JP2012007041A - Polyoxyalkylene-based polymer and curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyoxyalkylene-based polymer that is easily produced and curable by active energy rays or heat, and a composition excellent in curability and containing the polyoxyalkylene-based polymer.SOLUTION: The polyoxyalkylene-based polymer (A) has at least one substituent in the molecule represented by the following: -O-C(=O)-NH-R-O-C(=O)-C(R)=CH, and has a number-average molecular weight of 3,000 or more. In formula, Ris a divalent organic group, and Ris a hydrogen atom or a 1-20C substituted or unsubstituted hydrocarbon group.

Description

  The present invention relates to a polyoxyalkylene polymer that can be cured by active energy rays or heat, a method for producing the same, and a curable composition containing the same.

  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 polymerized and crosslinked, resulting in rubber. Gives a cured product. Among organic polymers, polyoxyalkylene polymers are characterized by excellent workability due to their relatively low viscosity, and the resulting cured product also exhibits good rubber elasticity.

  The mechanical properties of the cured product of the polyoxyalkylene polymer are greatly influenced by the molecular weight of the polymer. Generally, in a three-dimensional network structure that forms a cured product, when the molecular weight between cross-linking points is large, good stretchability tends to be obtained. In order to obtain a cured product having a large molecular weight between crosslinking points, use of a polymer having a large molecular weight can be mentioned. However, in general, (meth) acryloyl group-containing polyoxyalkylene compounds having a small molecular weight are used (for example, Patent Documents 1, 2, and 3). A cured product obtained from such a low molecular weight compound tends to be inferior in stretchability.

  One of the reasons for the small number of production examples of (meth) acryloyl group-containing polyoxyalkylene polymers having a large molecular weight is that the production method is difficult. For example, in (Patent Document 4), a polyoxyalkylene polymer having a (meth) acryloyl group is obtained by a reaction between a (meth) acryloyl group-containing polyoxyalkylene compound and diisocyanate, but the molecular weight is large ( It is substantially difficult to produce a (meth) acryloyl group-containing polyoxyalkylene compound, as seen in the Examples, and the molecular weight of the resulting polymer is also reduced.

  On the other hand, since it is easy to produce a polyoxyalkylene polymer having a large molecular weight and a hydroxyl group, the molecular weight is large by reacting such a polymer with an isocyanate compound having a (meth) acryloyl group ( It is conceivable to produce a (meth) acryloyl group-containing polyoxyalkylene polymer. (Patent Document 5) discloses a method of reacting a polyoxyalkylene polymer having a large molecular weight and having a hydroxyl group with an isocyanate compound having a (meth) acryloyl group. However, when a polymer having a hydroxyl group is reacted with an isocyanate compound having a (meth) acryloyl group, dibutyltin dilaurate generally used as a urethanization catalyst is used as a catalyst. In the method using dibutyltin dilaurate as a catalyst, the introduction rate of (meth) acryloyl groups is low, and a by-product tends to be produced in large quantities. Therefore, by using a catalyst capable of efficiently reacting a polymer having a hydroxyl group and an isocyanate compound having a (meth) acryloyl group, a polyoxyalkylene polymer having a high introduction rate of the (meth) acryloyl group Was expected to get.

JP 58-17555 A JP 2003-73331 A JP 2004-238572 A JP 2003-286340 A Japanese Patent Laid-Open No. 4-7330

  The present invention relates to a polyoxyalkylene polymer having a large molecular weight that can be cured by an active energy ray or heat, and a method for producing the same. It is an object of the present invention to provide a composition that can be introduced into a coalescence with high efficiency and exhibits excellent curability by using this polymer.

  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)
Polyoxyalkylene polymer (a) having a hydroxyl group and general formula (1):
^{O = C = N-R 1} -O-C (= O) -C (R 2) = CH 2 (1)
(Wherein R ¹ is a divalent organic group, R ² is a hydrogen atom, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms) dibutyl A polyoxyalkylene polymer obtained by reacting in the presence of tin (mercapto acid ester) (C), wherein the general formula (2):
—O—C (═O) —NH—R ¹ —O—C (═O) —C (R ² ) ═CH ₂ (2)
(Wherein R ¹ and R ² are the same as above) A polyoxyalkylene polymer (A) having a number average molecular weight of 3,000 or more and having one or more substituents in the molecule.

(II)
The polyoxyalkylene polymer (A) according to (I), wherein R ^{1 in the} general formula (1) is an ethylene group.

(III)
The polyoxyalkylene polymer (A) according to (I) or (II), wherein R ^{2 in the} general formula (1) is a hydrogen atom.

(IV)
The polyoxyalkylene polymer (A) according to any one of (I) to (III), wherein the polyoxyalkylene polymer is a polyoxypropylene polymer.

(V)
The polyoxyalkylene polymer (A) according to any one of (I) to (IV), wherein the substituent represented by the general formula (2) has only at the terminal of the polyoxyalkylene polymer (A). .

(VI)
A curable composition comprising the polyoxyalkylene polymer (A) according to any one of (I) to (V) and a polymerization initiator (D).

(VII)
The curable composition according to (VI), wherein the polymerization initiator (D) is a radical initiator (E) that generates radicals by active energy rays and / or heat.

(VIII)
The curable composition according to (VII), wherein the radical initiator (E) is a photo radical initiator (e1) that generates radicals by light.

(IX)
Curing according to (VIII), wherein the addition amount of the photo radical initiator (e1) is 0.001 to 10 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A). Sex composition.

(X)
A cured product obtained by curing the curable composition according to any one of (VI) to (IX).

  By using the polyoxyalkylene polymer of the present invention, a composition exhibiting excellent curability by active energy rays or heat can be obtained.

  The present invention will be described in detail below.

<Polyoxyalkylene polymer (A)>
The polyoxyalkylene polymer (A) of the present invention includes a polyoxyalkylene polymer (a) having a hydroxyl group and a general formula (1):
^{O = C = N-R 1} -O-C (= O) -C (R 2) = CH 2 (1)
(Wherein R ¹ is a divalent organic group, R ² is a hydrogen atom, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms) dibutyl It can be obtained by reacting in the presence of tin (mercapto acid ester) (C).

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

R ¹ in the general formula (1) is not particularly limited, and examples thereof include alkylene groups such as methylene group, ethylene group, propylene group, and hexylene group; cycloalkylene groups such as cyclobutylene group, cyclopentylene group, and cyclohexylene group. Groups; arylene groups such as a phenylene group and a benzylene group; and divalent organic groups including an ether bond, an ester bond, an amino bond, an amide bond, and the like. Among these, ethylene group and hexylene group are preferable and ethylene group is more preferable because of easy introduction.

R ² in the general formula (1) represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. As used herein, a substituted hydrocarbon group refers to a group in which a hydrogen atom on a hydrocarbon group is replaced by a heteroatom. R ² 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 polymer (A), and a hydrogen atom is more preferable.

  Although it does not restrict | limit especially as an isocyanate type compound (B), The following compound can be mentioned.

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

  Dibutyltin (mercapto ester) (C) is used when the polymer (a) is reacted with the isocyanate compound (B). Although it does not specifically limit as dibutyltin (mercapto ester) (C), 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.

  As usage-amount of dibutyltin (mercapto acid ester) (C), 10 ppm-500 ppm are preferable with respect to a polymer (a), 25 ppm-100 ppm are more preferable, 50 ppm is further more preferable. 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 polymer (a) is reacted with the isocyanate compound (B), 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 mentioned. The amount of the solvent used can be appropriately determined from the viewpoint of easiness of stirring.

The polyoxyalkylene polymer (A) obtained by the reaction of the polymer (a) and the isocyanate compound (B) has the general formula (2):
—O—C (═O) —NH—R ¹ —O—C (═O) —C (R ² ) ═CH ₂ (2)
Wherein R ¹ is a divalent organic group, R ² is a hydrogen atom, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms (hereinafter referred to as (meta)). One or more acryloyl-based substituents) in the molecule.

  The number of (meth) acryloyl-based substituents in the polymer (A) is not particularly limited, but the curability is lowered when the average is less than 1 per molecule from the viewpoint that the polymers (A) are crosslinked with each other. Since there exists a tendency, 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.

It can be said that R ¹ and R ^{2 in the} general formula (2) are the same as R ¹ and R ² in the general formula (1).

  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, and a polyoxypropylene polymer is preferable.

The polyoxyalkylene polymer essentially has the general formula (3):
—R ⁴ —O— (3)
(Wherein R ⁴ is a linear or branched alkylene group having 1 to 14 carbon atoms), and R ⁴ described in the general formula (3) 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 (3), 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.

<Curable composition>
The curable composition of the present invention contains a polyoxyalkylene polymer (A) and a polymerization initiator (D). Although it does not specifically limit as a polymerization initiator (D), The radical initiator (E) which generate | occur | produces a radical by an active energy ray and / or a heat | fever, a photoanion initiator, a redox initiator, etc. are mentioned. Among these, the radical initiator (E) that generates radicals by active energy rays and / or heat is preferable from the viewpoint of availability, and among these, the photo radical initiator (e1) is more preferable from the viewpoint of reactivity. .

  Although it does not specifically limit as a radical photoinitiator (e1), For example, 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 (e1) is not particularly limited, but is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the polymer (A). If the addition amount of the photo radical initiator (e1) 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 (e1) is used, it is preferable that the total amount of a mixture exists in the said range.

  Although it does not specifically limit as a thermal radical initiator, For example, an azo initiator, a peroxide initiator, a persulfate initiator etc. are mentioned.

  The azo initiator is not particularly limited, and examples thereof include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyronitrile), 2,2′-azobis-2-methylbutyronitrile, 1,1-azobis (1 -Cyclohexanecarbonitrile), 2,2'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (methylisobutyrate) and the like.

  The peroxide initiator is not particularly limited, and examples thereof include benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, and di (4-t-butylcyclohexyl) peroxydi. Examples include carbonate, di (2-ethylhexyl) peroxydicarbonate, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, and dicumyl peroxide.

  Although it does not specifically limit as a persulfate initiator, For example, potassium persulfate, sodium persulfate, ammonium persulfate, etc. are mentioned.

  A thermal radical initiator may be used independently or may use 2 or more types together. Among the above thermal radical initiators, those selected from the group consisting of azo initiators and peroxide initiators are preferable from the viewpoint of ease of handling. Also, because of its high reactivity, 2,2′-azobis (methylisobutyrate), benzoyl peroxide, t-butyl peroxypivalate, di (4-t-butylcyclohexyl) peroxydicarbonate, and These mixtures are more preferred.

  The addition amount of the thermal radical initiator is not particularly limited, but is preferably 0.01 to 3 parts by weight, more preferably 0.025 to 2 parts by weight with respect to 100 parts by weight of the polymer (A). If the addition amount of the thermal radical initiator 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 a thermal radical initiator is used, it is preferable that the total amount of a mixture exists in the said range.

  The curable composition of the present invention contains monomers and / or oligomers having radically polymerizable and / or anionic polymerizable groups for the purpose of adjusting viscosity and improving mechanical properties of the resulting cured product. You may do it. 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. Of these, those having a (meth) acryl group are preferred from the viewpoint of reactivity. 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.

  Specific examples of the above monomers include (meth) acrylate 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) acrylate monomers 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 these, a (meth) acryl monomer having a molecular weight of 500 or less is preferable from the viewpoint of reactivity and workability due to viscosity reduction. The (meth) acrylic monomer having a molecular weight of 500 or less 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, Soboronyl 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, Examples include 2-hydroxy-3-phenoxyethyl acrylate.

  Any two or more monomers and / or oligomers having the polymerizable group may be used in combination.

  The amount of the monomer having a polymerizable group and / or the amount of oligomer used is 1 to 100 parts by weight of the polymer (A) from the viewpoint of improving surface curability, imparting toughness, and workability by reducing viscosity. 200 parts by weight is preferable, and 10 to 100 parts by weight is more preferable. When the amount used is smaller than this, a sufficient effect tends not to be obtained, and when it is larger, the unreacted component may volatilize from the cured product.

  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 preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polymer (A). Part. 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 preferably used in an amount of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight per 100 parts by weight of the polymer (A). . 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.

  The curable composition of the present invention may contain a plasticizer for the purpose of adjusting physical properties and adjusting properties. Examples of plasticizers include phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, and butyl benzyl phthalate; non-aromatic dibasic esters such as dioctyl adipate and dioctyl sebacate; diethylene glycol dibenzoate Polyalkylene glycol esters such as triethylene glycol dibenzoate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Chlorinated paraffins; Hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl alone , Or a mixture of two or more types, but is not necessarily required. In addition, these plasticizers can also be mix | blended at the time of polymer manufacture. The amount of the plasticizer used is preferably in the range of 5 to 200 parts by weight and more preferably 10 to 100 parts by weight with respect to 100 parts by weight of the polymer (A). When the amount used is less than this, a sufficient effect may not be obtained, and when the amount used is larger than this, the mechanical properties of the obtained cured product may be lowered.

  Various adhesive property improving agents may be added to the curable composition of the present invention in order to improve the adhesiveness to various supports (plastic film, paper, etc.). Illustrative examples include alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and γ-glycidoxy Alkylisopropenoxysilane such as propylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane, γ-aminopropyltri Methoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane γ-mercaptopropyltrimethoxysila , Alkoxysilanes having a functional group such as γ- mercaptopropyl methyldimethoxysilane; silicone varnishes; polysiloxanes and the like. The amount of the adhesion improver used is preferably 0.1 to 50 parts by weight and more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the polymer (A). When the amount used is less than this, a sufficient effect may not be obtained, and when the amount used is larger than this, the mechanical properties of the obtained cured product may be lowered.

<Hardened product>
The curable composition of the present invention can be cured by active energy rays or heat.

  In the case of curing with active energy rays, the active energy rays include light (UV) or electron beam, and the active energy ray source is not particularly limited, but depends on the properties of the photopolymerization initiator used. Examples thereof include a high pressure mercury lamp, a low pressure mercury lamp, an electron beam irradiation device, a halogen lamp, a light emitting diode, a semiconductor laser, and a metal halide.

  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.

Example 1
4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy 0.02 part by weight, dibutyltin bis (mercapto ester) (100 parts by weight of polypropylene oxide (a-1) having a hydroxyl group ( C-1) (Nitto Kasei Co., Ltd. Neostan U-360) 50 ppm, 2-acryloyloxyethyl isocyanate (B-1) (Showa Denko Co., Ltd. Karenz AOI) 2.6 parts by weight was added, at 90 ° C. Stir 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.

(Example 2)
100 parts by weight of the polymer (A-1) is added to a minicup, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one (e1-1) (DAROCURE 1173 manufactured by Ciba Specialty Chemicals) 0 .2 parts by weight and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (e1-2) (IRGACURE 819, manufactured by Ciba Specialty Chemicals) are added and stirred well with a spatula. A curable composition was obtained.

The obtained curable composition was applied on a Teflon (registered trademark) sheet so as to have a thickness of 2 mm. The obtained sheet was irradiated with a UV irradiation device (model: LIGHT HAMMER 6, light source: mercury lamp lamp, integrated light quantity: 3000 mJ / cm ² ) manufactured by Fusion UV System, to obtain a cured product.

(Comparative Example 1)
4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy 0.02 part by weight, dibutyltin dilaurate 50 ppm, 2-acryloyloxy with respect to 100 parts by weight of polypropylene oxide (a-1) having a hydroxyl group 2.6 parts by weight of ethyl isocyanate (B-1) (Karenz AOI manufactured by Showa Denko KK) was added and stirred at 90 ° C. for 1 hour to obtain polypropylene oxide (P-1). After cooling to room temperature, the polypropylene oxide (P-1) was gelled.

(Comparative Example 2)
4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy 0.02 part by weight, titanium diisopropoxybis (ethyl acetoacetate) per 100 parts by weight of polypropylene oxide (a-1) having a hydroxyl group ) 50 ppm, 2.6 parts by weight of 2-acryloyloxyethyl isocyanate (B-1) (Karenz AOI manufactured by Showa Denko KK) was added and stirred at 80 ° C. for 5 hours to obtain polypropylene oxide (P-2). .

In the ¹ H-NMR spectrum of polypropylene oxide (P-2), the introduction rate of the (meth) acryloyl substituent calculated by the same method as in Example 1 was about 10%. Thereby, it turned out that a polypropylene oxide contains 0.2 (meth) acryloyl type substituent on an average per molecule.

(Comparative Example 3)
4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy 0.02 part by weight, 2-acryloyloxyethyl isocyanate (B-) with respect to 100 parts by weight of polypropylene oxide (a-1) having a hydroxyl group 1) 2.6 parts by weight (Showa Denko Co., Ltd. Karenz AOI) was added and stirred at 80 ° C. for 7 hours to obtain polypropylene oxide (P-3).

In the ¹ H-NMR spectrum of polypropylene oxide (P-3), the introduction rate of the (meth) acryloyl-based substituent calculated by the same method as in (Example 1) was about 25%. Thereby, it turned out that a polypropylene oxide contains 0.5 (meth) acryloyl type substituents on the average per molecule.

As in Example 1, an isocyanate compound (B) is easily reacted with a polyoxyalkylene polymer (a) having a hydroxyl group in the presence of dibutyltin (mercapto ester) (C). A polyoxyalkylene polymer (A) having a (meth) acryloyl substituent could be obtained. Moreover, as shown in Example 2, the composition containing the polymer (A) and the photo radical initiator (e1) showed excellent curability.

Claims (10)

Polyoxyalkylene polymer (a) having a hydroxyl group and general formula (1):
^{O = C = N-R 1} -O-C (= O) -C (R 2) = CH 2 (1)
(Wherein R ¹ is a divalent organic group, R ² is a hydrogen atom, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms) dibutyl A polyoxyalkylene polymer obtained by reacting in the presence of tin (mercapto acid ester) (C), wherein the general formula (2):
—O—C (═O) —NH—R ¹ —O—C (═O) —C (R ² ) ═CH ₂ (2)
(Wherein R ¹ and R ² are the same as above) A polyoxyalkylene polymer (A) having a number average molecular weight of 3,000 or more and having one or more substituents in the molecule. The polyoxyalkylene polymer (A) according to claim ¹ , wherein R ^{1 in the} general formula (1) is an ethylene group. The polyoxyalkylene polymer (A) according to claim 1 or ² , wherein R ^{2 in the} general formula (1) is a hydrogen atom. The polyoxyalkylene polymer (A) according to any one of claims 1 to 3, wherein the polyoxyalkylene polymer is a polyoxypropylene polymer. The polyoxyalkylene polymer (A) according to any one of claims 1 to 4, wherein the substituent represented by the general formula (2) has only at the terminal of the polyoxyalkylene polymer (A). A curable composition comprising the polyoxyalkylene polymer (A) according to any one of claims 1 to 5 and a polymerization initiator (D). The curable composition according to claim 6, wherein the polymerization initiator (D) is a radical initiator (E) that generates radicals by active energy rays and / or heat. The curable composition according to claim 7, wherein the radical initiator (E) is a photo radical initiator (e1) that generates radicals by light. The curing amount according to claim 8, wherein the addition amount of the photo radical initiator (e1) is 0.001 to 10 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A). Sex composition. A cured product obtained by curing the curable composition according to any one of claims 6 to 9.