JPWO2016104388A1 - Active energy ray-curable composition and use thereof - Google Patents

Abstract

[PROBLEMS] To provide an active energy ray-curable composition excellent in storage stability, which gives a cured product with little odor and excellent in shock absorption and vibration absorption, and its use. [Solution] Compound (A) having two or more allyl groups and at least one compound selected from pentaerythritol-tetrakis- (3-mercaptobutyrate) and trimethylolpropane-tris (3-mercaptobutyrate) ( An active energy ray-curable composition comprising B) and a polymerization initiator (C).

Description

  The present invention relates to an active energy ray-curable composition and use thereof.

  In the ene-thiol photocurable resin composition that is a radical polymerization type photocurable system, active thiyl radicals are regenerated even if radical deactivation occurs due to oxygen. Therefore, the composition has no polymerization inhibition due to oxygen as seen in acrylic materials, can reduce the amount of photopolymerization initiator used, has a small volume shrinkage at the time of curing, a few seconds from the start of polymerization Since it has an advantage that it can be cured in a short time of several minutes and a cured product having a thickness of 1 mm or more can be produced, it has attracted attention as a photo-curing material (Non-patent Document 1).

  As this ene-thiol-based photocurable resin composition, for example, Patent Document 1 contains polyene, polythiol, and a compound having a bromine-substituted aromatic ring having a specific structure, and includes polyene and polythiol. A photocurable resin composition having a mass ratio of 49: 1 to 1:49 is disclosed. Patent Document 2 discloses an ene-thiol photocurable resin composition containing a polyene compound and a (poly) thiol monomer composed of a reaction product of a polyvalent amine compound and a mercaptocarboxylic acid compound. It is disclosed.

  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. In addition, the technique disclosed in Patent Document 2 has no inhibition of polymerization by oxygen, can be cured in a short time, has a small volume shrinkage, can reduce the amount of photopolymerization initiator used, and has significantly improved moisture resistance. It is a technology that gives an improved cured product. However, Patent Documents 1 and 2 do not mention anything about the impact absorbability and vibration absorbability of the cured product.

  Patent Document 3 is characterized by comprising a cured product of a polymerizable composition containing at least one of diallyl phthalate, diallyl isophthalate and diallyl terephthalate and pentaerythritol tetra (3-mercaptopropionate). A transparent resin is disclosed. The technique disclosed in Patent Document 3 is a technique that provides a transparent resin excellent in coating property, adhesiveness, durability, and impact resistance. However, Patent Document 3 does not mention any odor generated from pentaerythritol tetra (3-mercaptopropionate).

Japanese Patent No. 4034098 JP 2007-70417 A JP-A-11-71458

“Prospects for UV / EB Curing Technology”, CMC Publishing, 2002, p. 39-50

  The present invention has been made in view of the above problems, and provides an active energy ray-curable composition excellent in storage stability, which gives a cured product with less odor and excellent impact absorption and vibration absorption, Another object of the present invention is to provide a cured product, a shock absorbing material, a vibration absorbing material and a sheet material obtained from the active energy ray-curable composition.

  As a result of intensive studies, the present inventors have determined from compound (A) having two or more allyl groups, pentaerythritol-tetrakis- (3-mercaptobutyrate) and trimethylolpropane-tris (3-mercaptobutyrate). By using an active energy ray-curable composition containing at least one selected compound (B) and a polymerization initiator (C), it was excellent in impact absorption, vibration absorption, etc. after irradiation with active energy rays. The inventors have found that a cured product suitable as a shock absorbing material and a vibration absorbing material can be obtained, and have completed the following present invention.

The present invention includes the following active energy ray-curable compositions (1) to (8), a cured product (9), a shock absorber (10), a vibration absorber (11), and a sheet (12). Regarding materials.
(1) Compound (A) having two or more allyl groups and at least one compound selected from pentaerythritol-tetrakis- (3-mercaptobutyrate) and trimethylolpropane-tris (3-mercaptobutyrate) (B ) And a polymerization initiator (C).
(2) The active energy ray-curable composition according to (1), wherein the compound (A) further has an aromatic ring.
(3) The active energy ray-curable composition according to (1), wherein the compound (A) has two allyl groups.
(4) The active energy ray-curable composition according to (1), wherein the compound (A) is at least one selected from diallyl phthalate, diallyl isophthalate, and diallyl terephthalate.
(5) The ratio of the number of allyl groups of the compound (A) and the number of mercapto groups of the compound (B) in the composition is in the range of 30:70 to 70:30, and the compound (A) and The active energy ray-curable composition according to any one of (1) to (4), containing 0.01 to 10 parts by mass of a polymerization initiator (C) with respect to 100 parts by mass in total with the compound (B). object.
(6) The active energy ray-curable composition according to any one of (1) to (5), further comprising urethane (meth) acrylate.
(7) The ratio of the total number of (meth) acryloyloxy groups of the allyl group and urethane (meth) acrylate of the compound (A) in the composition to the number of mercapto groups of the compound (B) is 30:70 to 70. : In the range of 30, the polymerization initiator (C) is 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass in total of the compound (A), the urethane (meth) acrylate, and the compound (B). The active energy ray-curable composition according to (6).
(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 absorber obtained by curing the active energy ray-curable composition according to any one of (1) to (8).
(11) A vibration absorber in which the active energy ray-curable composition according to any one of (1) to (7) is cured.
(12) A sheet material obtained by curing the active energy ray-curable composition according to any one of (1) to (7).

  In the present invention, an active energy ray-curable composition excellent in storage stability that gives a cured product with less odor and excellent shock absorption and vibration absorption properties, and obtained from the active energy ray-curable composition A cured product, a shock absorbing material, a vibration absorbing material, and a sheet material can be provided.

  The active energy ray-curable composition of the present invention (hereinafter also simply referred to as “the composition of the present invention”) includes a compound (A) having two or more allyl groups, pentaerythritol-tetrakis- (3-mercaptobutyrate). ) And trimethylolpropane-tris (3-mercaptobutyrate) and at least one compound (B), and a polymerization initiator (C).

[Composition ingredients]
Hereinafter, the component which comprises the composition of this invention is demonstrated.

<Compound (A)>
In the present invention, since the compound (A) contains two or more allyl groups in the molecule, the impact absorption and vibration absorption 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. In addition, the molecular weight of the oligomer or polymer in this application is a polystyrene (PS) conversion value measured by the gel permeation chromatography method (GPC method), and is a number average molecular weight unless otherwise specified.

  When the compound (A) is a monomer, the compound (A) includes a compound (a-1) having an aromatic ring, an alicyclic ring or a heterocyclic ring in the molecule, an acyclic compound (a-2), Is mentioned.

  Examples of the compound (a-1) include diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl trimellitic acid, tetraallyl pyromellitic acid, bisphenol A allyl ether, diallyl 1,2-cyclohexanedicarboxylate, 1,3-cyclohexane. Examples include diallyl dicarboxylate, triallyl isocyanurate, and triallyl cyanurate. Of these, compounds having an aromatic ring such as diallyl phthalate, diallyl isophthalate, and diallyl terephthalate are preferable, and diallyl phthalate is particularly preferable from the viewpoint of shock absorption and vibration absorption.

  Examples of the compound (a-2) include tetraallyl 1,2,3,4-butanetetracarboxylate, diallyl succinate, diallyl glutarate, diallyl adipate, diallyl sebacate, diallyl dimer, diallyl hydrogenated dimer, , 12-dodecanedioic acid diallyl, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, trimethylolpropane triallyl ether, pentaerythritol tetraallyl ether, and the like. Especially, pentaerythritol tetraallyl ether has shock absorption and vibration absorption. From the viewpoint of sex.

  When the compound (A) is an oligomer, an allyl ester resin is preferably used. Specific examples of the allyl ester resin include oligomers having structures represented by the following formulas (a-3), (a-4) and (a-5).

In formula (a-3), c is an integer of 1 to 5, more preferably 1 to 3, and most preferably 1. R ³ may have an alkyl group having 1 to 5 carbon atoms (preferably 1 to 3, more preferably 1) as a substituent, and 1 to 10 carbon atoms (preferably 1 to 5, more preferably 2 to 3 carbon atoms). ) Alkylene group. The n R ^{3 s} may be different from each other.

  X is a phenylene group or cyclohexylene group which may have an alkyl group having 1 to 4 carbon atoms as a substituent, preferably a phenylene group or cyclohexylene group having no substituent. (N + 1) Xs may be different from each other.

  Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group.

  The position at which the phenylene group or 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 the 1,4-position is preferred.

  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. preferable.

In formula (a-4), c is the same as described above, and X is the same as described above. (2m + 1) Xs may be different from each other. R ⁴ is an alkyl group having 1 to ⁴ carbon atoms (specific examples are the same as the specific examples of the substituent in X) or a group represented by the following formula (a-4 ′). The m R ^{4 s} may be different from each other.

  In formula (a-4 ′), c and X are the same as described above.

  m is an integer of 3 to 70, preferably 4 to 60, and 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 formula (a-5), c and X are as defined above, R ³ is independently the same as defined above, p is an integer of 1 to 10, preferably 1 to 9, and more preferably. Is 1-8. q is an integer of 5-50, preferably 5-45, more preferably 5-40. (Q + 1) X may be different from each other, and [(p + 1) × q] R ³ may 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.

  In addition to the allyl ester resin, specific examples when the compound (A) is an oligomer include polyene compounds derived from substituted or unsubstituted allyl alcohol, polyethylene glycol bisallyl carbonate, and the like.

  When the compound (A) is a polymer, there is no particular limitation as long as two or more allyl groups are introduced into the polymer skeleton, and known compounds 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.

  As the compound (A), one type may be used alone, or two or more types may be used in combination at any ratio.

  However, it is desirable not to use diallyl 1,4-cyclohexanedicarboxylate as the compound (A).

<Compound (B)>
All of the compounds (B) used in the present invention have a secondary mercapto group. The reason why the secondary mercapto group is suitable as compared with the primary mercapto group is that the composition has excellent storage stability and odor. Is very small.

  Pentaerythritol-tetrakis- (3-mercaptobutyrate) is available from Showa Denko KK under the product name Karenz MT (trademark) PE1, and trimethylolpropane-tris (3-mercaptobutyrate) is It is available from Showa Denko Co., Ltd. under the product name TPMB.

<Polymerization initiator (C)>
Although there exist a photoinitiator and a thermal-polymerization initiator in a polymerization initiator (C), if it is a compound which accelerates | stimulates the start of a polymerization of a compound (A), there will be no restriction | limiting in particular.

  The photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals that contribute to the initiation of radical polymerization upon irradiation with active energy rays such as near infrared rays, visible rays, and ultraviolet rays.

  Examples of the photopolymerization initiator include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1,2-hydroxy-2-methyl-1-phenylpropane-1- ON, α-hydroxycyclohexyl phenyl ketone, 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, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxy Benzopheno 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, benzophenone tetracarboxylic acid or tetramethyl ester thereof, 4, 4'-bis (dialkylamino) benzophenones (for example, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (dicyclohexylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4 '-Bis (dihydroxyethylamino) benzophenone), 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylamino Noacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, fluorenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (Dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholino-1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (eg benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl) Ether, benzoin iso Tilether, benzoin phenyl ether, benzyldimethyl 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, benzoyldi- (2,6-dimethylphenyl) phosphonate, 1- [4- (phenylthio) phenyl] -1, -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-cyclopentylpropanone-1- (O-acetyloxime), 1- [4- (phenylthio) phenyl] -3 -Cyclopentylpropane-1,2-dione-2- (O-benzoyloxime). Examples of 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) phenyl phosphite 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.

  Moreover, a metallocene compound can also be used as a photopolymerization initiator. As the metallocene compound, the transition metal represented by Fe, Ti, V, Cr, Mn, Co, Ni, Mo, Ru, Rh, Lu, Ta, W, Os, Ir, etc. can be used as the metallocene compound, An example is bis (η5-2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (pyrrol-1-yl) phenyl] titanium.

  In particular, 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are preferable from the viewpoint of the stability of the active energy ray-curable composition after the addition of the photopolymerization initiator. The former is available from BASF under the product name Irgacure 184, 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 physical properties such as impact resistance of the cured product, and known ones can be used. The thermal polymerization initiator used in the present invention is preferably one that is soluble in other components present in the composition to be cured and generates free radicals at 30 ° C to 120 ° C.

  Specific examples of the thermal polymerization initiator include diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, t-butyl perbenzoate, and the like. However, it is not limited to these. 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 with respect to a total of 100 parts by mass of the compound (A) and the compound (B). 5-5.0 mass parts is more preferable.

  Moreover, when urethane (meth) acrylate is included in the composition of this invention, content of a polymerization initiator (C) is 100 in total of a compound (A), urethane (meth) acrylate, and a compound (B). 0.01-10 mass parts is preferable with respect to mass parts, and 0.5-5.0 mass parts is more preferable.

  A polymerization initiator (C) can be used individually by 1 type, or can also be used in combination of 2 or more type by arbitrary ratios.

<Urethane (meth) acrylate>
The active energy ray-curable composition of the present invention may contain urethane (meth) acrylate as long as the object of the present invention is not impaired. In this specification, “urethane (meth) acrylate” is a general term for urethane acrylate and urethane methacrylate.

  The urethane (meth) acrylate is not particularly limited, but those having a flexible skeleton, that is, those having a polyether skeleton or a polyester skeleton are preferable from the viewpoint of sheet moldability. As said urethane (meth) acrylate, brand name UA-160TM, UA-122P, UA-290TM, UA-1013P, U-200PA (made by Shin-Nakamura Chemical Co., Ltd.), EBECRYL230, 270, 284, 8411, 8413, 8800 , 8804, 8413, 8402, KRM7735, 8296 (manufactured by Daicel Ornex Co., Ltd.), UV-3300B, 3310B, 3700B, 6640B (Nippon Synthetic Chemical Industry Co., Ltd.) and the like. More preferable from the viewpoint.

  Urethane (meth) acrylate can be used individually by 1 type, and can also be used combining 2 or more types by arbitrary ratios.

  Although the compounding quantity of urethane (meth) acrylate is not specifically limited, 10-60 mass% of the total mass of the said composition is preferable from a viewpoint of a moldability, and 20-40 mass% is more preferable.

<Inorganic filler>
The active energy ray-curable composition of the present invention may contain an inorganic filler as long as the object of the present invention is not impaired.

The inorganic filler used in the present invention is not particularly limited as long as it is dispersed in the compound (A) and the compound (B) to form a paste. Examples of such inorganic fillers include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), and silicon nitride (Si). ₃ N ₄ ), 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 ₂ O _3), spinel _{(MgO · Al 2 O 3)} , mullite _{(3Al 2 O 3 · 2SiO 2} ), cordierite _{(2MgO · 2Al 2 O 3 /} 5SiO 2), talc (3MgO · 4SiO ₂ · H ₂ O), aluminum titanate (TiO ₂ —Al ₂ O ₃ ), yttria-containing zirconia (Y ₂ O ₃ —ZrO ₂ ), barium silicate (BaO · 8Si) O ₂ ), boron nitride (BN), calcium carbonate (CaCO ₃ ), calcium sulfate (CaSO ₄ ), zinc oxide (ZnO), magnesium titanate (MgO · TiO ₂ ), barium sulfate (BaSO ₄ ), organic bentonite, It is possible to use fiber reinforcing materials such as carbon (C), glass powder, synthetic mica, boron nitride fiber, powders obtained by blending silicone oil into an inorganic carrier, and powdered silicone resins or silicone rubbers. These can be used alone or in combination of two or more.

  Of the inorganic fillers exemplified above, fine particle silica is preferably used from the viewpoint of viscosity adjustment and sheet formability, and is available from Nippon Aerosil Co., Ltd. under the trade name Aerosil (trademark). Aerosil (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, R976, R976S, RX300, R812, R812S, RY300, R106, 380, P25, T805, P90, NKT90, AluC, AluC805, etc. can be used. RX200 is more preferable from the viewpoint of dispersibility.

  Although the compounding quantity of an inorganic filler is not specifically limited, Less than 10 mass parts is good with respect to a total of 100 mass parts of a compound (A), a compound (B), and a urethane (meth) acrylate, Preferably 2-6 mass parts, More preferably, 0.1 to 5 parts by mass is sufficient from the viewpoint of moldability.

<Polymerization inhibitor>
In the active energy ray-curable composition of the present invention, a polymerization inhibitor may be added as necessary in order to improve the storage stability of the composition.

  As a polymerization inhibitor, 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, tertiary butylhydroquinone, 4-methoxyphenol, N-nitroso-N-phenylhydroxyamine aluminum, etc. Is mentioned. You may use these individually or in combination of 2 or more types. In particular, methylhydroquinone, pyrogallol, and tertiary butylhydroquinone are preferable from the viewpoint of storage stability of the active energy ray-curable composition.

  Although the compounding quantity of a polymerization inhibitor is not specifically limited, Less than 0.1 mass part is good with respect to a total of 100 mass parts of a compound (A) and a compound (B), Preferably 0.0001-0.05 mass part However, it may be from the viewpoint of storage stability.

<Other ingredients>
The active energy ray-curable composition of the present invention includes a urethane (meth) acrylate, an inorganic filler, and a polymerization as necessary in addition to the above-described compound (A), compound (B), and polymerization initiator (C). At least one selected from inhibitors may be added, and other components may be contained as optional components within a range not impairing the object of the present invention. However, from the viewpoint of impact resistance and the like, it is preferable not to use a compound having an ethylenically unsaturated group and an isocyanate group in one molecule in the composition of the present invention. For example, you may mix | blend mercapto compounds other than a compound (B) in the range which does not impair the effect of invention. However, the compounding amount of the mercapto compound other than the compound (B) is preferably 20% by mass or less of the total mercapto compound from the viewpoint of maintaining impact absorption, transparency, low odor characteristics, and the like.

  The composition of the present invention can be used without a solvent or a solvent, but it is preferably used without a solvent.

  Examples of materials that are preferably added as other components include color materials such as carbon materials, pigments, and dyes.

  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. Moreover, the composition of this invention may contain organic pigments, such as red, green, and blue. Commercially available gel nails or UV craft pigments may be used. Examples of such pigments include Pikaace coloring 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 means a substance having solubility in a solvent or compatibility with a resin and a property of coloring the dissolved or compatible substance. Examples of the plastic dye include KP PLAST (KP Plas Red B, KP Plas Blue GR, KP Plas Yellow HK).

  You may use a color material individually or in combination of 2 or more types.

  The content of the coloring material in the composition of the present invention is not particularly limited. However, if the concentration is too high, the transmittance of the active energy rays may be lowered, and there is a possibility of causing poor curing. Therefore, the content of the coloring material is usually 60% by mass or less, preferably 0.0001 to 40% by mass in the composition.

  In addition to the colorant, the composition of the present invention includes, as necessary, other components: (a) a thermoplastic resin; (b) a deodorant; (c) a silane coupling agent and a titanium coupling agent. (D) Antioxidants such as hindered amines, hydroquinones, hindered phenols; (e) Ultraviolet absorbers such as benzophenones, benzotriazoles, salicylic acid esters, metal complex salts; f) Stabilizers such as metal soaps, inorganic and organic salts of heavy metals (such as zinc, tin, lead, cadmium, etc.), organic tin compounds; (g) acetic acid, acrylic acid, palmitic acid, oleic acid, mercaptocarboxylic acid, etc. PH adjusters such as aliphatic carboxylic acids, phenols, naphthols, benzoic acid, salicylic acid and other aromatic organic acids; (h) phthalic acid esters, phosphoric acid esters Plasticizers such as fatty acid esters, epoxidized soybean oil, castor oil, liquid paraffin alkyl polycyclic aromatic hydrocarbons; (i) waxes such as paraffin wax, microcrystalline wax, polymer wax, beeswax, whale wax low molecular weight polyolefin (J) Non-reactive diluents such as benzyl alcohol, tar, and pitumen; (k) Fillers such as acrylic resin powder and phenol resin powder; (l) Ethyl acetate, toluene, alcohols, ethers, ketones, etc. (M) foaming agent; (n) dehydrating agent such as silane coupling agent, monoisocyanate compound, carbodiimide compound; (o) antistatic agent; (p) antibacterial agent; (q) antifungal agent; (S) perfume; (t) flame retardant; (u) leveling agent; (v) sensitizer; and (w) dispersant. Can. These other components can be used alone or in combination of two or more at any ratio.

[Preparation of active energy ray-curable composition]
The composition of the present invention suitably comprises a compound (A), a compound (B), a polymerization initiator (C), and, if necessary, a urethane (meth) acrylate, an inorganic filler, a polymerization inhibitor and other components. Can be prepared.

  A compound (A), a compound (B), and a polymerization initiator (C) may be used individually by 1 type, respectively, and 2 or more types may be mixed and used for them.

  At this time, the ratio (a: b) of the number of allyl groups (a) of the compound (A) to the number of mercapto groups (b) of the compound (B) is preferably 30:70 to 70:30, more preferably Is mixed so as to be 40:60 to 60:40.

  In addition, when compounding urethane (meth) acrylate, the total number (a ′) of allyl group of compound (A) and (meth) acryloyloxy group of urethane (meth) acrylate and the number of mercapto groups of compound (B) It mixes so that ratio (a ': b) with (b) may become 30: 70-70: 30, more preferably 40: 60-60: 40.

The method for preparing the composition of the present invention is not particularly limited as long as it is a method capable of mixing and dispersing the above components, and examples thereof include the following methods.
(I) Each component is kneaded in a suitable container such as a glass beaker, a can, a plastic cup, or an aluminum cup with a stir bar or spatula.
(Ii) Each component is kneaded with a double helical ribbon blade, a gate blade, or the like.
(Iii) Each component is kneaded by a planetary mixer.
(Iv) Each component is kneaded by a bead mill.
(V) Each component is kneaded with three rolls.
(Vi) Each component is kneaded by an extruder type kneading extruder.
(Vii) Each component is kneaded by a rotating / revolving mixer.

  Addition and mixing of each component can be performed in an arbitrary order, and all components may be added simultaneously or sequentially.

  When using the polymerization initiator (C), the above components are handled, mixed, and pre-cured under illumination through a filter that eliminates the absorption wavelength at which the photopolymerization initiator decomposes or without active energy rays. Or under a temperature at which the polymerization initiator (C) does not act before the curing treatment, such as at a temperature below the temperature at which the thermal polymerization initiator acts.

[Use of active energy ray-curable composition]
A cured product is obtained by irradiating the composition of the present invention with active energy rays.

  Active energy rays used during curing include visible light; ultraviolet rays; microwaves; high frequencies; ionizing radiation such as electron beams, X-rays, α-rays, β-rays, and γ-rays. Any energy species can be used as long as it can be released. For example, in the case of ultraviolet to visible light, a high-pressure mercury lamp, a metal halide lamp, laser light, LED light, sunlight, or the like can be used. Ultraviolet light is preferable because an inexpensive device is used.

  Various light sources can be used for curing the composition with ultraviolet rays, such as black light, UV-LED lamp, high-pressure mercury lamp or pressurized mercury lamp, metal halide lamp, xenon lamp, electrodeless. A discharge lamp is mentioned. Here, the black light is a lamp that radiates only near-ultraviolet light of 300 to 430 nm (peak near 350 nm) by applying a near-ultraviolet phosphor on a special outer tube glass cut from visible light and ultraviolet light of 300 nm or less. It is. The UV-LED lamp is a lamp using a light emitting diode that emits ultraviolet rays. Among these light sources, a black light, an LED lamp (UV-LED lamp) and a high-pressure mercury lamp are preferable because they are safe and economical.

The irradiation amount of the active energy ray may be an amount sufficient for curing, and can be selected according to the composition of the composition, the amount used, the thickness, the shape of the cured product to be formed, and the like. For example, when irradiated with ultraviolet rays coated layer formed by coating the composition, preferably from exposure of 200~5,000mJ / cm ^2, more preferably the exposure of 1,000~3,000mJ / cm ² The quantity can be adopted.

  When the composition of the present invention is applied on a substrate to form a coating layer, a conventionally known method can be appropriately employed as a coating (coating) method, for example, a natural coater or a curtain flow coater. , Comma coater, gravure coater, micro gravure coater, die coater, curtain coater, spray, dip, kiss roll, squeeze roll, reverse roll, air blade, knife belt coater, floating knife, knife over roll, knife on blanket It is done.

  A sheet material is obtained by curing the composition into a sheet. The sheet material may contain other components other than the composition as necessary.

  The thickness of the sheet material may be appropriately set according to the use, but is preferably 0.1 to 10 mm, and more preferably 0.3 to 8 mm from the viewpoint of molding. The said hardened | cured material and the said sheet | seat material can be used conveniently also as an impact-absorbing material or a vibration-absorbing material.

  The shock absorbing material and the vibration absorbing material can be obtained by curing the composition. The light source, irradiation amount, and application (coating) method for curing the composition are as described above.

  The shock absorbing material and vibration absorbing material of the present invention may contain other components as needed, and may be laminated with other materials. For example, building materials such as wood, concrete, mortar materials; thermoplastic resins such as PET (polyethylene terephthalate), PC (polycarbonate), PMMA (polymethyl methacrylate resin), epoxy resins, phenol resins, unsaturated polyester resins, etc. It may be laminated with a resin material such as a thermosetting resin, glass, or a metal such as iron, aluminum, or copper. For example, (a) the composition of the present invention is applied to a mortar material and cured by irradiating UV light to obtain a mortar-cured product laminate. (B) the composition of the present invention is cured into a sheet. Then, an adhesive layer is applied on one or both sides to form a tape material. (C) The composition of the present invention is applied to a thin film made of a thermoplastic resin such as PET, PC, PMMA, and cured to obtain a laminated film. (D) A laminated film in which a cured resin layer / thermoplastic resin layer obtained from the thermoplastic resin layer / the composition of the present invention is laminated in this order, and (e) a thermoplastic resin layer / adhesive layer / the composition of the present invention. (F) Thermoplastic resin layer / adhesive layer / hardened product layer / adhesive layer / thermoplastic resin obtained from the composition of the present invention. A laminated film laminated in the order of layers, ( ) The composition of the present invention was applied to glass and cured by irradiating with UV light to form a glass laminate, (h) laminated in the order of glass / cured material layer / glass obtained from the composition of the present invention, (I) Applying the composition of the present invention between a thermoplastic resin or thermosetting resin and glass, and irradiating with UV light to form a laminate of glass and resin; (J) A material having a three-dimensional shape is coated with the composition of the present invention and cured to form a coating material, and (k) a cured product obtained from the composition of the present invention is printed. . By laminating as in the above example, the impact absorbability and the vibration absorbability are improved as compared with the case where the cured product is used alone.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

<Compound>
The compounds used in Examples 1 to 11 and Comparative Examples 1 to 4 are the following compounds.
1. Compound (A) and (meth) acryloyloxy group-containing compound (a)
However, the (meth) acryloyloxy group-containing compound means at least one of a methacryloyloxy group-containing compound and an acryloyloxy group-containing compound. Hereinafter, the (meth) acryloyloxy group-containing compound (a) may be referred to as the compound (a).

1) DAP: diallyl phthalate, manufactured by Daiso Co., Ltd., trade name “Daiso Dup Monomer”, molecular weight 246, allyl group number 2
2) isoDAP: diallyl isophthalate, manufactured by Daiso Co., Ltd., trade name “Daiso Dup 100 monomer”, molecular weight 246, allyl group number 2
3) DATP: diallyl terephthalate manufactured by Showa Denko KK, molecular weight 246, allyl group number 2
4) P-30: Pentaerythritol tetraallyl ether, manufactured by Daiso Corporation, trade name "Neoallyl P-30", molecular weight 256, allyl group number 3
5) TMPTA: trimethylolpropane triacrylate, manufactured by Kyoeisha Chemical Co., Ltd., molecular weight 296, number of acryloyloxy groups 3
2. Compound (B) and mercapto group-containing compound (b) other than compound (B)
Hereinafter, the mercapto group-containing compound (b) other than the compound (B) may be referred to as a compound (b).

1) PE1: pentaerythritol-tetrakis (3-mercaptobutyrate)
Showa Denko Co., Ltd., trade name “Karenz MT (trademark) PE1” molecular weight 545, mercapto group number 4
2) TPMB: trimethylolpropane-tris (3-mercaptobutyrate)
Product name “TPMB”, molecular weight 441, mercapto group number 3
3) PEMP: Pentaerythritol-tetrakis (3-mercaptopropitonate)
Product name “PEMP”, molecular weight 489, mercapto group number 4
3. Polymerization initiator (C)
1-hydroxy-cyclohexyl-phenylketone manufactured by BASF, trade name “Irgacure 184”
4). Polymerization inhibitor Methylhydroquinone, manufactured by Kanto Chemical Co., Inc. Urethane acrylate EBECRYL230: manufactured by Daicel Ornex Co., Ltd., acryloyloxy group number 2
UA-160TM: Shin-Nakamura Chemical Co., Ltd., acryloyloxy group number 2
6). Inorganic filler Aerosil (trademark) RX200: manufactured by Nippon Aerosil Co., Ltd. <Examples 1 to 11 and Comparative Examples 1 to 4>
Compound (A) or compound (a), compound (B) or compound (b) of type shown in Table 1, polymerization initiator (C), polymerization inhibitor, and urethane (meth) acrylate and inorganic as required Fillers were mixed at a mass ratio shown in Table 1 to obtain an active energy ray-curable composition. Next, a polyethylene terephthalate (PET) film is placed on a glass plate, a silicon rubber spacer is sandwiched, and the obtained active energy ray-curable composition is poured so that the thickness after curing is 5 mm. And a glass plate was placed. A cured product having a thickness of 5 mm was obtained by irradiating ² J / cm ² of UV light using a conveyor type UV irradiator ECS-4011GX (high pressure mercury lamp) manufactured by Eye Graphics. Similarly, a silicon rubber spacer was sandwiched so that the thickness after curing was 1 mm and irradiated with UV light to obtain a cured product having a thickness of 1 mm.

  The following evaluation was performed using the obtained hardened | cured material.

(1) Impact absorption evaluation The obtained cured product having a thickness of 5 mm is allowed to stand on a horizontal iron plate, and a 60 g steel ball is freely dropped from the surface of the cured product at a height of 60 cm. The height of the bounce was measured. A rebound height of less than 7.5 cm was evaluated as A, 7.5 cm or more and less than 15 cm as B, and 15 cm or more as C.

(2) Vibration absorption evaluation Using a test piece obtained by cutting the obtained 1 mm thick cured product into a size of 10 mm × 40 mm, a dynamic viscoelasticity tester DMS6100 manufactured by SII Nanotechnology Inc. has a measurement frequency of 10 Hz. Then, under the condition of a heating rate of 3 ° C./min, the value of tan δ and the temperature giving the peak top of tan δ were measured. The larger the value of tan δ, the better the vibration absorption. Therefore, it is effective to have a peak top near room temperature in order to develop vibration absorption near room temperature. Therefore, the temperature range giving the tan δ peak top and the tan δ peak top was evaluated as follows.

  The peak top of tan δ was defined as A when the peak was 2 or more, B when 0.9 or more and less than 2, and C when less than 0.9.

  A temperature range giving a peak top of tan δ is 5 to 30 degrees, A is -5 to 5 degrees, 30 to 40 degrees B, -5 degrees or 40 degrees or more The thing was set to C.

(3) Odor evaluation The odor of the resulting cured product is pinched at a distance of 5 cm, and the number of persons who feel the odor is 7 or less in 10 subjects, and 8 or more in 10 subjects have odor. The feeling was rated as C.

  In Table 1, the unit of the numerical value of each component of the composition is part by mass. The functional group number ratio is (number of allyl groups of compound (A)) / (number of mercapto groups of compound (B) or compound (b)) or (number of acryloyloxy groups of compound (a)) / (compound (B) or the number of mercapto groups of the compound (b). When compound (A) and urethane (meth) acrylate are used in combination, {(number of allyl groups of compound (A)) + (number of (meth) acryloyloxy groups of urethane (meth) acrylate)} / ( Compound (B) or the number of mercapto groups in compound (b).

  As is clear from the results in Table 1, Examples 1 to 11 were all superior to Comparative Examples in impact absorption, vibration absorption and odor.

<Examples 12 to 22 and Comparative Examples 5 to 8>
Table 2 shows the types of compounds (A) or compounds (a), compounds (B) or compounds (b), polymerization initiators (C), urethane (meth) acrylates, and inorganic fillers as required. The active energy ray-curable composition was mixed by the mass ratio shown.

  The following evaluation was performed using the obtained active energy ray-curable composition.

(4) Storage stability evaluation The obtained composition was allowed to stand at room temperature (23 ° C.), and disproportionation and gelation were visually confirmed. By using a composition excluding the polymerization inhibitor, the difference in storage stability can be evaluated in a short period of time. A sample that was not disproportionated or gelled for 10 days or more was evaluated as A, and a sample that was disproportionated or gelled was evaluated as C.

The unit and functional group number ratio in Table 2 is the same as in Table 1.
As is clear from the results in Table 2, Examples 12 to 22 were superior in storage stability to Comparative Examples.

The active energy ray-curable composition of the present invention provides a cured product having excellent storage stability, low odor, and excellent shock absorption and vibration absorption properties. A cured product obtained from the active energy ray-curable composition is: Especially, it is suitably used as a shock absorber and a vibration absorber.

Claims (12)

  A compound (A) having two or more allyl groups, at least one compound (B) selected from pentaerythritol-tetrakis- (3-mercaptobutyrate) and trimethylolpropane-tris (3-mercaptobutyrate); An active energy ray-curable composition comprising a polymerization initiator (C).   The active energy ray-curable composition according to claim 1, wherein the compound (A) further has an aromatic ring.   The active energy ray-curable composition according to claim 1, wherein the number of allyl groups of the compound (A) is two.   The active energy ray-curable composition according to claim 1, wherein the compound (A) is at least one selected from diallyl phthalate, diallyl isophthalate, and diallyl terephthalate.   The ratio of the number of allyl groups of the compound (A) and the number of mercapto groups of the compound (B) in the composition is in the range of 30:70 to 70:30, and the compound (A) and the compound (B The active energy ray-curable composition according to any one of claims 1 to 4, comprising 0.01 to 10 parts by mass of a polymerization initiator (C) with respect to 100 parts by mass in total.   Furthermore, the active energy ray curable composition in any one of Claims 1-5 containing urethane (meth) acrylate.   The ratio of the total number of allyl groups of the compound (A) and the (meth) acryloyloxy group of the urethane (meth) acrylate and the number of mercapto groups of the compound (B) in the composition is 30:70 to 70:30. In the range, 0.01 to 10 parts by mass of the polymerization initiator (C) is included with respect to 100 parts by mass in total of the compound (A), the urethane (meth) acrylate, and the compound (B). Item 7. The active energy ray-curable composition according to Item 6.   Furthermore, the active energy ray curable composition in any one of Claims 1-7 containing an inorganic filler.   Hardened | cured material which the active energy ray curable composition in any one of Claims 1-8 hardened | cured.   The impact-absorbing material which the active energy ray curable composition in any one of Claims 1-8 hardened | cured.   A vibration-absorbing material obtained by curing the active energy ray-curable composition according to claim 1.   The sheet | seat material which the active energy ray curable composition in any one of Claims 1-7 hardened | cured.