TWI527837B - Hardened resin composition - Google Patents

Description

Curable resin composition

The present invention relates to a curable resin composition which is solvent-free, hardened by irradiation with an active energy ray or heat, and is excellent in heat-resistant yellow modification of a cured product, excellent in optical transparency, and does not cause a warp on a substrate. The adhesiveness of the degree of peeling is suitable for various uses such as an adhesive, an adhesive, and a coating agent.

In IT-related products such as liquid crystal displays, a large number of components including various materials or shapes are used as they are highly functionalized. Adhesives or coating agents have previously been used in the lamination or surface coating of such components. Among them, in the manufacturing sites of the above-mentioned IT-related products, in recent years, the productivity improvement of the final products has become a major issue. The reason for this is that the adhesive used in the prior art usually contains a solvent such as a solvent or water. Therefore, after the adhesive is applied to the surface of the substrate or the like, the step of removing the solvent contained in the adhesive requires a large amount of time, resulting in a final A cause of reduced production efficiency of the product. As an adhesive which can improve the production efficiency of the above-mentioned products, for example, an active energy ray-curable adhesive is known. The above active energy ray-curable adhesive generally does not contain a solvent such as a solvent or water, and therefore has a feature that the step of removing the solvent is not required when the adhesive layer is formed. As an adhesive having a degree of adhesion which can be used for the manufacture of the above-mentioned IT product or the like, and which can improve the production efficiency of the final product as compared with the prior art, for example, an adhesive composition is known which is characterized in that it has 2 More than one acrylate-based polymer 20 to 80% by mass, a plasticizer 20 to 80% by mass, an acrylate monomer 0 to 30% by mass, and a photopolymerization initiator.

(Refer to Patent Document 1) [Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-201786

However, the above-mentioned adhesive composition has a yellowing property of the cured product after the heat resistance test, and the transparency is impaired. An object of the present invention is to provide a curable resin composition which can obtain a cured product which is excellent in adhesion and transparency, and which is excellent in heat-resistant yellow modification.

The present invention is mainly directed to the following.

A curable resin composition comprising (A) a conjugated diene polymer polyol and (B) a compound having a (meth) acrylate group.

2: The curable resin composition according to the above 1, wherein the (A) conjugated diene polymer polyol has a 1,2-butadiene skeleton.

3: The curable resin composition according to the above 1 or 2, wherein the (B) compound having a (meth) acrylate group is at least a polymer polyol (a) having a hydroxyl group in the molecule and having a reactivity with a hydroxyl group The substituent (meth) acrylate is obtained by a reaction.

4. The curable resin composition according to the above 3, wherein the (B) compound having a (meth) acrylate group is a compound selected from the group consisting of: (B1) a polymer having a hydroxyl group in the molecule Alcohol (a), polyisocyanate (b) and (meth)acrylic acid urethane obtained by reacting a (meth) acrylate having a hydroxyl group in the molecule; (B2) polymerizing a hydroxyl group in the molecule a compound obtained by reacting a polyol (a) and a (meth) acrylate having an isocyanate group (d); and (B3) a polymer polyol (a) having a hydroxyl group in the molecule and a carboxyl group such as acrylic acid A polymer polyol obtained by reacting acrylate (e).

5: The curable resin composition according to the above 1 or 2, wherein the compound (B) having a (meth) acrylate group is a compound selected from the group consisting of: (B4) by Ding Er The conjugated diene prepolymer (f) obtained by anion polymerization of a conjugated diene compound such as an alkene or an isoprene is reacted with a dibasic unsaturated acid anhydride (g), and then the obtained prepolymer is obtained. a conjugated diene polymer obtained by reacting a part or all of an acid anhydride residue with a (meth) acrylate having a hydroxyl group in the molecule, and (B5) an acrylate modified with an aliphatic alcohol (h) .

In other words, the inventors of the present invention have repeatedly conducted research to obtain a curable resin composition which is excellent in heat-resistant yellow modification, is excellent in optical transparency, and exhibits no peeling over time on a substrate. The degree of adhesion of the hardened material. In the course of the present invention, it has been found that the desired object can be attained by the following curable resin composition characterized in that it contains (A) a conjugated diene polymerization. a polyol and (B) a compound having a (meth) acrylate group.

According to the present invention, it is possible to provide a curable resin composition which is excellent in heat-resistant yellow modification, is excellent in optical transparency, and exhibits an adhesive property to the substrate which does not cause adhesion with time.

Next, embodiments of the present invention will be described in detail.

The (A) conjugated diene polymer polyol used in the present invention is not particularly limited, and specifically, a polybutadiene polyol, a polyisoprene polyol, or a hydrogenated polybutadiene polyol can be used. , hydrogenated polyisoprene polyol. A polybutadiene polyol is preferred in view of ease of obtaining industrial products.

The number average molecular weight of the conjugated diene polymer polyol is not particularly limited, but is preferably 500 or more and 40,000 or less. If it is less than 500, the viscosity is too low, so there is a tendency for the self-hardened material to flow, and it becomes difficult to synthesize in the case of more than 40,000.

The content of the conjugated diene polymer polyol of the present invention (A) is preferably 1% by mass or more and 95% by mass or less, more preferably 2% by mass based on 100% by mass of the curable resin composition. The above 90% by mass or less is further preferably 3% by mass or more and 80% by mass or less. When the amount is less than 1% by mass, the effect on the cured product is less, and when it exceeds 95% by mass, the hardenability is remarkably deteriorated.

The (B) compound having a (meth) acrylate group in the present invention is not particularly limited, and may, for example, be a polymer polyol (a) having at least a hydroxyl group in the molecule and a substituent having a reactivity with a hydroxyl group. a compound obtained by reacting an acrylate. Specifically, (B1) is obtained by reacting a polymer polyol (a) having a hydroxyl group in the molecule, a polyisocyanate (b), and a (meth) acrylate having a hydroxyl group in the molecule (c). Acrylic acid urethane (hereinafter, referred to as (meth)acrylic acid urethane); (B2) a polymer polyol (a) having a hydroxyl group in the molecule, and (meth)acrylic acid having an isocyanate group a compound obtained by the reaction of the ester (d); and (B3) a polymer polyol obtained by a reaction of a polymer polyol (a) having a hydroxyl group in the molecule with an acrylate (e) having a carboxyl group such as acrylic acid.

In addition to the above, the (B) compound having a (meth) acrylate group in the present invention is exemplified by (B4) anion polymerization of a conjugated diene compound such as butadiene or isoprene to obtain a conjugated second. The olefinic prepolymer (f), after reacting the conjugated diene prepolymer (f) with the unsaturated dibasic acid anhydride (g), and then, by dissolving the anhydride in the obtained prepolymer a conjugated diene polymer obtained by reacting one or both of the base with a (meth) acrylate having a hydroxyl group in the molecule; (B5) an acrylate (h) obtained by modifying an aliphatic alcohol .

The polymer polyol (a) having a hydroxyl group is not particularly limited, and specifically, a polyester polyol, a polycarbonate polyol, a polyether polyol, an aliphatic hydrocarbon polyol, or an alicyclic hydrocarbon system can be used. Polyol. Among them, a polyether polyol is particularly preferable in terms of ease of production and excellent various properties.

The polyether polyol is not particularly limited, and polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or polytetramethylene glycol can be used. From the standpoint of heat resistance, low viscosity and softness In the polyether polyol, a polyether polyol containing a polyether chain moiety obtained by ring-opening polymerization of propylene oxide, butylene oxide or tetrafluoroethylene is particularly preferred.

The number average molecular weight of the polymer polyol (a) having a hydroxyl group is not particularly limited, but is preferably 500 or more and 20,000 or less. If it is less than 500, the hardened material is too hard, and the softness of the adhesive is lost. When it exceeds 20,000, it becomes difficult to synthesize.

The polyisocyanate (b) is not particularly limited, and specific examples thereof include an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate, and an aromatic aliphatic polyisocyanate. Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4. 4-trimethylhexamethylene diisocyanate, quaternary acid diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, and the like. Examples of the alicyclic polyisocyanate include isophorone diisocyanate, hydrogenated dimethyl diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, and methyl extension. Cyclohexyl diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, and the like. Examples of the aromatic polyisocyanate include toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate (MDI). , 4,4'-dibenzyl diisocyanate, 1,5-naphthalene diisocyanate, benzodimethyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, and the like. Examples of the aromatic aliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α,α,α',α'-tetramethylbenzenedimethyl diisocyanate, and the like. . Further, modified bodies such as dimers, trimers or biuret isocyanates of the organic polyisocyanates may be mentioned. These may be used alone or in combination of two or more. From the viewpoint of low viscosity, hexamethylene diisocyanate is preferred, and from the viewpoint of heat-resistant yellow modification, isophorone diisocyanate, hydrogenated dimethyl diisocyanate, and 4 are preferably used. 4'-Dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate.

The (meth) acrylate (c) having a hydroxyl group in the above molecule is not particularly limited, specifically In other words, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, caprolactone-modified acrylic acid -2-hydroxyethyl ester, polyethylene glycol mono (meth) acrylate, polypropylene glycol monoacrylate, polybutylene glycol mono (meth) acrylate, 2-(methyl) propylene methoxyethyl 2-hydroxyethyl phthalate, phenyl glycidyl ether (meth) acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, caprolactone modified dipentaerythritol penta (meth) acrylate Etc., these may be used alone or in combination. Among them, from the viewpoint of low viscosity, it is preferred to use 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, caprolactone-modified -2-hydroxyethyl acrylate, and poly Ethylene glycol mono(meth)acrylate, polypropylene glycol monoacrylate.

The (meth) acrylate (d) having an isocyanate group is not particularly limited, and specific examples thereof include 2-propenyloxyethyl isocyanate and 2-methylpropenyloxyethyl isocyanate. These may be used alone or in combination.

The acrylate (e) having a carboxyl group such as acrylic acid is not particularly limited, and specific examples thereof include 2-propenyloxyethyl succinic acid, 2-propenyloxyethyl phthalic acid, and 2- Propylene methoxyethyl hexahydrophthalic acid, acrylic acid, and the like. These may be used alone or in combination.

The conjugated diene-based prepolymer (f) obtained by anionic polymerization of a conjugated diene compound such as butadiene or isoprene may, for example, be butadiene, isoprene or 1,3- Pentadiene, 2,3-dimethylbutadiene, 1-phenylbutadiene, 2-phenylbutadiene, 1,1-diphenylbutadiene, 1,2-diphenylbutyl Diene, 2,3-diphenylbutadiene, and the like. The conjugated diene polymer may contain one type of these conjugated diene compounds alone or in combination of two or more. As the conjugated diene-based prepolymer, a copolymer of polybutadiene, polyisoprene, or a mixture of isoprene and butadiene is preferable. The conjugated diene prepolymer can be used as a starter by using an alkyl lithium such as a naphthalene sodium complex, n-butyl lithium, a second butyl lithium, methyl lithium, ethyl lithium or pentyl lithium. And anionic polymerization of the above conjugated diene compound such as butadiene or isoprene In the production, the above conjugated diene compound such as butadiene or isoprene may be obtained by using a peroxide such as azobisisobutyronitrile or a peroxide such as benzoyl peroxide as a starting agent. It is produced by radical polymerization. Further, the polymerization reaction is usually carried out in the presence of an aliphatic or aromatic hydrocarbon solvent such as hexane, heptane, toluene or xylene at a polymerization temperature of -80 to 150 ° C and a polymerization time of 1 to 100 hours. Under the conditions. The number average molecular weight of the above compound is not particularly limited, but is preferably 500 or more and 80,000 or less. It is difficult to synthesize in the case of less than 500, and becomes highly difficult to use in the case of more than 80,000.

The unsaturated dibasic acid anhydride (g) is not particularly limited, and specific examples thereof include phthalic anhydride, phthalic anhydride, pyromellitic dianhydride, and tetracarboxylic dianhydride. These may be used alone or in combination.

The acrylate (h) obtained by modifying the aliphatic alcohol is not particularly limited, and specific examples thereof include 3,3,5-trimethylcyclohexane (meth) acrylate, and (a) 2-(2-ethoxyethoxy)ethyl acrylate, cyclic trimethylolpropane formal (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate , isodecyl (meth) acrylate, isostearyl (meth) acrylate, isotridecyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylate Base ester, isodecyl (meth) acrylate, cyclohexyl (meth) acrylate, methoxy triethylene glycol acrylate, methoxy polyethylene glycol (meth) acrylate, (2-methyl Methyl 2-ethyl-1,3-dioxolan-4-yl)(methyl)acrylate, cyclohexanespiro-2-(1,3-dioxolane-4- Methyl (meth) acrylate, 3-ethyl-3-oxetanylmethyl acrylate, adamantyl (meth) acrylate, 1,6-hexanediol diacrylate, 1,9- Decanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, two Alkylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and the like. These may be used alone or in combination. In particular, from the viewpoint of low viscosity and low odor, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, 1,9-fluorene are preferred. Diol di(meth)acrylate.

The above (meth)acrylic acid urethane (B1) can be synthesized by a known method. example For example, it can be synthesized by adding a specific amount of the component (b) to the excess amount of the component (a), and reacting at 80 ° C to a specific amount of the free isocyanate, thereby obtaining a polyaminocarboxylic acid. Further, in the presence of a polymerization inhibitor such as hydroquinone monomethyl ether at 70 to 80 ° C, the component (c) is added at once, and the mixture is heated at 70 to 80 ° C and stirred until no free isocyanate is present. At this time, in order to promote the reaction, a tin-based catalyst such as dibutyltin dilaurate may be added.

The number of functional groups of the polyurethane obtained by reacting (a) with (b) of the above (meth)acrylic acid urethane (B1) is 1.0 or more and 4.0 or less. When the number of functional groups is less than 1.0, the cured product has fluidity and has a tendency to flow out over time. When it exceeds 4.0, the hardened material becomes too hard. Further, the ratio of the above (c) is 1.0 to 2.0 mol ratio, preferably 1.0 to 1.5 mol ratio, with respect to (b) to (a).

The above (B2) can be synthesized by a known method by reacting a polymer polyol (a) having a hydroxyl group in a molecule and a (meth)acrylate (d) having an isocyanate group. For example, it can be synthesized by adding a specific amount of the component (a), and adding the component (d) once, heating at 70 to 80 ° C, and stirring until no free isocyanate. At this time, in order to promote the reaction, a tin-based catalyst such as dibutyltin dilaurate may be added.

The above (B3) polymer polyol obtained by a reaction of a polymer polyol (a) having a hydroxyl group in a molecule with an acrylate (e) having a carboxyl group such as acrylic acid can be synthesized by a known method. For example, it can be obtained by inputting a specific amount of the component (a), and inputting the excess amount (e), and performing a dehydration esterification reaction using a catalyst such as p-toluenesulfonic acid. In this case, it can be usually carried out in the presence of an aliphatic or aromatic hydrocarbon solvent such as benzene, toluene or cyclohexane at a dehydration esterification temperature of 70 to 150 ° C and a reaction time of 1 to 20 hours.

The (B4) anion polymerization of a conjugated diene compound such as butadiene or isoprene to obtain a conjugated diene-based prepolymer (f), and a conjugated diene-based prepolymer (f) After reacting with the unsaturated dibasic acid anhydride (g), and then, by making the anhydride in the obtained prepolymer A commercially available product can be used as a conjugated diene polymer obtained by reacting a part or all of the residue with a (meth) acrylate (c) having a hydroxyl group in the molecule. For example, trade names manufactured by Kuraray Co., Ltd.: Kuraprene UC-102, UC-203, and the like can be cited.

The content of the (B) (meth) acrylate group-containing compound of the present invention is preferably 1% by mass or more and 99% by mass or less, more preferably 10% by mass based on 100% by mass of the curable resin composition. The amount is 98% by mass or less, and more preferably 20% by mass or more and 97% by mass or less. When it is less than 1% by mass, the hardenability deteriorates, and when it exceeds 99% by mass, there is a yellowing after the heat resistance test.

The curable resin composition of the present invention is optionally added with a polymerization initiator using an active energy ray. Here, the polymerization initiator using the active energy ray includes both a photopolymerization initiator and a polymerization initiator using an active energy ray such as ultraviolet rays.

As the photopolymerization initiator, for example, an aromatic ketone such as benzophenone, an aromatic compound such as hydrazine or α-chloromethylnaphthalene, or a sulfur compound such as diphenyl sulfide or thiocarbamate can be used.

Examples of the polymerization initiator which utilizes an active energy ray such as ultraviolet light other than visible light include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, and 2,2-dimethoxy group. 1,2-diphenylethane-1-one, xanthone, anthrone, benzaldehyde, hydrazine, hydrazine, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorodi Benzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1-(4 -isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 9-oxosulfur Diethyl-9-oxosulfur 2-isopropyl-9-oxosulfur 2-chloro-9-oxosulfur 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Morpholinylphenyl)-butanone-1,4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 2,4,6-trimethylbenzylidene Diphenylphosphine oxide, bis-(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide, oligo(2-hydroxy-2-methyl-1 -(4-(1-methylvinyl)phenyl)acetone), 2-[2-oxo-2-phenylethenyloxyethoxy]ethyl oxyphenylacetate and oxybenzene A mixture of 2-(2-hydroxyethoxy)ethyl acetate, and the like.

As a commercial item using the polymerization initiator of an active energy ray, the brand name of Irfacure 184, 369, 651, 500, 754, 819, 907, 784, 2959, 1000, 1300, 1700 is mentioned, for example. , 1800, 1850, Darocure 1116, 1173, Lucirin TPO; trade name manufactured by UCB: Ubecryl P36; trade name manufactured by Fratelli Lamberti: Esacure KIP150, KIP100F, KT37, KT55, KTO46, TZT, KIP75LT; Nippon Chemical Co., Ltd. Name of the product manufactured: kayacure DETX, etc.

The content of the polymerization initiator is different depending on the type and the like, and is 1 to 8 parts by weight based on 100 parts by weight of the ultraviolet curable resin composition. When the content is too small, the sensitivity of the active energy ray is insufficient. If the content is too large, the active energy ray does not reach the deep portion of the coating film, and the hardenability of the deep portion of the coating film tends to decrease.

In addition, the energy source source for curing the curable resin composition of the present invention is not particularly limited, and examples thereof include a high pressure mercury lamp, an electron beam, a gamma ray, a carbon arc lamp, a xenon lamp, and a metal halide lamp.

On the other hand, in the case of hardening by heating, it can be hardened by heating to a temperature range of 60-250 degreeC.

In the curable resin composition of the present invention, in addition to the above-mentioned organic solvent, monomer, and various initiators, various additives which are usually included in a coating material, a coating agent, and the like may be added as needed. Examples of the additive include a light stabilizer, an ultraviolet absorber, a catalyst, an antifoaming agent, a polymerization accelerator, an antioxidant, a flame retardant, an infrared ray absorbing agent, an antistatic agent, a plasticizer, a dispersing agent, and the like.

The curable resin composition of the present invention described in detail above has properties such as adhesiveness and heat-resistant yellow modification, and thus can be used as an electronic terminal such as a mobile phone, an electronic book, or a touch panel, or a liquid crystal television, a plasma television, an organic EL television, or the like. Display panel and protection of display device Used as a filler for the space between the plates.

[Examples]

The present invention will be more specifically described based on the examples, but the present invention is not limited thereto. Various changes, modifications, and changes can be made herein without departing from the scope of the invention.

(Synthesis example of urethane acrylate)

[Synthesis Example 1]

To the flask, 348 g (2 mol) of toluene diisocyanate and 10,000 g (1 mol) of a polyglycol polyol having a number average molecular weight Mn of 10,000 (manufactured by Asahi Glass Co., Ltd., product number PREMINOL S4011) were added at 80 ° C. The reaction was carried out until the free isocyanate was 0.81%, and the polyurethane was synthesized. To the obtained polyurethane, 5.5 g of hydroquinone monomethyl ether and 232 g (2 mol) of 2-hydroxyethyl acrylate (molecular weight 116) were added, and the reaction was carried out at 70-80 ° C to a free isocyanate. The amount of the urethane amide B-1 was obtained in an amount of 0.1% or less.

[Synthesis Example 2]

666 g (3 mol) of isophorone diisocyanate and 6000 g of polytetramethylene polyol having a number average molecular weight Mn of 3,000 (manufactured by First Industrial Pharmaceutical Co., Ltd., product number PBG-3000) 6000 g (available as a polyether polyol) 2 mol), the reaction was carried out at 80 ° C until the free isocyanate was 1.26%, and the polyurethane was synthesized. To the obtained polyurethane, 3.5 g of hydroquinone monomethyl ether and 232 g (2 mol) of 2-hydroxyethyl acrylate (molecular weight 116) were added, and the reaction was carried out at 70-80 ° C to a free isocyanate. The amount of the urethane amide B-2 was obtained in an amount of 0.1% or less.

[Synthesis Example 3]

To the flask, 666 g (3 mol) of isophorone diisocyanate and polytetrafluoroethylene as a polyether polyol having a number average molecular weight Mn of 1,000 (manufactured by Mitsubishi Chemical Corporation, product number PTMG-1000) were added. 2000g (2m), reacted to free isocyanate at 80 ° C As far as 3.2%, synthetic polyurethanes are synthesized. To the obtained polyurethane, 1.5 g of hydroquinone monomethyl ether, 232 g (2 mol) of 2-hydroxyethyl acrylate (molecular weight 116), and reacted to free isocyanate at 70-80 ° C The amount of the urethane amide B-3 was obtained in an amount of 0.1% or less.

[Synthesis Example 4]

To the flask, 888 g (4 mol) of isophorone diisocyanate and 10,000 g (3 mol) of polypropylene glycol having a number average molecular weight Mn of 10,000 (manufactured by Asahi Glass Co., Ltd., product number PREMINOL S4011) were added. The polyaminoformate was synthesized by reacting at 80 ° C until the free isocyanate was 0.27%. To the obtained polyurethane, 15.5 g of hydroquinone monomethyl ether and 232 g (2 mol) of 2-hydroxyethyl acrylate (molecular weight 116) were added, and the reaction was carried out at 70-80 ° C to a free isocyanate. The amount of the urethane amide B-4 was obtained in an amount of 0.1% or less.

[Synthesis Example 5]

Adding 282 g (2 mol) of 2-propenylmethoxyethyl isocyanate as a (meth) acrylate containing an isocyanate group, and polytetramethylene glycol having a number average molecular weight Mn of 3,000 as a polyether polyol (first industry) Manufactured by a pharmaceutical company, product number PBG-3000) 3000g (1 mole), hydroquinone monomethyl ether 1.64g, reacted at 70-80 ° C until the amount of free isocyanate is 0.1% or less, to obtain an amine amide group Acid ester B-5.

(Adjustment of curable resin composition)

Each component and the blending amount described in the following Table 1 were mixed at once, and mixed and stirred by a disperser to obtain a curable resin composition.

The symbols of the compounds described in Table 1 represent the following compounds.

(B-6) Composition having a (meth) acrylate group [trade name "New Frontier L-C9A" manufactured by Daiichi Pharmaceutical Co., Ltd.]

(B-7) A composition having a (meth) acrylate group [trade name "ISTA" manufactured by Osaka Organic Chemical Industry Co., Ltd.]

(A-1) conjugated diene polymer polyol [trade name "NISSO-PB G-1000" manufactured by Japan Soda Co., Ltd.]

(A-2) conjugated diene polymer polyol [Product name "Polybd R-45HT" manufactured by Idemitsu Kosan Co., Ltd.]

(A-3) conjugated diene polymer polyol [product name "Krasol LBH3000" manufactured by Cray Valley]

(C-1) 1-hydroxycyclohexyl phenyl ketone [trade name "IRGACURE 184" manufactured by BASF Corporation]

(C-2) 2,4,6-trimethylbenzimidyldiphenylphosphine oxide [trade name "LUCIRIN TPO" manufactured by BASF Corporation]

(production of hardened material)

The curable resin composition was dropped onto a glass of a specific size having a spacer of 300 μm disposed on four sides, and filled into a glass plate, and a glass plate of the same size was covered thereon. Then, a high-pressure mercury lamp 80 W/cm was used, and irradiation was performed under an air atmosphere with an accumulated illuminance of 5000 mJ/cm ² to harden it to obtain a cured product.

(Evaluation of curable resin composition and cured product)

The transparency of the above curable resin composition, the heat resistance of the cured product, and the yellow modification after the heat resistance test were evaluated based on the following evaluation criteria.

[transparency]

The cured resin composition was visually observed, and the transparent one was set to ○, and the white fog was set to × and evaluated.

[heat resistance]

The cured product (cured film) was heated in an oven at 110 ° C for 500 hours, and the amount of the cured product was not ○, and the amount of the cured product was set to ×.

[heat-resistant yellow modification]

The above cured product (hardened film) was heated in an oven at 110 ° C for 500 hours, using Nippon Electric A Spectrophotometer SD6000 manufactured by Sewing Industrial Co., Ltd. was used to measure the YI value, thereby evaluating the discoloration after heating. When the measured YI is less than 4, it is set to ○, and 4 or more is set to ×.

According to Table 1, the cured product (cured film) obtained by curing the curable resin composition of the present invention can obtain a cured product excellent in transparency and heat-resistant yellow modification. According to Comparative Example 1, it was confirmed that the cured product obtained by using the curable resin composition containing no conjugated diene polymer polyol was inferior in heat-resistant yellow modification. According to Comparative Example 2, it was confirmed that the cured product obtained by using the curable resin composition containing no (meth) acrylate group was inferior in heat resistance.

Furthermore, it is also confirmed that the composition of the conjugated diene polymer polyol and the (meth) acrylate group described in Examples 1 to 7 is obtained by using the curable resin composition. A cured product excellent in transparency and heat-resistant yellow modification.

[Industrial availability]

Since the curable resin composition of the present invention has properties such as adhesiveness and heat-resistant yellow modification, it can be used as an electronic terminal such as a mobile phone, an electronic book, or a touch panel, or a display device such as a liquid crystal television, a plasma TV, or an organic EL television. The space between the panel and the protection panel Used as a filler.

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

The present application is based on Japanese Patent Application No. 2014-084590, filed on Apr.

Claims (3)

A curable resin composition comprising (A) a conjugated diene polymer polyol having a 1,2-butadiene skeleton, and (B) a compound having a (meth) acrylate group, (B) The compound having a (meth) acrylate group is obtained by reacting at least a polymer polyol (a) having a hydroxyl group in a molecule and a (meth) acrylate having a substituent reactive with a hydroxyl group. The curable resin composition according to claim 1, wherein the compound (B) having a (meth) acrylate group is a compound selected from the group consisting of the following (B1) to (B3): (B1) in a molecule a (meth)acrylic acid urethane obtained by reacting a polymer polyol (a) having a hydroxyl group, a polyisocyanate (b), and a (meth) acrylate having a hydroxyl group in a molecule; (B2) a polymer polyol (a) having a hydroxyl group in the molecule and a compound obtained by reacting a (meth)acrylate (d) having an isocyanate group; (B3) a polymer polyol (a) having a hydroxyl group in the molecule and acrylic acid A polymer polyol obtained by reacting a carboxyl group-containing acrylate (e). A curable resin composition comprising (A) a conjugated diene polymer polyol having a 1,2-butadiene skeleton, and selected from the group consisting of the following (B4) and (B5) Compound: (B4) After reacting a conjugated diene-based prepolymer (f) obtained by anionic polymerization of a conjugated diene compound such as butadiene or isoprene with a dibasic unsaturated acid anhydride (g) And then conjugated diene polymer obtained by partially or completely reacting one or both of the acid anhydride residues in the obtained prepolymer with a (meth) acrylate having a hydroxyl group in the molecule; (B5) an aliphatic alcohol Modified acrylate (h).