JP2012122049A - Polyoxyalkylene-based polymer-containing curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition which causes no liquid dripping from just after active energy rays irradiation, is excellent in workability and has sufficient mechanical strength, and portions of which cannot be irradiated with active energy rays are also curable.SOLUTION: The curable composition includes the following components (A)-(E): (A) a polyoxyalkylene-based polymer which has in its molecule one or more substituents represented by general formula (1) "-Z-C(=O)-C(R)=CH(1)" and has a number-average molecular weight of at least 3,000; (B) a polyoxyalkylene-based polymer which has in its molecule one or more reactive silicon groups represented by general formula (2) "-[Si(R)(X)O]Si(R)X(2)" and has a number-average molecular weight of at least 3,000; (C) a tackiness-imparting resin; (D) a polymerization initiator; and (E) a silanol condensation catalyst.

Description

  The present invention relates to a curable composition containing a polyoxyalkylene polymer that can be cured by active energy rays and a polyoxyalkylene polymer having a reactive silicon group.

  The organic polymer having a reactive silicon group is crosslinked by the formation of a siloxane bond accompanied by a hydrolysis reaction of the reactive silicon group by moisture to give a rubbery cured product (for example, Patent Documents 1 and 2). Among them, polyoxyalkylene polymers having a reactive silicon group have already been widely used in applications such as sealing materials, adhesives, and paints because they give a cured product having excellent elongation and mechanical strength. However, it is difficult to achieve fast curing due to the characteristics of the reaction.

  An organic polymer having a (meth) acryloyl group is used in combination with a polymerization initiator, and when irradiated with active energy rays such as UV, electron beam, and heating, the (meth) acryloyl group is instantaneously polymerized and crosslinked. Fast curing is possible (for example, Patent Documents 3 and 4). However, a portion that cannot be irradiated with active energy rays or a portion that does not reach it is not cured at all, so that there is a problem that sufficient physical properties are not exhibited.

  Therefore, a composition containing both an organic polymer having a (meth) acryloyl group and an organic polymer having a reactive silicon group has a (meth) acryloyl group by irradiation with active energy rays. It has been proposed that only the organic polymer is cured and the organic polymer having a reactive silicon group is cured by moisture (for example, Patent Document 5).

  However, after irradiation with active energy rays, only the organic polymer having a (meth) acryloyl group is cured, and the organic polymer having a reactive silicon group is in an uncured cured physical property, particularly mechanical strength and handling are difficult. there were.

JP-A-52-73998 JP-A 63-6041 WO2005 / 030866 Publication JP 2005-105065 A WO2008 / 041768

  An object of the present invention is to provide a curable composition that has no dripping immediately after irradiation with active energy rays, has good workability, has sufficient mechanical strength, and can cure even a portion that cannot be irradiated with active energy rays. And

  As a result of intensive studies to solve the above problems, the present inventors have found the following and completed the present invention.

That is, the present invention
(I)
The curable composition containing the following (A)-(E) component.
(A) General formula (1):
^{-Z-C (= O) -C} (R 1) = CH 2 (1)
(Wherein R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and Z is a divalent organic group.) A number average molecular weight having one or more substituents in the molecule. Is 3,000 or more polyoxyalkylene polymer (B) general formula (2):
-[Si (R ² _2-b ) (X _b ) O] _n Si (R ² _3-a ) X _a (2)
(In the formula, R ² represents 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 a triorganosiloxy group represented by R ′ ₃ SiO—. , R ² may be the same or different when two or more R ² are present, where R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and X is a hydroxyl group Or a hydrolyzable group, where a represents 0, 1, 2 or 3, b represents 0, 1 or 2, and satisfies a + Σb ≧ 2, and n represents an integer of 0 to 19. ) A polyoxyalkylene polymer having a number average molecular weight of 3,000 or more (C) a tackifier resin (D) a polymerization initiator (E) a silanol condensation catalyst.

(II)
The curable composition according to (I), wherein Z in the general formula (1) is an oxygen atom.

(III)
Z in the general formula (1) is the general formula (3):
—NH—C (═O) —O—R ³ —O— (3)
(Wherein, R ³ is a divalent hydrocarbon group.) A group represented by (I) the curable composition.

(IV)
Z in the general formula (1) is the general formula (4):
—O—C (═O) —NH—R ³ —O— (4)
(In formula, R < ³ > is the same as the above.) The curable composition as described in (I) which is group represented.

(V)
The polyoxyalkylene polymer (a) in which the substituent represented by the general formula (1) has a hydroxyl group and the general formula (5):
^{O = C = N-R 3} -O-C (= O) -C (R 1) = CH 2 (5)
(Wherein R ¹ and R ³ are the same as described above) (IV) obtained by reacting the isocyanate compound (F) represented in the presence of dibutyltin (mercapto ester) (G). The curable composition as described.

(VI)
The curable composition according to any one of (I) to (V), wherein R ¹ is a hydrogen atom.

(VII)
The curable composition according to any one of (III) to (VI), wherein R ³ is an ethylene group.

(VIII)
The curable composition according to any one of (I) to (VII), wherein the polyoxyalkylene polymer (A) is a polyoxypropylene polymer.

(IX)
The curable composition according to any one of (I) to (VIII), wherein X in the general formula (2) is an alkoxy group.

(X)
The curable composition according to any one of (I) to (VIII), wherein X in the general formula (2) is a methoxy group.

(XI)
The curable composition according to any one of (I) to (X), wherein the polyoxyalkylene polymer (B) is a polyoxypropylene polymer.

(XII)
The addition amount of the tackifier resin (C) is 20 to 80 parts by weight with respect to 100 parts by weight in total of the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B) (I) To (XI). The curable composition according to any one of (XI).

(XIII)
The curable composition according to any one of (I) to (XII), wherein the tackifier resin (C) is a terpene resin.

(XIV)
The curable composition according to any one of (I) to (XII), wherein the tackifier resin (C) is a terpene phenol resin.

(XV)
The curable composition according to any one of (I) to (XIV), wherein the polymerization initiator (C) is a radical initiator (H) that generates radicals by active energy rays and / or heat.

(XVI)
The curable composition according to (XV), wherein the radical initiator (H) is a photo radical initiator (h1) that generates radicals by light.

(XVII)
The addition amount of the photo radical initiator (h1) is 0.001 to 10 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B). The curable composition as described in (XVI).

(XVIII)
The curable composition according to any one of (I) to (XVII), which contains a monomer and / or oligomer (I) having a polymerizable substituent.

(XIX)
The curable composition according to (XVIII), wherein the monomer and / or oligomer (I) having a polymerizable substituent is a (meth) acrylic monomer (i1) having a molecular weight of 500 or less.

(XX)
The curable composition according to any one of (I) to (XIX), which contains a silane coupling agent (J).

(XXI)
The curable composition according to any one of (I) to (XX), which contains a (meth) acrylic acid ester polymer (K) having a reactive silicon group.

(XXII)
Curable composition as described in (I) to (XXI) containing filler (L).

(XXIII)
From (I), the addition amount of the filler (L) is 10 parts by weight to 200 parts by weight with respect to 100 parts by weight in total of the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B). The curable composition according to any one of (XXII).

  By using the curable composition of the present invention, there is no dripping immediately after irradiation of active energy rays, workability is good, sufficient mechanical strength is obtained, and even a portion that cannot be irradiated with active energy rays can be cured. Sex composition can be obtained.

  The present invention will be described in detail below.

The curable composition of the present invention has the general formula (1):
^{-Z-C (= O) -C} (R 1) = CH 2 (1)
Wherein R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and Z is a divalent organic group (hereinafter referred to as a (meth) acryloyl-based substituent). A polyoxyalkylene polymer (A) having one or more in the molecule.

  The number of (meth) acryloyl substituents of the polyoxyalkylene polymer (A) is not particularly limited, but it is cured when the average is less than 1 per molecule from the point that the polymers (A) are crosslinked. Since the property tends to be low, an average of 1 or more is preferable. However, if the polymer (A) having one or more (meth) acryloyl substituents on average per molecule is included, the average of less than one per molecule is required to adjust the hardness and flexibility of the cured product. A polyoxyalkylene polymer having a (meth) acryloyl substituent may be included. Further, the (meth) acryloyl group may be present at any of the side chain and / or the terminal of the molecule, but is preferably present at the terminal of the molecule from the viewpoint of rubber elasticity.

R ¹ in the general formula (1) represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ¹ is not particularly limited, and examples thereof include a hydrogen atom; an alkyl group such as a methyl group and an ethyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group; and an aralkyl group such as a benzyl group. In these, a methyl group or a hydrogen atom is preferable from the high reactivity of a polyoxyalkylene type polymer (A), and a hydrogen atom is more preferable.

Z in the general formula (1) is not particularly limited, and examples thereof include an oxygen atom; a sulfur atom; and an amino group such as —NH— and —NCH ₃ —. Among these, in view of ease of introduction, oxygen atom, —NH— group, and groups represented by the following general formula (3) and general formula (4) are preferable, oxygen atom, general formula (3), general A group represented by the formula (4) is more preferable.
—NH—C (═O) —O—R ³ —O— (3)
(In the formula, R ² is a divalent hydrocarbon group.)
—O—C (═O) —NH—R ³ —O— (4)
(In the formula, R ³ is the same as above.)
R ³ in the general formulas (3) and (4) is not particularly limited as long as it is a divalent hydrocarbon group. Cycloalkylene groups such as cyclopentylene group and cyclohexylene group; arylene groups such as phenylene group and benzylene group; Among these, ethylene group and hexylene group are preferable and ethylene group is more preferable because of easy introduction.

  Examples of the method for introducing the (meth) acryloyl substituent represented by the general formula (1) into the polyoxyalkylene polymer include (a) a polyoxyalkylene polymer (a) having a hydroxyl group, A method of reacting the compound (M1) having a functional group and an unsaturated group having reactivity with respect to the hydroxyl group, (b) replacing the hydroxyl group of the polyoxyalkylene polymer (a) with another functional group, Examples thereof include a method of reacting a compound (M2) having a functional group and an unsaturated group that are reactive to a substituent.

  Examples of the compound (M1) to be reacted with the hydroxyl group of the polyoxyalkylene polymer (a) by the method (a) include unsaturated acid halogens such as chloro (meth) acrylic acid and bromated (meth) acrylic acid. Compounds; Carboxylic acid compounds such as (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid n-butyl, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid n-heptyl, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, (meth ) Decyl acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3- (meth) acrylic acid 3- Methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethyl (meth) acrylate Ethyl, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, perfluoroethyl (meth) acrylate, trifluoromethyl (meth) acrylate, Bis (trifluoromethyl) methyl (meth) acrylate, (meth ) 2-trifluoromethyl-2-perfluoroethylethyl acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexa (meth) acrylate Examples include ester compounds such as decylethyl. Among these, from the reactivity with the hydroxyl group of the polymer (a), among the unsaturated acid halogen compounds, chlorinated (meth) acrylic acid is preferred, and among the carboxylic acid compounds, (meth) acrylic acid is preferred. Among the ester compounds, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Isobutyl acrylate and tert-butyl (meth) acrylate are preferred.

  The amount of the compound (M1) to be reacted with the hydroxyl group of the polyoxyalkylene polymer (a) is preferably 0.1 molar equivalent to 10 molar equivalent, and 0.5 molar equivalent to 5 molar equivalent based on the hydroxyl group. More preferred. When the amount used is less than 0.1 molar equivalent, the reactivity may decrease, and when it is larger than 10 molar equivalent, it may be economically disadvantageous.

  Various additives (N) can be used in the reaction of the polyoxyalkylene polymer (a) and the compound (M1).

  When the hydroxyl group of the polyoxyalkylene polymer (a) is reacted with the unsaturated acid halogen compound, an amine compound or the like can be used as the additive (n1) for the purpose of capturing the generated acid. Examples of the amine compound include aliphatic tertiary amines such as triethylamine, triamylamine, trihexylamine, and trioctylamine; aliphatic unsaturated amines such as triallylamine and oleylamine; aniline, laurylaniline, and stearylaniline. , Aromatic amines such as triphenylamine; pyridine, 2-aminopyridine, 2- (dimethylamino) pyridine, 4- (dimethylaminopyridine), 2-hydroxypyridine, imidazole, 2-ethyl-4-methylimidazole, Morpholine, N-methylmorpholine, piperidine, 2-piperidinemethanol, 2- (2-piperidino) ethanol, piperidone, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,8-diazabicyclo (5 4,0) Unde -7 (DBU), 6- (dibutylamino) -1,8-diazabicyclo (5,4,0) undecene-7 (DBA-DBU), 1,5-diazabicyclo (4,3,0) nonene-5 (DBN), 1,4-diazabicyclo (2,2,2) octane (DABCO), nitrogen-containing heterocyclic compounds such as aziridine, and other amines include ethylenediamine, propylenediamine, hexamethylenediamine, N- Methyl-1,3-propanediamine, N, N′-dimethyl-1,3-propanediamine, diethylenetriamine, triethylenetetramine, benzylamine, 3-methoxypropylamine, 3-lauryloxypropylamine, 3-dimethylaminopropyl Amine, 3-diethylaminopropylamine, 3-dibutylaminopropylamine , 3-morpholinopropylamine, 2- (1-piperazinyl) ethylamine, xylylenediamine and other amines; guanidines such as guanidine, phenylguanidine and diphenylguanidine; butylbiguanide, 1-o-tolylbiguanide and 1-phenyl And biguanides such as biguanides. Among these, tertiary amines are preferable from the viewpoint of reactivity, and triethylamine is preferable from the viewpoint of ease of removal after the reaction and availability.

  The amount of the additive (n1) such as an amine compound used is preferably 0.1 molar equivalent to 10 molar equivalent, and preferably 0.5 molar equivalent to 5 molar equivalent based on the hydroxyl group. When the amount used is less than 0.1 molar equivalent, the acid may not be sufficiently captured, and when it is larger than 10 molar equivalent, removal may be difficult.

  When the hydroxyl group of the polyoxyalkylene polymer (a) is reacted with the carboxylic acid compound, a proton acid and Lewis acid, a salt of an amine compound and a sulfonic acid, a salt of a phosphorus compound and a sulfonic acid, etc. are used as the additive (n2). When used in combination, the reactivity may increase. Examples of such additives (n2) include inorganic acids such as hydrochloric acid, odorous acid, iodic acid, and phosphoric acid; acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, Capric acid, undecanoic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid, lactelic acid Linear saturated fatty acids such as: undecylenic acid, Lindellic acid, Tuzic acid, Fizeteric acid, myristoleic acid, 2-hexadecenoic acid, 6-hexadecenoic acid, 7-hexadecenoic acid, palmitoleic acid, petrothelic acid, oleic acid, elaidin Acid, asclepic acid, vaccenic acid, gadoleic acid, gondoic acid, cetate Mono-unsaturated fatty acids such as inic acid, erucic acid, brassic acid, ceracoleic acid, ximenic acid, lumenic acid, acrylic acid, methacrylic acid, angelic acid, crotonic acid, isocrotonic acid, 10-undecenoic acid; linoelaidic acid, linol Acid, 10,12-octadecadienoic acid, hiragoic acid, α-eleostearic acid, β-eleostearic acid, punicic acid, linolenic acid, 8,11,14-eicosatrienoic acid, 7,10,13 -Docosatrienoic acid, 4,8,11,14-hexadecatetraenoic acid, moloctic acid, stearidonic acid, arachidonic acid, 8,12,16,19-docosatetraenoic acid, 4,8,12,15,18- Polyene unsaturated fatty acids such as eicosapentaenoic acid, sardine acid, nisic acid, docosahexaenoic acid; 2-methylbutyric acid, iso Acid, 2-ethylbutyric acid, pivalic acid, 2,2-dimethylbutyric acid, 2-ethyl-2-methylbutyric acid, 2,2-diethylbutyric acid, 2-phenylbutyric acid, isovaleric acid, 2,2-dimethylvaleric acid, 2-ethyl-2-methylvaleric acid, 2,2-diethylvaleric acid, 2-ethylhexanoic acid, 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid, 2- Branched fatty acids such as ethyl-2,5-dimethylhexanoic acid, versatic acid, neodecanoic acid, tuberculostearic acid; propiolic acid, taliphosphoric acid, stearolic acid, crepenic acid, xymenic acid, 7-hexadesinic acid, etc. Fatty acids having a triple bond; naphthenic acid, malvalic acid, sterlic acid, hydnocalpsic acid, sorghumulinic acid, gorlic acid, 1-methylcyclopene Cyclohexane, 1-methylcyclohexanecarboxylic acid, 1-adamantanecarboxylic acid, bicyclo [2.2.2] octane-1-carboxylic acid, bicyclo [2.2.1] heptane-1-carboxylic acid and the like Carboxylic acids: acetoacetic acid, ethoxyacetic acid, glyoxylic acid, glycolic acid, gluconic acid, sabinic acid, 2-hydroxytetradecanoic acid, iprolic acid, 2-hydroxyhexadecanoic acid, yarapinolic acid, uniperic acid, ambrettlic acid, aleurit acid 2-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid, 9,10-dihydroxyoctadecanoic acid, 2,2-dimethyl-3-hydroxypropionic acid ricinoleic acid, camlorenic acid, ricanoic acid, ferronic acid, Including cerebronic acid Oxygen fatty acids; halogen substitution products of monocarboxylic acids such as chloroacetic acid, 2-chloroacrylic acid and chlorobenzoic acid; adipic acid, azelaic acid, pimelic acid, suberic acid, sebacic acid, glutaric acid, oxalic acid, malonic acid, Linear dicarboxylic acids such as ethylmalonic acid, dimethylmalonic acid, ethylmethylmalonic acid, diethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,2-diethylsuccinic acid, 2,2-dimethylglutaric acid; Saturated dicarboxylic acids such as 1,2,2-trimethyl-1,3-cyclopentanedicarboxylic acid and oxydiacetic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, acetylenedicarboxylic acid and itaconic acid; aconitic acid and citric acid , Isotric acid, 3-methylisocitric acid, 4,4-dimethylaconitic acid, etc. Acids; benzoic acid, 9-anthracenecarboxylic acid, atrolactic acid, anisic acid, isopropylbenzoic acid, salicylic acid, toluic acid and other aromatic monocarboxylic acids; phthalic acid, isophthalic acid, terephthalic acid, carboxyphenylacetic acid, pyromellitic Aromatic polycarboxylic acids such as acids; amino acids such as alanine, leucine, threonine, aspartic acid, glutamic acid, arginine, cysteine, methionine, phenylalanine, tryptophan, histidine; sulfonic acids such as trifluoromethanesulfonic acid and p-toluenesulfonic acid; Examples include salts of dimesitylamine and pentafluorobenzenesulfonic acid, salts of diphenylamine and trifluoromethanesulfonic acid, and salts of triphenylphosphine and trifluoromethanesulfonic acid.

  The additive (n2) may or may not be used, but when used, it is preferable to use 0.001 to 10 molar equivalents relative to the hydroxyl group, and 0.01 to 1 molar equivalents. A molar equivalent is more preferred. When the amount used is less than 0.001 molar equivalent, a sufficient effect may not be obtained, and when it is larger than 10 molar equivalent, removal may be difficult.

  In the method (b), examples of the polyoxyalkylene polymer having a substituent other than a hydroxyl group include a polymer having an alkoxide group, a polymer having a halogen atom, and a polymer having an amino group.

  Examples of the method for producing a polyoxyalkylene polymer having an alkoxide group include a method of reacting the polymer (a) with a metal alkoxide. Examples of the metal alkoxide used include sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, calcium diethoxide and the like.

  Furthermore, examples of the method for producing a polyoxyalkylene polymer having an alkoxide group include a method of reacting a polyoxyalkylene polymer (a) with a Grignard reagent (Q). The Grignard reagent (Q) is not particularly limited. For example, p-xylene-magnesium bromide, p-xylene-magnesium chloride, allylmagnesium bromide, allylmagnesium chloride, phenylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium iodide, Trimethylsilylmethylmagnesium chloride, vinylmagnesium bromide; benzylmagnesium halides such as benzylmagnesium bromide and benzylmagnesium chloride; tolylmagnesium halides such as m-tolylmagnesium bromide, o-tolylmagnesium bromide, p-tolylmagnesium bromide; butylmagnesium chloride, ethyl Magnesium bromide, ethyl magnesium chloride, hept Magnesium bromide, hexyl magnesium bromide, isobutyl magnesium bromide, isopropyl magnesium bromide, isopropyl magnesium chloride, methyl magnesium bromide, methyl magnesium iodide, n-octyl magnesium bromide, pentadecyl magnesium bromide, pentyl magnesium bromide, propyl magnesium bromide, sec-butyl Alkyl magnesium halides such as magnesium bromide and tert-butylmagnesium chloride; cycloalkyl magnesium halides such as cyclohexyl magnesium bromide, cyclopentyl magnesium bromide and cyclopropyl magnesium bromide; Of these, benzylmagnesium halide, tolylmagnesium halide, alkylmagnesium halide, and cycloalkylmagnesium halide are preferred from the viewpoint of availability. Specifically, benzylmagnesium bromide and benzylmagnesium are preferred from the viewpoint of by-products generated by the reaction. Benzylmagnesium halides such as chloride, m-tolylmagnesium bromide, o-tolylmagnesium bromide, p-tolylmagnesium bromide and other tolylmagnesium halides, heptylmagnesium bromide, hexylmagnesium bromide, n-octylmagnesium bromide and other alkylmagnesium halides, cyclohexyl Cycloalkyl magnesium halides such as magnesium bromide are preferred. Many of these Grignard reagents are usually marketed as solutions such as a diethyl ether solution and a tetrahydrofuran solution, and it is preferable to use them in a solution state.

  The amount of Grignard reagent (Q) used is preferably 0.1 to 5 equivalents, more preferably 0.5 to 1.5 equivalents, and equivalents with respect to the hydroxyl groups of the polyoxyalkylene polymer (a). Is more preferable. When the amount used is larger than this, there is a possibility of affecting the reaction with the compound (M2), and when it is small, there is a concern that the reactivity with the compound (M2) is lowered.

  In the reaction of the polyoxyalkylene polymer (a) and the Grignard reagent (Q), a reaction solvent can be used in addition to the solvent contained in the Grignard reagent (Q). As the reaction solvent, an aprotic solvent that does not react with the Grignard reagent (Q) is preferable. Specifically, ether solvents such as dimethyl ether, diethyl ether, and tetrahydrofuran, aromatic solvents such as benzene and toluene, hexane, and the like. There may be mentioned hydrocarbon solvents. Further, since the Grignard reagent (Q) easily reacts with moisture, it is preferable to use a dehydrated solvent.

  The reaction between the polyoxyalkylene polymer (a) and the Grignard reagent (Q) is preferably carried out in a nitrogen atmosphere because the Grignard reagent (Q) easily reacts with moisture. Moreover, as reaction temperature, -80 to 100 degreeC is preferable, and 0 to 30 degreeC is more preferable.

  As the compound (M2) to be reacted with the polyoxyalkylene polymer having an alkoxide group, unsaturated acid halogen compounds, carboxylic acid compounds and the like shown in the above-mentioned method (a) can be used. Of these, chloroacrylic acid is preferred from the viewpoint of the reactivity of the resulting polyoxyalkylene polymer (A).

  As a method for producing a polyoxyalkylene polymer having a halogen atom, a method in which a polyoxyalkylene polymer (a) is reacted with carbon tetrachloride or carbon tetrabromide in the presence of triphenylphosphine, a polymer Examples thereof include a method in which (a) is reacted with phosphorus pentachloride, thionyl chloride, and sulfynyl chloride to replace the hydroxyl group with a chlorine atom.

  Examples of the compound (M2) having an unsaturated group to be reacted with a polymer having a halogen atom include salts of the carboxylic acid compounds shown in the above method (a), such as sodium (meth) acrylate and (meth) acrylic. Potassium acid etc. can be used.

  As a method for producing a polyoxyalkylene polymer having an amino group, a method in which a polyoxyalkylene polymer (a) is reacted with an amino acid, a hydroxyl group of the polymer (a) is substituted with a halogen atom, hexamethylenetetramine and A method of reacting, a polymer having a hydroxyl group substituted with a halogen atom, reacting phthalimide and potassium hydroxide or potassium phthalimide to obtain a polymer having a phthalimide group, and then reacting with hydrazine or potassium hydroxide. The method of obtaining the polymer which has an amino group by this is mention | raise | lifted.

  As the compound (M2) to be reacted with the polyoxyalkylene polymer having an amino group, the same compound (M1) as shown in the above method (a) can be used. In addition, the above additive (N) may or may not be used in the reaction with the compound (M2).

  As a method for synthesizing the polyoxyalkylene polymer (A) having the structure of the general formula (3), after reacting the polyoxyalkylene polymer (a) having a hydroxyl group with the diisocyanate compound (S), an isocyanate group is reacted. The method of making it react with the (meth) acrylic-type monomer (T) which has a substituent which reacts with is mentioned.

  Although it does not specifically limit as a diisocyanate compound (S), For example, hexamethylene diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dicyclohexylmethane-4,4 Aliphatic and alicyclic such as' -diisocyanate, m-xylylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate, norbornane diisocyanate, trans-cyclohexane diisocyanate, dimer acid diisocyanate, lysine diisocyanate Diisocyanates; tolylene diisocyanate, diphenylmethane diisocyanate, polymeric MDI, 1,5-na Ji diisocyanate, o- tolylene diisocyanate, and aromatic diisocyanates such as p- phenylene isocyanate.

  The amount of the diisocyanate compound (S) used is preferably from 0.1 to 10 molar equivalents, more preferably from 0.5 to 5 molar equivalents, based on the hydroxyl groups of the polyoxyalkylene polymer (a). When the amount used is less than 0.1 molar equivalent, the reactivity may decrease. When the amount used is larger than 10 molar equivalent, the reaction with the (meth) acrylic monomer (T) may be adversely affected. There is.

  Although it does not specifically limit as (meth) acrylic-type monomer (T) which has a substituent which reacts with an isocyanate group, For example, (meth) acrylic acid, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, 2-aminoethyl (meth) acrylate, and the like. Of these, 2-hydroxyethyl acrylate is preferred from the viewpoint of availability and ease of handling.

  The amount of the (meth) acrylic monomer (T) used is preferably 0.1 molar equivalent to 10 molar equivalent, and 0.5 molar equivalent to 5 molar equivalent based on the hydroxyl group of the polyoxyalkylene polymer (a). Is more preferable. When the amount used is less than 0.1 molar equivalent, the reactivity may decrease. When the amount used exceeds 10 molar equivalent, there is a concern that it is economically disadvantageous.

  In the case of reacting the hydroxyl group of the polyoxyalkylene polymer (a) with the diisocyanate compound (S) and the (meth) acryloyl monomer (T) having a substituent that reacts with the isocyanate group, a titanium compound, a tin compound, a zirconium compound, etc. In combination with the additive (n3), the reactivity may increase. Examples of titanium compounds include tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), titanium diisopropoxybis (acetylacetonato), titanium diisopropoxybis (ethyl acetate), and the like. Examples of tin compounds include dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methyl maleate), dibutyltin bis (ethyl maleate) , Dibutyl tin bis (butyl maleate), dibutyl tin bis (octyl maleate), dibutyl tin bis (tridecyl maleate), dibutyl tin bis (benzyl maleate), dibutyl tin diacetate, dioctyl tin bis ( Tilmaleate), dioctyltin bis (octylmaleate), dibutyltin dimethoxide, dibutyltin bis (nonylphenoxide), dibutenyltin oxide, dibutyltin oxide, dibutyltin bis (acetylacetonate), dibutyltin bis (ethylacetoacetonate) ), A reaction product of dibutyltin oxide and a silicate compound, a reaction product of dibutyltin oxide and a phthalate ester, and the like, and examples of the zirconium compound include zirconium tetrakis (acetylacetonate).

  The additive (n3) may or may not be used, but when used, it is preferable to use 1 ppm to 1000 ppm, more preferably 5 ppm to 500 ppm, based on the polyoxyalkylene polymer (a). preferable. When the amount used is less than 1 ppm, a sufficient effect may not be obtained, and when it is more than 1000 ppm, the cured product obtained by curing the polyoxyalkylene polymer (A) may be affected. is there.

  Examples of the method for synthesizing the polyoxyalkylene polymer (A) having the structure of the general formula (4) include a method of reacting the polyoxyalkylene polymer (a) having a hydroxyl group with the isocyanate compound (F). .

Although it does not restrict | limit especially as an isocyanate type compound (F), General formula (5):
^{O = C = N-R 3} -O-C (= O) -C (R 1) = CH 2 (5)
(In the formula, R ¹ and R ³ are the same as above.)
The following compounds represented by the formula:

  Of these, 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyisocyanate are preferable and 2-acryloyloxyethyl isocyanate is more preferable from the viewpoints of reactivity and availability.

  As usage-amount of an isocyanate type compound (F), 0.1-5 equivalent is preferable with respect to the hydroxyl group of a polyoxyalkylene type polymer (a), 0.5-1.5 equivalent is more preferable, and is equivalent. More preferably. When the amount used is larger than this, it is economically disadvantageous, and when it is small, the curability of the resulting polyoxyalkylene polymer (A) tends to be lowered.

  When reacting the polyoxyalkylene polymer (a) and the isocyanate compound (F), dibutyltin (mercapto acid ester) (G) is used. Although it does not specifically limit as dibutyltin (mercapto acid ester) (G), For example, dibutyltin (methyl mercapto acid), dibutyltin (ethyl mercapto acid), dibutyltin (mercaptoic acid n-propyl), dibutyltin (mercapto) Isopropyl), dibutyltin (n-butyl mercaptoate), dibutyltin (isobutylmercaptoate), dibutyltin (sec-butylmercaptoate), dibutyltin (tert-butylmercaptoate), dibutyltin (n-pentylmercaptoate) ), Dibutyltin (neopentyl mercapto), dibutyltin (n-hexyl mercaptoate), dibutyltin (cyclohexyl mercaptoate), dibutyltin (n-heptylmercaptoate), dibutyltin (n-octylmercapto), dibutyltin (Mercapto acid 2-ethyl Sil), dibutyltin (nonyl mercaptoate), dibutyltin (decyl mercaptoate), dibutyltin (dodecylmercaptoate), dibutyltin (phenyl mercaptoate), dibutyltin (toluyl mercaptoate), dibutyltin (benzyl mercaptoate) Etc. More specifically, examples include Neostan U-360 and Neostan U-350 manufactured by Nitto Kasei Co., Ltd.

  The amount of dibutyltin (mercapto acid ester) (G) used is preferably 10 ppm to 500 ppm, more preferably 25 ppm to 100 ppm, and even more preferably 50 ppm, based on the polyoxyalkylene polymer (a). If the amount used is larger than this, a by-product may be generated, and if it is smaller than this amount, the reactivity may be lowered.

  When the polyoxyalkylene polymer (a) is reacted with the isocyanate compound (F), a solvent may or may not be used. When a solvent is used, a solvent in which the polymer (a) is dissolved is preferable. Although it does not restrict | limit especially as a solvent, For example, toluene, hexane, etc. are mention | raise | lifted. The amount of the solvent used can be appropriately determined from the viewpoint of easiness of stirring.

  Examples of the main chain skeleton of the polyoxyalkylene polymer (A) include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene- A polyoxybutylene copolymer or the like can be used, but a polyoxypropylene polymer is preferable.

The polyoxyalkylene polymer essentially has the general formula (6):
—R ⁴ —O— (6)
(Wherein R ⁴ is a linear or branched alkylene group having 1 to 14 carbon atoms), and R ⁴ described in the general formula (6) is A linear or branched alkylene group having 1 to 14 carbon atoms is preferred, and a linear or branched alkylene group having 2 to 4 carbon atoms is more preferred. There is no limitation in particular as a repeating unit as described in General formula (6), For example,

Etc. The main chain skeleton of the polyoxyalkylene polymer (A) may consist of only one type of repeating unit, or may consist of two or more types of repeating units. In particular, a polymer composed mainly of a propylene oxide polymer is preferred because it is amorphous and has a relatively low viscosity.

  The method for synthesizing the polyoxyalkylene polymer is not particularly limited. For example, a polymerization method using an alkali catalyst such as KOH, an organoaluminum compound disclosed in JP-A-61-215623, and porphyrin are reacted. Polymerization method using transition metal compound-porphyrin complex catalyst such as the obtained complex, Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, US Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3,278,459, US Pat. , US Pat. No. 3,427,334, US Pat. No. 3,427,335, etc., a polymerization method using a double metal cyanide complex catalyst, a polymerization method using a catalyst comprising a polyphosphazene salt disclosed in Japanese Patent Application Laid-Open No. 10-273512, Phosphine disclosed in Japanese Patent No. 11060722 A polymerization method using a catalyst comprising Azen compounds.

  The polyoxyalkylene polymer (A) may be linear or branched, and its number average molecular weight is preferably from 3,000 to 100,000, more preferably from 3,000 in terms of polystyrene in GPC. 50,000, particularly preferably from 3,000 to 30,000. If the number average molecular weight is less than 3,000, the cured product tends to be inconvenient in terms of stretchability, and if it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity.

  The molecular weight distribution of the polyoxyalkylene polymer (A) is not particularly limited, but is preferably narrow, preferably less than 2.00, more preferably 1.60 or less, and particularly preferably 1.40 or less. As the molecular weight distribution increases, the viscosity tends to increase, and therefore workability tends to deteriorate.

  The main chain skeleton and the synthesis method of the polyoxyalkylene polymer (a) having a hydroxyl group are the same as those of the polyoxyalkylene polymer (A).

The curable composition of the present invention has a general formula (2):
-[Si (R ² _2-b ) (X _b ) O] _n Si (R ² _3-a ) X _a (2)
(In the formula, R ² represents 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 a triorganosiloxy group represented by R ′ ₃ SiO—. , R ² may be the same or different when two or more R ² are present, where R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and X is a hydroxyl group Or a hydrolyzable group, where a represents 0, 1, 2 or 3, b represents 0, 1 or 2, and satisfies a + Σb ≧ 2, and n represents an integer of 0 to 19. The polyoxyalkylene polymer (B) having a reactive silicon group represented by

  Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3, and (a + Σb) is preferably in the range of 2 to 5. A is preferably 2 because the resulting cured product exhibits good curability, and a is preferably 3 in that the polymer (B) exhibits high reactivity. When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different.

In particular, the general formula (7):
-SiR ² _3-a X _a (7)
(In the formula, R ² and X are the same as described above. A represents 2 or 3.) A reactive silicon group represented by

  The hydrolyzable group represented by X in the general formula (2) or (7) is not particularly limited, and examples thereof include known hydrolyzable groups such as hydrogen atom, halogen atom, alkoxy group, acyloxy Group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group, alkenyloxy group and the like. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable, and the alkoxy group is mildly hydrolyzable and easy to handle. More preferred.

  Specific examples of the alkoxy group are not particularly limited. For example, methoxy group, ethoxy group, 1-propoxy group, 2-propoxy group, 1-butoxy group, 2-butoxy group, tert-butyloxy group, octoxy group, lauryl Examples thereof include an oxy group, a phenoxy group, and a benzyloxy group. Among these, a methoxy group and an ethoxy group are preferable because of easy synthesis, and a methoxy group is more preferable because of high reactivity of hydrolysis reaction.

R ² in the general formula (2) or (3) is not particularly limited, and examples thereof include alkyl groups such as a methyl group and an ethyl group, cycloalkyl groups such as a cyclohexyl group, aryl groups such as a phenyl group, and benzyl groups. Examples thereof include a hydrocarbon group such as an aralkyl group, or a triorganosiloxy group described by a general formula: R ′ ₃ SiO—, wherein R ′ is a methyl group, a phenyl group, or the like. Among these, a methyl group is preferable from the viewpoint of ease of introduction.

  The reactive silicon group of the polyoxyalkylene polymer (B) is not particularly limited, and examples thereof include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, and a diethoxymethylsilyl group. A diisopropoxymethylsilyl group, a dimethoxymethylsilyloxydimethylsilyl group, and a diethoxymethylsilyloxydimethylsilyl group. Among these, a trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group are preferable because they are easy to introduce. In order to obtain a composition having good curability, it is preferable to use a polymer (B) having a trimethoxysilyl group, and in order to obtain a cured product having higher elasticity, it has a dimethoxymethylsilyl group. It is preferable to use the polymer (B).

  The reactive silicon group contained in the polyoxyalkylene polymer (B) has a high strength, high elongation, and in order to obtain a rubber-like cured product having a low elastic modulus, it is averaged in one molecule of the polymer. There should be at least 1, preferably 1.1-5. When the number of reactive silicon groups contained in the molecule is less than 1 on average, curability becomes insufficient and it becomes difficult to exhibit good rubber elastic behavior. The reactive silicon group may be at the end of the main chain or the side chain of the polymer molecular chain, or at both ends. In particular, when the reactive silicon group is only at the end of the main chain of the molecular chain, the effective network length of the polymer component contained in the finally formed cured product is increased, so that the high strength, high elongation, A rubber-like cured product having a low elastic modulus is easily obtained.

  Examples of the method for introducing the reactive silicon group in the organic polymer (A) include known methods, and examples thereof include the following methods (c) to (e).

  (C) A method in which a hydrosilane having a reactive silicon group is reacted with a polymer having an unsaturated group to cause hydrosilylation.

  (D) A method of reacting a polymer having an unsaturated group with a compound having a mercapto group and a reactive silicon group.

  (E) A method in which a polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in the molecule is reacted with a compound having a reactive functional group and a reactive silicon group.

  Among the methods (c) to (e), among the methods (e), a method of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group, or (c) The method is preferable because a high conversion rate can be obtained in a relatively short reaction time. Among them, the polymer having a reactive silicon group obtained by the method (c) is more preferable than the polymer obtained by the method (e). However, the (c) method is particularly preferred because the polymer obtained by the (d) method has a strong odor based on mercaptosilane.

  (C) There is no particular limitation on the hydrosilane compound used in the method, for example, halogenated silanes such as trichlorosilane, dichloromethylsilane, dichlorophenylsilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethyl Alkoxysilanes such as silane, dimethoxyphenylsilane, dimethoxyethylsilane; acyloxysilanes such as diacetoxymethylsilane, diacetoxyphenylsilane; bis (dimethylketoximate) methylsilane, bis (cyclohexylketoximate) methylsilane, etc. Examples thereof include ketoximate silanes. Of these, halogenated silanes and alkoxysilanes are particularly preferable. Furthermore, the hydrolyzability of the curable composition from which alkoxysilanes can be obtained is more preferable because it is mild and easy to handle. Among alkoxysilanes, dimethoxymethylsilane is preferable because it is readily available.

  As a synthesis method of (d), for example, a compound having a mercapto group and a reactive silicon group is introduced into an unsaturated bond site of a polymer by a radical addition reaction in the presence of a radical initiator and / or a radical generation source. There are no particular limitations on the method. The compound having a mercapto group and a reactive silicon group is not particularly limited. For example, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyldi Examples thereof include ethoxymethylsilane and mercaptomethyltriethoxysilane.

  As a method of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group in the synthesis method (c), for example, the method described in JP-A-3-47825 can be mentioned. However, it is not particularly limited. The compound having an isocyanate group and a reactive silicon group is not particularly limited. For example, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyldimethoxymethylsilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropyldi Examples include ethoxymethylsilane, isocyanatemethyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyldimethoxymethylsilane, and isocyanatemethyldiethoxymethylsilane.

  The polyoxyalkylene polymer (B) may be linear or branched, and its number average molecular weight is about 3,000 to 100,000, more preferably 3,000 to 50 in terms of polystyrene in GPC. 3,000, particularly preferably 3,000 to 30,000. If the number average molecular weight is less than 3,000, the cured product tends to be inconvenient in terms of elongation characteristics, and if it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity.

  The main chain skeleton of the polyoxyalkylene polymer (B) can be explained in the same manner as the polyoxyalkylene polymer (A).

  The polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B) can be mixed and used at an arbitrary ratio, but the content of the polymer (A) is determined based on the polymer (A). / The weight ratio of the polymer (B), the upper limit is preferably 90/10 or less, and more preferably 60/40 or less. When the ratio of the polymer (A) is larger than this, there is a possibility that the portion that cannot be irradiated with the active energy ray will not be cured. On the other hand, the lower limit of polymer (A) / polymer (B) is preferably greater than 1/99 by weight and more preferably greater than 5/95. When the ratio of the polymer (A) is smaller than this, there is a concern that the mechanical properties immediately after irradiation with active energy rays are lowered.

  The curable composition of the present invention contains a tackifying resin (C) for the purpose of improving the mechanical properties of the cured product, particularly the mechanical properties immediately after irradiation with active energy rays. Further, it contains a tackifier resin (C) for the purpose of suppressing the uncured material from seeping out and dripping after irradiation with active energy rays. Although it does not specifically limit as tackifying resin (C), For example, a phenol resin, modified phenol resin, cyclopentadiene-phenol resin, xylene resin, chroman resin, petroleum resin, terpene resin, terpene phenol resin, rosin ester resin etc. can give. More specifically, YS Resin PX, YS Resin PXN, YS Polystar U, YS Polystar T, YS Polystar S, YS Polyster S, Mighty Ace G, Mighty Ace K, YS Resin TO, YS Resin TR , YS Resin SX, Clearon P, Clearon M, Clearon K; Arakawa Chemical Industry Co., Ltd. Archon, Ester Gum, Pencel, Superester, Tamanol, High Pale; Harima Kasei Co., Ltd. Harrier Star, Neotor, Hari Mac, Halitac, etc Can be given. Among these, from the viewpoint of compatibility with the polyoxyalkylene polymer (A), terpene resins YS resin PX, YS resin PXN, YS resin TO, YS resin TR, Clearon P, Clearon M, Clearon K YS Polystar U, YS Polyster T, YS Polyster S, Mighty Ace G and Mighty Ace K, which are terpene phenol resins, are preferred. Among them, YS Polystar U, YS Polystar T, YS Polyster S, Mighty Ace G and Mighty Ace K A terpene phenol resin such as is more preferable.

  The amount of the tackifying resin (C) used is not particularly limited, but is 5 to 100 parts by weight based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B). Part by weight is preferable, and 20 to 80 parts by weight is more preferable. If the amount used is less than this range, the effect may not be sufficiently obtained, and if it exceeds this range, the viscosity becomes too high, and the workability may be deteriorated.

  Moreover, in the curable composition of this invention, you may use together 2 or more types of tackifying resin.

  The curable composition of the present invention contains a polymerization initiator (D). Although it does not specifically limit as a polymerization initiator (D), The radical initiator which generate | occur | produces a radical by an active energy ray, a photoanion initiator, a redox initiator, etc. are mention | raise | lifted. Among these, the radical initiator (H) that generates radicals by active energy rays and / or heat is preferable from the viewpoint of availability, and among these, the photo radical initiator (h1) is more preferable from the viewpoint of reactivity. .

  The photo radical initiator (h1) is not particularly limited, and examples thereof include acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone. 3-pentylacetophenone, 2,2-diethoxyacetophenone, 4-methoxyacetophene, 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-nonylxanthate Benzoyl, benzoin methyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxy ketal, 2-chlorothioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1 -Hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1- ON, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and the like. Among these, phenyl ketone compounds are preferred in that they have tack-improving properties.

  In addition, an acylphosphine oxide photopolymerization initiator having excellent deep curability during UV irradiation can also be blended. Acylphosphine oxide polymerization initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) ) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,6-dimethylbenzoyl) -phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -isobutylphosphine oxide, bis (2 , 6-dimethoxybenzoyl) -isobutylphosphine oxide, bis (2,6-dimethoxybenzoyl) -phenylphosphine oxide, etc., preferably 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide Bis (2,4,6-trimethylbenzoyl) - phenyl phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl - a pentyl phosphine oxide. The above photo radical initiators may be used alone or in combination of two or more. Among them, because of high reactivity, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane -1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide are preferred.

  In the curable composition of the present invention, the acylphosphine oxide and the phenyl ketone compound can be used in combination.

  The addition amount of the photo radical initiator (h1) is not particularly limited, but from 0.001 part by weight to 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B). 10 parts by weight is preferred. If the addition amount of the photo radical initiator (h1) is below this range, sufficient curability may not be obtained, and if the addition amount exceeds this range, the cured product may be affected. . In addition, when the mixture of photoradical initiator (h1) is used, it is preferable that the total amount of a mixture exists in the said range.

  The main chain skeletons of the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B) may be the same or different, and each may be a single main chain skeleton. The above main chain skeletons may be mixed. However, the polymer (A) and the polymer (B) are preferably compatible with each other.

  The curable composition of the present invention may contain a monomer and / or oligomer (I).

  As the monomer and / or oligomer (I) having a polymerizable substituent, a monomer and / or oligomer having a radical polymerizable group, or a monomer and / or oligomer having an anion polymerizable group is preferable. . Examples of radical polymerizable groups include acrylic functional groups such as (meth) acrylic groups, styrene groups, acrylonitrile groups, vinyl ester groups, N-vinylpyrrolidone groups, acrylamide groups, conjugated diene groups, vinyl ketone groups, and vinyl chloride groups. Can be given. Examples of the anionic polymerizable group include (meth) acryl group, styrene group, acrylonitrile group, N-vinylpyrrolidone group, acrylamide group, conjugated diene group, vinyl ketone group and the like. Among these, those having an acrylic functional group are preferable from the viewpoint of compatibility with the polyoxyalkylene polymer (A).

  Specific examples of the above monomers include (meth) acrylic monomers, cyclic acrylates, N-vinyl pyrrolidone, styrene monomers, acrylonitrile, N-vinyl pyrrolidone, acrylamide monomers, conjugated diene monomers, vinyl ketone monomers, and the like. It is done.

  Examples of the (meth) acrylic monomer include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate and compounds of the following formula. it can.

  Styrene monomers include styrene and α-methylstyrene, acrylamide monomers include acrylamide and N, N-dimethylacrylamide, conjugated diene monomers include butadiene and isoprene, and vinyl ketone monomers. And methyl vinyl ketone.

  Examples of polyfunctional monomers include neopentyl glycol polypropoxydiacrylate, trimethylolpropane polyethoxytriacrylate, bisphenol F polyethoxydiacrylate, bisphenol A polyethoxydiacrylate, dipentaerythritol polyhexanolide hexaacrylate, tris (hydroxy) Ethyl) isocyanurate polyhexanolide triacrylate, tricyclodecane dimethylol diacrylate 2- (2-acryloyloxy-1,1-dimethyl) -5-ethyl-5-acryloyloxymethyl-1,3-dioxane, tetra Bromobisphenol A diethoxydiacrylate, 4,4-dimercaptodiphenyl sulfide dimethacrylate, polytetraethylene glycol diacrylate, 1,9 Nonanediol diacrylate, and ditrimethylolpropane tetraacrylate and the like.

  As the oligomer, epoxy acrylate resins such as bisphenol A type epoxy acrylate resin, phenol novolac type epoxy acrylate resin, cresol novolak type epoxy acrylate resin, COOH group-modified epoxy acrylate type resin, polyol (polytetramethylene glycol, ethylene glycol and adipine) Acid polyester diol, ε-caprolactone modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisobutylene, etc. and organic isocyanate (tolylene diisocyanate, isophorone diisocyanate, diphenylmethane) Diisocyanate, hexamethylene dii Urethane resin obtained from cyanate, xylylene diisocyanate, etc.) reacted with hydroxyl group-containing (meth) acrylate {hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, etc.} Examples thereof include urethane acrylate resins obtained by the above, resins obtained by introducing (meth) acrylic groups into the above polyols through ester bonds, polyester acrylate resins, and the like.

  Among the above-mentioned monomers (I) having a polymerizable substituent, a (meth) acrylic monomer (i1) having a molecular weight of 500 or less is preferred from the viewpoint of reactivity and workability due to viscosity reduction. The (meth) acrylic monomer (i1) is not particularly limited, but ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, vinyl acetate, acrylonitrile, acrylamide, styrene, methyl methacrylate, methyl acrylate, methacrylic acid, acrylic acid, itacon Acid, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, methylol acrylamide, glycidyl methacrylate, maleic anhydride, ethyl carbitol acrylate, lauryl acrylate, isooctyl acrylate, isostearyl acrylate, cyclohexyl acrylate, tricyclodecanyl Acrylate, tricyclodecanyloxyethyl acrylate, isoboro Acrylate, 2-ethylhexyl carbitol acrylate, methoxypropylene acrylate, tetrahydrofuryl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, benzyl acrylate, 2-phenoxyethyl acrylate, 2-phenoxydiethylene glycol, nonylphenoxyethyl acrylate, 2 -Hydroxy-3-phenoxyethyl acrylate and the like.

  The amount of the (meth) acrylic monomer (i1) used is that the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer are used from the viewpoint of improving surface curability, imparting toughness, and workability by reducing viscosity. 1 to 50 parts by weight is preferable and 5 to 40 parts by weight is more preferable with respect to 100 parts by weight of the total of (B). When the amount used is smaller than this, there is a tendency that a sufficient effect cannot be obtained, and when it is larger, the unreacted (meth) acrylic monomer (i1) may volatilize from the cured product.

  The curable composition of the present invention contains a silanol condensation catalyst (E). Although it does not specifically limit as a silanol condensation catalyst (E), The thing similar to what was illustrated by said additive (n1), (n2), (n3) can be used.

  The amount of the silanol condensation catalyst (E) such as the additives (n1), (n2), and (n3) is the sum of the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B). 0.001 to 20 parts by weight is preferable with respect to 100 parts by weight, and 0.1 to 10 parts by weight is more preferable. If the amount of the silanol condensation catalyst (E) is less than this range, the reaction rate may be slow, and the catalytic activity may decrease after storage. On the other hand, if the blending amount of the silanol condensation catalyst (E) exceeds this range, the pot life may be too short and the workability may deteriorate. In addition, two or more types of silanol condensation catalysts (E) may be used in combination.

  In the curable composition of the present invention, a photoacid generator can be used as a silanol condensation catalyst.

  The photoacid generator is not particularly limited, but sulfonium salts, iodonium salts, diazonium salts, ammonium salts, pyridinium salts, phosnium salts, oxonium salts, quinolinium salts and other onium salt photoacid generators, sulfonic acid derivatives, diazomethanes Carboxylic acid esters, iron arene complexes, and the like. In the present invention, the photo acid generator is synonymous with the photo cation initiator.

  Examples of onium salt photoacid generators include benzylmethylsulfonium salts such as p-phenylbenzylmethylsulfonium salt and p-hydroxyphenylbenzylmethylsulfonium salt, triphenylsulfonium salts, and triphenylsulfonium salts such as diphenyl-4-thiophenoxyphenylsulfonium salt. A disulfonium salt having a bis- [4- (diphenylsulfonio) phenyl] sulfide skeleton such as a reelsulfonium salt or 4,4-bis [di (β-hydroxyethoxy) phenylsulfonio] phenisulfide bishexafluoroantimonate; Iodonium such as diphenyliodonium salt, bis (4-tert-butylphenyl) iodonium salt, (4-tert-butoxyphenyl) phenyliodonium salt, (4-methoxyphenyl) phenyliodonium salt Salt. However, it is not limited to these.

  Examples of the sulfonic acid derivatives include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Specific examples of the sulfonic acid compound include benzoin tosylate, pyrogallol trimesylate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethyl). Sulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (Trifluoromethylsulfonyloxy) naphthylimide and the like can be mentioned. However, it is not limited to these.

  Diazomethanes include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, bis (2,4-xylylsulfonyl) diazomethane, bis (P-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane, etc. Can be mentioned. However, it is not limited to these.

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

Of these, triarylsulfonium salts such as a sulfonium salt having a bis- [4- (diphenylsulfonio) phenyl] sulfide skeleton and a diphenyl-4-thiophenoxyphenylsulfonium salt are preferable from the viewpoint of thermal stability. Examples of counter anions of these sulfonium salts include SbF ₆ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , special phosphorus anions, and the like. From the viewpoint of stability, SbF ₆ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ and special phosphorus anions are preferred. Specific product names of these photoacid generators include Adekaoptomer SP-172 (manufactured by ADEKA), Adekaoptomer SP-170 (manufactured by ADEKA), Adekaoptomer SP-152 (manufactured by ADEKA), Adekaoptomer SP- 150 (manufactured by ADEKA), Sun Aid SI-60L (manufactured by Sanshin Chemical Industry), Sun Aid SI-80L (manufactured by Sanshin Chemical Industry), Sun Aid SI-100L (manufactured by Sanshin Chemical Industry), Sun Aid SI-150L (manufactured by Sanshin Chemical) Kogyo), CPI-100P (San Apro), CPI-101A (San Apro), CPI-200K (San Apro), IRGACURE250 (Ciba Japan) and the like.

  The content of the photoacid generator is preferably 0.001 to 20 parts by weight based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B). More preferably, it is 1-10 weight part, and 0.5-5 weight part is further more preferable. If it is less than 0.001 part by weight, the curability may be insufficient, and if it is more than 20 part by weight, the physical properties and cost balance of the cured product may be lowered.

  The curable composition of this invention may contain additives, such as a sensitizer, with the photo-acid generator.

  The sensitizer increases the sensitivity of the photoacid generator to light, reduces the time and energy required to activate (react or decompose) the photoacid generator, and activates the photoacid generator. It has a function of changing the wavelength of light to a wavelength suitable for.

  Such a sensitizer is appropriately selected according to the sensitivity of the photoacid generator and the peak wavelength of absorption of the sensitizer, and is not particularly limited. For example, 9,10-dibutoxyanthracene (CAS No. 76275) is selected. -14-4)), such as anthracene, xanthone, anthraquinone, phenanthrene, chrysene, benzpyrene, fluoracene, rubrene, pyrene, indanthrine, thioxanthen-9-one These can be used alone or as a mixture.

  Specific examples of the sensitizer include 2-isopropyl-9H-thioxanthen-9-one, 4-isopropyl-9H-thioxanthen-9-one, 1-chloro-4-propoxythioxanthone, phenothiazine or a mixture thereof. can give.

  The content of the sensitizer is preferably 0.001 to 20 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B). The amount is more preferably 1 to 10 parts by weight, and further preferably 0.5 to 5 parts by weight. When the amount is less than 0.001 part by weight, the sensitization effect may be insufficient. When the amount is more than 20 parts by weight, the physical properties of the cured product may be deteriorated.

  The curable composition of the present invention may contain a silane coupling agent (J). Usually, an amino group-containing silane coupling agent is often used as an adhesion-imparting agent. However, when an amino group-containing silane coupling agent is used in the present invention, the curability of the polyoxyalkylene polymer (A) decreases. There are concerns. Therefore, examples of the functional group other than the reactive silicon group of the amino group-containing silane coupling agent include a substituted amino group, a mercapto group, an epoxy group, a carboxyl group, an isocyanate group, an isocyanurate, and a halogen. A silane coupling agent obtained by reacting an amino group-containing silane coupling agent with an epoxy group-containing compound or the like to modify the amino group can also be used. Of these, substituted (modified) amino groups, epoxy groups, isocyanate groups, isocyanurates and the like are preferred because of their higher effect of improving adhesiveness.

  Although it does not restrict | limit especially as a silane coupling agent (J), For example, (gamma) -isocyanate propyl trimethoxysilane, (gamma) -isocyanate propyl triethoxysilane, (gamma) -isocyanate propylmethyl diethoxysilane, (gamma) -isocyanate propyl methyl dimethoxysilane, Isocyanate group-containing silanes such as isocyanate methyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyldimethoxymethylsilane, isocyanatemethyldiethoxymethylsilane; N-phenyl-γ-aminopropyltrimethoxysilane, N-phenylaminomethyltri Methoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cycl Substituted amino group-containing silanes such as hexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine Ketimine type silanes such as N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ -Mercapto group-containing silanes such as mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltriethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ- Epoxy such as glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane Group-containing silanes; carboxysilanes such as β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane Vinyl trimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltriethoxysilane, methacryloyl Vinyl type unsaturated group-containing silanes such as oxymethyltrimethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (3-trimethoxysilylpropyl) isocyanurate be able to. Also, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-amino Ethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane , Γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane, γ- (6-aminohexyl) aminopropyltrimethoxysilane, 3- (N-ethylamino) Amino group-containing silanes such as 2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, and the above silanes Examples thereof include modified amino group-containing silanes in which an amino group is modified by reacting an epoxy group-containing compound, an isocyanate group-containing compound, or a (meth) acryloyl group-containing compound. Moreover, the condensate which condensed the said silane partially can also be used. A silane coupling agent (J) may be used only by 1 type, and may mix and use 2 or more types.

  The curable composition of the present invention may contain a (meth) acrylic acid ester polymer (K) having a reactive silicon group.

A method for producing a polymer obtained by blending a polyoxyalkylene polymer having a reactive silicon group and a (meth) acrylic acid ester polymer having a reactive silicon group is disclosed in JP-A-59-122541, JP-A-59-122541. Although proposed in Japanese Patent Application Laid-Open No. 63-112642, Japanese Patent Application Laid-Open No. 6-172631, and Japanese Patent Application Laid-Open No. 11-116763, the invention is not particularly limited thereto. Preferable specific examples include a reactive silicon group and a molecular chain substantially having the general formula (8):
^{_{-CH 2 -C (R 5) (}} COOR 6) - (8)
(Wherein R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkyl group having 1 to 8 carbon atoms.) (Meth) acrylic acid ester having an alkyl group having 1 to 8 carbon atoms Monomer unit and general formula (9):
—CH ₂ —C (R ⁵ ) (COOR ⁷ ) — (9)
(In the formula, R ⁵ is the same as above. R ⁷ represents an alkyl group having 10 or more carbon atoms.) (Meth) acrylic acid ester monomer unit having an alkyl group having 10 or more carbon atoms In which a polyoxyalkylene polymer having a reactive silicon group is blended with a copolymer of the above.

R ^{6 in the} general formula (8) is, for example, 1 to 8, preferably 1 to 4, carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, and a 2-ethylhexyl group. More preferred are 1 or 2 alkyl groups. The alkyl group of R ⁶ may alone, or may be a mixture of two or more.

R ^{7 in the} general formula (9) is, for example, a long-chain alkyl having 10 or more carbon atoms such as lauryl group, tridecyl group, cetyl group, stearyl group, behenyl group, etc., usually 10 to 30, preferably 10 to 20 Group. The alkyl group of R ⁷ is similar to the case of R ^6, alone may or may be a mixture of two or more.

The molecular chain of the (meth) acrylic acid ester copolymer is substantially composed of monomer units of the formulas (8) and (9). The term “substantially” as used herein means the copolymer. It means that the sum of the monomer units of formula (8) and formula (9) present therein exceeds 50% by weight. The total of the monomer units of the formula (8) and the formula (9) is preferably 70% by weight or more. Also, the abundance ratio of the monomer unit of the formula (8) and the monomer unit of the formula (9) is The weight ratio is preferably 95: 5 to 40:60, more preferably 90:10 to 60:40.

  Examples of monomer units other than those represented by formula (8) and formula (9) that may be contained in the copolymer include acrylic acid such as acrylic acid and methacrylic acid; acrylamide, methacrylamide, and N-methylolacrylamide. , Amide groups such as N-methylolmethacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, monomers containing amino groups such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate and aminoethyl vinyl ether; other acrylonitrile, styrene, α-methyl Examples thereof include monomer units derived from styrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.

  Furthermore, as a method for producing a polymer obtained by blending a (meth) acrylic acid ester-based copolymer having a reactive silicon functional group, in the presence of a polymer having a reactive silicon group (meta ) A method of polymerizing an acrylate monomer can be used. This production method is specifically disclosed in JP-A-59-78223, JP-A-59-168014, JP-A-60-228516, JP-A-60-228517, etc. It is not limited to these.

  The curable composition of the present invention may contain a filler (L). Filler (L) is an improvement in various physical properties such as ensuring workability by adjusting the viscosity and thixotropy of the curable composition, adjusting the strength of the cured product, improving adhesion, and imparting chemical resistance, coloring and design. It can be used to modify the surface of a cured product such as the property and to reduce the cost per weight.

  The filler (L) is not particularly limited. For example, reinforcing fillers such as fume silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; Calcium, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, shirasu balloon, glass microballoon, phenol Examples thereof include fillers such as organic microballoons of resins and vinylidene chloride resins, resin powders such as PVC powder and PMMA powders, and fibrous fillers such as glass fibers and filaments. When the filler (L) is used, the amount used is preferably 1 to 250 parts by weight with respect to 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B), More preferred is 10 to 200 parts by weight.

  A plasticizer can be added to the curable composition of the present invention as necessary. By adding the plasticizer, the viscosity and slump property of the composition and the mechanical properties such as tensile strength and elongation of the cured product obtained by curing the composition can be adjusted. The plasticizer is not particularly limited, and examples thereof include phthalates such as dibutyl phthalate, diheptyl phthalate, bis (2-ethylhexyl) phthalate, and butyl benzyl phthalate; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, succinic acid Non-aromatic dibasic esters such as isodecyl; Aliphatic esters such as butyl oleate and methyl acetyl ricinolinate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Chlorination Paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate.

  In addition to the plasticizer, a polymer plasticizer may be added for use. When a high-molecular plasticizer is used, the initial physical properties are maintained over a long period of time as compared with the case where a low-molecular plasticizer that is a plasticizer containing no polymer component in the molecule is used. Furthermore, the drying property (also referred to as paintability) when an alkyd paint is applied to the cured product can be improved. The polymer plasticizer is not particularly limited. For example, vinyl polymers obtained by polymerizing vinyl monomers by various methods; polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester. Esters of polyesters: Polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; molecular weight 500 or more, further 1,000 or more polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol or the like of these polyether polyols Polyethers such as acid ester group, derivatives obtained by converting such an ether group; polystyrenes such as polystyrene and polymethyl -α- methyl styrene; polybutadiene, polybutene, polyisobutylene, butadiene - acrylonitrile, etc. polychloroprene and the like.

  Of these polymer plasticizers, those compatible with the polymer (A) and the polymer (B) are preferred. From this point, polyethers and vinyl polymers are preferable. Use of polyethers as a plasticizer is preferred because surface curability and deep part curability are improved and curing delay after storage hardly occurs, and polypropylene glycol is more preferred. Moreover, a vinyl polymer is preferable from the viewpoint of compatibility, weather resistance, and heat resistance. Among vinyl polymers, acrylic polymers and / or methacrylic polymers are preferable, and acrylic polymers such as polyacrylic acid alkyl esters are more preferable. The polymer synthesis method is preferably a living radical polymerization method and more preferably an atom transfer radical polymerization method because the molecular weight distribution is narrow and viscosity can be lowered. Moreover, it is preferable to use a polymer obtained by so-called SGO process obtained by continuous bulk polymerization of an alkyl acrylate monomer shown in JP-A-2001-207157 at high temperature and high pressure.

  The number average molecular weight of the polymer plasticizer is preferably 500 to 15,000, more preferably 800 to 10,000, still more preferably 1,000 to 8,000, and particularly preferably 1,000 to 1,000. 5,000. Most preferably, it is 1,000-3,000. If the molecular weight is too low, the plasticizer will flow out over time due to heat and rain, the initial physical properties cannot be maintained over a long period of time, cause contamination due to dust adhesion, etc., and the alkyd paintability cannot be improved. Moreover, when molecular weight is too high, a viscosity will become high and workability | operativity will worsen. The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow and is preferably less than 1.80. 1.70 or less is more preferable, 1.60 or less is more preferable, 1.50 or less is more preferable, 1.40 or less is particularly preferable, and 1.30 or less is most preferable.

  The number average molecular weight is measured by a terminal group analysis method in the case of a polyether polymer, and by the GPC method in the case of other polymers. Moreover, molecular weight distribution (Mw / Mn) is measured by GPC method (polystyrene conversion).

  The polymer plasticizer can be either a compound having a reactive silicon group or a compound having no reactive silicon group. When it has a reactive silicon group, it acts as a reactive plasticizer and can prevent migration of the plasticizer from the cured product. In the case of having a reactive silicon group, the average number per molecule is preferably 1 or less, more preferably 0.8 or less. When using a plasticizer having a reactive silicon group, particularly an oxyalkylene polymer having a reactive silicon group, the number average molecular weight is preferably lower than that of the polymer (A) and the polymer (F). When the number average molecular weight of the polymer is higher than that of the polymer (A) and the polymer (F), the plasticizing effect may not be obtained.

  A plasticizer may be used independently and may use 2 or more types together. Further, a low molecular plasticizer and a high molecular plasticizer may be used in combination. In addition, these plasticizers can also be mix | blended at the time of polymer manufacture.

  The amount of the plasticizer used is 5 to 150 parts by weight, preferably 10 to 120 parts by weight, more preferably 100 parts by weight in total of the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B). Is 20 to 100 parts by weight. If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient.

  The curable composition of the present invention may contain a radical scavenger. The radical scavenger mentioned here generally includes what are called antioxidants and light stabilizers.

  The antioxidant is not particularly limited, and examples thereof include hindered phenol-based, monophenol-based, bisphenol-based, and polyphenol-based antioxidants. Among these, hindered phenol-based antioxidants are preferable. Similarly, Tinuvin 622LD, Tinuvin 144, CHIMASSORB 944LD, CHIMASSORB 119FL (all of which are manufactured by Ciba Specialty Chemicals); MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARK LA- 68 (all are manufactured by Asahi Denka Kogyo Co., Ltd.); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (All are Sankyo shares) The hindered amine light stabilizer shown by company) can also be used. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731. The amount of the antioxidant used is in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B). More preferably, it is 0.2 to 5 parts by weight. If the amount used is smaller than this, sufficient effects may not be obtained. If the amount used is larger than this, it is not only economically disadvantageous, but also radicals generated from the photo radical initiator. May be supplemented by an antioxidant, resulting in poor curing of the cured product, and the cured product may not exhibit good physical properties.

  Examples of the light stabilizer include benzotriazole-based, hindered amine-based, and benzoate-based compounds. Among these, hindered amine-based compounds are preferable. The light stabilizer is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B). Is preferable, and 0.2 to 5 parts by weight is more preferable. If the amount used is smaller than this, sufficient effects may not be obtained. If the amount used is larger than this, it may not only be economically disadvantageous, but also a photo radical initiator. There is a possibility that the antioxidant is supplemented by the generated radicals, and the cured product is poorly cured, and the cured product does not exhibit good physical properties. Specific examples of the light stabilizer are also shown in JP-A-9-194731.

  Examples of the active energy ray include light (UV) or electron beam, and the active energy ray source is not particularly limited, but may be, for example, a high-pressure mercury lamp or a low-pressure mercury lamp depending on the nature of the photopolymerization initiator used. And electron beam irradiation devices, halogen lamps, light emitting diodes, semiconductor lasers, metal halide lamps, and the like.

  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 cured by heat, the curing temperature is preferably 30 ° C to 200 ° C, more preferably 80 ° C to 180 ° C.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereby.

(Synthesis Example 1)
Polymerization of propylene oxide using a polyoxypropylene diol having a molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst, and a number-average molecular weight of 14,500 having a hydroxyl group at the end (Liquid feeding system: HLC manufactured by Tosoh Corporation) -8120 GPC, column: Tosoh TSK-GEL H type, polystyrene oxide molecular weight measured using THF as a solvent), polypropylene oxide (a-1) was obtained.

Subsequently, 0.02 part by weight of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy, dibutyltin bis (mercapto acid) with respect to 100 parts by weight of polypropylene oxide (a-1) having a hydroxyl group Ester) (F-1) (Nitto Kasei Co., Ltd. Neostan U-360) 50 ppm, 2-acryloyloxyethyl isocyanate (E-1) (Showa Denko Co., Ltd. Karenz AOI) 2.6 parts by weight, Stir at 90 ° C. for 1 hour. ^The peak derived from the hydroxyl group of polypropylene oxide (a-1) disappears as measured by ¹ H-NMR (Avance III 400 MHz NMR system manufactured by Bruker), and the peak derived from the proton on the carbon to which the carbamate group is bonded (4. 91 ppm (multiple lines)) appeared, and it was confirmed that polypropylene oxide (A-1) having a (meth) acryloyl substituent at the terminal was obtained.

^{In the 1} H-NMR spectrum, the introduction ratio of the (meth) acryloyl substituent calculated from the ratio between the integrated value of the peak derived from the methyl group in the main chain and the integrated value of the peak derived from the acryloyl group was 90%. It was. Thereby, it turned out that a polypropylene oxide (A-1) contains 1.8 (meth) acryloyl type substituents on the average per molecule. The molecular weight determined by GPC was 14,500.

(Synthesis Example 2)
The number average molecular weight is the same as in Synthesis Example 1 except that a 1/1 (weight ratio) mixture of a polyoxypropylene diol having a molecular weight of about 2,000 and a polyoxypropylene triol having a molecular weight of about 3,000 is used as an initiator. About 19,000 hydroxyl-terminated polypropylene oxide (a-2) was obtained.

  Subsequently, a 1.2-fold equivalent NaOMe methanol solution was added to the hydroxyl group of polypropylene oxide (a-2) to distill off the methanol, and allyl chloride was added to convert the terminal hydroxyl group to an allyl group. Converted to. Unreacted allyl chloride was removed by vacuum devolatilization. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polypropylene oxide, water was removed by centrifugation, and the resulting hexane solution was further added. 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by vacuum devolatilization. Thus, a trifunctional polypropylene oxide having a number average molecular weight of about 26,000 and having an allyl group at the end was obtained.

  For 100 parts by weight of the obtained trifunctional polypropylene oxide, methyldimethoxysilane was prepared by using 150 ppm of an isopropanol solution having a platinum content of 3 wt% of Pt / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex as a catalyst. It was made to react with 1.35 weight part at 90 degreeC for 5 hours, and the methyldimethoxysilyl group terminal polyoxypropylene type polymer (B-1) was obtained.

In addition, in measurement by ¹ H-NMR (measured in CDCl ₃ solvent using JNM-LA400 manufactured by JEOL), a signal corresponding to the exomethylene proton of the terminal allyl group of the polymer (p-1) (2H : Around 5.2 ppm), a signal derived from the main chain methyl proton (3H: around 1.1 ppm), a signal derived from the methyl group on the dimethoxymethylsilyl group of the polymer (B-1) (3H:. The number of dimethoxymethylsilyl groups in the polymer (B-1) calculated from the integral ratio (around 1 ppm) was about 1.7 on average per molecule.

(Synthesis Example 3)
A solution prepared by dissolving 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator was dropped into a 2-butanol solution of the following monomer mixture heated to 105 ° C. over 5 hours, and then for 1 hour. "Post polymerization" was performed to obtain a (meth) acrylic acid ester polymer (K-1).

  Methyl methacrylate 72.9 parts by weight, butyl acrylate 6.5 parts by weight, stearyl methacrylate 14.6 parts by weight, γ-methacryloxypropyldimethoxymethylsilane 6 parts by weight, mercaptopropyldimethoxymethylsilane 7.9 parts by weight Parts, 2,2′-azobis (2-methylbutyronitrile) · 3 parts by weight.

(Synthesis Example 4)
Solid content weight ratio of methyldimethoxysilyl group-terminated polyoxypropylene polymer (B-1) obtained in Synthesis Example 1 and (meth) acrylic acid ester polymer (K-1) obtained in Synthesis Example 3 After blending at 60/40, the solvent was distilled off to obtain a solventless polymer (P-1).

(Synthesis Example 5)
In the same manner as in Synthesis Example 1, a hydroxyl group-terminated polypropylene oxide (a-3) having a number average molecular weight of about 28,500 was obtained.

  Subsequently, a methanol solution of 1.2 times equivalent NaOMe is added to the hydroxyl group of polypropylene oxide (a-3) to distill off the methanol, and allyl chloride is added to convert the terminal hydroxyl group to an allyl group. Converted to. Unreacted allyl chloride was removed by vacuum devolatilization. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl-terminated polypropylene oxide, water was removed by centrifugation, and water was further added to the resulting hexane solution. After 300 parts by weight of the mixture were mixed and stirred, water was removed again by centrifugation, and then hexane was removed by devolatilization under reduced pressure. As a result, a bifunctional polypropylene oxide having a number average molecular weight of about 28,500 having an allyl group at the end was obtained.

  Using 100 parts by weight of the allyl group-terminated polypropylene oxide as a catalyst, 150 ppm of an isopropanol solution having a platinum content of 3 wt% of Pt / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was used as a catalyst. Reaction with 1.2 parts by weight of silane at 90 ° C. for 2 hours gave a triethoxysilyl group-terminated polypropylene oxide.

Further, as a result of ¹ H-NMR (measured in a CDCl ₃ solvent using JNM-LA400 manufactured by JEOL), the number of terminal triethoxysilyl groups was about 1.4 per molecule on average. Next, 15 parts of methanol and a 0.5 wt% hydrogen chloride-methanol solution were added and reacted at 70 ° C. for 2 hours, followed by addition of epoxidized soybean oil and neutralization at 70 ° C. for 2 hours. Thereafter, degassing under reduced pressure was performed at 90 ° C. for 1 hour to obtain a trimethoxysilyl group-terminated polypropylene oxide (B-2) having a methoxy exchange rate of about 95%. The viscosity of the polymer (B-2) at 23 ° C. was 46 Pa · s.

(Synthesis Example 6)
A solution prepared by dissolving 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator was dropped into a 2-butanol solution of the following monomer mixture heated to 105 ° C. over 5 hours, and then for 1 hour. “Post polymerization” was performed to obtain a (meth) acrylic acid ester polymer (K-2).

  Methyl methacrylate, 72.9 parts by weight, butyl acrylate, 6.5 parts by weight, stearyl methacrylate, 14.6 parts by weight, γ-methacryloxypropyltrimethoxysilane, 6 parts by weight, mercaptopropyldimethoxymethylsilane, 7.9 parts by weight Parts, 2,2′-azobis (2-methylbutyronitrile) · 3 parts by weight.

(Synthesis Example 7)
The trimethoxysilyl group-terminated polyoxypropylene oxide (B-2) obtained in Synthesis Example 5 and the (meth) acrylate polymer (K-2) obtained in Synthesis Example 6 were mixed at a solid content weight ratio of 70 / After blending at 30, the solvent was distilled off to obtain a solventless polymer (P-2).

(Examples 1 and 2)
After adding tackifying resin (C) dissolved in toluene to a mixture of polypropylene oxide (A-1) and solventless polymer (P-1), toluene was distilled off under reduced pressure at 100 ° C. A filler (L), a (meth) acrylic monomer (i1), a silane coupling agent (J), a photoradical initiator (h1), and a silanol condensation catalyst (E) are added to the resulting mixture to make a spatula. After thorough stirring, the mixture was further stirred and mixed with a centrifuge. By these operations, a curable composition was obtained. The following evaluation was performed about the obtained curable composition.

(Mechanical properties)
The obtained curable composition was filled into a sheet-like mold having a thickness of about 2 mm, and a UV irradiation device manufactured by Fusion UV System (model: LIGHT HAMMER 6, light source: mercury lamp lamp, integrated light amount: 2000 mJ / cm ² ). Irradiation was performed. Immediately after irradiation and 1 day later, the obtained cured product was punched into a mini dumbbell-shaped test piece and pulled by hand to evaluate the balance between elongation and strength. The evaluation was “◯” when both elongation and strength were good, “Δ” when only one was good, and “x” when both were poor.

(Workability)
The obtained curable composition was filled into a sheet-like mold having a thickness of about 2 mm, and a UV irradiation device manufactured by Fusion UV System (model: LIGHT HAMMER 6, light source: mercury lamp lamp, integrated light amount: 2000 mJ / cm ² ). Irradiation was performed. In the evaluation, the composition immediately after irradiation was set up vertically, and when the composition did not drip, “◯”, and when dripped, “×”.

(Curable)
The obtained curable composition is filled in a sheet-like mold having a thickness of about 2 mm, and a part thereof is shielded from light, and a UV irradiation device made by Fusion UV system (model: LIGHT HAMMER 6, light source: mercury lamp lamp, integrated light quantity: 2000 mJ / Cm ² ). One day later, each of the irradiated part and the light-shielding part of the obtained cured product was touched with a finger to determine curability. The evaluation was “◯” if cured, and “x” if not cured.

  Table 1 shows the blending amount of the curable composition and the results of mechanical properties, workability, and curability.

(Examples 3 and 4)
After adding tackifying resin (C) dissolved in ethyl acetate to a mixture of polypropylene oxide (A-1) and solventless polymer (P-2), ethyl acetate was distilled off under reduced pressure at 100 ° C. A filler (L), a (meth) acrylic monomer (i1), a silane coupling agent (J), a photoradical initiator (h1), and a silanol condensation catalyst (E) are added to the resulting mixture to make a spatula. After thorough stirring, the mixture was further stirred and mixed with a centrifuge. By these operations, a curable composition was obtained. About the obtained curable composition, evaluation similar to Example 1, 2 was performed.

(Comparative Example 1)
Except not adding tackifying resin (C), operation similar to Example 1 was performed and the curable composition was obtained. Evaluation similar to the Example was performed about the obtained curable composition.

(Comparative Example 2)
Except not adding tackifying resin (C), operation similar to Example 2 was performed and the curable composition was obtained. Evaluation similar to the Example was performed about the obtained curable composition.

(Comparative Example 3)
Add polypropylene oxide (A-1), filler (L), (meth) acrylic monomer (i1), silane coupling agent (J), photoradical initiator (h1) and stir well with a spatula. Then, the mixture was further stirred and mixed in a centrifuge. By these operations, a curable composition was obtained. About the obtained curable composition, evaluation similar to an Example was performed.

  The curable compositions of Examples 1 to 4 exhibit sufficient mechanical properties immediately after irradiation with UV light and at the same time exhibit good workability without dripping. Further, not only the irradiated portion of UV light but also the unirradiated portion is cured. From this result, the curable composition of the present invention has a good workability without dripping immediately after irradiation with active energy rays, has sufficient mechanical strength, and can cure even a portion that cannot be irradiated with active energy rays. It became clear that it was a sex composition.

Claims (23)

The curable composition containing the following (A)-(E) component.
(A) General formula (1):
^{-Z-C (= O) -C} (R 1) = CH 2 (1)
(Wherein R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and Z is a divalent organic group.) A number average molecular weight having one or more substituents in the molecule. Is 3,000 or more polyoxyalkylene polymer (B) general formula (2):
-[Si (R ² _2-b ) (X _b ) O] _n Si (R ² _3-a ) X _a (2)
(In the formula, R ² represents 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 a triorganosiloxy group represented by R ′ ₃ SiO—. , R ² may be the same or different when two or more R ² are present, where R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and X is a hydroxyl group Or a hydrolyzable group, where a represents 0, 1, 2 or 3, b represents 0, 1 or 2, and satisfies a + Σb ≧ 2, and n represents an integer of 0 to 19. ) A polyoxyalkylene polymer having a number average molecular weight of 3,000 or more (C) a tackifier resin (D) a polymerization initiator (E) a silanol condensation catalyst. The curable composition according to claim 1, wherein Z in the general formula (1) is an oxygen atom. Z in the general formula (1) is the general formula (3):
—NH—C (═O) —O—R ³ —O— (3)
The curable composition according to claim 1, wherein R ³ is a group represented by the formula (wherein R ³ is a divalent hydrocarbon group). Z in the general formula (1) is the general formula (4):
—O—C (═O) —NH—R ³ —O— (4)
The curable composition according to claim 1, wherein R ³ is the same as defined above. The polyoxyalkylene polymer (a) in which the substituent represented by the general formula (1) has a hydroxyl group and the general formula (5):
^{O = C = N-R 3} -O-C (= O) -C (R 1) = CH 2 (5)
Claim 5 wherein the isocyanate compound (F) represented by the formula (wherein R ¹ and R ³ are the same as described above) is reacted in the presence of dibutyltin (mercapto ester) (G). The curable composition as described. The curable composition according to any one of claims 1 to 5, wherein R ¹ is a hydrogen atom. The curable composition according to any one of claims 3 to 6, wherein R ³ is an ethylene group. The curable composition according to any one of claims 1 to 7, wherein the polyoxyalkylene polymer (A) is a polyoxypropylene polymer. X of general formula (2) is an alkoxy group, The curable composition of any one of Claim 1 to 8. X of general formula (2) is a methoxy group, The curable composition of any one of Claim 1 to 8. The curable composition according to any one of claims 1 to 10, wherein the polyoxyalkylene polymer (B) is a polyoxypropylene polymer. The addition amount of the tackifier resin (C) is 20 to 80 parts by weight with respect to 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B). To 11. The curable composition according to any one of 11 to 11. The curable composition according to any one of claims 1 to 12, wherein the tackifying resin (C) is a terpene resin. The curable composition according to any one of claims 1 to 12, wherein the tackifying resin (C) is a terpene phenol resin. The curable composition according to any one of claims 1 to 14, wherein the polymerization initiator (C) is a radical initiator (H) that generates radicals by active energy rays. 16. The curable composition according to claim 15, wherein the radical initiator (H) is a photo radical initiator (h1) that generates radicals by light. The addition amount of the photo radical initiator (h1) is 0.001 to 10 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B). The curable composition according to claim 16. The curable composition according to any one of claims 1 to 17, comprising a monomer and / or oligomer (I) having a polymerizable substituent. The curable composition according to claim 18, wherein the monomer and / or oligomer (I) having a polymerizable substituent is a (meth) acrylic monomer (i1) having a molecular weight of 500 or less. The curable composition according to any one of claims 1 to 19, comprising a silane coupling agent (J). 21. The curable composition according to any one of claims 1 to 20, comprising a (meth) acrylic acid ester polymer (K) having a reactive silicon group. The curable composition of Claim 1 to 21 containing a filler (L). The addition amount of the filler (L) is 10 to 200 parts by weight with respect to 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B). The curable composition according to any one of 22 above.