JP5715330B2 - Photocurable resin composition and pressure-sensitive adhesive sheet comprising the same - Google Patents

Description

  The present invention relates to a photocurable resin composition and an adhesive sheet comprising the same.

In recent years, various photocurable resins have been developed for adhesive materials.
For example, Patent Document 1 discloses a polyether polyol-based photocurable resin for surface processing of woodwork products such as woodworking plywood, furniture, and musical instruments. However, since polyether polyol has high hydrophilicity and high water vapor permeability, it has been unsuitable for use in adhesive materials and the like for applications where water vapor barrier properties are required.
Patent Document 2 discloses a polyester polyol-based photocurable resin composition for wood coatings. However, since polyester polyol undergoes hydrolytic degradation in a high-temperature and high-humidity environment, polyester polyols are inappropriate for use in adhesive materials and the like that are exposed to a high-temperature and high-humidity environment.
Furthermore, when using an adhesive material etc. for the use exposed to a vibration, the moderate hysteresis property for maintaining the high hysteresis loss characteristics for providing a damping characteristic and the shape of an adhesive material, etc. is requested | required.
As examples of improving the water vapor permeability (low moisture permeability), Patent Documents 3 to 8 include photocurable hydrogenated or non-hydrogenated liquid polyisoprene, photocurable hydrogenated or non-hydrogenated liquid polybutadiene. Alternatively, a photocurable hydrogenated or non-hydrogenated liquid styrene-butadiene copolymer has been proposed, but since all of them are blended with a large amount of an acrylate monomer, formability such as sheet shape is insufficient. Since the non-hydrogenated liquid polymer has low heat resistance and weather resistance, its adhesiveness is lowered after curing, and it is inappropriate to use it as an adhesive material such as an adhesive sheet.

Japanese Patent Laid-Open No. 5-202163 JP 2000-219714 A JP 2002-371101 A JP 2005-60465 A JP 2006-298964 A JP 2007-39587 A JP 2008-291126 A JP 2008-291127 A Japanese Patent Publication No. 1-53681

  Under such circumstances, the present invention has excellent curability as a pressure-sensitive adhesive material and is excellent in standing stability before curing, formability such as sheet shape, and pressure-sensitive adhesive after curing. It is an object of the present invention to provide a photocurable resin composition capable of improving moisture permeability and vibration damping characteristics (hysteresis loss), and a pressure-sensitive adhesive sheet comprising the same.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by combining a specific hydrogenated butadiene polymer and a polythiol compound. The present invention has been completed based on such findings.
That is, the present invention
[1] a hydrogenated butadiene-based polymer having a plurality of (meth) acryloyl groups , a polythiol compound, a photopolymerization initiator , and an oligomer having a single (meth) acryloyl group ,
The hydrogenated butadiene polymer is hydrogenated aromatic vinyl - butadiene copolymer, or hydrogenated aromatic vinyl - Ri butadiene copolymer and hydrogenated butadiene homopolymer der,
Mass ratio of the hydrogenated aromatic vinyl-butadiene copolymer and the oligomer having a single (meth) acryloyl group in a total of 100 parts by mass (the hydrogenated aromatic vinyl-butadiene copolymer / the single of (meth) oligomer having an acryloyl group) is, the photocurable resin composition according to claim 1/99 to 80/20 der Rukoto,
[2] The photocurable resin composition according to the above [1], wherein the aromatic vinyl monomer constituting the hydrogenated aromatic vinyl-butadiene copolymer is styrene, α-methylstyrene and / or paramethylstyrene. object,

[3] before Symbol polythiol compound, the above-mentioned [1] is a compound having 2 to 6 mercapto groups in the molecule or light-curable resin composition according to [2],

[ 4 ] The photocurable resin composition according to any one of the above [ 1 ] to [ 3 ] , wherein the oligomer having a single photocurable functional group is a monofunctional (meth) acrylate oligomer,
[ 5 ] The monofunctional (meth) acrylate oligomer is a mono (meth) acryloyl group-containing hydrogenated diene polymer, a polyester mono (meth) acrylate oligomer, an epoxy mono (meth) acrylate oligomer, or a urethane mono (meth). The photocurable resin composition according to the above [ 4 ], which is at least one selected from an acrylate oligomer, a polyether mono (meth) acrylate oligomer, and a polyol mono (meth) acrylate oligomer,

[ 6 ] The mono (meth) acryloyl group-containing hydrogenated diene polymer is a mono (meth) acryloyl group-containing hydrogenated aromatic vinyl-butadiene copolymer or a mono (meth) acryloyl group-containing hydrogenated butadiene homopolymer. And the photocurable resin composition according to the above [ 5 ], which is at least one selected from a mono (meth) acryloyl group-containing hydrogenated isoprene homopolymer,
[ 7 ] The photo-curing property according to [ 6 ], wherein the mono (meth) acryloyl group-containing hydrogenated aromatic vinyl-butadiene copolymer is a mono (meth) acryloyl group-containing hydrogenated styrene-butadiene copolymer. It is an adhesive sheet which consists of a resin composition and the photocurable resin composition in any one of [ 8 ] said [1]-[ 7 ].

  According to the present invention, while having moderate curability, it is excellent in standing stability before curing as an adhesive material and formability such as sheet shape, and adhesiveness after curing, moisture permeability resistance and damping characteristics after curing ( It is possible to provide a photocurable resin composition that can also improve (hysteresis loss) and a pressure-sensitive adhesive sheet comprising the same.

  The photocurable resin composition of the present invention comprises a hydrogenated butadiene polymer having a plurality of photocurable functional groups, a polythiol compound, and a photopolymerization initiator. Here, the hydrogenated butadiene-based polymer having a plurality of photocurable functional groups includes a hydrogenated aromatic vinyl-butadiene copolymer having a plurality of photocurable functional groups and / or a plurality of photocurable functional groups. The hydrogenated butadiene homopolymer is preferably a hydrogenated aromatic vinyl-butadiene copolymer having a plurality of photocurable functional groups.

Among the monomers constituting the hydrogenated aromatic vinyl-butadiene copolymer having a plurality of photocurable functional groups, the aromatic vinyl monomer may be styrene, α-methylstyrene or paramethyl. Styrene is preferable from the viewpoint of physical properties of rubber after curing, and styrene is particularly preferable. These may be used alone or in combination of two or more.
Accordingly, the hydrogenated butadiene-based polymer having a plurality of photocurable functional groups is particularly preferably a hydrogenated styrene-butadiene copolymer having a plurality of photocurable functional groups. This is because moderate curability is obtained, hysteresis loss is increased, and vibration damping characteristics are improved.
Hereinafter, “having a plurality of photocurable functional groups” is abbreviated as “polyfunctional”.

The weight average molecular weight of the polyfunctional hydrogenated butadiene polymer according to the present invention is preferably 5,000 to 40,000, and more preferably 6,000 to 30,000. This is because if it is in the range of 5,000 to 40,000, the curability, moldability and tackiness can be suitably obtained. The molecular weight distribution is preferably 3.0 or less, particularly preferably 2.0 or less.
The polyfunctional hydrogenated butadiene polymer according to the present invention may be used alone or in combination of two or more.

  In the present invention, the photocurable functional group contained in the polyfunctional hydrogenated butadiene-based polymer is preferably a photocurable unsaturated hydrocarbon group, and the photocurable unsaturated hydrocarbon group is a (meth) acryloyl group. It is particularly preferred that Here, the (meth) acryloyl group refers to an acryloyl group or a methacryloyl group.

The polyfunctional hydrogenated butadiene-based polymer used in the photocurable resin composition of the present invention is produced, for example, as follows, taking a preferable polyfunctional hydrogenated aromatic vinyl-butadiene copolymer as an example.
(A) Polymerization of 1,3-butadiene and an aromatic vinyl monomer (especially styrene) with a dilithium initiator in a saturated hydrocarbon solvent, and a weight average molecular weight of 5,000 to 40,000 and a molecular weight distribution Producing an aromatic vinyl-butadiene copolymer having 3.0 or less;
(B) reacting the aromatic vinyl-butadiene copolymer with an alkylene oxide to produce an aromatic vinyl-butadiene copolymer polyol;
(C) hydrogenating the aromatic vinyl-butadiene copolymer polyol to produce a hydrogenated aromatic vinyl-butadiene copolymer polyol;
And (D) a step of reacting the hydrogenated aromatic vinyl-butadiene copolymer polyol with a photocurable functional group-containing compound.

First, as a first step (A), 1,3-butadiene and an aromatic vinyl monomer are polymerized with a dilithium initiator in a saturated hydrocarbon solvent to produce an aromatic vinyl-butadiene copolymer. To do. Since the main polymerization is living anionic polymerization, the polymerization can be performed while controlling the molecular weight and molecular weight distribution. The molecular weight can be obtained by polymerizing a polymer having a predetermined molecular weight depending on the amount of the dilithium initiator and the above monomer. In particular, when the weight average molecular weight is 5,000 or more, a narrow polymer having a molecular weight distribution of 2 or less is used. Easy to get. If desired, anionic polymerization may be carried out in the presence of a randomizer.
Next, as a second step (B), the aromatic vinyl-butadiene copolymer is aromatic having hydroxyl groups at both ends by an equivalent reaction between the copolymer end which is a living anion and alkylene oxide. A vinyl-butadiene copolymer polyol (hereinafter sometimes referred to as “copolymer polyol according to the present invention”) can be obtained.
Furthermore, as a third step (C), the copolymer polyol according to the present invention having a double bond in the main chain is subjected to a hydrogenation reaction (hereinafter referred to as a hydrogenation reaction), whereby the main chain is unsaturated. Hydrogenated aromatic vinyl-butadiene copolymer polyol having no double bond or few unsaturated double bonds in the main chain (hereinafter sometimes referred to as “hydrogenated copolymer polyol according to the present invention”). Can be obtained.
As the fourth step (D), the hydrogenated copolymer polyol according to the present invention obtained as described above is reacted with a photocurable functional group-containing compound to produce a bifunctional polyfunctional hydrogenated aromatic. A vinyl-butadiene copolymer is obtained.

  The dilithium initiator is not particularly limited, and known ones can be used. For example, Patent Document 9 describes a method for producing a dilithium initiator by reacting a monolithium compound with a disubstituted vinyl or an alkenyl group-containing aromatic hydrocarbon in the presence of a tertiary amine.

  Monolithium compounds used when producing a dilithium initiator include ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, tert-octyl lithium, and n-decyl. Examples thereof include lithium, phenyl lithium, 2-naphthyl lithium, 2-butyl-phenyl lithium, 4-phenyl-butyl lithium, cyclohexyl lithium, cyclopentyl lithium, and among these, sec-butyl lithium is preferable.

Examples of the tertiary amine used when producing the dilithium initiator include lower aliphatic amines such as trimethylamine and triethylamine, N, N-diphenylmethylamine, and the like, and triethylamine is particularly preferable.
Examples of the disubstituted vinyl or alkenyl group-containing aromatic hydrocarbon include 1,3- (diisopropenyl) benzene, 1,4- (diisopropenyl) benzene, 1,3-bis (1-ethylethenyl). ) Benzene, 1,4-bis (1-ethylethenyl) benzene and the like are preferred.

  The solvent used in the preparation of the dilithium initiator and the production of the copolymer may be an organic solvent inert to the reaction, and is a hydrocarbon solvent such as an aliphatic, alicyclic or aromatic hydrocarbon compound. For example, n-butane, l-butane, n-pentane, l-pentane, cis-2-butene, trans-2-butene, l-butene, n-hexane, n-heptane, n-octane, One or two kinds selected from l-octane, methylcyclopentane, cyclopentane, cyclohexane, 1-hexene, 2-hexene, 1-pentene, 2-pentene, benzene, toluene, xylene, ethylbenzene and the like are used. Of these, n-hexane and cyclohexane are usually used.

  Further, examples of the alkylene oxide used in the polyolization reaction that reacts with the terminal which is the living anion of the copolymer according to the present invention to generate a hydroxyl group at both terminals include ethylene oxide, propylene oxide, butylene oxide, and the like. . This polyol reaction is preferably performed immediately after the polymerization reaction.

If the weight average molecular weight of the copolymer polyol according to the present invention obtained by the above polyol reaction is 5,000 or more, the molecular weight between cross-linking points can be increased, and after the photocuring reaction, the elastic modulus is lowered and the elongation is reduced. On the other hand, if the weight average molecular weight is 40,000 or less, the polymerization viscosity does not become too high when the polymerization is carried out with a dilithium catalyst, and there is no need to lower the solid content concentration as a polymerization process. Therefore, it becomes low cost and preferable.
Moreover, various influences by a low molecular weight component and a high molecular weight component can be suppressed as molecular weight distribution is 3.0 or less. In particular, since the viscosity is greatly affected by the molecular weight, slight fluctuations in the molecular weight cause viscosity variations. In the present invention in which a copolymer having a narrow molecular weight distribution can be synthesized, a copolymer having the same molecular weight can be obtained with good reproducibility, so that an effect of stabilizing the viscosity can be expected. In many cases, the liquid material as in the present invention is processed into a sheet shape. In this case, the variation in material viscosity causes variation in the size of the sheet. Therefore, stabilization of the viscosity is important, and the molecular weight distribution is 3 0.0 or less is preferable.

The hydrogenation reaction for obtaining the hydrogenated copolymer polyol according to the present invention is carried out by hydrogenating the copolymer polyol according to the present invention in the presence of a hydrogenation catalyst in an organic solvent under hydrogen pressure. . The hydrogenation catalyst used in this hydrogenation reaction is a heterogeneous catalyst such as palladium-carbon, reduced nickel, rhodium, or the like, or an organic nickel compound such as nickel naphthenate or nickel octoate, or cobalt naphthenate or cobalt octoate. A homogeneous catalyst in which an organocobalt compound and an organoaluminum compound such as triethylaluminum and triisobutylaluminum or an organolithium compound such as n-butyllithium and sec-butyllithium are combined can be used. As a cocatalyst, an ether compound such as tetrahydrofuran, ethylene glycol dimethyl ether, or diethylene glycol dimethyl ether may be used. In addition, as another hydrogenation reaction method, for example, the copolymer according to the present invention before hydrogenation may be prepared by converting dicyclopentadienyl titanium halide, organic carboxylate nickel, organic carboxylate nickel and periodic table I to I Hydrogenation catalysts composed of Group III organometallic compounds, nickel, platinum, barium, ruthenium, rhenium, rhodium metal catalysts supported on carbon, silica, diatomaceous earth, etc., cobalt, nickel, rhodium, ruthenium complexes, etc. as catalysts Under hydrogen pressurized to about 0.1 to 10 MPa, or in the presence of lithium aluminum hydride, p-toluenesulfonyl hydrazide, Zr—Ti—Fe—V—Cr alloy, Zr—Ti—Nb—Fe—V— pressurized presence of Cr alloy, a hydrogen storage alloy such as LaNi ₅ alloy, or about 0.1~10MPa pressure Obtained by mixing a hydrogenated di-p-tolyl-bis (1-cyclopentadienyl) titanium / cyclohexane solution and an n-butyllithium / n-hexane solution under hydrogen. Examples of the method include hydrogenation using a hydrogenation catalyst under hydrogen pressurized to about 0.1 to 10 MPa.

Among the various hydrogenation catalysts described above, a Ziegler hydrogenation catalyst or a palladium-carbon hydrogenation catalyst comprising a combination of a transition metal compound and an alkylaluminum compound is preferred.
Such transition metal compounds include tris (acetylacetonato) cobalt, bis (acetylacetonato) nickel, tris (acetylacetonato) iron, tris (acetylacetonato) chromium, tris (acetylacetonato) manganese, bis (acetyl). Acetonato) manganese, tris (acetylacetonato) ruthenium, bis (acetylacetonato) cobalt, bis (cyclopentadienyl) dichlorotitanium, bis (cyclopentadienyl) dichlorozirconium, bis (triphenylphosphine) cobalt dichloride, Examples thereof include bis (2-hexanoate) nickel, bis (2-hexanoate) cobalt, titanium tetraisopropoxide, and titanium tetraethoxide. Among these, bis (acetylacetonato) nickel and tris (acetylacetonato) cobalt are preferable from the viewpoint of high hydrogenation activity.

  Alkyl aluminum compounds used for Ziegler hydrogenation catalysts include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-butylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, methylaluminum Examples include dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, diethylaluminum hydride, diisobutylaluminum hydride, ethylaluminum sesquichloride and the like. Among these, triisobutylaluminum, triethylaluminum, and diisobutylaluminum hydride are preferable from the viewpoint of hydrogenation activity, and triisobutylaluminum is most preferable.

  Although there is no particular limitation on the use form of the Ziegler-type hydrogenation catalyst in the hydrogenation reaction, a method in which a catalyst solution in which a transition metal compound and an alkylaluminum compound are reacted in advance is prepared and added to the polymerization solution is preferably cited. I can do it. The amount of the alkylaluminum compound used in this case is preferably 0.2 to 5 mol with respect to 1 mol of the transition metal compound. The catalyst preparation reaction is carried out in a temperature range of about -40 to 100 ° C, preferably 0 to 80 ° C, and the reaction time is usually in the range of 1 minute to 3 hours.

  The hydrogenation reaction is usually performed at a temperature of 50 to 180 ° C., preferably 70 to 150 ° C., and at a hydrogen pressure of about 0.5 to 10 MPa, preferably 1 to 5 MPa. When the hydrogenation temperature is lower than 50 ° C., and when the hydrogen pressure is lower than 0.5 MPa, the catalytic activity is lowered, which is not preferable. Therefore, it is not preferable. In general, a Ziegler-type hydrogenation catalyst is a catalyst having a very high hydrogenation activity, and it is not preferable to set the hydrogen pressure higher than 10 MPa because it is not necessary and increases the burden on the apparatus.

In order to introduce a photocurable functional group into the terminal of the hydrogenated copolymer polyol according to the present invention, a photocurable functional group-containing compound, preferably a photocurable non-functional group, is added to the hydrogenated copolymer polyol. A saturated hydrocarbon group-containing compound, particularly preferably a (meth) acryloyl group-containing compound is reacted. Here, as the (meth) acryloyl group-containing compound, acryloyloxyalkyl isocyanate and methacryloyloxyalkyl isocyanate are preferable, and the hydrogenated copolymer polyol is (meth) acrylated by reaction with these.
Examples of the acryloyloxyalkyl isocyanate include 2-acryloyloxyethyl isocyanate, and examples of the methacryloyloxyalkyl isocyanate include 2-methacryloyloxyethyl isocyanate.

  When a polyfunctional hydrogenated butadiene homopolymer is used as the polyfunctional hydrogenated butadiene polymer according to the present invention, in the method for producing a polyfunctional hydrogenated aromatic vinyl-butadiene copolymer as described above, The monomer charged in the first stage (A) may be changed from 1,3-butadiene and aromatic vinyl monomer to 1,3-butadiene and polymerized in the same manner. The second stage (B), the third stage (C) and the fourth stage (D) are the same as described above. Thereby, the polyfunctional hydrogenated butadiene homopolymer which is bifunctional is obtained.

  In order to obtain a trifunctional polyfunctional hydrogenated butadiene-based polymer, in the first step (A), the dilithium initiator is changed to the trilithium initiator, and the charged monomer is 1 1,3-butadiene and an aromatic vinyl monomer, or 1,3-butadiene alone may be polymerized.

The photocurable resin composition of the present invention is required to contain a polythiol compound in addition to the above-mentioned polyfunctional hydrogenated butadiene polymer. Thereby, the crosslinking density by photocuring can be made low and adhesiveness can be improved.
Although it does not restrict | limit especially as a polythiol compound, The compound which has 2-6 mercapto groups in a molecule | numerator is preferable, for example, aromatic polythiols, such as C2-C20 alkanedithiol, aromatics, such as xylylene dithiol Polythiols, polythiols obtained by replacing halogen atoms of halohydrin adducts of alcohols with mercapto groups, polythiols comprising hydrogen sulfide reaction products of polyepoxide compounds, polyhydric alcohols having 2 to 6 hydroxyl groups in the molecule And polythiols composed of esterified products of thioglycolic acid, β-mercaptopropionic acid, or β-mercaptobutanoic acid.

Among the above polythiols, polyhydric alcohols having 2 to 6 hydroxyl groups in the molecule, which have good reactivity and easy chemical structure control, thioglycolic acid, β-mercaptopropionic acid, or β -Polythiols comprising an esterified product with mercaptobutanoic acid, particularly an esterified product with β-mercaptopropionic acid or an esterified product with β-mercaptobutanoic acid are preferred.
Examples of the polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule include alkanediol having 2 to 20 carbon atoms, poly (oxyalkylene) glycol, glycerol, diglycerol, trimethylolpropane, ditrimethylolpropane, and pentaerythritol. And dipentaerythritol.

The alkanediol having 2 to 20 carbon atoms may be linear, branched or cyclic, for example, ethylene glycol, trimethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butane. Examples include diol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,12-dodecanediol, cyclohexane-1,4-dimethanol, hydrogenated bisphenol A, and the like. It is done.
Examples of the poly (oxyalkylene) glycol include diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, polytetramethylene ether glycol, cyclohexane-1,4-dimethanol ethylene oxide adduct, water Examples thereof include a bisphenol A ethylene oxide adduct, a cyclohexane-1,4-dimethanol propylene oxide adduct, and a hydrogenated bisphenol A propylene oxide adduct.

  Examples of the polythiol compound according to the present invention include ethylene glycol di (thioglycolate), ethylene glycol di (β-mercaptopropionate), ethylene glycol di (β-mercaptobutanate), and trimethylene glycol di (thioglycolate). , Trimethylene glycol di (β-mercaptopropionate), trimethylene glycol di (β-mercaptobutanate), propylene glycol di (thioglycolate), propylene glycol di (β-mercaptopropionate), propylene glycol di (Β-mercaptobutanate), 1,3-butanediol di (thioglycolate), 1,3-butanediol di (β-mercaptopropionate), 1,3-butanediol di (β-mercaptobutanate) ), 1,4-butane Diol di (thioglycolate), 1,4-butanediol di (β-mercaptopropionate), 1,4-butanediol di (β-mercaptobutanate), neopentyl glycol di (thioglycolate), neopentyl Glycol di (β-mercaptopropionate), neopentyl glycol di (β-mercaptobutanate), 1,6-hexanediol di (thioglycolate), 1,6-hexanediol di (β-mercaptopropionate) ), 1,6-hexanediol di (β-mercaptobutanate), 1,8-octanediol di (thioglycolate), 1,8-octanediol di (β-mercaptopropionate), 1,8- Octanediol di (β-mercaptobutanate), 1,9-nonanediol di (thioglycolate) ), 1,9-nonanediol di (β-mercaptopropionate), 1,9-nonanediol di (β-mercaptobutanate), cyclohexane-1,4-dimethanoldi (thioglycolate), cyclohexane-1, 4-dimethanoldi (β-mercaptopropionate), cyclohexane-1,4-dimethanoldi (β-mercaptobutanate), diethylene glycol di (thioglycolate), diethylene glycol di (β-mercaptopropionate), diethylene glycol di (β -Mercaptobutanate), triethylene glycol di (thioglycolate), triethylene glycol di (β-mercaptopropionate), tetraethylene glycol di (β-mercaptopropionate), triethylene glycol di (β-mercapto) Titanate), polyethylene glycol di (thioglycolate), polyethylene glycol di (β-mercaptopropionate), polyethylene glycol di (β-mercaptobutanate), dipropylene glycol di (thioglycolate), dipropylene glycol di ( β-mercaptopropionate), dipropylene glycol di (β-mercaptobutanate), tripropylene glycol di (thioglycolate), tripropylene glycol di (β-mercaptopropionate), tripropylene glycol di (β- Mercaptobutanate), polypropylene glycol di (thioglycolate), polypropylene glycol di (β-mercaptopropionate), polypropylene glycol di (β-mercaptobutanate), polytetramethyl Ether glycol di (thioglycolate), polytetramethylene ether glycol di (β-mercaptopropionate), polytetramethylene ether glycol di (β-mercaptobutanate), cyclohexane-1,4-dimethanol ethylene oxide addition Di (thioglycolate) of product, di (β-mercaptopropionate) of cyclohexane-1,4-dimethanol ethylene oxide adduct, di (β-mercapto of cyclohexane-1,4-dimethanol ethylene oxide adduct Butanate), hydrogenated bisphenol A ethylene oxide adduct di (thioglycolate), hydrogenated bisphenol A ethylene oxide adduct di (β-mercaptopropionate), hydrogenated bisphenol A ethylene oxide adduct di ( β- Lucaptobutanate), di (thioglycolate) of cyclohexane-1,4-dimethanol propylene oxide adduct, di (β-mercaptopropionate) of cyclohexane-1,4-dimethanol propylene oxide adduct, cyclohexane -1,4-dimethanol propylene oxide adduct (β-mercaptobutanate), hydrogenated bisphenol A propylene oxide adduct di (thioglycolate), hydrogenated bisphenol A propylene oxide adduct di (β-mercapto) Propionate), hydrogenated bisphenol A propylene oxide adduct di (β-mercaptobutanoate), glycerol tri (thioglycolate), glycerol tri (β-mercaptopropionate), glycerol tri (β-mercaptobutanate) ), Diglycerol tetra (thioglycolate), diglycerol tetra (β-mercaptopropionate), diglycerol tetra (β-mercaptobutanate), trimethylolpropane tri (thioglycolate), trimethylolpropane tri (β -Mercaptopropionate), trimethylolpropane tri (β-mercaptobutanate), ditrimethylolpropanetetra (thioglycolate), ditrimethylolpropanetetra (β-mercaptopropionate), ditrimethylolpropanetetra (β-mercapto Butaneate), pentaerythritol tetra (thioglycolate), pentaerythritol tetra (β-mercaptopropionate), pentaerythritol tetra (β-mercaptobutanoate), dipentaerythritol It is preferable to use hexyl hexa (thioglycolate), dipentaerythritol hexa (β-mercaptopropionate), dipentaerythritol hexa (β-mercaptobutanate) and the like.

  Among these polythiol compounds, poly (β-mercaptopropionate) and poly (β-mercaptobutanate) are preferred, and in particular, polyethylene glycol di (β-mercaptopropionate), pentaerythritol tetra (β- Mercaptopropionate), dipentaerythritol hexa (β-mercaptopropionate), polyethylene glycol di (β-mercaptobutanate), pentaerythritol tetra (β-mercaptopropionate) (tetrafunctional polythiol compound: SC organic chemistry (Trade name “PEMP”), pentaerythritol tetra (β-mercaptobutanate), dipentaerythritol hexa (β-mercaptobutanate) (hexafunctional polythiol compound: SC Organic Chemicals, trade name “DPMP”) And Tet Ethylene glycol di (beta-mercaptopropionate) (2-functional polythiol compound: SC Organic Chemical Co., Ltd., trade name "EGMP4") are preferred from the viewpoint of the performance of availability and the resulting elastomer.

  In addition, when a large amount of a polythiol compound is blended in the photocurable resin composition of the present invention, the polyfunctional hydrogenated butadiene polymer and the monofunctional oligomer may phase separate and become cloudy, and the uniform photocurable resin composition May not be obtained. From this viewpoint, the compounding amount of the polythiol compound is 100 parts by mass of a polyfunctional hydrogenated butadiene polymer (however, an oligomer having a single photocurable functional group and / or a monofunctional (meth) acrylate monomer described later) Is also 10 parts by mass or less with respect to the polyfunctional hydrogenated butadiene-based polymer, the oligomer having a single photocurable functional group, and the monofunctional (meth) acrylate monomer in a total of 100 parts by mass). Is preferable, and it is more preferable that it is 8 mass parts or less.

  As the photopolymerization initiator used in the photocurable resin composition of the present invention, aminoacetophenones, benzoin derivatives, benzyl ketals, hydroxyacetophenones, aminoacetophenones and thioxanthones (for example, as intramolecular cleavage types) Isopropylthioxanthone, diethylthioxanthone), acylphosphine oxides and the like. Examples of the hydrogen abstraction type include benzophenones and amines, and thioxanthone and amines. Further, an intramolecular cleavage type and a hydrogen abstraction type may be used in combination.

Of these, aminoacetophenones are preferable, for example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907], 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 369], 2- (dimethylamino) -2 -[(4-Methylphenyl) methyl] -1- (4-morpholinophenyl) -1-butanone [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 379] and the like. Aminoacetophenones may be used alone or in combination with other photopolymerization initiators.
Aminoacetophenones have a high reaction activity as a photopolymerization initiator, and are less susceptible to oxygen inhibition of the surface of the photocurable resin composition due to the presence of nitrogen atoms, thereby improving the curability of the entire photocurable resin composition, The tackiness of the photocurable resin composition after curing can be reduced, and the compression set can be reduced.

  Examples of the benzoin derivatives include benzoin, benzoin alkyl ether (alkyl having 1 to 6 carbon atoms), specifically, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like. Examples of benzyl ketals include 2,2-dimethoxy-1,2-diphenylethane-1-one [manufactured by Ciba Specialty Chemicals, Inc., trade name: Irgacure 651]. Examples of hydroxyacetophenones 2-hydroxy-2-methyl-1-phenyl-propan-1-one [manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Darocur 1173], 1-hydroxy-cyclohexyl-phenyl ketone [Ciba Specialty Chemicals Product name: Irgacure 184], 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one [Product name: Irgacure 127, manufactured by Ciba Specialty Chemicals Co., Ltd.] It is below. And a combination of aminoacetophenones and thioxanthones (eg, isopropylthioxanthone, diethylthioxanthone), acylphosphine oxides {eg, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide [Ciba Specialty Chemicals (Product name: Irgacure 819]}, etc., and oligomerized α-hydroxyacetophenone {specifically, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) ) Phenyl] propanone, such as Lamberti S. et al. p. Manufactured by A, trade name: ESACURE KIP150, etc.] and acrylated benzophenones [specifically, acrylated benzophenone, for example, manufactured by Daicel UC Corporation, trade name: Ebecryl P136, etc.] Can be mentioned.

  Further, benzoyl methyl ether, benzoyl ethyl ether, benzoyl butyl ether, benzoyl isopropyl ether, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl ] Propanol oligomer, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer and 2-hydroxy-2-methyl-1-phenyl-1-propanone, isopropylthioxanthone, o-benzoyl Examples thereof also include methyl benzoate, [4- (methylphenylthio) phenyl] phenylmethane, and imide acrylate.

  The amount of the photopolymerization initiator blended in the photocurable resin composition of the present invention is 100 parts by mass of a polyfunctional hydrogenated butadiene-based polymer (however, an oligomer having a single photocurable functional group described later and In the case where the monofunctional (meth) acrylate monomer is also included, the polyfunctional hydrogenated butadiene polymer, the oligomer having a single photocurable functional group, and the monofunctional (meth) acrylate monomer in total 100 parts by mass) On the other hand, it is preferable that it is 0.1-6 mass parts, More preferably, it is 0.4-5 mass parts, More preferably, it is 0.6-4 mass parts.

If desired, the photocurable resin composition of the present invention may be blended with an oligomer having a single photocurable functional group. This is because, in combination with the above polythiol compound, the cross-linking density by photocuring can be lowered and the tackiness can be improved.
The oligomer having a single photocurable functional group (hereinafter abbreviated as “monofunctional oligomer”) is preferably a monofunctional (meth) acrylate oligomer. Examples of the monofunctional (meth) acrylate oligomer include a mono (meth) acryloyl group-containing hydrogenated diene polymer, a polyester mono (meth) acrylate oligomer, an epoxy mono (meth) acrylate oligomer, and a urethane mono (meth) acrylate oligomer. Examples include oligomers, polyether mono (meth) acrylate oligomers and polyol mono (meth) acrylate oligomers, and mono (meth) acryloyl group-containing hydrogenated diene polymers are more preferred.
The monofunctional oligomer according to the present invention may be used alone or in combination of two or more.

Examples of the mono (meth) acryloyl group-containing hydrogenated diene polymer include mono (meth) acryloyl group-containing hydrogenated aromatic vinyl-butadiene copolymers, mono (meth) acryloyl group-containing hydrogenated butadiene homopolymers, and mono A (meth) acryloyl group-containing hydrogenated isoprene homopolymer is preferred. Here, the aromatic vinyl monomer constituting the mono (meth) acryloyl group-containing hydrogenated aromatic vinyl-butadiene copolymer is at least one selected from styrene, α-methylstyrene and paramethylstyrene. Styrene is particularly preferred.
Therefore, the mono (meth) acryloyl group-containing hydrogenated diene polymer is more preferably a mono (meth) acryloyl group-containing hydrogenated aromatic vinyl-butadiene copolymer, and the mono (meth) acryloyl group-containing hydrogenated styrene. -Butadiene copolymers are particularly preferred.

When a mono (meth) acryloyl group-containing hydrogenated diene polymer is used as the monofunctional oligomer according to the present invention, the first in the production method of the above-mentioned bifunctional polyfunctional hydrogenated aromatic vinyl-butadiene copolymer. In step (A), the polymerization initiator is changed from the dilithium initiator to the monolithium compound, and the monomers to be charged are 1,3-butadiene and an aromatic vinyl monomer, or 1,3-butadiene. The polymerization may be performed alone.
The second stage (B), the third stage (C) and the fourth stage (D) are the same as described above. As a result, a mono (meth) acryloyl group-containing hydrogenated aromatic vinyl-butadiene copolymer or a mono (meth) acryloyl group-containing hydrogenated butadiene homopolymer is obtained.

The weight average molecular weight of these mono (meth) acryloyl group-containing hydrogenated diene polymers is preferably 1,000 to 10,000, and more preferably 1,500 to 8,000. If it is the range of 1,000-10,000, adhesiveness and sheet moldability become more favorable and are preferable.
The molecular weight distribution is preferably 3.0 or less, particularly preferably 2.0 or less.
The weight average molecular weight and molecular weight distribution of the polyfunctional hydrogenated butadiene polymer and mono (meth) acryloyl group-containing hydrogenated diene polymer are converted to polystyrene using standard polystyrene using the GPC method (Gel Permeation Chromatography). Is the weight average molecular weight and molecular weight distribution obtained by

In the present invention, the polyester mono (meth) acrylate oligomer blended as a monofunctional (meth) acrylate oligomer as desired is, for example, a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol. By esterifying the hydroxyl group at one end with (meth) acrylic acid, or by esterifying the hydroxyl group at one end of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with (meth) acrylic acid Can be obtained.
The epoxy mono (meth) acrylate oligomer can be obtained, for example, by reacting and esterifying 1 equivalent of (meth) acrylic acid on the oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin. it can. A carboxyl-modified epoxy acrylate oligomer obtained by partially modifying this epoxy-based mono (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used.

The urethane mono (meth) acrylate oligomer can be obtained, for example, by esterifying one end of a polyurethane oligomer obtained by the reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. it can.
The polyether mono (meth) acrylate oligomer can be obtained by esterifying one hydroxyl group in the polyether polyol with (meth) acrylic acid.
Other polyol mono (meth) acrylate oligomers other than the above can also be obtained by esterifying one hydroxyl group in the polyol with (meth) acrylic acid.

The blending amount of the monofunctional oligomer blended as desired in the present invention is 100 parts by mass of the polyfunctional hydrogenated butadiene polymer and the monofunctional oligomer. The polymer / monofunctional oligomer) is preferably (1/99) to (80/20), and more preferably (10/90) to (50/50). When a monofunctional oligomer is blended, the viscosity-reducing effect of the photo-curable resin composition can be enjoyed, it becomes easy to roll, extrude, discharge, etc., and the shape can be easily maintained before being cured with ultraviolet rays, etc. It becomes easy to form. Moreover, if it is 99 mass parts or less, the viscosity of this composition will not become low too much, it will become difficult to flow down the sheet | seat material etc. immediately after formation, and the standing stability before photocuring will improve. Furthermore, adhesiveness and vibration damping characteristics of the cured sheet material and the like are ensured.
Note that a low-crosslinking photocurable resin composition having a mass part ratio of (polyfunctional hydrogenated butadiene polymer / monofunctional oligomer) of (1/99) to (5/95) is also suitably used as an adhesive. It is done.

The photocurable resin composition of the present invention is used for the purpose of adjusting the viscosity of the photocurable resin composition before curing (reducing viscosity) and adjusting the physical properties after curing (preparation of curability and adhesiveness). If desired, a monofunctional (meth) acrylate monomer may be contained as long as the solution of the problem of the invention is not impaired. The molecular weight of the monofunctional (meth) acrylate monomer is preferably less than 1,000, more preferably 100 to 900, and even more preferably 150 to 600.
The monofunctional (meth) acrylate monomer according to the present invention may be used alone or in combination of two or more.

Specific examples of the monofunctional (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, isoamyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (Meth) acrylate, tridecyl (meth) acrylate, behenyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) ) Acrylate, butoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy Tetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, Benzyl (meth) acrylate, phenoxyethyl (meth) acryl , Dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, allyl (meth) acrylate, Diethylene glycol monoethyl ether (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylol dicyclopentane (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxylated phenyl (meth) acrylate, Lauroxypolyethylene glycol (meth) acrylate, methoxytrypylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate And various mono (meth) acrylates such as cartons. These may be used alone or in combination of two or more.
In addition, (meth) acrylate means an acrylate or a methacrylate.
Among these, in the present invention, isobornyl acrylate, dicyclopentanyl acrylate and dicyclopentenyl acrylate are preferable.

  The compounding amount of the monofunctional (meth) acrylate monomer is the ratio of the total amount of the polyfunctional hydrogenated butadiene polymer and monofunctional oligomer and the mass part of the monofunctional (meth) acrylate monomer {(multifunctional hydrogenated butadiene type The total amount of the combined and monofunctional oligomer) / monofunctional (meth) acrylate monomer} is preferably (100/0) to (30/70), and (100/0) to (50/50). More preferably.

In order to improve the weather resistance of the photocurable resin composition of the present invention, an antioxidant may be blended as desired. Examples of the antioxidant include phenol-based, sulfur-based, and phosphorus-based antioxidants.
Examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4- Hydroxy-5-tert-butylphenylbutane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis -[Methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis- (4′-hydroxy-3′-t-butyl) Phenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H , 5H) trione, α-tocopherol and the like.

  Examples of sulfur-based antioxidants include dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, and phosphorus-based oxidation. Examples of the inhibitor include triphenyl phosphite, diphenylisodecyl phosphite, phenylisodecyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, 2,2 ′. -Methylenebis (4,6-di-t-butylphenyl) octyl phosphite and the like are exemplified.

These antioxidants may be used alone or in combination of two or more, and among them, a phenolic antioxidant is suitable.
The blending amount of the antioxidant is appropriately selected according to the type, but is 100 parts by mass in total of the polyfunctional hydrogenated butadiene polymer, monofunctional oligomer, polythiol compound and monofunctional (meth) acrylate monomer. Usually, 0.01 to 5 parts by mass, preferably 0.1 to 3 parts by mass.

In order to improve the light stability of the photocurable resin composition of the present invention, a light stabilizer may be blended as desired. Examples of the light stabilizer include ultraviolet absorbers such as benzophenone, benzotriazole, benzoate, and triazine, and hindered amine light stabilizers. Among these, hindered amine light stabilizers are preferable.
Examples of the hindered amine light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4- Benzoyloxy-2,2,6,6-tetramethylpiperidine, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, Bis (1,2,2,6,6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] Tilmalonate, decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, N, N ′, N ″, N ″ ′-tetrakis- (4,6- Bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine -1,3,5-triazine-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6- Polycondensate of tetramethyl-4-piperidyl) butylamine, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2 , 2,6,6-Tetramethyl-4-piperidyl ) Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol Polymer, 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7-oxa-3,20-diazadispiro [5.1.1.12] heneicosane-21-one, β -Alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl) -dodecyl ester / tetradecyl ester, N-acetyl-3-dodecyl-1- (2,2,6,6-tetra Methyl-4-piperidinyl) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro [5.1.1.12] heneicosane-21 -One, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5.1.1.12] -heneicosane-20-propanoic acid dodecyl ester / tetradecyl ester propanedioic acid , [(4-Methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, higher fatty acid ester of 2,2,6,6-tetramethyl-4-piperidinol 1,3-benzenedicarboxamide-N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) and the like.

  These light stabilizers may be used individually by 1 type, and may be used in combination of 2 or more type. The blending amount of the light stabilizer is appropriately selected according to the type, but is 100 parts by mass in total of the polyfunctional hydrogenated butadiene polymer, monofunctional oligomer, polythiol compound, and monofunctional (meth) acrylate monomer. Usually, 0.01 to 5 parts by mass, preferably 0.1 to 3 parts by mass.

A stabilizer or the like may be further added to the photocurable resin composition of the present invention. As a stabilizer, triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate] [for example, Ciba Specialty Chemicals Co., Ltd., trade name: IRGANOX245, Asahi Manufactured by Denka Kogyo Co., Ltd., trade name: ADK STAB AO-70, etc.], 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1, 1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane [for example, manufactured by Asahi Denka Kogyo Co., Ltd., trade name: ADK STAB AO-80, etc.] Etc.
The amount of the stabilizer that is optionally blended in the photocurable resin composition of the present invention is 100 parts by mass in total of the polyfunctional hydrogenated butadiene polymer, monofunctional oligomer, polythiol compound, and monofunctional (meth) acrylate monomer. On the other hand, it is preferable that it is 0.1-5 mass parts, More preferably, it is 0.5-3 mass parts, More preferably, it is 0.5-2 mass parts.

Further, the photo-curable resin composition of the present invention includes a terpene resin, a terpene phenol resin, a coumarone resin, a coumarone-indene resin, a petroleum hydrocarbon for improving adhesion within a range not impairing the effects of the present invention. , Various tackifiers such as rosin derivatives, colorants such as titanium white and titanium black, inorganic fillers such as silica (SiO ₂ ), alumina, titania and viscosity minerals, hydrogenated castor oil, amide wax or mixtures thereof Additives such as organic thickeners can be added.

The photocurable resin composition of the present invention can be reacted and cured by irradiation with active energy rays to obtain a cured product having tackiness.
The active energy ray used for reacting and curing the photocurable resin composition of the present invention refers to ionizing radiation such as ultraviolet rays and electron beams, α rays, β rays, γ rays, etc. Ultraviolet light is preferred. Examples of the ultraviolet light source include a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and a microwave excimer lamp. The atmosphere for irradiation with ultraviolet rays is preferably an inert gas atmosphere such as nitrogen gas or carbon dioxide gas, or an atmosphere with a reduced oxygen concentration, but can be sufficiently cured even in a normal air atmosphere. The irradiation atmosphere temperature can usually be 10 to 200 ° C.
In addition, the properties of the photo-curable resin can be stabilized by irradiating active energy rays again after curing or by applying heat.

The manufacturing method of the photocurable resin composition of this invention is not specifically limited, A well-known method is applicable. For example, kneading each component and optionally used additive components using a kneader capable of adjusting the temperature, such as a single screw extruder, twin screw extruder, planetary mixer, twin screw mixer, high shear mixer, etc. Can be manufactured.
A sheet material such as the pressure-sensitive adhesive sheet of the present invention can be produced by rolling or extruding the photocurable resin composition thus obtained into a sheet shape and curing it by irradiation with energy rays. As the adherend of these sheet materials, for example, a plastic material made of hard resin or soft resin or a metal material is preferable. There is no restriction | limiting in particular as a plastic material.
The metal is not particularly limited, and is appropriately selected from, for example, cold rolled steel sheet, galvanized steel sheet, aluminum / zinc alloy plated steel sheet, stainless steel sheet, aluminum plate, aluminum alloy plate, magnesium plate, magnesium alloy plate, etc. Can be used.

  The sheet material obtained from the photocurable resin composition of the present invention is suitably used as a sealing member, an adhesive member, a vibration damping member, etc., such as various electronic parts, automobile parts, housing members, furniture members, etc. as an adhesive sheet. The thickness of the sheet material can be appropriately selected depending on the application, but is usually about 0.1 to 5.0 mm.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
The weight average molecular weight and molecular weight distribution of the polyfunctional hydrogenated butadiene-based polymer and monofunctional oligomer, the standing stability and moldability of the photocurable resin composition before curing, and the adhesion of the photocurable resin composition after curing. The properties, moisture permeability, curability and vibration damping properties were measured according to the following methods.
(1) Weight average molecular weight and molecular weight distribution Using the GPC method (Gel Permeation Chromatography), the weight average molecular weight and molecular weight distribution were obtained by polystyrene conversion using standard polystyrene.

(2) Moisture permeability The moisture permeability cup of method A described in JIS L1099 was used, and measurement was performed under the conditions of 40 ° C, relative humidity 90%, and 24 hours in accordance with JIS Z0208. As a test body, a sheet of a photocurable resin composition after UV curing having a thickness of 1 mm was used.
(3) Curability The photocurable resin composition is formed on a glass plate with a coater to a thickness of about 1 mm, cured under conditions of illuminance of 160 mW / mm ² and integrated light quantity of 9000 mJ / m ² , and peeled off while maintaining the sheet shape. And evaluated according to the following evaluation criteria.
Good: The photocurable resin composition could be peeled off while maintaining the sheet shape.
Defect: The photocurable resin composition could not be removed while maintaining the sheet shape.

(4) Storage stability before ultraviolet (UV) curing (Left for half a day)
After stirring the photocurable resin composition, it was allowed to stand at 23 ° C. for half a day, the degree of separation was visually confirmed, and evaluation was performed according to the following evaluation criteria.
Good: The components of the photocurable resin composition were not separated, and the compatibility was good.
Defect: The components of the photocurable resin composition were separated, and the compatibility was poor.
(5) Damping characteristics {tan δ (23 ° C)}
Using a dynamic viscoelasticity measuring device, a parallel plate was used, and measurement was performed at −50 to 80 ° C. under conditions of dynamic strain 1% and frequency 1 Hz, and a tan δ value at 23 ° C. was obtained. The greater the value, the better the damping characteristics.

(6) Moldability Moldability The photocurable resin composition was molded to 1 mm with a coater and then left for 1 minute before ultraviolet irradiation to evaluate whether the thickness changed.
Good: The thickness of the photocurable resin composition did not change.
Defect: The thickness of the photocurable resin composition was changed.
(7) Adhesion After a cured photocurable resin composition sheet having a thickness of about 1 mm is adhered to a polypropylene plate, a weight of about 2 kg is placed on it for 1 minute, and then peeled off at 180 ° C. (peeling test). The gender was measured and expressed in units of gf.

Production Example 1 Production of polyfunctional hydrogenated butadiene-based polymer After 1 mol of 1,3- (diisopropenyl) benzene was added to a fully dehydrated and purified cyclohexane solvent, 2 mol of triethylamine and 2 mol of sec-butyllithium. Were sequentially added and stirred at 50 ° C. for 2 hours to prepare a dilithium polymerization initiator.
In a 7 liter polymerization reactor purged with argon, 1.90 kg of dehydrated and purified cyclohexane, 2.00 kg of a hexane solution of 22.9% by mass of 1,3-butadiene monomer, and a cyclohexane solution of 20.0% by mass of styrene monomer were added. After adding 130.4 ml of a hexane solution of 0.765 kg, 1.6 mol / liter of 2,2-di (tetrahydrofuryl) propane, 108.0 ml of a 0.5 mol / liter dilithium polymerization initiator was added. Polymerization was started.
Polymerization was carried out for 1.5 hours while raising the temperature of the polymerization reactor to 50 ° C., then 108.0 ml of a 1 mol / liter ethylene oxide cyclohexane solution was added, and the mixture was further stirred for 2 hours, and then 50 ml of isopropyl alcohol was added. did. A hexane solution of the copolymer was precipitated in isopropyl alcohol and sufficiently dried to obtain a copolymer polyol. This copolymer polyol was a OH group styrene-butadiene copolymer at both terminals, the styrene content was 25% by mass, the weight average molecular weight was 14,500, and the molecular weight distribution was 1.20.

Next, 120 g of copolymer polyol was dissolved in 1 liter of hexane that had been sufficiently dehydrated and purified, and then nickel naphthenate, triethylaluminum, and butadiene prepared in separate containers in a 1: 3: 3 (molar ratio) ratio. The catalyst solution was charged so that the amount of nickel was 1 mol with respect to 1,000 mol of the butadiene portion in the copolymer solution. Hydrogen was added under pressure to 27,580 hPa (400 psi) in a sealed reaction vessel, and a hydrogenation reaction was performed at 110 ° C. for 4 hours. Thereafter, the catalyst residue was extracted and separated with hydrochloric acid having a concentration of 3 mol / L, and further centrifuged to separate and separate the catalyst residue. Thereafter, the hydrogenated copolymer polyol was precipitated in isopropyl alcohol and further sufficiently dried.
100 g of the fully dried hydrogenated copolymer polyol was dissolved in cyclohexane, and 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK: Karenz AOI) was slowly added dropwise while maintaining the temperature at 40 ° C. and sufficiently stirring. Thereafter, the mixture was further stirred for 4 hours, precipitated in isopropyl alcohol and dried. The addition amount of 2-acryloyloxyethyl isocyanate was 3.76 g. As described above, a bifunctional polyfunctional hydrogenated styrene-butadiene copolymer having acryloyl groups at both ends of the molecular chain was obtained as a polyfunctional hydrogenated butadiene polymer from the hydrogenated polymer polyol.

Production Example 2 Production of Monofunctional Oligomer 1 In a 7-liter polymerization reactor purged with argon, 1.90 kg of dehydrated purified cyclohexane, 2.00 kg of 22.9% by mass of a 1,3-butadiene monomer hexane solution, 20.0 kg After adding 0.70.4 kg of a cyclohexane solution of styrene monomer of mass% and 1.60.4 mol / liter of a hexane solution of 2,2-di (tetrahydrofuryl) propane, 0.5 mol / liter of n- 108.0 ml of butyllithium polymerization initiator was added to initiate polymerization.
Polymerization was carried out for 1.5 hours while raising the temperature of the polymerization reactor to 50 ° C., then 108.0 ml of a 1 mol / liter ethylene oxide cyclohexane solution was added, and the mixture was further stirred for 2 hours, and then 50 ml of isopropyl alcohol was added. did. A hexane solution of the copolymer was precipitated in isopropyl alcohol and sufficiently dried to obtain a copolymer monool. This copolymer monool was a one-terminal OH group styrene-butadiene copolymer, the styrene content was 25% by mass, the weight average molecular weight was 14,500, and the molecular weight distribution was 1.2.

Next, 120 g of copolymer monool was dissolved in 1 liter of hexane that was sufficiently dehydrated and purified, and then nickel naphthenate, triethylaluminum, and butadiene prepared in separate containers in advance were 1: 3: 3 (molar ratio). The catalyst solution was charged so that the amount of nickel was 1 mol with respect to 1,000 mol of the butadiene portion in the copolymer solution. Hydrogen was added under pressure to 27,580 hPa (400 psi) in a sealed reaction vessel, and a hydrogenation reaction was performed at 110 ° C. for 4 hours. Thereafter, the catalyst residue was extracted and separated with hydrochloric acid having a concentration of 3 mol / L, and further centrifuged to separate and separate the catalyst residue. Thereafter, the hydrogenated copolymer monool was precipitated in isopropyl alcohol and further sufficiently dried.
100 g of fully dried hydrogenated copolymer monool was dissolved in cyclohexane, and 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK: Karenz AOI) was slowly added dropwise while maintaining the temperature at 40 ° C. and sufficiently stirring. Then, the mixture was further stirred for 4 hours, precipitated in isopropyl alcohol and dried. The amount of 2-acryloyloxyethyl isocyanate added was 1.87 g. As described above, a monoacryloyl group-containing hydrogenated styrene-butadiene copolymer having an acryloyl group at one end of the molecular chain was obtained as a monofunctional oligomer from the hydrogenated polymer monool.

Examples 1 to 4, Reference Examples 1 to 5 and Comparative Examples 1 to 4
Using the above-mentioned polyfunctional hydrogenated styrene-butadiene copolymer and monoacryloyl group-containing hydrogenated styrene-butadiene copolymer, kneaded in a planetary mixer according to the formulation shown in Table 1, respectively. 4, 13 types of photocurable resin compositions of Reference Examples 1 to 5 and Comparative Examples 1 to 4 were obtained. Using the obtained composition, the standing stability and moldability of the photocurable resin composition before curing were evaluated. The results are shown in Table 1.
Furthermore, using the obtained composition, it formed into the shape prescribed | regulated to said measuring method, and irradiated this with the ultraviolet-ray which is an energy ray, and obtained hardened | cured material. A metal halide lamp was used as an ultraviolet light source, and irradiation was performed in an air atmosphere under conditions of an illuminance of about 160 mW / cm ² (wavelength 320 to 390 nm) and an integrated light amount of about 9,000 mJ / cm ² . About the obtained hardened | cured material, the adhesiveness of the photocurable resin composition after hardening by said method, moisture permeability, sclerosis | hardenability, and the damping characteristic were evaluated. The results are shown in Table 1.

［注］
多官能水添ブタジエン系重合体： 製造例１により得られた、アクリロイル基を分子鎖両末端に有する２官能である多官能水添スチレン−ブタジエン共重合体
単官能オリゴマー １： 製造例２により得られた、アクリロイル基を分子鎖片末端に有するモノアクリロイル基含有水添スチレン−ブタジエン共重合体
単官能オリゴマー ２： 片末端メタクリル化水添ポリブタジエン（重量平均分子量：約７，０００）、株式会社クラレ製、商品名「Ｌ−１２５３」、
ポリチオール化合物Ａ： ４官能ポリチオール化合物：ペンタエリスリトールテトラ（β−メルカプトプロピオネート）、ＳＣ有機化学社製、商品名「ＰＥＭＰ」
ポリチオール化合物Ｂ： ２官能ポリチオール化合物：テトラエチレングリコールジ（β−メルカプトプロピオネート）、ＳＣ有機化学社製、商品名「ＥＧＭＰ４」
ポリチオール化合物Ｃ： ６官能ポリチオール化合物：ジペンタエリスリトールヘキサ（β−メルカプトプロピオネート）、ＳＣ有機化学社製、商品名「ＤＰＭＰ」
単官能アクリレートモノマー： イソミリスチルアクリレート、共栄社化学（株）製、商品名「ＩＭＡ」
光重合開始剤Ｐ： ２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン、チバ・スペシャルティ・ケミカルズ（株）製、商品名「ダロキュア １１７３」

[note]
Polyfunctional hydrogenated butadiene polymer: obtained by Production Example 1, bifunctional polyfunctional hydrogenated styrene-butadiene copolymer monofunctional oligomer having acryloyl groups at both ends of the molecular chain 1: obtained by Production Example 2 Monoacryloyl group-containing hydrogenated styrene-butadiene copolymer monofunctional oligomer having an acryloyl group at one end of the molecular chain 2: One-end methacrylated hydrogenated polybutadiene (weight average molecular weight: about 7,000), Kuraray Co., Ltd. Product name "L-1253",
Polythiol compound A: Tetrafunctional polythiol compound: Pentaerythritol tetra (β-mercaptopropionate), manufactured by SC Organic Chemical Co., Ltd., trade name “PEMP”
Polythiol compound B: Bifunctional polythiol compound: Tetraethylene glycol di (β-mercaptopropionate), manufactured by SC Organic Chemical Co., Ltd., trade name “EGMP4”
Polythiol compound C: Hexafunctional polythiol compound: Dipentaerythritol hexa (β-mercaptopropionate), manufactured by SC Organic Chemical Co., Ltd., trade name “DPMP”
Monofunctional acrylate monomer: Isomyristyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd., trade name “IMA”
Photopolymerization initiator P: 2-hydroxy-2-methyl-1-phenyl-propan-1-one, manufactured by Ciba Specialty Chemicals Co., Ltd., trade name “Darocur 1173”

As is clear from Table 1, all of the photocurable resin compositions of Examples 1 to 4 of the present invention were compared with the photocurable resin composition of Comparative Example 1 after ultraviolet (UV) curing. Excellent tackiness and damping properties. In addition, all of the photocurable resin compositions of Examples 1 to 4 of the present invention had good moldability and low moisture permeability as compared with the photocurable resin composition of Comparative Example 4. It was. In addition, since the photocurable resin composition of Comparative Examples 2 and 3 had poor moldability and curability, it was not possible to evaluate moisture permeability, vibration damping characteristics and adhesiveness after ultraviolet (UV) curing.

  The photocurable resin composition of the present invention is suitably used as a sheet material for various uses. For example, as an adhesive sheet, it is suitably used for sealing members, adhesive members, vibration damping members, etc., such as various electronic parts, automobile parts, housing members, furniture members, etc., gaskets for electronic parts, ink tank seals, liquid crystal seals, etc. Etc. are also used suitably.

Claims (8)

A hydrogenated butadiene-based polymer having a plurality of (meth) acryloyl groups , a polythiol compound, a photopolymerization initiator , and an oligomer having a single (meth) acryloyl group ;
The hydrogenated butadiene polymer is hydrogenated aromatic vinyl - butadiene copolymer, or hydrogenated aromatic vinyl - Ri butadiene copolymer and hydrogenated butadiene homopolymer der,
Mass ratio of the hydrogenated aromatic vinyl-butadiene copolymer and the oligomer having a single (meth) acryloyl group in a total of 100 parts by mass (the hydrogenated aromatic vinyl-butadiene copolymer / the single of (meth) oligomer having an acryloyl group), 1/99 to 80/20 der Rukoto photocurable resin composition characterized.   The photocurable resin composition according to claim 1, wherein the aromatic vinyl monomer constituting the hydrogenated aromatic vinyl-butadiene copolymer is styrene, α-methylstyrene and / or paramethylstyrene. The photocurable resin composition according to claim 1 or 2 , wherein the polythiol compound is a compound having 2 to 6 mercapto groups in the molecule. The photocurable resin composition according to any one of claims 1 to 3, wherein the oligomer having the single photocurable functional group is a monofunctional (meth) acrylate oligomer. The monofunctional (meth) acrylate oligomer is a mono (meth) acryloyl group-containing hydrogenated diene polymer, polyester mono (meth) acrylate oligomer, epoxy mono (meth) acrylate oligomer, urethane mono (meth) acrylate oligomer The photocurable resin composition according to claim 4 , which is at least one selected from polyether mono (meth) acrylate oligomers and polyol mono (meth) acrylate oligomers. The mono (meth) acryloyl group-containing hydrogenated diene polymer comprises a mono (meth) acryloyl group-containing hydrogenated aromatic vinyl-butadiene copolymer, a mono (meth) acryloyl group-containing hydrogenated butadiene homopolymer and a mono ( The photocurable resin composition according to claim 5 , which is at least one selected from a (meth) acryloyl group-containing hydrogenated isoprene homopolymer. The photocurable resin composition according to claim 6 , wherein the mono (meth) acryloyl group-containing hydrogenated aromatic vinyl-butadiene copolymer is a mono (meth) acryloyl group-containing hydrogenated styrene-butadiene copolymer. The adhesive sheet which consists of a photocurable resin composition in any one of Claims 1-7.