polarizing plate was used by using a cellulose triacetate film having a thickness of 80 μm to a polyvinyl alcohol polarizing film having a film thickness of 30 μm (average degree of polymerization: 1,700, an average degree of saponification of 99 mol%, iodine dyed, A polarizing plate in which the layers are laminated on both sides of the four-fold extension (the inclination direction of the polyvinyl alcohol polarizing film is inclined by 45 degrees, and cut into 100 mm × 100 mm).

(Examples 9-13 and Comparative Examples 3 and 4)

The same operation as in Example 8 was carried out by using the compounding composition as shown in Table 3 to obtain a polarizing plate with an adhesive layer.

Further, a polyethylene terephthalate film (thickness: 38 μm) was used in place of the polarizing plate in the same manner as described above to obtain a sample for measuring gel fraction and surface resistance.

(gel rate)

After the obtained sample was cut into 40×40 mm, the release sheet was peeled off, and the adhesive layer side was attached to a 50×100 mm SUS mesh sheet (200 mesh), and then to the SUS mesh sheet. In the longitudinal direction, the sample was folded from the center portion, and then the gel fraction (%) was measured by the weight change when immersed in a sealed container to which 250 g of toluene was added.

(durability)

The obtained release sheet of the polarizing plate with the adhesive layer was peeled off, and the adhesive layer side was pressed against an alkali-free glass plate (Corning 1737, manufactured by Corning Incorporated), and the polarizing plate was bonded to the glass plate, and then the autoclave was placed. The treatment (50 ° C, 0.5 MPa, 20 minutes) was followed by evaluation of foaming, peeling, and light leakage in the following endurance test (damp heat resistance test, heat cycle test). The evaluation criteria are as follows. The evaluation results are shown in Table 4.

Further, in the heat resistance test, only the same sample was bonded to both surfaces of the front surface and the back surface to make the polarizing plate a crossed polarizer, and it was used for light leakage observation.

Regarding the size of the test piece to be used, 10 cm × 10 cm was used for the heat resistance and heat cycle test, and 20 cm × 15 cm was used for the heat resistance test.

[Durability Test]

(1) Heat resistance test

80 ° C, 100 hours endurance test

(2) Heat and humidity resistance test

60 ° C, 90% RH, 100 hours endurance test

(3) Thermal cycle test

After standing at -40 ° C for 30 minutes, and then standing at 85 ° C for 30 minutes as a cycle, and performing 100 cycles of endurance test

[evaluation benchmark] (foaming)

○...no foaming

△... visible micro foaming

×... visible large amount of foaming

(stripping)

○...no peeling or peeling or floating of less than 0.5mm

△... produces peeling or floating of less than 1mm

×... Produces peeling or floating of 1 mm or more

(light leakage)

○...no light leakage or almost no light leakage

△...generate light leakage

×... generates a lot of light leakage on all four sides

[adhesion]

The prepared polarizing plate with the adhesive layer was cut into a width of 25 mm, the release film was peeled off, and the adhesive layer side was pressed against an alkali-free glass plate ("Corning 1737" manufactured by Corning Co., Ltd.) to make a polarizing plate and a glass. The board is fitted. Thereafter, autoclave treatment (50 ° C, 0.5 MPa, 20 minutes) was carried out, and after 180 hours, a 180 ° C peel test was performed. A small adhesion is expected in terms of peelability, and the target is 10 N/25 mm or less after one day.

According to the above results, in Comparative Examples 3 and 9 and Comparative Example 3 in which the antistatic agent (F) was not prepared, Comparative Example 3 of the acrylic resin (A-9) having a small content of a monomer containing a hydroxyl group was used. The adhesives of Examples 8 and 9 have higher antistatic properties than the adhesives.

Further, when focusing on Examples 10 to 13 and Comparative Example 4 in which the antistatic agent (F) was formulated, it was found that by disposing the antistatic agent, the antistatic properties of the two adhesives were higher than those in the unmixed case, and the use contained 30. Examples 10 to 13 of the acrylic resin (A-2) having a part by weight of the OH group-containing monomer have more excellent antistatic properties than Comparative Example 4.

In addition, the acrylic resin (A) containing a large amount of a hydroxyl group-containing monomer is excellent in antistatic property, and further, as a result of Table 4, it is excellent in durability as an adhesive for optical members.

(Example of adhesive for temporary surface protection) [Acrylic resin (A-10)]

100 parts of ethyl acetate was placed in a reactor equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, and the temperature was raised while stirring, and after reaching 78 ° C, 70 parts of butyl acrylate was added dropwise over 2 hours, and 0.044 parts of azo was added dropwise. A mixture of diisobutyronitrile (AIBN) dissolved in 30 parts of 2-hydroxyethyl acrylate. Further, a polymerization catalyst solution obtained by dissolving 0.05 part of AIBN in 7 parts of ethyl acetate was added to the polymerization process for 7 hours, and then diluted with ethyl acetate to obtain an acrylic resin ( A-10) (weight average molecular weight (Mw) is 810,000, dispersion (Mw / Mn = 4.6), glass transition temperature is -45 ° C, solid form is 40%, viscosity is 10500 mPa.s (25 ° C)) 40% solution.

[Acrylic resin (A-11)]

Into a reactor equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, 64 parts of ethyl acetate was placed, and the temperature was raised while stirring. After reaching 78 ° C, 97 parts of butyl acrylate was added dropwise over 2 hours to make 0.06 parts of azo. A mixture of diisobutyronitrile (AIBN) dissolved in 3 parts of 2-hydroxyethyl acrylate. Further, a polymerization catalyst solution obtained by dissolving 0.05 part of AIBN in 10 parts of ethyl acetate was added to the polymerization process, and the mixture was polymerized for 7 hours, and then diluted with ethyl acetate to obtain an acrylic resin (A). -11) (weight average molecular weight (Mw) is 860,000, dispersion (Mw / Mn = 5.4), glass transition temperature is -55 ° C, solid shape is 40%, viscosity is 8140 mPa.s (25 ° C)) 40 % solution.

[Unsaturated group-containing compound (B-2)]

94.1 g (0.42 mol) of isophorone diisocyanate (isocyanate group content: 37.8%) and 2.0 g of 2,6-di-t-butyl cresol were placed in a four-necked flask equipped with a thermometer, a stirrer, and a water-cooled condenser. 0.1 g of dibutyltin di(dodecanoate), dipentaerythritol pentaacrylate (0.51 mol) was added dropwise at about 60 ° C for about 2 hours (as a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) The value was 50.0 mgKOH/g), and the reaction was carried out at 60 ° C for 2 hours. When the residual isocyanate group reached 2.1%, 336.2 g (0.34 mol) of polyethylene glycol was further added at 55 ° C. (weight average molecular weight: 993.1, ethylene oxide addition molar number is 22, hydroxyl value: 113 mgKOH/g), and it was reacted at 60 ° C for 4 hours, and the reaction was terminated when the residual isocyanate group reached 0.3%. A composition containing a compound (B-2) containing an unsaturated group (resin component concentration: 100%).

The composition obtained in the above preparation contains 69.4% of the unsaturated group-containing compound (B-2) and 30.6% of the ethylenically unsaturated monomer (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), and the average weight The molecular weight is 2,500.

The following was prepared as the unsaturated group-containing compound (B-3).

‧ Dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD DPHA")

[Crosslinking agent (D-2)]

The following was prepared as a crosslinking agent (D-2).

‧ Ethyl acetate 75% solution of hexamethylene diisocyanate trimethylolpropane adduct (manufactured by Japan Polyurethane Co., Ltd. under the trade name "CoronateHL")

[antistatic agent (F-5)]

Prepare the following as an antistatic agent (F-5).

‧Lithium iodide (manufactured by Wako Pure Chemical Industries Co., Ltd., trade name "Hikaru lithium iodide (anhydrous)"

[antistatic agent (F-6)]

Prepare the following as an antistatic agent (F-6).

‧Lithium Perchlorate (manufactured by Wako Pure Chemical Industries Co., Ltd., trade name "Huangguang Lithium Perchlorate (Anhydrous)")

[Antistatic agent (F-7)]

Prepare the following as an antistatic agent (F-7).

‧Ethyl acetate 30% solution of lithium trifluoromethanesulfonate (manufactured by Sanko Chemical Industry Co., Ltd., trade name "Sankonol EAc-30T")

(Examples 14 to 20, Comparative Examples 5 and 6) [Embodiment 14]

100 parts of acrylic resin (A-10), 50 parts of unsaturated group-containing compound (B-2), and 0.5 part of lithium iodide (F-5) were placed in a container equipped with a blender, and 7 parts of acetone was added as a dilution. The agent is stirred and mixed and dissolved. To the solution, 10 parts of the photopolymerization initiator (C-1) was added to the solution and stirred to obtain a uniform active energy ray-polymerizable composition.

The active energy ray-polymerizable composition obtained above was applied onto a polyethylene terephthalate (PET) substrate having a thickness of 38 μm so as to have a thickness of 25 μm after drying, and dried at 100 ° C for 2 minutes. Further, the release-treated PET substrate was used to cover the coated surface so that the release-treated surface was in contact with the coated surface. Thereafter, the high-pressure mercury lamp adjusted to have an irradiation intensity of 200 mW/cm ² was irradiated with ultraviolet rays to have an integrated light amount of 520 mJ/cm ² , and photopolymerization was carried out to obtain an adhesive sheet.

[Example 15]

In the same manner as in Example 14, except that the dipentaerythritol pentaacrylate (B-3) was used instead of the unsaturated group-containing compound (B-2), the active energy ray-polymerizable composition was obtained in the same manner as in Example 14. . Then, using the active energy ray polymerizable composition, an adhesive sheet was obtained in the same manner as in Example 14.

[Example 16]

An active energy ray-polymerizable composition was obtained in the same manner as in Example 14 except that 2 parts of lithium perchlorate (F-6) was used instead of the antistatic agent (F-5). Then, using the active energy ray polymerizable composition, an adhesive sheet was obtained in the same manner as in Example 14.

[Example 17]

In Example 14, an active energy ray was obtained in the same manner as in Example 14 except that 1 part of the crosslinking agent (D-2) was used, and it was aged for 3 days in an environment of a temperature of 40 ° C after ultraviolet irradiation. Polymeric composition. Then, using the active energy ray polymerizable composition, an adhesive sheet was obtained in the same manner as in Example 14.

[Embodiment 18]

In Example 14, an active energy ray-polymerizable composition was obtained in the same manner as in Example 14 except that lithium iodide (F-5) was not added. Then, using the active energy ray polymerizable composition, an adhesive sheet was obtained in the same manner as in Example 14.

[Embodiment 19]

In a room where ultraviolet rays are blocked, 100 parts of acrylic resin (A-10) (solid content), 0.5 part of antistatic agent (F-7) (solid content), and 9.5 parts of crosslinking agent are added to the container with the mixer. (D-2) (solid fraction), using ethyl acetate as a diluent, diluted to a solid content of 27%, stirred and dissolved.

The resin composition obtained above was applied onto a polyethylene terephthalate (PET) substrate having a thickness of 38 μm so that the thickness after drying became 25 μm. It was dried at 100 ° C for 2 minutes. Thereafter, the release-treated PET was adhered to the coated surface for protection, and aged at a temperature of 40 ° C for 3 days to obtain an adhesive sheet.

[Example 20]

An adhesive sheet was obtained in the same manner as in Example 19 except that the acrylic resin (A-10) of Example 19 was changed to (A-2).

[Comparative Example 5]

An active energy ray-polymerizable composition was obtained in the same manner as in Example 14 except that the acrylic resin (A-11) was used instead of the acrylic resin (A-10). Then, using the active energy ray polymerizable composition, an adhesive sheet was obtained in the same manner as in Example 14.

[Comparative Example 6]

In the same manner as in Example 19, an adhesive sheet was obtained in the same manner as in Example 19 except that the acrylic resin (A-11) was used instead of the acrylic resin (A-10).

The compositions of the adhesives obtained in the above Examples 14 to 20 and Comparative Examples 5 and 6 are shown in [Table 5].

The obtained adhesive sheet was evaluated for the following adhesive properties. The results are shown in [Table 3].

[surface resistivity]

The adhesive sheet of the release-treated PET was peeled off and allowed to stand at a temperature of 23 ° C and a relative humidity of 50% for 3 hours. After the humidity was adjusted, the surface resistance value was measured using a Hiresta-UP (manufactured by Mitsubishi Chemical Corporation). The smaller the value, the higher the antistatic property.

[Coating film transparency]

The transparency of the coating film was determined by visually determining the turbidity of the coating film after the adhesive sheet was formed.

○: Confirm that there is no turbidity at all.

△: A slight amount of turbidity was confirmed.

×: It was confirmed that there was significant turbidity and it was white turbid.

[Initial adhesion]

After the obtained adhesive sheet was cut into 25 mm × 100 mm, the adhesive sheet was crimped to the adherend by using a 2 kg rubber roller twice at 23 ° C and a relative humidity of 50%. A test piece was prepared on a stainless steel plate (SUS304BA plate). After the test piece was allowed to stand in this environment for 30 minutes, a 180-degree peeling test was performed at a peeling speed of 0.3 m/min, and the initial adhesion (N/25 mm) was measured.

[High speed peelability]

After the obtained adhesive sheet was cut into 25 mm × 100 mm, the adhesive sheet was crimped to the adherend by using a 2 kg rubber roller twice at 23 ° C and a relative humidity of 50%. A test piece was prepared on a stainless steel plate (SUS304BA plate). After the test piece was allowed to stand in this environment for 30 minutes, the adhesion at high speed peeling (N/25 mm) was measured at a peeling speed of 30 m/min.

[tolerance]

The contamination resistance of the adherend was observed for each of the surfaces of the adherends after the high-speed peelability measurement, and the evaluation was performed on the following basis.

○: Confirm that there is no pollution at all.

△: A slight amount of contamination was confirmed.

×: It was confirmed that there was significant contamination.

According to the above results, the adhesive sheets of Examples 14, 15, 16, and 17 were more excellent in antistatic properties than in Comparative Example 5, and the coating film was more excellent in transparency. Further, it is also known that the high-speed peeling value is not so large as compared with the low-speed peeling value of the adhesive sheets, and the stain resistance is also excellent. Therefore, it is excellent when used as an adhesive sheet for surface protection. Since the anti-static agent was not added to the sheet of Example 18, the antistatic property was slightly inferior to those of Examples 14, 15, 16, and 17, but it was excellent in transparency as compared with Comparative Example 5 having turbidity. . It can be seen that the adhesive sheets of Examples 19 and 20 are superior in comparison with Comparative Example 6 in terms of antistatic properties and transparency of the coating film, and it is generally considered that these properties are due to the large use of hydroxyl groups in the acrylic resin. The monomer imparts high antistatic properties and transparency of the coating film. In view of the above physical properties, it is understood that the adhesive sheets of Examples 14 to 20 are excellent as an adhesive sheet for surface protection.

The present invention has been described in detail above with reference to the specific embodiments thereof. It is understood that various changes and modifications may be made without departing from the spirit and scope of the invention.

The present application is based on a Japanese patent application filed on Nov. 7, 2007 (Japanese Patent Application No. 2007-289605), and Japanese Patent Application No. 2007-331346 filed on Dec. 25, 2007, It is hereby incorporated by reference.

(industrial availability)

The adhesive of the present invention is not easy to carry the static electricity generated in each step, and the adhesion between the optical laminate and the glass substrate is excellent even under high temperature and high humidity conditions, and no adhesion occurs between the adhesive layer and the glass substrate. It is very useful because foaming or peeling can suppress the light leakage phenomenon caused by shrinkage of the optical film, and thus a liquid crystal display panel excellent in durability can be obtained.

Claims (5)

An adhesive for an optical member, which is obtained by crosslinking a resin composition [I] containing 50% by weight or more of the acrylic resin (A), and the acrylic resin (A) is made to be a total of the copolymerization component. The polymer component containing 25 to 90% by weight of a hydroxyl group-containing monomer is polymerized, wherein the acrylic resin (A) is a radical polymerization of a solution in an organic solvent, and the resin composition [I] contains a solvent. The unsaturated group-containing compound (B), the polymerization initiator (C), the crosslinking agent (D), and the decane coupling agent (E) are obtained by crosslinking at least one of an active energy ray and heat, and It is formed by crosslinking with a crosslinking agent. The adhesive for optical members according to the first aspect of the invention, wherein the acrylic resin (A) has a weight average molecular weight of 100,000 to 3,000,000, and further has a degree of dispersion of 7 or less. The adhesive for optical members according to the first aspect of the invention, wherein the resin composition [I] further contains an antistatic agent (F). The adhesive for optical members according to any one of claims 1 to 3, wherein the optical member is a polarizing plate. An optical member with an adhesive layer, comprising an adhesive layer containing an adhesive for an optical member according to any one of claims 1 to 3.