CN101356204B - Photocurable resin composition - Google Patents
Photocurable resin composition Download PDFInfo
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- CN101356204B CN101356204B CN2006800503979A CN200680050397A CN101356204B CN 101356204 B CN101356204 B CN 101356204B CN 2006800503979 A CN2006800503979 A CN 2006800503979A CN 200680050397 A CN200680050397 A CN 200680050397A CN 101356204 B CN101356204 B CN 101356204B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
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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
Technical field
The present invention relates to and to come solidified Photocurable resin composition and cured body through the rayed of ultraviolet ray, visible rays etc., in more detail, relate to good Photocurable resin composition of vibratory fatigue weather resistance and cured body.
Background technology
In general, the compsn of having given such as so-called rubber properties such as flexibility, retractility, elasticity is referred to as elastomerics, its fatigue durability to vibration is more much better than other macromolecular materials.Therefore, be suitable for as structures such as trolley part, building, building such as tire with sound equipments such as liner component, speaker such as sealing element, O shape rings with parts, mobile telephone with plate member such as keypad, vibration isolating material, various structure units etc.
As elastomerics (hereinafter is represented with mark R) in the past, elastomeric material such as the known mixture that tree elastomer, modified natural rubber, grafting tree elastomer, cyclized hatural rubber, chlorinated natural rubber, SBR styrene butadiene rubbers, neoprene, acrylonitrile-butadiene rubber, carboxylated nitrile rubber, paracril/vinyl chloride resin mixture, paracril/EPDM rubber arranged, butyl rubber, brominated butyl rubber, Chlorobutyl, ethylene-vinyl acetate rubber, acrylic rubber, ethylene-propylene acids rubber, chlorosuphonated-polyethylene, chlorinatedpolyethylene, epichloro hydrin rubber, Epicholorohydrin-oxyethane rubber, methyl silicone rubber, vinyl-methyl silicone rubber, phenyl-methyl silicone rubber, fluorinated silicone rubber; Thermoplastic elastic materials such as polystyrene-type thermoplastic elastomers, SE analog thermoplastic elastomer, polyolefins thermoplastic elastomer, polyurethanes thermoplastic elastomer, polyester thermoplastic elastomer, polyamide-based thermoplastic elastomer, polyvinyl chloride-base thermoplastic elastomer, fluororubber thermoplastic elastomer, chlorinatedpolyethylene class elastomerics.
In general, as the method for the formed body that obtains elastomerics (R), through the abundant mixing mixing operation of the elastomerics raw material that will be combined with solidifying agent and other additives; Then compounding raw materials being adopted vacuum forming, presses the empty method of forming, utilizes the patrix counterdie is that the heating and pressurizing method of forming, the injection molding method of one group shaping mould (upper and lower mould hereinafter referred to as) waits and carry out moulding; Make its sulfuration or solidified curing process (vulcanization process) through heating, pressurization, thereby obtain the target formed body.
But, at above-mentioned vacuum forming, press the empty method of forming, utilize in the heating and pressurizing method of forming etc. of upper and lower mould, must the metal die temperature be increased near the fusing point of material, in order to heat, need huge energy.And owing to must treat to take out after the metal die cooling, therefore, shaping cycle will expend for a long time.
In injection molding method, because the fused resin is cooled mobile extremely reduction immediately after contacting with the metal die with temperature head; Therefore; Be difficult to the formed body that obtains to approach, and in operations such as heating, injection moulding, pressurize, equipment also needs the expense of great number.In addition, owing to must thermoplastic material be heated near the fusing point, therefore, heat energy is huge.
At above-mentioned vacuum forming, press the empty method of forming, utilize in the heating and pressurizing method of forming etc. of upper and lower mould; Formed material in use; To after being shaped to the planar materials that is slightly larger than the target component size, cut out the parts part again, therefore; Produce many wastes, all unfavorable with economic aspect aspect environment.
Vacuum forming, press the empty method of forming, utilize the above-mentioned constituent material of the heating and pressurizing method of forming of upper and lower mould; General all is the material of uniform thickness; Therefore, the each several part after the moulding also has identical thickness, and the thickness that is changed each several part by same material is difficult.
In addition, the thickness of making in the industry is limited, is difficult to obtain the material beyond this thickness specification usually.Though the processing such as extension when also the someone proposes through moulding change the method for thickness, the problems such as internal stress distortion increase after the moulding can take place.
As the means of the problem that solves the aforesaid method of forming, in patent documentation 1, proposed to form the photocuring casting moulding of formed body through it being solidified to being filled in light such as Photocurable liquid material irradiation ultraviolet radiation in the upper and lower mould, visible rays.
Patent documentation 1: the spy opens the 2004-357020 communique
In more detail, be a kind of like this method, promptly; The arbitrary at least side that forms in the pattern who is made up of upper die and lower die forms with the material of printing opacity; And wherein place and can come the solidified resin through rayed, mold closing is from the outside irradiates light of the mould of printing opacity; Make resin solidification, obtain the cured body of target shape.Adopt this method, can use less energy and less operation, make the formed body of any thickness easily and at an easy rate.
On the other hand; Perhaps demonstrate the resin combination of caoutchouc elasticity as photo curable elastomerics; Resin combination as sealing material use is disclosed in patent documentation 2, patent documentation 3, and, the resin combination of using as optical three-dimensional contouring is disclosed in patent documentation 4.Yet, still do not know to be applicable at present above-mentioned photocuring casting moulding and satisfy the resin combination of the desired vibratory fatigue weather resistance of elastomerics in the past.
Patent documentation 2: special table 2002-501109 communique
Patent documentation 3: special table 2003-505525 communique
Patent documentation 4: the spy opens the 2000-290328 communique
Summary of the invention
The present invention accomplishes in view of the situation of above-mentioned known technology; Its purpose is; Photocurable resin composition and cured body are provided, said composition be can be through rayed solidified, be suitable for the Photocurable resin composition of photocuring casting moulding, and the vibratory fatigue weather resistance is good.
That is, the present invention has following main idea.
1. Photocurable resin composition; It is characterized in that; Containing (A) is selected from least a kind of resin, (B) Photoepolymerizationinitiater initiater in optical free radical polymerizability resin, optical free radical addition polymerization property resin and the cationically photopolymerizable resin and is selected from arbitrary side or the both sides in (C) inhibitor and (D) photostabilizer; The modulus of elasticity in direct stress of the cured body of this Photocurable resin composition is 1～30MPa, and the fail in tension elongation is more than 200%.
2. the Photocurable resin composition described in above-mentioned 1 wherein, also contains (E) rubber combination.
3. the Photocurable resin composition described in above-mentioned 1 or 2; Wherein, Rubber combination is served as reasons and is selected from the multipolymer that at least a monomer in (methyl) acryliccompound, vinylic and the olefines hydrocarbon compound forms, and weight-average molecular weight is 500～50,000 scope.
4. the Photocurable resin composition described in above-mentioned 3, wherein, rubber combination is served as reasons and is selected from the multipolymer that the monomer more than 3 kinds in (methyl) acryliccompound, vinylic and the olefines hydrocarbon compound forms, and above-mentioned monomer contains:
The second-order transition temperature of (first) homopolymer be lower than 25 ℃ free radical polymerization monomer 20～90 quality %,
The second-order transition temperature of (second) homopolymer 0.1～70 quality % of the free radical polymerization monomer more than 25 ℃ and
(the third) intramolecularly has at least one free radical polymerization monomer 1～50 quality % for the reactive group of non-free radical polymerizability.
5. the Photocurable resin composition described in above-mentioned 4, wherein, (first) composition monomer is (methyl) alkyl acrylate of carbonatoms 1～20.
6. the Photocurable resin composition described in above-mentioned 5, wherein, (first) composition monomer is (methyl) alkyl acrylate of carbonatoms 1～8.
7. each described Photocurable resin composition in above-mentioned 4～6, wherein, (second) composition monomer contains at least a kind that is selected from TEB 3K and the vinylbenzene.
8. each described Photocurable resin composition in above-mentioned 4～7, wherein, (third) composition monomer has more than one groups that are selected from hydroxyl, carboxyl, glycidyl, NCO, amino and the alkoxysilyl.
9. the Photocurable resin composition described in above-mentioned 8, wherein, (third) composition monomer is perhaps (methyl) vinylformic acid hydroxyalkyl acrylate of (methyl) glycidyl acrylate.
10. each described Photocurable resin composition in above-mentioned 1～9, wherein, rubber combination has at least 1 aromatic group at its intramolecularly.
11. each described Photocurable resin composition in above-mentioned 1～10, wherein, the viscosity of rubber combination under 25 ℃ is in 100～100, the scope of 000mPas.
12. each described Photocurable resin composition in above-mentioned 1～11, wherein, the second-order transition temperature of rubber combination is lower than 25 ℃.
13. each described Photocurable resin composition in above-mentioned 1～12, wherein, rubber combination shared ratio in Photocurable resin composition is 0.01～30 quality %.
14. each described Photocurable resin composition in above-mentioned 1～13, wherein, optical free radical polymerizability resin is an acrylics.
15. the Photocurable resin composition described in above-mentioned 14, wherein, acrylics constitutes by following (a-1) with (a-2):
(a-1) on the terminal or side chain of molecule, having (methyl) acryl, molecular weight more than 1 is that 5,000～100,000 urethane (methyl) origoester acrylate is more than a kind;
(a-2) simple function (methyl) propenoate.
16. the Photocurable resin composition described in above-mentioned 15, wherein, (a-2) simple function (methyl) propenoate be by following formula (1) perhaps (2) expression simple function (methyl) propenoate:
(in the formula, R
1Be Wasserstoffatoms or methyl; R
2For the straight or branched alkyl of carbonatoms 1～22, cyclohexyl, by the substituted cyclohexyl of straight or branched alkyl of carbonatoms 1～4, phenyl, by the substituted phenyl of straight or branched alkyl of carbonatoms 1～4, tetrahydro-dicyclopentadiene base (dicyclopentanyl), dihydro bicyclic pentadiene (dicyclopentenyl), bornyl, isobornyl, adamantyl, methyl adamantane base or allyl group.)
(in the formula, R
1Be Wasserstoffatoms or methyl; R
3Straight or branched alkyl for carbonatoms 1～4; R
4For the straight or branched alkyl of carbonatoms 1～4, cyclohexyl, by the substituted cyclohexyl of straight or branched alkyl of carbonatoms 1～4, phenyl, by the substituted phenyl of straight or branched alkyl, tetrahydro-dicyclopentadiene base, dihydro bicyclic pentadiene, bornyl, isobornyl, adamantyl, methyl adamantane base or the allyl group of carbonatoms 1～4; N is 1～12 integer.)
17. the Photocurable resin composition described in above-mentioned 15 or 16, wherein, (a-2) simple function (methyl) propenoate is that the second-order transition temperature of homopolymer is at the simple function more than 20 ℃ (methyl) propenoate.
18. each described Photocurable resin composition in above-mentioned 1～13; Wherein, optical free radical addition polymerization property resin has the polyenic compounds of 2 above carbon-to-carbon unsaturated double-bonds by intramolecularly and multi-thioalcohol compound that intramolecularly has 2 above sulfydryls forms.
19. each described Photocurable resin composition in above-mentioned 1～13, wherein, the cationically photopolymerizable resin has epoxy group(ing), oxetanyl or vinyl ether group at its intramolecularly.
20. each described Photocurable resin composition in above-mentioned 1～19, cure shrinkage is below 10%.
21. cured body is formed by each described Photocurable resin composition in above-mentioned 1～20.
Photocurable resin composition of the present invention has following characteristic: the instantaneous solidification through the light of irradiation ultraviolet radiation or visible rays etc., and also the vibratory fatigue weather resistance of its cured body is good.Therefore, be suitable for very much structures such as trolley part, building, building such as tire with sound equipments such as liner component, speaker such as sealing element, O shape rings with, mobile telephone with plate member such as keypad, parts, vibration isolating material, various structure units etc.In addition, Photocurable resin composition of the present invention because its good resistent fatigue characteristic can also be applicable to the sealing agent that structures such as building, building are used, is applicable to the caking agent that metal, magnet, pottery, glass, plastics are used.
Embodiment
In this manual, " molecular weight " all represented weight-average molecular weight in the occasion that does not have to specify.
In this manual, " Tg " all representes second-order transition temperature in the occasion that does not have to specify.
In this manual, " alkyl " all represented straight chain, side chain and cyclic saturated hydrocarbon base in the occasion that does not have to specify.
In Photocurable resin composition of the present invention, contain the light-cured resin that forms cured body as (A) irradiation composition, that receive light.Said refer to that only with ultraviolet ray, visible rays etc. be the active energy beam of representative here; In Photocurable resin composition of the present invention; As light-cured resin, can use at least a kind of resin from optical free radical polymerizability resin, optical free radical addition polymerization property resin and cationically photopolymerizable resin, selecting.Wherein, therefore optical free radical polymerizability resin is preferential the selection owing to comprise the acrylics that material selectivity is abundant.
As optical free radical addition polymerization property resin, known have through producing radical make thiol group add to the alkene-thiol reactant on the carbon-to-carbon unsaturated bond.Consider preferably have the alkene-mercaptan resin of the compound formation of 2 above carbon-to-carbon unsaturated bonds especially at least by compound that has 2 above thiol groups at intramolecularly and intramolecularly from the reason that light solidified is good.
As the cationically photopolymerizable resin, can enumerate out resin of resin, the resin that intramolecularly has epoxy group(ing), resin, resin, resin, spiro orthocarbonate base etc. with dicyclo ortho acid ester group with spiro orthoester base with vinyl ether group with oxetanyl.Wherein, consider preferably have the resin of epoxy group(ing), oxetanyl or vinyl ether group from the rich reason of light solidified and material selection.
As optical free radical polymerizability resin, can enumerate out acrylics, styron, Vinylite, unsaturated polyester, polyolefine etc., wherein, consider preferred acrylics from the rich reason of light solidified and material selection.
As acrylics, can enumerate out and gather (methyl) propenoate, (methyl) acrylate monomer, (methyl) propenoate dimer, polyester (methyl) propenoate, urethane (methyl) propenoate, epoxy (methyl) propenoate, polyolefine (methyl) propenoate, silicone (methyl) propenoate etc.In order to reach the object of the invention, the resin combination that preferably constitutes by urethane (methyl) propenoate and (methyl) acrylate monomer.Particularly preferably be by (a-1) and on the terminal or side chain of molecule, have more than 1 (methyl) acryl and its molecular weight is 5; 000～100,000 urethane (methyl) origoester acrylate is the resin combination that constitutes of simple function (methyl) propenoate more than a kind and (a-2).
Urethane (methyl) origoester acrylate as above-mentioned (a-1) composition is urethane (methyl) origoester acrylate that forms through polyol compound (hereinafter is represented with X), organic polyisocyanate compounds (hereinafter is represented with Y) and hydroxyl (methyl) propenoate (hereinafter is represented with Z) are reacted.
As polyol compound (X), for example can enumerate out terepthaloyl moietie, glycol ether, triglycol, Tetraglycol 99, polyoxyethylene glycol, Ucar 35, dipropylene glycol, W 166, butyleneglycol, 1; 4-butyleneglycol, polytetramethylene glycol, 1; 5-pentanediol, 1,6-pinakon, 1,8-ethohexadiol, 1; 9-nonanediol, 3-methyl isophthalic acid; 5-pentanediol, 2,4-diethylammonium-1,5-pentanediol, 2; 2-butyl ethyl-1, gathers polyvalent alcohols such as TriMethylolPropane(TMP), tetramethylolmethane, polypentaerythritol, Sorbitol Powder, mannitol, glycerine, poly-glycerol, polytetramethylene glycol at ammediol, NSC 6366, cyclohexanedimethanol, Hydrogenated Bisphenol A 99, polycaprolactone, trimethylolethane, TriMethylolPropane(TMP); The polyether glycol of at least a kind of structure of polyethylene oxide, polypropyleneoxide, block or random copolymerization with ethylene oxide/propylene oxide; Polyester polyol as the condenses that forms by polyprotonic acids such as this polyvalent alcohol or polyether glycol and maleic anhydride, toxilic acid, fumaric acid, itaconic anhydride, methylene-succinic acid, hexanodioic acid, m-phthalic acids; Caprolactone modification polyvalent alcohols such as caprolactone modification polytetramethylene polyvalent alcohol; The polyolefins polyvalent alcohol; Polycarbonate-based polyvalent alcohol; Polybutadiene polyvalent alcohols such as hydrogenated butadiene polymer polyvalent alcohol; Silicone polyvalent alcohols such as YSR 3286 polyvalent alcohol etc.Particularly preferably be polyether glycol, polyester polyol.
Wherein, special preferred molecular weight is 200～10,000, is preferably 500～8,000, more preferably 1,000～6,000.If the vibratory fatigue weather resistance that molecular weight more than 200, then can obtain to suit; And if in 10,000, then solidified nature also can not reduce, be preferred therefore.
(Y) do not have particular determination as organic polyisocyanate compounds, can enumerate out polymeric polyisocyanates such as the for example fragrant same clan, aliphatic category, ring type aliphatic category, ester ring type class.Wherein, Preferred tolylene vulcabond (TDI), diphenylmethanediisocyanate (MDI), hydrogenated diphenyl methane diisocyanate (H-MDI), polyphenylene methane polymeric polyisocyanate (crudeMDI), modified diphenylmethane diisocyanate (modification MDI), hydrogenation eylylene diisocyanate (H-XDI), eylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), trimethyl hexamethylene diisocyanate (TMXDI), tetramethyl-eylylene diisocyanate (m-TMXDI), isophorone diisocyanate (IPDI), the norbornylene vulcabond (NBDI), 1 of using, the resultant of reaction of tripolymer compound, these polymeric polyisocyanates and the polyvalent alcohol of two (isocyanato-methyl) hexanaphthene polymeric polyisocyanates such as (H6XDI) of 3-or these polymeric polyisocyanates etc.Wherein, preferred hydrogenation eylylene diisocyanate (H-XDI), isophorone diisocyanate (IPDI).The molecular weight of this polyisocyanate compounds (Y) is preferably below 500.If below 500, then the reactivity with glycol can not reduce yet.
As hydroxyl (methyl) propenoate (Z); For example can enumerate out (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, 2-hydroxyethyl acryl SULPHOSUCCINIC ACID ESTER, 4-butylhydroxy (methyl) propenoate, 2-(methyl) acryloxy ethyl-2-hydroxypropyl phthalic ester, two (methyl) vinylformic acid glyceryl ester, 2-hydroxyl-3-acryloxy propyl group (methyl) propenoate, caprolactone modification (methyl) vinylformic acid 2-hydroxy methacrylate, three (methyl) vinylformic acid pentaerythritol ester, five (methyl) vinylformic acid dipentaerythritol ester, caprolactone modification (methyl) vinylformic acid 2-hydroxy methacrylate etc.Wherein, preferred (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester of using.
In above-mentioned urethane (methyl) origoester acrylate, the number of (methyl) acryl in the preferred molecule is, on the terminal or side chain of molecule, have more than 1 to below 6, more preferably more than 2 to (methyl) acryl below 4.In the occasion that does not have (methyl) acryl, can not with simple function (methyl) acrylic ester copolymer as above-mentioned (B) composition; And more than 6 occasion, the formed body of acquisition becomes really up to the mark, can not obtain good vibratory fatigue weather resistance sometimes.
The molecular weight of above-mentioned urethane (methyl) origoester acrylate can selected to the scope below 100,000 more than 5,000, is more preferably selecting to the scope below 50,000 more than 10,000.As long as as long as molecular weight is more than 5,000, the formed body that then obtains just can not become really up to the mark, and below 100,000, and then solidified nature just can variation, can obtain the good cured body of vibratory fatigue weather resistance.
Simple function (methyl) propenoate as above-mentioned (a-2) composition so long as intramolecularly contains 1 (methyl) acryl, does not just have particular determination.Wherein, containing by the perhaps resin combination of simple function (methyl) propenoate of (2) expression of following formula (1), can obtain the good cured body of vibratory fatigue weather resistance, is preferred therefore.
In the formula (1), R
1Be Wasserstoffatoms or methyl; R
2For the straight or branched alkyl of carbonatoms 1～22 (preferred carbonatoms 1～12), cyclohexyl, by the substituted cyclohexyl of straight or branched alkyl of carbonatoms 1～4, phenyl, by the substituted phenyl of straight or branched alkyl, tetrahydro-dicyclopentadiene base, dihydro bicyclic pentadiene, bornyl, isobornyl, adamantyl, methyl adamantane base, the allyl group of carbonatoms 1～4.
In the formula (2), R
1Be Wasserstoffatoms or methyl; R
3Straight or branched alkyl for carbonatoms 1～4; R
4For the straight or branched alkyl of carbonatoms 1～4, cyclohexyl, by the substituted cyclohexyl of straight or branched alkyl of carbonatoms 1～4, phenyl, by the substituted phenyl of straight or branched alkyl, tetrahydro-dicyclopentadiene base, dihydro bicyclic pentadiene, bornyl, isobornyl, adamantyl, methyl adamantane base, the allyl group of carbonatoms 1～4.
N is 1～12 integer, is preferably 1～10.
Specifically, can enumerate out (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) NSC 20949, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) isodecyl acrylate, (methyl) dodecylacrylate, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid isooctadecane base ester, (methyl) tridecyl acrylate, (methyl) vinylformic acid docosyl ester, (methyl) vinylformic acid methoxyl group ethyl ester, (methyl) vinylformic acid ethoxy ethyl ester, (methyl) vinylformic acid propoxy-ethyl ester, (methyl) vinylformic acid butoxy ethyl ester, methoxyl group glycol ether (methyl) propenoate, methoxyl group triglycol (methyl) propenoate, methoxyl group four ethylidene (methyl) propenoate, (methyl) vinylformic acid phenoxy ethyl, phenoxy glycol ether (methyl) propenoate, phenoxy Tetraglycol 99 (methyl) propenoate, phenoxy hexaethylene glycol (methyl) propenoate, methoxyl group dipropylene glycol (methyl) propenoate, methoxyl group tripropylene glycol (methyl) propenoate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid tertiary butyl cyclohexyl, (methyl) benzyl acrylate, (methyl) vinylformic acid phenoxy ethyl, (methyl) vinylformic acid tetrahydro-dicyclopentadiene base ester, (methyl) vinylformic acid dihydro bicyclic pentadiene ester, (methyl) vinylformic acid norbornene ester, (methyl) IBOA, (methyl) vinylformic acid 2-methyl-2-adamantane esters, (methyl) allyl acrylate etc.Should explain that for propenoate and methacrylic ester, methacrylic ester can obtain the good cured body of vibratory fatigue weather resistance preferably.
(a-2) Tg of preferred its homopolymer of simple function (methyl) propenoate is at the simple function more than 20 ℃ (methyl) propenoate.Tg is more preferably more than 50 ℃, particularly preferably in more than 80 ℃.If Tg is more than 20 ℃, it is too soft that the cured body that then obtains just can not become, and solidified nature can variation yet.Should explain that the measuring method of the Tg of Photocurable resin composition of the present invention does not have particular restriction, can adopt known method such as DSC, dynamic viscoelastic to measure, preferably adopt the DSC method.
In Photocurable resin composition of the present invention; About (a-1) composition and (a-2) proportioning of composition; When processing when containing the compsn of (a-1) composition 5～95 quality %, preferred especially 20～85 quality % with respect to the total amount of (a-1) composition and (a-2) composition; The cured article that obtains through rayed has good vibratory fatigue weather resistance, is preferred especially therefore.
Photoepolymerizationinitiater initiater as (B) composition has ultraviolet polymerization initiator, visible light polymerization starter etc., and wherein any all can use without restriction.As the optical free radical polymerization starter, can enumerate out bitter almond oil camphor class, benzophenone, acetophenones, acylphosphine oxide class, thioxanthene ketone, metallocene class, benzoquinones class etc.As the light cationic polymerization initiators, can enumerate out salt compounded of iodine compound, sulfonium salt compound 、 phosphonium salt compound, pyridinium salt compound, iron-aromatic hydrocarbons coordination compound etc.
In the present invention, as Photoepolymerizationinitiater initiater, can there be particular determination ground to use known Photoepolymerizationinitiater initiater.For example can enumerate out; UVNUL MS-40,4-phenyl benzophenone, benzoyl-phenylformic acid, 2; 2-diethoxy acetophenone, two (diethylamino) UVNUL MS-40, dibenzoyl; Bitter almond oil camphor, benzoyl-isopropyl ether, benzil dimethyl ketal, 1-hydroxycyclohexylphenylketone, thioxanthone, 1-(4-isopropyl phenyl) 2-hydroxy-2-methyl propane-1-ketone, 1-(4-(2-hydroxyl-oxethyl)-phenyl)-2-hydroxy-2-methyl-1-propane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, camphorquinone, 2; 4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4; The 6-trimethylbenzoyl)-phenyl phosphine oxide, 2-methyl isophthalic acid-(4-(methylthio group) phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-1-butanone-1, two (2; 6-dimethoxy benzoyl-)-2,4,4-trimethylammonium-amyl group phosphine oxide etc.
Inhibitor as (C) composition; For example can enumerate out; β-Nai Kun, 2-methoxyl group-1,4-naphthoquinones, toluhydroquinone, quinhydrones, hydroquinone monomethyl ether, single tertiary butylated hydroquinone, DBH 2,5 di tert butylhydroquinone, para benzoquinone, 2; 5-phenylbenzene-para benzoquinone, 2, quinoness such as 5-di-t-butyl-para benzoquinone; Thiodiphenylamine, 2,2-methylene radical-two (4-methyl-6-tert butyl phenol), catechol, tert-butyl catechol, 2-butyl-4-hydroxyanisol, 2,6-di-t-butyl-p-cresol, the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl propenoate, 2-(1-(2-hydroxyl-3; The 5-di-tert-pentyl-phenyl) ethyl)-4,6-di-tert-pentyl-phenyl propenoate, 4,4 '-butylidene two (the 6-tertiary butyl-3-methylphenol), 4; 4 '-thiobis (the 6-tertiary butyl-3-methylphenol), 3, two (2-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy)-1, the 1-dimethyl ethyls)-2 of 9-; 4,8,10-four oxaspiros (5; 5) undecane, tetramethylolmethane four (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester), sulfo-di ethylene bis (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester), octadecyl-3-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic ester, N, N '-hexane-1,6-two bases are two, and (3-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid amide), phenylpropionic acid, 3,5-two (1; The 1-dimethyl ethyl)-and the 4-hydroxyl, C
7-C
9Side chain alkyl ester, 2,4-dimethyl--6-(1-methyl pentadecyl) phenol, diethylammonium ((3, two (1, the 1-the dimethyl ethyl)-4-hydroxy phenyls of 5-) methyl) phosphonic acid ester, 3,3 ', 3 "; 5,5 ', 5 " six tertiary butyls-a, a ', a " (sym-trimethylbenzene-2; 4,6-three bases), three p-cresol, diethylammonium two ((3, two (1, the 1-the dimethyl ethyl)-4-hydroxy phenyls of 5-) methyl) phosphonic acid ester close calcium, 4, two (hot sulfenyl the methyl)-ortho-cresols of 6-, ethylenebis (oxyethylene group) two (3-(a 5-tertiary butyl-4-hydroxy-tolyl) propionic esters), hexa-methylene two (3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester, 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-1,3; 5-triazine-2,4,6 (1H, 3H, 5H)-triketone, 1; 3,5-three ((the 4-tertiary butyl-3-hydroxyl-2,6-xylyl) methyl)-1,3,5-triazines-2; 4,6 (1H, 3H, 5H)-triketone, N-phenylaniline and 2,4; The resultant of reaction of 6-2,4,4-Trimethyl-1-pentene, 2, phenols such as 6-di-t-butyl-4-(4, two (hot the sulfenyl)-1,3,5-triazines of 6--2-base is amino) phenol, TNP, Hydrocerol A; (2-((2,4,8 for three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, three; 10-tetra-tert dibenzo (d, f) (1,3,2) dioxy phosphorus heterocycle heptane (dioxaphosphephine)-6-yl) amine, two (2 ethyl oxygen)); The 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2, two (1, the 1-the dimethyl ethyl)-6-aminomethyl phenyls of 4-) ethyl ester phosphorous acid, four (2, the 4-di-tert-butyl-phenyl) (1; The 1-xenyl)-4,4 '-two basic biphosphinate, 6-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propoxy-)-2,4,8; Phosphorus compounds such as 10-tetra-tert dibenzo (d, f) (1,3,2) dioxy phosphorus heterocycle heptane; 3,3 '-thio-2 acid two lauryl alcohol esters, 3,3 '-thio-2 acid two Semen Myristicae alcohol esters, 3,3 '-sulphur compounds such as thio-2 acid 2 stearyl ester, tetramethylolmethane base four (3-lauryl thiopropionate), 2-mercaptobenzimidazole; Aminated compoundss such as thiodiphenylamine; Lactone compound; Vitamin E compounds etc.Wherein, preferred phenolic cpd.
As the photostabilizer of (D) composition, for example can enumerate out two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two (1,2; 2,6,6-pentamethyl--4-piperidyl) sebate, 4-benzoyloxy-2,2,6, (2-(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyloxy) ethyl)-(3-(3 for 4-for 6-tetramethyl piperidine, 1-; The 5-di-tert-butyl-hydroxy phenyl) propionyloxy)-2,2,6,6-tetramethyl piperidine, 1,2,2,6; 6-pentamethyl--4-piperidyl-methacrylic ester, two (1,2,2,6,6-pentamethyl--4-piperidyl) ((3, two (1, the 1-the dimethyl ethyl)-4-hydroxy phenyls of 5-) methyl) butyl malonic acid ester, sebacic acid two (2; 2,6,6-tetramethyl--1 (octyloxy)-4-piperidyl) ester, 1, the resultant of reaction of 1-dimethyl ethyl hydrogen peroxide and octane, N, N ', N "; N " '-four-(4,6-pair-(butyl-(N-methyl-2,2,6,6-tetramethyl piperidine-4-yl) amino)-triazine-2-yl)-4,7-diaza decane-1,10-diamines, dibutylamine 1; 3,5-triazine N, N '-two (2,2,6,6-tetramethyl--4-piperidyl-1,6-hexamethylene-diamine and N-(2; 2,6,6-tetramethyl--4-piperidyl) polycondensate of butylamine, gather that ((6-(1,1,3, the 3-tetramethyl butyl) amino-1,3; 5-triazine-2,4-two bases) ((2,2,6,6-tetramethyl--4-piperidyl) imino-) hexa-methylene ((2,2,6; 6-tetramethyl--4-piperidyl) imino-)), Succinic acid dimethylester and 4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines alcoholic acid polymkeric substance, 2,2,4,4-tetramethyl--20-(β-bay oxygen base carbonyl) ethyl-7-oxa--3; 20-diaza two spiral shells (51112) heneicosane-21-ketone, Beta-alanine, N ,-(2,2,6,6-tetramethyl--4-piperidyl)-dodecyl ester/tetradecyl ester, N-ethanoyl-3-dodecyl-1-(2,2; 6,6-tetramethyl--4-piperidyl) tetramethyleneimine-2,5-diketone, 2,2,4,4-tetramethyl--7-oxa--3,20-diaza two spiral shells (5; 1,11,2) heneicosane-21-ketone, 2,2,4,4-tetramethyl--21-oxa--3; 20-diazabicylo-(5,1,11,2)-heneicosane-20-propionic acid dodecyl ester/tetradecyl ester, propanedioic acid, ((4-p-methoxy-phenyl)-methylene radical)-two (1,2; 2,6,6-pentamethyl--4-piperidyl) ester, 2,2,6, the high-grade aliphatic ester, 1 of 6-tetramethyl--4-piperidines alcohol; The 3-benzenedicarboxamide, N, N '-two hindered aminess such as (2,2,6,6-tetramethyl--4-piperidyl); Benzophenone compounds such as octabenzone; 2-(2H-benzotriazole-2-yl)-4-(1; 1; 3; The 3-tetramethyl butyl) phenol, 2-(2-hydroxy-5-methyl base phenyl) benzotriazole, (2-hydroxyl-3-(3,4,5 for 2-; 6-tetrahydric phthalimide-methyl)-and the 5-aminomethyl phenyl) resultant of reaction, the 2-(2H-benzotriazole-2-yl)-6-dodecyl-benzotriazole compounds such as 4-methylphenol of benzotriazole, 2-(the 3-tertiary butyl-2-hydroxy-5-methyl base phenyl)-5-chlorobenzotriazole, 2-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) benzotriazole, methyl 3-(3-(2H-benzotriazole-2-yl)-5-tert-butyl-hydroxy phenyl) propionic ester and polyoxyethylene glycol; 2,4-di-tert-butyl-phenyl-3, benzoate compounds such as 5-di-tert-butyl-4-hydroxybenzoic acid ester; 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-compound in triazine class such as 5-((hexyl) oxygen base) phenol etc.Preferred especially hindered amine compound.
In Photocurable resin composition of the present invention, when the total amount with (A)～(D) composition is 100 quality %,, preferably contain 85.00～99.99 quality % as (A) composition, especially preferably contain 90.0～99.9 quality %.As (B) composition, preferably contain 0.01～15 quality %, especially preferably contain 0.1～10 quality %.As (C) composition and (D) total of composition, preferably contain 0.01～5 quality %, especially preferably contain 0.05～3 quality %.In (C) composition and (D) composition, (C) proportionally be preferably 0/10～10/0 containing of the composition of composition/(D), be preferably 1/9～9/1 especially.When the content of (A)～(D) composition was in this scope, the cured article that is obtained by Photocurable resin composition of the present invention had good vibratory fatigue weather resistance, was preferred therefore.
And then; Photocurable resin composition of the present invention; It is characterized in that; Except above-mentioned light-cured resin, also contain (B) Photoepolymerizationinitiater initiater and be selected from arbitrary side or the both sides in (C) inhibitor and (D) photostabilizer, when the cured body of this Photocurable resin composition according to JIS K7113 (stretching test methods of plastics) when carrying out stretching test measurement; Demonstrate following good vibratory fatigue weather resistance: the modulus of elasticity in direct stress is 1～30MPa, is preferably 1.5～28.5MPa, and the fail in tension elongation is more than 200%, is preferably 201～1500%.If the modulus of elasticity in direct stress of cured body is more than the 1MPa, the cured body that then can not produce acquisition is too soft and can not keep the problem of shape.In addition, if the modulus of elasticity in direct stress of cured body is below the 30MPa, and the fail in tension elongation is more than 200%, then can obtain good vibratory fatigue weather resistance, thereby can positively obtain the effect of inventing.
And then, in Photocurable resin composition of the present invention, contain the rubber combination of conduct (E) composition more than a kind at least, can obtain good vibratory fatigue weather resistance, be preferred therefore.
As rubber combination; Can enumerate out above-mentioned elastomerics (R); Wherein, From consider preferred especially rubber combination with the intermiscibility aspect of light-cured resin as the multipolymer that forms by at least a monomer that is selected from (methyl) acryliccompound, vinylic and the olefines hydrocarbon compound.
The molecular weight of rubber combination is preferably 500～50, and 000, be preferably 750～20,000 especially, further preferably 1,000～10,000 scope.If molecular weight is more than 500, then light-cured resin can obtain sufficient vibratory fatigue weather resistance, if molecular weight is then also good with the intermiscibility of light-cured resin below 50,000, is preferred therefore.
The MWD of rubber combination (when weight-average molecular weight is Mw, Mw/Mn when number-average molecular weight is Mn) be to below 5.0, be preferably more than 1.1 to below 3.0 especially more than 1.0; Then mix with light-cured resin; And can give good vibratory fatigue weather resistance, be preferred therefore.
As the monomer that constitutes rubber combination; When the Tg that contains (first) homopolymer is lower than 25 ℃ the Tg of free radical polymerization monomer, (second) homopolymer when the free radical polymerization monomer more than 25 ℃ and (third) intramolecularly have at least one for the free radical polymerization monomer of the reactive group of non-free radical polymerizability; The intermiscibility of rubber combination and light-cured resin is good; And can give good vibratory fatigue weather resistance, be preferred especially therefore.
The monomer of (first) composition can be given flexibility to rubber combination.(first) composition shared ratio in rubber combination is preferably 20～90 quality %, is preferably 30～80 quality % especially.
As (first) composition; C1～20 alkyl esters (for example can to enumerate out (methyl) vinylformic acid; Bing Xisuandingzhi, n-BMA, ethyl propenoate, vinylformic acid n-octyl and (methyl) 2-EHA), diene monomers (for example, divinyl, isoprene), vinyl-acetic ester monomer etc.Reach stability in order to obtain flexibility, preferred (methyl) vinylformic acid C1～20 alkyl esters, preferred especially (methyl) vinylformic acid C1～8 alkyl esters to the light and heat deterioration.
The monomer of (second) composition can be given the intermiscibility with light-cured resin.(second) composition shared ratio in rubber combination is preferably 0.1～70 quality %, is preferably 1～60 quality % especially.As (second) composition, can enumerate out vinyl aromatic compounds such as (methyl) propenoate, (methyl) vinyl cyanide or vinylbenzene such as TEB 3K, Jia Jibingxisuanyizhi, methacrylic tert-butyl acrylate, cyclohexyl methacrylate, (methyl) IBOA, (methyl) vinylformic acid tetrahydro-dicyclopentadiene base ester etc.Consider special preferable methyl methyl acrylate, vinylbenzene from the balance aspect of intermiscibility and copolymerization property.
(the third) monomer of composition can be given with the bridging property of light-cured resin, or give bridging property each other to rubber combination.As reactive group, be preferably the non-free radical polymerizability.This is because if free-radical polymerised, then can react simultaneously with the radical polymerization of rubber combination.As the reactive group of non-free radical polymerizability, can enumerate out hydroxyl, carboxyl, glycidyl, NCO, amino and alkoxysilyl etc.(the third) composition shared ratio in rubber combination is preferably 1～50 quality %, is preferably 5～40 quality % especially.
As (third) composition; Can enumerate out (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) glycidyl acrylate, (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl succsinic acid, 2-(methyl) acryloxy ethyl isocyanate, 1,1-(two (methyl) acryloyl-oxy ylmethyl) ethyl isocyanate, diethylamino (methyl) propenoate, dimethylamino (methyl) propenoate, 3-(methyl) acryloxy propyl trimethoxy silicane, 3-(methyl) acryloxy propyl-triethoxysilicane etc.From consider (methyl) vinylformic acid hydroxyalkyl acrylate, (methyl) glycidyl acrylates such as preferred especially (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester with the reactive aspect of light-cured resin.
As the polymerization method of rubber combination, can adopt known method such as radical polymerization and anionoid polymerization.
As radical polymerization, can adopt known method such as mass polymerization, suspension polymerization, body-suspension polymerization, solution polymerization, letex polymerization, successive polymerization.In addition, as required, can use free radical generating agent.
Polymerizing conditions such as the solvent that in radical polymerization, uses, polymerization temperature do not have particular determination.Polymerization can be carried out under condition of no solvent or in all kinds of SOLVENTS.Under condition of no solvent, carry out polymerization, polymerization velocity is fast, and productivity improves, and is preferred therefore.
Fast and the polymerization velocity aspect consideration of control easily from polymerization velocity, polymerization temperature is that 50～500 ℃ TR is preferred, preferred especially polymerization temperature is 100～400 ℃.
As free radical generating agent, can use all cpds, preferably can enumerate out the superoxide that under conditions of polymerization temperature vary, can produce radical.Unqualified as superoxide; For example can enumerate out; Lucidol, acetylperoxide, peroxo-isobutyryl, peroxo-decoyl, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylammonium peroxo-hexanoyl, 2, diacyl peroxide classes such as 4-dichlorobenzoperoxide, m-toluyl peroxide; Dialkyl peroxide classes such as di-t-butyl peroxide, tert-butyl peroxide cumyl, dicumyl peroxide, α, α '-two (tert-butyl hydroperoxide sec.-propyl) benzene, 2,5-dimethyl--2,5-two (tert-butyl hydroperoxide) hexane, 2,5-dimethyl--2,5-two (tert-butyl hydroperoxide) hexin-3; 2, ketal peroxide classes such as two (tert-butyl hydroperoxide) butane, 2 of 2-, two (tert-butyl hydroperoxide) octanes, 1 of 2-, two (tert-butyl hydroperoxides) 3,3 of 1-, 5-trimethyl-cyclohexane, 4, two (tert-butyl hydroperoxide) n-butyl pentanoates of 4-; Peroxycarbonates classes such as di-isopropyl peroxydicarbonate, peroxy dicarbonate two (the 2-ethyl is own) ester, peroxy dicarbonate di-n-propyl ester, peroxy dicarbonate two (3-methoxyl group fourth) ester, peroxy dicarbonate two (2-oxyethyl group second) ester, peroxy dicarbonate two (methoxyl group different third) ester, peroxy dicarbonate two (3-methyl-3-methoxyl group fourth) ester, two (the 4-tertiary butyl hexamethylene) esters of peroxy dicarbonate; Peroxide acetic acid butyl ester, peroxo-tert-butyl isobutyrate, the peroxo-PIVALIC ACID CRUDE (25) tert-butyl ester, new peroxide tert-butyl caprate, peroxo-neodecanoic acid cumyl ester, peroxo-(the 2 one thylhexoic acid) tert-butyl ester, peroxo-(3; 5; The 5-tri-methyl hexanoic acid) tert-butyl ester, the peroxo-LAURIC ACID 99 MIN tert-butyl ester, peroxidized t-butyl perbenzoate, di-t-butyl diperoxy isophthalic acid ester, 2; 5-dimethyl--2, peroxyesters such as 5-two (benzoyl-peroxo-) hexane, tert-butyl hydroperoxide sec.-propyl carbonic ether; Ketone peroxide classes such as diacetone peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, peroxo-(3,3, the 5-trimethylcyclohexanone), peroxo-methylcyclohexanone; Cumene hydroperoxide, di-isopropylbenzene hydroperoxide, hydrogen peroxide are to
alkane, 2; 5-dimethylhexane 2; 5-dihydro-peroxidase, 1; 1,3, hydroperoxide kinds such as 3-tetramethyl butyl hydroperoxide; Many acyl peroxides class of 2 yuan of acid; 2 yuan of acid and polyvalent alcohol form gathers peroxyester (polyperoxyester) type.Wherein, preferably use Lucidol.
In addition, also can use radical generation property azo cpd etc. to replace superoxide as free radical generating agent.As radical generation property azo cpd, can enumerate out for example Diisopropyl azodicarboxylate etc.
In order to reach the purpose of adjustment molecular weight etc., can merge and use solvent, radical end-capping reagent, polymerization accelerator, chain-transfer agent, reaction terminating agent etc. as required.
Rubber combination contains the polymer chain that has 1 aromatic group at intramolecularly at least, and is then good with the intermiscibility of light-cured resin, and gives good vibratory fatigue weather resistance, is preferred therefore.Aromatic group can be any in main chain, side chain, the chain end, and particularly when chain end was aromatic group, intermiscibility was good, gives good vibratory fatigue weather resistance, is preferred therefore.The polymer chain that intramolecularly has 1 aromatic group at least shared ratio in rubber combination is preferably more than the 1 quality %, is preferably especially more than the 10 quality %, more preferably more than the 50 quality %.If be more than the 1 quality %, then can not damage with the intermiscibility of light-cured resin give the vibratory fatigue weather resistance.What should explain is, above-mentioned polymer chain shared ratio in rubber combination is preferably below the 99.99 quality %, is preferably especially below the 99.9 quality %.
As aromatic group being introduced intramolecular means, can enumerate method that method through using aromatic solvents such as toluene, YLENE to introduce of method that the method (1) introduced through the free radical polymerization monomer that uses vinylbenzene etc. to have aromatic group, (2) introduce through the free radical generating agent that uses Lucidol etc. to have aromatic group, (3), (4) introduce through the chain-transfer agent that uses aromatic mercaptans such as benzenethiol, thiophenol etc. to have aromatic group etc.
In order light-cured resin to be given good vibratory fatigue weather resistance, the Tg of rubber combination preferably is lower than 25 ℃.More preferably less than 0 ℃, further preferably be lower than-20 ℃.
Rubber combination is 25 ℃ viscosity, preferably 100～100, and the scope of 000mPas.If more than 100mPas, then can give sufficient vibratory fatigue weather resistance, and if 100, below the 000mPas, then can obtain the intermiscibility with light-cured resin, and can not make the tackify of light-cured resin own, be preferred therefore.Should explain that the measuring method of viscosity does not have particular restriction, can use known viscometers such as Brookfield viscometer, E type viscometer, rheometer to measure.
Rubber combination shared ratio in Photocurable resin composition is preferably 0.01～70 quality %, and more preferably 0.05～50 quality % is preferably 0.1～30 quality % especially.This be because, if be less than 0.01 quality %, then can not get sufficient vibratory fatigue weather resistance, and if more than 70 quality %, the light-cured resin that then obtains is too soft, and solidified nature can reduce.
And then; The characteristic of cured body that contains the Photocurable resin composition of rubber combination of the present invention is; Demonstrate following good vibratory fatigue weather resistance: when implementing stretching test measurement according to JIS K7113 (stretching test methods of plastics); The modulus of elasticity in direct stress is 1～30MPa, and the fail in tension elongation is more than 200%.If it is too soft and can not keep the problem of shape that the modulus of elasticity in direct stress of cured body more than 1MPa, then can not produce resulting cured body.In addition, if the modulus of elasticity in direct stress of cured body below the 30MPa and the fail in tension elongation more than 200%, then can obtain good vibratory fatigue weather resistance, thereby can positively obtain the effect of inventing.
In the present invention; As required; In the scope of not damaging effect of the present invention, also can cooperate pigment (that titanium white, phthalocyanine blue, Wo Qiuge red (Watching Red), red iron oxide, carbon black, nigrosine, manganese indigo plant, iron oxide black, ultramarine blue, the Chinese spread is red, chrome yellow, chrome green etc.), inorganic filler (SiO 2 powders such as lime carbonate, kaolin, clay, talcum, mica, permanent white, lithopone, gypsum, Zinic stearas, perlite, quartz, silica glass, fused silica, preparing spherical SiO 2 etc.; Ball-aluminium oxide, pulverizing aluminum oxide, Natural manganese dioxide, beryllium oxide, titanium oxide etc. are oxide-based; SP 1, silicon nitride, aluminum nitride and other nitride class; Carbon compounds such as silit; Oxyhydroxide such as white lake, Marinco H class; Metal species, alloy type such as copper, silver, iron, aluminium, nickel, titanium; Carbon such as diamond, carbon class material etc.); Thermoplastic resin and thermosetting resin (homopolymer, ethylene-propylene copolymer, nylon-6, the nylon-6 of high-density, middle density, low-density various Vilaterm, Vestolen PP 7052, polybutylenes, polypenthylene etc., graft copolymers such as various elastomer resins such as 6 polyamide-based resins such as grade, vinyl chloride resin, Nitrocellulose resinoid, vinylidene chloride resin, acrylics, acrylic amide resinoid, styrene resin, vinyl ester resinoid, polyester resin, silicone resin, fluorine-type resin, acrylic rubber, urethanes, TEB 3K-butadiene-styrene quasi-graft copolymer, acrylonitrile-butadiene-styrene (ABS) quasi-graft copolymer etc.), strengthening agent (spun glass, thomel etc.), anti-sagging agent (THIXCIN, silicas etc.), flatting agent (fine particle silica, paraffin etc.), abrasive (Zinic stearas etc.), internal mold release (fatty amide, fatty ester, polyolefin-wax, paraffin etc. such as the fatty acid metal salt of lipid acid such as Triple Pressed Stearic Acid, calcium stearate, stearylamide).
In the present invention; When the total amount of (A)～(D) composition, when perhaps the total amount of (A)～(E) composition is 100 quality %, the use level of pigment can be at 0.0001～50 quality %, and the use level of inorganic filler can be at 0.0001～50 quality %; The use level of flow agent can be at 0.0001～5 quality %; The use level of thermoplastic resin and thermosetting resin can be at 0.01～30 quality %, and the use level of anti-sagging agent can be at 0.01～5 quality %, and the use level of flatting agent can be at 0.001～10 quality %; The use level of abrasive can be at 0.01～5 quality %, and the use level of internal mold release can be selected in the scope of 0.001～20 quality % aptly.
In addition, except mentioned component, also can merge and use skimmer, fire retardant, static inhibitor, softening agent, thermal polymerization, silane coupling agent, sticking power imparting agent etc.
Through to above-mentioned such Photocurable resin composition irradiates light of the present invention that obtains, can make its instantaneous solidification, obtain the good cured body of vibratory fatigue weather resistance.
In addition, when the formed body of moulding Photocurable resin composition of the present invention, its means can adopt the whole bag of tricks.Particularly preferably be: (1) forms the arbitrary at least side that forms in the pattern who is made up of upper die and lower die with the material of printing opacity, splashes into this Photocurable resin composition before solidifying by specified amount.Then, with the upper die and lower die pressing, mold closing, the outside irradiates light of the mould of processing from the material of printing opacity makes resin solidification, obtains the method for target cured body; (2) with the material of printing opacity form by upper die and lower die constitute one forms pattern arbitrary at least side, then, with the upper die and lower die pressing, mold closing, then, this Photocurable resin composition from the mould before the curing of preformed inlet injection specified amount.Then, the outside irradiates light of the mould of processing from the material of printing opacity makes resin solidification, obtains the method for target cured body.
Material as the mould that can be used for printing opacity; Can enumerate out for example resin materials such as glass materials such as quartz, silica glass, pyrex, soda glass, acrylics, polycarbonate resin, polystyrene resin, vibrin, polyvinyl resin, acrylic resin, fluoro-resin, celluosic resin, styrene-butadiene copolymer, copolymer of methyl methacrylatestyrene, but be not limited thereto.Particularly preferably be acrylicss such as polymethylmethacrylate.
As light source, can enumerate out halogen lamp, metal halide lamp, high-power metallic halide lamp (containing indium etc.), Cooper-Hewitt lamp, high pressure mercury vapour lamp, extra-high-pressure mercury vapour lamp, xenon lamp, xenon excimer lamp, xenon flash lamp etc., this there is not particular determination.
Because various radiation wavelength, energy distribution difference, therefore, above-mentioned light source can wait according to the reaction wavelength of Photoepolymerizationinitiater initiater and select.In addition, natural light (sunshine) also can be used as reaction initiation light source.
Above-mentioned light source can direct irradiation, carry out the light harvesting irradiation, carry out the light harvesting irradiation with fiber etc. with speculum etc., also can use low wavelength cut-off wave filter, infrared ray cut off filter, cold mirror etc.
In addition, in the occasion that adopts above-mentioned forming method with Photocurable resin composition moulding of the present invention, the cure shrinkage of resin combination is preferably below 10%.This is because if surpass 10%, then can be made by cure shrinkage between mould and die accuracy and the cured article and produce difference, and be difficult to obtain the cured body of target shape.
In addition, the viscosity of Photocurable resin composition is preferably 100～100 at 25 ℃, and 000mPas is preferably 3,000～90,000mPas especially.This be because, if be lower than 100mPas, then cause fluid seepage etc. sometimes, can not get the formed body of target shape.And if surpass 100,000mPas then is difficult to fill, and roof pressure mould etc. sometimes, can not get the cured body of target shape.
Embodiment
Below illustrate in greater detail the present invention, but the present invention does not receive the qualification of these embodiment with embodiment and comparative example.Should explain that the data shown in embodiment and the comparative example are measured according to following method.
The molecular weight of compsn and MWD adopt the GPC method, make calibration curve with polystyrene standard, measure according to following condition.
Solvent (moving phase): THF,
De-gassing vessel: ERMA corporate system ERC-3310,
Pump: Japanese beam split corporate system PU-980,
Sample IR: 100 μ l (test liquid concentration 1mg/ml),
Flow velocity: 1.0ml/min,
Liquor charging pressure: 39kg/cm
2,
Automatic sampler: TOSOH corporate system AS-8020,
Column oven: the corporate system L-5030 of Hitachi,
Design temperature: 40 ℃,
Post constitutes: TOSOH corporate system TSKguardcolumnMP (* L) 1 of 6.0mmID * 4.0cm and 2 of TOSOH corporate system TSK-GEL MULTIPORE HXL-M7.8mmID * 30.0cm, amount to 3,
Detector: the corporate system L-3350 of RI Hitachi,
Data processing: SIC480 data station.
The nuclear magnetic resonance spectrum of compsn (below be called
1H-NMR) measure according to following condition.
Determinator: JOEL corporate system ECP-300 (300MHz),
Solvent: deuterochloroform,
Sample solution concentration: 0.48 quality %,
Integral number of times: 25,000 times.
The mensuration of the viscosity of compsn is measured according to following condition.
Viscometer: E type viscometer (cone-plate type),
Measure temperature: 25 ℃.
< the polymerization example 1～5 of rubber combination >
< the polymerization example 1 of rubber combination >
With the stainless steel autoclave of 1L with nitrogen replacement after; Under nitrogen atmosphere, add n-butyl acrylate (below be called nBA): 270g, TEB 3K (below be called MMA): 270g, SY-Monomer G (below be called GMA): 60g, Lucidol (below be called BPO): 13.9g; Sealing; With oil bath oil bath temperature is heated to 130 ℃, under 200 ℃, carries out polymerization in about 60 minutes.Be chilled to room temperature then, polyreaction is stopped.Residual volatile component 240 ℃ of following vacuum-dryings 2 hours, is obtained solids component thus.With it as rubber combination (E-1).Yield is 92%, and the number-average molecular weight Mn that adopts GPC to record is 1,170, and weight-average molecular weight Mw is 2,350, and molecular weight distribution mw/mn is that 2.01,25 ℃ of viscosity are 5,000mPas.In addition, containing of the constituent of the rubber combination of acquisition (E-1) is proportional, by
1The integrated intensity of H-NMR spectrum is respectively nBA:44.7 quality %, MMA:45.4 quality %, GMA:9.9 quality % than the result who calculates.
< the polymerization example 2 of rubber combination >
Except in the fill process of polymerization example 1, use nBA:420g, MMA:18g, GMA:162g, the BPO:6.95g, all the other are same with polymerization example 1, acquisition rubber combination (E-2).Yield is 95%, and the number-average molecular weight Mn that adopts GPC to record is 2,000, and weight-average molecular weight Mw is 4,710, and molecular weight distribution mw/mn is that 2.36,25 ℃ of viscosity are 9,500mPas.Containing of the constituent of the rubber combination (E-2) that obtains is proportional, and the result who is recorded by the 1H-NMR spectrum is respectively nBA:68.6 quality %, MMA:3.1 quality %, GMA:28.3 quality %.
< the polymerization example 3 of rubber combination >
Except in the fill process of polymerization example 1, use nBA:480g, vinylbenzene: 90g, GMA:30g, the BPO:3.475g, all the other are same with polymerization example 1, acquisition rubber combination (E-3).Yield is 96%, and the number-average molecular weight Mn that adopts GPC to record is 4,500, and weight-average molecular weight Mw is 9,900, and molecular weight distribution mw/mn is that 2.20,25 ℃ of viscosity are 5,900mPas.Containing of the constituent of the rubber combination (E-3) that obtains is proportional, by
1The result that the H-NMR spectrum records is respectively nBA:78.4 quality %, vinylbenzene: 16.1 quality %, GMA:5.5 quality %.
< the polymerization example 4 of rubber combination >
Except in the fill process of polymerization example 1, use nBA:228g, MMA:240g, vinylbenzene: 90g, vinylformic acid 2-hydroxy methacrylate (below be called 2-HEA): 12g, the BPO:13.9g, all the other are same with polymerization example 1, acquisition rubber combination (E-4).Yield is 92%, and the number-average molecular weight Mn that adopts GPC to record is 780, and weight-average molecular weight Mw is 1,680, and molecular weight distribution mw/mn is that 2.15,25 ℃ of viscosity are 1,200mPas.Containing of the constituent of the rubber combination (E-4) that obtains is proportional, by
1The result that the H-NMR spectrum records is respectively nBA:37.3 quality %, MMA:38.9 quality %, vinylbenzene: 19.5 quality %, 2-HEA:4.3 quality %.
< the polymerization example 5 of rubber combination >
Except in the fill process of polymerization example 1, use 2-EHA (below be called 2-EHA): 300g, MMA:30g, GMA:270g, the BPO:1.39g, all the other are same with polymerization example 1, acquisition rubber combination (E-5).Yield is 98%, and the number-average molecular weight Mn that adopts GPC to record is 10,000, and weight-average molecular weight Mw is 19,600, and molecular weight distribution mw/mn is that 1.96,25 ℃ of viscosity are 95,000mPas.Containing of the constituent of the rubber combination (E-5) that obtains is proportional, by
1The result that the H-NMR spectrum records is respectively 2-EHA:49.8 quality %, MMA:5.1 quality %, GMA:45.1 quality %.
< embodiment 1～17 and comparative example 1～7 >
Below, each composition of showing kind shown in 1-1, table 1-2, the table 1-3 is mixed the preparation Photocurable resin composition according to the composition (weight %) shown in the table.
Should explain, as each composition in the complexing compositions of putting down in writing in embodiment and the comparative example, the compound below selecting.
As (A) composition,
(A-1) polyester polyol class urethane acrylate
(Japanese synthetic chemical industry corporate system trade(brand)name UV-3000B)
(weight-average molecular weight that is scaled PS 18000 that adopts GPC to record)
(A-2) polyether glycol class urethane acrylate
(Japanese synthetic chemical industry corporate system trade(brand)name UV-3700B)
(weight-average molecular weight that is scaled PS 37000 that adopts GPC to record)
(A-3) polyester polyol class urethane acrylate
(root is attend the system trade(brand)name KHP-11 of industrial)
(weight-average molecular weight that is scaled PS 25000 that adopts GPC to record)
(A-4) polyester polyol class urethane acrylate
(root is attend the system trade(brand)name SD-7 of industrial)
(weight-average molecular weight that is scaled PS 3500 that adopts GPC to record)
(A-5) n-BMA (the system LIGHT-ESTERNB of chemical company of common prosperity society)
(A-6) 2-hydroxyethyl methacrylate (the system LIGHT-ESTER HO of chemical company of common prosperity society)
(A-7) Propenoic acid, 2-methyl, isobutyl ester (the system LIGHT-ESTER IB of chemical company of common prosperity society)
(A-8) methacrylic tert-butyl acrylate (the system LIGHT-ESTERTB of chemical company of common prosperity society)
(A-9) cyclohexyl methacrylate (the system LIGHT-ESTERCH of chemical company of common prosperity society)
(A-10) isobornyl methacrylate (the system LIGHT-ESTER IB-X of chemical company of common prosperity society)
(A-11) methylacrylic acid tetrahydro-dicyclopentadiene base ester (Hitachi changes into the system FANCRYL FA-513M of industrial)
(A-12) dimethacrylate 1, and 9-nonanediol ester (the system LIGHT-ESTER 1 of chemical company of common prosperity society, 9ND)
(A-13) polyethylene glycol dimethacrylate (number of repeat unit of oxyethane=9) (the system LIGHT-ESTER 9EG of chemical company of common prosperity society)
As the Photoepolymerizationinitiater initiater of (B) composition,
Two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxides (Ciba corporate system IRGACURE819)
As the inhibitor of (C) composition,
Octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester (Ciba corporate system IRGANOX1076)
As the photostabilizer of (D) composition,
Two (2,2,6,6-tetramethyl--4-piperidyl) sebates (SANKYOLIFETECH corporate system SANOLLS-770)
Various rerum naturas are measured according to following method.
(preparation of cured body test film)
Use a kind of copy target test film shape constitute the shaping mould of one group acrylics system, the Photocurable resin composition before the counterdie that places splashes into the curing of necessary amount by upper die and lower die.Then, patrix is covered counterdie, pressing, mold closing, the outside irradiates light from mould makes resin solidification, obtains target cured body test film.
(rayed condition)
When irradiates light, use the Fusion corporate system solidification equipment that carries electrodeless discharge bulb (D bulb), be 4000mJ/cm with integrating irradiation dose to light-cured resin
2Condition (365nm) makes its curing.
(resin stretched test)
According to JIS K7113 (stretching test methods of plastics), according to the thick test film of 2 (1/2) numbers dumbbell shapes (gauge length 12mm) preparation 1mm, under the environment of 23 ℃ of temperature, humidity 50%, 50mm/min measures with draw speed under these conditions.Obtain each value of fail in tension intensity, the modulus of elasticity in direct stress, fail in tension elongation according to JIS K7113.
(vibratory fatigue long duration test)
The test film for preparing total length 150mm * wide 25mm * thickness 1mm under these conditions; With JIS K6260 (the crooked bursting test method of the De Mattia of vulcanized rubber and plasticity-rubber) is reference; The test film that has formed about 2mm be full of cracks at the test film central part in advance is fixed on the 75mm grip separation on the last lower clamp of the crooked bursting test machine of De Mattia (go up the island and make institute's corporate system); In the room temperature atmosphere, it is moved back and forth under amplitude 56mm, 300 times/minute condition.Mensuration is to be 0 time (initial stage), 3,000 times, 54,000 times, 144,000 times chronometry be full of cracks width at number of bends.At this moment, number of bends is meant that with 1 to-and-fro movement as 1 time, number of bends reads with the number of times meter.In addition, the mensuration of be full of cracks width is that grip separation is to measure under the condition of 65mm.In addition, about estimating, it is good that the sample that will not reach 25mm (=fracture) at 144,000 times moment be full of cracks width is evaluated as the vibratory fatigue weather resistance.
The mensuration of the resin stretched test of the cured body of the Photocurable resin composition that obtains and the result of vibratory fatigue long duration test gather and are shown among table 1-1, table 1-2, the table 1-3.
[table 1-1]
[table 1-2]
[table 1-3]
Photocurable resin composition of the present invention has following characteristic: receive the rayed of ultraviolet ray or visible rays etc. and in the extremely short time, solidify, the vibratory fatigue weather resistance of its cured body is good.Therefore; Applicable to works such as trolley parts such as tire, building, buildings with sound equipments such as liner component, speaker such as sealing element, O shape rings with parts, mobile telephone with plate member such as keypad, vibration isolating material, various mechanism part etc., very useful on industry.In addition; Photocurable resin composition of the present invention is because its good resistent fatigue characteristic; Therefore can also be applicable to that the structure of building, building etc. uses sealing agent; And be applicable to the caking agent that metal, magnet, pottery, glass, plastics are used, and then can also be applicable to synthetic resins such as plastic lens.
Should explain; Be incorporated in and in the full content of Japanese patent application 2006-036181 number specification sheets, claims and summary of application on February 14th, 2006 at this Japanese patent application 2006-001360 number of on January 6th, 2006 application, and as the content of specification sheets of the present invention.
Claims (13)
1. Photocurable resin composition; It is characterized in that; Containing (A) is selected from least a kind of resin, (B) Photoepolymerizationinitiater initiater in optical free radical polymerizability resin and the cationically photopolymerizable resin, is selected from arbitrary side or both sides and (E) rubber combination in (C) inhibitor and (D) photostabilizer; The modulus of elasticity in direct stress of the cured body of this Photocurable resin composition is 1～30MPa, and the fail in tension elongation is more than 200%.
2. Photocurable resin composition according to claim 1, wherein, said optical free radical polymerizability resin is an optical free radical addition polymerization property resin.
3. according to claim 1 or 2 described Photocurable resin compositions; Wherein, Rubber combination is served as reasons and is selected from the multipolymer that at least a monomer in (methyl) acryliccompound, vinylic and the olefines hydrocarbon compound forms; Weight-average molecular weight is 500～50,000 scope.
4. Photocurable resin composition according to claim 3, wherein, rubber combination is served as reasons and is selected from the multipolymer that the monomer more than 3 kinds in (methyl) acryliccompound, vinylic and the olefines hydrocarbon compound forms, and above-mentioned monomer contains:
The second-order transition temperature of (first) homopolymer be lower than 25 ℃ free radical polymerization monomer 20～90 quality %,
The second-order transition temperature of (second) homopolymer 0.1～70 quality % of the free radical polymerization monomer more than 25 ℃ and
(the third) intramolecularly has at least one free radical polymerization monomer 1～50 quality % for the reactive group of non-free radical polymerizability.
5. Photocurable resin composition according to claim 4, wherein, (first) composition monomer is (methyl) vinylformic acid C1-20 alkyl ester.
6. according to claim 4 or 5 described Photocurable resin compositions, wherein, (second) composition monomer contains at least a kind that is selected from TEB 3K and the vinylbenzene.
7. Photocurable resin composition according to claim 4, wherein, (third) composition monomer has more than one groups that are selected from hydroxyl, carboxyl, glycidyl, NCO, amino and the alkoxysilyl.
8. Photocurable resin composition according to claim 1 and 2, wherein, rubber combination is in 100～100 25 ℃ viscosity, the scope of 000mPas.
9. Photocurable resin composition according to claim 1 and 2, wherein, optical free radical polymerizability resin is an acrylics, this acrylics constitutes by (a-1) with (a-2):
(a-1) on the terminal or side chain of molecule, having (methyl) acryl, molecular weight more than 1 is that 5,000～100,000 urethane (methyl) origoester acrylate is more than a kind;
(a-2) simple function (methyl) propenoate.
10. Photocurable resin composition according to claim 9, wherein, (a-2) simple function (methyl) propenoate is perhaps simple function (methyl) propenoate of (2) expression of following formula (1):
In the formula (1), R
1Be Wasserstoffatoms or methyl; R
2For the straight or branched alkyl of carbonatoms 1～22, cyclohexyl, by the substituted cyclohexyl of straight or branched alkyl of carbonatoms 1～4, phenyl, by the substituted phenyl of straight or branched alkyl, tetrahydro-dicyclopentadiene base, dihydro bicyclic pentadiene, bornyl, isobornyl, adamantyl, methyl adamantane base or the allyl group of carbonatoms 1～4;
In the formula (2), R
1Be Wasserstoffatoms or methyl; R
3Straight or branched alkyl for carbonatoms 1～4; R
4For the straight or branched alkyl of carbonatoms 1～4, cyclohexyl, by the substituted cyclohexyl of straight or branched alkyl of carbonatoms 1～4, phenyl, by the substituted phenyl of straight or branched alkyl, tetrahydro-dicyclopentadiene base, dihydro bicyclic pentadiene, bornyl, isobornyl, adamantyl, methyl adamantane base or the allyl group of carbonatoms 1～4; N is 1～12 integer.
11. Photocurable resin composition according to claim 1 and 2; Wherein, optical free radical addition polymerization property resin forms by the polyenic compounds that have 2 above carbon-to-carbon unsaturated double-bonds at intramolecularly with at the multi-thioalcohol compound that intramolecularly has 2 above sulfydryls.
12. Photocurable resin composition according to claim 1 and 2, wherein, the cationically photopolymerizable resin has epoxy group(ing), oxetanyl or vinyl ether group at intramolecularly.
13. cured body is formed by each described Photocurable resin composition in the claim 1～12.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006001360 | 2006-01-06 | ||
| JP001360/2006 | 2006-01-06 | ||
| JP036181/2006 | 2006-02-14 | ||
| JP2006036181 | 2006-02-14 | ||
| PCT/JP2006/323491 WO2007077691A1 (en) | 2006-01-06 | 2006-11-24 | Photocurable resin composition |
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| CN101356204A CN101356204A (en) | 2009-01-28 |
| CN101356204B true CN101356204B (en) | 2012-04-11 |
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| CN2006800503979A Active CN101356204B (en) | 2006-01-06 | 2006-11-24 | Photocurable resin composition |
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|---|---|
| JP (1) | JP5348893B2 (en) |
| CN (1) | CN101356204B (en) |
| WO (1) | WO2007077691A1 (en) |
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| JP2012521877A (en) * | 2009-03-31 | 2012-09-20 | アクゾ ノーベル コーティングス インターナショナル ビー ヴィ | Radiation curing of coating |
| CN103429629B (en) * | 2011-03-11 | 2016-06-08 | 日立化成株式会社 | Liquid curing resin combination, use the image of said composition to show with manufacture method and the image demonstration device of device |
| JP6136095B2 (en) * | 2011-03-28 | 2017-05-31 | 日立化成株式会社 | Photosensitive resin composition, photosensitive film, pattern forming method, hollow structure forming method, and electronic component |
| TWI625340B (en) * | 2011-04-15 | 2018-06-01 | Denka Company Ltd | Sclerosing composition |
| JP6061728B2 (en) * | 2013-02-27 | 2017-01-18 | 株式会社オートネットワーク技術研究所 | Radical and anion combined photo-curing material |
| CN104109328A (en) * | 2014-06-23 | 2014-10-22 | 东莞智维立体成型股份有限公司 | Photocuring wax material used for 3D printing |
| CN105017492A (en) * | 2015-07-28 | 2015-11-04 | 孟庆华 | 3D printing material with aldehyde removal property and application thereof |
| WO2020137843A1 (en) * | 2018-12-26 | 2020-07-02 | 東洋スチレン株式会社 | Resin composition and molded body |
| KR20210132023A (en) * | 2019-02-19 | 2021-11-03 | 나가세케무텍쿠스가부시키가이샤 | Photocurable resin composition and three-dimensional stereolithography using same |
| WO2021000191A1 (en) * | 2019-06-30 | 2021-01-07 | 瑞声声学科技(深圳)有限公司 | Light-transmitting rubber composition, preparation method, and application in electroacoustic devices |
| WO2021019756A1 (en) * | 2019-08-01 | 2021-02-04 | 株式会社オートネットワーク技術研究所 | Wire harness, wire harness manufacturing method, photocurable composition, and cured product of same |
| CN111463372B (en) * | 2020-05-08 | 2022-11-29 | 浙江道明光电科技有限公司 | Battery packaging film and preparation process thereof |
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| CN101356204A (en) | 2009-01-28 |
| WO2007077691A1 (en) | 2007-07-12 |
| JP5348893B2 (en) | 2013-11-20 |
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