WO2007077691A1 - Photocurable resin composition - Google Patents

Abstract

Disclosed is a photocurable resin composition suitable for photocuring cast molding, particularly a photocurable resin composition having excellent vibration fatigue durability. The photocurable resin composition comprises (A) at least one resin selected from a photoradical-polymerizable resin, photoradical-addition-polymerizable resin and a photocation-polymerizable resin, (B) a photopolymerization initiator, and one or both of (C) an antioxidant and (D) a photostabilizer. When cured, the photocurable resin composition shows a tensile elastic modulus of 1-30 MPa and a tensile elongation at break of 200% or more. The photocurable resin composition may additionally comprise (E) a rubber composition.

Description

 Specification

 Photocurable resin composition

 Technical field

 TECHNICAL FIELD [0001] The present invention relates to a photocurable resin composition and a cured product that can be cured by irradiation with light such as ultraviolet rays and visible light, and more specifically, a photocurable resin composition having excellent vibration fatigue durability. Product and cured product.

 Background art

 [0002] In general, a composition that gives so-called rubber properties such as flexibility, stretchability, and elasticity is called an elastomer, and its fatigue durability against vibration is far superior to that of other polymer materials. ing. Therefore, automobile parts such as tires, sealing members for structures such as civil engineering and construction, packing members such as O-rings, acoustic members such as speakers, sheet members such as mobile phone key sheets, vibration-proof materials, various types It is applied as a mechanism member.

 [0003] Conventional elastomers (hereinafter referred to as R) include natural rubber, modified natural rubber, natural rubber, cyclized natural rubber, chlorinated natural rubber, styrene butadiene rubber, chloroprene rubber, acrylonitrile monobutadiene. Rubber, carboxylated nitrile rubber, nitrile rubber

Z-Butyl chloride resin blend, nitrile rubber ZEPDM rubber blend, butyl rubber, brominated butyl rubber, chlorinated butyl rubber, ethylene acetate rubber, acrylic rubber, ethylene-acrylic rubber, chlorosulfonated polyethylene, chlorinated polyethylene, epichlorohydrin rubber, Rubber materials such as picrohydrin ethylene oxide rubber, methyl silicone rubber, vinyl-methyl silicone rubber, ferrumethyl silicone rubber, fluorosilicone rubber; polystyrene thermoplastic elastomer, polychlorinated bur thermoplastic elastomer Polyolefin thermoplastic elastomers, polyurethane thermoplastic elastomers, polyester thermoplastic elastomers, polyamide thermoplastic elastomers, chlorinated thermoplastic elastomers, fluoro rubber Thermoplastic elastomers of all, a thermoplastic elastomer first material of chlorinated polyethylene elastomers, First is known.

[0004] In general, a method of obtaining a molded product of elastomer (R) includes a kneading step in which an elastomer raw material containing a curing agent and other additives is sufficiently kneaded, and a kneaded dough is vacuum-formed. Molding method, pressure forming method, molding using upper and lower molds (hereinafter referred to as upper and lower molds), molding by pressure molding method, injection molding method, etc., and curing or curing by heating and pressurizing Through the curing process (vulcanization process), the desired molded product is obtained! / Speak.

 [0005] However, in the vacuum forming method, the pressure forming method, and the heating and pressing forming method using the upper and lower molds, it is necessary to raise the mold temperature to near the melting point of the material. Requires energy. In addition, since it is necessary to cool and remove the mold, it takes a long time for the molding cycle.

 [0006] In the injection molding method, the molten resin is cooled immediately after coming into contact with a mold having a temperature difference, and the fluidity is extremely lowered. Therefore, it is difficult to obtain a thin molded body, and heating, Equipment is expensive due to the injection, pressure and other processes. Further, since the thermoplastic material is heated to near the melting point, the heating energy is enormous.

 [0007] In the above-described vacuum forming method, pressure forming method, heating and press forming method using upper and lower molds, etc., the molding material is formed by molding a planar material substantially larger than the target part dimensions and then cutting out the part portion. Therefore, a lot of waste is generated, which is unfavorable environmentally and economically.

 [0008] The above-described constituent materials of the vacuum forming method, the pressure forming method, and the heating and press forming method using the upper and lower molds are generally uniform thickness materials. From the same material, it is difficult to change the thickness of each part.

 [0009] Thickness that is produced industrially is limited, and it is usually difficult to obtain materials with other thicknesses. A method of changing the thickness by a process such as stretching at the time of molding has also been proposed, but problems such as increased internal stress distortion after molding occur.

 [0010] As a means for solving the problems of the molding method as described above, the photocurable liquid substance filled in the upper and lower molds is cured by irradiating with light such as ultraviolet rays and visible rays to form a molded body. Patent Document 1 proposes a photocuring cast molding method.

 Patent Document 1: Japanese Patent Application Laid-Open No. 2004-357020

[0011] More specifically, at least one of a pair of molds including an upper mold and a lower mold is formed of a material that transmits light, and a mold is set by setting a resin that can be cured by light irradiation. This is a method of closing the and irradiating light from the outside of the mold that transmits light to cure the resin and obtain a cured product of the desired shape. By this method, it is possible to achieve an arbitrary thickness with less energy and less man-hours. The shape can be easily and inexpensively manufactured.

 On the other hand, as a photocurable elastomer or a resin composition exhibiting rubber elasticity, Patent Document 2 and Patent Document 3 are for sealing materials, and Patent Document 4 is for optical three-dimensional modeling. A rosin composition is disclosed. However, a resin composition suitable for the above-mentioned photo-curing cast molding method and satisfying vibration fatigue durability as required for a conventional elastomer has not been known.

 Patent Document 2: Japanese Translation of Special Publication 2002-501109

 Patent Document 3: Japanese Translation of Special Publication 2003-505525

 Patent Document 4: Japanese Patent Laid-Open No. 2000-290328

 Disclosure of the invention

 Problems to be solved by the invention

[0013] The present invention has been made in view of the above-mentioned publicly known technology, and is a photocurable resin composition that can be cured by light irradiation and is suitable for a photocuring cast molding method, and vibration fatigue. An object of the present invention is to provide a photocurable resin composition and a cured product excellent in durability.

 Means for solving the problem

That is, the present invention has the following gist.

 1. (A) At least one resin selected from the group consisting of a photoradical polymerizable resin, a photoradical addition polymerizable resin, and a photothion polymerizable resin, and (B) a photopolymerization initiator ( C) a photocurable resin composition containing an antioxidant and (D) a light stabilizer and / or a light stabilizer, the photocurable resin composition and a cured product of the photocurable resin thread and composition. A photocurable resin composition having a tensile elastic modulus of 1 to 30 MPa and a tensile strength of 200% or more.

 2. The photocurable resin composition according to the above 1, further comprising (E) a rubber composition.

 3. The rubber composition is a copolymer having at least one monomer power selected from (meth) acrylic acid ester compound, bulle compound, and olefinic hydrocarbon compound, and having a weight average molecular weight. The photocurable resin composition according to the above 1 or 2, which is in the range of 500 to 50,000.

[0015] 4. The rubber composition is a (meth) acrylic acid ester compound, a bure compound, and an olefinic hydrocarbon compound. (Ii) 20-90% by mass of a radically polymerizable monomer having a glass transition temperature of less than 25 ° C.

 (Mouth) 0.1 to 70% by mass of a radical polymerizable monomer having a glass transition temperature of 25 ° C. or higher of the homopolymer,

 (C) 1-50 mass% of a radically polymerizable monomer having at least one reactive group that is non-radically polymerizable in the molecule;

 4. The photocurable resin composition according to 3 above, comprising

[0016] 5. The monomeric power of component (i) The photocurable resin composition according to 4 above, which is an alkyl (meth) acrylate having 1 to 20 carbon atoms.

 6. The photocurable resin composition according to 5 above, wherein the monomer of component (i) is an alkyl (meth) acrylate having 1 to 8 carbon atoms.

 7. The photocurable resin composition according to any one of 4 to 6 above, wherein the monomer of the (mouth) component contains at least one selected from the group strength of methyl metatalylate and styrene power object.

 8. The component (c) wherein the monomer of the component has one or more groups selected from the group consisting of a hydroxyl group, a carboxylic acid group, a glycidyl group, an isocyanate group, an amino group, and an alkoxysilyl group. The photocurable resin composition as described in any one of Claims.

 9. The photocurable resin composition according to 8 above, wherein the monomer of component (c) is glycidyl (meth) acrylate or hydroxyalkyl (meth) acrylate.

 [0017] 10. Rubber yarn and composition strength The photocurable resin composition according to any one of 1 to 9, which has at least one aromatic group in a molecule.

 11. The photocurable resin composition according to any one of 1 to 10 above, wherein the rubber composition has a viscosity at 25 ° C of 100 to 100, OOOmPa's.

 12. The photocurable resin composition according to any one of the above 1 to L1, wherein the rubber composition has a glass transition temperature of less than 25 ° C.

13. The photocurable resin composition according to any one of 1 to 12 above, wherein the proportion of the rubber composition in the photocurable resin composition is 0.01 to 30% by mass. 14. The photocurable resin composition according to any one of 1 to 13 above, wherein the photoradically polymerizable resin is an acrylic resin.

 C

 15. A H-acrylyl saccharine has (a-1) one or more (meth) attalyloyl at the end or side chain of the molecule.

 2

 A urethane (meth) acrylate oligomer having at least one group and a content of R c R Ο ll is from 5,000 to 100,000, and (a-2) a monofunctional (meth) acrylate. 14. The photocurable resin composition according to 14,

 [0018] 16. (a-2) The photocurable cocoon according to 15 above, wherein the monofunctional (meth) acrylate is a monofunctional (meth) acrylate represented by the following formula [1] or [2]: Fat composition.

 [Chemical 1]

(In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is a straight or branched alkyl group having 1 to 22 carbon atoms, a cyclohexyl group, a straight or branched chain having 1 to 4 carbon atoms. A cyclohexyl group, a phenyl group, a phenyl group substituted with a linear or branched alkyl group having 1 to 4 carbon atoms, a dicyclopental group, a dicyclopental group, or a bornyl group. , An isobornyl group, an adamantyl group, a methyladamantyl group or an aryl group.)

[0019] [Chemical 2]

R

 [2]

(Wherein R ¹ is a hydrogen atom or a methyl group, R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms, and R ⁴ is a linear or branched alkyl group having 1 to 4 carbon atoms. Cyclohexyl substituted with a cyclohexyl group or a linear or branched alkyl group having 1 to 4 carbon atoms Group, a phenyl group, a phenyl group substituted by a linear or branched alkyl group having 1 to 4 carbon atoms, a dicyclopental group, a dicyclopental group, a bornyl group, an isobornyl group, an adamantyl group, methyl An adamantyl group or an aryl group, and n is an integer of 1 to 12. )

 [0020] 17. The photocurable resin composition according to the above 15 or 16, wherein (a-2) the monofunctional (meth) acrylate is a glass transition temperature of the homopolymer of 20 ° C or higher.

 18. A photoradical addition-polymerizable resin comprising a polyene compound having two or more carbon-carbon unsaturated double bonds in the molecule and a polythiol compound having two or more mercapto groups in the molecule. The photocurable resin composition according to any one of 1 to 13 above

19. The photocurable resin composition according to any one of 1 to 13 above, wherein the photopower thione polymerizable resin has an epoxy group, an oxetanyl group, or a vinyl ether group in the molecule.

 20. The photocurable resin composition according to any one of 1 to 19 above, which has a curing shrinkage rate of 10% or less.

 21. A cured product that also has the power of the photocurable resin composition according to any one of 1 to 20 above. The invention's effect

 [0021] The photocurable resin composition of the present invention has characteristics that it is instantly cured by irradiation with light such as ultraviolet rays or visible light, and that the cured product has excellent vibration fatigue durability. Therefore, automobile members such as tires, sealing members for structures such as civil engineering and construction, packing members such as o-rings, acoustic members such as speakers, sheet members such as key sheets for mobile phones, members, vibration-proof materials It can be suitably used for various mechanism members. The photocurable resin composition of the present invention can also be applied to adhesives for structural and structural seals for civil engineering and construction, metals, magnets, ceramics, glass, and plastics.

 BEST MODE FOR CARRYING OUT THE INVENTION

 In the present specification, “molecular weight” means a weight average molecular weight unless otherwise specified.

In this specification, “Tg” means a glass transition temperature unless otherwise specified. In the present specification, an “alkyl group” means a straight chain, a branched chain or a ring unless otherwise specified. Mean saturated hydrocarbon group.

 [0023] The photocurable resin composition of the present invention contains a photocurable resin that is a component (A) and forms a cured body upon irradiation with light. The term “light” as used herein refers to an active energy ray typified by ultraviolet rays and visible rays. In the photocurable resin composition of the present invention, the photocurable resin is a photo-radical polymerizable resin. It is possible to use at least one resin selected from the group consisting of a resin, a photo-radical addition polymerizable resin, and a light power thione polymerizable resin. Of these, the photo-radically polymerizable resin is preferably selected because it contains an acrylic resin rich in material selectivity.

 [0024] As the photoradical addition-polymerizable resin, a well-known thiol reaction in which a thiol group is added to a carbon-carbon unsaturated bond by radical generation is known. In particular, the reason that an enthiol resin comprising a compound having at least two thiol groups in the molecule and a compound having at least two carbon-carbon unsaturated bonds in the molecule is excellent in photocurability. Is preferable.

 [0025] Examples of the photopower thione-polymerizable resin include an epoxy group-containing resin, an oxetanyl group-containing resin, a vinyl ether group-containing resin, a spiro orthoester group-containing resin, and a bicycloorthoester group. And the like having a spiro orthocarbonate group. Of these, a resin having an epoxy group, an oxetal group or a butyl ether group is preferred because of its photocurability and abundant selection of materials.

[0026] Examples of the photo-radically polymerizable resin include acrylic resin, styrene resin, vinyl resin, unsaturated polyester, polyolefin, etc. Among them, acrylic resin has photocurability and abundant selection of materials.で Preferred for reasons U ヽ.

[0027] Acrylic resins include poly (meth) acrylate, (meth) acrylate monomer, (meth) acrylate dimer, polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) Examples thereof include acrylate, polyolefin (meth) acrylate, and silicone (meth) acrylate. In achieving the object of the present invention, a resin composition comprising urethane (meth) acrylate and (meth) acrylate monomers is preferred. Particularly preferably, (a-1) one kind of urethane (meth) acrylate oligomer having one or more (meth) attalyloyl groups at the end or side chain of the molecule and having a molecular weight of 5,000-100,000. And (a-2) monofunctional (meta) finished It is a rosin composition consisting of tartrate.

 [0028] The urethane (meth) acrylate oligomer as the component (a-1) is a polyol compound.

 (Hereinafter referred to as X), an organic polyisocyanate compound (hereinafter referred to as Y), and a hydroxy (meth) acrylate (hereinafter referred to as Z). O for rate oligomer

 [0029] Examples of powerful polyol compounds (X) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, 1,4 butanediol, polybutylene diol, 1,5 pentanediol, 1,6 hexanediol, 1,8 octanediol, 1,9-nonanediol, 3 methyl-1,5 pentanediol, 2,4 jetyl 1, 5 Pentanediol, 2, 2 Butylethyl-1,3 Propanediol, Neopentyl glycol, Cyclohexane dimethanol, Hydrogenated carbphenol A, Poly-strength prolatatone, Trimethylolethane, Trimethylololepropane, Polytrimethylolono Polyhydric alcohols such as pronone, pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerin, polyglycerin, polytetramethylene glycol; polyethylene oxide, polypropylene oxide, ethylene oxide Z propylene oxide block or random Polyether polyol having at least one structure of copolymerization; such polyhydric alcohol or polyether polyol and maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid, etc. Polyester polyol that is a condensate with polybasic acid; force prolatatone modified polyol such as caprolatatone modified polytetramethylene polyol; polyolefin polyol; polycarbonate polyol; Examples thereof include polybutadiene-based polyols such as hydrogenated polybutadiene polyol; and silicone polyols such as polydimethylsiloxane polyol. Particularly preferred are polyether polyols and polyester polyols.

[0030] Among these, a molecular weight of 200 to 10,000 is particularly preferable, preferably 500 to 8,000, and more preferably 1,000 to 6,000. If the molecular weight to be applied is 200 or more, suitable vibration fatigue durability can be obtained, and if it is within 10,000, the curability is reduced. It is preferable.

 [0031] The organic polyisocyanate compound (Y) is not particularly limited, and examples thereof include aromatic, aliphatic, cycloaliphatic, and alicyclic polyisocyanates. Can be mentioned. Among them, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H—MDI), polyphenylmethane polyisocyanate ( Crude MDI), modified diphenylmethane diisocyanate (modified MDI), hydrogenated xylylene diisocyanate (H—XDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), to trimethyl Xamethylene diisocyanate (TMXDI), tetramethylxylylene diisocyanate (m—TMXDI), isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), 1,3-bis (isocyanatomethyl) ) Polyisocyanates such as cyclohexane (H6XDI), trimer compounds of these polyisocyanates, and reaction products of these polyisocyanates and polyols Etc. are preferably used. Of these, hydrogenated xylylene diisocyanate (H-XDI) and isophorone diisocyanate (IPDI) are preferred. The molecular weight of the polyisocyanate compound (Y) is preferably 500 or less. If it is 500 or less, the reactivity with the diol does not decrease.

 [0032] Examples of the hydroxy (meth) acrylate (Z) include 2-hydroxyethyl (meth) ateryl

, 2-Hydroxyethyl allyloyl phosphate, 4-Butylhydroxy (meth) atrelate, 2— (Meth) atariloy cicchitil 1-hydroxypropyl phthalate, Glycerin di (meth) acrylate, 2-Hydroxy 1-Atari Leyloxypropyl (meth) acrylate, force Prolataton modified 2-hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, force prolatathone modified 2—Hydroxetil ( And (meth) acrylate. Of these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate are preferably used.

[0033] In the urethane (meth) acrylate oligomer, the number of (meth) attaroyl groups in the molecule is 1 or more and 6 or less, more preferably 2 or more and 4 or less at the end or side chain of the molecule. Those having a (meth) atallyloyl group are preferred. If there is no (meth) atalyloyl group, then (B) Component (B) cannot be copolymerized with monofunctional (meth) acrylate, and if it is more than 6, the resulting molded product becomes too hard and excellent vibration fatigue durability cannot be obtained. There is.

 c

 [0034] The molecular weight of the urethane (meth) atarylate oligomer is 5,000 or more and 100,000 or less, and more preferably c RcΟ ΝΠ l l is 10,000 or more and 50,000 or less. If the molecular weight is 5,000 or more, the resulting molded o body will not be too hard. If it is 100,000 or less, the curability will be low.

 R

 Vibration that does not worsen 2 A cured product with excellent fatigue durability can be obtained.

 [0035] The monofunctional (meth) acrylate which is the component (a-2) is not particularly limited as long as it contains one (meth) attayl group in the molecule. Among these, a resin composition containing a monofunctional (meth) acrylate represented by the following formula [1] or [2] is particularly preferable because a cured product excellent in vibration fatigue durability can be obtained.

 [Chemical 3]

In C 1 [1], R ¹ is a hydrogen atom or a methyl group, R ² is a linear or branched alkyl group having 1 to 22 carbon atoms (preferably having 1 to 12 carbon atoms), A cyclohexyl group, a cyclohexyl group substituted with a linear or branched alkyl group having 1 to 4 carbon atoms, a phenyl group, a phenyl group substituted with a linear or branched alkyl group having 1 to 4 carbon atoms, a dicyclo group A pental group, a dicyclopentayl group, a boryl group, an isobolyl group, an adamantyl group, a methyladamantyl group, and an aryl group.

 [Chemical 4]

R ¹

[2] In the formula [2], R ¹ is a hydrogen atom or a methyl group, and R is a straight chain having 1 to 4 carbon atoms. Or a branched alkyl group, R ⁴ is a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, or a cyclohexyl group substituted by a linear or branched alkyl group having 1 to 4 carbon atoms. , A phenyl group, a phenyl group substituted with a linear or branched alkyl group having 1 to 4 carbon atoms, a dicyclopental group, a dicyclopental group, a boryl group, an isobornyl group, an adamantyl group , A methyladamantyl group and an aryl group.

 n is an integer of 1 to 12, preferably 1 to 10.

[0036] Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meta ) Atarylate, 2-Ethylhexyl (meth) acrylate, Isodecyl (meth) acrylate, Lauryl (meth) acrylate, Stearyl (meth) acrylate, Isostearyl (meth) acrylate, Tridecyl (meth) acrylate , Beryl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxy ethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxetyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, Methoxytriethylene glycol (meth) acrylate, Butoxy tetraethylene (meth) Atarire

Rate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, cyclohexyl ( (Meth) Atalylate, ter t-butylcyclohexyl (Meth) acrylate, Benzyl (Meth) acrylate, Phenoxetyl (Meth) acrylate, Dicyclopentayl (Meth) acrylate, Dicyclopentale (Meth) acrylate Boryl (meth) acrylate, isobornyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, aryl (meth) acrylate, and the like can be exemplified. It should be noted that the talate and the metatalylate give a hardened body excellent in vibration fatigue durability, which is more suitable for the metatalate.

[0037] (a-2) The monofunctional (meth) acrylate is preferably a monofunctional (meth) acrylate having a Tg of the homopolymer of 20 ° C or higher. More preferably, Tg is 50 ° C or higher, particularly preferably 80 ° C or higher. If the Tg is 20 ° C or higher, the resulting cured product will not be too flexible or harden. The Tg of the photocurable resin composition of the present invention is measured. Although the method is not particularly limited, it is measured by a known method such as DSC or dynamic viscoelasticity, and DSC is preferably used.

 [0038] In the photocurable resin composition of the present invention, the blending ratio of the components (a-1) and (a-2) is:

 When a composition containing 5 to 95% by mass, particularly preferably 20 to 85% by mass of the component (a-1) with respect to the total of the components (a-1) and (a-2), Cured products obtained by irradiation are particularly preferred because they have excellent vibration fatigue durability.

 [0039] The photopolymerization initiator as the component (B) includes an ultraviolet polymerization initiator and a visible light polymerization initiator, both of which are used without limitation. Examples of the radical photopolymerization initiator include benzoin-based, benzophenone-based, acetophenone-based, acyl-phosphine oxide-based, thixanthone-based, meta-octene-based, and quinone-based initiators. As photoinitiated thione polymerization initiators, iodine salt compounds, sulfur salt compounds, phosphorium salt compounds, pyridinium salt compounds, iron arene complex compounds Etc.

 In the present invention, the photopolymerization initiator is not particularly limited, and known ones can be used. For example, benzophenone, 4-phenol penzophenone, benzoyl benzoic acid, 2,2-jetoxyacetophenone, bisjetylaminobenzobenzoenone, benzyl, benzoin, benzoyl isopropyl ether, benzyl dimethyl ketal, 1-hydroxysic Xylphenol ketone, thixanthone, 1— (4-isopropylphenol) 2 hydroxy-2-methylpropane-1-one, 1- (4- (2-hydroxyethoxy) monophenyl) — 2-hydroxy-2- —Methyl 1-propane 1-one, 2-hydroxy 1 2-methyl 1 phenylpropane 1-one, camphorquinone, 2, 4, 6 trimethylbenzoyl phenylphosphine oxide, bis (2, 4, 6 trimethylbenzo 1) Phylphosphine oxide, 2-methyl-1 1 (4 (methylthio) 2) 2 Morpholinopropan 1-one, 2 benzyl 1-dimethylamino 1- (4 morpholinophenol) 1-butanone 1, 1, bis (2,6 dimethoxybenzoyl) 1, 2, 4, 4 trimethyl monopenti Examples include ruphosphine oxide.

[0041] Examples of the anti-oxidation agent that is component (C) include β-naphthoquinone, 2-methoxy-1,4-naphthoquinone, methyl hydroquinone, hydroquinone, hydroquinone monomethyl ether, mono-tert butyl hydroquinone, 2, 5 G-tert butyl hydroquinone, p— Quinone compounds such as benzoquinone, 2,5 diphenyl mono-benzoquinone, 2,5 di-tert-butyl p-benzoquinone; phenothiazine, 2,2-methylene monobis (4-methyl-6-tert-butylenophenol) , Force teconole, tert-butinole force teconole, 2-butynole —4 hydroxyvaninol, 2, 6 di-tert-butyl p cresol, 2-tert-butyl 6- (3-tert-butyl 2-hydroxy-5-methylbenzyl) 4 Methyl phenol acrylate, 2— [1— (2 hydroxy-1,3,5 di tert pentylphenol) ethyl] 4,6—di tert—pentyl phthalate, 4, 4 ′ —butylidenebis ( 6- tert-butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol), 3, 9 bis [2- [3- (3-tert-butyl 4-hydroxy-5-methylphenol) Propio-dioxy] 1,1-dimethylethyl] -2,4,8,10-tetraxaspiro [5,5] undecane, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenol) Propionate], Thiodethylenebis [3- (3,5-Di-tert-butyl-4-hydroxyphenol) propionate], Octadecyl-3— (3,5-Di-tert-butyl-4-hydroxyphenol) propionate , N, N 'xan-1,6 diylbis [3- (3,5 di-tert-butyl-4-hydroxyphenol) propionamide], benzenepropanoic acid, 3,5 bis (1,1-dimethylethyl) -4 -Hydroxy, C7-C9 side chain alkyl ester, 2,4 dimethyl-6- (1-methylpentadecyl) phenol, jetyl [[3,5 bis (1,1-dimethylethyl) -4-hydroxyphenol] me Phosphonate, 3, 3 ', 3 ", 5, 5', 5 gxa tert-butyl 1 a, a ', a" — (mesitylene 1, 2, 4, 6 tolyl) tri p- Talesol, calcium jetyl bis [[3,5 bis (1,1-dimethylethyl) -4 hydroxyphenol] methyl] phosphonate, 4,6-bis (octylthiomethyl) o cresol, ethylene bis (oxyethylene) bis [ 3- (5-tert-butyl 4-hydroxy m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate, 1, 3, 5 tris (3,5 di-tert-butyl-4 hydroxybenzyl) — 1, 3, 5 triazine— 2, 4, 6 (1H, 3H, 5H) —trione, 1, 3, 5 tris [(4—t ert— (Butyl 3hydroxy-1,2,6xylyl) methyl] 1,3,5 Triazine 1,2,4,6 (1H, 3H, 5H) -trione N- Hue - Rubenzenamin and 2, 4, 6 Torimechirupen Reaction products with ten, 2, 6 di tert-butyl-4 (4,6 bis (octylthio) -1,3,5 triazine-1 2-ylamino) phenols such as phenol, picric acid, citrate; 2,4 Di-tert-butylphenol) phosphite, tris [2-[[2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphephine 6-yl] oxy] ethyl] amine, bis (2,4 di-tert-butylphenol) pentaerythritol diphosphite, bis [2,4 bis (1,1 dimethylethyl) -6 methylphenyl] ethyl ester Phosphorous acid, tetrakis (2,4 di-tert-butylphenol) [1,1-bisphenol] 4,4'-diylbisphosphonite, 6- [3- (3-tert-butyl 4- Hydroxy-5-methylphenol) propoxy] 2, 4, 8, 10-tetra-tert-butyl Phosphorus compounds such as Ruzi benz [d, f] [l, 3, 2] dioxaphosphephine; dilauryl 3, 3 'thiodipropionate, dimyristinole 3, 3' — thiodipropionate, distearinole 3, 3'-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), 2-mercaptobenzimidazole and other amine compounds; phenothiazine and other amine compounds; rataton compounds; vitamin E compounds Is mentioned. Of these, phenol compounds are preferred.

Examples of the light stabilizer that is component (D) include bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate and bis (1, 2, 2, 6, 6 pentamethyl-4-piperidyl) sebacate. 1、4 Benzyloxy-2,2,6,6-tetramethylpiperidine, 1- [2- [3-((3,5--di-tert-butyl-4-hydroxyphenol) propio-loxy] Ethyl] -4-4- [3 (3,5 di tert-butyl-4-hydroxyphenyl) propio-loxy] 2, 2, 6, 6-tetramethylpiperidine, 1, 2, 2, 6, 6 pentamethyl-4 piperizi -Lumethyl relay, bis (1,2,2,6,6 pentamethyl-4piberidyl) [[3,5 bis (1,1-dimethylethyl) 4-hydroxyphenyl] methyl] butyl malonate, decane Bis (2, 2, 6, 6-tetramethyl-1 (octyloxy) -4-piveridyl) ester, 1, 1- Reaction product of dimethylethyl hydroperoxide and octane, N, Ν ', N ", Ν ,,' —tetrakis (4, 6 bis ((butyl-1, (Ν-methyl 2, 2, 6, 6— Tetramethylbiperidine—4-yl) amino) —triazine—2-yl) —4, 7 Diazadecane— 1, 10 Diamine, dibutylamine • 1, 3, 5 Triazine • Ν, N ′ —bis (2, 2, 6 , 6— Polycondensate of tetramethyl-4-piveridyl 1, 6 hexamethylenediamine and N— (2, 2, 6, 6-tetramethyl-4-piperidyl) butyramine, poly [[6- (l, 1, 3, 3-tetra (Methylbutyl) amino-1,3,5 triazine-2,4-dinole] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino] ), A polymer of dimethyl succinate and 4-hydroxy 2, 2, 6, 6-tetramethyl-1-piperidine ethanol, 2, 2, 4, 4-tetramethyl-20- (j8-lauryloxycarboxyl) ethyl 7 oxa3 , 20 Diazadispiro [5 · 1 · 11 · 2] Henicosone 2 1-one, 13-alanine, N,-(2, 2, 6, 6-tetramethyl-4-piberidyl) monododecyl ester Z-tetra Decyl ester, N-acetylyl 3 Dodecyl 1— (2, 2 , 6, 6-tetramethyl-4-piperidinyl) pyrrolidine 2,5 dione, 2, 2, 4, 4-tetramethyl-7-oxa-3,20 diazadispiro [5,1,11,2] neicosane-21-one, 2 , 2, 4, 4-tetramethyl-21-oxa-3, 20 diazadicyclo- [5, 1, 11, 2] monohenecosan 20-propanoic acid dodecyl ester Z tetradecyl ester, propandioic acid, [( 4-Methoxyphenyl) monomethylene] monobis (1, 2, 2, 6, 6 pentamethyl-4-piperidinyl) ester, 2, 2, 6, 6-tetramethyl-4-piperidinol higher fatty acid ester, 1, 3 benzene Hindered amines such as dicarboxamide, N, N '—bis (2, 2, 6, 6-tetramethyl-4-piberidyl); benzophenone compounds such as octabenzone; 2— (2H benzotriazole 2—4) (1, 1, 3 , 3-tetramethylbutyl) phenol, 2- (2 hydroxy-5 methylphenol) benzotriazolene, 2- (2-hydroxy-3- (3, 4, 5, 6-tetrahydrophthalimide monomethyl) 5 methylphenol] Benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenol) -15-clobenzobenzolazole, 2- (2-hydroxy-1,3-di-tertpentylphenol) benzotriazole, Methyl 3- (3- (2H Benzotriazole-2-yl) -5- tert-Butyl-4-hydroxyphenol) Propionate and polyethylene glycol reaction product, 2- (2H Benzotriazole- 2-yl) 6-dodecyl-benzotriazole compounds such as 4-methylphenol; 2,4-di-tert-butylphenyl 3,5-di-tert-butyl 4-hydroxybenzoate, etc. Zoate compounds; 2— (4, 6 Diphenyl— 1, 3, 5 Triazine— 2—yl) —5 — [( And triazine compounds such as (hexyl) oxy] phenol. Particularly preferred are hindered amine compounds.

[0043] In the photocurable resin composition of the present invention, when the total amount of the components (A) to (D) is 100% by mass, the component (A) is preferably 85.00- 99.99 mass _^0/0, and particularly preferably contained from 90.0 to 99.9 wt%. Component (B) is preferably contained in an amount of 0.01 to 15% by mass, particularly preferably 0.1 to 10% by mass. The total of the component (C) and the component (D) is preferably 0.01 to 5% by mass, particularly preferably 0.05 to 3% by mass. Component (C) and component (D) are preferably such that the content ratio of component (C) Z (D) is 0Z10 to 10Z0, particularly preferably 1Z9 to 9Zl. In the case where the content of components (A) to (D) is high, a cured product obtained from the photocurable resin composition of the present invention is preferable because it has excellent vibration fatigue durability.

[0044] Further, the photocurable resin composition of the present invention includes, in addition to the photocurable resin, (B) a photopolymerization initiator, (C) an acid-proofing agent, and (D) light. The cured product of the photocurable resin composition containing either or both of the stabilizers has a tensile modulus when subjected to a tensile test measurement in accordance with JIS K7113 (plastic tensile test method). Is 1 to 30 MPa, preferably 1.5 to 28.5 MPa, and exhibits excellent vibration fatigue durability with a tensile elongation at break of 200% or more, preferably 201 to 1500%. If the tensile modulus of the cured product is IMPa or more, there will be no problem that the resulting cured product is too soft to maintain its shape! Further, if the cured product has a tensile modulus of 30 MPa or less and a tensile strength of 200% or more, excellent vibration fatigue durability can be obtained, and the effects of the invention can be reliably obtained.

 [0045] Further, in the photocurable resin composition of the present invention, it is preferable to include at least one rubber composition as the component (E) in order to obtain excellent vibration fatigue durability.

 As the rubber composition, the power that can be exemplified by the above-mentioned elastomer (R), particularly, the surface power of compatibility with the photocurable resin, particularly preferably a (meth) acrylic acid ester compound, a vinyl compound, and A rubber composition which is a copolymer having at least one selected monomer force is preferable.

[0046] The molecular weight of the rubber composition is preferably 500 to 50,000, particularly preferably 750 to 20,000. It is 0, and more preferably in the range of 1,000 to 10,000. A photocurable resin having a molecular weight of 500 or more is preferable because sufficient vibration fatigue durability can be obtained, and if it is 50,000 or less, the compatibility with the photocurable resin is excellent.

 The molecular weight distribution of the rubber composition (MwZMn when the weight average molecular weight is Mw and the number average molecular weight is Mn) is 1.0 or more and 5.0 or less, particularly preferably 1.1 or more and 3.0 or less. It is preferable because it is compatible with the photocurable resin and gives excellent vibration fatigue durability.

 [0047] The monomer constituting the rubber composition includes (i) a radically polymerizable monomer having a Tg of the homopolymer of less than 25 ° C, and (mouth) a Tg of the homopolymer of 25 ° C or more. When the rubber composition contains a certain radically polymerizable monomer and (c) a radically polymerizable monomer having at least one reactive group that is non-radically polymerizable in the molecule, the rubber composition has a photocurable property. This is particularly preferred because it provides excellent vibration fatigue durability with good compatibility with fats.

 [0048] The monomer of component (i) imparts flexibility to the rubber composition. The proportion of the component (ii) in the rubber composition is preferably 20 to 90% by mass, particularly preferably 30 to 80% by mass.

 (I) Component includes alkyl (meth) acrylate having 1 to 20 carbon atoms (for example, butyl acrylate, n-butyl methacrylate, ethyl acrylate, n-octyl acrylate, and 2-ethyl). Hexyl (meth) acrylate], gen monomers [for example, butadiene, isoprene], butyl acetate monomers and the like. In order to obtain flexibility and stability against light and heat deterioration, an alkyl (meth) acrylate having 1 to 20 carbon atoms is preferable, and an alkyl (meth) acrylate having 1 to 8 carbon atoms is particularly preferable. It is.

 [0049] The monomer of the (mouth) component provides compatibility with the photocurable resin. Occupies in rubber composition

 The proportion of the (mouth) component is preferably from 0.1 to 70% by mass, particularly preferably from 1 to 60% by mass. (Mouth) components include methyl methacrylate, ethyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl (meth) acrylate, dicyclopental (meth) acrylate. Examples thereof include (meth) acrylic acid esters such as (meth) acrylonitrile, and butyl aromatic compounds such as styrene. Methyl methacrylate and styrene are particularly preferable from the viewpoint of the balance between compatibility and copolymerization.

[0050] The monomer of component (c) provides crosslinkability with the photocurable resin or crosslinkability between the rubber compositions. The reactive group is preferably non-radical polymerizable. Radical polymerization This is because, if it is characteristic, it reacts simultaneously with radical polymerization of the rubber composition. Examples of the non-radical polymerizable reactive group include a hydroxyl group, a carboxylic acid group, a glycidyl group, an isocyanate group, an amino group, and an alkoxysilyl group. The proportion of the component (c) in the rubber composition is preferably 1 to 50% by mass, particularly preferably 5 to 40% by mass.

 As the component (c), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid, 2- (meth) ateloy loyal succinic succinic acid , 2— (Meth) Ataryllooxychetyl isocyanate, 1, 1— (Beat, Dimethylamino (meth) Athalylate, 3- (Meth) Atalylyloxypropyltrimethoxysilane, 3- (Metal ) Atalylyloxypropyltriethoxysilane, etc. Photo-curing properties Particularly preferred in terms of reactivity with the resin are hydroxy compounds such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Alkyl (meth) acrylate and daricidyl (meth) acrylate.

[0051] As a method for polymerizing the rubber composition, known methods such as radical polymerization and ion polymerization can be used.

 [0052] As the radical polymerization, known methods such as bulk polymerization, suspension polymerization, bulk-suspension polymerization, solution polymerization, emulsion polymerization, and continuous polymerization can be used. Further, a radical generator can be used as necessary.

 [0053] The polymerization conditions such as the solvent used in the radical polymerization and the polymerization temperature are not particularly limited. The polymerization can be carried out without solvent or in various solvents. Polymerization without solvent is preferred because the polymerization rate is high and productivity is improved.

 [0054] The polymerization temperature is preferably in the temperature range of 50 to 500 ° C, and a high polymerization rate and a point that allows easy control of the polymerization rate are also preferred. The polymerization temperature is 100 to 400 ° C.

[0055] The radical generator may be a compound capable of using various compounds, preferably a peroxide capable of generating radicals under polymerization temperature conditions. Examples of peroxides include, but are not limited to, for example, benzoyl peroxide, acetylyl peroxide, isobutyroyl peroxide, otatanyl peroxide, decanol peroxide. Di-silver oxides such as oxides, lauroyl peroxide, 3, 5, 5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide; Butyl Tamil Peroxide, Diecyl Peroxide, α, α, Monobis (t-butylperoxyisopropyl) benzene, 2, 5 Dimethyl-2, 5 Di (t-butylperoxy) hexane, 2, 5 Dimethyl 2, 2, 2-di (t-butylperoxy) hexyne 3 and other dialkyl peroxides; 2, 2-bis (t-butylperoxy) butane, 2, 2-bis (t-butylperoxy) otatan, 1, 1-bis ( (t-Butylperoxy) 3, 3, 5 Trimethylcyclohexane, n-Butyl 4, 4 Bis (t-butylperoxy) Peroxyketals such as citrate; diisopropyl peroxydicarbonate, di-2-ethylhexyloxydicarbonate, di-n-propylperoxydicarbonate, di-3-methoxybutyl dicarboxylate , Di-2-ethoxy shechinol peroxydicarbonate, dimethyoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, bis (4 tert-butylcyclohexyl) peroxy Peroxycarbonates such as dicarbonate; _t- butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypiparate, t-butyl peroxyne decanoate, tamil peroxyneo Decanoate, t-butylperoxy 2-ethyl hexanoate, t Butylperoxy 3, 5, 5--trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, di-t-butyl diveroxyisophthalate, 2, 5-dimethyl-2, 5-di (benzoylperoxy) Peroxyesters such as hexane, t-butylperoxyisopropyl carbonate; acetyl acetone peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3, 3, 5-trimethylcyclohexanone peroxide, methylcyclo Ketone peroxides such as hexanone peroxide; Tamennoxide mouth peroxide, G-propylene hydride mouth peroxide, p-menthane hydride mouth peroxide, 2, 5 1-dimethyl hexane 2, 5-Dihydride mouth peroxide Iodide, 1, 1, 3, 3-Hide mouth peroxides such as tetramethylbutyl hydride peroxide; Polybasic oxides of dibasic acids; Polyperoxyesters of dibasic acids and polyols . this Among them, benzoyl peroxide is preferably used.

 [0056] Further, a radical-generating azo compound or the like can be used as a radical generator instead of peroxide. Examples of the radical-generating azoi compound include azobisisobutyl-tolyl.

 [0057] For the purpose of adjusting the molecular weight, a solvent, a radical cabbing agent, a polymerization accelerator, a chain transfer agent, a reaction terminator and the like can be used in combination as necessary.

 [0058] The rubber thread composition contains a polymer chain having at least one aromatic group in the molecule, and is excellent in compatibility with the photocurable resin and provides excellent vibration fatigue durability. Therefore, it is preferable. The aromatic group may be any of a main chain, a side chain, and a chain end. In particular, when the chain end is an aromatic group, the aromatic group is excellent in compatibility and excellent in vibration fatigue durability. Good. The proportion of the polymer chain having at least one aromatic group in the molecule in the rubber composition is preferably 1% by mass or more, particularly preferably 10% by mass or more, and further preferably 50% by mass or more. If it is 1% by mass or more, vibration fatigue durability can be imparted without impairing the compatibility with the photocurable resin. The proportion of the polymer chain in the rubber composition is preferably 99.99% by mass or less, particularly preferably 99.9% by mass or less.

 [0059] Means for introducing an aromatic group into the molecule include (1) a method of introducing by using a radically polymerizable monomer having an aromatic group such as styrene, and (2) a benzoyl peroxide or the like. A method of introducing by using a radical generator having an aromatic group, (3) a method of introducing by using an aromatic solvent such as toluene and xylene, and (4) aroma such as aromatic thiol such as benzenethiol and thiophenol. Examples thereof include a method of introduction by use of a chain transfer agent having a group.

 [0060] The Tg of the rubber composition is preferably less than 25 ° C in order to give excellent vibration fatigue durability to the photocurable resin. More preferably, it is less than 0 ° C, and still more preferably less than 20 ° C.

[0061] The viscosity of the rubber composition at 25 ° C is preferably in the range of 100 to 100, OOOmPa's. Above lOOmPa 's, sufficient vibration fatigue durability can be given, and at 100, OOOm Pa's or less, compatibility with photocurable resin is obtained, and the photocurable resin itself thickens. This is preferable. The viscosity measurement method is not particularly limited, but B type viscometer, E type It can be measured using a known viscometer such as a viscometer or a rheometer.

 [0062] The proportion of the rubber composition in the photocurable resin composition is preferably 0.01 to 70% by mass, more preferably 0.05 to 50% by mass, and particularly preferably 0.1. -30 mass%. When the amount is less than 01% by mass, sufficient vibration fatigue durability cannot be obtained. When the amount is more than 70% by mass, the resulting photocurable resin is too soft, and the curable resin and curability are lowered. .

 [0063] Furthermore, the cured product of the photocurable resin composition containing the rubber composition of the present invention has a tensile modulus when subjected to a tensile test measurement in accordance with JIS K7113 (plastic tensile test method). It is characterized by exhibiting excellent vibration fatigue durability with a tensile fracture elongation of 200% or more. If the tensile modulus of the cured product is IMPa or more, there will be no problem that the resulting cured product is too soft to maintain its shape. Moreover, if the cured body has a bow I tension elastic modulus of 30 MPa or less and a tensile elongation at break of 200% or more, excellent vibration fatigue durability can be obtained, and the effects of the invention can be reliably obtained.

[0064] In the present invention, if necessary, a pigment (titanium white, cyanine blue, watching red, bengara, carbon black, Ryoji phosphorus black, manganese blue, iron is used as long as the effect of the present invention is not impaired. Black, ultramarine blue, hansa red, chrome yellow, chrome green, etc.), inorganic fillers (calcium carbonate, kaolin, clay, talc, my strength, barium sulfate, lithobon, stone KO, zinc stearate, perlite, quartz, quartz Silica powder such as glass, fused silica, spherical silica, etc., spherical alumina, crushed alumina, oxides such as magnesium oxide, beryllium oxide, titanium oxide, nitrides such as boron nitride, silicon nitride, aluminum nitride , Carbides such as silicon carbide, hydroxide 匕 aluminum, hydroxide マ グ ネ シ ウ ム magnesium, etc. Hydroxides, metals such as copper, silver, iron, aluminum, nickel, titanium and alloys, carbon-based materials such as diamond and carbon), thermoplastic resins and thermosetting resins (high density) , Medium and low density polyethylene, polypropylene, polybutene, polypentene and other homopolymers, ethylene propylene copolymer, nylon 6, nylon-6, 6, etc. , Nitrocellulose resin, vinylidene chloride resin, acrylic resin, acrylamide resin, styrene resin, vinyl ester resin, polyester resin, silicone resin, fluorine resin Fat, acrylic go Various types of elastomers such as rubber and urethane rubber, graft copolymers such as methyl methacrylate-butadiene styrene graft copolymers and acrylonitrile butadiene styrene graft copolymers), reinforcing agents (glass fibers, carbon fibers) ), Anti-sagging agents (hydrogenated castor oil, fine particulate succinic anhydride, etc.), matting agents (fine powder silica, paraffin wax, etc.), abrasives (such as zinc stearate), internal mold release agents (stearic acid, etc.) Fatty acid, fatty acid metal salts of calcium stearate, fatty acid amides such as stearic acid amide, fatty acid esters, polyolefin wax, and raffin wax may be added.

[0065] In the present invention, when the total amount of the components (A) to (D) or the total amount of the components (A) to (E) is 100% by mass, the blending amount of the pigment is 0. . 0001-50 mass%, the amount of the inorganic filler is 0.0001 to 50 mass _^0/0, the amount of leveling agent is 0.0001 to 5 mass _^0/0, thermoplastic榭butter and thermosetting The blending amount of greaves is 0.01-30% by weight, the blending amount of anti-sagging agent is 0.01-5% by weight, the blending amount of defrosting agent is 0.001-10% by weight, the blending amount of abrasive Is appropriately selected from the range of 0.01 to 5% by mass, and the amount of the internal mold release agent is 0.001 to 20% by mass.

[0066] In addition to the above-described components, an antifoaming agent, a flame retardant, an antistatic agent, a plasticizer, a thermal polymerization initiator, a silane coupling agent, an adhesion imparting agent, and the like can be used in combination.

 [0067] By irradiating the photocurable resin composition of the present invention obtained as described above with light, a cured product excellent in vibration fatigue durability can be obtained.

[0068] In addition, when the molded article of the photocurable resin composition of the present invention is molded, various means can be adopted as the means. Particularly preferably, (1) at least one of a pair of molds composed of an upper mold and a lower mold is formed of a material that transmits light, and a predetermined amount of the photocurable resin composition before curing is formed. Dripping. Next, the upper mold and the lower mold are pressure-bonded, the mold is closed, light is irradiated from the outside of the mold made of a material that transmits light, and the resin is cured to obtain the desired cured body. (2) At least one of a pair of molds consisting of a mold and a lower mold is formed of a material that transmits light, and then the upper mold and the lower mold are crimped, the mold is closed, and then the mold is formed in advance. A predetermined amount of the photocurable resin composition before curing is injected from the inlet. Then, light is irradiated from the outside of the mold made of a material that transmits light, and the resin is cured to obtain a desired cured body. [0069] Examples of materials used for the mold that transmits light include glass materials such as quartz, quartz glass, borosilicate glass, and soda glass, acrylic resin, polycarbonate resin, polystyrene resin, polyester resin, and polyethylene. Examples of the resin material include, but are not limited to, a resin, a polypropylene resin, a fluorine resin, a cellose resin, a styrene-butadiene copolymer, and a methyl methacrylate-styrene copolymer. Particularly preferred is an acrylic resin such as polymethyl methacrylate.

 [0070] Halogen lamp, metal halide lamp, high power metal halide lamp as light source

 (Including indium), low-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, xenon excimer lamp, xenon flash lamp, and the like.

 [0071] Since the emission wavelength and energy distribution are different from each other, the light source is selected depending on the reaction wavelength of the photopolymerization initiator. Natural light (sunlight) can also be a reaction initiation light source.

 [0072] The above-mentioned light source can be directly irradiated, focused with a reflecting mirror, or focused with a fiber, etc., and can be a low wavelength cut filter, a heat ray cut filter, a cold mirror, etc. .

 [0073] When the photocurable resin composition of the present invention is molded by the above molding method, the curing shrinkage of the resin composition is preferably 10% or less. If it exceeds 10%, curing shrinkage causes a difference in mold accuracy and the cured product, making it difficult to obtain a cured product of the desired shape.

 [0074] Further, the viscosity of the photocurable resin composition is 100 to 100, OOOmPa-s, particularly preferably 3,000 to 90, OOOmPa's at 25 ° C.ヽ. If it is less than lOOmPa's, liquid leakage may occur and a molded product with the desired shape may not be obtained. If it exceeds 100, OOOmPa's, it may be difficult to fill, and the mold may be pushed up, resulting in failure to obtain a cured product of the desired shape.

 Example

[0075] Hereinafter, the present invention will be described in more detail using examples and comparative examples, but the present invention is not limited to these examples. The data shown in the examples and comparative examples were measured according to the following method. [0076] The molecular weight and molecular weight distribution of the composition were measured under the following conditions by preparing a calibration curve with standard polystyrene by the GPC method.

 Solvent (mobile phase): THF,

 Deaerator: ERC A 3310, manufactured by ERM A

 Pump: JASCO PU-980,

 Sample injection volume: 100 1 (sample solution concentration lmg / ml),

 Flow rate: 1.0ml, mm,

Fluid pressure: 39kg / cm ²

 Autosampler: AS-8020 manufactured by Tosoh Corporation

 Column oven: Hitachi L-5030

 Set temperature: 40 ° C,

 Column configuration: Tosoh TSKguardcolumnMP (XL) 6.0mmID X 4.0cm 1 and Tosoh TSK—GEL MULTIPORE HXL—M 7.8mmID X 30.0cm m2, 3 in total

 Detector: RI Hitachi L 3350,

 Data processing: SIC480 data station.

[0077] The nuclear magnetic resonance spectrum (hereinafter referred to as ¾-NMR) of the composition was measured under the following conditions: Measuring device: ECP-300 (300 MHz) manufactured by JOEL

 Solvent: Deuterium black form,

 Sample concentration: 0.48% by mass,

 Integration count: 25,000 times.

[0078] The viscosity of the composition was measured under the following conditions.

 Viscometer: E-type viscometer (cone plate type),

 Measurement temperature: 25 ° C.

<Rubber composition polymerization examples 1 to 5>

 <Example of polymerization of rubber composition 1>

After replacing the 1L stainless steel autoclave with nitrogen, n-butyl acrylate (hereinafter n BA and!): 270g, methinoremethacrylate (hereinafter referred to as MMA): 270g, gucidinoremethacrylate (hereinafter referred to as GMA): 60g, benzoyl peroxide (hereinafter referred to as BPO) ): 13.9 g was charged in a nitrogen gas atmosphere, sealed, heated in an oil bath to 130 ° C, and polymerized at 200 ° C for about 60 minutes. Thereafter, the polymerization reaction was stopped by rapidly cooling to room temperature. The residual volatile matter was dried under vacuum at 240 ° C. for 2 hours to obtain a solid content. This was designated as a rubber composition (E-1). The yield is 92%, the number average molecular weight Mn by GPC measurement is 1,170, the weight average molecular weight Mw is 2,350, the molecular weight distribution Mw / Mn is 2.01, and the viscosity at 25 ° C is 5,5. It was OOOmPa's. In addition, the content ratio of the constituent components of the obtained rubber composition (E-1) was calculated as an integral strength specific force of ¹ H-NMR ^ vector. As a result, nBA: 44.7 mass%, MMA: 45.4 mass %, GMA: 9.9% by mass.

 <Rubber composition polymerization example 2>

A rubber composition (E-2) was obtained in the same manner as in Polymerization Example 1, except that nBA was 420 g, MMA was 18 g, GMA was 162 g, and BPO was 6.95 g. Yield is 95%, number average molecular weight Mn by GPC measurement is 2,000, weight average molecular weight Mw is 4,710, molecular weight distribution MwZMn is 2.36, viscosity at 25 ° C is 9,500 mPa ' s. Of the component ratio of the resulting rubber composition (E- 2) is, ^ -NMR ^ resulting vector, nBA: 68. 6 wt _^0/0, MMA: 3. 1 mass _^0/0, GMA: 28 It was found to be 3% by mass.

 <Rubber composition polymerization example 3>

A rubber composition (E-3) was obtained in the same manner as in Polymerization Example 1, except that the amount of nBA was 480 g, styrene: 90 g, GMA: 30 g, and BPO: 3.475 g in the preparation of Polymerization Example 1. Yield is 96%, number average molecular weight Mn by GPC measurement is 4,500, weight average molecular weight Mw is 9,900, molecular weight distribution MwZMn is 2.20, viscosity at 25 ° C is 5,900 mPa ' s. The resulting of the component ratio of the rubber composition (E- 3) is, iH-NMR ^ vectors result, nBA: 78. 4 wt _^0/0, styrene: 16.1 mass _^0/0, GMA: 5 . it was found that 5 mass ^_0/0

<Rubber composition polymerization example 4>

In the preparation of Polymerization Example 1, except that nBA: 228 g, MMA: 240 g, styrene: 90 g, 2-hydroxyxetyl acrylate (hereinafter referred to as 2-HEA): 12 g, BPO: 13.9 g In the same manner as in Polymerization Example 1, a rubber composition (E-4) was obtained. The yield is 92%, the number average molecular weight Mn by GPC measurement is 780, the weight average molecular weight Mw is 1,680, the molecular weight distribution MwZMn is 2.15, and the viscosity at 25 ° C is 1,200 mPa's. there were. The resulting of the component ratio of the rubber composition (E-4) is, NMR ^ vector result, ηΒΑ: 37. 3 mass _^0/0, MM A: 38. 9 mass _^0/0, styrene: 19. 5 mass _^0/0, 2-HEA: was found to be 4 3 mass ^_0/0.

<Rubber composition polymerization example 5>

 In the preparation of polymerization example 1, 2-ethylhexyl acrylate (hereinafter referred to as 2-EHA)

: A rubber composition (E-5) was obtained in the same manner as in Polymerization Example 1 except that 300 g, MMA: 30 g, GMA: 270 g, and BPO: l. 39 g were used. Yield is 98%, number average molecular weight by GPC measurement

Mn is 10,000, weight average molecular weight Mw is 19,600, molecular weight distribution MwZMn is 1

The viscosity at 96, 25 ° C was 95, OOOmPa's. The resulting content structure Ingredients of the rubber composition (E- 5) is, H- NMR results of the spectrum, 2- EHA:. 49 8 Mass _^0/0, MMA: 5

. 1 Mass _^0/0, GMA:. 45 was found to be 1% by mass.

<Examples 1 to 17 and Comparative Examples 1 to 7>

 Next, the composition (weight) of each component of the types shown in Table 11, 1, 12 and 13 is shown in the table.

%) To prepare a photocurable resin composition.

 In addition, the following compounds were selected for each component in the blend compositions described in Examples and Comparative Examples.

[0085] As the component (A),

 (A-1) Polyester polyol urethane acrylate

 (Product name: UV-3000B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)

 (GPC polystyrene equivalent weight average molecular weight 18000)

 (A-2) Polyether polyol urethane acrylate

 (Product name: UV-3700B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)

 (GPC polystyrene equivalent weight average molecular weight 37000)

 (A-3) Polyester polyol urethane acrylate

(Negami Kogyo brand name KHP-11) (GPC polystyrene equivalent weight average molecular weight 25000)

 (A-4) Polyester polyol urethane acrylate

 (Product name SD—7, manufactured by Negami Kogyo Co., Ltd.)

 (GPC polystyrene equivalent weight average molecular weight 3500)

 (A-5) n-Butylmetatalylate (Kyoeisha Co., Ltd. Light Ester NB)

 (A-6) 2-Hydroxyethyl metatalylate (Kyoeisha Co., Ltd., Light Ester HO)

(A-7) Isobutyl metatalylate (Light Ester IB, manufactured by Kyoeisha Co., Ltd.)

 (A— 8) tert-Butyl metatalylate (Kyoeisha Co., Ltd., Light Ester TB)

 (A-9) Cyclohexylmetatalylate (Light Ester CH manufactured by Kyoeisha Co., Ltd.)

 (A-10) Isobornyl metatalylate (Kyoeisha Co., Ltd., Light Ester IB—X)

(A—11) Dicyclopenta-methyl methacrylate (Hitakuri FA Co., Ltd.

3M)

 (A— 12) 1, 9 Nonane Dimethatalylate (Light Ester 1, 9ND manufactured by Kyoeisha Co., Ltd.)

 (A—13) Polyethylene glycol dimetatalylate (repeated number of ethylene oxide = 9) (Light Ester 9EG manufactured by Kyoeisha Co., Ltd.

 As a photopolymerization initiator of component (B),

 Bis (2, 4, 6 trimethylbenzoyl) monophenylphosphine oxide (Chinoku 'Special 1' IRGACURE819)

 As an antioxidant for component (C),

 Octadecyl 3-(3,5-Di-tert-butyl 4-hydroxyphenol) Probione (Chinoku 'Specialty I' Chemicals IRGANOX 1076)

 As a light stabilizer for component (D)

 Bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate (Sannore LS-770, manufactured by Sankyo Lifetech Co., Ltd.)

[0086] Various physical properties were measured as follows.

[Preparation of Cured Body Test Piece]

A set of molds made of acrylic resin made of an upper mold and a lower mold, in the shape of the desired specimen The required amount was dropped onto the lower mold on which the photocurable rosin yarn and the composition before curing were set. Next, the upper mold was put on the lower mold, and the mold was crimped and closed, irradiated with light from the outside of the mold, and the resin was cured to obtain a desired cured specimen.

 [0088] [Light irradiation conditions]

For light irradiation, a curing device manufactured by Fusion Co., Ltd. equipped with an electrodeless discharge lamp (D bulb) was used, and the photocurable resin was cured under the condition that the integrated irradiation amount to 4000 mjZcm ² (365 nm).

 [0089] [Fabric tensile test]

 In accordance with JIS K7113 (plastic tensile test method), 2 mm (1Z2) dumbbell shape (12 mm distance between gauge points) and 1 mm thick test piece was prepared under the above conditions, temperature 23 ° C, humidity 50% The measurement was performed at a tensile speed of 50 mmZmin in the environment described above. The values for tensile fracture strength, tensile modulus, and tensile elongation at break were determined according to JIS K7113.

 [0090] [Vibration fatigue endurance test]

 Prepare a test piece with a total length of 150mm X width 25mm X thickness lmm under the above conditions, and place it in the center of the test piece in advance by referring to JIS K62 60 (Dematia flex crack test method for vulcanized rubber and plastic rubber). A specimen with a crack of about 2 mm is fixed to the upper and lower grips of a Demacia bending crack tester (manufactured by Ueshima Manufacturing Co., Ltd.) with a grip spacing of 75 mm, under conditions of room temperature atmosphere, amplitude 56 mm, 300 times Z And reciprocated. For the measurement, the crack width was measured when the number of bendings was 0 (initial), 3,000, 54,000, and 144,000. In this case, the number of flexing times is one reciprocating motion, and the number of flexing times is read with a counter. The crack width was measured with the distance between grips set to 65 mm. Regarding the evaluation, vibration fatigue durability was evaluated as good when the crack width reached 25 mm (= rupture) at 144,000 times.

 [0091] Tables 11, 12, and 13 summarize the results of the measurement of the resin tensile test and vibration fatigue endurance test of the cured product of the obtained photocurable resin composition.

[0092] [Table 1-1] Table 1 1 1

Table 1 2

It can be suitably used as a packing member such as a speaker, an acoustic member such as a speaker, a sheet member such as a key sheet for a mobile phone, an anti-vibration material, and various mechanism members, and is very useful in industry. In addition, the photocurable resin composition of the present invention has an excellent fatigue resistance, so that it is a sealing agent for structures such as civil engineering and construction, an adhesive for metals, magnets, ceramics, glass, plastics, and a plastic lens. The present invention can also be applied to a molded resin product. The specification, claims and abstract of Japanese Patent Application 2006-001360 filed on January 6, 2006 and Japanese Patent Application 2006-036181 filed on February 14, 2006 The entire contents of this document are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims

The scope of the claims

 [1] (A) At least one resin selected from the group consisting of a photoradical polymerizable resin, a photoradical addition polymerizable resin, and a photothion polymerizable resin; (B) a photopolymerization initiator; (C) an antioxidant or (D) a photocurable resin composition containing either or both of a light stabilizer and a cured product of the photocurable resin thread and the cured product. A photocurable resin composition having a tensile elastic modulus of 1 to 30 MPa and a tensile strength at breakage of 200% or more.

 [2] The photocurable resin composition according to claim 1, further comprising (E) a rubber composition.

 [3] Rubber composition strength A copolymer consisting of (meth) acrylic ester compound, a bulle compound, and an olefinic hydrocarbon compound, a copolymer having at least one monomer strength selected, and having a weight average molecular weight. The photocurable resin composition according to claim 1 or 2, which is in the range of 500 to 50,000.

 [4] Rubber composition strength A copolymer consisting of (meth) acrylic acid ester compound, bur-based compound, and olefin-based hydrocarbon compound. The mass is

 (Ii) 20-90% by mass of a radically polymerizable monomer having a glass transition temperature of less than 25 ° C.

 (Mouth) 0.1 to 70% by mass of a radical polymerizable monomer having a glass transition temperature of 25 ° C. or higher of the homopolymer,

 (C) 1-50 mass% of a radically polymerizable monomer having at least one reactive group that is non-radically polymerizable in the molecule;

 The photocurable resin composition according to claim 3, comprising:

5. The photocurable resin composition according to claim 4, wherein the monomer of component (i) is an alkyl (meth) acrylate having 1 to 20 carbon atoms.

[6] The photocurable resin composition according to [4] or [5], wherein the monomer of the (mouth) component contains at least one selected from the group strength of methyl metatalylate and styrene power.

[7] The monomer of component (c) has one or more groups selected from a group force consisting of a hydroxyl group, a carboxylic acid group, a glycidyl group, an isocyanate group, an amino group, and an alkoxysilyl group. 6. The photocurable resin composition according to any one of 6 above.

[8] The viscosity of the rubber composition at 25 ° C is in the range of 100 to 100, OOOmPa's.

The photocurable resin composition as described in any one of -7.

 C

 [9] Optical Radical H-polymerizable resin is acrylic resin, and acrylic resin is (a-1) molecular end

 2

 RcΟ ll ll at the end or side chain c One or more urethane (meth) acrylate oligomers having one or more (meth) atalyloyl groups and a molecular weight of 5,000-100,000, and (a-2) single The photocurable resin composition according to any one of claims 1 to 8, wherein the photocurable resin composition is composed of a functional (meth) acrylate.

 [10] The photocurable resin according to claim 9, wherein the (a-2) monofunctional (meth) acrylate is a monofunctional (meth) acrylate represented by the following formula [1] or [2]: Composition.

 [Chemical 1]

(In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is a straight or branched alkyl group having 1 to 22 carbon atoms, a cyclohexyl group, a straight or branched chain having 1 to 4 carbon atoms. A cyclohexyl group, a phenyl group, a phenyl group substituted with a linear or branched alkyl group having 1 to 4 carbon atoms, a dicyclopental group, a dicyclopental group, or a bornyl group. , An isobornyl group, an adamantyl group, a methyladamantyl group or an aryl group.)

 [Chemical 2]

R

 [2]

(Wherein R ¹ is a hydrogen atom or a methyl group, R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms, and R ⁴ is a linear or branched alkyl group having 1 to 4 carbon atoms. Cyclohexyl substituted with a cyclohexyl group or a linear or branched alkyl group having 1 to 4 carbon atoms Group, a phenyl group, a phenyl group substituted by a linear or branched alkyl group having 1 to 4 carbon atoms, a dicyclopental group, a dicyclopental group, a bornyl group, an isobornyl group, an adamantyl group, methyl An adamantyl group or an aryl group, and n is an integer of 1 to 12. )

 [11] The photoradical addition polymerizable resin comprises a polyene compound having two or more carbon-carbon unsaturated double bonds in the molecule and a polythiol compound having two or more mercapto groups in the molecule. Item 1-8! The photocurable rosin composition according to claim 1.

 [12] The photocurable resin composition according to any one of [1] to [8], wherein the light-powered thione polymerizable resin has an epoxy group, an oxetanyl group, or a vinyl ether group in the molecule.

 [13] A cured product comprising the photocurable resin composition according to any one of claims 1 to 12.