JPWO2007077691A1 - Photocurable resin composition - Google Patents

Abstract

Provided is a photocurable resin composition suitable for a photocurable casting method, and in particular, a photocurable resin composition excellent in vibration fatigue durability. (A) at least one resin selected from the group consisting of a photoradical polymerizable resin, a photoradical addition polymerizable resin, and a photocationic polymerizable resin, (B) a photopolymerization initiator, and (C) an antioxidant or (D) A photocurable resin composition containing either or both of the light stabilizers, wherein the cured product of the photocurable resin composition has a tensile elastic modulus of 1 to 30 MPa, and a tensile breaking elongation. Is a photocurable resin composition characterized by being 200% or more. Furthermore, the photocurable resin composition may include (E) a rubber composition.

Description

  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 particularly to a photocurable resin composition and a cured product excellent in vibration fatigue durability.

  In general, a composition that imparts so-called rubber properties such as flexibility, stretchability, and elasticity is called an elastomer, and its fatigue durability against vibration is far superior to other polymer materials. 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, vibration-proof materials, various mechanism members Etc. are applied.

  Conventional elastomers (hereinafter denoted by symbol R) include natural rubber, modified natural rubber, grafted natural rubber, cyclized natural rubber, chlorinated natural rubber, styrene-butadiene rubber, chloroprene rubber, acrylonitrile-butadiene rubber, carboxylated Nitrile rubber, nitrile rubber / vinyl chloride resin blend, nitrile rubber / EPDM rubber blend, butyl rubber, brominated butyl rubber, chlorinated butyl rubber, ethylene-vinyl acetate rubber, acrylic rubber, ethylene-acrylic rubber, chlorosulfonated polyethylene, chlorinated polyethylene , Rubber materials such as epichlorohydrin rubber, epichlorohydrin-ethylene oxide rubber, methyl silicone rubber, vinyl-methyl silicone rubber, phenyl-methyl silicone rubber, fluorosilicone rubber; polystyrene-based heat Plastic elastomer, Polyvinyl chloride thermoplastic elastomer, Polyolefin thermoplastic elastomer, Polyurethane thermoplastic elastomer, Polyester thermoplastic elastomer, Polyamide thermoplastic elastomer, Vinyl chloride thermoplastic elastomer, Fluoro rubber thermoplastic elastomer, Chlorine Thermoplastic elastomer materials such as fluorinated polyethylene elastomers are known.

  In general, as a method for obtaining a molded body of elastomer (R), a kneading step for sufficiently kneading an elastomer raw material containing a curing agent and other additives, and a kneaded dough for a vacuum forming method, a pressure forming method, an upper die After a curing process (vulcanizing process) in which the lower mold is molded by a heating mold and an injection molding process using a molding mold (hereinafter referred to as an upper and lower mold), and vulcanized or cured by heating and pressing. The desired molded body is obtained.

  However, in the vacuum forming method, the pressure forming method, the heat pressing method using the upper and lower molds, etc., it is necessary to raise the mold temperature to near the melting point of the material, and enormous energy is required for heating. Moreover, since it is necessary to cool and take out the metal mold, it takes a long time for the molding cycle.

  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 reduced, so that it is difficult to obtain a thin molded body, such as heating, injection, holding pressure, etc. This makes the equipment expensive. Further, since the thermoplastic material is heated to near the melting point, the heating energy is enormous.

  In the above-mentioned 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 that is substantially larger than the target part size, and then cutting out the part part for use. A lot of waste is generated, which is not preferable environmentally and economically.

  The above-mentioned constituent materials of the vacuum forming method, the pressure forming method, and the heat and pressure forming method using the upper and lower molds are generally uniform thickness materials. It is difficult to change the thickness of each part.

  In addition, the thickness 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.

As a means for solving the problems of the molding method as described above, a photo-curing injection which forms a molded body by curing the photo-curable liquid material filled in the upper and lower molds by irradiating light such as ultraviolet rays and visible light. A mold forming method is proposed in Patent Document 1.
JP 2004-357020 A

  More specifically, 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 resin that can be cured by light irradiation is set to close the mold, In this method, light is irradiated from the outside of a transmitting mold and the resin is cured to obtain a cured body having a desired shape. By this method, it is possible to easily and inexpensively produce a molded body having an arbitrary thickness with less energy and less man-hours.

On the other hand, as a resin composition exhibiting photocurable elastomer or rubber elasticity, Patent Documents 2 and 3 disclose resin compositions for sealing materials, and Patent Document 4 discloses optical resin compositions for optical three-dimensional modeling. ing. However, a resin composition that is suitable for the above-mentioned photo-curing cast molding method and satisfies vibration fatigue durability as required for conventional elastomers has not been known.
Japanese translation of PCT publication No. 2002-501109 Special table 2003-505525 JP 2000-290328 A

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

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 photocationic polymerizable resin, (B) a photopolymerization initiator, (C) an antioxidant, and (D) A photocurable resin composition containing either or both of the light stabilizers, wherein the cured product of the photocurable resin composition has a tensile elastic modulus of 1 to 30 MPa, and a tensile breaking elongation. Is a photocurable resin composition characterized by being 200% or more.
2. Furthermore, (E) The photocurable resin composition of said 1 containing a rubber composition.
3. The rubber composition is a copolymer composed of at least one monomer selected from the group consisting of (meth) acrylic acid ester compounds, vinyl compounds, and olefinic hydrocarbon compounds, and has a weight average molecular weight of 500 to 500. 3. The photocurable resin composition according to the above 1 or 2, which is in the range of 50,000.

4). The rubber composition is a copolymer composed of three or more monomers selected from the group consisting of (meth) acrylic acid ester compounds, vinyl compounds, and olefinic hydrocarbon compounds, wherein the monomers are ,
(Ii) 20-90% by mass of a radical polymerizable monomer having a glass transition temperature of less than 25 ° C. of the homopolymer,
(B) 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 to 50% by 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

5. (A) The photocurable resin composition according to 4 above, wherein the component monomer is an alkyl (meth) acrylate having 1 to 20 carbon atoms.
6). (A) The photocurable resin composition as described in 5 above, wherein the component monomer is an alkyl (meth) acrylate having 1 to 8 carbon atoms.
7). (B) The photocurable resin composition according to any one of the above 4 to 6, wherein the monomer of the component contains at least one selected from the group consisting of methyl methacrylate and styrene.
8). (C) Any one of the above 4 to 7 wherein the component monomer 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 according to Item.
9. (C) The photocurable resin composition according to 8 above, wherein the monomer of the component is glycidyl (meth) acrylate or hydroxyalkyl (meth) acrylate.

10. The photocurable resin composition according to any one of 1 to 9, wherein the rubber composition has at least one aromatic group in the molecule.
11. The photocurable resin composition as described in any one of said 1-10 whose viscosity in 25 degreeC of a rubber composition exists in the range of 100-100,000 mPa * s.
12 The photocurable resin composition according to any one of 1 to 11 above, 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, wherein a ratio 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 photoradical polymerizable resin is an acrylic resin.
15. The acrylic resin (a-1) has one or more (meth) acryloyl groups at the end or side chain of the molecule, and one or more urethane (meth) acrylate oligomers having a molecular weight of 5,000 to 100,000; (A-2) The photocurable resin composition according to the above 14, comprising a monofunctional (meth) acrylate.

（式中、Ｒ^１は水素原子またはメチル基であり、Ｒ^２は、炭素数１〜２２である直鎖もしくは分岐アルキル基、シクロヘキシル基、炭素数１〜４の直鎖もしくは分岐アルキル基により置換されたシクロヘキシル基、フェニル基、炭素数１〜４の直鎖もしくは分岐アルキル基により置換されたフェニル基、ジシクロペンタニル基、ジシクロペンテニル基、ボルニル基、イソボルニル基、アダマンチル基、メチルアダマンチル基またはアリル基である。）16. (A-2) The photocurable resin composition according to 15 above, wherein the monofunctional (meth) acrylate is a monofunctional (meth) acrylate represented by the following formula [1] or [2].

(In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is substituted by a linear or branched alkyl group having 1 to 22 carbon atoms, a cyclohexyl group, or a linear or branched alkyl group having 1 to 4 carbon atoms. Cyclohexyl group, phenyl group, phenyl group substituted by a linear or branched alkyl group having 1 to 4 carbon atoms, dicyclopentanyl group, dicyclopentenyl group, bornyl group, isobornyl group, adamantyl group, methyladamantyl group Or an allyl group.)

（式中、Ｒ^１は水素原子またはメチル基であり、Ｒ^３は、炭素数１〜４である直鎖もしくは分岐アルキル基、Ｒ^４は、炭素数１〜４である直鎖もしくは分岐アルキル基、シクロヘキシル基、炭素数１〜４の直鎖もしくは分岐アルキル基により置換されたシクロヘキシル基、フェニル基、炭素数１〜４の直鎖もしくは分岐アルキル基により置換されたフェニル基、ジシクロペンタニル基、ジシクロペンテニル基、ボルニル基、イソボルニル基、アダマンチル基、メチルアダマンチル基またはアリル基であり、ｎは１〜１２の整数である。）

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. 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 dicyclopentanyl group , Dicyclopentenyl group, bornyl group, isobornyl group, adamantyl group, methyladamantyl group or allyl group, and n is an integer of 1 to 12.)

17. (A-2) The photocurable resin composition according to 15 or 16 above, wherein the monofunctional (meth) acrylate has a glass transition temperature of the homopolymer of 20 ° C. or higher.
18. 1 to 13 above, wherein 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. The photocurable resin composition as described in any one of these.
19. 14. The photocurable resin composition according to any one of 1 to 13, wherein the photocationically polymerizable resin has an epoxy group, an oxetanyl group, or a vinyl ether group in the molecule.
20. 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. The hardening body which consists of a photocurable resin composition as described in any one of said 1-20.

  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 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, various mechanisms It can be suitably used for members and the like. Moreover, the photocurable resin composition of the present invention can also be applied to structural and structural sealants for civil engineering and construction, and adhesives for metals, magnets, ceramics, glass and plastics due to its excellent fatigue properties.

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, the “alkyl group” means a linear, branched and cyclic saturated hydrocarbon group unless otherwise specified.

  In the photocurable resin composition of this invention, the photocurable resin which receives the irradiation of light and forms a hardening body which is (A) component is contained. 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 includes a photo-radical polymerizable resin, a light At least one resin selected from the group consisting of radical addition polymerizable resins and photocationic polymerizable resins can be used. Of these, the radical photopolymerizable resin is preferably selected because it contains an acrylic resin rich in material selectivity.

  As the photoradical addition polymerizable resin, an ene-thiol reaction in which a thiol group is added to a carbon-carbon unsaturated bond by radical generation is known as known. In particular, an ene-thiol resin composed of a compound having at least two or more thiol groups in the molecule and a compound having two or more carbon-carbon unsaturated bonds in the molecule is preferable because of excellent photocurability.

  Examples of the cationic photopolymerizable resin include resins having an epoxy group in the molecule, resins having an oxetanyl group, resins having a vinyl ether group, resins having a spiro ortho ester group, resins having a bicyclo ortho ester group, and spiro ortho carbonate groups. And the like. Of these, a resin having an epoxy group, an oxetanyl group or a vinyl ether group is preferable because of photocurability and abundant selection of materials.

  Examples of the photo-radical polymerizable resin include acrylic resins, styrene resins, vinyl resins, unsaturated polyesters, polyolefins, etc. Among them, acrylic resins are preferable because of their photocurability and abundant material selection.

  Acrylic resins include poly (meth) acrylate, (meth) acrylate monomer, (meth) acrylate dimer, polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyolefin (meth) acrylate, silicone (meth) ) Acrylate and the like. In achieving the object of the present invention, a resin composition comprising urethane (meth) acrylate and (meth) acrylate monomer is preferred. Particularly preferably, (a-1) one or more urethane (meth) acrylate oligomers having one or more (meth) acryloyl groups at the end or side chain of the molecule and having a molecular weight of 5,000 to 100,000; (A-2) A resin composition comprising monofunctional (meth) acrylate.

  The urethane (meth) acrylate oligomer as the component (a-1) is composed of a polyol compound (hereinafter represented by X), an organic polyisocyanate compound (hereinafter represented by Y), and a hydroxy (meth) acrylate (hereinafter represented by Z). Represents a urethane (meth) acrylate oligomer.

  Examples of the polyol compound (X) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, 1,4-butanediol, and polybutylene glycol. 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5- Pentanediol, 2,2-butylethyl-1,3-propanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone, trimethylolethane, trimethylo Polyhydric alcohols such as propane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerin, polyglycerin, polytetramethylene glycol; polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide block or random copolymerization A polyether polyol having at least one structure of: a polyhydric alcohol or polyether polyol and a polybasic acid such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, and isophthalic acid Polyester polyol that is a condensate; caprolactone-modified polyol such as caprolactone-modified polytetramethylene polyol; polyolefin-based polyol; Boneto polyol; polybutadiene polyols such as hydrogenated polybutadiene polyol; silicone polyols such as polydimethylsiloxane polyols and the like. Particularly preferred are polyether polyols and polyester polyols.

  Especially, it is preferable that molecular weight is 200-10,000, Preferably it is 500-8,000, More preferably, it is 1,000-6,000. If the molecular weight is 200 or more, suitable vibration fatigue durability can be obtained, and if it is 10,000 or less, the curability does not deteriorate, which is preferable.

  The organic polyisocyanate compound (Y) is not particularly limited, and examples thereof include aromatic, aliphatic, cycloaliphatic, and alicyclic polyisocyanates. 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), trimethylhexamethylene diisocyanate (TMXDI), tetramethylxylylene diisocyanate (m-TMXDI), isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), Polyisocyanate such as 1,3-bis (isocyanatomethyl) cyclohexane (H6XDI) or Trimer compounds of Luo polyisocyanates, reaction products of these polyisocyanates with polyols 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 a diol will not fall.

  Examples of the hydroxy (meth) acrylate (Z) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl acryloyl phosphate, and 4-butyl. Hydroxy (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, caprolactone modified 2-hydroxyethyl (Meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, etc. . Of these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate are preferably used.

  In the urethane (meth) acrylate oligomer, the number of (meth) acryloyl groups in the molecule is 1 or more and 6 or less, more preferably 2 or more and 4 or less (meth) acryloyl groups at the end or side chain of the molecule. Those having the following are preferred. When there is no (meth) acryloyl group, it cannot be copolymerized with the monofunctional (meth) acrylate as the component (B), and when there are more than six, the resulting molded product becomes too hard and has excellent vibration fatigue durability. Sexuality may not be obtained.

  The molecular weight of the urethane (meth) acrylate oligomer is selected from 5,000 to 100,000, more preferably from 10,000 to 50,000. If the molecular weight is 5,000 or more, the resulting molded product will not be too hard, and if it is 100,000 or less, the curability will not be deteriorated and a cured product having excellent vibration fatigue durability can be obtained. it can.

式〔１〕中、Ｒ^１は水素原子またはメチル基であり、Ｒ^２は、炭素数１〜２２（好ましくは、炭素数１〜１２である。）である直鎖もしくは分岐アルキル基、シクロヘキシル基、炭素数１〜４の直鎖もしくは分岐アルキル基により置換されたシクロヘキシル基、フェニル基、炭素数１〜４の直鎖もしくは分岐アルキル基により置換されたフェニル基、ジシクロペンタニル基、ジシクロペンテニル基、ボルニル基、イソボルニル基、アダマンチル基、メチルアダマンチル基、アリル基である。

式〔２〕中、Ｒ^１は水素原子またはメチル基であり、Ｒ^３は、炭素数１〜４である直鎖もしくは分岐アルキル基、Ｒ^４は、炭素数１〜４である直鎖もしくは分岐アルキル基、シクロヘキシル基、炭素数１〜４の直鎖もしくは分岐アルキル基により置換されたシクロヘキシル基、フェニル基、炭素数１〜４の直鎖もしくは分岐アルキル基により置換されたフェニル基、ジシクロペンタニル基、ジシクロペンテニル基、ボルニル基、イソボルニル基、アダマンチル基、メチルアダマンチル基、アリル基である。
ｎは１〜１２の整数であり、好ましくは、１〜１０である。The monofunctional (meth) acrylate as the component (a-2) is not particularly limited as long as it contains one (meth) acryloyl 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 having excellent vibration fatigue durability can be obtained.

In the formula [1], R ¹ is a hydrogen atom or a methyl group, and R ² is a linear or branched alkyl group or cyclohexyl group having 1 to 22 carbon atoms (preferably 1 to 12 carbon atoms). 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 dicyclopentanyl group, a dicyclo A pentenyl group, a bornyl group, an isobornyl group, an adamantyl group, a methyladamantyl group, and an allyl group.

In Formula [2], 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 group having 1 to 4 carbon atoms. An alkyl group, a cyclohexyl group, a cyclohexyl group substituted by a linear or branched alkyl group having 1 to 4 carbon atoms, a phenyl group, a phenyl group substituted by a linear or branched alkyl group having 1 to 4 carbon atoms, dicyclopenta Nyl group, dicyclopentenyl group, bornyl group, isobornyl group, adamantyl group, methyladamantyl group and allyl group.
n is an integer of 1 to 12, preferably 1 to 10.

Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meta ) Acrylate, isodecyl (meth) acrylate, lauryl (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 (meta) Acrylate, methoxytetraethylene (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene 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) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (Meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate 2-methyl-2-adamantyl (meth) acrylate, allyl (meth) acrylate and the like. Incidentally, with acrylate and methacrylate, methacrylate provides a cured body with better vibration fatigue durability.

  (A-2) The monofunctional (meth) acrylate is preferably a monofunctional (meth) acrylate having a homopolymer Tg of 20 ° C. or higher. More preferably, Tg is 50 ° C. or more, and particularly preferably 80 ° C. or more. If Tg is 20 ° C. or higher, the obtained cured product will not be too flexible and the curability will not deteriorate. In addition, although Tg of the photocurable resin composition of this invention does not have a restriction | limiting in particular in a measuring method, It measures by well-known methods, such as DSC and dynamic viscoelasticity, Preferably DSC is used.

  In the photocurable resin composition of the present invention, the blending ratio of the component (a-1) to the component (a-2) is (total of the component (a-1) and the component (a-2) ( When a composition containing the component a-1) is contained in an amount of 5 to 95% by mass, particularly preferably 20 to 85% by mass, a cured product obtained by light irradiation is particularly preferable because it has excellent vibration fatigue durability.

  The photopolymerization initiator as the component (B) includes an ultraviolet polymerization initiator and a visible light polymerization initiator, and both are used without limitation. Examples of the photo radical polymerization initiator include benzoin, benzophenone, acetophenone, acylphosphine oxide, thioxanthone, metallocene, and quinone. Examples of the cationic photopolymerization initiator include iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, pyridinium salt compounds, and iron-arene complex compounds.

  In the present invention, the photopolymerization initiator is not particularly limited, and known ones can be used. For example, benzophenone, 4-phenylbenzophenone, benzoylbenzoic acid, 2,2-diethoxyacetophenone, bisdiethylaminobenzophenone, benzyl, benzoin, benzoylisopropyl ether, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, thioxanthone, 1- (4 -Isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2- Hydroxy-2-methyl-1-phenylpropan-1-one, camphorquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxy Id, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone- 1, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and the like.

  Examples of the antioxidant as component (C) include β-naphthoquinone, 2-methoxy-1,4-noftquinone, methyl hydroquinone, hydroquinone, hydroquinone monomethyl ether, mono-tert-butyl hydroquinone, 2,5-di- quinone compounds such as tert-butylhydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-di-tert-butyl-p-benzoquinone; phenothiazine, 2,2-methylene-bis (4- Methyl-6-tert-butylphenol), catechol, tert-butylcatechol, 2-butyl-4-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2-tert-butyl-6- (3- tert-Butyl-2-hydroxy-5-methylbenz ) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 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-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, pentaerythritol tetrakis [3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydride) Loxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenyl) propionamide], benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, 2,4-dimethyl-6 -(1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ', 3 ", 5,5' , 5 "-hexa-tert-butyl-a, a ', a"-(mesitylene-2,4,6-tolyl) tri-p-cresol, calcium diethylbis [3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3 -(5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) 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 -Tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, N-phenylbenze Reaction product of amine and 2,4,6-trimethylpentene, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) Phenols such as phenol, picric acid, citric acid; tris (2,4-di-tert-butylphenyl) phosphite, tris [2-[[2,4,8,10-tetra-tert-butyldibenzo [d , F] [1,3,2] dioxaphosphine-6-yl] oxy] ethyl] amine, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis [2 , 4-Bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid, tetrakis (2,4-di-tert-butylphenyl) [1,1-bispheny L] -4,4′-diylbisphosphonite, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert- Phosphorus compounds such as butyl dibenz [d, f] [1,3,2] dioxaphosphine; dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3, 3'-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), sulfur compounds such as 2-mercaptobenzimidazole; amine compounds such as phenothiazine; lactone compounds; vitamin E compounds Can be mentioned. Of these, phenol compounds are preferred.

  Examples of the light stabilizer as component (D) include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and 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] methy Butyl malonate, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, N, N ', N ", N"'-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazine-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-tetramethyl-4-piperidyl) butylamine polycondensate, poly [[6- (1,1,3,3-tetramethylbutyl) amino- 1,3,5-G Azine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], Polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7 -Oxa-3,20-diazadispiro [5 · 1 · 11 · 2] heneicosan-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-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl- -Oxa-3,20-diazadispiro [5,1,11,2] heneicosane-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5,1,11 , 2] -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 Hindered amines such as -piperidinyl); benzophenone compounds such as octabenzone; 2- (2H-benzotriazol-2-yl) -4- (1 , 1,3,3-tetramethylbutyl) phenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimide-methyl) ) -5-methylphenyl] benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert- Pentylphenyl) benzotriazole, methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol reaction product, 2- (2H-benzotriazole -2-yl) -6-dodecyl-4-methylphenol and other benzotriazole compounds Benzoate compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2- (4,6-diphenyl-1,3,5-triazine-2; -Il) -5-[(hexyl) oxy] phenol and other triazine compounds. Particularly preferred are hindered amine compounds.

  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 to 99.99% by mass, The content is particularly preferably 90.0 to 99.9% by mass. (B) component becomes like this. Preferably it is 0.01-15 mass%, Most preferably, 0.1-10 mass% is contained. The total of component (C) and component (D) is preferably 0.01 to 5% by mass, particularly preferably 0.05 to 3% by mass. Component (C) and component (D) preferably have a content ratio of component (C) / component (D) of 0/10 to 10/0, particularly preferably 1/9 to 9/1. When the content of the components (A) to (D) is within such a range, a cured product obtained from the photocurable resin composition of the present invention is preferable because it has excellent vibration fatigue durability.

  Furthermore, in addition to the photocurable resin, the photocurable resin composition of the present invention includes (B) a photopolymerization initiator, (C) an antioxidant, and (D) one or both of a light stabilizer. The cured product of the photocurable resin composition has a tensile modulus of 1 to 30 MPa, preferably 1.5 when a tensile test measurement is performed in accordance with JIS K7113 (plastic tensile test method). It is characterized by exhibiting excellent vibration fatigue durability of ˜28.5 MPa and a tensile fracture elongation of 200% or more, preferably 201 to 1500%. When the tensile elastic modulus of the cured body is 1 MPa or more, there is no problem that the obtained cured body is too soft to hold the shape. If the tensile modulus of the cured product is 30 MPa or less and the tensile elongation at break is 200% or more, excellent vibration fatigue durability can be obtained, and the effects of the invention can be obtained with certainty.

Furthermore, 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 elastomer (R) can be exemplified, and among them, the (meth) acrylic acid ester compound, the vinyl compound, and the olefin carbonization are particularly preferable from the viewpoint of compatibility with the photocurable resin. A rubber composition which is a copolymer comprising at least one monomer selected from the group consisting of hydrogen compounds is preferred.

The molecular weight of the rubber composition is preferably in the range of 500 to 50,000, particularly preferably 750 to 20,000, and more preferably 1,000 to 10,000. When the molecular weight is 500 or more, the photocurable resin can obtain sufficient vibration fatigue durability, and when it is 50,000 or less, the compatibility with the photocurable resin is excellent, which is preferable.
The molecular weight distribution of the rubber composition (Mw / Mn when the weight average molecular weight is Mw and the number average molecular weight is Mn) is 1.0 to 5.0, particularly preferably 1.1 to 3.0. Is preferable because it is compatible with the photocurable resin and gives excellent vibration fatigue durability.

  As the monomer constituting the rubber composition, (a) a radical polymerizable monomer having a Tg of the homopolymer of less than 25 ° C., and (b) a radical polymerizable monomer having a Tg of the homopolymer of 25 ° C. or more. And (c) a radically polymerizable monomer having at least one reactive group that is non-radically polymerizable in the molecule, the rubber composition has good compatibility with the photocurable resin. It is particularly preferable because it provides excellent vibration fatigue durability.

(A) The monomer of the component gives flexibility to the rubber composition. The proportion of the component (A) in the rubber composition is preferably 20 to 90% by mass, particularly preferably 30 to 80% by mass.
(A) As a component, C1-C20 alkyl (meth) acrylate [For example, butyl acrylate, n-butyl methacrylate, ethyl acrylate, n-octyl acrylate, and 2-ethylhexyl (meth) acrylate], diene monomer [ For example, butadiene, isoprene], vinyl acetate monomer 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.

  The component (b) monomer provides compatibility with the photocurable resin. The proportion of the component (b) in the rubber composition is preferably 0.1 to 70% by mass, particularly preferably 1 to 60% by mass. As the component (b), methyl methacrylate, ethyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl (meth) acrylate, (meth) acrylic ester such as dicyclopentanyl (meth) acrylate, (meth) acrylonitrile, or And vinyl aromatic compounds such as styrene. Methyl methacrylate and styrene are particularly preferred from the viewpoint of the balance between compatibility and copolymerization.

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. It is because it reacts simultaneously with radical polymerization of a rubber composition as it is radically polymerizable. 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) acryloyloxyethyl succinic acid, 2 -(Meth) acryloyloxyethyl isocyanate, 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate, diethylamino (meth) acrylate, dimethylamino (meth) acrylate, 3- (meth) acryloyloxypropyltrimethoxysilane , 3- (meth) acryloyloxypropyltriethoxysilane and the like. Particularly preferred in terms of reactivity with the photocurable resin are hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, and glycidyl (meth) acrylate.

  As a polymerization method of the rubber composition, known methods such as radical polymerization and anionic polymerization can be used.

  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. Moreover, a radical generator can be used as needed.

  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 preferable because the polymerization rate is high and productivity is improved.

  The polymerization temperature is preferably in the temperature range of 50 to 500 ° C. from the viewpoint of high polymerization rate and easy control of the polymerization rate, and particularly preferred polymerization temperature is 100 to 400 ° C.

  As the radical generator, various compounds can be used, and preferably, a peroxide capable of generating a radical under polymerization temperature conditions is used. Examples of the peroxide include, but are not limited to, benzoyl peroxide, acetyl peroxide, isobutyroyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide. Diacyl peroxides such as oxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide; di-t-butyl peroxide, t-butyl cumyl peroxide, di-cumyl peroxide, α, α′- Bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne -3 etc. dialkyl peroxides; 2 2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, n- Peroxyketals such as butyl-4,4-bis (t-butylperoxy) valerate; di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, Di-3-methoxybutyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, bis (4 Peroxycarbons such as -t-butylcyclohexyl) peroxydicarbonate T-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypiparate, t-butyl peroxyneodecanoate, cumylperoxyneodecanoate, t-butylper Oxy-2-ethylhexanoate, t-butylperoxy 3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-butyldiperoxyisophthalate, 2 Peroxyesters such as 5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyisopropyl carbonate; acetylacetone peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3, 3, 5-trimethylcyclohexanone Ketone peroxides such as oxide and methylcyclohexanone peroxide; cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane 2,5-dihydroperoxide, 1, 1 Hydroperoxides such as 3,3-tetramethylbutyl hydroperoxide; polyacyl peroxides of dibasic acids; polyperoxy esters of dibasic acids and polyols. Of these, benzoyl peroxide is preferably used.

  Further, a radical-generating azo compound or the like can be used as a radical generator instead of peroxide. Examples of the radical-generating azo compound include azobisisobutyronitrile.

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

  The rubber composition preferably contains a polymer chain having at least one aromatic group in the molecule because it is excellent in compatibility with the photocurable resin and gives excellent vibration fatigue durability. The aromatic group may be any of a main chain, a side chain, and a chain end. In particular, an aromatic group at the chain end is preferable because of excellent compatibility and excellent vibration fatigue durability. 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 mass% or more, vibration fatigue durability can be provided 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.

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

  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 degreeC, More preferably, it is less than -20 degreeC.

  The viscosity at 25 ° C. of the rubber composition is preferably in the range of 100 to 100,000 mPa · s. Sufficient vibration fatigue durability can be imparted at 100 mPa · s or more, compatibility with a photocurable resin can be obtained at 100,000 mPa · s or less, and the photocurable resin itself does not thicken. ,preferable. In addition, there is no restriction | limiting in particular in the measuring method of a viscosity, However, It can measure using well-known viscometers, such as a B-type viscosity meter, an E-type viscosity meter, and a rheometer.

  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 to 30% by mass. . When the amount is less than 0.01% by mass, sufficient vibration fatigue durability cannot be obtained. When the amount is more than 70% by mass, the resulting photocurable resin is too flexible and further the curability is lowered.

  Furthermore, the cured product of the photocurable resin composition containing the rubber composition of the present invention has a tensile modulus of 1 to 30 MPa when a tensile test measurement is performed in accordance with JIS K7113 (plastic tensile test method). Furthermore, it is characterized by exhibiting excellent vibration fatigue durability having a tensile fracture elongation of 200% or more. When the tensile elastic modulus of the cured body is 1 MPa or more, there is no problem that the obtained cured body is too soft to hold the shape. If the tensile modulus of the cured product is 30 MPa or less and the tensile elongation at break is 200% or more, excellent vibration fatigue durability can be obtained, and the effects of the invention can be obtained with certainty.

  In the present invention, if necessary, pigments (titanium white, cyanine blue, watching red, bengara, carbon black, aniline black, manganese blue, iron black, ultramarine blue are used as long as the effects of the present invention are not impaired. , Hansa Red, Chrome Yellow, Chrome Green, etc.), inorganic fillers (calcium carbonate, kaolin, clay, talc, mica, barium sulfate, lithopone, limestone, zinc stearate, perlite, quartz, quartz glass, fused silica, spherical Silica powder such as silica, spherical alumina, crushed alumina, oxides such as magnesium oxide, beryllium oxide and titanium oxide, nitrides such as boron nitride, silicon nitride and aluminum nitride, carbides such as silicon carbide, hydroxide Hydroxides such as aluminum and magnesium hydroxide, copper Metals and alloys such as silver, iron, aluminum, nickel and titanium, carbon-based materials such as diamond and carbon), thermoplastic resins and thermosetting resins (high density, medium density, low density polyethylene, polypropylene , Homopolymers such as polybutene and polypentene, ethylene-propylene copolymers, polyamide resins such as nylon-6 and nylon-6, 6, vinyl chloride resins, nitrocellulose resins, vinylidene chloride resins, acrylic resins Acrylamide resins, styrene resins, vinyl ester resins, polyester resins, silicone resins, fluorine resins, acrylic rubber, urethane rubber and other elastomer resins, methyl methacrylate-butadiene-styrene graft copolymers, Acrylonitrile-butadiene-styrene graph Graft copolymers such as copolymers), reinforcing agents (glass fibers, carbon fibers, etc.), anti-sagging agents (hydrogenated castor oil, fine succinic anhydride, etc.), matting agents (fine silica, paraffin wax, etc.) , Abrasives (zinc stearate, etc.), internal mold release agents (fatty acids such as stearic acid, fatty acid metal salts of calcium stearate, fatty acid amides such as stearic acid amide, fatty acid esters, polyolefin wax, paraffin wax, etc.) Is also possible.

  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 to 50% by mass. The compounding amount of the inorganic filler is 0.0001 to 50% by mass, the compounding amount of the leveling agent is 0.0001 to 5% by mass, the compounding amount of the thermoplastic resin and the thermosetting resin is 0.01 to 30% by mass, The blending amount of the anti-sagging agent is 0.01 to 5% by mass, the blending amount of the matting agent is 0.001 to 10% by mass, the blending amount of the abrasive is 0.01 to 5% by mass, and the blending of the internal release agent The amount is appropriately selected from the range of 0.001 to 20% by mass.

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

  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 instantaneously.

  Moreover, when shape | molding the molded object of the photocurable resin composition of this invention, the method can employ | adopt various methods. Particularly preferably, (1) at least one of a pair of molds consisting 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 dropped. . 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 a desired cured body. (2) Upper mold And forming at least one of a set of molds composed of a lower mold with a material that transmits light, then crimping the upper mold and the lower mold, closing the mold, and then pre-forming the mold A predetermined amount of the photo-curable resin composition before curing is injected from the injection port. And it is the method of irradiating light from the outer side of the type | mold which consists of a material which permeate | transmits light, and hardening a resin and obtaining the target hardening body.

  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, polyethylene resin, polypropylene resin, fluororesin, Although resin materials, such as a cellulose resin, a styrene-butadiene copolymer, and a methyl methacrylate-styrene copolymer, can be illustrated, it is not limited to these. Particularly preferred is an acrylic resin such as polymethyl methacrylate.

  Examples of the light source include halogen lamps, metal halide lamps, high power metal halide lamps (containing indium, etc.), low pressure mercury lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, xenon lamps, xenon excimer lamps, xenon flash lamps, etc. It is not limited.

  Since the emission wavelength and energy distribution are different, 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.

  The light source can be directly irradiated, focused with a reflecting mirror or the like, or focused with a fiber or the like, and a low wavelength cut filter, a heat ray cut filter, a cold mirror, or the like can also be used.

  Moreover, when shape | molding the photocurable resin composition of this invention with said shaping | molding method, it is preferable that the cure shrinkage rate of a resin composition is 10% or less. If it exceeds 10%, a difference in mold accuracy and a cured product occurs due to curing shrinkage, so that it is difficult to obtain a cured product having a desired shape.

  The viscosity of the photocurable resin composition is preferably 100 to 100,000 mPa · s at 25 ° C., particularly preferably 3,000 to 90,000 mPa · s. If it is less than 100 mPa · s, liquid leakage or the like may occur, and a molded product having a desired shape may not be obtained. This is because if it exceeds 100,000 mPa · s, it is difficult to fill and a cured product having a desired shape may not be obtained, such as pushing up the mold.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, the data shown in an Example and a comparative example were measured in accordance with the following method.

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,
Deaeration device: ERC-3310 manufactured by ERMA,
Pump: PU-980 manufactured by JASCO,
Sample injection volume: 100 μl (sample solution concentration 1 mg / ml),
Flow rate: 1.0 ml / min,
Liquid feeding pressure: 39 kg / cm ² ,
Autosampler: AS-8020 manufactured by Tosoh Corporation
Column oven: Hitachi, Ltd. L-5030,
Set temperature: 40 ° C
Column configuration: Tosoh TSK guard column MP (× L) 6.0 mm ID × 4.0 cm 1 and Tosoh TSK-GEL MULTIPORE HXL-M 7.8 mm ID × 30.0 cm 2 in total, 3 in total
Detector: RI L-3350 manufactured by Hitachi, Ltd.
Data processing: SIC480 data station.

The nuclear magnetic resonance spectrum (hereinafter referred to as ¹ H-NMR) of the composition was measured under the following conditions.
Measuring device: ECP-300 (300 MHz) manufactured by JOEL,
Solvent: deuterium chloroform,
Sample concentration: 0.48% by mass
Integration count: 25,000 times.

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>
<Rubber composition polymerization example 1>
After 1L stainless steel autoclave was purged with nitrogen, n-butyl acrylate (hereinafter referred to as nBA): 270 g, methyl methacrylate (hereinafter referred to as MMA): 270 g, glycidyl methacrylate (hereinafter referred to as GMA): 60 g, benzoyl peroxide (hereinafter referred to as “NO”) , BPO): 13.9 g was charged in a nitrogen gas atmosphere, sealed, heated to 130 ° C. using an oil bath, and polymerized at 200 ° C. for about 60 minutes. Thereafter, the polymerization reaction was stopped by quenching to room temperature. The residual volatile matter was dried at 240 ° C. under vacuum for 2 hours to obtain a solid content. This was designated as a rubber composition (E-1). The yield was 92%, the number average molecular weight Mn by GPC measurement was 1,170, the weight average molecular weight Mw was 2,350, the molecular weight distribution Mw / Mn was 2.01, and the viscosity at 25 ° C. was 5,000 mPa · s. Moreover, as a result of calculating the content rate of the structural component of the obtained rubber composition (E-1) from the integrated intensity ratio of the ¹ H-NMR spectrum, nBA: 44.7 mass%, MMA: 45.4 mass%, GMA: It was found to be 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: 420 g, MMA: 18 g, GMA: 162 g, and BPO: 6.95 g were used in Preparation of Polymerization Example 1. The yield was 95%, the number average molecular weight Mn by GPC measurement was 2,000, the weight average molecular weight Mw was 4,710, the molecular weight distribution Mw / Mn was 2.36, and the viscosity at 25 ° C. was 9,500 mPa · s. s. As a result of ¹ H-NMR spectrum, the content ratio of the constituent components of the obtained rubber composition (E-2) was nBA: 68.6% by mass, MMA: 3.1% by mass, GMA: 28.3% by mass. It turned out that.

<Example 3 of polymerization of rubber composition>
A rubber composition (E-3) was obtained in the same manner as in Polymerization Example 1, except that nBA: 480 g, styrene: 90 g, GMA: 30 g, and BPO: 3.475 g were used in the preparation of Polymerization Example 1. The yield was 96%, the number average molecular weight Mn by GPC measurement was 4,500, the weight average molecular weight Mw was 9,900, the molecular weight distribution Mw / Mn was 2.20, and the viscosity at 25 ° C. was 5,900 mPa · s. As a result of ¹ H-NMR spectrum, the content ratio of the constituent components of the obtained rubber composition (E-3) was nBA: 78.4% by mass, styrene: 16.1% by mass, GMA: 5.5% by mass. It turned out that.

<Rubber composition polymerization example 4>
Polymerization Example 1 was the same as Polymerization Example 1 except that nBA: 228 g, MMA: 240 g, styrene: 90 g, 2-hydroxyethyl acrylate (hereinafter referred to as 2-HEA): 12 g, and BPO: 13.9 g. Thus, a rubber composition (E-4) was obtained. The yield was 92%, the number average molecular weight Mn by GPC measurement was 780, the weight average molecular weight Mw was 1,680, the molecular weight distribution Mw / Mn was 2.15, and the viscosity at 25 ° C. was 1,200 mPa · s. It was. As a result of ¹ H-NMR spectrum, the content ratio of the constituent components of the obtained rubber composition (E-4) was nBA: 37.3 mass%, MMA: 38.9 mass%, and styrene: 19.5 mass%. 2-HEA: It was found to be 4.3% by mass.

<Example 5 of polymerization of rubber composition>
The rubber composition was the same as in Polymerization Example 1, except that 2-ethylhexyl acrylate (hereinafter referred to as 2-EHA): 300 g, MMA: 30 g, GMA: 270 g, and BPO: 1.39 g were used in the preparation of Polymerization Example 1. A product (E-5) was obtained. The yield was 98%, the number average molecular weight Mn by GPC measurement was 10,000, the weight average molecular weight Mw was 19,600, the molecular weight distribution Mw / Mn was 1.96, and the viscosity at 25 ° C. was 95,000 mPa · s. Met. As a result of ¹ H-NMR spectrum, the content ratio of the constituent components of the obtained rubber composition (E-5) was as follows: 2-EHA: 49.8 mass%, MMA: 5.1 mass%, GMA: 45.1 It was found to be mass%.

<Examples 1 to 17 and Comparative Examples 1 to 7>
Subsequently, each component of the kind shown in Table 1-1, Table 1-2, and Table 1-3 was mixed with the composition (weight%) shown in the table | surface, and the photocurable resin composition was prepared.
In addition, the following compounds were selected for each component in the composition described in the examples and comparative examples.

As component (A),
(A-1) Polyester polyol urethane acrylate (trade 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 (trade name UV-3700B manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
(Polystyrene equivalent weight average molecular weight of 37,000 by GPC)
(A-3) Polyester polyol-based urethane acrylate (trade name KHP-11 manufactured by Negami Kogyo Co., Ltd.)
(Weight average molecular weight 25000 in terms of polystyrene by GPC)
(A-4) Polyester polyol urethane acrylate (trade name SD-7, manufactured by Negami Kogyo Co., Ltd.)
(GPC polystyrene equivalent weight average molecular weight 3500)
(A-5) n-butyl methacrylate (Kyoeisha Chemical Co., Ltd. light ester NB)
(A-6) 2-hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd. light ester HO)
(A-7) Isobutyl methacrylate (Kyoeisha Chemical Company Light Ester IB)
(A-8) tert-butyl methacrylate (Kyoeisha Chemical Co., Ltd. Light Ester TB)
(A-9) Cyclohexyl methacrylate (Kyoeisha Chemical Co., Ltd. light ester CH)
(A-10) Isobornyl methacrylate (Kyoeisha Chemical Co., Ltd. Light Ester IB-X)
(A-11) Dicyclopentanyl methacrylate (Hankuri FA-513M manufactured by Hitachi Chemical Co., Ltd.)
(A-12) 1,9-nonanediol dimethacrylate (Kyoeisha Chemical Co., Ltd. light ester 1,9ND)
(A-13) Polyethylene glycol dimethacrylate (repetition number of ethylene oxide = 9) (Kyoeisha Chemical Co., Ltd. Light Ester 9EG)
As a photopolymerization initiator of component (B),
Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE 819, manufactured by Ciba Specialty Chemicals)
As an antioxidant for component (C),
Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX 1076, manufactured by Ciba Specialty Chemicals)
(D) Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Sanol LS-770 manufactured by Sankyo Lifetech Co., Ltd.) as a light stabilizer for component (D)

  Various physical properties were measured as follows.

[Preparation of cured specimen]
Using a set of acrylic resin molds composed of an upper mold and a lower mold, which were modeled on the shape of the target test piece, a required amount was dropped onto the lower mold on which the photocurable resin composition before curing was set. Next, the upper mold was put on the lower mold, pressure-bonded and the mold was closed, and light was irradiated from the outside of the mold to cure the resin, thereby obtaining a desired cured body test piece.

[Light irradiation conditions]
In the light irradiation, a curing device manufactured by Fusion Corp. equipped with an electrodeless discharge lamp (D bulb) was used, and curing was performed under the condition that the cumulative irradiation amount to the photocurable resin was 4000 mJ / cm ² (365 nm).

(Resin tensile test)
In accordance with JIS K7113 (plastic tensile test method), a 2 (1/2) dumbbell shape (distance between gauge points 12 mm) and a 1 mm thick test piece were prepared under the above conditions, and the temperature was 23 ° C. and the humidity was 50%. The measurement was performed at a tensile speed of 50 mm / min. Each value of tensile fracture strength, tensile elastic modulus, and tensile fracture elongation was determined according to JIS K7113.

[Vibration fatigue endurance test]
A test piece having a total length of 150 mm, a width of 25 mm, and a thickness of 1 mm was prepared under the above-described conditions, and about 2 mm was previously provided at the center of the test piece with reference to JIS K6260 (demach bending crack test method for vulcanized rubber and plastic rubber). The test piece with the cracks is fixed to the upper and lower grips of the Demacha flex crack tester (manufactured by Ueshima Seisakusho Co., Ltd.) with a grip spacing of 75 mm, and reciprocating at room temperature with an amplitude of 56 mm and 300 times / minute. I let you. In 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 was one reciprocating motion, and the number of flexing times was read with a counter. The crack width was measured with a gripping tool spacing of 65 mm. Regarding the evaluation, vibration fatigue durability was evaluated as good when the crack width did not reach 25 mm (= break) at 144,000 times.

  The results of the measurement of the resin tensile test and the vibration fatigue endurance test of the cured product of the obtained photocurable resin composition are shown together in Table 1-1, Table 1-2, and Table 1-3.

The photocurable resin composition of the present invention is cured in an extremely short time by irradiation with light such as ultraviolet rays or visible light, and the cured product has a characteristic that it is excellent in 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, vibration-proof materials, various mechanism members Etc., and is very useful industrially. In addition, the photocurable resin composition of the present invention is a structural sealant for civil engineering and construction due to its excellent fatigue resistance characteristics, metal, magnet, ceramics, glass, adhesive for plastic, and plastic lens, etc. It can also be applied to other resin molded products.

The specification, claims and abstract of Japanese Patent Application No. 2006-001360 filed on January 6, 2006 and Japanese Patent Application No. 2006-036181 filed on February 14, 2006 are as follows. The entire contents are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims (13)

  (A) at least one resin selected from the group consisting of a photoradical polymerizable resin, a photoradical addition polymerizable resin, and a photocationic polymerizable resin, (B) a photopolymerization initiator, and (C) an antioxidant or (D) A photocurable resin composition containing either or both of the light stabilizers, wherein the cured product of the photocurable resin composition has a tensile elastic modulus of 1 to 30 MPa, and a tensile breaking elongation. Is a photocurable resin composition characterized by being 200% or more.   The photocurable resin composition according to claim 1, further comprising (E) a rubber composition.   The rubber composition is a copolymer composed of at least one monomer selected from the group consisting of (meth) acrylic acid ester compounds, vinyl compounds, and olefinic hydrocarbon compounds, and has a weight average molecular weight of 500 to 500. The photocurable resin composition according to claim 1 or 2, which is in the range of 50,000. The rubber composition is a copolymer composed of three or more monomers selected from the group consisting of (meth) acrylic acid ester compounds, vinyl compounds, and olefinic hydrocarbon compounds, wherein the monomers are ,
(Ii) 20-90% by mass of a radical polymerizable monomer having a glass transition temperature of less than 25 ° C. of the homopolymer,
(B) 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 to 50% by mass of a radically polymerizable monomer having at least one reactive group that is non-radically polymerizable in the molecule;
The photocurable resin composition of Claim 3 containing this.   The photocurable resin composition according to claim 4, wherein the monomer of component (a) is an alkyl (meth) acrylate having 1 to 20 carbon atoms.   (B) The photocurable resin composition according to claim 4 or 5, wherein the monomer of the component contains at least one selected from the group consisting of methyl methacrylate and styrene.   The component (c) monomer 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 according to one item.   The photocurable resin composition as described in any one of Claims 1-7 whose viscosity in 25 degreeC of a rubber composition exists in the range of 100-100,000 mPa * s.   The radical photopolymerizable resin is an acrylic resin, and the acrylic resin has (a-1) one or more (meth) acryloyl groups at the end or side chain of the molecule and has a molecular weight of 5,000 to 100,000. The photocurable resin composition as described in any one of Claims 1-8 which consists of 1 or more types of urethane (meth) acrylate oligomers, and (a-2) monofunctional (meth) acrylate. The photocurable resin composition according to claim 9, wherein the (a-2) monofunctional (meth) acrylate is a monofunctional (meth) acrylate represented by the following formula [1] or [2].

(In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is substituted by a linear or branched alkyl group having 1 to 22 carbon atoms, a cyclohexyl group, or a linear or branched alkyl group having 1 to 4 carbon atoms. Cyclohexyl group, phenyl group, phenyl group substituted by a linear or branched alkyl group having 1 to 4 carbon atoms, dicyclopentanyl group, dicyclopentenyl group, bornyl group, isobornyl group, adamantyl group, methyladamantyl group Or an allyl group.)

(In the formula, 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. 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 dicyclopentanyl group A dicyclopentenyl group, a bornyl group, an isobornyl group, an adamantyl group, a methyladamantyl group or an allyl group, and n is an integer of 1 to 12.)   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. The photocurable resin composition according to any one of 8.   The photocurable resin composition according to any one of claims 1 to 8, wherein the cationic photopolymerizable resin has an epoxy group, an oxetanyl group, or a vinyl ether group in the molecule.   The hardening body which consists of a photocurable resin composition as described in any one of Claims 1-12.