JP6166576B2 - Active energy ray-curable composition and cured product thereof - Google Patents

Description

  The present invention relates to an active energy ray-curable composition and a cured product thereof. More specifically, a vinyl polymer (I) having at least one active energy ray crosslinkable group on average, an active energy ray polymerization initiator (II), and a non-polymerizable aromatic compound having a halogenated alkyl group ( The present invention relates to an active energy ray-curable composition containing III) and a cured product thereof.

  Active energy ray-curable materials are known as materials that are cured by irradiation with active energy rays such as ultraviolet rays and electron beams. Active energy ray curable materials have the advantages of being capable of rapid curing at low energy, high productivity, and being capable of curing at room temperature, and taking advantage of these advantages, adhesives, adhesives, paints, It is used for applications such as inks, coating materials, various electric / electronic materials, and optical modeling materials (Non-Patent Document 1).

  In particular, organic polymers and low molecular weight compounds having a (meth) acryloyl group are generally short in curing time and can be cured at low temperatures by radical polymerization using active energy rays. Since it is excellent in storage stability under light shielding, it is used for various applications (Patent Documents 1 and 2).

  However, since radical polymerization is inhibited by dissolved oxygen in the composition, oxygen in the air, etc., curing may be delayed and productivity may be problematic. In addition, there is a problem that uncured portions and stickiness remain on the surface of the cured product having a relatively high oxygen concentration. In particular, when obtaining a low-elasticity soft cured product, surface curing inhibition and tack are major problems (Non-patent Document 2).

  Such problems can be solved by performing polymerization in an inert atmosphere such as nitrogen, but there is a strong demand for shortening and simplification of work processes aimed at saving space and labor. There is a need for other solutions. In the case of a soft cured product with low elasticity, even when polymerization is performed in an inert atmosphere, the stickiness of the surface remains, which is a problem.

  The present inventors have so far reported on a polymer having a main chain as an acrylic polymer obtained by living radical polymerization and having a (meth) acryloyl group at its terminal (Patent Documents 3 to 5). The polymer is excellent in flexibility, heat resistance, oil resistance, vibration resistance and shock absorption, but in photo radical curing, it has surface tackiness (tack) resulting from inhibition of curing by oxygen, and the surface feel is uncomfortable. In addition to the above, there are problems such as the occurrence of paste and the difficulty of handling. In response to this problem, photo radical initiators that are generally effective for inhibiting oxygen on the surface of commercially available cured products, such as nitrogen and sulfur atoms that are effective in inhibiting oxygen inhibition, are used. Even when a photoradical initiator containing (for example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one) was used, although an improvement effect was seen, it was not sufficient. .

  For the purpose of suppressing polymerization inhibition by oxygen, Patent Document 6 proposes a method of adding a surface tack modifier having a melting point of 30 ° C. or more and 200 ° C. or less to a (meth) acrylic polymer having a crosslinkable functional group. Has been. However, with this method, the final surface tack is improved, but when cured with active energy rays, a certain amount of time is required for the effect of tack reduction to occur, and surface uncured by oxygen is not cured. There was a problem that could not be solved.

  In Patent Document 7, a vinyl polymer having a crosslinkable functional group at the molecular end, a radical photopolymerization initiator having two or more structures in the molecule that decomposes by light, and three or more aromatic rings in the molecule A method of using a hydrogen abstraction-type photoradical initiator having the same has been proposed. However, with this method, the surface curability is improved and tack is reduced. However, since ultraviolet absorption at the surface is large, when trying to produce a cured product with a thickness of mm, sufficient ultraviolet rays can reach the deep part. However, there was a problem that the deep part curability was insufficient.

  Patent Document 8 discloses that an active energy curable composition containing a combination of a hindered phenol-based antioxidant and a sulfur-based or phosphorus-based antioxidant and a compound having a polyether structure inhibits surface curing after UV curing. Although it has been proposed to be improved, such a method requires a complicated operation for adding various compounds, and is inferior in heat resistance for adding a compound having a polyether structure. There was a problem that moisture permeability decreased.

  Patent Document 9 discloses a resin composition for an optical disc protector comprising a photo radical polymerization reactive oligomer and a photo radical polymerization initiator, and the viewpoint of protecting the optical disc surface from scratches and contamination by the softness of the cured product and low surface tackiness. Therefore, as the photoradical initiator, a hydrogen abstraction type or self-cleavage type photoinitiator is preferable. As the hydrogen abstraction type photoinitiator, benzophenones, dibenzosuberones, anthraquinones, xanthones, thioxanthone, etc. are proposed. ing. However, in this method, the surface curability is improved and tack is reduced, but because the ultraviolet absorption at the surface is large, when trying to produce a slightly thick cured product, sufficient ultraviolet rays cannot reach the deep part, There is a problem that deep part curability is insufficient.

  Patent Document 10 discloses that an active energy ray-curable oligomer is used in combination with a photopolymerization initiator having an absorption region at a wavelength of 350 to 400 nm and a photosensitizer capable of reacting with ultraviolet light at a wavelength of 350 to 400 nm. , A method for obtaining a cured product by irradiating ultraviolet light having a wavelength of 350 to 400 nm is described. Specifically, Irgacure 369 (manufactured by BASF; 2-benzyl-2-dimethylamino-1- (4-morpholino) is described. (Phenyl) -butanone-1), Narcure CS (manufactured by Futoshi Chemical Co., Ltd .; 4,4′-diethylaminobenzophenone), Speed Cure DETX (manufactured by Rambson Co., Ltd .; 2,4-diethylthioxanthone) have been proposed. Is effective for thin films of the order of μm and high-hardness coatings. The tack reduction effect is low, and when trying to produce a cured product having a thickness in mm, there is a problem that sufficient ultraviolet rays cannot reach the deep part and the deep part curability is insufficient.

  Patent Document 11 discloses a light-emitting diode curable ink composition or coating composition that provides a cured product excellent in non-tacking properties and has no unnecessary absorption in the visible range and excellent hue. A method of combining diethylthioxanthone) with other photopolymerization initiators as an essential component has been proposed. However, a compound having a carbon-halogen bond is also exemplified as one of the photopolymerization initiators. However, there is no description regarding deep curability when such a compound is added, and in this method, the absorption wavelength of diethylthioxanthone Has a problem that it is inferior in deep-part curability.

  In Patent Document 12, in a radical polymerization reaction of a vinyl monomer, a polymerization reaction is performed by light irradiation or heating in the presence of a halogen compound having a structure in which a halogen atom is bonded to a carbon atom bonded to an aromatic ring. A method has been proposed. However, this method is intended to obtain a vinyl polymer having a halogen halogen atom at the terminal, and it does not describe what effect is exerted when the vinyl polymer coexists. Moreover, it is not envisaged to obtain a cured product by this method, and it is unclear to those skilled in the art whether or not a cured product can be obtained, and what the properties of the obtained cured product are, It cannot be assumed at all.

  Patent Document 6, Patent Document 13, and Patent Document 14 propose using a compound having a halogen at the benzyl position as an initiator in atom transfer radical polymerization. However, in the atom transfer radical polymerization, the polymerization inhibition by oxygen is remarkable, and the polymerization cannot actually proceed in the presence of oxygen. In these documents, it is not assumed that a cured product is obtained using an atom transfer radical polymerization method, and it is unknown to those skilled in the art whether a cured product can be obtained using active energy ray curing. Moreover, it is impossible to assume what the characteristics of the cured product obtained will be.

  When there is little inhibition of curing even under oxygen, the surface of the resulting cured product is small, and an active energy ray-curable composition that cures sufficiently to the deep part has been sought for many years, especially when obtaining a soft cured product with low elasticity Was particularly sought after.

JP 2005-105065 A WO2008 / 041768 WO2007 / 069600 JP 2000-72816 A JP 2000-95826 A WO2005 / 003230 Publication JP 2009-292898 A JP 2011-256239 A JP 2013-40244 A JP 2011-256331 A JP 2012-31388 A WO2000 / 61641 Japanese Patent Laid-Open No. 9-272715 JP-A-11-158449

'99 UV / EB Curing Material Product Market Handbook CMC Publishing Co., Ltd. Curing failure / inhibition factors in UV curing and countermeasures (Information Technology Association, Inc. (issued in 2003))

  The present invention is a curable composition that can be quickly cured by an active energy ray, and can reduce the surface tack of the cured product, and can provide a curable composition that is excellent in deep part curability and the cured product thereof. Objective.

In view of the above circumstances, as a result of intensive studies on the active energy ray-curable composition by the present inventor, the vinyl polymer (I) having an average of at least one active energy ray crosslinkable group, an active energy ray polymerization initiator ( II) and a non-polymerizable aromatic compound (III) in which at least one functional group represented by the following general formula (1) is bonded to an aromatic ring. It has been found that a product can solve the above-mentioned problems, and the present invention has been obtained.
-C (R ¹ ) _3-a (X) _a (1)
That is, the present invention provides a vinyl polymer (I) having at least one active energy ray crosslinkable group on average, an active energy ray polymerization initiator (II), and a functional group represented by the following general formula (1): And a non-polymerizable aromatic compound (III) having at least one bonded to an aromatic ring.
-C (R ¹ ) _3-a (X) _a (1)
(In the formula, R ¹ is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or two R ^{1 s} (when a is 1 They may be the same or different, and X is a chlorine, bromine or iodine atom, and when two or more X are present, they may be the same. And may be different, a represents 1, 2 or 3.)

  In a preferred embodiment, the vinyl polymer (I) having at least one active energy ray crosslinkable group on average is a vinyl polymer having an active energy ray crosslinkable carbon-carbon double bond at the molecular end. It relates to a certain active energy ray-curable composition.

  As a preferred embodiment, a vinyl polymer having an active energy ray-crosslinkable carbon-carbon double bond group at the molecular end has an active energy ray-crosslinkable carbon-carbon double bond at both ends of the polymer. The present invention relates to an active energy ray-curable composition, both of a vinyl polymer and a vinyl polymer having an active energy ray-crosslinkable carbon-carbon double bond at one end of the polymer.

  As a preferred embodiment, the present invention relates to an active energy ray-curable composition in which the vinyl polymer (I) having an average of at least one active energy ray crosslinkable group is a (meth) acrylic polymer.

  A preferred embodiment relates to an active energy ray-curable composition in which the molecular weight distribution of the vinyl polymer (I) having at least one active energy ray crosslinkable group on average is less than 1.8.

As a preferred embodiment, the present invention relates to an active energy ray-curable composition in which the active energy ray crosslinkable group is represented by the general formula (2).
—OC (O) C (R ² ) ═CH ₂ (2)
(Wherein R ² represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)

  As a preferred embodiment, 0.01 to 10 parts by weight of the active energy ray polymerization initiator (II) with respect to 100 parts by weight of the vinyl polymer (I) having an average of at least one active energy ray crosslinkable group, The present invention relates to an active energy ray-curable composition containing 0.1 to 10 parts by weight of the non-polymerizable aromatic compound (III) represented by the general formula (1).

As a preferred embodiment, an active energy ray comprising a non-polymerizable aromatic compound (III) in which at least one functional group represented by the following general formula (1) is bonded to an aromatic ring: The present invention relates to a cured product obtained from the curable composition.
-C (R ¹ ) _3-a (X) _a (1)
(In the formula, R ¹ is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or two R ^{1 s} (when a is 1 They may be the same or different, and X is a chlorine, bromine or iodine atom, and when two or more X are present, they may be the same. And may be different, a represents 1, 2 or 3.)

  According to the present invention, there is provided an active energy ray-curable composition or cured product that is a curable composition that can be quickly cured by active energy rays, can reduce the surface tack of the cured product, and is excellent in deep part curability. Can be obtained.

  Below, the component contained in the active energy ray hardening-type composition of this invention is demonstrated.

<Vinyl polymer (I)>
<Main chain of vinyl polymer (I)>
It does not specifically limit as a vinyl-type monomer which comprises the principal chain of vinyl-type polymer (I) of this invention, Various things can be used.

  Specifically, (meth) acrylic acid; (meth) methyl acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n- Butyl, isobutyl (meth) acrylate, (tert-butyl) (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) Phenyl acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ( T) 3-methoxypropyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acryl 2-aminoethyl acid, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (Meth) acrylic acid-2-perfluoroethyl ethyl, (meth) acrylic acid-2-perfluoroethyl-2-perfluorobutyl ethyl, (meth) acrylic acid-2-perfluoroethyl, (meth) acrylic acid per Fluoromethyl, diperfluoromethylmethyl (meth) acrylate, (Meth) acrylic acid-2-perfluoromethyl-2-perfluoroethylmethyl, (meth) acrylic acid-2-perfluorohexylethyl, (meth) acrylic acid-2-perfluorodecylethyl, (meth) acrylic acid (Meth) acrylic acid ester monomers such as 2-perfluorohexadecyl ethyl; styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; perfluoroethylene, perfluoro Fluorine-containing vinyl monomers such as propylene and vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, fumarate Acid Alkyl esters and dialkyl esters; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; acrylonitrile, methacrylonitrile, etc. Nitrile group-containing vinyl monomers; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; Alkenes such as ethylene and propylene Conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, etc. Yes.

  These may be used alone or a plurality of these may be copolymerized. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  The vinyl polymer (I) used in the present invention has (meth) acrylic acid and (meth) acrylic acid ester monomers from the viewpoint of excellent properties such as flexibility, viscosity and elongation at low temperatures of the cured product. It is preferably a (meth) acrylic polymer produced mainly by polymerization, and more preferably a (meth) acrylic ester polymer produced mainly by polymerizing a (meth) acrylic acid ester monomer. Preferably, it is more preferably an acrylate ester polymer produced by mainly polymerizing acrylate ester monomers. Here, “mainly” means that 50 mol% or more of the monomer units constituting the vinyl polymer is the above monomer, and preferably 70 mol% or more.

  Particularly preferred acrylic ester monomers include acrylic acid alkyl ester monomers, specifically, ethyl acrylate, 2-methoxyethyl acrylate, stearyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic 2-methoxybutyl acid.

  In the present invention, these preferable monomers may be copolymerized with other monomers, and further block copolymerized.

  The molecular weight distribution of the vinyl polymer (I) in the present invention, that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is Although not limited, Preferably it is less than 1.8, More preferably, it is 1.7 or less, More preferably, it is 1.6 or less, More preferably, it is 1.5 or less, Especially preferably, it is 1.4. Or less, most preferably 1.3 or less. If the molecular weight distribution is too large, the viscosity at the molecular weight between the same cross-linking points increases and the handling tends to be difficult. In the GPC measurement in the present invention, chloroform is used as the mobile phase, the measurement is performed with a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.

  The number average molecular weight of the vinyl polymer (I) in the present invention is not particularly limited, but is preferably in the range of 500 to 1,000,000, more preferably 1,000 to 100,000 when measured by GPC. 5,000 to 80,000 are more preferred, and 8,000 to 50,000 are even more preferred. If the molecular weight is too low, handling is easy due to low viscosity, but the cured product obtained is insufficiently stretched or only a cured product with poor flexibility can be obtained. There is a tendency that it becomes difficult and the effect of tack improvement cannot be obtained sufficiently.

<Synthesis Method of Vinyl Polymer (I)>
The vinyl polymer (I) used in the present invention can be obtained by various polymerization methods, and is not particularly limited, but is preferably a radical polymerization method from the viewpoint of versatility of the monomer, ease of control, etc. Among these, controlled radical polymerization is more preferable. This controlled radical polymerization method can be classified into a “chain transfer agent method” and a “living radical polymerization method”. Living radical polymerization, in which the molecular weight and molecular weight distribution of the resulting vinyl polymer can be easily controlled, is further preferred, and atom transfer radical polymerization is particularly preferred from the viewpoint of availability of raw materials and ease of introduction of a functional group at the polymer terminal. The radical polymerization, controlled radical polymerization, chain transfer agent method, living radical polymerization method, and atom transfer radical polymerization are known polymerization methods. For example, JP-A-2005-232419 and JP-A-2005-234419 The description of 2006-291073 gazette etc. can be referred to.

  The atom transfer radical polymerization, which is one of the preferred methods for synthesizing the vinyl polymer (I) in the present invention, will be briefly described below.

  In atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl-position), or a sulfonyl halide. A compound or the like is preferably used as an initiator.

  In order to obtain a vinyl polymer having two or more active energy ray crosslinkable groups in one molecule, an organic halide having two or more starting points or a sulfonyl halide compound is preferably used as an initiator. .

  There is no restriction | limiting in particular as a vinyl-type monomer used in atom transfer radical polymerization, All the illustrated vinyl-type monomers can be used suitably.

  Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex which uses a periodic table group 7, 8, 9, 10, or 11 element as a central metal, More preferably, it is 0. A transition metal complex having valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel as a central metal, particularly preferably a copper complex. Specific examples of the monovalent copper compound used to form the copper complex include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, and oxidized oxide. Cuprous, cuprous perchlorate, and the like. In the case of using a copper compound, 2,2′-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltriethylenetetraamine or hexamethyltris ( Polyamines such as 2-aminoethyl) amine are added as ligands.

The polymerization reaction can be carried out without solvent, but can also be carried out in various solvents. It does not specifically limit as a kind of solvent, The solvent of Unexamined-Japanese-Patent No. 2005-232419 Paragraph [0067] is mentioned. These may be used alone or in combination of two or more. Polymerization can also be performed in an emulsion system or a system using supercritical fluid CO ₂ as a medium.

  Although superposition | polymerization temperature is not limited, It can carry out in the range of 0-200 degreeC, Preferably, it is the range of room temperature-150 degreeC.

<Active energy ray crosslinkable group>
Next, the active energy ray crosslinkable group of the vinyl polymer (I) will be described.

The active energy ray crosslinkable group includes a (meth) acryloyl group and an epoxy group, and any functional group may be used. Although not particularly limited, for example, in the case of a vinyl polymer produced by the above-described atom transfer radical polymerization method, since the (meth) acryloyl group is easily introduced, the active energy ray crosslinkable group is represented by the general formula (2). It is preferable that it is group represented.
—OC (O) C (R ² ) ═CH ₂ (2)
(Wherein R ² represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
In the general formula (2) is not particularly limited as specific examples of ^{R 2,} for _{example, -H, -CH 3, -CH 2} CH 3, - (CH 2) n CH 3 (n is an integer of 2 to 19 the _{represented), - C 6 H 5,} -CH 2 OH, but -CN, and the like, preferably -H, -CH _3.

A method for introducing a (meth) acryloyl group will be described.
A known method can be used to introduce the (meth) acryloyl group. Examples thereof include the methods described in paragraphs [0080] to [0091] of JP-A No. 2004-203932. Among these methods, from the viewpoint of easier control, it is preferable that the method is produced by replacing the terminal halogen group of the vinyl polymer with a compound having a (meth) acryloyl group.

  The (meth) acrylic polymer having a terminal halogen group is a method of polymerizing vinyl monomers using the above-described organic halides or sulfonyl halide compounds as initiators and transition metal complexes as catalysts, or chain transfer of halogen compounds. Although it is manufactured by a method of polymerizing a vinyl monomer as an agent, the former is preferred.

Although it does not specifically limit as a compound which has a (meth) acryloyl group, The compound represented by following General formula (3) can be used,
M ⁺ -OC (O) C (R) = CH ₂ (3)
Specific examples of R in the above formula (3) include, for example, —H, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) _n CH ₃ (n represents an integer of 2 to 19), — _{C 6 H 5, -CH 2 OH} , -CN, etc., and is preferably -H, -CH _3.

M ⁺ in the above formula (3) is a counter cation of the oxyanion, and examples of M ⁺ include alkali metal ions, specifically lithium ions, sodium ions, potassium ions, and quaternary ammonium ions. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, and dimethylpiperidinium ion. Are sodium ion and potassium ion.

  The usage-amount of the oxyanion of General formula (3) becomes like this. Preferably it is 1-5 equivalent with respect to a halogen group, More preferably, it is 1.0-1.2 equivalent. Since this reaction proceeds almost quantitatively, if the amount is too small, a sufficient amount of (meth) acryloyl groups is not introduced relative to the halogen group, and if the amount is too large, it is economically undesirable.

  The solvent for carrying out this reaction is not particularly limited but is preferably a polar solvent because it is a nucleophilic substitution reaction. For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric Triamide, acetonitrile and the like are used.

  Although the temperature which performs reaction is not limited, Generally it is 0-150 degreeC, In order to hold | maintain a polymeric terminal group, Preferably it carries out at room temperature-100 degreeC. The number of (meth) acryloyl groups in the vinyl polymer (I) may be the same or different. Although not particularly limited, it is preferable that the molecule has an average of 1 or more, more preferably 1.1 or more and 4.0 in view of curability and physical properties such as flexibility, elongation, and strength of the cured product. Hereinafter, it is 1.2 or more and 3.5 or less more preferably.

  When the cured product of the present invention is particularly required to have rubber-like properties, the molecular weight between crosslinking points that greatly affects rubber elasticity can be increased. Therefore, at least the (meth) acryloyl group of the vinyl polymer (I) can be obtained. One is preferably at the end of the molecular chain. More preferably, it has all (meth) acryloyl groups at the molecular chain ends.

  When the cured product of the present invention is required to have more flexible properties, the vinyl polymer (I) having a (meth) acryloyl group at the molecular end has (meth) acryloyl groups at both ends of the polymer. It is preferable to include both the vinyl polymer having a vinyl polymer having a (meth) acryloyl group at one end of the polymer. When mixing a vinyl polymer having a (meth) acryloyl group at both ends and a vinyl polymer having a (meth) acryloyl group at one end of the polymer, a vinyl system having a (meth) acryloyl group at both ends The vinyl polymer having a (meth) acryloyl group at one end is preferably 0 to 900 parts by weight with respect to 100 parts by weight of the polymer. The less the vinyl polymer having a (meth) acryloyl group at one end, the harder the cured product. Conversely, the more the vinyl polymer having a (meth) acryloyl group at one end, the softer the resulting cured product will grow. It will be excellent.

< Active energy ray polymerization initiator (II) >
The active energy ray polymerization initiator (II) used in the curable composition of the present invention is not particularly limited, and examples thereof include a photo radical initiator and a photo anion initiator.

 Examples of the photo radical initiator include acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2, 2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4 -Chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoy Methyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxy ketal, 2-chlorothioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade names IRGACURE651, BASF Japan 1-hydroxy-cyclohexyl-phenyl-ketone (trade name IRGACURE184, manufactured by BASF Japan), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name DAROCUR1173, manufactured by BASF Japan), 1 -[4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name IRGACURE 2959, manufactured by BASF Japan), 2-methyl-1- [4- (methylthio ) Phenyl] 2-morpholinopropan-1-one (trade name IRGACURE907, manufactured by BASF Japan), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name IRGACURE369, manufactured by BASF Japan) 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholin-4-yl-phenyl) -butan-1-one (trade name IRGACURE379, manufactured by BASF Japan), dibenzoyl and the like.

  Among these, α-hydroxy ketone compounds (for example, benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxy-cyclohexyl-phenyl-ketone, etc.), phenyl ketone derivatives (for example, acetophenone, propiophenone, benzophenone, 3-methyl) Acetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2,2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4-chloro-4′-benzylbenzophenone, bis (4-dimethylaminophenyl) ketone, etc.) are preferred.

  Furthermore, as an initiator species that can suppress oxygen inhibition on the surface of the cured product, as a photoradical initiator having two or more photodegradable groups in the molecule, 2-hydroxy-1- [4- [4- (2- Hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one (trade name IRGACURE127, manufactured by BASF Japan), 1- [4- (4-Benzoxylphenylsulfanyl) phenyl] -2-Methyl-2- (4-methylphenylsulfonyl) propan-1-one (trade name ESURE1001M), methylbenzoylformate (trade name: SPEDCURE MBF manufactured by LAMBSON), O-ethoxyimino-1-phenylpropane-1 -ON (product name: SPEDCURE PDO LAMBSON), oligo [2-hydroxy-2- Methyl- [4- (1-methylvinyl) phenyl] propanone (trade name ESCURE KIP150 manufactured by LAMBERTI), 1- [4- (phenylthio)-as a hydrogen abstraction type photoradical initiator having three or more aromatic rings in the molecule , 2- (O-benzoyloxime)] 1,2-octanedione (trade name IRGACURE OXE 01, manufactured by BASF Japan), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- Yl] -1- (0-acetyloxime) ethanone (trade name IRGACURE OXE 02, manufactured by BASF Japan), 4-benzoyl-4'methyldiphenyl sulfide, 4-phenylbenzophenone, 4,4 ', 4 "-(hexamethyl) (Triamino) triphenylmethane, etc. Deep-curability 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name DAROCUR TPO, manufactured by BASF Japan), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name IRGACURE 819) And acyl phosphine oxide-based photoradical initiators such as bis (2,6-dimethylbenzoyl) -2,4,4-trimethyl-pentylphosphine oxide.

  As a radical photoinitiator, 1-hydroxy-cyclohexyl-phenyl-ketone (trade name IRGACURE 184, manufactured by BASF Japan), 2-hydroxy- in terms of balance between curability and storage stability of the curable composition of the present invention. 2-methyl-1-phenyl-propan-1-one (trade name DAROCUR1173, manufactured by BASF Japan), bis (4-dimethylaminophenyl) ketone, 2-hydroxy-1- [4- [4- (2-hydroxy- 2-Methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one (trade name IRGACURE127, manufactured by BASF Japan), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butanone-1 (trade name IRGACURE369, manufactured by BASF Japan), 2- (4-methyl Benzyl) -2-dimethylamino-1- (4-morpholin-4-yl-phenyl) -butan-1-one (trade name IRGACURE 379, manufactured by BASF Japan), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Trade name DAROCUR TPO, manufactured by BASF Japan), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name IRGACURE819, manufactured by BASF Japan), bis (2,6-dimethylbenzoyl) -2,4 1,4-trimethyl-pentylphosphine oxide is more preferred.

  These photo radical initiators may be used alone or in combination of two or more, or may be used in combination with other compounds.

  Examples of the photoanion initiator include 1,10-diaminodecane, 4,4′-trimethylenedipiperazine, carbamates and derivatives thereof, cobalt-amine complexes, aminooxyiminos, ammonium borates and the like. . These photoanion initiators may be used alone or in combination of two or more, or may be used in combination with other compounds.

  Specific examples of combinations with other compounds include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, diethanolmethylamine, dimethylethanolamine, triethanolamine, and ethyl. Combinations with amines such as -4-dimethylaminobenzoate and 2-ethylhexyl-4-dimethylaminobenzoate, further combinations with iodonium salts such as diphenyliodonium chloride, combinations with pigments and amines such as methylene blue, etc. Can be mentioned.

  In addition, when using the said photoradical initiator, if necessary, hydroquinone, hydroquinone monomethyl ether, benzoquinone, para tertiary butyl techol, 2,2,6,6-tetramethylpiperidine-1-oxyl, N, N- Polymerization inhibitors such as N, N-dialkylhydroxylamine such as diethylhydroxylamine and N, N-distearylhydroxylamine can also be added.

  When the active energy ray crosslinkable group of the vinyl polymer (I) is an epoxy group, the active energy ray polymerization initiator (II) includes aromatic diazonium salt, diallyl iodonium salt, triallyl sulfonium salt, triallyl selenium. Light and ultraviolet curing agents such as salts and antimony compounds are used.

  The addition amount of the active energy ray polymerization initiator (II) is not particularly limited, but is 0.01 to 10 parts by weight with respect to 100 parts by weight of the vinyl polymer (I) from the viewpoint of curability and storage stability. The content is preferably 0.1 to 5 parts by weight because the curability and physical properties of the cured product are good.

< Aromatic compound (III) >
The aromatic compound (III) used in the curable composition of the present invention is a non-polymerizable aromatic compound (III) in which at least one functional group represented by the following general formula (1) is bonded to an aromatic ring. is there.
-C (R ¹ ) _3-a (X) _a (1)
(In the formula, R ¹ is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or when two or more R ¹ are present (a is 1 They may be the same or different, X is a chlorine, bromine or iodine atom, and when two X are present, they may be the same. And may be different, a represents 1, 2 or 3.)
Among these aromatic compounds (III), hydrogen, methyl group, ethyl group, propyl group, and isopropyl group are preferable as R ^{1 because} they are excellent in the effect of improving tack and hydrogen because they are easily available economically. Is most preferred. X is most preferably a chlorine atom from the viewpoint that the resulting curable composition and the cured product have little environmental impact and are economically superior.

  The aromatic ring to which the functional group represented by the general formula (1) is bonded includes an aromatic hydrocarbon ring such as a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, Examples include benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc., and aromatic heterocycle includes furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring Oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, Benzimidazo Ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring Etc. Among these, a benzene ring, a naphthalene ring, an anthracene ring, and a triazine ring are used as an aromatic ring from the viewpoint of economical availability, compatibility with the vinyl polymer (I), and good tack improvement effect. These aromatic rings may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the linear or branched alkyl group and cycloalkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an i-butyl group, a t-butyl group, and an n-hexyl group. And a cyclohexyl group. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, an acyl group, and an acyloxy group.

  Here, the non-polymerizable aromatic compound is an aromatic compound having no polymerizable group in the molecule, and specifically indicates that it does not have a polymerizable carbon-carbon double bond. An aromatic compound in which at least one functional group represented by the general formula (1) is bonded to an aromatic ring and further has a polymerizable group is effective for improving the surface curability and tackiness of the resulting cured product. However, it is not suitable because it is inferior in deep-part curability due to the influence of having a polymerizable group and an aromatic ring.

  Specific examples of the non-polymerizable aromatic compound (III) in which at least one functional group represented by the general formula (1) is bonded to an aromatic ring include the following compounds. It is not limited.

  Compounds in which X is a chlorine atom include benzyl chloride, 2-methylbenzyl chloride, 3-methylbenzyl chloride, 4-methylbenzyl chloride, 3,5-dimethylbenzyl chloride, 2,4,6-trimethylbenzyl chloride, ethyl Benzyl chloride, 2-ethylbenzyl chloride, 3-ethylbenzyl chloride, 4-ethylbenzyl chloride, 3,5-diethylbenzyl chloride, 2,4,6-triethylbenzyl chloride, 2-isopropylbenzyl chloride, 3-isopropylbenzyl chloride 4-isopropylbenzyl chloride, 3,5-diisopropylbenzyl chloride, 2,4,6-triisopropylbenzyl chloride, 2-tert-butylbenzyl chloride, 3-tert Butyl benzyl chloride, 4-tert-butyl benzyl chloride, 3,5-di-tert-butyl benzyl chloride, 2,4,6-tri-tert-butyl benzyl chloride, 2-phenyl benzyl chloride, 3-phenyl benzyl chloride, 4-phenylbenzyl chloride, 3,5-diphenylbutylbenzyl chloride, 2,4,6-triphenylbenzyl chloride, 4-methoxybenzyl chloride, 4-aminobenzyl chloride, 4-hydroxybenzyl chloride, 4-nitrobenzyl chloride, 4-cyanobenzyl chloride, 4-sulfonylbenzyl chloride, 4-trifluoromethylbenzyl chloride, methyl 4-chloromethylbenzoate, ethyl 4-chloromethylbenzoate, 4-chlorobenze Chloride, 3,5-dichlorobenzyl chloride, 2,4,6-trichlorobenzyl chloride, 4-bromobenzyl chloride, 3,5-dibromobenzyl chloride, 2,4,6-tribromobenzyl chloride, 1-chloro-1 -Phenylethane, 2-chloro-2-phenylpropane, dichloromethylbenzene and its alkyl substituents, trichloromethylbenzene and its alkyl substituents, chloromethylnaphthalene, bis (chloromethyl) naphthalene, chloromethylacenaphthylene, chloromethyl Anthracene, bis (chloromethyl) anthracene, α, α'-dichloro-p-xylene, α, α'-dichloro-o-xylene, α, α'-dichloro-m-xylene, trichloro-trimethylbenzene, dichloro-diethylbenzene The Chloro - triethylbenzene, dichloro chromatography diisopropylbenzene, trichloro - can be exemplified triisopropylbenzene, etc., likewise bromine atom instead of the chlorine atom can be exemplified substituents similar substituted by an iodine atom.

  Among these, 4-methylbenzyl chloride, 2,4-dimethylbenzyl chloride, 3,4-dimethylbenzyl chloride, and 2,6-dimethylbenzyl are excellent because they are easily available and excellent in stability and safety of the compound. Chloride, 2,4,6-trimethylbenzyl chloride, 4-isopropylbenzyl chloride, 4-tert-butylbenzyl chloride, 4-phenylbenzyl chloride, 4-trifluoromethylbenzyl chloride, ethyl 4-chloromethylbenzoate, chloromethyl Naphthalene and α, α′-dichloro-p-xylene are preferable, and are excellent in the effect of improving the deep curability and surface tack of the curable composition. Therefore, 4-methylbenzyl chloride, 4-isopropylbenzyl chloride, 2,4- Dimethylbenzyl chloride, α, α'-dichloro-p-xylene is preferred.

  These aromatic compounds (III) may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular in the addition amount of aromatic compound (III), 0.1-10 weight part is preferable with respect to 100 weight part of vinyl-type polymer (I) from the point of sclerosis | hardenability and storage stability, 0.5-5 weight part is preferable from the point that the effect of tack improvement is favorable and there is no adverse effect on deep part curability.

< Curable composition >
In the curable composition of the present invention, various compounding agents may be added according to the intended physical properties.

  <Reactive Diluent> Monomers having a radical polymerizable group can be used in combination with the curable composition of the present invention for the purpose of improving workability by reducing the viscosity, improving the properties of the cured product, and the like.

  Examples of the radical polymerizable group include (meth) acryloyl group such as (meth) acryl group, styrene group, acrylonitrile group, vinyl ester group, N-vinylpyrrolidone group, acrylamide group, conjugated diene group, vinyl ketone group, and chloride. A vinyl group etc. are mentioned. Among these, those having a (meth) acryloyl group similar to the ultraviolet crosslinkable group used in the vinyl polymer (I) used in the present invention are preferable.

  Specific examples of the monomer include (meth) acrylate monomers, styrene monomers, acrylonitrile, vinyl ester monomers, N-vinyl pyrrolidone, acrylamide monomers, conjugated diene monomers, vinyl ketone monomers, vinyl halides and halogenated monomers. Examples include vinylidene monomers and polyfunctional monomers.

  (Meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Isobutyl acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, (meth ) N-octyl acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate , Dodecyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic Stearyl acid, tridecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate , 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxy) Propyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate , (Meth) acrylic acid 2-perfluoroethyl- 2-perfluorobutylethyl, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2 (meth) acrylate -Perfluoroethylethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate, and the like.

  Examples of the styrenic monomer include styrene and α-methylstyrene.

  Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, and vinyl butyrate.

  Examples of the acrylamide monomer include acrylamide and N, N-dimethylacrylamide.

  Examples of the conjugated diene monomer include butadiene and isoprene. Examples of the vinyl ketone monomer include methyl vinyl ketone.

  Examples of the vinyl halide / vinylidene halide monomer include vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, and vinylidene bromide.

  Multifunctional monomers include trimethylolpropane triacrylate, neopentyl glycol polypropoxy diacrylate, neopentyl glycol diacrylate, trimethylol propane polyethoxy triacrylate, bisphenol F polyethoxy diacrylate, bisphenol A polyethoxy diacrylate, dipenta Erythritol polyhexanolide hexaacrylate, tris (hydroxyethyl) isocyanurate polyhexanolide triacrylate, tricyclodecane dimethylol diacrylate 2- (2-acryloyloxy-1,1-dimethyl) -5-ethyl-5 -Acryloyloxymethyl-1,3-dioxane, tetrabromobisphenol A diethoxydiacrylate, 4,4-dimercaptodiphenyl Phi blunder methacrylate, polytetramethylene glycol diacrylate, 1,9-nonanediol diacrylate, Cyclohexanedicarboxylic acrylate 1,6, dimethylol tricyclodecane acrylate, ditrimethylolpropane tetraacrylate.

  The addition amount in the case of adding the reactive diluent is not particularly limited, but 100 parts by weight of the vinyl polymer (I) from the viewpoint that the workability of the curable composition is good and the effect on the cure shrinkage is small. Is preferably 0.1 to 100 parts by weight, and more preferably 0.1 to 70 parts by weight.

  Commercially available urethane acrylate resin, epoxy acrylate resin, polyester acrylate resin, acrylic acrylate resin, unsaturated polyester resin for imparting mechanical strength and abrasion resistance to the cured product of the present invention and adjusting the viscosity. Further, a silicone acrylate resin or the like can be used in combination. When these resins are used in combination, the addition amount is preferably from 0.1 to 500 parts by weight, more preferably from 1 to 50 parts by weight, based on 100 parts by weight of the vinyl polymer (I).

<Filler>
A filler can be added to the curable composition of the present invention as long as it does not interfere with active energy ray curing. Specific examples include various fillers and fine hollow particles described in paragraphs [0134] to [0151] of JP-A-2006-291073. As the filler, fine silica that is reinforcing silica such as fumed silica, wet process silica, wood powder, pulp, cotton chips, mica, walnut shell powder, rice husk powder, graphite, white clay, silica (crystalline silica, Fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, etc.), carbon black, heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, oxidized first Ferrous iron, bengara, aluminum fine powder, flint powder, zinc oxide, activated zinc white, zinc dust, zinc carbonate, shirasu balloon, beads such as polyacrylic resin, polyacrylonitrile-vinylidene chloride resin, phenolic resin, polystyrene resin and the like Hollow fine particles, glass balloon, shirasu balloon, fly-up Inorganic hollow fine particles such as Yubarun, glass fibers, glass filaments, carbon fibers, Kevlar fibers, fibrous fillers such as polyethylene fiber and the like.

  From the point of being excellent in transparency and reinforcement, fumed silica and wet process silica are preferred.

  The amount of addition in the case of adding a filler is not particularly limited, but from the viewpoint that the workability of the curable composition is good and the mechanical properties of the resulting cured product are improved, relative to 100 parts by weight of the vinyl polymer. 1 to 50 parts by weight is preferable, and 5 to 30 parts by weight is more preferable.

<Plasticizer>
A plasticizer can be added to the curable composition of the present invention. By adding a plasticizer, it is possible to adjust mechanical properties such as the viscosity of the curable composition, the tensile strength and elongation of the resulting cured product, and to improve the transparency of the cured product. Although it does not specifically limit as a plasticizer, According to the objectives, such as adjustment of a physical property and adjustment of properties, phthalic acid esters, such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, etc .; Dioctyl adipate , Non-aromatic dibasic acid esters such as dioctyl sebacate, dibutyl sebacate, isodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyl ricinolinate; diethylene glycol dibenzoate, triethylene glycol dibenzoate, penta Esters of polyalkylene glycols such as erythritol esters; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Pyromellitic acid esters; Polystyrene Polystyrenes such as poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; polyethylene Polyether polyols such as glycol, polypropylene glycol, polytetramethylene glycol and the like, and polyethers such as derivatives obtained by converting the hydroxyl groups of these polyether polyols to ester groups, ether groups, etc .; epoxidized soybean oil, epoxy such as epoxy benzyl stearate Plasticizers: dibasic acids such as sebacic acid, adipic acid, azelaic acid, phthalic acid, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene Polyester plasticizers obtained from dihydric alcohols such as Nglycol; Vinyl polymers obtained by polymerizing vinyl monomers such as acrylic plasticizers such as ARUFON series manufactured by Toagosei Co., Ltd. by various methods Etc. These may be used alone or in combination of two or more.

  The addition amount in the case of adding a plasticizer is not particularly limited, but the vinyl polymer (I) from the viewpoint that the workability of the curable composition is good and the effect on the mechanical properties of the resulting cured product is small. The amount is preferably 1 to 100 parts by weight and more preferably 1 to 50 parts by weight with respect to 100 parts by weight.

<Solvent>
A solvent can be mix | blended with the curable composition used by this invention as needed.

  Solvents that can be blended include, for example, aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone Examples of the solvent include alcohol solvents such as methanol, ethanol and isopropanol; hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, heptane and octane. These may be used alone or in combination of two or more.

  The amount of the solvent added is not particularly limited, but the vinyl polymer (I) is 100 weights because the workability of the curable composition is good and the effect on the curing shrinkage associated with ultraviolet curing is small. The amount is preferably 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight with respect to parts.

<Thixotropic agent (anti-sagging agent)>
A thixotropic agent (anti-sagging agent) may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability.

  The thixotropic inhibitor is not particularly limited, and examples thereof include hydrogenated castor oil derivatives, metal soaps having long-chain alkyl groups, ester compounds having long-chain alkyl groups, inorganic fillers such as silica, amide waxes, and the like. Can be mentioned. These thixotropic agents may be used alone or in combination of two or more.

  The addition amount in the case of adding the thixotropy imparting agent is not particularly limited, but is 0.1% with respect to 100 parts by weight of the vinyl polymer (I) because the workability of the curable composition is good. 10 to 10 parts by weight is preferable, and 0.1 to 5 parts by weight is more preferable.

<Antioxidant>
An antioxidant (antiaging agent) can be used in the curable composition of the present invention. When antioxidant is used, the heat resistance of hardened | cured material can be improved. Antioxidants include general hindered phenolic antioxidants, amine antioxidants, lactone antioxidants, primary antioxidants such as ethanolamine antioxidants, sulfur-based antioxidants and phosphorus-based antioxidants. Secondary antioxidants such as an oxidant are listed. As the antioxidant, those described in paragraphs [0232] to [0235] of JP-A-2007-308692 and paragraphs [0089] to [0093] of WO05 / 116134 can be used.

  The addition amount in the case of adding an antioxidant is not particularly limited, but is 100 parts by weight of the vinyl polymer (I) from the viewpoint that the effect on heat resistance is sufficiently exhibited and is not disadvantageous economically. The amount is preferably 0.1 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight.

<Other additives>
Various additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include, for example, compatibilizers, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, antifoams. Agents, foaming agents, termite-proofing agents, fungicides, UV absorbers, light stabilizers and the like. Specific examples other than the specific examples of the additives listed in the present specification include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-62-2904, It is described in Japanese Laid-Open Patent Publication No. 2001-72854.

<Preparation of curable composition>
The curable composition of the present invention can be prepared as a one-pack type in which all compounding components are preliminarily blended and stored and cured by irradiation with active energy rays after construction.

  The method for preparing the curable composition of the present invention is not particularly limited. For example, the components described above are mixed and mixed with a hand mixer or a static mixer, or at room temperature or using a planetary mixer, a disper, a roll, a kneader, or the like. Ordinary methods such as kneading under heating or using a small amount of a suitable solvent to dissolve and mix the components may be employed.

<About the curing method of the curable composition>
The active energy ray irradiation of the present invention can be used as long as it is a light source used for normal active energy ray curing. For example, sunlight, low-pressure mercury lamp (sterilization lamp, fluorescent chemical lamp, black light), fluorescent lamp, Incandescent lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, carbon arc lamp, metal halide lamp, gallium lamp, tungsten lamp, xenon lamp, mercury xenon lamp, chemical lamp, electrodeless discharge lamp, zirconium lamp, UV- LED etc. are mentioned. Among these, a high pressure mercury lamp, a metal halide lamp, an electrodeless discharge lamp, and a UV-LED are preferable from the viewpoint of easy handling and economical efficiency.

  In addition, the irradiation intensity and integrated light amount of ultraviolet rays are appropriately adjusted depending on the shape such as the type and amount of the active energy ray crosslinkable group, the type and amount of the active energy ray polymerization initiator, and the desired thickness and size of the cured product. Irradiated.

  As a method of irradiating active energy rays, for example, a method of continuously irradiating active energy rays on a belt conveyor, a method of stopping the belt conveyor only when irradiating active energy rays, and irradiating active energy rays uniformly, or For example, a method (batch type) in which a curable composition is charged into or taken out from an active energy ray irradiation apparatus for each irradiation. The belt conveyor system is suitable for continuous curing. The batch method does not require a large-scale apparatus such as a belt conveyor, and has an advantage that it is easy to uniformly irradiate the target with active energy rays. In the case of the belt conveyor type, for example, the curable composition is placed on the belt conveyor, and the active energy beam is irradiated from an active energy beam irradiation device fixed on the upper side, the side or the lower side of the conveyor.

  Alternatively, the curable composition can be applied and cured in accordance with the movement of the application robot, the irradiation robot, or the stage using a spot type active energy ray irradiation apparatus.

  Active energy ray-curable resins are known to easily cause surface hardening inhibition due to oxygen inhibition. To avoid this, for example, active energy ray-curable compositions are made of PP film, PET film, Teflon (registered trademark). ) Method of irradiating active energy ultraviolet rays through the film so that the surface is not in contact with oxygen by covering with the film, active energy in the inert zone where oxygen is replaced by inert gas such as nitrogen gas or carbon dioxide gas A line may be irradiated. In the latter method, in order to improve the reaction rate of the active energy ray-curable composition, the oxygen concentration in the irradiation atmosphere is preferably 5000 ppm or less, and more preferably 500 ppm or less.

  However, it is clear that the curing method of the present invention is not limited to the above method.

<How to use the active energy ray cured product>
The cured product of the present invention may be used alone or in combination with other members as necessary. The active energy ray-curable composition may be poured into a mold and solidified and then taken out, or may be cured using a desired mold and used for each mold. Or you may apply | coat and use for dot shape, bead shape, planar shape, or arbitrary shapes with a roller, a dispenser, etc. In addition, the obtained cured product may be bonded to other members such as film, rubber, plastic, metal, ceramics, paper, and nonwoven fabric, or may be inserted or sandwiched. After making it contact with another member in the state of an energy beam curable composition, it may harden by irradiating with an active energy beam, and a composite molded object may be obtained.

  However, it is obvious that the molded body of the present invention is not limited to the above-described method of use.

<Application>
Applications of the active energy ray-curable composition and the cured product of the present invention are not limited, but include sports equipment, toys / playground equipment, stationery, pharmaceutical / medical / care products, footwear, bedding / bedding, furniture, clothing, various types Miscellaneous goods, transport goods, OA equipment, home appliances, audio equipment, portable equipment, industrial machinery / equipment, precision equipment, electrical / electronic equipment, electrical / electronic components, sealing materials / coating materials / adhesives / adhesives for building materials・ Molded bodies, sealing materials, molded parts, paints, inks, foams, resist materials, on-site molded gaskets, shock absorbing materials, shock absorbing materials, pressure dispersion materials, vibration damping materials, vibration damping materials, sound absorbing materials, soundproofing materials -It can be used for various applications such as heat insulating materials and feel improving members.

  Moreover, when using for various uses, the utilization as a shock absorber, an insulator, a bush, various mounts, a roller, a film, a sheet | seat, a tape, a seal | sticker, a chip | tip, and a shaping | molding member is also possible.

  For sports use, impact cushioning materials installed on fences and floors of gymnasiums, stadiums, gymnasiums, landing mats for gymnastics and exercise, floor exercise mats, gym stretch mats, kids mats, bouldering Mat (crash pad), beat board, high jump cushion material, wet suit, golf club, bat, tennis racket grip and heartwood, grab and mitt heartwood, sports shoe overlay, insole, insole, shoe sole, Ski boots, snowboard boot liners, toe shoes, ballet shoes, golf club heads, golf balls, baseball balls and other ball sports balls, sports protectors (for example, headgear and baseball used in martial arts such as rugby and boxing) And football helmets, baseball, soccer, Elbows for fighting, leggers (singards, etc.), rackets, balls, suits for riders, gloves (soccer keeper gloves, golf, skis, riders), rifle jackets (eg shoulder pads), molded products, seals It is useful for material applications, sealant applications, impact absorption applications, impact buffer applications, pressure dispersion applications, vibration suppression applications, vibration isolation applications, sound absorption applications, sound insulation applications, and touch improvement applications for human body contacts.

  For toys and play equipment, seals, hand exercisers, healing goods, key holders, plush toys, moving stuffed animals, mannequin bodies, balls, massage balls and other cushion materials and fillings, game controllers and mats, mobile phones and smartphones, etc. Fabrication materials for articles and other decorative items, animal models, monsters, dolls, figures and other molded object applications, sealing material applications, sealant applications, shock absorption applications, shock absorbing applications, pressure dispersion applications, vibration control applications, and prevention It is useful for vibration application, sound absorption application, soundproofing application, touch improvement part of the contact part with the human body, and the like.

  For medical / nursing care, artificial skin, artificial bone, artificial cartilage, artificial organ, artificial cornea, artificial crystalline lens, artificial vitreous body, artificial muscle, artificial blood vessel, artificial joint, human body model, swimsuit and breast pad for breast augmentation Use as insertion material, other biocompatible materials, chemical liquid exuding pad, hemostatic pad, gas-liquid separation filter (indwelling needle filter), patch, medical liquid absorption tool, mask, compression pad, surgical disposable product , Medical tubes, caps, bags, gaskets, hoses, medical beds, treatment tables, chairs, electrocardiogram measurement electrode materials, electrode pads for low frequency treatment devices, sensor pads, bedsore prevention mattresses, posture change cushions, wheelchairs Cushion, wheelchair seating, shower chair, etc., bathing care pillow, taping, cast liner, soft contact lens material Prosthetic hand, prosthetic leg itself, cushioning material (liner etc.) for connection to the prosthetic leg and prosthetic human body, or prosthetic leg and prosthetic hand joint parts, denture base, other dental supplies, shock absorbing pad, hip protector, elbow / knee It can also be used for protectors, post-operative body shape auxiliary materials, poultice materials, wound dressings, cell culture sheets, adult models for therapeutic training, and the like. Other items that can be used in contact with the human body include, for example, fish eye or octopus pain cushioning materials, supporters, pumps and other slip prevention materials, or elbow or heel drying prevention pads, hallux valgus and wound nails. It is useful for shock absorption applications for foot care. In addition, transdermally absorbable preparations, adhesives for sticking, medical / medical sealing materials, medical adhesives, medical rubber stoppers, impression materials, dental fillers, syringe gaskets, and rubber stoppers for vacuum vessels, artificial dialysis O-rings or flat gaskets for devices, packaging materials for pharmaceuticals and medical devices, caps, cap liners, caps for vacuum blood collection tubes, catheter sealing materials and adhesives, sealing materials for implantable medical devices and attached sensors, etc. It can be used for adhesives.

  As footwear applications, it can be used for men's shoes, women's shoes, children's shoes, elderly shoes, sports shoes, safety shoes, etc. Each shoe's skin material, lining, insole (inner sole), shoes Sole (outsole, midsole, heel), shoe rub pad, various shoe pads, inner boots, slippers, slipper core, sandals, sandals, insoles, etc., shock buffering applications, shock absorption applications, comfort improvement applications Useful for beauty and slimming applications.

  Bedding and bedding products include pillows, comforters, mattresses, beds, barber / beauty beds, mattresses, bed mats, bed pads, cushions, cribs, baby bed pillows, bed slip prevention, body pressure dispersion, Examples include sleeping comfort improvement applications, impact absorption applications, and molded product applications.

  Furniture applications include chairs, seat chairs, cushions, sofas, sofa cushions / seat cushions, waist cushions, and other cushions, carpets / mats, tatami mats / comforters, toilet seat mats for spreading body pressure and improving sitting comfort , Impact absorbing applications, feel improving applications and the like. Desk, chest, clothes case, bookshelf, staircase, door, door, bran, shoji, sliding door handle and handle, handrail, door stop, etc. Can be mentioned.

  Examples of clothing applications include pad materials such as shoulders and bras, cold protection materials, helmets, bulletproof vests, etc., impact absorption applications, heat insulation applications, molded object applications, and the like.

  Various miscellaneous goods can be used for bath products such as bath pillows, massage puffs, mouse pads, personal computer armrests and wrist rests, non-slip cushions, stationery (pen grips, penetrating sealants), desk pillows, earplugs, cotton swabs, hot Pack sheet, cold pack sheet, compress, eyeglass pad, underwater spectacles pad, face protector, watch pad, headphone ear pad, earphone, heat retaining cup, beverage can, ice pillow cover, folding pillow, writing instrument, bag (eg school bag) ), Daily goods / carpenter's grips, carpets, rugs such as artificial turf materials, elbow pads, knee pads, gloves, fish fishing, etc. Molded products such as anti-wrinkle prevention materials, sealing materials, shock absorbing applications, shock absorbing applications, anti-vibration applications, control Applications, sound absorption applications, silencing applications, can be utilized as the feeling improving part application of the contact portion of the human body.

  Transportation applications include automobiles, motorcycles, bicycles, electric bicycles, tricycles, strollers, construction machinery, railway vehicles, ships, aircraft seats, child seats, headrests, armrests, footrests, headliners, saddles, rider cushions, helmets, custom Car bed mat, camper cushion, ceiling material, door trim, floor cushion instrument panel, dashboard, door panel, inner panel, shift knob, handle, grip, pillar, console box, airbag cover, parking brake cover, quarter trim , Interior materials such as lining, center pillar garnish, sun visor, in-vehicle electronics such as recording / playback devices and various sensors, control equipment for in-vehicle road navigation system Engine, harness, dust cover, hose, engine, battery, oil pan, front cover, rocker cover, etc., engine, tire, bumper, floor, under floor, door, roof, panel, wheel house, transmission, weather strip, various Auxiliary machine covers, window packings, roof moldings, door moldings, seat backs, trunk rooms, cargo bed and other molded body applications, sealing materials, vibration control applications, vibration isolation applications, shock absorption applications, sound absorption applications, sound insulation Applications, buffer applications, applications for improving the feeling of contact with the human body, and the like. Also included are vibration isolation applications, vibration suppression applications, shock absorption applications, and vibration absorption applications for carrying goods such as carry bags, carts, containers, flexible containers, and pallets. Examples of materials to be transported include fine arts, precision instruments, fruits, fresh fish, eggs, pottery and porcelain, and can be used for direct packaging, indirect packaging, or packaging. Further, it can be used as shock absorbers, insulators, bushes, various mounts, film sheets, tapes, seals, chips, and molded members for transportation, transportation, and transportation. As the anti-vibration rubber, it can be used for anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, anti-vibration materials and the like.

  Furthermore, in the automobile field, it can be used as a body part as a sealing material for maintaining airtightness, an anti-vibration material for glass, an anti-vibration material for vehicle body parts, particularly a wind seal gasket and a door glass gasket. As chassis parts, it can be used for vibration-proof and sound-proof engines and suspension rubbers, especially engine mount rubbers. Engine parts can be used for hoses for cooling, fuel supply, exhaust control, etc., gaskets for engine covers and oil pans, sealing materials for engine oil, and the like. It can also be used for exhaust gas cleaning device parts and brake parts. As tire parts, in addition to bead parts, sidewall parts, shoulder parts and tread parts, it can be used as a resin for inner liners and as a sealing material for air pressure sensors and puncture sensors. Further, it can be used as a sealing material, sealing material, gasket, coating material, mold member, adhesive, and pressure-sensitive adhesive for various electronic parts and control parts. It can also be used as a covering material for copper / aluminum wire harnesses and a sealing material for connector parts. In addition, lamps, batteries, window washer fluid units, air conditioner units, coolant units, brake oil units, electrical components, various interior and exterior products, sealing materials such as oil filters, adhesives, adhesives, gaskets, O-rings and packings, It can also be used as molded parts such as belts, potting materials for igniter HICs or hybrid ICs for automobiles, and the like.

  Various equipment applications include OA equipment (displays, personal computers, telephones, copiers, printers, copiers, game machines, TVs, DVD recorders, Blu-ray recorders, HDD recorders, various recorders, DVD players, Blu-ray players, etc. Players, projectors, digital cameras, home videos, antennas, speakers, electronic dictionaries, IC recorders, fax machines, photocopiers, telephones, stepping motors, magnetic disks, hard disks, etc.), molding materials, sealing materials, sealants , Anti-vibration use, vibration control use, shock absorption use, shock absorbing use, sound absorption use, sound insulation use, touch improvement part for contact with human body, adhesive, adhesive, packing, O-ring, belt .

  Household appliances (refrigerator, washing machine, washing dryer, futon dryer, vacuum cleaner, air purifier, water purifier, electric toothbrush, lighting equipment, air conditioner, air conditioner outdoor unit, dehumidifier, humidifier, fan heater, fan, ventilator・ Dryers, massagers, blowers, sewing machines, dishwashers, tableware dryers, door phones, rice cookers, microwave ovens, microwave ovens, IH cooking heaters, hot plates, various chargers, and irons) Absorption applications, shock absorbing applications, sound absorption applications, soundproof applications, handles, handles, doors, doors, handrails and other parts that touch the human body, seal materials, adhesives, adhesives, packing, O-rings, belts Useful as.

  As an anti-vibration application, a vibration control application, an impact absorption application, and an impact buffer application for audio equipment (speakers, turntables, optical pickup devices, optical recording / reproducing devices, magnetic pickup devices, magnetic recording / reproducing devices, insulators, and spacers) Useful.

  Useful as anti-vibration applications, vibration suppression applications, shock-absorbing applications, and touch-improving touch areas of human bodies, such as notebook computers, portable hard disks, mobile phones, smartphones, portable music information devices, and portable game machines It is.

  In electrical and electronic applications, for example, LED materials, various battery peripheral materials, sensors, semiconductor peripheral materials, circuit substrate peripheral materials, display peripheral materials such as liquid crystal, lighting materials, optical communication / optical circuit peripheral materials, optical recording peripheral materials It can be used for magnetic recording materials.

  LED materials include LED element molding materials, sealing materials, sealing films, die-bonding materials, coating materials, sealing materials, adhesives, adhesives, lens materials, LED bulbs, LED display lamps, LEDs It can be used for sealing materials such as display boards and LED displays, adhesives, adhesives, coating materials and the like.

  Battery peripheral materials include lithium ion batteries, sodium / sulfur batteries, molten sodium batteries, organic radical batteries, nickel metal hydride batteries, nickel cadmium batteries, redox flow batteries, lithium sulfur batteries, air batteries, electrolytic capacitors, electric double layer capacitors , Sealing materials for lithium ion capacitors, fuel cells, solar cells, dye-sensitized solar cells, back surface sealing materials, molding materials for each element, adhesives, adhesives, sealing materials, sealing films, coating materials, It can be used for potting materials, fillers, separators, catalyst fixing films, protective films, electrode binders, refrigerant oil sealing materials, hose materials, and the like.

  Sensors include force, load, impact, pressure, rotation, vibration, contact, flow rate, solar radiation, light, odor, time, temperature, humidity, wind speed, distance, position, inertia, tilt, speed, acceleration, angular velocity, hardness・ Seal, Sound, Magnetism, Current, Voltage, Power, Electron, Radiation, Infrared, X-ray, UV, Liquid, Weight, Gas, Ion, Metal, Color, etc. It can be used as a vibration absorbing material, vibration suppressing material, lens material, adhesive, pressure-sensitive adhesive, coating agent, film and the like.

  Circuit board peripheral materials include rigid or flexible wiring boards on which various elements such as ICs, LSIs, semiconductor chips, transistors, diodes, thyristors, capacitors, resistors, and coils are mounted, and MEMS (micro electro mechanical system) sealing materials , Coating materials, conformal coating materials, potting materials, molding materials, underfill materials, die-bonding materials, die-bonding films, adhesives, pressure-sensitive adhesives, sealing materials, and sealing films for the above elements.

  Peripheral display materials include liquid crystal displays, plasma displays, LED displays, organic EL (electroluminescence) displays, field emission displays, electronic paper, flexible displays, 3D holograms, organic thin film transistor displays, head mounted displays, and other molds. Materials, various filters, protective films, antireflection films, viewing angle correction films, polarizer protective films, optical correction films, etc., sealing materials, adhesives, adhesives, sealing materials, sealing films, substrates and members It can be used as a coating material, potting material, filler, visibility improving material, lens material, light guide plate, prism sheet, polarizing plate, retardation plate, and liquid crystal dam material.

  As a lighting material, it can be used as a sealing material / coating material / adhesive / sealing material / molded part of a lighting LED, a lighting organic EL, and a lighting inorganic EL.

  Optical communication and optical circuit peripheral materials include organic photorefractive elements, optical fibers, optical switches, lenses, optical waveguides, light emitting elements, photodiodes, optical amplification elements, optoelectronic integrated circuits, optical connectors, optical couplers, optical arithmetic elements, photoelectrics Molding materials, sealing materials, adhesives, adhesives, sealing materials, sealing films, coating materials, potting materials, fillers, protective films, lens materials, light guide plates, prisms for elements such as conversion devices and laser elements It can be used as a sheet, a polarizing plate and a ferrule.

  Optical recording materials include VD (video disc), CD, CD-ROM, CD-R, CD-RW, DVD, DVD-ROM, DVD-R, DVD-RW, BD, BD-ROM, BD-R, BD-RE, MO, MD, PD (phase change disk), hologram, disk substrate material for optical card, protective film such as pickup lens, sealing material, adhesive, adhesive, sealing material, sealing film, coating It can be used as a material, anti-vibration material, and damping material.

  Magnetic recording materials can be used as anti-vibration materials, damping materials, sealing materials, adhesives, adhesives, sealing materials, coating materials, cover gaskets, and card materials for magnetic cards such as hard disks, magnetic tapes, and credit cards. It is.

  As information electrical equipment, mobile phones, media players, tablet terminals, smartphones, portable game machines, computers, printers, scanners, projectors, inkjet tanks and other sealing materials, sealing materials, adhesives, adhesives, packing, O-rings, It can be used for belts, vibration-proof materials, vibration-damping materials and sound-proof materials.

  In addition, antifouling films for touch panels, lubricant films, IC chip molding materials, Peltier element molding materials, electrolytic capacitor sealing bodies, cable joint potting materials, IGBT (vehicle propulsion control device) potting materials, and semiconductor wafer processing Dicing tape, die bond agent, die bond film, underfill, anisotropic conductive adhesive, anisotropic conductive film, conductive adhesive, conductive paste, heat conductive adhesive, heat conductive paste, film for temporary fixing, It can be used for fixing films, sealing films and the like.

  Other industrial machines, electrical / electronic devices and their components, such as micro electromechanical elements called MEMS, various sensors, control devices, batteries, battery peripheral members, LED materials, semiconductor peripheral materials, circuit board peripheral materials, liquid crystal, etc. Display peripheral materials, lighting materials, optical communication / optical circuit peripheral materials, optical recording peripheral materials, magnetic recording materials, electron microscopes and other scientific and engineering equipment, various measuring devices, vending machines, TV cameras, registers, cabinets, robot skins Shuters, elevators, escalators, moving walkways, conveyors, lifts, tractors, bulldozers, generators, compressors, containers, hoppers, conveyors for fruit sorting machines, automatic teller machines (ATMs), currency exchange machines, counting machines, vending machines, Cash dispensers (CD), secondary batteries such as lithium batteries, IC trays and conveyors Anti-vibration applications such as conductor manufacturing equipment, damping steel plates, rock drills, cutting machines, chainsaws, hand mixers, mowers, etc., machines with strong motor vibration, damping applications, shock buffering applications, shock absorbing applications, human body This is useful for improving the touch of the contact portion.

  In the home appliance field, it can be used for packing, O-rings, belts and the like. Specifically, decorations for lighting fixtures, waterproof packings, anti-vibration rubbers, insect-proof packings, anti-vibration / sound absorption and air sealing materials for cleaners, drip-proof covers for electric water heaters, waterproof packings, heater parts Packing, electrode packing, safety valve diaphragm, hose for sake cans, waterproof packing, solenoid valve, waterproof packing for steam microwave oven and jar rice cooker, water tank packing, water absorption valve, water receiving packing, connection hose, belt, heat insulation Oil packing for combustion equipment such as heater packing, steam outlet seal, O-ring, drain packing, pressure tube, blower tube, feed / intake packing, anti-vibration rubber, oil filler packing, oil meter packing, oil feed tube, Speaker gaskets, speaker edges, turntables for acoustic equipment such as diaphragm valves and air pipes Seat, belts, pulleys, and the like.

  Soundproof panels, soundproof glass, general glass, ceiling materials, inner wall materials, outer wall materials, flooring materials, plumbing materials, water supply materials, building materials such as fences, air membrane structure roof materials, structural gaskets (zip gaskets), exemption Seismic rubber, anti-vibration rubber, sheet, waterproof sheet, non-standard gasket, fixed gasket, waterproof material, sealing material, packing, grommet, packaging transport material, residential vibration damping sheet, vibration damper material, bridge damping material, Soundproofing materials, setting blocks, sliding materials, laminated glass and double-glazed glass sealing materials, rustproof and waterproofing sealing materials for meshed glass and laminated glass end faces (cut parts), shutters, curtain rails, curtain walls, Vibration isolation applications such as vibration isolation isolators, ground improvement materials, vibration suppression applications, shock absorbing applications, shock absorption applications, low and high frequency sounds near the audible threshold It is useful as soundproof damping applications such as corresponding.

  In the marine and civil engineering fields, structural materials include rubber expansion joints, bearings, waterstops, waterproof sheets, rubber dams, elastic pavements, anti-vibration pads, protective bodies, etc., rubber molds, rubber packers, rubber skirts as construction secondary materials , Sponge mats, mortar hoses, mortar strainers, etc., rubber sheets, air hoses, etc. as construction auxiliary materials, rubber buoys, wave-absorbing materials, etc. as safety measures products, oil fences, silt fences, antifouling materials, marine hoses, etc. Can be used for draging hoses, oil skimmers, etc. In addition, it can be used for sheet rubber, mats, foam boards and the like.

  In addition, applications that require vibration, vibration control, soundproof, and seismic isolation materials include electrical and electronic equipment such as stepping motors, magnetic disks, hard disks, vending machines, speaker frames, BS antennas, and vibration control materials for VTR covers. ; Building applications such as roofs, floors, shutters, curtain rails, floors, piping ducts, deck plates, curtain walls, stairs, doors, vibration-isolating isolators, damping materials for structural materials; building applications such as viscoelastic dampers and earthquake-resistant mats ; Marine use for engine room and measurement room damping material; engine (oil pan, front cover, rocker cover), car body (dash, floor, door, roof, panel, wheel house), transmission, parking brake cover, seat Automotive applications such as damping materials for bags; TV cameras, copiers, computers, Applications for cameras and office equipment such as linters, registers, cabinet damping materials; shooters, elevators, escalators, conveyors, tractors, bulldozers, generators, compressors, containers, hoppers, soundproof boxes, mowing machine motor damping materials, etc. Industrial machinery-related applications; railway vehicle roofs, side plates, doors, under floors, various auxiliary equipment covers, railway damping materials such as bridge damping materials; damping materials for precision vibration isolator for semiconductor applications; near audible threshold It can be used as a vibration damping material for soundproofing such as for low frequency sound and high frequency sound.

  In addition, the cured product of the present invention can be used as a molded body for packing, O-rings, belts, tubes, hoses, valves, seats, and the like.

  Reactive hot melt agent for wiring connectors, reactive hot melt adhesive, OCA (transparent adhesive for optics), elastic adhesive, contact adhesive, anaerobic adhesive, tile adhesive, UV curable adhesive, electronic It can be used as various adhesives such as a linear curable adhesive, an adhesive for a touch panel and a touch sensor.

  It can be used as various adhesives such as modification of butyl-based adhesives, masking tapes, pipe anticorrosion tapes, architectural waterproofing tapes, electrical self-fusing tapes, re-peeling adhesives, electric wire fusion tapes, and the like.

  Covering materials for electric wires, cables, optical fibers or their repair materials, insulation sealing materials for connection parts, gas pipes, pipe lining materials such as water pipes, inorganic fillers, organic filler coating materials, release materials for molding in epoxy molds, etc. It can be used for various coating applications.

  It can be used as various sheets such as a heat conductive sheet, a heat radiating sheet, an electromagnetic wave absorbing sheet, a conductive sheet, a waterproof sheet, an automobile protective sheet, and a panel shock absorbing sheet.

  Shock absorbing gel, impact absorbing material such as bed, shoes, interlayer film of laminated glass, elastic paint, paint such as aqueous emulsion, prepreg, various rollers for OA equipment and transport, cap liner, ink repellent agent, ink, Seals for various refrigerants, seals and gaskets for industrial and food cans, foam gaskets, paints, powder paints, foams, seals for can lids, films, gaskets, marine deck caulking, casting materials, It can be used as various molding materials and artificial marble.

  It can also be used for resist applications such as dry film resist applications and electrodeposition resist applications.

  However, it is obvious that the cured product of the present invention is not limited to the above-mentioned use.

  Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. In the following Examples and Comparative Examples, “part” and “%” represent “part by weight” and “% by weight”, respectively. “Number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column filled with polystyrene cross-linked gel (shodex GPC K-804, K-802.5; manufactured by Showa Denko KK) was used as the GPC solvent with chloroform.

The number of functional groups introduced per molecule of polymer was calculated based on the concentration analysis by ¹ H-NMR and the number average molecular weight determined by GPC. NMR was measured at 23 ° C. using Bruker ASX-400 and deuterated chloroform as a solvent.

(Synthesis Example 1) Synthesis example of poly (n-butyl acrylate) polymer [P1] having an acryloyl group According to a known method (for example, described in JP 2012-212216 A), cuprous bromide is a catalyst, Pentamethyldiethylenetriamine as a ligand, diethyl-2,5-dibromoadipate as an initiator, n-butyl acrylate as a monomer, and a ratio of (n-butyl acrylate) / (diethyl-2,5-dibromoadipate) to 160 To obtain terminal bromine group n-butyl polyacrylate.

  This polymer was dissolved in N, N-dimethylacetamide, potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. in a nitrogen atmosphere. N, N-dimethylacetamide in this mixed solution was distilled off under reduced pressure, butyl acetate was added to the residue, and insoluble matter was removed by filtration. The butyl acetate in the filtrate was distilled off under reduced pressure to obtain a poly (n-butyl acrylate) polymer [P1] having acryloyl groups at both ends.

The number average molecular weight of the polymer [P1] was 23,000, the molecular weight distribution was 1.1, and the average number of acryloyl groups introduced per molecule of the polymer was determined by ¹ H-NMR analysis to be about 1.9. It was a piece.

<Physical property evaluation method>
Each physical property evaluation of the cured products prepared in Examples and Comparative Examples was performed according to the following methods and conditions.

(Surface hardening)
A 0.1 mm thick polyethylene sheet is adhered to the surface of the cured product and slowly peeled off after 3 seconds. No resin adhesion is seen on the polyethylene (◎), thin resin is attached (○), many resins Is attached (×).

(tack)
A finger was pressed against the surface of the cured product and slowly peeled off, and it was assumed that there was no tack with the finger (◎), a little tack (○), and there was tack (×).

(Deep part curability)
Irradiate ultraviolet rays from above the container filled with the curable composition so as to have a thickness of 3 mm, evaluate the curability in the depth direction, and are fully cured to the bottom (◎), slightly to the bottom An uncured portion remains (◯), the inside is soft and many uncured portions remain (Δ), only the surface layer is cured, and the inside remains liquid (×).

(Thin film curability)
Irradiate UV to the curable composition applied to a thickness of 50 μm, slowly press the finger against the surface of the cured product, peel off slowly, no resin sticking to the finger and no tack (◎), resin sticking to the finger Is not seen, and there is a little tack (◯), and there is resin adhesion on the finger and there is a tack (×).

(Comparative Example 1)
One part of IRGANOX1010 (manufactured by BASF Japan) as an antioxidant and 100 parts of polymer [P1] obtained in Synthesis Example 1 and DAROCUR1173 (manufactured by BASF Japan, 2-hydroxy-2-methyl-1) as a photo radical initiator 0.2 parts of -phenylpropan-1-one) and 0.1 part of IRGACURE819 (manufactured by BASF Japan, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide) are added and sufficiently dissolved and mixed. And defoamed to obtain an active energy ray-curable composition [A1]. The obtained active energy ray-curable composition [A1] was poured into a container so as to have a thickness of 3 mm, and peaked using LH-6 (bulb: H-bulb) manufactured by Fusion Japan as an ultraviolet irradiation device. Illuminance: 500 mW / cm ² and an integrated light quantity of 4000 mJ / cm ² were irradiated with ultraviolet rays in the air to produce a rubber-like cured product having a thickness of 3 mm. The resulting cured product was evaluated for surface curability, tack and deep curability. Similarly, the curable composition was applied so as to have a thickness of 50 μm, and irradiated with ultraviolet rays under air so that the peak illuminance was 500 mW / cm ² and the integrated light amount was 4000 mJ / cm ^2, and the thin film curability was evaluated. . The results are shown in Table 1.

(Examples 1-3)
As a non-polymerizable aromatic compound (III) having a functional group bonded to an aromatic ring, a cured product was prepared in the same manner as in Comparative Example 1 except that it was added as shown in Table 1. The cured product obtained Were evaluated for surface curability, tack, deep curability, and thin film curability. The results are shown in Table 1.

(Comparative Examples 2-6)
As other compounds, except that they are added as shown in Table 1, a cured product is prepared in the same manner as in Comparative Example 1, and the surface cured property, tack, deep curable property, and thin film curable property of the obtained cured product are evaluated. did. The results are shown in Table 1.

The compounds listed in Table 1 are
[C1]: 4-methylbenzyl chloride
[C2]: α, α′-dichloro-p-xylene
[D1]: 4-chloromethylstyrene
[D2]: ethyl 2-chloropropionate
[D3]: ethyl 2-bromobutyrate
[D4]: Benzophenone
[D5]: 4,4′-bis (diethylamino) benzophenone.

  From Table 1, by adding a non-polymerizable aromatic compound in which at least one halogenated alkyl group of the present invention is bonded to an aromatic ring, there is no inhibition of surface hardening, tack is greatly reduced, and deep curability It is clear that the thin film curability is excellent.

  In Comparative Example 2 having a polymerizable functional group, the effects of improving surface hardening and reducing tack are seen, but the deep part curability is remarkably lowered. In Comparative Examples 3 and 4 using one kind of initiator of atom transfer radical polymerization, the effects of surface curability and tack improvement, and thin film curability are not seen at all.

  Conventionally, compounds such as benzophenone and diethylaminobenzophenone (Michler's ketone), which have been considered to be effective in improving surface curability, are insufficient in surface tack improvement effect, and further deteriorate deep curability.

Claims (8)

The vinyl polymer (I) having at least one active energy ray crosslinkable group on average, the active energy ray polymerization initiator (II), and the functional group represented by the following general formula (1) are aromatic hydrocarbon rings And a non-polymerizable aromatic compound (III) bonded to at least one of the active energy ray-curable compositions.
-C (R ¹ ) _3-a (X) _a (1)
(In the formula, R ¹ is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or two R ^{1 s} (when a is 1 They may be the same or different, and X is a chlorine, bromine or iodine atom, and when two or more X are present, they may be the same. And may be different, a represents 1, 2 or 3.)   The vinyl polymer (I) having at least one active energy ray crosslinkable group on average is a vinyl polymer having an active energy ray crosslinkable carbon-carbon double bond at the molecular end. The curable composition according to claim 1.   Vinyl polymers and polymers having active energy ray crosslinkable carbon-carbon double bonds at the molecular ends, wherein the polymer is a vinyl polymer having active energy ray crosslinkable carbon-carbon double bonds at both ends of the polymer The active energy ray-curable composition according to claim 2, comprising a vinyl polymer having an active energy ray-crosslinkable carbon-carbon double bond at one end of each.   The active energy ray-curable composition according to any one of claims 1 to 3, wherein the vinyl polymer (I) having at least one active energy ray crosslinkable group on average is a (meth) acrylic polymer. .   The active energy ray-curable composition according to any one of claims 1 to 4, wherein the molecular weight distribution of the vinyl polymer (I) having at least one active energy ray crosslinkable group on average is less than 1.8. . The active energy ray-curable composition according to any one of claims 1 to 5, wherein the active energy ray crosslinkable group is represented by the general formula (2).
—OC (O) C (R ² ) ═CH ₂ (2)
(Wherein R ² represents a hydrogen atom or an organic group having 1 to 20 carbon atoms) 0.01 to 10 parts by weight of the active energy ray polymerization initiator (II) per 100 parts by weight of the vinyl polymer (I) having at least one active energy ray crosslinkable group on average, the following general formula (1) The non-polymerizable aromatic compound (III) in which at least one functional group represented by the formula is bonded to an aromatic hydrocarbon ring is contained in an amount of 0.1 to 10 parts by weight. The active energy ray-curable composition according to any one of the above.
-C (R ¹ ) _3-a (X) _a (1)
(In the formula, R ¹ is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or two R ^{1 s} (when a is 1 They may be the same or different, and X is a chlorine, bromine or iodine atom, and when two or more X are present, they may be the same. And may be different, a represents 1, 2 or 3.)   Hardened | cured material obtained from the active energy ray curable composition of any one of Claims 1-7.