TWI572691B - Ultraviolet-curable resin composition, cured substance and article - Google Patents

Description

UV curable resin composition, cured product and articles

The present invention relates to an ultraviolet curable resin composition having a bonding for an optically transparent member.

In recent years, in a display screen of a display device such as a liquid crystal display, a plasma display, or an organic EL display, a display device in which a touch panel is bonded and a screen can be input is widely used. The display device has a touch panel laminated on a display screen thereof, wherein the touch panel is formed by a glass plate or a resin film formed with a transparent electrode in a manner that the transparent electrodes are opposed to each other, and the touch panel is The touch surface has a structure in which a transparent protective plate made of a glass or a resin is laminated. Further, in a display device that does not have a touch panel, a structure in which a transparent protective plate made of glass or resin is laminated on a display screen is used.

Bonding a transparent protective plate made of glass or resin to a touch surface of a glass plate or a film on which a transparent electrode is formed in a touch panel, or a transparent protective plate for a display device and a screen thereof, or a display device The touch panel or the like is attached to the screen, and has a technique of using a double-sided adhesive sheet, but there is a problem that air bubbles are easily entered. There is a proposal to disclose a technique of bonding a photocurable resin composition as a technique for replacing a double-sided adhesive sheet (Patent Documents 1 to 3).

On the other hand, the thinning and large screen of the display device are progressing. Therefore, for example, the transparent protective plate or the substrate of the touch panel, and the glass plate or the resin transparent plate for the display screen in the display device are gradually thinned. Therefore, in the above-mentioned layering or lamination, when the photocurable resin composition is used for bonding, the resin composition is cured and shrunk, and the touch panel and the display screen are deformed. Moreover, in the case where the material of the two of the substrates is different, such as glass/acrylic resin, glass/polycarbonate resin, etc., the difference between the thermal expansion and the hygroscopicity of the two materials is in the heat and humidity resistance test. Then peel off the problem. In order to solve such problems, a photocurable resin composition capable of suppressing shrinkage during curing and providing a cured product excellent in adhesion to a substrate and flexibility is required. However, when polyisoprene described in Patent Document 1 is used as a main component, it is necessary to remove it by using an organic solvent such as heptane or hexane when performing rework, and the reworkability is deteriorated. The problem. In addition, when the epoxy resin having a cycloalkane skeleton described in Patent Document 2 is used, the flexibility is deteriorated, and in the composition described in Patent Document 3, yellowing during curing is also feared. Therefore, Patent Documents 1 to 3 cannot be satisfied.

Prior technical literature Patent literature

[Patent Document 1] International Publication No. 2010/027041

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-248387

[Patent Document 3] Japanese Patent Publication No. 2011-511851

An object of the present invention is to provide an ultraviolet curable resin composition which is excellent in curability, small in shrinkage upon hardening, transparency of a cured product, and a substrate. An optically transparent adhesive agent which is excellent in adhesiveness and flexibility, and an optical member obtained by using the ultraviolet curable resin composition, for example, a touch panel or a display device, and an electronic device in which the same is incorporated.

In order to solve the above problems, the inventors of the present invention have repeatedly conducted intensive studies and found that an ultraviolet curable resin comprising a compound having the structure of the following formula (1), a (meth) acrylate compound, and a photopolymerization initiator is used. The present invention has been accomplished by achieving the above problems.

That is, the present invention relates to the following (1) to (22).

(1) An ultraviolet curable resin composition containing a compound (A) having a structure represented by the following formula (1), a (meth) acrylate compound (B), and a photopolymerization initiator ( C),

Wherein n is an integer of 0 to 40, m is an integer of 10 to 80, and R ¹ and R ² each may be the same or different, and are an alkyl group having 1 to 18 carbon atoms and an alkenyl group having 2 to 18 carbon atoms; An alkynyl group having 2 to 18 carbon atoms or an aryl group having 5 to 18 carbon atoms.

(2) The ultraviolet curable resin composition according to the above (1), wherein R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 3 to 10 carbon atoms.

(3) The ultraviolet curable resin composition according to (1) above, wherein the compound (A) is selected from the group consisting of polypropylene glycol diallyl ether, polypropylene glycol dimethyl ether, polypropylene glycol dibutyl ether, and polypropylene glycol. Propyl butyl ether, polyethylene glycol-polypropylene glycol diallyl ether, At least one of the group consisting of polyethylene glycol-polypropylene glycol dibutyl ether and polyethylene glycol-polypropylene glycol allyl butyl ether.

(4) The ultraviolet curable resin composition according to any one of the above items (1) to (3), which comprises a (meth) acrylate compound (B') having one (meth) acrylonitrile group or A (meth) acrylate compound having two (meth) acrylonitrile groups is used as the (meth) acrylate compound (B).

(5) The ultraviolet curable resin composition according to any one of the above items (1) to (4), which contains a urethane (meth) acrylate (D) as a (meth) acrylate compound (B) ).

(6) The ultraviolet curable resin composition according to any one of the above items (1) to (5), which contains a urethane (meth) acrylate (D) and has one (meth) acrylonitrile The (meth) acrylate compound (B') is used as the (meth) acrylate compound (B).

The ultraviolet curable resin composition according to any one of the above items (1) to (6), wherein the content of the aforementioned compound (A) is from 10 to 60% by weight, and the content of the photopolymerization initiator (C) It is 0.2 to 5% by weight, and the remainder is a (meth) acrylate compound (B).

(8) The ultraviolet curable resin composition according to the above (6), which contains a polymer selected from the group consisting of 10 to 30 alkyl esters of (meth)acrylic acid; polyalkylene glycol diol (meth) acrylate; Propylene oxide modified decyl phenyl (meth) acrylate; 1 to 5 alkyl (meth) acrylate having a hydroxyl group; acryloyl morpholine; tetrahydrofurfuryl (meth) acrylate and (methyl) At least one of the group consisting of dicyclopentenyloxyethyl acrylate is a (meth) acrylate compound (B') having one (meth) acrylonitrile group.

(9) The ultraviolet curable resin composition according to any one of the above items (4) to (8), which contains a selected from the group consisting of lauryl (meth)acrylate, 2-ethylhexyl carbitol acrylate, and propylene oxime Base morpholine, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isostearyl (meth) acrylate, propylene oxide modified (meth) phenyl methacrylate , At least one of a group consisting of dicyclopentenyloxyethyl (meth)acrylate, isostearyl (meth)acrylate, and 2-decyltetradecyl (meth)acrylate has one (A) (meth) acrylate (meth) acrylate compound (B').

(10) The ultraviolet curable resin composition according to any one of the above items (4) to (9), which is selected from the group consisting of polypropylene glycol diallyl ether, polypropylene glycol dimethyl ether, and polypropylene glycol dibutyl ether. , polypropylene glycol allyl butyl ether, polyethylene glycol-polypropylene glycol diallyl ether, polyethylene glycol-polypropylene glycol dibutyl ether and polyethylene glycol-polypropylene glycol allyl butyl ether At least one of the group is as the above compound (A), and contains a group selected from the group consisting of lauryl (meth)acrylate, 2-ethylhexyl carbitol acrylate, acryloyl morpholine, 4-hydroxybutyl (meth) acrylate Ester, tetrahydrofurfuryl (meth) acrylate, isostearyl (meth) acrylate, propylene oxide modified (meth) phenyl methacrylate, dicyclopentenyl (meth) acrylate At least one of the group consisting of an ester, isostearyl (meth)acrylate, and 2-decyltetradecyl (meth)acrylate as a (meth) acrylate having one (meth) acrylonitrile group Compound (B').

The ultraviolet curable resin composition according to any one of the above items (1) to (10), which comprises a (meth) acrylate compound (B') having one (meth) acrylonitrile group and A urethane (meth) acrylate (D), and m in the formula (1) is an integer of 10 to 50.

(12) The ultraviolet curable resin composition according to any one of the above items (1) to (11), wherein the urethane (meth) acrylate (D) polyether polyol, the polyisocyanate, and the A reactant of a hydroxyl (meth) acrylate.

(A) The ultraviolet curable resin composition according to any one of the above items (1) to (12), which contains a urethane (meth) acrylate (D) and has one (meth) propylene hydride. The (meth) acrylate compound (B') as the (meth) acrylate compound (B), and contains 1 to 60% by weight of the above compound (A), 20 to the total amount of the composition 80% by weight of urethane (meth) acrylate (D), 10 to 70% by weight of (meth) acrylate compound (B') having 1 (meth) acrylonitrile group, and 0.2 to 5 wt% of a photopolymerization initiator (C).

(14) The ultraviolet curable resin composition according to the above item (13), wherein the (meth) acrylate group (B') having one (meth) acrylonitrile group and the total amount of the resin composition The total content of the urethane (meth) acrylate (D) is at least 40% by weight.

(15) The ultraviolet curable resin composition according to any one of the items (1) to (14), wherein the curing shrinkage ratio is 3.0% or less.

The ultraviolet curable resin composition according to any one of the above (6), wherein (i) the above compound (A) is selected from the group consisting of polypropylene glycol diallyl ether and polypropylene glycol dimethyl glycol. Ether, polypropylene glycol dibutyl ether, polypropylene glycol allyl butyl ether, polyethylene glycol-polypropylene glycol diallyl ether, polyethylene glycol-polypropylene glycol dibutyl ether, and polypropylene glycol-polypropylene glycol allyl At least one group consisting of butyl ethers, (ii) containing a group selected from the group consisting of lauryl (meth)acrylate, 2-ethylhexyl carbitol acrylate, acryloyl morpholine, (meth)acrylic acid 4- Hydroxybutyl ester, tetrahydrofurfuryl (meth) acrylate, isostearyl (meth) acrylate, propylene oxide modified (meth) phenyl methacrylate, dicyclopentene (meth) acrylate At least one group consisting of ethyl ethyl ester, isostearyl (meth)acrylate, and 2-decyltetradecyl (meth)acrylate as (meth) having one (meth) acrylonitrile group An acrylate compound (B'), (iii) a urethane (meth) acrylate (D)-based polyether polyol, a reaction product with a polyisocyanate and a hydroxyl group-containing (meth) acrylate.

(A) The ultraviolet curable resin composition of any one of the above (6) to (16), wherein the urethane (meth) acrylate (D) has a weight average molecular weight of 7,000 to 7,000 25,000.

(18) (6) of an ultraviolet curable resin composition to (17) described in any above wherein compound (A) based formula R (1) in the ¹ and R ² each may be the same as described above, can also be different R ¹ and R ² are a C 1 to 10 alkyl group or a C 3 to 10 alkenyl group compound, a urethane (meth) acrylate (D) polyether polyol, and a polyisocyanate. a hydroxyl group-containing (meth) acrylate reactant having a weight average molecular weight of 7,000 to 25,000 and containing a urethane (meth) acrylate (D) and having one (meth) propylene hydride The (meth) acrylate compound (B') is used as the (meth) acrylate compound (B), and further contains 1 to 60% by weight of the above compound (A), 20 to the total amount of the composition. 80% by weight of urethane (meth) acrylate (D), 10 to 70% by weight of (meth) acrylate compound (B') having 1 (meth) acrylonitrile group, and 0.2 to 5% by weight of the photopolymerization initiator (C), and having one (meth) acrylonitrile-based (meth) acrylate compound (B') and an urethane (relative to the total amount of the composition) The total content of methyl acrylate (D) is 40 to 90 weight%.

(19) An optical member which is a cured layer of the ultraviolet curable resin composition according to any one of the above (1) to (18), followed by at least two optical substrates.

(20) A cured product obtained by irradiating an active energy ray to an ultraviolet curable resin composition according to any one of the above (1) to (18).

(21) A touch panel comprising the cured layer of the ultraviolet curable resin composition according to any one of the above (1) to (18), followed by at least two optical substrates.

(22) A display device having a protective optical substrate or a touch panel, which is a cured layer of the ultraviolet curable resin composition according to any one of the above (1) to (18), followed by Protective optical substrate or touch panel and display device.

According to the present invention, it is possible to provide an ultraviolet curable resin composition and an optical member obtained by laminating a cured layer of the resin composition, wherein the ultraviolet curable resin composition can be used as a curable property and hardened. An optically clear adhesive which is small in shrinkage, transparent to cured material, excellent in adhesion to a substrate, and excellent in flexibility.

The ultraviolet curable resin composition of the present invention (hereinafter referred to as the resin composition of the present invention or the composition of the present invention) contains the compound (A) having a structure represented by the formula (1) and (meth) Acrylate compound (B) and photopolymerization initiator (C).

The resin composition of the present invention contains the compound (A) having a structure represented by the following formula (1).

Wherein n represents an integer of 0 to 40, m represents an integer of 10 to 80, and R ¹ and R ² each may be the same or different, and R ¹ and R ² are an alkyl group having 1 to 18 carbon atoms and a carbon number of 2 to An alkenyl group of 18, an alkynyl group having 2 to 18 carbon atoms, and an aryl group having 5 to 18 carbon atoms.

In the formula (1), as a preferred aspect, n may be 0, or n may be 5 to 40, preferably 10 to 30. The m system is preferably from 20 to 80, more preferably from 30 to 70. Here, from the viewpoint of imparting adhesion to the substrate and improving compatibility with the urethane (meth) acrylate, m/(m+n) is preferably from 0.2 to 1, more preferably It is 0.4 to 1.

Further, R ¹ and R ^{2 are} preferably each independently an alkyl group having 1 to 18 carbon atoms or an alkenyl group having 2 to 18 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms or a carbon number of 3 to 10 carbon atoms. Alkenyl. More preferably, R ¹ and R ² are each independently an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 3 to 5 carbon atoms. The most preferred pattern is n to 5 to 40, m is 10 to 40, any of R ¹ and R ² is butyl and the other is allyl, or n is 0, and m is 20 to 80. R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms, preferably a methyl group.

The compound (A) having a structure represented by the formula (1) can impart flexibility to the adhesive. The compound (A) having a structure represented by the formula (1) can be used without limitation as long as it is an integer of 0 to 40 and m is in the range of 10 to 80.

Specific examples of the compound (A) include polypropylene glycol diallyl ether, polypropylene glycol dimethyl ether, polypropylene glycol dibutyl ether, polypropylene glycol allyl butyl ether, and polyethylene glycol- Polypropylene glycol diallyl ether, polyethylene glycol-polypropylene glycol dibutyl ether, polyethylene glycol-polypropylene glycol allyl butyl ether.

This compound (A) can also be easily obtained as a commercial item. For example, polyethylene glycol-polypropylene glycol allyl butyl ether (UNISAFE PKA-5015, PKA-5016, PKA-5017, manufactured by Nippon Oil Co., Ltd.), polypropylene glycol diallyl ether (UNISAFE PKA-5018) The method of the company made by Nippon Oil Co., Ltd.). In particular, polyethylene glycol-polypropylene glycol allyl butyl ether (PKA-5016, PKA-5017, manufactured by Nippon Oil Co., Ltd.) is excellent in compatibility with urethane (meth) acrylate. It is better.

The compound (A) has a number average molecular weight of usually from 100 to 10,000, preferably from 500 to 8,000, more preferably from 1,000 to 8,000, particularly preferably from 1,500 to 5,000. Since the number average molecular weight is too small, the flexibility and the adhesion may be deteriorated, and when it is too large, the compatibility may be deteriorated.

The weight ratio of the compound (A) in the photocurable transparent adhesive composition of the present invention is preferably from about 1% by weight to about 60% by weight, particularly preferably from about 10% by weight to about 50% by weight. When it is too small, the softness is deteriorated, and when it is too much, the hardenability is deteriorated.

The composition of the present invention contains a (meth) acrylate compound (B) (hereinafter also referred to as a component (B)). Any (meth) acrylate compound is not particularly limited and can be used as long as it is well known.

The (meth) acrylate compound (B) is preferably a (meth) acrylate compound having 1 or 2 (meth) acrylonitrile groups, and the component (B) is 100 The case of % by weight is preferred.

In particular, as the component (B), the (meth) acrylate compound (B') having one (meth) acrylonitrile group (hereinafter also referred to as (B') component) and the uric acid which will be described later are used. The ester (meth) acrylate (D) (hereinafter also referred to as (D) component) is preferred. Other polyfunctional (meth) acrylates can also be used. In a preferred embodiment, the total content of the (B') component and the (D) component is 50 to 100% by weight based on the total amount of the (meth) acrylate compound (B) (hereinafter, unless otherwise specified) % means % by weight, preferably 70 to 100%, more preferably 90 to 100%. The remainder is the other (meth) acrylate compound. It is preferable that the component (B) is composed of the above two (in the case where the total of the components (B) is 100%).

In the present specification, the term "(meth)acrylate" means either or both of methacrylate and acrylate.

As the (meth) acrylate compound (B) contained in the resin composition of the present invention, a (meth) acrylate compound (B') having one (meth) acrylonitrile group is suitably used.

Specifically, isooctyl (meth)acrylate and isoamyl (meth)acrylate can be mentioned. Ester, lauryl (meth)acrylate, isodecyl (meth)acrylate, stearyl (meth)acrylate, cetyl (meth)acrylate, isomyristyl (meth)acrylate, (methyl) a (meth)acrylic acid having a carbon number of 5 to 30 alkyl esters such as tridecyl acrylate or 2-decyltetradecyl (meth) acrylate, preferably 10 to 30 alkyl (meth) acrylate; Benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, acryloylmorpholine, phenylglycidyl (meth)acrylate, tricyclodecyl (meth)acrylate, acrylic acid Cyclopentenyl ester, dicyclopentenyloxyethyl (meth)acrylate, isodecyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 1-adamantyl acrylate, 2-methyl acrylate -2-adamantyl ester, 2-ethyl-2-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentadienyloxyethyl (meth)acrylate, etc. a acrylate, preferably a 3 to 10 membered ring having 3 to 10 carbon atoms and which may contain either or both of an oxygen atom or a nitrogen atom, preferably a 3 to 10 membered aliphatic ring or Benzyl (meth)acrylic acid Ester; 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. 1 to 5 alkyl (meth)acrylate having a hydroxyl group; ethoxy diethylene glycol (methyl) Acrylate, 2-ethylhexyl diethylene glycol (meth) acrylate (alias 2-ethylhexyl carbitol (meth) acrylate), polypropylene glycol (meth) acrylate, polypropylene oxide Modified polyalkylene glycol (meth) acrylate such as mercaptophenyl (meth) acrylate or polyalkylene glycol modified (meth) methacrylate, preferably poly C2 to C4 Alkyl diol (meth) acrylate or polypropylene oxide modified (meth) methacrylate; ethylene oxide modified phenoxylated phosphoric acid (meth) acrylate, ethylene oxide Ethylene oxide modified-phenoxylated or C3 to C10 alkoxy groups such as modified butoxylated phosphoric acid (meth) acrylate and ethylene oxide modified octoxylated phosphoric acid (meth) acrylate - Phosphate (meth) acrylate and the like.

Preferred examples of the (B') component include a carbon number of (meth)acrylic acid To 30 alkyl esters; poly C2 to C4 alkylene glycol (meth) acrylate; polypropylene oxide modified (meth) methacrylate; carbonic acid (meth) acrylic carbon number 1 to 5 Alkyl ester; propylene decylmorpholine; tetrahydrofurfuryl (meth) acrylate or / and dicyclopentenyloxyethyl (meth) acrylate.

In particular, it is a 10 to 30 alkyl ester of (meth)acrylic acid, 2-ethylhexyl carbitol acrylate, acryloyl morpholine, 4-hydroxybutyl (meth) acrylate, (meth)acrylic acid Hydroquinone ester, dicyclopentenyloxyethyl (meth)acrylate, propylene oxide modified (meth) methacrylate (for example, propylene oxide 2 to 10 mole modified (meth)acrylic acid Mercaptophenyl ester) is preferred. In particular, from the viewpoint of flexibility of the resin, 10 to 30 alkyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and modified by polypropylene oxide (methyl) Mercaptophenyl acrylate (for example, 2 to 10 moles of propylene oxide (meth) phenyl methacrylate) and tetrahydrofurfuryl (meth) acrylate are preferred.

On the other hand, from the viewpoint of improving the adhesion to the glass, it is preferred to use a 1 to 5 alkyl (meth) acrylate having a hydroxyl group, an acryloyl morpholine, and an acryloyl morpholine. Very good.

It is preferred that the component (B') is a preferred compound as described above and is composed entirely of (100%).

The preferred compound is a 12 to 25 alkyl (meth) acrylate having a carbon number of 10 to 30 alkyl (meth) acrylate, specifically from the above-exemplified lauryl (meth) acrylate to (methyl). An exemplary compound up to 2-decyltetradecyl acrylate is preferably lauryl (meth)acrylate and 2-decyltetradecyl (meth)acrylate.

The resin composition of the present invention can contain a polyfunctional (meth) acrylate compound in a range that does not impair the characteristics of the present invention. For example, tricyclodecane dimethylol (meth)acrylate, two Alkanediol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, alkylene oxide modified bisphenol A type di(methyl) Acrylate, caprolactone modified hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate and ethylene oxide modified di(meth)acrylate, trimethylolpropane tri(methyl) Trimethylol C2 to C10 alkyl tri(meth)acrylate such as acrylate or trimethylol octane tri(meth)acrylate, trimethylolpropane polyethoxy tri(meth)acrylate, a trimethylol C2 to C10 alkoxy alkoxy group such as trimethylolpropane polypropoxy tri(meth)acrylate or trimethylolpropane polyethoxypolypropoxy tri(meth)acrylate Methyl) acrylate, gin[(meth) propylene methoxyethyl] isocyanurate, neopentyl alcohol tri(meth) acrylate, ethylene oxide modified trimethylolpropane Ethylene oxide modified trimethylolpropane tri(meth)acrylate such as (meth) acrylate or propylene oxide modified trimethylolpropane tri(meth)acrylate, neopentyl alcohol polyethoxylate Tetrakis(meth)acrylate, Pentaerythritol polypropoxy tetra (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (methyl) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

In the present invention, in order to suppress hardening shrinkage, it is preferred to use a 1 or 2 functional (meth) acrylate.

In order to make the hardening shrinkage small, the resin composition of the present invention is a component of the component (B) other than the urethane (meth) acrylate (D), and the total of the component (B) other than the component (D). The amount of the component (B') is at least 50% by weight, preferably at least 70% by weight, preferably at least 80% by weight, more preferably at least 90% by weight, most preferably 100% by weight.

In the resin composition of the present invention, the component (B) other than the urethane (meth) acrylate (D) may be used alone or in combination of two at any ratio. Use it up. The weight ratio of the component (B) other than the urethane (meth) acrylate (D) in the photocurable transparent adhesive composition of the present invention is usually 5 to 70% by weight, preferably 5 Up to 50% by weight, more preferably 10 to 40%.

It is particularly preferable that the (meth) acrylate compound (B') having one (meth) acrylonitrile group has the above content.

When the content of the above component (B) other than the urethane (meth) acrylate (D) is too small, the curing property is insufficient, and when it is too large, the shrinkage becomes large.

The urethane (meth) acrylate (D) which can be contained in the composition of the present invention can be used as long as it is a urethane (meth) acrylate. A urethane (meth) acrylate obtained by reacting a polyol, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate is preferred. More preferred is a polyether urethane (meth) acrylate having a polyether structure.

Examples of the polyhydric alcohol used for the synthesis of the urethane (meth) acrylate include neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, and 1, 4-butanediol, 1,6-hexanediol and other alkylene glycols having a carbon number of 1 to 10, triols such as trimethylolpropane and neopentyl alcohol, tricyclodecane dimethylol, double An alcohol having a cyclic skeleton such as [hydroxymethyl]-cyclohexane, or the like, by such a polyol and a polybasic acid (for example, succinic acid, citric acid, hexahydrophthalic anhydride, citric acid, adipic acid, hydrazine a polyester polyol obtained by the reaction of a diacid, a tetrahydrophthalic anhydride or the like, a caprolactone obtained by reacting a polyhydric alcohol with ε-caprolactone, or a polycarbonate polyol (for example, by 1,6- Polyethylene glycol, polypropylene glycol, polytetramethylene glycol A, etc.). From the viewpoint of the flexibility of the resin after curing, a polyether polyol is preferred. From the viewpoint of compatibility with the component (A), polypropylene glycol is preferred, and from the viewpoint of adhesion to the substrate, Polypropylene glycol having a molecular weight of 2,000 or more is particularly preferred.

Examples of the organic polyisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate or dicyclopentyl diisocyanate. Wait.

From the viewpoint of transparency, isophorone diisocyanate or toluene diisocyanate is preferred.

Further, as the hydroxyl group-containing (meth) acrylate, for example, (meth)acrylic acid hydroxy group C2 such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate or hydroxybutyl (meth)acrylate can be used. To C4 alkyl ester, dimethylolcyclohexyl (meth) acrylate, hydroxy caprolactone (meth) acrylate, and the like.

The above reaction is carried out, for example, in the following manner. That is, the organic polyisocyanate is mixed in an amount of from 1.1 to 2.0 equivalents, more preferably from 1.1 to 1.5 equivalents, per 1 equivalent of the hydroxyl group in the polyol, and the reaction temperature is preferably 70 to 70. The reaction was carried out at 90 ° C to synthesize a urethane oligomer. Next, the isocyanate group of the urethane oligomer has a hydroxyl group (meth) acrylate compound mixed so that its hydroxyl group is preferably from 1 to 1.5 equivalents, and is reacted at 70 to 90 ° C. A target urethane (meth) acrylate can be obtained.

The weight average molecular weight of the urethane (meth) acrylate (D) is preferably from 7,000 to 25,000, more preferably from 10,000 to 20,000. When the weight average molecular weight is too small, the shrinkage becomes large, and when the weight average molecular weight is too large, the hardenability becomes insufficient.

In the resin composition of the present invention, the component (D) can be used alone or in combination of two or more kinds in any ratio. The weight ratio of the component (D) in the photocurable transparent adhesive composition of the present invention is usually from 20 to 80% by weight, preferably from 25 to 50% by weight.

In the resin composition of the present invention, the total content of the component (D) and the (meth) acrylate compound (B') having one (meth) acrylonitrile group is compared with the total amount of the resin composition. The amount is preferably at least 40% by weight, preferably at least 50% by weight.

The resin composition of the present invention can contain a (meth) acrylate oligomer (B) having a polyisoprene or/and a polybutadiene skeleton as a (meth) acrylate compound (B). The (meth) acrylate oligomer having a polyisoprene or a polybutadiene skeleton is not particularly limited and can be used as long as it is well known.

As the above (meth) acrylate oligomer having a polyisoprene or/and a polybutadiene skeleton, (a) first synthesis of an isoprene polymer, a butadiene polymer or the like can be suitably employed. Copolymer, and secondly, reacting the polymer with an unsaturated acid anhydride, and then, by reacting a part or all of the obtained polymer with a hydroxy (meth) acrylate compound a polymer or (b) an oligomer obtained by reacting a hydroxyl-terminated isoprene polymer, a hydroxyl-terminated butadiene polymer, or a copolymer of the same with an unsaturated carboxylic acid or a derivative thereof.

First, for (a) first synthesizing an isoprene polymer, a butadiene polymer or the like, and secondly, reacting the polymers with an unsaturated acid anhydride, followed by polymerization The oligomer obtained by reacting a part or all of the substance with a hydroxy (meth) acrylate compound will be described.

As the isoprene polymer or the butadiene polymer, an isoprene polymer or a butadiene polymer obtained by separately polymerizing one type of isoprene and/or butadiene can be used. An isoprene-butadiene copolymer obtained by copolymerizing a mixture of isoprene and butadiene may also be used. Hereinafter, these are collectively referred to simply as polymers for oligomers.

As a method of polymerizing it, by using isoprene and/or butadiene, An alkyl lithium such as a lithium base, an ethyl lithium, a second butyl lithium, a n-butyl lithium or a pentyl lithium, or a sodium naphthalene complex as an initiator, can be obtained by anionic polymerization, and can also be obtained by using benzoyl peroxide. An azobisnitrile compound such as a hydrazine or a azobisisobutyronitrile such as acetamidine is produced as a starter by radical polymerization.

Further, the polymerization reaction can be carried out by reacting at -100 ° C to 200 ° C for 0.5 to 100 hours in the presence of a solvent such as hexane, heptane, toluene or xylene.

The number average molecular weight of the polymer for oligomers used in the present invention is usually from 2,000 to 100,000, more preferably from 5,000 to 50,000, and particularly preferably from 20,000 to 50,000, from the viewpoint of imparting flexibility.

Next, the oligomer polymer obtained by the above method is reacted with an unsaturated acid anhydride. The reaction can be carried out, for example, in the presence of a solvent which is inert to the reaction, such as a solvent such as hexane, heptane, toluene or xylene, or a solvent which is inert to the reaction, in the absence of a solvent. The reaction is carried out at 300 ° C for 0.5 to 100 hours.

As the unsaturated acid anhydride, for example, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride or the like can be used.

The amount of the acid anhydride to be used is usually preferably in the range of 0.1 to 200 parts by weight, based on 100 parts by weight of the polymer for oligomers, and preferably in the range of 0.1 to 100 parts by weight.

The addition of the reaction of the acid anhydride group to the polymer is carried out under the above conditions, and usually, the number of additions per molecule is in the range of 1 to 30, preferably in the range of 2 to 20. .

Next, by reacting a part or all of the acid anhydride group introduced by the above polymer with a hydroxy (meth) acrylate compound, polyisoprene can be obtained. a (meth) acrylate oligomer of a skeleton, a (meth) acrylate oligomer having a polybutadiene skeleton, or a (meth) group having a polyisoprene-polybutadiene copolymer matrix Acrylate oligomer.

The reaction system can be mixed in a solvent such as hexane or heptane or in a solvent-free manner, usually by mixing the hydroxy (meth) acrylate compound so that its hydroxyl group is preferably from 1 to 1.5 equivalents, and at 20 to 200 ° C. The reaction is obtained in 0.1 to 100 hours.

As the hydroxy (meth) acrylate compound, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate or the like (meth) acrylate C 2 to C 4 can be used. An alkyl ester, dimethylolcyclohexyl mono(meth)acrylate, hydroxycaprolactone (meth) acrylate, or the like.

Next, a method for obtaining (b) an oligomer obtained by reacting a hydroxyl group-containing isoprene polymer, a butadiene polymer or the above-mentioned copolymer with an unsaturated carboxylic acid or a derivative thereof will be described. .

By reacting a part or all of a hydroxyl-terminated isoprene polymer, a hydroxyl-terminated butadiene polymer, or a hydroxyl-terminated isoprene-butadiene copolymer with an unsaturated carboxylic acid or a derivative thereof, Obtaining a (meth) acrylate oligomer having a polyisoprene skeleton, a (meth) acrylate oligomer having a polybutadiene skeleton, or having an isoprene-butadiene copolymer skeleton (meth) acrylate oligomer.

The reaction system can be obtained by reacting with an unsaturated carboxylic acid or a derivative thereof at 20 to 200 ° C for 0.1 to 100 hours under a solvent such as hexane or heptane or without a solvent.

As the unsaturated carboxylic acid or a derivative thereof, for example, acrylic acid, methacrylic acid, maleic acid, α-ethylacrylic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrofurfuric acid, or the like can be used. An unsaturated carboxylic acid such as methyltetrahydrofurfuric acid, or a derivative such as an acid halide, a guanamine, a quinone imine, an anhydride or an ester.

As a specific example of the compound obtained in this way, UC-203 (a maleate anhydride of an isoprene polymer and an esterified oligomer of 2-hydroxyethyl methacrylate) can be exemplified by KURARAY Co., Ltd. ), NISSO-PB TE-2000 (two-terminal methacrylate-modified butadiene-based oligomer) manufactured by Japan Soda Co., Ltd., and the like.

In the resin composition of the present invention, the (meth) acrylate oligomer having a polyisoprene or a polybutadiene skeleton can be used in combination of two or more kinds in any ratio. The weight ratio of the (meth) acrylate oligomer having a polyisoprene or polybutadiene skeleton in the ultraviolet curable adhesive of the present invention is usually 5 to 90% by weight, and is 20 to 80% by weight. Preferably, it is preferably from 25 to 50% by weight.

The (meth) acrylate oligomer may be used in combination with the above urethane (meth) acrylate (D), and may be used in place of the urethane (meth) acrylate (D), as the case may be.

The photopolymerization initiator (C) to be contained in the composition of the present invention is not particularly limited, and examples thereof include 1-hydroxycyclohexyl phenyl ketone (IRGACURE (registered trademark, the same applies 184); manufactured by BASF). , 2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol oligomer (ESACURE ONE; manufactured by Lamberti), 1-[4-(2-hydroxyethoxy) -Phenyl]-2-hydroxy-2-methyl-1-propan-1-one (IRGACURE-2959; manufactured by BASF), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl) -Methyl propyl)-benzyl]-phenyl}-2-methyl-propan-1-one (IRGACURE-127; manufactured by BASF), 2,2-dimethoxy-2-phenyl phenyl Ketone (IRGACURE-651; manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (DAROCUR (registered trademark, the same below) 1173; manufactured by BASF), 2-methyl-1 -[4-(Methylthio)phenyl]-2-(N-morpholinyl)propan-1-one (IRGACURE-907; manufactured by BASF), oxy-phenyl-acetic acid 2-[2- side oxygen Mixture of benzyl-2-phenyl-ethoxycarbonyl-ethoxy]-ethyl ester with oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester (IRGACURE-754; BASF , 2-Benzyl-2-dimethylamino-1-(4-(N-morpholinyl)phenyl)-butan-1-one, 2-chlorothioxanthone, 2,4- Dimethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, double (2,4 , 6-trimethylbenzimidyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide, and the like. From the viewpoint of transparency, 1-hydroxycyclohexyl phenyl ketone (IRGACURE-184; manufactured by BASF), 2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol Polymer (ESACURE KIP-150; manufactured by Lamberti), methyl phenylglyoxylate (DAROCUR MBF; manufactured by BASF), oxy-phenyl-acetic acid 2-[2- oxo-2-phenyl-ethyl A mixture of methoxy-ethoxy]-ethyl ester and oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester (IRGACURE-754; manufactured by BASF) is preferred. Further, from the viewpoint of improving the internal hardenability of the adhesive, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide (SPEEDCURE TPO; manufactured by LAMBSON Co., Ltd.) is preferred.

In the resin composition of the present invention, the components (C) can be used singly or in combination of two or more kinds in any ratio. The weight ratio of the component (C) in the photocurable transparent adhesive composition of the present invention is usually 0.2 to 5% by weight, preferably 2 to 5% by weight.

Here, in order to improve the transparency, when only 2,4,6-trimethylbenzimidyldiphenylphosphine oxide is used as a photopolymerization initiator, the photocurable transparent adhesive composition of the present invention is used. The weight ratio is usually from 0.3 to 1.0% by weight, particularly preferably from 0.3 to 0.8% by weight.

In addition, as the other components other than the above (A), (B), and (C), an amine or the like which can be used as a photopolymerization initiation aid can be used in combination with the above-mentioned photopolymerization initiator. Examples of the amines and the like which can be used include 2-dimethylaminoethyl benzoate, dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate or p-dimethylaminobenzoic acid. Isoamyl acid and the like. When the photopolymerization initiation aid such as the amine is used, the content of the resin composition for subsequent use of the present invention is usually from 0 to 5% by weight, and is from 0.005 to 5% by weight, preferably from 0.01 to 3% by weight, based on the addition.

Further, as other components, an oxetane compound can be contained as needed. The oxetane compound which can be used is not particularly limited as long as it is well known.

Specific examples of the oxetane compound include 4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene and 4-bis[(3-A). 3-oxobutanealkylmethoxy)methyl]benzene, 3-methyl-3-epoxypropyloxetane, 3-ethyl-3-hydroxymethyloxetane Alkane, 3-methyl-3-hydroxymethyloxetane, bis(1-ethyl(3-oxetanyl))methyl ether, 3-ethyl-3-(phenoxy) Methyl)oxetane, 3-(cyclohexyloxy)methyl-3-ethyloxetane, benzoyldioxetane, phenol novolac oxetane Wait. The oxetane compound which is usually used is not limited to these. These systems may be used alone or in combination of two or more.

In the ultraviolet curable adhesive of the present invention, the oxetane compounds can be used singly or in combination of two or more kinds in any ratio. The weight ratio of the oxetane compound in the photocurable adhesive composition of the present invention is usually from 0 to 70% by weight, and is from 5 to 70% by weight, preferably from 5 to 50% by weight, based on the addition.

Further, the composition of the present invention can use epoxy (meth) acrylate as another component without impairing the characteristics of the present invention. The epoxy (meth) acrylate has a function of improving the hardenability and improving the hardness and curing speed of the cured product. Further, the epoxy (meth) acrylate can be used as long as it is obtained by reacting a epoxidized propyl ether epoxy compound with (meth)acrylic acid, and is suitably used as a product. Epoxy (meth) acrylate epoxy propyl ether type epoxy compound, which may be bisphenol A or a dialkyl propyl ether of an alkylene oxide adduct thereof, bisphenol F or Is a diepoxypropyl ether of an alkylene oxide adduct, hydrogenated bisphenol A or a dialkyl epoxide of an alkylene oxide adduct thereof, hydrogenated bisphenol F or an alkylene oxide adduct thereof Diepoxypropyl ether, ethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, butanediol diepoxypropyl ether, hexanediol Di-epoxypropyl ether, cyclohexane dimethanol diepoxypropyl ether, polypropylene glycol diepoxypropyl ether, and the like.

The epoxy (meth) acrylate can be obtained by reacting these epoxidized propyl ether type epoxy compounds with (meth)acrylic acid under the following conditions.

The (meth)acrylic acid is reacted at a ratio of 0.9 to 1.5 mol, preferably 0.95 to 1.1 mol, relative to 1 equivalent of the epoxy group of the epoxy propyl ether type epoxy compound. The reaction temperature is preferably from 80 to 120 ° C, and the reaction time is from about 10 to 35 hours. In order to promote the reaction, for example, a catalyst such as triphenylphosphine, TAP, triethanolamine or tetraethylammonium chloride is preferably used. Further, in the reaction, in order to prevent polymerization, for example, p-methoxyphenol, methylhydroquinone or the like can be used as a polymerization inhibitor.

The epoxy (meth) acrylate which can be suitably used in the present invention is a bisphenol A type epoxy (meth) acrylate obtained from a bisphenol A type epoxy compound. In the present invention, the weight average molecular weight of the epoxy (meth) acrylate (G) is preferably from 500 to 10,000.

In the resin composition of the present invention, these epoxy (meth) acrylates can be used singly or in combination of two or more kinds in any ratio. The weight ratio of the epoxy (meth) acrylate in the photocurable transparent adhesive composition of the present invention is usually from 0 to 90% by weight, and is from 5 to 90% by weight, preferably from 10 to 85% by weight, based on the addition. .

In the resin composition of the present invention, as the other component, a softening component can be used as needed. Specific examples of the softening component that can be used include a (meth) acrylate oligomer having a polyisoprene or a polybutadiene skeleton or an ester thereof. Compounds, polymers, oligomers, phthalates, phosphates, glycol esters, aliphatic dibasic acid esters, fatty acid esters, citric acid esters, epoxy plasticizers, castor oil, Terpene-based hydrogenated resin. Examples of the oligomer and the polymer include polyisoprene-based, polybutadiene-based or xylene-based oligomers or polymers.

The weight ratio of such a softening component in the photocurable clear adhesive composition is usually from 10 to 80% by weight, preferably from 10 to 70% by weight.

Further, a (meth)acrylic polymer can be used as the softening component.

The (meth)acrylic polymer may be a polymer obtained by polymerizing an acrylic or methacrylic monomer as a raw material, or a copolymerization of a polymerizable monomer other than the monomer with the monomer. The material can be produced by a usual method such as solution polymerization, suspension polymerization, or bulk polymerization.

As a particularly preferable production method, it is preferable to carry out radical polymerization continuously at a high temperature. Specifically, it is manufactured by the following processes. First, a small amount of a polymerization initiator and a trace amount of a solvent are mixed with respect to an acrylic or methacrylic monomer. Then, it is allowed to react at a temperature of 150 ° C or higher for 10 minutes or more under high pressure. Subsequently, it can be obtained by separating the unreacted component and the (meth)acrylic polymer obtained by the reaction using a separator.

Here, when the polymerization initiator is mixed, there is a possibility that the storage stability is deteriorated. Therefore, after the solvent is distilled off, the reaction is carried out, or the (meth)acrylic polymer is separated and obtained, It is preferred to distill off the solvent.

Examples of the acrylic or methacrylic monomer used as a raw material of the (meth)acrylic polymer include (meth)acrylic acid and α-ethylacrylic acid; methyl (meth)acrylate; Methyl) n-propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, dibutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylbutyl (meth)acrylate, 1,3-dimethylbutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (methyl) ) octyl acrylate, 3-ethoxypropyl (meth) acrylate, 3-ethoxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (meth) acrylate 2 -hydroxyethyl ester, hydroxybutyl (meth)acrylate, α-(hydroxymethyl)ethyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, (methyl) An ester-based (meth) acrylate such as phenylethyl acrylate or the like can be used alone or in combination of two or more.

As the other polymerizable monomer which can be copolymerized, a well-known compound having an unsaturated double bond, for example, styrene, 3-nitrostyrene, 4-methoxystyrene, α-methylstyrene, or the like, can be used. Alkyl styrenes such as β-methylstyrene, 2,4-dimethylstyrene, vinyltoluene, α-ethylstyrene, α-butylstyrene, α-hexylstyrene; 4-chloro Halogenated styrenes such as styrene, 3-chlorostyrene, 3-bromostyrene; crotonic acid, α-methyl crotonic acid, α-ethyl crotonic acid, isocrotonic acid, maleic acid, antibutene A carboxylic acid having an unsaturated double bond such as diacid, itaconic acid, citraconic acid, mesaconic acid or glutaconic acid.

Among these, from the viewpoint of the solubility of other components of the composition and the adhesion of the cured product, methyl methacrylate or (meth) is used as the acrylic or methacrylic monomer. C1-C10 alkyl (meth)acrylate such as n-butyl acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (methyl) A C1 to C10 alkyl (meth)acrylate having a hydroxyl group such as hydroxybutyl acrylate is preferred, and as the other polymerizable monomer, styrene or the like is preferred.

In the present invention, the weight average molecular weight of the (meth)acrylic polymer is 1,500 to 30,000, preferably 3,000 to 20,000, particularly preferably 5,000 to 15,000. When the weight average molecular weight is too small, the adhesion of the cured product tends to deteriorate, and the other side When it is too large, it is not good because it is not easily dissolved in other monomers or it is cloudy.

The (meth)acrylic polymer system can be easily obtained by a commercially available product. For example, the "ARUFON series" manufactured by Toagosei Co., Ltd. can be obtained as UP-1170 or UH-2190.

The weight ratio of the (meth)acrylic polymer in the photocurable adhesive composition of the present invention is usually from 20% by weight to 95% by weight, preferably from 50% by weight to 95% by weight, and from 70% by weight to 95% by weight. Approximately 100% is preferred, and 70% to 90% by weight is particularly preferred.

The resin composition of the present invention may further contain an antioxidant, an organic solvent, a decane coupling agent, a polymerization inhibitor, a leveling agent, an antistatic agent, a surface lubricant, a fluorescent whitening agent, a light stabilizer (for example, Additives such as hindered amine compounds and the like, and fillers are used as other components.

Specific examples of the antioxidant include BHT and 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3. , 5-three , pentaerythritol-indole [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-di-extension ethyl bis[3-(3 ,5-di-t-butyl-4-hydroxyphenyl)propionate], triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propane Acid ester], 1,6-hexanediol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], octadecyl-3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamate), 1,3,5-trimethyl-2,4,6-paran (3,5-di-t-butyl-4-hydroxybenzyl)benzene, ginseng (3,5-di-t-butyl 4-hydroxybenzyl)-isocyanate, octylated diphenylamine, 2,4-bis[(octylthio)methyl-O-cresol, isooctyl-3-( 3,5-di-t-butyl-4-hydroxyphenyl)propionate], dibutylhydroxytoluene, and the like.

Specific examples of the organic solvent include alcohols such as methanol, ethanol, and isopropanol, and dimethylhydrazine, dimethyl hydrazine, tetrahydrofuran, and Alkane, toluene, xylene, and the like.

Specific examples of the decane coupling agent include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, and 3-epoxypropoxy group. Propylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, N-(2-aminoethyl)3-aminopropylmethyldimethoxydecane , γ-hydrothiopropyltrimethoxydecane, N-(2-aminoethyl) 3-aminopropylmethyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-hydrogenthio Propyltrimethoxydecane, vinyltrimethoxydecane, N-(2-(vinylbenzylamino)ethyl)3-aminopropyltrimethoxydecane hydrochloride, 3-methylpropionamidine a decane coupling agent such as oxypropyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane or 3-chloropropyltrimethoxydecane; isopropyl (N-ethylamine ethylamino) ) titanate, isopropyl triisostearyl decyl titanate, bis(dioctyl pyrophosphate) oxyacetate, tetraisopropyl bis(dioctyl phosphite) titanate, new A titanium-based coupling agent such as alkoxytris(p-N-(β-aminoethyl)amine phenyl) titanate; Zr-acetamidine acetone salt, Zr-methyl propylene Salt, Zr-propionate, neoalkoxy zirconate, neoalkoxy ginseng zirconate, neoalkoxy(dodecyldecyl)benzenesulfonyl zirconate, new Alkoxy ginseng (ethylenediamine ethyl) zirconate, neoalkoxy (m-aminophenyl) zirconate, zirconium ammonium carbonate, Al-acetonitrile, Al-methacrylate, Zirconium such as AI-propionate or aluminum coupling agent.

Specific examples of the polymerization inhibitor include p-methoxyphenol and methylhydroquinone.

Specific examples of the photostabilizer include 1,2,2,6,6-pentamethyl-4-piperidyl alcohol and 2,2,6,6-tetramethyl-4-piperidinyl. Alcohol, 1,2,2,6,6-pentamethyl-4-piperidyl (meth)acrylate (made by ADEKA Co., LA-82), 肆 (1,2,2,6,6 -pentamethyl-4-piperidinyl-1,2,3,4-butanetetracarboxylate, hydrazine (2,2,6,6-tetramethyl-4-piperidinyl)-1, 2,3,4-butane tetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9 a mixed esterified product of bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, azelaic acid bis(2,2, 6,6-tetramethyl-4-piperidinyl) sebacate, bis(undecyloxy-2,2,6,6-tetramethylpiperidin-4-yl)carboxylate, A 2,2,6,6,-tetramethyl-4-piperidyl acrylate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, double (1 , 2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 4-benzylideneoxy-2,2,6,6-tetramethylpiperidine, 1-[2 -[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoxy]ethyl]-4-[3-(3,5-di-t-butyl-4- Hydroxyphenyl)propoxycarbonyl]-2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, double (1 , 2, 2, 6, 6 -pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, azelaic acid Reaction product of (2,2,6,6-tetramethyl-1(octyloxy)-4-piperidyl) ester, 1,1-dimethylethylhydroperoxide and octane, N ,N',N'',N'''-肆-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)) Amino)-three -2-yl)-4,7-diazadecane-1,10-diamine, dibutylamine. 1,3,5-three . N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl- Polycondensate of 4-piperidinyl)butylamine, poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-three -2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imido]hexamethylene[(2,2,6,6-tetramethyl- 4-piperidinyl)imido)], dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol polymer, 2, 2, 4, 4 -tetramethyl-20-(β-lauroyloxycarbonyl)ethyl-7-oxa-3,20-diazabispiro[5.1.1.1.2]hexadecane-21-one, β- Alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl)-dodecyl ester/tetradecyl ester, N-ethinyl-3-dodecyl-1 -(2,2,6,6-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3,20 -diazaspiro[5,1,11,2]icecane-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazabicyclo -[5,1,11,2]-docosane-20-propanoic acid dodecyl ester/tetradecyl ester, malonic acid [(4-methoxyphenyl)-methylene]-double (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, higher fatty acid ester of 2,2,6,6-tetramethyl-4-piperidinol, 1,3- a hindered amine such as phenyldicarboxyguanamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl) or a diphenylketone compound such as octabenzone ,2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2-hydroxy- 5-methylphenyl)benzotriazole, 2-(2-hydroxy-3-(3,4,5,6-tetrahydroindenylimine-methyl)-5-methylphenyl)benzo Triazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-third pentyl Reaction of phenyl)benzotriazole, methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propanoate with polyethylene glycol a product, a benzotriazole compound such as 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, 2,4-di-t-butylphenyl a benzoate such as -3,5-di-t-butyl-4-hydroxybenzoate, 2-(4,6-diphenyl-1,3,5-three -2-yl)-5-[(hexyl)oxy]phenol, etc. A compound or the like is particularly preferred as a hindered amine compound.

Specific examples of the filler include crystalline cerium oxide, molten cerium oxide, aluminum oxide, zircon, calcium silicate, calcium carbonate, cerium carbide, tantalum nitride, boron nitride, zirconium oxide, and magnesium ruthenate. Powders such as forsterite, steatite, spinel, titania, talc, or the like, or beads obtained by spheroidizing the spheroids.

Since the various additives are optional, they can usually be zero. When various additives are present in the composition, the weight ratio of the various additives in the photocurable transparent adhesive composition is 0.01 to 3% by weight, preferably 0.01 to 1% by weight, preferably 0.02 to 0.5% by weight.

In order to improve the compatibility and the adhesion, the resin composition of the present invention is preferably a combination of components having an acryl skeleton.

Specifically, the compound containing the value of m of the general formula (1) / (the value of m + the value of n) is 0.4 to 1.0, and the resin of the urethane (meth) acrylate obtained from polypropylene glycol The system can be used.

The resin composition of the present invention can be obtained by mixing and dissolving each of the above components at a normal temperature to 80 ° C, and the inclusions can be removed by filtration or the like as necessary. Considering the coatability, the resin composition of the present invention is such that the viscosity at 25 ° C is 300 to 15000 mPa. In the manner of the range of s, it is preferred to appropriately adjust the blending ratio of the components.

The curing shrinkage ratio of the resin composition of the present invention is preferably 3.0% or less, and particularly preferably 2.0% or less. By this, when the ultraviolet curable resin composition is cured, the internal stress accumulated in the cured resin can be reduced, and strain can be effectively prevented from occurring at the interface between the substrate and the layer composed of the cured product of the ultraviolet curable resin composition. .

Further, when the substrate such as glass is too thin, since the hardening shrinkage ratio is large, the warpage at the time of curing becomes large, and the display performance is greatly adversely affected. From this viewpoint, the hardening shrinkage ratio is less good.

The cured product (thickness: 200 μm) of the resin composition of the present invention preferably has an average transmittance of from 90 nm to 800 nm in an amount of 90% or more. When the transmittance is too low, since the light is not easily transmitted, the visibility is lowered when used in a display device.

Further, when the cured product has a high transmittance at 400 to 450 nm, the visibility can be further improved, and the transmittance at 400 to 450 nm is preferably 90% or more. The higher the transmittance, the better, and the upper limit is preferably 100%. In fact, it is below 99%.

The resin composition of the present invention contains a structure having a structure represented by the general formula (1) A compound, a urethane (meth) acrylate, a (meth) acrylate having one (meth) acrylonitrile group, and excellent reworkability.

Usually, in order to perform reworking, after bonding the bonded base material, the adhesive layer is cut into the adhesive layer using a wire, and peeling of the base material and the adhesive layer is performed. In this case, in order to facilitate the peeling, a solvent is used, and in the present invention, since the component is excellent in peeling property, even if an alcohol such as isopropyl alcohol is used as a solvent, peeling can be easily performed.

Hereinafter, preferred aspects of the resin composition of the present invention are exemplified.

(i) an ultraviolet curable resin composition containing the compound (A) of the formula (1), the (meth) acrylate compound (B), and the ultraviolet curable resin composition of the photopolymerization initiator (C) Wherein the compound (A) of the formula (1) has a molecular weight of from 100 to 10,000.

(ii) The ultraviolet curable resin composition of the above (i), wherein the compound (A) of the formula (1) has a molecular weight of from 500 to 8,000.

(iii) The ultraviolet curable resin composition of the above (i), wherein the compound (A) of the formula (1) has a molecular weight of from 1,000 to 8,000.

(iv) The ultraviolet curable resin composition of the above (i), wherein the compound (A) of the formula (1) has a molecular weight of from 1,500 to 5,000.

(v) The ultraviolet curable resin composition according to any one of the above items (i) to (iv), wherein R ¹ and R ² in the compound (A) of the formula (1) are each independently a carbon number of 1 An alkyl group of 10 or an alkenyl group having 3 to 10 carbon atoms.

(vi) The ultraviolet curable resin composition according to the above (v), wherein R ¹ and R ² are each independently an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 3 to 5 carbon atoms.

(vii) The ultraviolet curable resin composition according to any one of the above items (i) to (vi), wherein m/(m+n) is from 0.2 to 1. (viii) The ultraviolet curable resin composition according to the above (vii), wherein m/(m+n) is from 0.4 to 1.

(ix) The ultraviolet curable resin composition according to the above (vi), wherein n is 5 to 40, m is 10 to 40, any of R ¹ and R ^{2 is} a butyl group, and the other is an allyl group, or n 0, m is 20 to 80, and R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms, preferably a methyl group.

(x) The ultraviolet curable resin composition according to (vi) above, wherein the compound (A) is selected from the group consisting of polypropylene glycol diallyl ether, polypropylene glycol dimethyl ether, polypropylene glycol dibutyl ether, and polypropylene glycol. At least a group consisting of propyl butyl ether, polyethylene glycol-polypropylene glycol diallyl ether, polyethylene glycol-polypropylene glycol dibutyl ether, and polyethylene glycol-polypropylene glycol allyl butyl ether One.

(xi) The ultraviolet curable resin composition according to any one of the above items (i) to (x), which contains a urethane (meth) acrylate (D) and has one (meth) acrylonitrile The (meth) acrylate compound (B') is used as the (meth) acrylate compound (B).

(xii) The ultraviolet curable resin composition of (xi) above, wherein the urethane (meth) acrylate (D) has a weight average molecular weight of 7,000 to 25,000.

(xiii) The ultraviolet curable resin composition of (xi) above, wherein the urethane (meth) acrylate (D) has a weight average molecular weight of 10,000 to 20,000.

(Xiv) The ultraviolet curable resin composition according to any one of the above items (xi) to (xiii), wherein the urethane (meth) acrylate (D) polyether polyol, the polyisocyanate, and the A reactant of a hydroxyl (meth) acrylate.

(Xv) The ultraviolet curable resin composition according to any one of the above items (xi) to (xiv), which contains an alkyl group selected from the group consisting of 10 to 30 alkyl esters of (meth)acrylic acid; and a poly C2 to C4 alkylene group Alcohol (meth) acrylate; polypropylene oxide modified (meth) methacrylate; a 1 to 5 alkyl (meth) acrylate having a hydroxyl group; an acryloyl morpholine; a group consisting of tetrahydrofurfuryl (meth) acrylate and dicyclopentenyloxyethyl (meth) acrylate At least one of the (meth) acrylate compounds (B') having one (meth) acrylonitrile group.

(xvi) The ultraviolet curable resin composition according to the above (xv), which contains a selected from the group consisting of lauryl (meth)acrylate, 2-ethylhexyl carbitol acrylate, acryloyl morpholine, (meth)acrylic acid 4-hydroxybutyl ester, tetrahydrofurfuryl (meth) acrylate, isostearyl (meth) acrylate, propylene oxide modified (meth) phenyl methacrylate, dicyclopentyl (meth) acrylate At least one group consisting of alkenyloxyethyl ester, isostearyl (meth)acrylate, and 2-decyltetradecyl (meth)acrylate as a group having one (meth) acrylonitrile group Base) acrylate compound (B').

(Xvii) The ultraviolet curable resin composition according to any one of the above items (xi) to (xiv), wherein the content of the aforementioned compound (A) is from 10 to 60% by weight, and the content of the photopolymerization initiator (C) It is 0.2 to 5% by weight, and the remainder is a (meth) acrylate compound (B).

(xviii) The ultraviolet curable resin composition of the above (xvii), wherein the urethane (meth) acrylate (D) has one with respect to the total amount of the (meth) acrylate compound (B) The total content of the (meth)acrylonitrile-based (meth) acrylate compound (B') is from 50 to 100% by weight.

(xix) The ultraviolet curable resin composition of the above (xviii), wherein the total content of the component (D) and the component (B') is from 90 to 100% by weight based on the total amount of the component (B).

(xx) The ultraviolet curable resin composition according to any one of the above items (i) to (xix), wherein the curing shrinkage ratio is 3% or less.

(xxi) The ultraviolet curable resin composition according to the above (xx), wherein the curing shrinkage ratio is 2% or less. (xxii) The ultraviolet curable resin composition according to any one of the above (i) to (xxi), wherein the cured product having a thickness of 200 μm has an average transmittance of at least 90% at 400 to 800 nm.

(xxiii) The ultraviolet curable resin composition according to any one of the above items (i) to (xxii), wherein the cured product having a thickness of 200 μm has an average transmittance of at least 90% at 400 to 450 nm.

The resin composition of the present invention is applied to one of the substrates by using a coating device such as a slit coater, a roll coater, a spin coater, or a screen printing method so that the film thickness of the applied resin is 10 to 300 μm. Further, another substrate is bonded, and the active energy ray is irradiated from the side of the transparent substrate, for example, by irradiating ultraviolet rays to near ultraviolet rays (near the wavelength of 200 to 400 nm) and hardening them to be followed. The irradiation amount is preferably from about 100 to 4,000 mJ/cm ² , particularly preferably from about 200 to 3,000 mJ/cm ² . By hardening the ultraviolet to near-ultraviolet light, as long as it is a light that illuminates ultraviolet to near-ultraviolet light, regardless of the light source. For example, a low pressure, high pressure or ultra high pressure mercury lamp, a metal halide lamp, a (pulse) xenon lamp, or an electrodeless lamp can be cited.

The resin composition of the present invention can be suitably used for bonding two or more optical substrates. Further, the optical member of the present invention can be obtained by bonding the at least two optical substrates described above. More specifically, after the at least two optical substrates are bonded together using the resin composition of the present invention, the ultraviolet ray-curable resin composition layer sandwiched between the two optical substrates is irradiated with ultraviolet rays to make the resin The composition layer is cured to form a cured layer, and the optical member of the present invention can be obtained.

The bonding of the optical substrate is applied, for example, to the bonding surface of one of the optical substrates, the resin composition of the present invention, or the bonding surface of the two optical substrates to be bonded, and the present invention is applied. Resin composition, and the bonding surface of two optical substrates The coating layer of the resin composition of the present invention may be laminated so as to be sandwiched.

The optical substrate is not particularly limited, and is preferably a plate-shaped or sheet-like optical substrate. Examples of the plate-like or sheet-shaped optical substrate include the following transparent plate, sheet, display (or display unit), touch panel (or touch panel unit), and the like.

One of the preferred optical members of the present invention is a touch panel having a protective optical substrate.

For example, in the touch panel, an optical substrate having a transparent electrode or a transparent sheet-like or transparent plate-shaped optical substrate having a transparent electrode, such as an ITO film for two electrodes, is used as a transparent electrode surface. In the opposite direction, a small gap is vacated and an adhesive is applied. One of the optical substrate is a substrate, and the other optical substrate is an optical substrate for the touch surface. Further, if necessary, the surface of the touch surface side of the optical substrate for the touch surface is provided, and the protective sheet (or sheet), the icon sheet (or sheet), or the cosmetic sheet is adhered by an adhesive. A structure in which a protective optical substrate such as (or a sheet) is bonded using an adhesive. The touch panel as the optical member of the present invention is a touch panel obtained by using the resin composition of the present invention as an adhesive for at least one of the touch panels of the structure. Therefore, the touch panel is at least two optical substrates which are obtained by using a cured layer of the resin composition of the present invention.

A touch panel according to a preferred aspect of the present invention is characterized in that, on the touch surface of the touch panel and the upper surface thereof, there is a cured layer of the resin composition of the present invention, followed by a touch of the protective optical substrate. Control panel.

In another preferred embodiment, a touch panel having a protective optical substrate is provided with a cured layer of the resin composition of the present invention, and then a touch panel is attached to the display surface. Display device.

Further, as one of the other preferred optical members of the present invention, a display device for image display including an optical member, wherein the optical member is at least two of the above optical substrates, the resin composition of the present invention is used. The hardened layer followed by the optical member. As a most representative example, a display device in which a cured material layer of a resin composition of the present invention is bonded to a surface of a video display screen using a protective optical substrate or a touch panel is used. In this case, in the present invention, the optical substrate includes both the touch panel before bonding and the display body.

Further, in the touch panel of the present invention, the resin composition can be suitably used as an adhesive for bonding a plurality of transparent plates or sheets.

As the transparent plate or sheet, a transparent plate or sheet using a wide variety of materials can be used.

Specifically, a composite of polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), PC and PMMA, glass, cyclic olefin copolymer (COC) can be used. , a transparent plate or sheet made of a resin (plastic) such as a cycloolefin polymer (COP), cellulose triacetate (TAC), or an acrylic resin, and a functional transparent laminate such as a polarizing plate in which a plurality of layers are laminated. Or a sheet, a transparent plate made of inorganic glass {inorganic glass plate, and processed products thereof (for example, lens, enamel, ITO glass)} and the like.

Further, in the present invention, the plate-like or sheet-like optical substrate includes a display such as a touch panel or a liquid crystal display panel or an LED, in addition to the transparent transparent laminate or sheet such as the transparent plate or sheet or the polarizing plate. A laminate of a plurality of functional plates or sheets (hereinafter also referred to as a functional laminate).

In the present invention, the above-mentioned plate-like or sheet-like optical substrate is preferred.

The resin composition of the present invention can be used as a touch panel with a sheet or a sheet Adhesive for bonding.

Here, as the sheet, an icon sheet, a cosmetic sheet, and a protective sheet are exemplified, and as the sheet system, a cosmetic sheet or a protective sheet may be mentioned. Further, as a material of the sheet or the sheet, those which are listed as the material of the transparent sheet can be applied. Further, examples of the material of the touch panel surface include glass, PET, PC, PMMA, a composite of PC and PMMA, COC, and COP.

The resin composition of the present invention can be suitably used for bonding an optical functional material to a display surface of a display device. Examples of the display device include a display device such as an LCD, an EL display, an EL illumination, an electronic paper, or a plasma display in which a polarizing plate is attached to glass. Further, examples of the optical functional material include a transparent plastic plate such as an acrylic plate, a PC plate, a PET plate, and a PEN plate, and a tempered glass or a touch panel.

When used as a backing material for laminating a transparent plate, in order to improve visibility, the refractive index of the cured product is preferably 1.45 to 1.55.

When the refractive index is within the range of the refractive index, the difference in refractive index from the substrate used as the transparent plate can be reduced, and the light reflection can be suppressed and the light loss can be reduced.

Further, an electronic device in which a display device is incorporated, such as a television, a mini game machine, a mobile phone, a personal computer, or the like, is also included in the optical member of the present invention, wherein the display device has a resin composition bonded using the present invention. An optical substrate (such as an optical functional material).

Hereinafter, preferred aspects of the optical member of the present invention are shown below.

(I) An optical member in which at least two optical substrates are bonded by using a cured layer of the ultraviolet curable resin composition according to any one of the above items (i) to (xxiii).

(II) The optical member according to (1) above, wherein the optical substrate to be bonded is a plate-shaped or sheet-like optical substrate.

(III) The optical member according to (II) above, wherein one of the plate-shaped or sheet-shaped optical substrates to be bonded is a protective optical substrate, and the other one of the plate-shaped or sheet-shaped optical substrate is a touch panel. The obtained optical member is a touch panel having a protective optical substrate.

(IV) A display device in which one optical substrate is a protective optical substrate or a touch panel, and another optical substrate is a display device, and the obtained optical member is provided on a display screen of the display device. A protective optical substrate or a touch panel that is bonded to the cured layer.

[Examples]

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited by the examples.

Examples 1 to 11 and Comparative Example 1

Each of the raw material compounds was mixed to prepare a respective ultraviolet curable resin composition composed of a uniform composition, as shown in the following Table 1, to obtain a resin composition of the present invention and comparative use.

In addition, each component shown by the abbreviation in Table 1 is as follows. UNISAFE PKA-5016 (trade name): polyethylene glycol-polypropylene glycol allyl butyl ether (in the formula (1), R ₁ is allyl, R ₂ -butyl, n = 15, m = 15 , a compound having a number average molecular weight of 1600), UNISAFE PKA-5017 (trade name) manufactured by Nippon Oil Co., Ltd.: polyethylene glycol-polypropylene glycol allyl butyl ether (in the formula (1), R ₁ system Allyl, R ₂ -butyl, n=23, m=23, a compound having a number average molecular weight of 2,500), PPG2000-DME: Polypropylene glycol dimethyl ether manufactured by Nippon Oil Co., Ltd. (in general formula (1) Wherein R ₁ is a methyl group, R ₂ is a methyl group, n=0, m=34, a compound having a number average molecular weight of 2000) PPG4000-DME: polypropylene glycol dimethyl ether (in the formula (1), R ₁ Methyl, R ₂ methyl, n = 0, m = 68, a compound having a number average molecular weight of 4000) UA-1: polypropylene glycol (molecular weight 3000), isophorone diisocyanate, 2-hydroxyethyl acrylate The 3 component is a molar ratio 1:1.3:2 reactant.

ACMO: acryloyl morpholine, manufactured by Xingren Co., Ltd.

4-HBA: 4-hydroxybutyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.

LA: Lauryl Acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.

FA-512AS: Dicyclopentenyloxyethyl acrylate, manufactured by Hitachi Chemical Co., Ltd.

THFA: tetrahydrofurfuryl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.

M-117: propylene oxide 2.5 mol modified decyl phenyl acrylate, manufactured by Toagosei Co., Ltd.

NP-5P: propylene oxide 5 molar modified decyl phenyl acrylate, manufactured by Daiichi Kogyo Co., Ltd.

S-1800A: Isostearyl acrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

DTD-A: 2-decyltetradecyl acrylate, manufactured by Kyoeisha Chemical Industry Co., Ltd.

IRGACURE-184 (trade name): 1-hydroxycyclohexyl phenyl ketone, manufactured by BASF

KIP-150 (trade name): 2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol oligomer, manufactured by Lamberti

SPEEDCURE TPO (trade name): 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, manufactured by LAMBSON

Z-6062 (commodity number): 3-hydrothiopropyltrimethoxydecane, manufactured by TORAY-DOW CORNING

The following evaluation was carried out using the obtained resin composition of the present invention.

Hardenability:

Two glass slides each having a thickness of 1 mm were bonded so that the film thickness of the obtained resin composition was 200 μm. The resin composition sandwiched between the glass slides was irradiated with ultraviolet rays of 2000 mJ/cm ² through a glass using a high-pressure mercury lamp (80 W/cm, no ozone) to cure the resin composition, and the cured state was confirmed.

○...completely hardened

△...semi-hardened state

×...not hardened

Hardening shrinkage rate:

Two slides each having a thickness of 1 mm coated with a fluorine-based release agent were applied so that the film thickness of the obtained resin composition became 200 μm. The resin composition sandwiched between the glass slides was irradiated with ultraviolet rays of 2000 mJ/cm ² through a glass using a high-pressure mercury lamp (80 W/cm, no ozone) to produce a cured product for measuring the specific gravity of the film. The specific gravity (DS) of the cured product was measured in accordance with JIS K7112 B. Further, the liquid specific gravity (DL) of the resin composition was measured at 25 ° C, and the curing shrinkage ratio was calculated by the following formula.

Hardening shrinkage ratio (%) = (DS-DL) ÷ DS × 100

◎...not up to 2.0%

○...2.0% or more and less than 3.0%

×...3.0% or more

Follow-up:

A glass slide having a thickness of 0.8 mm and an acrylic plate having a thickness of 0.8 mm were bonded so that the film thickness of the obtained ultraviolet curable resin composition was 200 μm. A sample for evaluation was produced by irradiating ultraviolet rays of 2000 mJ/cm ² through a glass with a high-pressure mercury lamp (80 W/cm, no ozone) using a resin composition sandwiched between glass slides. This was allowed to stand in an environment of 85 ° C and 85% RH for 250 hours, and peeling was confirmed by visual observation.

○...not peeling off

×... there is peeling off

Softness:

The obtained ultraviolet curable resin composition was sufficiently cured, and the hardness of the rubber Durometer E was measured in accordance with JIS K7215, and the flexibility was evaluated.

◎...not up to 10

○...10 or more and less than 20

×...20 or more

Transparency: Two slides each having a thickness of 1 mm coated with a fluorine-based release agent were applied so that the film thickness of the cured layer of the obtained ultraviolet curable resin composition was 200 μm. The resin composition sandwiched by the glass slide was irradiated with ultraviolet rays of 2000 mJ/cm ² through a glass using a high-pressure mercury lamp (80 W/cm, no ozone) to produce a cured product for transparency measurement. Transparency The transmittances of 400 to 800 nm and 400 to 450 nm were measured using a spectrophotometer (U-3310, Hitachi High-Technologies Co., Ltd.).

◎... transmittance of 400 to 800 nm is 90% or more and transmittance of 400 to 450 nm is 90%

○... transmittance of 400 to 800 nm is 90% or more and transmittance of 400 to 450 nm is 88 to 90%

×...the transmittance of 400 to 800 nm is less than 90%

According to the results of Table 1, it was confirmed that Examples 1 to 11 containing the polyether compound (component (B)) and the (meth) acrylate compound (component (A)) having the structure represented by the general formula (1) The resin composition of the present invention can provide optical transparency which is excellent in curability, small in shrinkage during curing, transparency of a cured product, and excellent in adhesion to a substrate and flexibility. Follow-up agent.

Claims (22)

An ultraviolet curable resin composition containing a compound (A), a (meth) acrylate compound (B) having a structure represented by the following formula (1), and a photopolymerization initiator (C), Wherein n is an integer of 0 to 40, m is an integer of 10 to 80, and R ¹ and R ² each may be the same or different, and are an alkyl group having 1 to 18 carbon atoms and an alkenyl group having 2 to 18 carbon atoms; An alkynyl group having 2 to 18 carbon atoms or an aryl group having 5 to 18 carbon atoms. The ultraviolet curable resin composition according to claim 1, wherein R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 3 to 10 carbon atoms. The ultraviolet curable resin composition according to claim 1, wherein the compound (A) is selected from the group consisting of polypropylene glycol diallyl ether, polypropylene glycol dimethyl ether, polypropylene glycol dibutyl ether, and poly a group consisting of propylene glycol allyl butyl ether, polyethylene glycol-polypropylene glycol diallyl ether, polyethylene glycol-polypropylene glycol dibutyl ether, and polyethylene glycol-polypropylene glycol allyl butyl ether At least one of them. The ultraviolet curable resin composition according to claim 1, which comprises a (meth) acrylate compound (B') having one (meth) acryl fluorenyl group or two (meth) groups. A (meth) acrylate compound (B) is used as the (meth) acrylate compound (B). The ultraviolet curable resin composition according to claim 1 or 4, which comprises a urethane (meth) acrylate (D) as a (meth) acrylate. Compound (B). The ultraviolet curable resin composition according to claim 1, which comprises a urethane (meth) acrylate (D) and a (meth) acryl having one (meth) acrylonitrile group. The ester compound (B') is referred to as a (meth) acrylate compound (B). The ultraviolet curable resin composition according to claim 1, wherein the content of the compound (A) is 10 to 60% by weight, and the content of the photopolymerization initiator (C) is 0.2 to 5% by weight. The remainder is the (meth) acrylate compound (B). The ultraviolet curable resin composition according to claim 6, which comprises a polymer selected from the group consisting of 10 to 30 alkyl esters of (meth)acrylic acid; polyalkyl C2 to C4 alkylene glycol (meth)acrylate Polypropylene oxide modified decyl phenyl (meth) acrylate; 1 to 5 alkyl (meth) acrylate having a hydroxyl group; acryloyl morpholine; tetrahydrofurfuryl (meth) acrylate and At least one of the group consisting of dicyclopentenyloxyethyl methacrylate is used as the (meth) acrylate compound (B') having one (meth) acrylonitrile group. The ultraviolet curable resin composition according to claim 4, which is selected from the group consisting of lauryl (meth)acrylate, 2-ethylhexyl carbitol acrylate, acryloyl morpholine, (methyl) ) 4-hydroxybutyl acrylate, tetrahydrofurfuryl (meth) acrylate, isostearyl (meth) acrylate, propylene oxide modified (meth) phenyl methacrylate, (meth) acrylate At least one of a group consisting of cyclopentenyloxyethyl ester and 2-mercaptotetradecyl (meth)acrylate as a (meth) acrylate compound having one (meth) acrylonitrile group (B' ). The ultraviolet curable resin composition according to claim 5, which is selected from the group consisting of polypropylene glycol diallyl ether, polypropylene glycol dimethyl ether, polypropylene glycol dibutyl ether, and polypropylene glycol allyl butyl Ether, polyethylene glycol-polypropylene glycol At least one selected from the group consisting of allyl ether, polyethylene glycol-polypropylene glycol dibutyl ether, and polyethylene glycol-polypropylene glycol allyl butyl ether as the above compound (A), and containing Lauryl acrylate, 2-ethylhexyl carbitol acrylate, propylene decylmorpholine, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acrylate a group consisting of stearyl ester, polypropylene oxide modified decyl phenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and 2-decyltetradecyl (meth) acrylate At least one of the groups is a (meth) acrylate compound (B') having one (meth) acrylonitrile group. The ultraviolet curable resin composition according to claim 1, which comprises a (meth) acrylate compound (B') having one (meth) acrylonitrile group and a carbamate (methyl group) Acrylate (D), and m in the formula (1) is an integer of 10 to 50. The ultraviolet curable resin composition according to claim 5, wherein the urethane (meth) acrylate (D) polyether polyol, the polyisocyanate, and the hydroxyl group-containing (meth) acrylate are used. The reactant of the ester. The ultraviolet curable resin composition according to claim 1, which comprises a urethane (meth) acrylate (D) and a (meth) acryl having one (meth) acrylonitrile group. The ester compound (B') is used as the (meth) acrylate compound (B), and contains 1 to 60% by weight of the above compound (A) and 20 to 80% by weight of the urethane relative to the total amount of the composition. (meth) acrylate (D), 10 to 70% by weight of a (meth) acrylate group (meth) acrylate compound (B'), and 0.2 to 5% by weight of photopolymerization initiation Agent (C). The ultraviolet curable resin composition according to claim 13, wherein the (meth) acrylate group (B') having one (meth) acrylonitrile group is added to the total amount of the resin composition. Combined with urethane (meth) acrylate (D) The content is at least 40% by weight. The ultraviolet curable resin composition according to claim 12, wherein the curing shrinkage ratio is 3.0% or less. The ultraviolet curable resin composition according to claim 6, wherein (i) the compound (A) is selected from the group consisting of polypropylene glycol diallyl ether, polypropylene glycol dimethyl ether, and polypropylene glycol dibutyl glycol. a group consisting of ether, polypropylene glycol allyl butyl ether, polyethylene glycol-polypropylene glycol diallyl ether, polyethylene glycol-polypropylene glycol dibutyl ether, and polypropylene glycol-polypropylene glycol allyl butyl ether At least one of the group, (ii) containing a selected from the group consisting of lauryl (meth)acrylate, 2-ethylhexyl carbitol acrylate, acryloyl morpholine, 4-hydroxybutyl (meth) acrylate, (methyl) ) tetrahydrofurfuryl acrylate, isostearyl (meth) acrylate, propylene oxide modified (meth) phenyl methacrylate, dicyclopentenyloxyethyl (meth) acrylate, (methyl) At least one of the group consisting of 2-mercaptotetradecyl acrylate as a (meth) acrylate compound (B') having one (meth) acrylonitrile group, (iii) uric acid A reaction product of an ester (meth) acrylate (D)-based polyether polyol, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate. The ultraviolet curable resin composition according to claim 6 or 16, wherein the urethane (meth) acrylate (D) has a weight average molecular weight of 7,000 to 25,000. The ultraviolet item 6 of the patent scope of curable resin composition, wherein the compound (A) based formula R (1) in the ¹ and R ² also may be the same or different, and R ^{2 1} R & lt a compound having 1 to 10 carbon atoms or 3 to 10 carbon atoms, a urethane (meth) acrylate (D) polyether polyol, a polyisocyanate, and a hydroxyl group (methyl group) a acrylate reactant having a weight average molecular weight of 7,000 to 25,000 and containing a urethane (meth) acrylate (D) and a (meth) acrylonitrile group (methyl) The acrylate compound (B') is used as the (meth) acrylate compound (B), and further contains 1 to 60% by weight of the above compound (A) and 20 to 80% by weight of the amine A based on the total amount of the composition. Acid ester (meth) acrylate (D), 10 to 70% by weight of a (meth) acrylate group (meth) acrylate compound (B'), and 0.2 to 5% by weight of photopolymerization Starting agent (C), and having one (meth) acrylonitrile-based (meth) acrylate compound (B') and urethane (meth) acrylate (relative to the total amount of the composition) D) total content is 40 to 90% by weight. An optical member which is obtained by applying a cured layer of an ultraviolet curable resin composition according to claim 1 to at least two optical substrates. A cured product obtained by irradiating an active energy ray to an ultraviolet curable resin composition according to claim 1 of the patent application. A touch panel which is obtained by applying a cured layer of an ultraviolet curable resin composition according to claim 1 and then having at least two optical substrates. A display device having a protective optical substrate or a touch panel, which is a cured layer of the ultraviolet curable resin composition according to claim 1 above, followed by a protective optical substrate or a touch panel With the display device.