JP2009292898A - Curable composition and cured product of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curable composition excellent in curability, which gives a cured product having reduced surface stickiness and excellent heat resistance and oil resistance. <P>SOLUTION: The curable composition contains (a) a vinyl polymer having at least one group expressed by general formula (1):-OC(O)C(R)=CH<SB>2</SB>at a molecular terminal per one molecule (wherein R represents a hydrogen atom or a 1-20C organic group) and (b) a photo-radical polymerization initiator, wherein (b1) a photo-radical polymerization initiator having a structure decomposed by light in at least two sites in the molecule and/or (b2) a hydrogen abstraction type photo-radical initiator having at least three aromatic rings in the molecule are used for the (b) photo-radical polymerization initiator. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a room temperature, heated, active energy curable composition and a cured product produced using the composition. More specifically, the present invention relates to an ancestral composition containing a vinyl polymer having a (meth) acryloyl group at a molecular terminal as an essential component and a cured product produced using the composition.

  Acrylic resins are used in a wide range of applications such as building seals, functional parts centered around automobile engines, security parts, adhesives, adhesives, and coating materials due to their heat and oil resistance characteristics. Yes.

  However, taking acrylic rubber as an example, it can be obtained by vulcanization molding after blending fillers, vulcanizing agents, etc. with unvulcanized rubber, but in the case of acrylic rubber, it adheres to the roll during kneading. It is difficult to smooth during sheeting, or it is difficult to process such as non-fluidity during molding and slow vulcanization speed, or long post-curing is required. There's a problem. There are also problems such as the reliability of the seal and the necessity of precision machining of the flange surface.

  Although the thing which improved workability and curability is reported (patent document 1), photocuring in which quick hardening is possible is possible and productivity cannot be improved.

  In addition, as a sealing material, a silicone material or a urethane (meth) acrylate resin as a main component is used. When a silicone material is used, SJ grade engine oil, which is a recent high-performance engine oil, Incorporates basic zinc carbonate that is highly damaged by the use of some transmission oils and gear oils for automatic vehicles, and the content of iminoxysilane and zinc hydroxide is 5 to 50% by weight (hereinafter referred to as "%") The conventional technology such as the method (Patent Document 2) cannot solve the problem.

  On the other hand, when the main component is a urethane (meth) acrylate resin, some have excellent oil resistance (Patent Document 3), but since the main chain has an ether bond or an ester bond, it has long-term heat resistance. There 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 4 and 5). While the polymer is excellent in heat resistance and oil resistance, the photo-radical curing has a problem that it has surface tackiness resulting from the inhibition of curing by dissolved oxygen on the surface of the cured product, which hinders the assembly process of parts. In addition, photoradical initiators that are generally considered effective for inhibiting oxygen on the surface of commercially available cured products, for example, photoradicals containing atoms with high electrical attraction such as nitrogen and sulfur that are effective for inhibiting oxygen inhibition Even when an initiator (for example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one) is used, although an improvement effect is observed, it is not sufficient.
JP 2000-1 54370 A Japanese Patent Laid-Open No. 3-20 3960 JP-A 64-112 Japanese Unexamined Patent Publication No. 2000-72816 JP 2000-95826 A

  An object of the present invention is to provide an active energy curable composition having excellent curability, in which the surface tackiness of a cured product is reduced, and a cured product having excellent heat resistance and oil resistance is provided.

  As a result of intensive studies by the present inventors in view of the above-mentioned present situation, a vinyl polymer having a group having a polymerizable carbon-carbon double bond at at least one molecular end and polymerization by photolysis in the molecule. Cured by adding a photo-radical initiator having two or more functional groups capable of generating a functional radical and / or a hydrogen abstraction type photo-initiator having three or more aromatic rings in the molecule to cure. The present inventors have found that the surface tackiness (tackiness) can be improved and have completed the present invention.

That is, in the present invention, (a) a group represented by the following general formula (1) (hereinafter sometimes referred to as “polymerizable carbon-carbon double bond” or “(meth) acryloyl group”). Vinyl polymer having at least one molecule terminal per molecule —OC (O) C (R) ═CH ₂ (1)
(Wherein R represents hydrogen or an organic group having 1 to 20 carbon atoms), and
(B) containing a radical photopolymerization initiator,
As said (b) photoradical polymerization initiator,
(B1) a photoradical polymerization initiator having two or more structures in the molecule that decomposes by light, and / or (b2) a hydrogen abstraction type photoradical initiator having three or more aromatic rings in the molecule, It is a curable composition.

  (B1) As a radical photopolymerization initiator having a structure that decomposes by light in two or more positions in a molecule, a polymer photopolymerization initiator can be used, and a photodegradable compound and a polymer photopolymerization initiator are used. You can also

  The (b1) radical photopolymerization initiator having two or more structures in the molecule that decomposes by light preferably has an aromatic structure.

  It is preferable that the value (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the (a) vinyl polymer is less than 1.8.

  (A) The main chain of the vinyl polymer produced by living radical polymerization is preferred, and atom transfer radical polymerization is more preferred. The atom transfer radical polymerization preferably uses a copper complex as a catalyst.

  The main chain of the vinyl polymer (a) is preferably produced by polymerization of a vinyl monomer using a chain transfer agent.

  The main chain of the (a) vinyl polymer is at least one selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. It is preferable that it is mainly produced by polymerizing, more preferably one produced mainly by polymerizing (meth) acrylic acid ester, and more preferably one produced mainly by polymerizing acrylic acid ester.

The number average molecular weight of the (a) vinyl polymer is preferably 3000 or more.
The cured product of the present invention is obtained by curing the curable composition.

The cured product can be obtained by curing with active energy rays. UV and / or electron beams can be used for the active energy rays.
In addition, cured products obtained from the above curable compositions include sealing materials, electrical / electronic component materials, electrical insulation materials, adhesives, adhesives, potting agents, heat dissipation materials, waterproofing materials, anti-vibration / vibration / isolation methods. It can be used for materials, films, marine deck coking, casting materials, or molding materials.

  According to the curable composition of the present invention, it exhibits excellent curability and (a) has excellent heat resistance and oil resistance inherently possessed by a cured product obtained from a vinyl polymer alone. A cured product having improved surface tackiness (tackiness) can be obtained.

The curable composition of the present invention is (a) a vinyl polymer having at least one group represented by the following general formula (1) at the molecular end per molecule—OC (O) C (R) ═CH ₂ (1)
(Wherein R represents hydrogen or an organic group having 1 to 20 carbon atoms), and (b) a radical photopolymerization initiator, wherein (b) the radical photopolymerization initiator (B1) Photoradical polymerization initiator having a structure that decomposes by light in two or more positions in the molecule and / or (b2) Hydrogen abstraction type photoradical initiator having three or more aromatic rings in the molecule. To do. Hereinafter, each component will be described.

<< (a) Vinyl-based polymer >>
<Main chain>
The (a) vinyl polymer in the present invention is a vinyl polymer containing at least one group (polymerizable carbon-carbon double bond) represented by the general formula (1) in the molecule. The vinyl monomer constituting the main chain is not particularly limited, and various types can be used. Specifically, (meth) acrylic acid-based monomers, aromatic vinyl-based monomers, fluorine-containing vinyl-based monomers, silicon-containing vinyl-based monomers, maleimide-based monomers such as various monomers described in JP 2005-232419 A paragraph [0018] Examples include monomers, nitrile group-containing vinyl monomers, amide group-containing vinyl monomers, vinyl esters, alkenes, conjugated dienes, vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. 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 main chain of the (a) vinyl polymer used in the curable composition of the present invention is a (meth) acrylic monomer, an acrylonitrile monomer, an aromatic vinyl monomer, a fluorine-containing vinyl monomer, or a silicon-containing vinyl polymer. It is preferable that it is produced mainly by polymerizing at least one monomer selected from the group consisting of monomers. Here, “mainly” means that 50 mol% or more of the monomer units constituting the vinyl polymer (a) is the above monomer, and preferably 70 mol% or more.

  Of these, aromatic vinyl monomers and / or (meth) acrylic acid monomers are preferred, acrylic acid ester monomers and / or methacrylic acid ester monomers are more preferred, and acrylic acid ester monomers are even more preferred from the physical properties of the product. . Particularly preferred acrylic ester monomers include alkyl acrylate monomers, specifically ethyl acrylate, 2-methoxyethyl acrylate, stearyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic acid. Examples include 2-methoxybutyl.

  In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in this case, these preferred monomers may be contained in a weight ratio of 40% by weight or more. preferable.

  In the present invention, (a) the molecular weight distribution of the vinyl polymer, 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 (a) vinyl polymer in the present invention is not particularly limited, but is more preferably 3,000 to 100,000, which is in the range of 500 to 1,000,000 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, (a) the original characteristics of the vinyl polymer tend to be difficult to be expressed, whereas if it is too high, handling tends to be difficult.

<(A) Method for synthesizing vinyl polymer>
The (a) vinyl polymer used in the present invention can be obtained by various polymerization methods and is not particularly limited. However, radical polymerization is preferable from the viewpoint of versatility of the monomer, ease of control, etc., and radical polymerization. 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”. (A) Living radical polymerization in which the molecular weight and molecular weight distribution of the obtained vinyl polymer are easy to control is more preferred, and atom transfer radical polymerization is particularly preferred because of availability of raw materials and ease of introduction of functional groups at the polymer ends. preferable. 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 (a) 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. Specific examples include compounds described in paragraphs [0040] to [0064] of JP-A-2005-232419.

  In order to obtain a vinyl polymer having two or more alkenyl groups capable of hydrosilylation in one molecule, an organic halide having two or more starting points or a sulfonyl halide compound is used as an initiator. preferable. For example,

等が挙げられる。

Etc.

  There is no restriction | limiting in particular as a vinyl-type monomer used in atom transfer radical polymerization, All the illustrated vinyl-type monomers mentioned above 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, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity These polyamines 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.

<Polymerizable carbon-carbon double bond introduction method>
As a method for introducing a polymerizable carbon-carbon double bond into the obtained vinyl polymer, a known method can be used. 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, the terminal halogen group of the vinyl polymer of the following general formula (2) has a radical polymerizable carbon-carbon double bond of the following general formula (3). It is preferable that it is manufactured by substituting with a compound.
-CR ¹ R ² X (2)
(In the formula, R ¹ and R ² are groups bonded to an ethylenically unsaturated group of a vinyl monomer. X represents chlorine, bromine, or iodine.)
M ^{+ −} OC (O) C (R) ═CH ₂ (3)
(In the formula, R represents hydrogen or an organic group having 1 to 20 carbon atoms. M ⁺ represents an alkali metal or a quaternary ammonium ion.)
The (meth) acrylic polymer having a terminal structure represented by the general formula (2) is a method of polymerizing a vinyl monomer using the above-described organic halide or halogenated sulfonyl compound as an initiator and a transition metal complex as a catalyst. Alternatively, it is produced by a method in which a vinyl monomer is polymerized using a halogen compound as a chain transfer agent, but the former is preferred.

Formula is not particularly restricted but includes compounds represented by (3), specific examples of R, for _{example, -H, -CH 3, -CH 2} CH 3, - (CH 2) n CH 3 (n is It represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, etc., and is preferably -H, -CH _3.

M ⁺ is a counter cation of an 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, dimethylpiperidinium ion, and the like, preferably 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 the halogen group of General formula (2), More preferably, it is 1.0-1.2 equivalent. 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, etc. 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.

<< (b) Photoradical polymerization initiator >>
In the curable composition of the present invention, (b) a photoradical polymerization initiator, (b1) a photoradical polymerization initiator having two or more structures decomposed by light in the molecule, and / or (b2) molecule A hydrogen abstraction type photoradical initiator having three or more aromatic rings is used. In addition to the above (b1) and / or (b2), other radical photopolymerization initiator as described later may be used in combination with the curable composition of the present invention.

<(B1) Photoradical polymerization initiator having two or more structures in the molecule that decomposes by light>
Examples of the structure that is decomposed by light in the (b1) photoradical polymerization initiator of the present invention include a phenylketone group, a benzoyl group, and a phenylphosphine oxide group.

  The (b1) photoradical polymerization initiator of the present invention needs to have two or more structures in the molecule that are decomposed by the above light, preferably larger than 2, more preferably three or more.

  In the curable composition of this invention, it is preferable to use a polymer type photoinitiator as (b1) photoradical polymerization initiator, and the aspect using a polymer type photoinitiator and a photodegradable compound is also preferable.

  The polymer type photoinitiator means a polymer or oligomer containing a plurality of the photodegradable functional groups in the side chain. Specific examples include oligo [2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanone (trade name ESCURE KIP150 manufactured by LAMBERTI) and the like.

  The photodegradable compound is a compound having two or more photodegradable functional groups such as a benzoyl group, benzyl ketal, and benzoylphosphine oxide group. Specific examples include 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (trade name IRGACURE127, Ciba Made in Japan), 1- [4- (4-Benzoxylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one (trade name ESURE1001M), methylbenzoylphospho- Mate (product name: SPEDDCURE MBF manufactured by LAMBSON) O-ethoxyimino-1-phenylpropan-1-one (product name: manufactured by SPEDDCURE PDO LAMBSON) and the like.

  These radical photopolymerization initiators may be used alone or in combination of two or more.

<(B2) Hydrogen abstraction type photo radical initiator having three or more aromatic rings in the molecule >>>
The hydrogen abstraction type photoradical initiator (b2) having 3 or more aromatic rings in the molecule of the present invention is not particularly limited, and examples thereof include 1,2-octanedione, 1- [4- (phenylthiol). )-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime), 4 -Benzoyl-4'methyldiphenyl sulfide, 4-phenylbenzophenone, 4,4 ', 4 "-(hexamethyltriamino) triphenylmethane, etc. These photo radical polymerization initiators may be used alone or in combination with 2 You may use more than one kind together.

    In the curable composition of the present invention, the addition amount of the component (b) is preferably 0.001 to 50 parts by weight with respect to 100 parts by weight of the (a) vinyl polymer, and 0.01 to 20 Part by weight is more preferable, and 0.1 to 10 parts by weight is further preferable.

<Initiator component>
In the curable composition of the present invention, a polymerization initiator other than the above (b) can be used in combination. Examples of the polymerization initiator that can be used in combination include a thermal polymerization initiator, a photopolymerization initiator, and a redox initiator. . The thermal polymerization initiator, the photopolymerization initiator, and the Redox initiator may be used alone or as a mixture of two or more, but when used as a mixture, each initiator It is preferable that the usage-amount of exists in each range mentioned later.

  Although there is no restriction | limiting in particular as a thermal-polymerization initiator, An azo initiator, a peroxide initiator, a persulfate initiator, etc. are mentioned, A well-known thing can be used. Examples thereof include those described in paragraphs [0104] to [0106] of JP-A-2006-2654888.

  As the thermal polymerization initiator, an azo initiator or a peroxide initiator can be used, and is not particularly limited. Preferably, 2,2′-azobis (methylisobutylate), t-butyl is used. Examples include peroxypivalate, di (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyisopropyl monocarbonate, benzoyl peroxide, and mixtures thereof.

  A thermal polymerization initiator may be used independently or may use 2 or more types together.

  When a thermal polymerization initiator is used in combination in the curable composition of the present invention, the thermal polymerization initiator is present in a catalytically effective amount, and the amount of addition is not particularly limited. 0.001-50 weight part is preferable with respect to 100 weight part of coalescence. 0.01-20 weight part is more preferable, and 0.1-10 weight part is further more preferable.

  In the curable composition of the present invention, a redox (redox) initiator can be used in a wide temperature range. In particular, the following initiator species can be advantageously used at room temperature. Suitable redox initiators include, but are not limited to, those described in paragraph [0109] of JP-A-2006-264884.

  In the redox initiator system, a combination of an organic peroxide and a tertiary amine, an organic oxide and a transition metal are preferable, a combination of cumene hydroperoxide and anilines, and a combination of cumene hydroperoxide and cobalt naphthate are more preferable. .

  A redox initiator may be used independently or may use 2 or more types together.

  When a redox initiator is used in combination in the curable composition of the present invention, the redox initiator is present in a catalytically effective amount, and the amount added is not particularly limited. 0.001-50 weight part is preferable with respect to 100 weight part of unification, 0.01-20 weight part is more preferable, 0.1-10 weight part is further more preferable.

  Examples of the photopolymerization initiator include a photo radical initiator and a photo anion initiator. Examples of the photo radical initiator include those described in paragraph [0097] of JP-A-2006-265488. Furthermore, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethylbenzoyl) -2,4,4- Examples thereof include acyl phosphine oxide photo radical initiators such as trimethyl-pentylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

  As the photo radical initiator, 1-hydroxy-cyclohexyl-phenyl-ketone and 2-hydroxy-2-methyl-1-phenyl-propane are used in view of the balance between curability and storage stability of the curable composition of the present invention. -1-one, bis (4-dimethylaminophenyl) ketone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2 , 6-Dimethylbenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide are more preferred.

  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. .

  As the near infrared photopolymerization initiator, a near infrared light absorbing cationic dye or the like may be used. As the near-infrared light absorbing cationic dye, near-infrared light which is excited by light energy in the region of 650 to 1500 nm, for example, disclosed in JP-A-3-111402, JP-A-5-194619, etc. It is preferable to use an absorbing cationic dye-borate anion complex or the like, and it is more preferable to use a boron sensitizer together.

  These photopolymerization 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 combinations with amines such as diethanolmethylamine, dimethylethanolamine, and triethanolamine, and combinations with iodonium salts such as diphenyliodonium chloride, methylene blue, and the like. Examples include those combined with a dye and an amine.

  In addition, when using the said photoinitiator, polymerization inhibitors, such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, para tertiary butyl catechol, can also be added as needed.

  When the photopolymerization initiator is used in combination in the curable composition of the present invention, the addition amount is not particularly limited, but from the viewpoint of curability and storage stability, (a) with respect to 100 parts by weight of the vinyl polymer. 0.001 to 50% by weight. 0.01-20 weight% is preferable and 0.1-10 weight% is more preferable.

<< Curable composition >>
The curable composition of the present invention comprises the above-mentioned (a) vinyl polymer and (b) photo radical polymerization initiator. In order to adjust the physical properties, various additives such as, for example, , Polymerizable monomer and / or oligomer curing modifier, metal soap, filler, fine hollow particles, plasticizer, adhesion-imparting agent, solvent, flame retardant, antioxidant, light stabilizer, UV absorber, physical property adjustment An agent, a radical inhibitor, a metal deactivator, an ozone deterioration inhibitor, a phosphorus peroxide decomposer, a lubricant, a pigment, a foaming agent, a photocurable resin, and the like may be appropriately blended as necessary. These various additives may be used alone or in combination of two or more.

<Polymerizable monomer and / or oligomer>
A monomer and / or an oligomer can be added to the curable composition of the present invention as long as the effects of the present invention are not impaired. A monomer and / or oligomer having a radical polymerizable group or a monomer and / or oligomer having an anion polymerizable group is preferred from the viewpoint of curability.

  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 vinyl polymer used in the present invention are preferable.

  Examples of the anionic polymerizable group include a (meth) acryloyl group such as a (meth) acryl group, a styrene group, an acrylonitrile group, an N-vinylpyrrolidone group, an acrylamide group, a conjugated diene group, and a vinyl ketone group. Among these, those having a (meth) acryloyl group similar to the vinyl polymer used in the present invention are preferable.

  Specific examples of the monomer include those described in paragraphs [0123] to [0131] of JP-A-2006-265488.

  Examples of the oligomer include those described in paragraph [0132] of JP-A-2006-265488.

  Of the above, monomers and / or oligomers having a (meth) acryloyl group are preferred. The number average molecular weight of the monomer and / or oligomer having a (meth) acryloyl group is preferably 5000 or less. Furthermore, in the case of using a monomer for improving the surface curability and reducing the viscosity for improving workability, it is more preferable that the molecular weight is 1000 or less because of good compatibility.

  The amount of the polymerizable monomer and / or oligomer used is from 1 to 200 with respect to 100 parts by weight of the vinyl polymer (a) from the viewpoint of improving surface curability, imparting toughness, and workability due to viscosity reduction. Part by weight is preferable, and 5 to 100 parts by weight is more preferable.

<Metal soap>
The curable composition of the present invention may further contain a metal soap as necessary in order to enhance mold releasability.

  The metal soap is not particularly limited, but is generally a combination of long-chain fatty acids and metal ions. One molecule consists of a nonpolar or low-polar part based on fatty acids and a polar part based on the metal-bonded part. Any known one can be used as long as it is contained inside.

  Examples of the long chain fatty acid include saturated fatty acids having 1 to 18 carbon atoms, unsaturated fatty acids having 3 to 18 carbon atoms, and aliphatic dicarboxylic acids. Among these, a saturated fatty acid having 1 to 18 carbon atoms is preferable from the viewpoint of availability, and a saturated fatty acid having 6 to 18 carbon atoms is particularly preferable from the viewpoint of the releasability effect. Examples of the metal ions include alkali metals (lithium, sodium, potassium), alkaline earth metals (magnesium, calcium, barium), zinc, lead, cobalt, aluminum, manganese, strontium, and the like.

  Specifically, the metal soap described in paragraph [0155] of JP-A-2005-232419 can be mentioned.

  Among these metal soaps, metal stearates are preferable from the viewpoint of availability and safety, and particularly from the viewpoint of economy, one or more selected from the group consisting of calcium stearate, magnesium stearate, and zinc stearate. Is most preferred.

  Although there is no restriction | limiting in particular as addition amount of this metal soap, (a) It is preferable to use in 0.025-5 weight part with respect to 100 weight part of vinyl polymer component total, 0.05-4 More preferably, parts by weight are used. If the blending amount is more than 5 parts by weight, the physical properties of the cured product tend to decrease, and if it is less than 0.025 part by weight, mold releasability tends to be difficult to obtain.

<Filler>
Although it does not specifically limit as a filler, The filler of Unexamined-Japanese-Patent No. 2005-232419 Paragraph [0158] is mentioned.

  Of these fillers, crystalline silica, fused silica, dolomite, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable.

In particular, when it is desired to obtain a cured product having high strength with these fillers, mainly crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay and activity A filler selected from zinc oxide and the like can be added. Among them, the specific surface area (according to BET adsorption method) of ^{50 m} 2 / g or more, usually 50 to 400 m ² / g, is preferably 100 to 300 m ² / g approximately ultrafine powdery silica preferred. Further, silica whose surface has been previously hydrophobically treated with an organosilicon compound such as organosilane, organosilazane, diorganopolysiloxane, etc. is more preferred.

  Moreover, when it is desired to obtain a cured product having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like can be added. In general, when calcium carbonate has a small specific surface area, the effect of improving the breaking strength and breaking elongation of the cured product may not be sufficient. The larger the specific surface area value, the greater the effect of improving the breaking strength and breaking elongation of the cured product.

  Furthermore, it is more preferable that the calcium carbonate is subjected to a surface treatment using a surface treatment agent. When surface-treated calcium carbonate is used, the workability of the curable composition of the present invention is improved as compared with the case where calcium carbonate that is not surface-treated is used, and the storage stability effect of the curable composition is improved. It is thought that it will improve further.

  As the surface treatment agent, known ones can be used, and examples thereof include surface treatment agents described in paragraph [0161] of JP-A-2005-232419.

  The treatment amount of the surface treatment agent is preferably in the range of 0.1 to 20% by weight and more preferably in the range of 1 to 5% by weight with respect to calcium carbonate. When the treatment amount is less than 0.1% by weight, the workability improving effect may not be sufficient, and when it exceeds 20% by weight, the storage stability of the curable composition may be lowered.

  Although there is no particular limitation, when calcium carbonate is used, colloidal calcium carbonate is preferably used when the effect of improving the thixotropy of the blend, the breaking strength of the cured product, the elongation at break and the like is particularly expected.

  On the other hand, those described in paragraph [0163] of Japanese Patent Application Laid-Open No. 2005-232419 in which heavy calcium carbonate is sometimes added for the purpose of increasing the amount of the compound, reducing costs, or the like can be used.

  The said filler may be used independently according to the objective and necessity, and may use 2 or more types together. When the filler is used, the addition amount is preferably 5 to 1000 parts by weight, preferably 20 to 500 parts by weight with respect to 100 parts by weight of the vinyl polymer (a). It is more preferable to use in the range of 40 to 300 parts by weight. If the blending amount is less than 5 parts by weight, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product may not be sufficient, and if it exceeds 1000 parts by weight, the work of the curable composition May decrease.

<Micro hollow particles>
For the purpose of reducing the weight and cost without causing a significant decrease in physical properties, fine hollow particles can be added in combination with these reinforcing fillers.

Such fine hollow particles (hereinafter sometimes referred to as “balloons”) are not particularly limited, but have a diameter as described in “Latest Technology for Functional Fillers” (CMC). Examples thereof include hollow bodies (inorganic balloons and organic balloons) made of inorganic or organic materials of 1 mm or less, preferably 500 μm or less, more preferably 200 μm or less. In particular, it is preferable to use a micro hollow body having a true specific gravity of 1.0 g / cm ³ or less, and more preferably to use a micro hollow body having a specific gravity of 0.5 g / cm ³ or less.

  As the inorganic balloon and the organic balloon, balloons described in paragraphs [0168] to [0170] of JP-A-2005-232419 can be used.

  The balloons may be used alone or in combination of two or more. Furthermore, the surface of these balloons is made of fatty acid, fatty acid ester, rosin, rosin acid lignin, silane coupling agent, titanium coupling agent, aluminum coupling agent, polypropylene glycol, etc. to improve dispersibility and workability of the compound. Those processed in the above can also be used. These balloons are used for weight reduction and cost reduction without impairing flexibility and elongation / strength among physical properties when the compound is cured.

  The addition amount of the balloon is not particularly limited, but it is preferably 0.1 to 50 parts by weight, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the (a) vinyl polymer. . If the amount is less than 0.1 parts by weight, the effect of reducing the weight is small. If the amount is more than 50 parts by weight, a decrease in tensile strength may be observed among the mechanical properties when the compound is cured. Moreover, when the specific gravity of a balloon is 0.1 or more, the addition amount is preferably 3 to 50 parts by weight, more preferably 5 to 30 parts by weight.

<Antioxidant>
Various antioxidants may be used in the curable composition of the present invention as necessary. These antioxidants include p-phenylenediamine-based antioxidants, amine-based antioxidants, hindered phenol-based antioxidants, secondary antioxidants such as phosphorus-based antioxidants, sulfur-based antioxidants, etc. Is mentioned.

<Plasticizer>
A plasticizer can be mix | blended with the curable composition of this invention as needed.

  Although it does not specifically limit as a plasticizer, For example, the plasticizer of Unexamined-Japanese-Patent No. 2005-232419 Paragraph [0173] is mentioned by the objectives, such as adjustment of a physical property and adjustment of a property. Among these, polyester plasticizers and vinyl polymers are preferable because the effect of reducing the viscosity is remarkable and the volatilization rate during the heat resistance test is low. Further, by adding a polymer plasticizer which is a polymer having a number average molecular weight of 500 to 15000, the viscosity of the curable composition and the tensile strength and elongation of the cured product obtained by curing the curable composition are added. The mechanical properties such as the above can be adjusted, and the initial physical properties can be maintained over a long period of time as compared with the case where a low molecular plasticizer which is a plasticizer not containing a polymer component in the molecule is used. Although not limited, the polymer plasticizer may or may not have a functional group.

  Although the number average molecular weight of the said polymeric plasticizer was described as 500-15000, Preferably it is 800-10000, More preferably, it is 1000-8000. If the molecular weight is too low, the plasticizer may flow out over time when exposed to heat or in contact with a liquid, and the initial physical properties may not be maintained over a long period of time. Moreover, when molecular weight is too high, a viscosity will become high and there exists a tendency for workability | operativity to fall.

  Of these polymer plasticizers, those compatible with (a) vinyl polymers are preferred. Of these, vinyl polymers are preferred from the viewpoints of compatibility, weather resistance, and heat aging resistance. Among the vinyl polymers, (meth) acrylic polymers are preferable, and acrylic polymers are more preferable. Examples of the method for synthesizing the acrylic polymer include those obtained by conventional solution polymerization and solvent-free acrylic polymers. The latter acrylic plasticizer does not use a solvent or a chain transfer agent, and is a high-temperature continuous polymerization method (USP 4414370, JP 59-6207, JP-B-5-58005, JP 1-331522, USP 5010166). It is more preferable for the purpose of the present invention. Examples thereof include, but are not limited to, Toagosei UP series and the like (see the Industrial Materials October 1999 issue). Of course, the living radical polymerization method can also be mentioned as another synthesis method. According to this method, the molecular weight distribution of the polymer is narrow and the viscosity can be lowered, and the atom transfer radical polymerization method is more preferable, but it is not limited thereto.

  The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow and is preferably less than 1.8. 1.7 or less is more preferable, 1.6 or less is still more preferable, 1.5 or less is more preferable, 1.4 or less is especially preferable, and 1.3 or less is the most preferable.

  The plasticizer containing the above-mentioned polymer plasticizer may be used alone or in combination of two or more, but is not necessarily required. Further, if necessary, a high molecular plasticizer may be used, and a low molecular plasticizer may be further used in a range that does not adversely affect the physical properties.

  These plasticizers can also be blended at the time of polymer production.

Although the usage-amount in the case of using a plasticizer is not limited, Preferably it is 1-100 weight part with respect to 100 weight part of (a) vinyl polymer, More preferably, it is 5-50 weight part. If the amount is less than 1 part by weight, the effect as a plasticizer tends to be hardly exhibited, and if it exceeds 100 parts by weight, the mechanical strength of the cured product tends to be insufficient.
In addition to the plasticizer, a reactive diluent described below may be used in the present invention.

  If a low-boiling compound that can be volatilized during curing is used as a reactive diluent, it will change shape before and after curing, or it may adversely affect the environment due to volatiles. An organic compound having a boiling point of 100 ° C. or higher is particularly preferable.

  Specific examples of the reactive diluent include 1-octene, 4-vinylcyclohexene, allyl acetate, 1,1-diacetoxy-2-propene, methyl 1-undecenoate, 8-acetoxy-1,6-octadiene and the like. However, it is not limited to these.

The amount of the reactive diluent added is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 70 parts by weight, and still more preferably 1 to 50 parts by weight with respect to 100 parts by weight of the (a) vinyl polymer. Part.
<Light stabilizer>
You may add a light stabilizer to the curable composition of this invention as needed. Various types of light stabilizers are known, and are described in, for example, “Antioxidant Handbook” issued by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242) issued by CM Chemical Co., Ltd. Although various things are mentioned, it is not necessarily limited to these.

  Although not particularly limited, among the light stabilizers, an ultraviolet absorber is preferable. Specifically, for example, tinuvin P, tinuvin 234, tinuvin 320, tinuvin 326, tinuvin 327, tinuvin 329, and tinuvin 213 (all above) Examples include benzotriazole compounds such as Ciba Geigy (Japan), triazines such as Tinuvin 1577, benzophenone compounds such as CHIMASSORB 81, and benzoate compounds such as Tinuvin 120 (Ciba Geigy Japan).

  Further, hindered amine compounds are also preferable, and specific examples of such compounds include, but are not limited to, those described in JP 2006-274084 A.

  Furthermore, since the combination of the ultraviolet absorber and the hindered amine compound may exhibit more effect, it is not particularly limited but may be used in combination, and it is preferable to use in combination.

  The light stabilizer may be used in combination with the above-described antioxidant, and it is particularly preferable because the effect is further exhibited and the weather resistance may be improved. Tinuvin C353, Tinuvin B75 (all of which are manufactured by Ciba Geigy Japan, Inc.) in which a light stabilizer and an antioxidant are mixed in advance may be used.

  The amount of the light stabilizer used is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the (a) vinyl polymer. If the amount is less than 0.1 parts by weight, the effect of improving the weather resistance is small.

<Adhesive agent>
When the curable composition of the present invention is used alone as a molding rubber, it is not particularly necessary to add an adhesion-imparting agent, but the adhesion can be compounded when used for two-color molding with different substrates. The agent is not particularly limited as long as it further imparts adhesiveness to the curable composition, but a crosslinkable silyl group-containing compound is preferable, and a silane coupling agent is more preferable.

  Specific examples thereof include the adhesion-imparting agent described in paragraph [0184] of JP-A-2005-232419.

  In addition, in the range that does not inhibit the hydrosilylation reaction, carbon atoms such as epoxy groups, isocyanate groups, isocyanurate groups, carbamate groups, amino groups, mercapto groups, carboxyl groups, halogen groups, (meth) acryl groups and the like in the molecule A silane coupling agent having both an organic group having an atom other than a hydrogen atom and a crosslinkable silyl group can be used.

  Specific examples thereof include a silane coupling agent having both a crosslinkable silyl group and an organic group having an atom other than a carbon atom and a hydrogen atom described in paragraph [0185] of JP 2005-232419 A.

  Among these, alkoxysilanes having an epoxy group or a (meth) acryl group in the molecule are more preferable from the viewpoint of curability and adhesiveness.

  These may be used alone or in combination of two or more.

  Specific examples of the adhesion-imparting agent other than the silane coupling agent are not particularly limited. For example, epoxy resin, phenol resin, modified phenol resin, cyclopentadiene-phenol resin, xylene resin, coumarone resin, petroleum resin, terpene resin , Terpene phenol resin, rosin ester resin sulfur, alkyl titanates, aromatic polyisocyanate, alicyclic structure-containing (meth) acrylic monomer, aromatic structure-containing (meth) acrylic monomer, alicyclic structure and carboxyl group (meta ) Acrylic monomers, (meth) acrylic monomers containing aromatic and carboxyl groups, (meth) acrylic monomers having a phosphate group, and the like.

  Moreover, in order to further improve adhesiveness, a crosslinkable silyl group condensation catalyst can be used in combination with the above-mentioned adhesiveness-imparting agent. Examples of the crosslinkable silyl group condensation catalyst include those described in paragraph [0187] of JP-A-2005-232419.

  The adhesiveness-imparting agent is preferably blended in an amount of 0.01 to 20 parts by weight per 100 parts by weight of the (a) vinyl polymer. If the amount is less than 0.01 part by weight, the effect of improving the adhesiveness is small. If the amount exceeds 20 parts by weight, the cured product properties tend to be lowered. Preferably it is 0.1-10 weight part, More preferably, it is 0.5-5 weight part.

The adhesiveness-imparting agent may be used alone or in combination of two or more.
<Solvent>
A solvent can be mix | blended with the curable composition of 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 A solvent etc. are mentioned. These solvents may be used during production of the polymer.
<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 its cured product. Examples of such additives include, for example, flame retardants, anti-aging agents, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, etc. Can be given. These various additives may be used alone or in combination of two or more.

  Specific examples of such additives are described in, for example, each specification of JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, and JP-A-64-22904. Yes.

<< Method for producing cured product >>
The curable composition of the present invention can be prepared as a one-pack type in which all blending components are blended and sealed in advance, and the A liquid from which only the initiator is removed and the initiator is mixed with a filler, a plasticizer, a solvent, and the like. It can also be prepared as a two-component type in which the prepared B solution is mixed immediately before molding.

<< cured product >>
The cured product of the present invention is obtained by curing the resin curable composition.

  The method for curing the curable composition is not particularly limited.

  The curable composition of the present invention can be cured by irradiating light (UV) or an electron beam with an active energy ray source.

  Although there is no limitation in particular as an active energy ray source, According to the property of the photoinitiator to be used, a high pressure mercury lamp, a low pressure mercury lamp, an electron beam irradiation apparatus, a halogen lamp, a light emitting diode, a semiconductor laser, a metal halide etc. are mentioned, for example.

  The curing temperature is preferably 0 ° C to 150 ° C, more preferably 5 ° C to 120 ° C.

  When a redox initiator is used in combination as another initiator, the curing temperature is preferably −50 ° C. to 250 ° C., more preferably 0 ° C. to 180 ° C.

  When a thermal polymerization initiator is used in combination, the curing temperature varies depending on the type of the thermal polymerization initiator used and the glass transition point, molecular weight, functional group density, (b) component structure, etc. Usually, 50 ° C to 250 ° C is preferable, and 70 ° C to 200 ° C is more preferable.

<< Molding method >>
The molding method when the curable composition of the present invention is used as a molded body is not particularly limited, and various commonly used molding methods can be used. For example, cast molding, compression molding, transfer molding, injection molding, extrusion molding, rotational molding, hollow molding, thermoforming, and the like can be given. In particular, from the viewpoint of being able to be automated and continuous and being excellent in productivity, roll molding, calender molding, extrusion molding, liquid injection molding, and injection molding are preferred.

<< Usage >>
The curable composition of the present invention is not particularly limited, but includes sealing materials (including architectural sealing materials and oil sealing materials), electrical / electronic component materials, electrical insulation materials such as electric wire / cable insulation coating materials, and adhesion. Used in adhesives, adhesives, electrical and electronic potting agents, heat dissipation materials, waterproofing materials, anti-vibration / vibration control / isolation materials, films, marine deck caulking, casting materials, or molding materials. Furthermore, it can be used for various applications such as automotive materials, coating materials, foams, gaskets, O-rings, packings, hoses and tubes, rolls, diaphragms, casting materials, and various molding materials.

  For example, 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 include transmission oil cooler hose, engine oil cooler hose, air duct hose, turbo intercooler hose, hot air hose, radiator hose, power steering hose, fuel hose, drain hose, etc. for cooling, fuel supply, intake and exhaust Hoses, engine cam covers and oil pan gaskets, oil pump gaskets, power steering vane pump gaskets, intake manifold gaskets, throttle body gaskets, compressor gaskets, timing belt cover gaskets, crankshaft seal gaskets, Camshaft seal gaskets, transmission seal gaskets, etc., various O-rings, oil seals Power steering seal belt cover seal, seal washer, oil receiver, plug tube seal, squeeze seal, lip seal seal, bore plug, injection pipe seal, brake drum seal, connector seal for wire harness, oil level gauge, breather, Various rubber parts such as valves and diaphragms, fuel injection devices, fuel heating devices, air dampers, pressure detection devices, oil coolers for resin tanks for heat exchangers, variable compression ratio engines, cylinder devices, regulators for compressed natural gas, pressure vessels, in-cylinder Fuel injection system for direct injection internal combustion engine or high pressure pump O-ring, igniter HIC or automotive hybrid IC botting material, constant velocity joint boot material and rack and pinion boot material, The coating material for emission gin control board, it is possible to use molding, head lamp lens, the adhesive for a sunroof seal or mirror. It can also be used for exhaust gas cleaning device parts and brake parts.

  In the electrical field, it can be used for coating, potting, packing, O-rings, belts and the like. Specifically, high-voltage thick film resistors, hybrid IC circuit elements, HICs, electrical insulation components, semiconductive components, conductive components, modules, printed circuits, ceramic substrates, diodes, transistors or buffer materials for bonding wires, Semi-conductor element or coating material such as optical fiber for optical communication, transformer high-voltage circuit, printed circuit board, high-voltage transformer with variable resistance, electrical insulation component, semi-conductive component, conductive component, solar cell or TV flyback Potting materials such as transformers, heavy electrical components, weak electrical components, solar cell backside sealing, sealing materials for circuits and boards of electrical and electronic equipment, decorations for lighting fixtures, waterproof packings, anti-vibration rubbers, insect protection Anti-vibration / sound absorption and air sealant for packing, drip-proof cover for electric water heater, heater , Electrode packing, safety valve diaphragm, hoses for sake cans, waterproof packing, solenoid valves, waterproof packing for steam microwave ovens and jar rice cookers, water supply 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, etc., O-ring, drain packing, pressure tube, blower tube, feed / intake packing, anti-vibration rubber, oil filler packing, oil meter packing, oil feed tube Rubber parts such as speaker valves, speaker edges, turntable seats, belts, pulleys, etc. for acoustic devices such as diaphragm valves and air pipes. Also, cathode ray tube wedges, necks, electrical insulation parts, adhesives for semi-conductive parts or conductive parts, wire covering repair materials, insulation joints for wire joint parts, rolls for office automation equipment, ink wipers, vibration absorbers, gels It can also be used for etc.

  In the construction field, it can be used for structural gaskets (zipper gaskets), air membrane roof materials, waterproof materials, fixed sealing materials, vibration-proof materials, sound-proof materials, setting blocks, sliding materials, and the like.

  In the sports field, it can be used for all-weather pavement materials and gymnasium floors as sports floors, shoe sole materials and midsole materials as sports shoes, and golf balls as ball for ball games.

  In the field of anti-vibration rubber, it can be used as anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, anti-vibration materials, and the like.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

  In the following examples, “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 packed with polystyrene cross-linked gel (shodex GPC K-804 and K-802.5; manufactured by Showa Denko KK) and chloroform as a GPC solvent were used.

In the following examples, “average number of terminal (meth) acryloyl groups” is “number of (meth) acryloyl groups introduced per molecule of polymer”, and the number average molecular weight determined by ¹ H-NMR analysis and GPC. Calculated.
(However, ¹ H-NMR was measured at 23 ° C. using Bruker ASX-400 and deuterated chloroform as a solvent.)
In the examples and comparative examples below, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

(Production Example 1)
Table 1 shows the amount of each raw material used.
(1) Polymerization process Acrylic acid ester (premixed acrylic acid ester) was deoxygenated. The inside of the stainless steel reaction vessel equipped with a stirrer was deoxygenated, and cuprous bromide and a part of the total acrylic ester (described as the initial charge monomer in Table 1) were charged and stirred with heating. Acetonitrile (denoted as acetonitrile for polymerization in Table 1), diethyl 2,5-dibromoadipate (DBAE) as an initiator were added and mixed, and pentamethyldiethylenetriamine (hereinafter, referred to as “the temperature of the mixture” was adjusted to about 80 ° C.). (Abbreviated as triamine) was added to initiate the polymerization reaction. The remaining acrylic ester (described as an additional monomer in Table 1) was added sequentially to proceed the polymerization reaction. During the polymerization, triamine was appropriately added to adjust the polymerization rate. The total amount of triamine used during the polymerization is shown in Table 1 as a triamine for polymerization. As the polymerization proceeds, the internal temperature rises due to the heat of polymerization, so the polymerization was allowed to proceed while adjusting the internal temperature to about 80 ° C to about 90 ° C.
(2) Oxygen treatment step When the monomer conversion rate (polymerization reaction rate) was about 95% or more, an oxygen-nitrogen mixed gas was introduced into the gas phase part of the reaction vessel. While maintaining the internal temperature at about 80 ° C. to about 90 ° C., the reaction solution was heated and stirred for several hours to bring the polymerization catalyst in the reaction solution into contact with oxygen. Acetonitrile and unreacted monomer were removed by devolatilization under reduced pressure to obtain a concentrate containing a polymer. The concentrate was markedly colored.
(3) The first crude purified toluene was used as a diluent solvent for the polymer. Dilute the concentrate (2) with about 100-150 kg of toluene to 100 kg of polymer, and add filter aid (Radiolite R900, Showa Chemical Industry) and adsorbent (Kyoward 700 SEN, Kyoward 500 SH) did. After introducing an oxygen-nitrogen mixed gas into the gas phase part of the reaction vessel, the mixture was heated and stirred at about 80 ° C. for several hours. Insoluble catalyst components were removed by filtration. The filtrate was colored and slightly turbid due to the polymerization catalyst residue.
(4) Second crude purification The filtrate was charged into a stainless steel reaction vessel equipped with a stirrer, and adsorbents (Kyoward 700SEN, Kyoward 500SH) were added. After introducing an oxygen-nitrogen mixed gas into the gas phase and heating and stirring at about 100 ° C. for several hours, insoluble components such as an adsorbent were removed by filtration. The filtrate was almost clear and clear. The filtrate was concentrated to obtain an almost colorless and transparent polymer.
(5) (Meth) acryloyl group introduction step 100 kg of polymer is dissolved in about 100 kg of N, N-dimethylacetamide (DMAC), and potassium acrylate (about 2 molar equivalents relative to the terminal Br group), thermal stabilizer (H -TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-n-oxyl) and an adsorbent (Kyoward 700SEN) were added, and the mixture was heated and stirred at about 70 ° C for several hours. DMAC was distilled off under reduced pressure, the polymer concentrate was diluted with about 100 kg of toluene with respect to 100 kg of the polymer, a filter aid was added, the solid content was filtered off, the filtrate was concentrated, and an acryloyl group was added to the end. A polymer [P1] having was obtained. Table 1 shows the number of acryloyl groups introduced per molecule of the obtained polymer, the number average molecular weight, and the molecular weight distribution.

（実施例１）
（ａ）成分として製造例１で得られた重合体［Ｐ１］１００部、（ｂ）成分として２−ヒドロキシ−１−{４-[４−（２−ヒドロキシ−２−メチル−プロピオニル）−ベンジル]−フェニル}−２−メチル−プロパン−１−オン（商品名；ＩＲＧＡＣＵＲＥ１２７、チバ・ジャパン製）１．５部、酸化防止剤としてテトラキス［メチレン−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］メタン（商品名ＩＲＧＡＮＯＸ１０１０：チバ・スペシャルティ・ケミカルズ製）１部、（ｂ）成分以外の光ラジカル開始剤として、ビス（２、４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド（ＩＲＧＡＣＵＲＥ８１９；チバ・スペシャルティ・ケミカルズ製）０．７５部を加え、十分に溶解・混合後、６０℃で１時間加熱脱泡を行った。さらに型枠に流し込んでＵＶ照射装置に（ＬＨ−６；フュージョン・ジャパン社製）ランプエネルギー＝１８４Ｗ／ｃｍ、照射距離５４ｃｍ、１ｍ／分の速度で１回通して（積算光量＝３０３０ｍＪ／ｃｍ^２）硬化させて２ｍｍの厚のシートを得た。得られた硬化物を用いて、引張り物性、指触による表面の粘着性、ボールタックを評価した。硬化性組成物配合処方および評価結果を表２に示す。
＜測定方法 ＞
引張り特性
ＪＩＳ Ｋ ６２５１に準じて、（１／３号ダンベル）サイズに切り出し、引張り特性を評価した。
指触による表面の粘着性
得られた２ｍｍ厚のシートの表面を指で軽く押して、表面粘着性を確認した。
評価基準・・・○；タックが殆どなく、平滑性に優れる。×；表面に粘着性があり、指に付く状態。
ボールタック試験
ＪＩＳ Ｚ ０２３７に準拠して測定実施（スチールボールのサイズによりタックのレベルを１〜３２に区分した。）した。

(Example 1)
100 parts of the polymer [P1] obtained in Production Example 1 as the component (a), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl as the component (b) ] -Phenyl} -2-methyl-propan-1-one (trade name; IRGACURE 127, manufactured by Ciba Japan), tetrakis [methylene-3- (3,5-di-tert-butyl) as an antioxidant -4- (hydroxyphenyl) propionate] methane (trade name IRGANOX1010: manufactured by Ciba Specialty Chemicals) 1 part, as photo radical initiator other than component (b), bis (2,4,6-trimethylbenzoyl) -phenylphosphine Add 0.75 part of fin oxide (IRGACURE819; manufactured by Ciba Specialty Chemicals), and dissolve and mix thoroughly. It was carried out for 1 hour heating degassing at 60 ° C.. Further, it was poured into a mold and passed through a UV irradiation device (LH-6; manufactured by Fusion Japan) once at a lamp energy of 184 W / cm, an irradiation distance of 54 cm, and a speed of 1 m / min (integrated light amount = 3030 mJ / cm ^2). ) Cured to obtain a 2 mm thick sheet. Using the obtained cured product, tensile physical properties, surface tackiness by finger touch, and ball tack were evaluated. Table 2 shows the curable composition formulation and the evaluation results.
<Measurement method>
Tensile properties According to JIS K 6251, they were cut into (No. 1/3 dumbbell) size and evaluated for tensile properties.
Surface tackiness by finger touch The surface of the obtained 2 mm thick sheet was lightly pressed with a finger to confirm the surface tackiness.
Evaluation criteria: ○: Almost no tack and excellent smoothness. X: The surface is sticky and sticks to the finger.
Ball tack test Measured in accordance with JIS Z 0237 (the tack level was divided into 1 to 32 depending on the size of the steel ball).

(Example 2)
A cured product was prepared in the same manner as in Example 1 except that 2 parts of IRGACURE127 and 1 part of IRGACURE819 were used in Example 1, and the physical properties of the cured product were evaluated.

(Example 3)
A cured product was produced in the same manner as in Example 1 except that 1.5 parts of methylbenzoyl formate (trade name: SPEDCURE MBF, manufactured by Nippon Siebel Hegner) was used instead of IRGACURE 127 of Example 1. Evaluated.

Example 4
A cured product was prepared in the same manner as in Example 3 except that 2 parts of SPPEDCURE MBF of Example 3 and 1 part of IRAGACURE 819 were used, and the physical properties of the cured product were evaluated.

(Example 5)
Example 2 except that IRGACURE127 of Example 2 was replaced by oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane} (trade name; ESACURE KIP 150, manufactured by Nippon Siebel Hegner) In the same manner as above, a cured product was produced, and the physical properties of the cured product were evaluated.

(Example 6)
A cured product was prepared in the same manner as in Example 2 except that IRGACURE127 of Example 2 was replaced with 4-phenylbenzophenone (trade name; SPEEDCURE PBZ, manufactured by Nippon Shibel Hegner), and physical properties of the cured product were evaluated.

(Comparative Example 1)
A cured product was obtained in the same manner as in Example 2 except that IRGACURE127 of Example 2 was replaced with 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name; DAROCUR1173, manufactured by Ciba Japan). And the physical properties thereof were evaluated.

(Comparative Example 2)
The same as Example 2 except that IRGACURE127 of Example 2 was changed to 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name; IRGACURE907, manufactured by Ciba Japan). A cured product was prepared by the method and its physical properties were evaluated.

実施例１〜５では、分子内に１箇所しか光分解構造を有しない光ラジカル開始剤２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オンを用いた比較例１と比較して機械物性（ダンベル物性）大きな影響はなく表面のタック（粘着性）が改善されている。また、一般の反応性オリゴマー、多官能性アクリレート／ラジカル反応性単量体系でタック改善（表面硬化性）効果のあるとされる２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパン−１−オンを用いた比較例２と比較しても、表面のタック改善効果に有意性が見られる。また、芳香環を３個有する水素引き抜き型光ラジカル開始剤４−フェニルベンゾフェノンを用いた実施例６でも同様の効果が確認できている。よって、本発明の（ｂ）成分の特定構造の光ラジカル開始剤を使用することで、表面タックを劇的に改善できることが理解できる。

In Examples 1 to 5, as compared with Comparative Example 1 using a photo radical initiator 2-hydroxy-2-methyl-1-phenyl-propan-1-one having a photolytic structure in only one position in the molecule. Mechanical properties (dumbbell properties) have no significant effect, and surface tack (adhesiveness) is improved. In addition, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopro, which is considered to have a tack-improving (surface curing) effect in a general reactive oligomer, polyfunctional acrylate / radical reactive monomer system Even in comparison with Comparative Example 2 using pan-1-one, the surface tack improvement effect is significant. Moreover, the same effect has been confirmed also in Example 6 using hydrogen abstraction type photo radical initiator 4-phenylbenzophenone having three aromatic rings. Therefore, it can be understood that the surface tack can be drastically improved by using the photoradical initiator having the specific structure of the component (b) of the present invention.

  The curable composition of the present invention is a photo-radical polymerization initiator having a structure in which a vinyl polymer is decomposed by light at two or more positions in the molecule and / or a hydrogen-drawing light having at least three aromatic rings in the molecule. By adding a radical initiator and curing it, the tackiness of the vinyl polymer cured product surface can be reduced. Sealing materials that require non-tackiness on the surface of cured products, electrical / electronic component materials, electrical insulation materials, adhesives, adhesives, potting agents, heat dissipation materials, waterproofing materials, anti-vibration / damping / isolation materials, films Suitable for applications such as marine deck caulking, casting materials, coating materials and molding materials.

Claims (17)

(A) A vinyl polymer having at least one group represented by the following general formula (1) per molecule terminal: —OC (O) C (R) ═CH ₂ (1)
(Wherein R represents hydrogen or an organic group having 1 to 20 carbon atoms), and
(B) containing a radical photopolymerization initiator,
As the (b) photo radical polymerization initiator,
(B1) a radical photopolymerization initiator having two or more structures in the molecule that decomposes by light, and / or
(B2) a hydrogen abstraction type photo radical initiator having three or more aromatic rings in the molecule,
A curable composition using   The curable composition of Claim 1 whose said (b1) is a polymer type photoinitiator.   The curable composition according to claim 1 or 2, wherein (b1) is a photodegradable compound and a polymer-type photopolymerization initiator.   The curable composition according to any one of claims 1 to 3, wherein the component (b1) has an aromatic structure. (A) The value of the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the vinyl polymer is less than 1.8, according to any one of claims 1 to 4. Curable composition   The curable composition according to any one of claims 1 to 5, wherein the main chain of the (a) vinyl polymer is produced by living radical polymerization.   The curable composition according to claim 6, wherein the living radical polymerization is atom transfer radical polymerization.   The cured composition according to claim 7, wherein the atom transfer radical polymerization uses a copper complex as a catalyst.   The curable composition according to any one of claims 1 to 5, wherein the main chain of the (a) vinyl polymer is produced by polymerization of a vinyl monomer using a chain transfer agent.   The main chain of the (a) vinyl polymer is at least one selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. The curable composition according to any one of claims 1 to 9, which is produced mainly by polymerization.   The curable composition according to claim 10, wherein the main chain of the (a) vinyl polymer is produced mainly by polymerizing a (meth) acrylic acid ester.   The curable composition according to claim 11, wherein the main chain of the (a) vinyl polymer is produced mainly by polymerizing an acrylate ester.   The curable composition according to any one of claims 1 to 12, wherein the number average molecular weight of the (a) vinyl polymer is 3000 or more.   Hardened | cured material obtained by hardening the curable composition as described in any one of Claims 1-13.   The hardened | cured material of Claim 14 obtained by hardening the said hardened | cured material with an active energy ray.   The hardened | cured material of Claim 15 whose said active energy ray is UV and / or an electron beam.   Seal materials, electrical / electronic component materials, electrical insulation materials, adhesives, adhesives, potting agents, heat dissipation materials, waterproofing materials, anti-vibration / vibration control / isolation materials, films, marine deck caulking, casting materials, coating materials Or the curable composition in any one of Claims 1-13 used for a molding material.