JPWO2017014039A1 - Active energy ray-curable composition and use thereof - Google Patents

Abstract

The present invention can provide a cured product having low odor, excellent transparency, excellent shock absorption, vibration absorption, and excellent storage stability, and its active energy. Provided are a cured product, a shock absorbing material, a vibration absorbing material, and a sheet material using the linear curable composition. In the present invention, component (A): diethylene glycol bis (allyl carbonate), component (B): all mercapto groups are bonded to secondary carbon atoms or tertiary carbon atoms, and two or more mercapto groups are present. It is an active energy ray curable composition containing the compound which has, 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 does not inhibit the polymerization due to oxygen as seen in acrylic materials, can reduce the amount of photopolymerization initiator used, has a small volume shrinkage during curing, and from several seconds after 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). Such a composition is desired to have high storage stability, and since it is a thiol type, odor is regarded as a problem. The cured product is required to have transparency, shock absorption, vibration absorption, and the like depending on the application.

  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 the mass of polyene and polythiol. A photocurable resin composition having a 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. Furthermore, Patent Document 4 discloses a transparent resin comprising a cured product of a polymerizable composition containing diethylene glycol bis (allyl carbonate) and pentaerythritol tetra (3-mercaptopropionate). . However, Patent Documents 3 and 4 do not mention anything about the odor generated from pentaerythritol tetra (3-mercaptopropionate) and describe turbidity (haze) which is an index of transparency. Absent.

Japanese Patent No. 4034098 JP 2007-70417 A Japanese Patent Laid-Open No. 11-71458 Japanese Patent Laid-Open No. 11-236498

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

  The present invention has been made in view of the above problems, can provide a cured product with low odor, excellent transparency, excellent shock absorption, vibration absorption, and excellent storage stability. It is an object of the present invention to provide an active energy ray curable composition, and a cured product, an impact absorbing material, a vibration absorbing material, and a sheet material using the active energy ray curable composition.

  Active energy rays are visible light, ultraviolet rays, microwaves, high frequencies, and ionizing radiation such as electron beams, X-rays, α rays, β rays, and γ rays, but release substances that initiate polymerization. Any energy species is acceptable if possible. 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.

  As a result of intensive studies, the present inventors have determined that component (A): a component containing diethylene glycol bis (allyl carbonate), component (B): two or more mercapto groups, and all mercapto groups are secondary carbons. By using an active energy ray-curable composition containing a compound bonded to an atom or a tertiary carbon atom, and a polymerization initiator (C), after absorbing the active energy ray, shock absorption, vibration absorption, etc. As a result, it was found that a cured product suitable as a shock absorbing material and a vibration absorbing material excellent in the above can be obtained.

The present invention includes the following active energy ray-curable compositions [1] to [6], a cured product [7], a shock absorber [8], a vibration absorber [9], and a sheet [10]. Regarding materials.
[1] Component (A): a component containing diethylene glycol bis (allyl carbonate),
Component (B): an active energy comprising a compound having two or more mercapto groups and all mercapto groups bonded to secondary or tertiary carbon atoms, and a polymerization initiator (C) A linear curable composition.
[2] The active energy ray-curable composition according to [1], wherein the component (B) includes a group represented by the following formula (1).

（式（１）中、Ｒ¹およびＲ²は各々独立して水素原子または炭素数１〜１０のアルキル基を表し、その少なくとも一方は炭素数１〜１０のアルキル基である。ｍは０〜２の整数である。）
［３］成分（Ｂ）は、１，４−ビス（３−メルカプトブチリルオキシ）ブタン、ペンタエリスリトールテトラキス（３−メルカプトブチレート）、１，３，５−トリス（３−メルカプトブチリルオキシエチル）−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン、およびトリメチロールプロパン−トリス（３−メルカプトブチレート）から選ばれる少なくとも１つである［１］に記載の活性エネルギー線硬化性組成物。
［４］成分（Ａ）がさらにウレタン（メタ）アクリレートを含む、［１］〜［３］のいずれかに記載の活性エネルギー線硬化性組成物。
［５］前記成分（Ａ）が有するエチレン性二重結合の数ａと前記成分（Ｂ）のメルカプト基の数ｂとの比（ａ：ｂ）が、３０：７０〜７０：３０の範囲内にあり、前記成分（Ａ）および前記成分（Ｂ）の合計１００質量部に対し前記重合開始剤（Ｃ）を０．０１質量部〜１０質量部含む、［１］〜［４］のいずれかに記載の活性エネルギー線硬化性組成物。
［６］さらに無機充填剤を含む、［１］〜［５］のいずれかに記載の活性エネルギー線硬化性組成物。
［７］［１］〜［６］のいずれかに記載の活性エネルギー線硬化性組成物を硬化させた硬化物。
［８］［７］に記載の硬化物を含む衝撃吸収材。
［９］［７］に記載の硬化物を含む振動吸収材。
［１０］［７］に記載の硬化物を含むシート材。

(In Formula (1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, at least one of which is an alkyl group having 1 to 10 carbon atoms. (It is an integer of 2.)
[3] Component (B) is 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyryloxyethyl) ) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and trimethylolpropane-tris (3-mercaptobutyrate) [1] The active energy ray-curable composition described.
[4] The active energy ray-curable composition according to any one of [1] to [3], wherein the component (A) further contains urethane (meth) acrylate.
[5] The ratio (a: b) of the number a of ethylenic double bonds in the component (A) to the number b of mercapto groups in the component (B) is in the range of 30:70 to 70:30. Any one of [1] to [4], comprising 0.01 to 10 parts by mass of the polymerization initiator (C) with respect to 100 parts by mass in total of the component (A) and the component (B). The active energy ray-curable composition described in 1.
[6] The active energy ray-curable composition according to any one of [1] to [5], further including an inorganic filler.
[7] A cured product obtained by curing the active energy ray-curable composition according to any one of [1] to [6].
[8] A shock absorber comprising the cured product according to [7].
[9] A vibration absorber comprising the cured product according to [7].
[10] A sheet material comprising the cured product according to [7].

  In the present invention, it is possible to give a cured product having low odor, excellent transparency, shock absorption, vibration absorption, and excellent storage stability, as well as its active energy. A cured product, a shock absorbing material, a vibration absorbing material and a sheet material using the linear curable composition 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 component (A): a component containing diethylene glycol bis (allyl carbonate), component (B): 2 mercapto groups. A compound having at least one and all mercapto groups bonded to secondary carbon atoms or tertiary carbon atoms, and a polymerization initiator (C).

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

<Component (A)>
The component (A) is a component containing diethylene glycol bis (allyl carbonate). Diethylene glycol bis (allyl carbonate) is available from ACOMON under the product name RAV7. By using a component (A), the transparency of the hardened | cured material formed from the composition of this invention can be improved.

  The component (A) may contain other components other than diethylene glycol bis (allyl carbonate) as long as the object of the present invention is not impaired. Examples of other components include urethane (meth) acrylate.

  The urethane (meth) acrylate means a compound having at least one (meth) acrylate structure and further having at least one urethane bond. Such compounds are known to be obtained by reacting hydroxy functional (meth) acrylates with isocyanate functional compounds. Here, (meth) acrylate means acrylate and methacrylate.

  Urethane (meth) acrylates are not particularly limited, but those having a flexible skeleton, that is, those having a polyether skeleton or a polyester skeleton, are from the viewpoint of sheet formability of a cured product formed from the present composition. To preferred. As said urethane (meth) acrylate, UA-160TM (made by Shin-Nakamura Chemical Co., Ltd.), U-200PA, UA-290TM, UA-103, U-122P, UA-1013P (made by Shin-Nakamura Chemical Co., Ltd.), EBECRYL230 270, 284, 8804, 8413, 8402, 8411, K8296, 7735 (manufactured by Daicel Ornex Co., Ltd.), commercially available urethane (meth) acrylates, and the like. From the viewpoint of impact absorption of a cured product formed from

  When component (A) contains urethane (meth) acrylate, the content of urethane (meth) acrylate is not particularly limited, but from the viewpoint of moldability of a cured product formed from the composition, the total amount of the composition 10-60 mass% of mass is preferable, and 20-40 mass% is more preferable.

  In the composition of the present invention, the ratio (a: b) of the number a of ethylenic double bonds of the component (A) to the number b of mercapto groups of the component (B) is determined by impact absorption and vibration absorption. From this viewpoint, it is preferably within the range of 30:70 to 70:30, and more preferably within the range of 40:60 to 60:40. For example, when component (A) contains only diethylene glycol bis (allyl carbonate), the number of allyl groups that diethylene glycol bis (allyl carbonate) has is a, and component (A) is diethylene glycol bis (allyl carbonate) and When urethane (meth) acrylate is included, the sum of the number of allyl groups of diethylene glycol bis (allyl carbonate) and the number of ethylenic double bonds of urethane (meth) acrylate is a.

<Component (B)>
Component (B) is a compound having two or more mercapto groups, and all mercapto groups are bonded to secondary carbon atoms or tertiary carbon atoms. That is, the component (B) has a mercapto group-containing group in which a substituent is bonded to a carbon atom at the α-position with respect to the mercapto group, and has two or more mercapto groups. At least one of the substituents is preferably an alkyl group.

  The fact that the substituent is bonded to the carbon atom at the α-position with respect to the mercapto group means that the carbon at the α-position of the mercapto group is bonded to 2 or 3 carbon atoms. That at least one of the substituents is an alkyl group means that at least one of the groups other than the main chain among the groups bonded to the carbon atom at the α-position with respect to the mercapto group is an alkyl group. Here, the main chain refers to the longest-chain structural site other than the mercapto group and the hydrogen atom bonded to the α-position carbon atom.

  As the mercapto group-containing group, a group represented by the following formula (1) is preferable.

式（１）中、Ｒ¹およびＲ²は各々独立して水素原子または炭素数１〜１０のアルキル基を表し、その少なくとも一方はアルキル基である。すなわち、Ｒ¹およびＲ²がともに水素原子となることはない。なお、Ｒ¹およびＲ²がともにアルキル基の場合は、両者は同じであっても異なっていても良い。

In formula (1), R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, at least one of which is an alkyl group. That is, R ¹ and R ² are not both hydrogen atoms. When R ¹ and R ² are both alkyl groups, they may be the same or different.

The alkyl group having 1 to 10 carbon atoms represented by R ¹ and R ² may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, Examples thereof include an n-butyl group, an iso-butyl group, a tert-butyl group, an n-hexyl group, and an n-octyl group, and a methyl group or an ethyl group is preferable.

  m is an integer of 0 to 2, preferably 0 or 1.

  The component (B) is not particularly limited as long as it is a compound in which all mercapto groups are bonded to secondary carbon atoms or tertiary carbon atoms and has two or more mercapto groups. A polyfunctional thiol compound having two or more containing groups is preferred.

  Thus, since the component (B) is polyfunctional, it is possible to increase the photopolymerization sensitivity as compared with the monofunctional compound.

  As the mercapto group-containing group, a group having a carboxylic acid derivative structure represented by the following formula (2) is more preferable.

成分（Ｂ）は、さらには、式（３）で表されるメルカプト基含有カルボン酸と、アルコール類とのエステルであることが好ましい。

The component (B) is preferably an ester of a mercapto group-containing carboxylic acid represented by the formula (3) and an alcohol.

式（２）及び（３）におけるＲ¹、Ｒ²及びｍの定義は、式（１）におけるこれらの定義と同様である。

The definitions of R ¹ , R ² and m in the formulas (2) and (3) are the same as those in the formula (1).

  The alcohol is preferably a polyfunctional alcohol. By using a polyfunctional alcohol, the compound after the esterification reaction can be made into a polyfunctional thiol compound.

  As the polyfunctional alcohol, alkylene glycol (however, the alkylene group preferably has 2 to 10 carbon atoms, and the carbon chain thereof may be branched), diethylene glycol, glycerin, dipropylene glycol, trimethylolpropane, pentaerythritol. And dipentaerythritol. Examples of the alkylene glycol include ethylene glycol, trimethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, and tetramethylene glycol.

  Preferred polyfunctional alcohols are readily available as raw materials, and have 2 carbon atoms in the alkylene main chain, such as ethylene glycol, 1,2-propylene glycol, 1,2-butanediol, from the viewpoint of the number of functional groups and vapor pressure. Alkylene glycol, trimethylolpropane, pentaerythritol and tris (2-hydroxy) ethyl isocyanurate.

  Examples of the mercapto group-containing carboxylic acid of the formula (3) include 2-mercaptopropionic acid, 3-mercaptobutyric acid, 2-mercaptoisobutyric acid, and 3-mercaptoisobutyric acid.

  Specific examples of the compound having two or more mercapto group-containing group structures of the formula (1) and having all mercapto groups bonded to secondary carbon atoms or tertiary carbon atoms include the following compounds. be able to.

  Examples of the hydrocarbon dithiol include 2,5-hexanedithiol, 2,9-decanedithiol, 1,4-bis (1-mercaptoethyl) benzene, and the like.

  Examples of the compound containing an ester bond structure include di (1-mercaptoethyl ester) phthalate, di (2-mercaptopropyl ester) phthalate, di (3-mercaptobutyl ester) phthalate, and di (3-mercaptoisobutyl phthalate). Ester), ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis ( 3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptobutyrate), ethylene Recall bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis ( 2-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate), dipentaerythritol hexakis (2-mercaptopropionate), ethylene glycol bis (4-mercaptovalerate), propylene glycol bis (4-mercaptoisovalerate), diethylene glycol bis (4-mercaptovalerate), butanediol bis (4-mercaptovalere) G), octanediol bis (4-mercaptovalerate), trimethylolpropane tris (4-mercaptovalerate), pentaerythritol tetrakis (4-mercaptovalerate), dipentaerythritol hexakis (4-mercaptovalerate), Ethylene glycol bis (3-mercaptovalerate), propylene glycol bis (3-mercaptovalerate), diethylene glycol bis (3-mercaptovalerate), butanediol bis (3-mercaptovalerate), octanediol bis (3-mercapto) Valerate), trimethylolpropane tris (3-mercaptovalerate), pentaerythritol tetrakis (3-mercaptovalerate), dipentaerythritol hexakis (3-mercaptovalere) ), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 ( 1H, 3H, 5H) -trione and the like are exemplified.

  From the viewpoint of low odor, transparency, shock absorption and vibration absorption, 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5- Preferably, tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane-tris (3-mercaptobutyrate) is preferably used. Can do.

  Although the molecular weight of a component (B) is not specifically limited, From a viewpoint of the impact absorption improvement of the hardened | cured material formed from the composition of this invention, Preferably it is 200-1,000.

  Component (B) can also be easily obtained as a commercial product. As a secondary thiol compound containing two or more mercapto groups in a commercially available molecule of component (B), 1,4-bis (3-mercaptobutyryloxy) butane (trade name: Karenz MT BD1, manufactured by Showa Denko KK), pentaerythritol tetrakis (3-mercaptobutyrate) (trade name: Karenz MT PE1, manufactured by Showa Denko KK), 1,3,5-tris (3-mercaptobutyloxyethyl) ) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (trade name: Karenz MT NR1, manufactured by Showa Denko KK), trimethylolpropane-tris (3-mercaptobuty Rate) (trade name TPMB, manufactured by Showa Denko KK) and the like.

  In the component (B) used in the present invention, since all mercapto groups are bonded to secondary carbon atoms or tertiary carbon atoms, the composition of the present invention is excellent in storage stability and has a very odor. The effect that there is little is acquired.

  In addition, in the composition of this invention, you may mix | blend mercapto compounds other than a component (B) in the range which does not impair the effect of invention. However, the blending amount of the mercapto compound other than the component (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.

<Polymerization initiator (C)>
The polymerization initiator (C) includes a photopolymerization initiator and a thermal polymerization initiator, and any compound that accelerates the initiation of polymerization of the compound (A) is not particularly limited.

  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 photoactive 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), bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethyl Phenylphosphine 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-trimethylpentylphos Fin oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethylbenzoyl) 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, etc. .

  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 Irgacure 184 and is available from BASF, and the latter is LUCIRIN TPO and is available from BASF.

  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 of the composition, diisopropyl peroxydicarbonate is preferred.

  In the composition of the present invention, the content of the polymerization initiator (C) is 0.01 to 10 parts by mass from the viewpoint of curability with respect to a total of 100 parts by mass of the component (A) and the component (B). Is preferable 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.

<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.

If the inorganic filler used for this invention disperse | distributes to a component (A) and a component (B) and forms a paste, there will be no restriction | limiting in particular. 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 preferable from the viewpoint of adjusting the viscosity of the present composition and the sheet formability of a cured product formed from the present composition. The fine-particle silica is available from Nippon Aerosil Co., Ltd. under the trade name Aerosil (trademark). Aerosil (trademark) as a fine particle silica includes 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 And AluC805, among which RX200 is more preferable from the viewpoint of dispersibility.

  Although content of an inorganic filler is not specifically limited, From a viewpoint of the moldability of the hardened | cured material formed from this composition, it is 100 mass parts in total of a component (A), a component (B), and urethane (meth) acrylate. On the other hand, it is preferably less than 10 parts by mass, more preferably 2 to 6 parts by mass.

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

  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. These may be used alone or in combination of two or more. As the polymerization inhibitor, methylhydroquinone, pyrogallol, and tertiary butylhydroquinone are particularly preferred from the viewpoint of storage stability of the active energy ray-curable composition.

  Although content of a polymerization inhibitor is not specifically limited, From a viewpoint of the storage stability of this composition, less than 0.1 mass part is preferable with respect to a total of 100 mass parts of a component (A) and a component (B), 0.0001-0.05 mass part is more preferable.

<Other ingredients>
The active energy ray-curable composition of the present invention includes the component (A), the component (B) and the polymerization initiator (C) described above, and the inorganic filler and polymerization inhibitor which are optional components. Other components may be contained as long as the purpose is not impaired. 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.

  Although the composition of this invention may contain a solvent, even if it does not contain a solvent, it is preferable not to contain a solvent.

  Examples of materials that are preferably contained 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. For example, commercially available gel nails and pigments for UV craft 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) and the like.

  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. Examples of the plastic dye include KP PLAST (KP Plast Red B, KP Last Blue GR, KP Last Yellow HK) and the like. 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.

  The color materials can be used alone or in combination of two or more.

  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 photoactive energy ray may be lowered, resulting in poor curing. Therefore, the content of the color material in the composition is preferably 0.0001 to 40% by mass.

  In addition to the colorant, the composition of the present invention includes, as other components, (a) a thermoplastic resin; (b) a deodorant; (c) an adhesion improver such as a silane coupling agent or 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) metal soaps; Stabilizers such as inorganic and organic salts of heavy metals (eg zinc, tin, lead, cadmium, etc.), organic tin compounds; (g) aliphatic carboxylic acids such as acetic acid, acrylic acid, palmitic acid, oleic acid, mercaptocarboxylic acid, phenol PH adjusters such as aromatic organic acids such as naphthol, benzoic acid and salicylic acid; (h) phthalic acid ester, phosphoric acid ester, fatty acid ester Plasticizers such as 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; ) Non-reactive diluents such as benzyl alcohol, tar and pitumen; (k) Fillers such as acrylic resin powder and phenol resin powder; (l) Solvents such as ethyl acetate, toluene, alcohols, ethers and ketones; (M) foaming agent; (n) dehydrating agent such as silane coupling agent, monoisocyanate compound, carbodiimide compound; (o) antistatic agent; (p) antibacterial agent; (q) antifungal agent; (r) viscosity adjustment Formulation; (s) perfume; (t) flame retardant; (u) leveling agent; (v) sensitizer; and (w) dispersant. 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 may be prepared by appropriately mixing the component (A), the component (B), the polymerization initiator (C), and, if necessary, an inorganic filler, a polymerization inhibitor and other components. it can.

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

  At this time, the ratio (a: b) of the number a of ethylenic double bonds of component (A) to the number of mercapto groups b of component (B) is preferably 30:70 to 70:30, more preferably Mix to 40: 60-60: 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.
(A) Each component is kneaded in a suitable container such as a glass beaker, a can, a plastic cup, or an aluminum cup with a stirring rod, a spatula, or the like.
(B) Each component is kneaded with a double helical ribbon blade, a gate blade, or the like.
(C) Kneading each component with a planetary mixer.
(D) Each component is kneaded by a bead mill.
(E) Each component is kneaded with three rolls.
(F) Each component is kneaded by an extruder-type kneading extruder.
(G) 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.

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

  Examples of the active energy rays used at the time of curing include ultraviolet rays, electron beams, and X-rays, and ultraviolet rays are preferable because inexpensive devices can be 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 high-pressure mercury lamp and an LED lamp (UV-LED lamp) are preferable from the viewpoint of curability.

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.

  By curing the composition into a sheet, a sheet-like cured product, that is, a sheet material is obtained. The sheet material may include a material other than the cured product 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.
[Hardened products and their uses]
The composition of the present invention has low odor and excellent storage stability. Since the composition of the present invention has a low odor, the resulting cured product also has a low odor. The cured product obtained from the composition of the present invention is excellent in transparency, impact absorption and vibration absorption.

  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 absorber and vibration absorber of the present invention include the cured product.

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

  The impact absorbing material and vibration absorbing material of the present invention may contain other materials than the cured product as necessary, and may be a laminate of the cured product and 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, and a metal such as iron, aluminum, or copper. As these examples, (a) the composition of the present invention is applied to a mortar material and cured by irradiating UV light to form a mortar-cured product laminate, and (b) the composition is cured into a sheet. Then, an adhesive layer is applied to 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, and a laminated film and (D) a thermoplastic resin layer / a cured product layer of the present invention / a thermoplastic resin layer are laminated in this order to form a laminated film, and (e) a thermoplastic resin layer / an adhesive layer / a cured product layer of the present invention / heat. A laminated film laminated in the order of a plastic resin layer, and (f) a laminated film laminated in the order of a thermoplastic resin layer / adhesive layer / cured layer of the present invention / adhesive layer / thermoplastic resin layer (g ) Apply the composition of the present invention to glass and irradiate with UV light And cured into a glass laminate, (h) a glass laminate laminated in the order of glass / cured material layer of the present invention / glass, (i) between thermoplastic or thermosetting resin and glass (J) The composition of the present invention is applied to a material having a three-dimensional shape and cured to form a coating material by irradiating UV light and irradiating with UV light. ) Printing on the cured product of the present invention. By laminating as in the above example, the impact absorbability and 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 6 and Comparative Examples 1 to 5 are as follows.
1. Ingredient (A)
1) RAV7: Diethylene glycol bis (allyl carbonate)
Product name “RAV 7AT”, molecular weight 274, allyl group number 2 manufactured by ACOMON
2) UA-160TM: Urethane acrylate Shin-Nakamura Chemical Co., Ltd., acryloyloxy group number 2
2. An ethylenically unsaturated group-containing compound other than the component (A) and the (meth) acryloyloxy group-containing compound (a) (hereinafter, both may be collectively referred to as “compound (a)”).
However, the (meth) acryloyloxy group-containing compound means a methacryloyloxy group-containing compound and an acryloyloxy group-containing compound.

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) TMPTA: trimethylolpropane triacrylate, manufactured by Kyoeisha Chemical Co., Ltd., molecular weight 296, acryloyloxy group number 3
3. Component (B) and mercapto group-containing compound (b) other than component (B)
Hereinafter, the mercapto group-containing compound (b) other than the component (B) may be referred to as a compound (b).

1) PE1: pentaerythritol-tetrakis (3-mercaptobutyrate)
Product name “Karenz MT (trademark) PE1” manufactured by Showa Denko KK, molecular weight 545, mercapto group number 4
2) TPMB: trimethylolpropane-tris (3-mercaptobutyrate)
Product name “TPMB”, molecular weight 441, mercapto group number 3
3) NR1: 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione Karenz MT (trademark) NR1 ", molecular weight 568, mercapto group number 3
4) PEMP: Pentaerythritol-tetrakis (3-mercaptopropionate)
Product name “PEMP”, molecular weight 489, mercapto group number 4
4). Polymerization initiator (C)
1-Hydroxy-cyclohexyl ruphenyl ketone manufactured by BASF, trade name “Irgacure 184”
5. Polymerization inhibitor Methylhydroquinone, manufactured by Kanto Chemical Co., Ltd. <Examples 1-6 and Comparative Examples 1-5>
Active energy rays obtained by mixing the components (A) or compounds (a), components (B) or compounds (b), polymerization initiators (C) and polymerization inhibitors shown in Table 1 in the mass ratio shown in Table 1. A curable composition was obtained. In Table 1, “functional group number ratio” indicates (number of ethylenic double bonds of component (A) or compound (a)) / (number of mercapto groups of component (B) or compound (b)). .

Next, a polyethylene terephthalate (PET) film is placed on a glass plate, a silicon rubber spacer is placed thereon, and the active energy ray-curable composition is poured so that the thickness after curing is 5 mm. And the glass plate was mounted in order. 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 silicone 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 active energy ray-curable composition and cured product. The results are shown in Table 1.

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

(2) Vibration absorption property Using a test piece obtained by cutting the obtained cured product having a thickness of 1 mm into a rectangular shape having a length of 10 mm and a width of 40 mm, a dynamic viscoelasticity tester DMS6100 manufactured by SII Nanotechnology Co., Ltd. was used. Then, the temperature giving the value of tan δ and the peak top of tan δ was measured under the conditions of a measurement frequency of 10 Hz and a heating rate of 3 ° C./min. 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 case where the peak top of tan δ was 2 or more was designated as A, the case where it was 0.9 or more and less than 2 was designated as B, and the case where it was less than 0.9 was designated as C.

  The temperature range that gives the peak top of tan δ is 5 ° C. or higher and lower than 30 ° C. A, −5 ° C. or higher and lower than 5 ° C., or 30 ° C. or higher and lower than 40 ° C. The case of 40 ° C. or higher was evaluated as C.

(3) Evaluation of turbidity The haze of the obtained cured product having a thickness of 1 mm was measured with a haze meter NDH-5000 manufactured by Nippon Denshoku Co., Ltd. It shows that turbidity is so high that haze is large. The case where the haze was less than 0.5 was evaluated as A, the case where it was 0.5 or more and less than 1, and the case where it was 1 or more was evaluated as C.

(4) Storage stability evaluation The active energy ray-curable composition was allowed to stand at room temperature (23 ° C), and disproportionation and gelation were visually confirmed. The case where disproportionation and gelation did not occur for 10 days or more was evaluated as A, and the case where disproportionation and gelation occurred before 10 days had elapsed was evaluated as C.

(5) Odor evaluation The odor of the active energy ray-curable composition was pinched at a distance of 5 cm, and the number of persons who felt the odor was 7 or less in 10 subjects, and A or 8 or more. The case was rated C.

表１の結果から明らかなように、実施例１〜６は衝撃吸収性、振動吸収性、透明性、保存安定性および臭気のすべてが比較例よりも優れていた。

As is clear from the results in Table 1, Examples 1 to 6 were all superior to the comparative examples in impact absorption, vibration absorption, transparency, storage stability, and odor.

  The active energy ray-curable composition of the present invention has a low odor, is excellent in transparency and storage stability, can give a cured product excellent in impact absorption and vibration absorption, and is excellent in storage stability. The cured product obtained from the active energy ray-curable composition is particularly preferably used as a shock absorber and a vibration absorber.

Claims (10)

Component (A): a component containing diethylene glycol bis (allyl carbonate),
Component (B): an active energy comprising a compound having two or more mercapto groups and all mercapto groups bonded to secondary or tertiary carbon atoms, and a polymerization initiator (C) A linear curable composition. The active energy ray-curable composition according to claim 1, wherein the component (B) contains a group represented by the following formula (1).

(In Formula (1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, at least one of which is an alkyl group having 1 to 10 carbon atoms. (It is an integer of 2.)   Component (B) is 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyryloxyethyl) -1 , 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, and trimethylolpropane-tris (3-mercaptobutyrate) Energy ray curable composition.   The active energy ray-curable composition according to any one of claims 1 to 3, wherein the component (A) further contains urethane (meth) acrylate.   The ratio (a: b) of the number a of ethylenic double bonds of the component (A) to the number b of mercapto groups of the component (B) is in the range of 30:70 to 70:30, The active energy according to any one of claims 1 to 4, comprising 0.01 to 10 parts by mass of the polymerization initiator (C) with respect to a total of 100 parts by mass of the component (A) and the component (B). A linear curable composition.   Furthermore, the active energy ray curable composition in any one of Claims 1-5 containing an inorganic filler.   Hardened | cured material which hardened the active energy ray curable composition in any one of Claims 1-6.   A shock absorber comprising the cured product according to claim 7.   A vibration absorber comprising the cured product according to claim 7.   A sheet material comprising the cured product according to claim 7.