CN107001631B - Active energy ray-curable composition and use thereof - Google Patents
Active energy ray-curable composition and use thereof Download PDFInfo
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- CN107001631B CN107001631B CN201580066630.1A CN201580066630A CN107001631B CN 107001631 B CN107001631 B CN 107001631B CN 201580066630 A CN201580066630 A CN 201580066630A CN 107001631 B CN107001631 B CN 107001631B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
- C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
- C08G75/0213—Polyarylenethioethers derived from monomers containing one aromatic ring containing elements other than carbon, hydrogen or sulfur
- C08G75/0222—Polyarylenethioethers derived from monomers containing one aromatic ring containing elements other than carbon, hydrogen or sulfur containing nitrogen
Abstract
The present invention addresses the problem of providing an active energy ray-curable composition which can give a cured product having little unpleasant odor and excellent impact and vibration absorption properties, and which has excellent storage stability, and use thereof. The solution of the present invention is an active energy ray-curable composition comprising: a compound (A) having 2 or more allyl groups, a compound (B) selected from at least one of pentaerythritol tetrakis (3-mercaptobutyrate) and trimethylolpropane tris (3-mercaptobutyrate), and a polymerization initiator (C).
Description
Technical Field
The present invention relates to an active energy ray-curable composition and use thereof.
Background
The living sulfur-containing radicals can be regenerated even when the radical deactivation by oxygen occurs in the radical-polymerizable photocurable ene-thiol photocurable resin composition. Therefore, the aforementioned composition has the following advantages, and the like, and therefore has attracted attention as a photocurable material, among which: there is no inhibition of polymerization by oxygen, which is seen in acrylic materials, and the amount of photopolymerization initiator used can be reduced, the volume shrinkage during curing is small, and a cured product having a thick film of 1mm or more can be produced even by curing in a short time of several seconds to several minutes from the start of polymerization (non-patent document 1).
As the ene-thiol photocurable resin composition, for example, patent document 1 discloses a photocurable resin composition containing a polyene, a polythiol, and a compound having a bromine-substituted aromatic ring with a specific structure, wherein the mass ratio of the polyene to the polythiol is 49:1 to 1: 49. Further, patent document 2 discloses an ene-thiol photocurable resin composition containing a polyene compound and a (poly) thiol monomer containing a reaction product of a polyamine compound and a mercaptocarboxylic acid compound.
The technique disclosed in patent document 1 is a technique for providing a photocurable resin composition having a high refractive index and capable of adjusting the refractive index with high accuracy. Further, the technique disclosed in patent document 2 is a technique that does not inhibit polymerization by oxygen, can be cured in a short time, is reduced in volume shrinkage, can reduce the amount of a photopolymerization initiator used, and can obtain a cured product having greatly improved moisture resistance. However, in patent documents 1 and 2, nothing is mentioned about the shock absorption and vibration absorption of the cured product.
Patent document 3 discloses a transparent resin formed from a cured product of a polymerizable composition containing at least one of diallyl phthalate, diallyl isophthalate, and diallyl terephthalate, and pentaerythritol tetrakis (3-mercaptopropionate). Patent document 3 discloses a technique for providing a transparent resin excellent in coatability, adhesiveness, durability and impact resistance. However, patent document 3 does not mention anything about the odor caused by pentaerythritol tetrakis (3-mercaptopropionate).
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 4034098
Patent document 2: japanese patent laid-open No. 2007 and 70417
Patent document 3: japanese laid-open patent publication No. 11-71458
Non-patent document
Non-patent document 1: "expectation of UV/EB curing technique (expectation of UV/EB curing technique)", published by シーエムシー in 2002, p.39 to 50
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above problems, and an object thereof is to provide an active energy ray-curable composition having excellent storage stability, which can give a cured product having less unpleasant odor and excellent impact absorbability and vibration absorbability, and a cured product, an impact absorbing material, a vibration absorbing material, and a sheet obtained from the active energy ray-curable composition.
Means for solving the problems
As a result of intensive studies, the present inventors have found that a cured product suitable as an impact absorbing material and a vibration absorbing material having excellent impact absorbability, vibration absorbability and the like can be obtained after irradiation with active energy rays by using an active energy ray-curable composition containing a compound (a) having 2 or more allyl groups, a compound (B) of at least one selected from pentaerythritol tetrakis (3-mercaptobutyrate) and trimethylolpropane tris (3-mercaptobutyrate), and a polymerization initiator (C), and have completed the following present invention.
The present invention relates to the following active energy ray-curable compositions (1) to (8), cured products of (9), impact-absorbing materials of (10), vibration-absorbing materials of (11), and sheets of (12).
(1) An active energy ray-curable composition comprising:
a compound (A) having 2 or more allyl groups,
at least one compound (B) selected from pentaerythritol tetrakis (3-mercaptobutyrate) and trimethylolpropane tris (3-mercaptobutyrate), and
a polymerization initiator (C).
(2) The active energy ray-curable composition according to the item (1), wherein the compound (A) further has an aromatic ring.
(3) The active energy ray-curable composition according to (1), wherein the number of allyl groups contained in the compound (A) is 2.
(4) The active energy ray-curable composition according to the item (1), wherein the compound (A) is at least one selected from diallyl phthalate, diallyl isophthalate and diallyl terephthalate.
(5) The active energy ray-curable composition according to any one of (1) to (4), wherein the ratio of the number of allyl groups of the compound (A) to the number of mercapto groups of the compound (B) in the composition is in the range of 30:70 to 70:30, and the active energy ray-curable composition contains 0.01 to 10 parts by mass of the polymerization initiator (C) per 100 parts by mass of the total of the compound (A) and the compound (B).
(6) The active energy ray-curable composition according to any one of (1) to (5), further comprising a urethane (meth) acrylate.
(7) The active energy ray-curable composition according to item (6), wherein the ratio of the total number of allyl groups of compound (A) and (meth) acryloyloxy groups of urethane (meth) acrylate to the number of mercapto groups of compound (B) in the composition is in the range of 30:70 to 70:30, and the active energy ray-curable composition contains 0.01 to 10 parts by mass of polymerization initiator (C) per 100 parts by mass of the total of compound (A), urethane (meth) acrylate and compound (B).
(8) The active energy ray-curable composition according to any one of (1) to (7), further comprising an inorganic filler.
(9) A cured product obtained by curing the active energy ray-curable composition according to any one of (1) to (8).
(10) An impact absorbing material obtained by curing the active energy ray-curable composition according to any one of (1) to (8).
(11) A vibration absorbing material obtained by curing the active energy ray-curable composition according to any one of (1) to (7).
(12) A sheet obtained by curing the active energy ray-curable composition according to any one of (1) to (7).
Effects of the invention
The present invention can provide an active energy ray-curable composition which can give a cured product having less unpleasant odor and excellent impact and vibration absorbability and has excellent storage stability, and a cured product, an impact absorbing material, a vibration absorbing material and a sheet obtained from the active energy ray-curable composition.
Detailed Description
The active energy ray-curable composition of the present invention (hereinafter also simply referred to as "the composition of the present invention") is characterized by containing a compound (a) having 2 or more allyl groups, a compound (B) selected from at least one of pentaerythritol tetrakis (3-mercaptobutyrate) and trimethylolpropane tris (3-mercaptobutyrate), and a polymerization initiator (C).
[ compounding ingredients ]
The following description will be made of the components constituting the composition of the present invention.
< Compound (A) >
In the present invention, since the compound (a) contains 2 or more allyl groups in the molecule, the impact absorbability and the vibration absorbability of the cured product can be improved.
The compound (A) may be a monomer, an oligomer or a polymer, and is preferably a compound having a molecular weight of 200 to 20,000 from the viewpoint of viscosity. Unless otherwise specified, the molecular weight of the oligomer or polymer in the present application is a Polystyrene (PS) converted value measured by gel permeation chromatography (GPC method), and is a number average molecular weight.
When the compound (A) is a monomer, examples of the compound (A) include a compound (a-1) having an aromatic ring, an alicyclic ring or a heterocyclic ring in the molecule and a non-cyclic compound (a-2).
Examples of the compound (a-1) include diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl trimellitate, tetraallyl pyromellitate, bisphenol A allyl ether, diallyl 1, 2-cyclohexanedicarboxylate, diallyl 1, 3-cyclohexanedicarboxylate, triallyl isocyanurate, and triallyl cyanurate. Among them, compounds having an aromatic ring such as diallyl phthalate, diallyl isophthalate, and diallyl terephthalate are preferable, and in particular, diallyl phthalate is preferable from the viewpoint of impact absorbability and vibration absorbability.
Examples of the compound (a-2) include tetraallyl 1,2,3, 4-butanetetracarboxylic acid, diallyl succinate, diallyl glutarate, diallyl adipate, diallyl sebacate, diallyl dimer acid, diallyl hydrogenated dimer acid, diallyl 1, 12-dodecanedioate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, trimethylolpropane triallyl ether, pentaerythritol tetraallyl ether and the like, and pentaerythritol tetraallyl ether is particularly preferable from the viewpoint of impact absorbability and vibration absorbability.
In the case where the compound (a) is an oligomer, allyl ester resin is preferably used. Specific examples of the allyl ester resin include oligomers having structures represented by the following formulae (a-3), (a-4) and (a-5).
In the formula (a-3), c is an integer of 1 to 5, more preferably 1 to 3, and most preferably 1. R3Is an alkylene group having 1 to 10 (preferably 1 to 5, more preferably 2 to 3) carbon atoms which may have an alkyl group having 1 to 5 (preferably 1 to 3, more preferably 1) carbon atoms as a substituent. n number of R3May be different from each other.
X is a phenylene group or a cyclohexylene group which may have an alkyl group having 1 to 4 carbon atoms as a substituent, and is preferably a phenylene group or a cyclohexylene group which does not have a substituent. The (n +1) xs may be different from each other.
Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
The position at which the phenylene group or the cyclohexylene group is bonded to the adjacent carbonyl carbon may be any of the 1, 2-position, 1, 3-position, and 1, 4-position, but is preferably the 1, 4-position.
n is an integer of 1 to 20, preferably 1 to 18, and more preferably 1 to 15. The molecular weight of the compound represented by the formula (a-3) is preferably about 300 to 20,000, more preferably 800 to 18,000, and most preferably 1,000 to 16,000.
In the formula (a-4), c is the same as described above, and X is the same as described above. The (2m +1) xs may be different from each other. R4Is an alkyl group having 1 to 4 carbon atoms (specific examples are the same as those of the substituent in X) or a group represented by the following formula (a-4'). m R4May be different from each other.
In the formula (a-4'), c and X are the same as described above.
m is an integer of 3 to 70, preferably 4 to 60, more preferably 4 to 50. The molecular weight of the compound represented by the formula (a-4) is preferably 300 to 20,000, more preferably 800 to 18,000, and most preferably 1,000 to 16,000.
In the formula (a-5), c and X are the same as described above, and R3Each independently of the other, p is an integer of 1 to 10, preferably 1 to 9, more preferably 1 to 8. q is an integer of 5 to 50, preferably 5 to 45, and more preferably 5 to 40. (q +1) X's may be different from each other, [ (p + 1). times.q]R is3May be different from each other.
The molecular weight of the compound represented by the formula (a-5) is preferably about 300 to 20,000, more preferably 500 to 19,000, and most preferably 8,000 to 18,000.
Specific examples of the case where the compound (a) is an oligomer other than the allyl ester resin include a polyene compound derived from a substituted or unsubstituted allyl alcohol, polyethylene glycol bisallyl carbonate, and the like.
When the compound (a) is a polymer, the polymer is not particularly limited as long as it has 2 or more allyl groups introduced into the polymer skeleton, and a known polymer can be used.
Examples of the polymer skeleton include a polyethylene skeleton, a polyurethane skeleton, a polyester skeleton, a polyamide skeleton, a polyimide skeleton, a polyoxyalkylene skeleton, and a polyphenylene skeleton.
The compound (a) may be used alone in 1 kind, or may be used in combination of 2 or more kinds at an arbitrary ratio.
Among them, it is preferable not to use diallyl 1, 4-cyclohexanedicarboxylate as the compound (A).
< Compound (B) >
The compounds (B) usable in the present invention all have a secondary mercapto group, and the reason why a secondary mercapto group is suitable as compared with a primary mercapto group is that the composition has excellent storage stability and has very little unpleasant odor.
Pentaerythritol tetrakis (3-mercaptobutyrate) is available from Showa Denko K.K. under the product name of カレンズ MT (trademark) PE1, and trimethylolpropane tris (3-mercaptobutyrate) is available from Showa Denko K.K. under the product name of TPMB.
< polymerization initiator (C) >
The polymerization initiator (C) includes a photopolymerization initiator and a thermal polymerization initiator, and is not particularly limited as long as it is a compound that promotes the initiation of polymerization of the compound (a).
The photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals contributing to the initiation of radical polymerization by irradiation with active energy rays such as near infrared rays, visible rays, and ultraviolet rays.
Examples of the photopolymerization initiator include acetophenone, 2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, 1, 2-hydroxy-2-methyl-1-phenylpropan-1-one,. alpha. -hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropanone, 2-hydroxy-2-methyl-1- (4-isopropylphenyl) propanone, 2-hydroxy-2-methyl-1- (4-dodecylphenyl) propanone, 2-hydroxy-2-methyl-1- [ (2-hydroxyethoxy) phenyl ] propanone, benzophenone, and mixtures thereof, 2-methylbenzophenone, 3-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, benzophenone tetracarboxylic acid or the tetramethyl ester thereof, 4 ' -bis (dialkylamino) benzophenones (e.g., 4 ' -bis (dimethylamino) benzophenone, 4 ' -bis (dicyclohexylamino) benzophenone, 4 ' -bis (diethylamino) benzophenone, 4 ' -bis (dihydroxyethylamino) benzophenone), 4-methoxy-4 ' -dimethylaminobenzophenone, 4-methoxybenzophenone, 4-methylbenzophenone, 4-, 4, 4' -dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzil, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, phenanthrenequinone, fluorenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl ] propanol oligomer, mixtures thereof, and mixtures thereof, Benzoin, benzoin ethers (e.g. benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin phenyl ether, benzil dimethyl ketal), acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2, 6-dimethoxybenzoyldiphenylphosphine oxide, 2, 6-dichlorobenzoyldiphenylphosphine oxide, 2,4, 6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4, 6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5, 6-tetramethylbenzoyldiphenylphosphine oxide, benzoylbis (2, 6-dimethylphenyl) phosphonate, 1- [4- (phenylthio) phenyl ] -1, 2-octanedione-2- (O-benzoyloxime), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetyloxime), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylacetone-1- (O-acetyloxime), 1- [4- (phenylthio) phenyl ] -3-cyclopentylpropane-1, 2-dione-2- (O-benzoyloxime). The bisacylphosphine oxides include bis- (2, 6-dichlorobenzoyl) phenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -2, 5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2, 6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide, bis- (2, 6-dimethoxybenzoyl) -2, 5-dimethylphenylphosphine oxide, bis- (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, bis (2, 6-dichlorobenzoyl) phenylphosphine oxide, (2,5, 6-trimethylbenzoyl) -2,4, 4-trimethylpentylphosphine oxide, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.
Further, as the photopolymerization initiator, a metallocene compound may be used. As the metallocene compound, transition elements represented by Fe, Ti, V, Cr, Mn, Co, Ni, Mo, Ru, Rh, Lu, Ta, W, Os, Ir and the like can be used as the central metal, and examples thereof include bis (. eta.5-2, 4-cyclopentadien-1-yl) -bis [2, 6-difluoro-3- (pyrrol-1-yl) phenyl ] titanium.
In particular, from the viewpoint of stability of the active energy ray-curable composition after addition of the photopolymerization initiator, 1-hydroxycyclohexylphenyl ketone and 2,4, 6-trimethylbenzoyldiphenylphosphine oxide are preferable. The former is available from BASF under the product name Irgacure184, and the latter is available from BASF under the product name LUCIRIN TPO.
The thermal polymerization initiator is not particularly limited as long as it does not adversely affect the physical properties such as impact resistance of the cured product, and a known thermal polymerization initiator can be used. The thermal polymerization initiator used in the present invention is preferably soluble in other components present in the composition to be cured and generates radicals at 30 ℃ to 120 ℃.
Specific examples of the thermal polymerization initiator include, but are not limited to, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, and tert-butyl perbenzoate. From the viewpoint of curability, diisopropyl peroxydicarbonate is preferred.
In the composition of the present invention, the content of the polymerization initiator (C) is preferably 0.01 to 10 parts by mass, more preferably 0.5 to 5.0 parts by mass, based on 100 parts by mass of the total of the compound (a) and the compound (B).
When the composition of the present invention contains a urethane (meth) acrylate, the content of the polymerization initiator (C) is preferably 0.01 to 10 parts by mass, and more preferably 0.5 to 5.0 parts by mass, based on 100 parts by mass of the total of the compound (a), the urethane (meth) acrylate, and the compound (B).
The polymerization initiator (C) may be used alone in 1 kind, or may be used in combination of 2 or more kinds at an arbitrary ratio.
< urethane (meth) acrylate >
The active energy ray-curable composition of the present invention may contain urethane (meth) acrylate within a range not impairing the object of the present invention. In the present specification, the term "urethane (meth) acrylate" refers to a general term for urethane acrylate and urethane methacrylate.
The urethane (meth) acrylate is not particularly limited, but a urethane (meth) acrylate having a soft skeleton, that is, a polyether skeleton or a polyester skeleton is preferable from the viewpoint of sheet moldability. The urethane (meth) acrylates include trade names UA-160TM, UA-122P, UA-290TM, UA-1013P, U-200PA (manufactured by Ninghamu chemical Co., Ltd.), EBECRYL230, 270, 284, 8411, 8413, 8800, 8804, 8413, 8402, KRM7735, 8296 (manufactured by ダイセル and オルネクス Co., Ltd.), UV 3300B, 3310B, 3700B, and 6640B (manufactured by Nippon synthetic chemical Co., Ltd.), and the use of these urethane (meth) acrylates is more preferable from the viewpoint of impact absorbability.
The urethane (meth) acrylate may be used alone in 1 kind, or 2 or more kinds may be used in combination in an arbitrary ratio.
The amount of the urethane (meth) acrylate is not particularly limited, but is preferably 10 to 60% by mass, more preferably 20 to 40% by mass, of the total mass of the composition, from the viewpoint of moldability.
< inorganic Filler >
The active energy ray-curable composition of the present invention may contain an inorganic filler in a range not to impair the object of the present invention.
The inorganic filler usable in the present invention is not particularly limited as long as it is an inorganic filler dispersed in the compound (a) and the compound (B) to form a paste. As such an inorganic filler, for example, Silica (SiO) can be used2) Alumina (Al)2O3) Titanium dioxide (TiO)2) Tantalum oxide (Ta)2O5) Zirconium oxide (ZrO)2) Silicon nitride (Si)3N4) Barium titanate (BaO. TiO)2) Barium carbonate (BaCO)3) Lead titanate (PbO. TiO)2) Lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga)2O3) Spinel (MgO. Al)2O3) Mullite (3 Al)2O3·2SiO2) Cordierite (2 MgO.2Al)2O3/5SiO2) Talc (3 MgO.4SiO)2·H2O), aluminum Titanate (TiO)2-Al2O3) Yttria-containing zirconia (Y)2O3-ZrO2) Barium silicate (BaO 8 SiO)2) Boron Nitride (BN), calcium carbonate (CaCO)3) Calcium sulfate (CaSO)4) Zinc oxide (ZnO), magnesium titanate (MgO. TiO)2) Barium sulfate (BaSO)4) A fiber reinforcing material such as organobentonite, carbon (C), glass powder, synthetic mica, boron nitride fiber, a filler obtained by blending silicone oil into an inorganic carrier and powdering the mixture, and a filler obtained by powdering silicone resin or silicone rubber, and 1 or 2 or more of these fillers may be used.
Among the above-exemplified inorganic fillers, microsilica is preferably used from the viewpoint of viscosity control and sheet formability, and is available from japanese アエロジル under the trade name of アエロジル (trademark). アエロジル (trademark) OX50, RX50, RY50, 50, NAX50, NY50, NA50H, NA50Y, 90G, NX90G, 130, R972, RY200S, 150, R202, 200, R974, R9200, RX200, R8200, RY200, R104, RA200H, RA200HS, NA200Y, R805, R711, R7200, 300, R976S, RX300, R812S, RY300, R106, 380, P25, T805, P90, NKT90, AluC805, etc. may be used, but RX200 is more preferable from the viewpoint of dispersibility.
The amount of the inorganic filler to be blended is not particularly limited, but may be less than 10 parts by mass relative to 100 parts by mass of the total of the compound (a), the compound (B) and the urethane (meth) acrylate, and is preferably 2 to 6 parts by mass, and more preferably 0.1 to 5 parts by mass, from the viewpoint of moldability.
< polymerization inhibitor >
The active energy ray-curable composition of the present invention may contain a polymerization inhibitor as needed to improve the storage stability of the composition.
Examples of the polymerization inhibitor include 4-methoxy-1-naphthol, 1, 4-dimethoxynaphthalene, 1, 4-dihydroxynaphthalene, 4-methoxy-2-methyl-1-naphthol, 4-methoxy-3-methyl-1-naphthol, 1, 4-dimethoxy-2-methylnaphthalene, 1, 2-dihydroxynaphthalene, 1, 2-dihydroxy-4-methoxynaphthalene, 1, 3-dihydroxy-4-methoxynaphthalene, 1, 4-dihydroxy-2-methoxynaphthalene, 1, 4-dimethoxy-2-naphthol, 1, 4-dihydroxy-2-methylnaphthalene, pyrogallol, methylhydroquinone, tert-butylhydroquinone, 4-methoxyphenol, pyrogallol, and the like, And N-nitroso-N-phenylhydroxyamine aluminum. These polymerization inhibitors may be used alone or in combination of 2 or more. In particular, from the viewpoint of storage stability of the active energy ray-curable composition, methylhydroquinone, pyrogallol, and tert-butylhydroquinone are preferable.
The amount of the polymerization inhibitor to be blended is not particularly limited, but may be less than 0.1 part by mass relative to 100 parts by mass of the total of the compound (a) and the compound (B), and is preferably 0.0001 to 0.05 part by mass from the viewpoint of storage stability.
< other ingredients >
The active energy ray-curable composition of the present invention may contain, in addition to the compound (a), the compound (B) and the polymerization initiator (C), at least 1 selected from urethane (meth) acrylates, inorganic fillers and polymerization inhibitors as needed, and may further contain other components as optional components within a range not impairing the object of the present invention. However, it is preferable that the composition of the present invention does not contain a compound having an ethylenically unsaturated group and an isocyanate group in 1 molecule, from the viewpoint of impact resistance and the like. For example, a mercapto compound other than the compound (B) may be blended within a range not impairing the effects of the present invention. However, the amount of the mercapto compound other than compound (B) is preferably 20 mass% or less of the total mercapto compound, from the viewpoint of maintaining impact absorbability, transparency, low odor properties, and the like.
The composition of the present invention may be used in the state of no solvent or may be used in the state of a solvent, but is preferably used in the state of no solvent.
Examples of the component to be preferably added as the other component include a coloring agent such as a carbon material, a pigment, and a dye.
Examples of the carbon material include carbon black, acetylene black, lamp black, and graphite.
Examples of the pigment include black pigments such as iron black, aniline black, cyanine black, and titanium black. The composition of the present invention may contain an organic pigment such as red, green or blue. Commercially available nail polish Gel (Gel oil) or pigments for UV process (craft) may be used, and examples of such pigments include ピカエース (Pikaace) colored pigments (701, 731, 741, 755, 762), and transparent pigments (900, 901, 910, 920, 921, 922, 924, 930, 932, 941, 942, 945, 947, 950, 955, 957, 960, 963, 968, 970, 980, 981, 982, 985).
Examples of the dye include direct dyes, acid dyes, basic dyes, mordant dyes, acid mordant dyes, vat dyes, disperse dyes, reactive dyes, fluorescent whitening dyes, and plastic dyes. The dye is a substance having solubility in a solvent or compatibility with a resin, and having a property of coloring a substance dissolved or compatible with the solvent. Examples of the plastic dye include KP PLATE (KP Plast Red B, KP Plast Blue GR, KP Plast yellow HK).
The coloring agent may be used alone or in combination of 2 or more.
The content of the colorant in the composition of the present invention is not particularly limited, but if the concentration is too high, the transmittance of active energy rays may be lowered to cause poor curing. Therefore, the content of the colorant in the composition is usually 60% by mass or less, preferably 0.0001 to 40% by mass.
The composition of the present invention may contain, as other components than the colorant, if necessary, (a) a thermoplastic resin; (b) a deodorant; (c) adhesion improvers such as silane coupling agents and titanium coupling agents; (d) antioxidants such as hindered amines, hydroquinones, and hindered phenols; (e) ultraviolet absorbers such as benzophenones, benzotriazoles, salicylates, metal complex salts and the like; (f) stabilizers such as metal soaps, inorganic and organic salts of heavy metals (e.g., zinc, tin, lead, cadmium, etc.), and organotin compounds; (g) pH regulators such as aliphatic carboxylic acids (e.g., acetic acid, acrylic acid, palmitic acid, oleic acid, and mercaptocarboxylic acid), and aromatic organic acids (e.g., phenol, naphthol, benzoic acid, and salicylic acid); (h) plasticizers such as phthalic acid esters, phosphoric acid esters, fatty acid esters, epoxidized soybean oil, castor oil, liquid paraffin alkyl polycyclic aromatic hydrocarbons, and the like; (i) waxes such as paraffin wax, microcrystalline wax, polymeric wax, beeswax, and spermaceti wax low molecular weight polyolefin; (j) non-reactive diluents such as benzyl alcohol, tar, and pitch; (k) fillers such as acrylic resin powder and phenol resin powder; (l) Solvents such as ethyl acetate, toluene, alcohols, ethers, ketones, and the like; (m) a blowing agent; (n) dehydrating agents such as silane coupling agents, monoisocyanate compounds, carbodiimide compounds and the like; (o) an antistatic agent; (p) an antibacterial agent; (q) a mold inhibitor; (r) a viscosity modifier; (s) a fragrance; (t) a flame retardant; (u) a leveling agent; (v) a sensitizer; and (w) a dispersant, and the like. These other components can be used alone in 1, also can be used in 2 or more in any ratio combination.
[ preparation of active energy ray-curable composition ]
The composition of the present invention can be prepared by appropriately mixing the compound (a), the compound (B), the polymerization initiator (C), and if necessary, urethane (meth) acrylate, the inorganic filler, the polymerization inhibitor, and other components.
The compound (a), the compound (B) and the polymerization initiator (C) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
In this case, the compound (A) is mixed so that the ratio (a: B) of the number (a) of allyl groups to the number (B) of mercapto groups is preferably 30:70 to 70:30, more preferably 40:60 to 60: 40.
When a urethane (meth) acrylate is blended, the mixture is mixed so that the ratio (a ': B) of the total number (a') of allyl groups of the compound (a) and (meth) acryloyloxy groups of the urethane (meth) acrylate to the number (B) of mercapto groups of the compound (B) is preferably 30:70 to 70:30, more preferably 40:60 to 60: 40.
The method for preparing the composition of the present invention is not particularly limited as long as the above components can be mixed and dispersed, and examples thereof include the following methods.
(i) The respective components are kneaded in a suitable container such as a glass beaker, a jar, a plastic cup, an aluminum cup, or the like with a stirring bar, a spatula, or the like.
(ii) The components are kneaded by means of twin-screw blades, gate-shaped blades (ゲート wings) and the like.
(iii) The components were kneaded using a planetary mixer.
(iv) The components were kneaded using a bead mill.
(v) The components were kneaded with three rolls.
(vi) The respective components were kneaded by an extrusion type kneading extruder.
(vii) The components were kneaded by a rotation and revolution mixer.
The addition and mixing of the respective components may be performed in any order, and all the components may be added simultaneously or sequentially.
When the polymerization initiator (C) is used, the operation, mixing, and curing pretreatment of the above components may be performed under a condition that the polymerization initiator (C) does not act before the curing treatment, such as under illumination with a filter for eliminating an absorption wavelength at which the photopolymerization initiator is decomposed, or under a temperature at which the active energy ray is not irradiated or the thermal polymerization initiator acts.
[ use of active energy ray-curable composition ]
The cured product can be obtained by irradiating the composition of the present invention with an active energy ray.
The active energy ray used for curing means visible light; ultraviolet rays; microwave; a high frequency wave; ionizing radiation such as electron beam, X-ray, α -ray, β -ray, and γ -ray, and any energy type may be used if it can release a substance that initiates polymerization. For example, in the case of ultraviolet to visible light, a high-pressure mercury lamp, a metal halide lamp, a laser, an LED light, sunlight, or the like can be used. Ultraviolet rays are preferred because they can be used inexpensively.
As the light source for curing the composition by ultraviolet rays, various light sources can be used, and examples thereof include black light, UV-LED lamps, high-pressure mercury lamps, pressurized mercury lamps, metal halide lamps, xenon lamps, and electrodeless discharge lamps. The black light is a lamp in which a near ultraviolet light-emitting phosphor is coated on a special outer tube glass that blocks visible light and ultraviolet light of 300nm or less, and emits only near ultraviolet light of 300 to 430nm (near peak 350 nm). The UV-LED lamp is a lamp using a light emitting diode that emits ultraviolet light. Among these light sources, black light, LED lamps (UV-LED lamps) and high-pressure mercury lamps are safe and economical, and are therefore preferable.
The irradiation amount of the active energy ray may be an amount sufficient for curing, and may be selected according to the composition, the amount used, the thickness, the shape of the formed cured product, and the like of the composition. For example, when ultraviolet rays are irradiated to a coating layer formed by coating the composition, it is preferable to use 200 to 5,000mJ/cm2More preferably 1,000 to 3,000mJ/cm2The amount of exposure.
When the composition of the present invention is applied to a substrate to form a coating layer, conventionally known methods can be suitably used as a coating (application) method, and examples thereof include a natural coater, a curtain coater, a comma coater, a gravure coater, a micro gravure coater, a die coater, a curtain coater, spraying, dipping, a kiss roll, a squeeze roll, an inverted roll, an air knife, a knife-belt coater, a float knife, a roller-over-roll, and a knife-on-blanket.
By curing the composition into a sheet form, a sheet can be obtained. The sheet may contain other components than the composition as necessary.
The thickness of the sheet may be set as appropriate depending on the application, but is preferably 0.1 to 10mm, and more preferably 0.3 to 8mm from the viewpoint of molding. The cured product and the sheet can be suitably used as a shock absorbing material or a vibration absorbing material.
The impact absorber and the vibration absorber can be obtained by curing the aforementioned composition. The light source, the irradiation amount, and the coating (application) method in curing the aforementioned composition are as described above.
The impact absorbing material and the vibration absorbing material of the present invention may contain other components as needed, or may be laminated with other materials. For example, it can be used in combination with building materials such as wood, concrete, mortar, etc.; resin materials such as thermoplastic resins such as PET (polyethylene terephthalate), PC (polycarbonate), and PMMA (polymethyl methacrylate resin) and thermosetting resins such as epoxy resins, phenol resins, and unsaturated polyester resins; glass; and a metal laminate of iron, aluminum, copper, or the like. Examples thereof include (a) a mortar-cured product laminate obtained by applying the composition of the present invention to a mortar material and curing the composition by irradiation with UV light, (b) a tape obtained by curing the composition of the present invention in a sheet form and applying an adhesive layer to one or both surfaces of the sheet, (c) a laminate film obtained by applying the composition of the present invention to a film made of a thermoplastic resin such as PET, PC or PMMA and curing the film, (d) a laminate film obtained by laminating a thermoplastic resin layer/a cured product layer obtained from the composition of the present invention/a thermoplastic resin layer in this order, (e) a laminate film obtained by laminating a thermoplastic resin layer/an adhesive layer/a cured product layer obtained from the composition of the present invention/a thermoplastic resin layer in this order, (f) a laminate film obtained by laminating a thermoplastic resin layer/an adhesive layer/a cured product layer obtained from the composition of the present invention/an adhesive layer/a thermoplastic resin layer A laminated film laminated in this order, (g) a glass laminate obtained by applying the composition of the present invention to a glass and irradiating the glass with UV light, (h) a glass laminate obtained by laminating glass/a cured product layer obtained from the composition of the present invention/glass in this order, (i) a glass-resin laminate obtained by applying the composition of the present invention between a thermoplastic resin or a thermosetting resin and glass and irradiating the glass with UV light, (j) a coated material obtained by applying the composition of the present invention to a material having a three-dimensional shape and curing the composition, and (k) a cured product obtained from the composition of the present invention is printed; and the like. By laminating as in the above example, the impact absorbability and the vibration absorbability are improved as compared with the case of using a cured product alone.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
< Compound >
The compounds used in examples 1 to 11 and comparative examples 1 to 4 were the following compounds.
1. Compound (A) and (meth) acryloyloxy group-containing compound (a)
The (meth) acryloyloxy group-containing compound means at least one of a methacryloyloxy group-containing compound and an acryloyloxy group-containing compound. Hereinafter, the compound (a) containing a (meth) acryloyloxy group may be referred to as a compound (a).
1) DAP: diallyl phthalate
ダイソー trade name "ダイソー ダ ッ プ モノマー", molecular weight 246, number of allyl groups 2
2) isoDAP: diallyl isophthalate
ダイソー trade name "ダイソー ダ ッ プ 100 モノマー", molecular weight 246, number of allyl groups 2
3) DATP: diallyl terephthalate
Showa Denko K.K., molecular weight 246, number of allyl groups 2
4) P-30: pentaerythritol tetraallyl ether
ダイソー trade name "ネオアリル P-30", molecular weight 256, number of allyl groups 3
5) TMPTA: trimethylolpropane triacrylate
Molecular weight 296 and acryloyl oxygen number 3 manufactured by Kyoeisha chemical Co., Ltd
2. Compound (B) and a mercapto-containing compound (B) other than compound (B)
The mercapto group-containing compound (B) other than the compound (B) may be hereinafter referred to as a compound (B).
1) PE 1: pentaerythritol-tetra (3-mercaptobutyrate)
Showa Denko K.K., trade name "カレンス゛ MT (trademark) PE 1", molecular weight 545, mercapto number 4
2) TPMB (TPMB): trimethylolpropane tris (3-mercaptobutyrate)
Showa Denko K.K., trade name "TPMB", molecular weight 441, mercapto number 3
3) And (3) PEMP: pentaerythritol-tetrakis (3-mercaptopropionate)
Made by Sakai chemical corporation, trade name "PEMP", molecular weight 489, mercapto number 4
3. Polymerization initiator (C)
1-hydroxy-cyclohexyl-phenyl ketones
Product name "Irgacure 184" manufactured by BASF corporation "
4. Polymerization inhibitor
Methylhydroquinone, manufactured by KANTO CHEMICAL CO., LTD
5. Urethane acrylate
EBECRYL 230: ダイセル & オルネクス K, having an acryloyloxy group of 2
UA-160 TM: acryloxy number 2, manufactured by Mitsumura chemical Co., Ltd
6. Inorganic filler
アエロジル (trade mark) RX 200: manufactured by Nippon Kogyo アエロジル K
< examples 1 to 11 and comparative examples 1 to 4>
An active energy ray-curable composition was prepared by mixing a compound (a) or a compound (a), a compound (B) or a compound (B), a polymerization initiator (C), a polymerization inhibitor, and if necessary, a urethane (meth) acrylate and an inorganic filler at the mass ratio shown in table 1. Then, on the glass plateA polyethylene terephthalate (PET) film was placed on the substrate, a silicone rubber spacer was interposed between the films, the obtained active energy ray-curable composition was injected so that the thickness after curing was 5mm, and the PET film and a glass plate were placed on the composition. Using a conveyor belt type UV irradiation apparatus ECS-4011GX (high pressure mercury lamp) manufactured by アイグラフィックス Co., Ltd., irradiation of 2J/cm2The UV light of (1) was adjusted to obtain a cured product having a thickness of 5 mm. In addition, similarly, a cured product having a thickness of 1mm was obtained by irradiating UV light through a silicone rubber spacer so that the cured thickness was 1 mm.
The following evaluation was performed using the obtained cured product.
(1) Evaluation of impact absorbability
The obtained cured product having a thickness of 5mm was left to stand on a horizontal iron plate, 60g of a steel ball was allowed to freely fall from a height of 60cm from the surface of the cured product, and the height of spring back after collision with the cured product was measured. A was evaluated as A when the spring height was less than 7.5cm, B was evaluated as B when the spring height was 7.5cm or more and less than 15cm, and C was evaluated as C when the spring height was 15cm or more.
(2) Evaluation of vibration absorbability
Using a test piece obtained by cutting the obtained cured product having a thickness of 1mm into pieces having a size of 10 mm. times.40 mm, the value of tan. delta. and the temperature at which the peak of tan. delta. can be obtained were measured under the conditions of a measurement frequency of 10Hz and a temperature rise rate of 3 ℃/min by using a brake viscoelasticity tester DMS6100 manufactured by エスアイアイ & ナノテクノロジー. Since the greater the value of tan δ, the more excellent the vibration absorbability, it is effective to have a peak at around room temperature in order to express the vibration absorbability at around room temperature. Therefore, the peak top of tan δ and the temperature range in which the peak top of tan δ can be obtained are evaluated as follows.
The peak top of tan δ was designated as a, the peak top was designated as B when the peak top was 2 or more, the peak top was designated as 0.9 or more and less than 2, and the peak top was designated as C when the peak top was less than 0.9.
A indicates that the temperature range in which the peak top of tan. delta. is obtained is 5 degrees or more and less than 30 degrees, B indicates that the temperature range is-5 degrees or more and less than 5 degrees, or 30 degrees or more and less than 40 degrees, and C indicates that the temperature range is less than-5 degrees or 40 degrees or more.
(3) Evaluation of bad smell
The odor of the resulting cured product was smelled at a distance of 5cm, and a case where 7 or less out of 10 subjects felt bad odor was evaluated as a, and a case where 8 or more out of 10 subjects felt bad odor was evaluated as C.
[ Table 1]
In table 1, the unit of the numerical value of each component of the composition is part by mass. The functional group ratio represents (the number of allyl groups of the compound (a)/(the number of mercapto groups of the compound (B) or the compound (B)), or (the number of acryloyloxy groups of the compound (a)/(the number of mercapto groups of the compound (B) or the compound (B)). In the case of using the compound (A) and the urethane (meth) acrylate in combination, it represents { (the number of allyl groups of the compound (A) + (the number of (meth) acryloyloxy groups of the urethane (meth) acrylate) }/(the number of mercapto groups of the compound (B) or the compound (B)).
As is clear from the results in Table 1, examples 1 to 11 are superior in impact absorbability, vibration absorbability and bad smell to those of comparative examples.
< examples 12 to 22 and comparative examples 5 to 8>
An active energy ray-curable composition was prepared by mixing a compound (a) or a compound (a), a compound (B) or a compound (B), a polymerization initiator (C), if necessary, a urethane (meth) acrylate, and an inorganic filler, each in the type shown in table 2, at the mass ratio shown in table 2.
The following evaluation was performed using the obtained active energy ray-curable composition.
(4) Evaluation of storage stability
The resulting composition was left at room temperature (23 ℃ C.), and the non-homogenization and gelation were visually confirmed. By setting the composition excluding the polymerization inhibitor, the difference in storage stability can be evaluated in a short time. The cases of no homogenization and gelation for 10 days or longer were evaluated as A, and the cases of homogenization and gelation were evaluated as C.
[ Table 2]
The unit and the ratio of functional groups in Table 2 are the same as those in Table 1.
As is clear from the results in Table 2, the storage stability of examples 12 to 22 was superior to that of comparative example.
Industrial applicability
The active energy ray-curable composition of the present invention can provide a cured product having excellent storage stability, less unpleasant odor, and excellent impact absorption and vibration absorption properties, and the cured product obtained from the active energy ray-curable composition is particularly suitable for use as an impact absorbing material and a vibration absorbing material.
Claims (8)
1. An active energy ray-curable composition comprising:
a compound (A) having 2 or more allyl groups,
compound (B), and
a polymerization initiator (C),
the compound (A) is diallyl phthalate,
the compound (B) is pentaerythritol tetrakis (3-mercaptobutyrate),
the ratio of the number of allyl groups of the compound (A) to the number of mercapto groups of the compound (B) in the composition is in the range of 30:70 to 70:30, and the active energy ray-curable composition contains 0.01 to 10 parts by mass of the polymerization initiator (C) per 100 parts by mass of the total of the compound (A) and the compound (B).
2. The active energy ray-curable composition according to claim 1, further comprising a urethane (meth) acrylate.
3. The active energy ray-curable composition according to claim 2, wherein the ratio of the total number of allyl groups of the compound (A) and (meth) acryloyloxy groups of the urethane (meth) acrylate to the number of mercapto groups of the compound (B) is in the range of 30:70 to 70:30, and the active energy ray-curable composition contains 0.01 to 10 parts by mass of the polymerization initiator (C) per 100 parts by mass of the total of the compound (A), the urethane (meth) acrylate and the compound (B).
4. The active energy ray-curable composition according to any one of claims 1 to 3, further comprising an inorganic filler.
5. A cured product obtained by curing the active energy ray-curable composition according to any one of claims 1 to 4.
6. An impact absorbing material obtained by curing the active energy ray-curable composition according to any one of claims 1 to 4.
7. A vibration absorber obtained by curing the active energy ray-curable composition according to any one of claims 1 to 4.
8. A sheet obtained by curing the active energy ray-curable composition according to any one of claims 1 to 3.
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| PCT/JP2015/085606 WO2016104388A1 (en) | 2014-12-22 | 2015-12-21 | Active energy ray-curable composition and use of same |
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| JP2017206572A (en) * | 2016-05-16 | 2017-11-24 | 株式会社大阪ソーダ | Photocurable composition, and cured product thereof |
| CN111263777B (en) * | 2017-10-31 | 2023-03-28 | 阿科玛法国公司 | Curable composition containing thiol compound |
| WO2019224699A1 (en) | 2018-05-22 | 2019-11-28 | 3M Innovative Properties Company | Process of processing a radiation-curable thiolen based composition with additive-manufacturing technology |
| EP3853291A1 (en) * | 2018-09-19 | 2021-07-28 | 3M Innovative Properties Company | Composition including a polythiol, an unsaturated compound, and a filler and a two-part composition made therefrom |
| JP7041215B2 (en) * | 2019-11-07 | 2022-03-23 | 三菱ケミカルインフラテック株式会社 | Curable compositions, moldings and laminates |
| CN112778462A (en) * | 2019-11-07 | 2021-05-11 | 株式会社菱晃 | Curable composition, molded article, and laminate |
| TWI767248B (en) | 2020-06-10 | 2022-06-11 | 新應材股份有限公司 | White photosensitive resin composition, white spacer, light conversion layer, and light emitting device |
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| WO2009011211A1 (en) * | 2007-07-13 | 2009-01-22 | Showa Denko K.K. | Curable composition and cured product thereof |
| JP5595709B2 (en) * | 2009-10-23 | 2014-09-24 | 電気化学工業株式会社 | Resin composition |
| JP2011219727A (en) * | 2010-03-24 | 2011-11-04 | Sekisui Chem Co Ltd | Ultraviolet-curing resin composition, transparency material and transparent composite sheet |
| JP5647533B2 (en) * | 2010-06-07 | 2014-12-24 | 昭和電工株式会社 | Stabilized polyene-polythiol curable resin composition |
| CN103261280B (en) * | 2010-12-16 | 2016-01-20 | 日立化成株式会社 | The display of Photocurable resin composition, image device, its manufacture method |
| JP5926598B2 (en) * | 2012-04-11 | 2016-05-25 | 株式会社カネカ | Photocurable composition |
| JP2014143195A (en) * | 2012-12-27 | 2014-08-07 | Sekisui Chem Co Ltd | Vapor deposition material for protecting organic thin film element, resin protective film and organic optical device |
| CN105121513B (en) * | 2013-06-17 | 2017-05-10 | 昭和电工株式会社 | Ene-thiol-type curable composition and cured product thereof |
| CN105764885B (en) * | 2013-11-25 | 2018-11-09 | 富士胶片和光纯药株式会社 | The production method of acid and free-radical generating agent and acid and free radical |
| JP2015129074A (en) * | 2014-01-09 | 2015-07-16 | 昭和電工株式会社 | Composition for reinforcing glass end face, glass plate material, and method of producing glass plate material |
| JP6373181B2 (en) * | 2014-12-10 | 2018-08-15 | 日本化薬株式会社 | Liquid crystal sealant and liquid crystal display cell using the same |
| JP2016117833A (en) * | 2014-12-22 | 2016-06-30 | 昭和電工株式会社 | Photocurable composition and use thereof |
| CN107001632B (en) * | 2014-12-22 | 2020-06-19 | 昭和电工株式会社 | Active energy ray-curable composition and use thereof |
| JP2016117832A (en) * | 2014-12-22 | 2016-06-30 | 昭和電工株式会社 | Photocurable composition and use thereof |
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| CN102558459A (en) * | 2010-11-25 | 2012-07-11 | 株式会社日本触媒 | Optical ultraviolet curable resin composition, cured product and display device |
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Effective date of registration: 20230518 Address after: Tokyo, Japan Patentee after: Showa electrical materials Co.,Ltd. Address before: Tokyo, Japan Patentee before: SHOWA DENKO Kabushiki Kaisha |