JPH07206971A - Curing composition - Google Patents

Abstract

PURPOSE:To obtain a curing composition which contains, as essential components, a specific (meth)acrylate copolymer, a specific polyalkylene oxide and a specific low-molecular-weight compound, thus having no surface tack, high weatherability heat resistance, adhesion and staining resistance, thus is useful as an elastic sealing material. CONSTITUTION:The curing composition comprises, as essential components, (A) a (meth)acrylate ester copolymer having one or more hydroxyl groups on each chain terminal, (meth)acrylate ester monomer units as essential recurring units, 1,000 to 50,000 number-average molecular weight, 10 to 400 hydroxyl value, (B) a polyalkylene oxide modified with isocyanate on its chain terminal and (C) a low-molecular-weight compound having an acid anhydride as a functional group, and less than 500 molecular weight such as maleic anhydride, succinic anhydride, or phthalic anhydride.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a curable composition, and more particularly to heat resistance (almost no change in physical properties after heating), weather resistance, durability, stain resistance, adhesion to substrate. ,
The present invention relates to an elastic sealing material which is excellent in paint glue, has no surface tack, and is inexpensive.

[0002]

2. Description of the Related Art Elastic sealing materials are indispensable materials in industries such as construction and civil engineering, and their use amount is increasing year by year.

At present, various elastic sealing materials such as silicone-based, modified silicone-based, polysulfide-based, acrylic urethane-based, and polyurethane-based are used, but each has its own problems. At present, there is no product that satisfies the required physical properties of.

For example, although the silicon type has excellent weatherability and heat resistance, it has major drawbacks such as insufficient adhesion to the substrate, the inability to overcoat the coating, and the high price. The polysulfide type is yellow. However, polyurethane has poor weather resistance and has tack on the surface, and acrylic urethane has tack on the surface. The modified silicone resin also has the disadvantages of poor adhesion to the substrate, selection of a topcoat paint, and some tack remaining on the surface.

[0005]

In view of such circumstances, the present invention not only has excellent weather resistance and heat resistance (almost no change in physical properties after heating), but also has excellent adhesion to a substrate,
It is an object of the present invention to provide an elastic sealing material which is excellent in adhesion to a top coat, excellent in stain resistance without surface tack, and inexpensive.

[0006]

In order to solve the above-mentioned problems, the curable composition according to the present invention has at least one hydroxyl group at each terminal and contains a (meth) acrylic acid ester monomer unit. It is constituted as an essential repeating unit and has a number average molecular weight of 1,000 to 50,000 and a hydroxyl value of 10.
An essential component is a (meth) acrylic acid ester-based copolymer (b) of 400, a polyalkylene oxide (c) whose terminal is isocyanate-modified, and a low molecular weight compound (v) having an acid anhydride as a functional group and having a molecular weight of 500 or less. By virtue of this, not only excellent weather resistance and heat resistance (almost no change in physical properties after heating) but also excellent adhesion to the base material and adhesion to the top coating,
Further, it is possible to obtain an inexpensive elastic sealing material having no surface tack and excellent in stain resistance.

Here, the term "terminal" refers to a starting terminal (α terminal) and a terminating terminal (ω terminal), which are commonly used in vinyl polymerization, and the side chains usually contained in a vinyl monomer are not included in this. Not included.

The curable composition according to the present invention will be described below.

First, the (meth) which is an essential component of the (meth) acrylate copolymer (b) according to the present invention.
The acrylic acid ester-based monomer is not particularly limited as long as it is a conventionally known (meth) acrylic acid ester-based monomer. For example, (meth) acrylic acid; methyl (meth) acrylate, (meth) Ethyl acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, etc. (Meth) acrylic acid alkyl esters; (meth) acrylic acid aryl esters such as benzyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylic acid Glycidyl, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) Such as trimethoxysilane (meth)
Acrylic acid substituent-containing alkyl esters; (meth) acrylic acid methoxyethyl, (meth) acrylic acid derivatives such as ethylene oxide adducts of (meth) acrylic acid; (meth) acrylic acid perfluoromethyl, (meth)
Perfluoroethyl acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluorooctyl (meth) acrylate,
Trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, (meth)
2-perfluoroethylethyl acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, triperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl-2 (meth) acrylate -Perfluorobutylethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, (meth) acrylic acid 2
-Perfluorohexadecylethyl, γ- (methacryloyloxypropyl) trimethoxysilane silicon-containing (meth) acrylic acid ester-based monomers and the like, and these may be used alone or in combination. You may use together a seed.

The hydroxyl group-containing addition polymerizable monomer (a) according to the present invention is not particularly limited as long as it is a conventionally known hydroxyl group-containing addition polymerizable monomer. For example, (meth) acryl Acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-
Hydroxypropyl, mono (meth) acrylic acid ester of polyethylene glycol, mono (meth) acrylic acid ester of polypropylene glycol, polycaprolactone modified product of 2-hydroxyethyl (meth) acrylate (trade name: Praxel F series (Daicel Chemical Industries (Manufactured by K.K.)), (meth) allyl alcohol 4-hydroxymethylstyrene and the like, and one kind of them may be used alone, or a plurality of kinds thereof may be used in combination.

Further, in the present invention, only the (meth) acrylic acid ester-based monomer may be used, or other known vinyl-based monomers may be used in combination therewith. The conventionally known vinyl-based monomer other than the above-mentioned hydroxyl group-containing addition-polymerizable monomer (a) and (meth) acrylic acid ester-based monomer is not particularly limited, and examples thereof include maleic anhydride and maleic acid. , Maleic acid monoalkyl and dialkyl esters; fumaric acid, fumaric acid monoalkyl and dialkyl esters; aromatic vinyl-based compounds such as styrene, α-methylstyrene, methylstyrene, chlorostyrene, styrenesulfonic acid and sodium salts thereof Monomers: Fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, vinylidene fluoride; Trialkyloxysilyl group-containing vinyl monomers such as vinyltrimethoxysilane, vinyltriethoxysilane; Maleimide , Methylmaleimide, ethylmale Bromide, propyl maleimide, butyl maleimide, octyl maleimide, dodecyl maleimide,
Maleimide derivatives such as stearyl maleimide, phenyl maleimide, cyclohexyl maleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamido; vinyl acetate, propion Vinyl esters such as vinyl acetate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride and the like. May be used alone or in combination of two or more.

The content of the (meth) acrylic acid ester-based monomer in the monomers constituting the (meth) acrylic acid ester-based copolymer (b) according to the present invention is not particularly limited unless it is 0. However, in order to fully exert the characteristics such as good weather resistance of the (meth) acrylic acid ester-based polymer, it is preferably 30% by weight or more, and 50
It is more preferable that the content is at least wt%.

Next, the hydroxyl value of the (meth) acrylic acid ester-based copolymer (b) according to the present invention is from 10 to 400.
Must be within the range. If the hydroxyl value is less than 10, the crosslinking density after curing will be insufficient, and not only surface tack will remain, but also sufficient mechanical strength will not be obtained. When the hydroxyl value is 400 or more, the crosslinking density is too high and sufficient elongation cannot be obtained.

Next, the number average molecular weight of the (meth) acrylate copolymer (b) according to the present invention is 1000.
Must be in the range of ~ 50,000. If this number average molecular weight is 1000 or less, not only the molecular weight is too small to exhibit good physical properties as a (meth) acrylic acid ester-based polymer, but also the distance between cross-linking points after curing is too short. Elongation cannot be obtained. Also,
If it is 50,000 or more, the polymer viscosity becomes too high and sufficient workability cannot be secured.

In the present invention, the (meth) acrylic acid ester-based copolymer (b) and another polymer compound having an OH group at the end, such as polyethylene glycol, polypropylene glycol, polybutylene glycol, polyolefin polyol, etc. , Polybutadiene polyol,
B. F. It is also possible to use Goodrich OH-terminated HTBN, polyester polyol, and polycarbonate polyol.

Next, the low molecular weight compound (v) having a molecular weight of 500 or less and having an acid anhydride as a functional group according to the present invention will be described.

The low molecular weight compound (v) in the present invention is not particularly limited as long as it is a low molecular weight compound having a conventionally known acid anhydride as a functional group and having a molecular weight of 500 or less. For example, acetic anhydride or propionic anhydride. Compounds, isobutyric anhydride, succinic anhydride, glutaric anhydride, phthalic anhydride, maleic anhydride, itaconic anhydride, trimellitic anhydride, pyromellitic anhydride, diphenic anhydride, naphthalenedicarboxylic anhydride, 3 , 3'-dithiodipropionic acid anhydride, etc., and these can be used alone or in combination of two or more. Of these, maleic anhydride, succinic anhydride, and phthalic anhydride are preferable.

Next, the low molecular weight compound (v) of the present invention having a molecular weight of 500 or less must have a molecular weight of 500 or less. When the molecular weight is more than 500, the concentration of the acid anhydride group is too low, and unless the present low molecular weight compound (v) is added in a considerably large amount (to such an extent that the physical properties of the cured product are adversely affected), deterioration of physical properties during heating is prevented. Not only the effect is not sufficient, but in some cases, the viscosity of the composition increases, which deteriorates the workability of the composition.

Next, the amount of the low molecular weight compound (v) to be added varies depending on the acid value, viscosity, etc. of the low molecular weight compound to be added, but the (meth) acrylic acid ester-based copolymer (v 0.01 to 20 wt% is preferable, 0.1 to 10 wt% is more preferable, and 0.1 to 5 wt%
Is most preferred.

The polyisocyanate (c) having isocyanate modified at the terminal according to the present invention is not particularly limited, but polyethylene glycol, polypropylene glycol having a terminal OH functional group of difunctional or trifunctional or more,
In addition to conventionally known polyalkylene oxides such as polybutylene glycol and polyethylene glycol-polypropylene glycol brick polymers, conventionally known polyfunctional isocyanate compounds such as tolylene diisocyanate (also referred to as “TDI”) and 4,4′-diphenylmethane diisocyanate (“ MDI "), hexamethylene diisocyanate, xylylene diisocyanate,
Isocyanate compounds such as meta-xylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate; Burette poly such as Sumidure N (Sumitomo Bayer Urethane Co.) Isocyanate compound; Desmodur IL, HL (Bayer A.
G. Polyisocyanate compound having an isocyanurate ring such as Coronate EH (manufactured by Nippon Polyurethane Industry Co., Ltd.); adduct polyisocyanate compound such as Sumidule L (manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate HL (Japan (Manufactured by Polyurethane Co., Ltd.) and the like, whose end is modified with an isocyanate by reacting an adduct polyisocyanate compound and the like. These may be used alone or in combination of two or more.

In order to make use of the excellent weather resistance of the curable composition of the present invention, examples of the polyfunctional isocyanate compound include hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate and Sumidule N.
It is preferable to use an isocyanate compound having no aromatic ring such as (Sumitomo Bayer Urethane Co., Ltd.).

As described above, the polyalkylene oxide (c) whose end is modified with isocyanate according to the present invention is mainly bifunctional or more, but monofunctional end-capped isocyanate is used as long as the curing of the composition is not significantly impaired. The use of modified polyalkylene oxides is free. From the viewpoints of water resistance, reactivity, and price, it is preferable to use polypropylene glycol (bifunctional or trifunctional) modified with terminal TDI, among the above examples.

The mixing ratio of the (meth) acrylic acid ester-based copolymer (b) used in the curable composition of the present invention and the polyalkylene oxide (c) whose terminal is modified with isocyanate is not particularly limited, but ( Weight ratio of (meth) acrylic acid ester-based copolymer (b) to isocyanate-terminated polyalkylene oxide (c) ((meth) acrylic acid ester-based copolymer (b) / isocyanate-terminated polyalkylene Oxide (c)) is 5/9
5 to 95/5 is preferable, and 10/90 to 90 is preferable.
It is more preferably / 10.

Next, the method for producing the (meth) acrylic acid ester copolymer (b) according to the present invention is not particularly limited, but it is preferable to synthesize it by the following production method.

(1) General formula (I) HO-A- (S) x -B-OH (I) (In the formula, A and B each represent a divalent organic group, x
Is an integer of 2 to 5. In the presence of the compound (d) represented by the formula (d), a vinyl-based monomer (e) is polymerized with a radical polymerization initiator (f). The radical polymerization initiator (f) is present in an amount of 50 mol times or more, and the compound (d), the vinyl monomer (e) and the radical polymerization initiator (f) are substantially not used, and A method for producing a polymer having hydroxyl groups at both ends, which comprises polymerizing.

The compound (d) in this production method is not particularly limited, but for example, hydroxymethyl disulfide, hydroxymethyl trisulfide, hydroxymethyl tetrasulfide, 2-hydroxyethyl disulfide, 2-hydroxyethyl trisulfide, 2 -Hydroxyethyl tetrasulfide, 2-hydroxyethyl pentasulfide, 3-hydroxypropyl disulfide, 3-hydroxypropyl trisulfide, 3-hydroxypropyl tetrasulfide, 2-hydroxypropyl disulfide, 2-hydroxypropyl trisulfide, 2-hydroxypropyl Tetrasulfide, 4-hydroxybutyl disulfide, 4-hydroxybutyl trisulfide, 4-hydroxybutyl tetrasulfide, 8 Hydroxyalkyl di-, tri-, tetra- or penta-sulfides such as hydroxyoctyl disulfide, 8-hydroxyoctyl trisulfide, 8-hydroxyoctyl tetrasulfide and their ethylene oxide adducts; 2,2'-dithiodiglycolic acid, 2, 2'trithiodiglycolic acid,
2,2'-tetrathiodiglycolic acid, 3,3'-dithiodipropionic acid, 3,3'-trithiodipropionic acid, 3,3'-tetrathiodipropionic acid, 3,3'-
Pentathiodipropionic acid, 4,4'-dithiodibutanoic acid, 4,4'-trithiodibutanoic acid, 4,4'-tetrathiodibutanoic acid, 8,8'-dithiodioctanoic acid, 8,
8'-trithiodioctanoic acid, 8,8'-tetrathiodioctanoic acid, 2,2'-dithiodibenzoic acid, 2,2'-
Di-, tri- or tetra-, such as trithiodibenzoic acid, 2,2'-tetrathiodibenzoic acid, 2,2'-dithiodinicotinic acid, 2,2'-trithiodinicotinic acid, 2,2'-tetrathiodinicotinic acid Examples thereof include di (2-hydroxyethyl) esters (ethylene oxide adducts) of sulfide dicarboxylic acids, and these are one kind or two kinds.
A combination of two or more species can be used. Moreover, as the vinyl-based monomer (e) used in this production method,
There is no particular limitation as long as it essentially contains a (meth) acrylic acid ester-based monomer. For example, the above-mentioned hydroxyl group-containing addition polymerizable monomer (a), (meth) acrylic acid ester-based monomer and Other examples of vinyl-based monomers can be mentioned as they are.

The radical polymerization initiator (f) is not particularly limited, but examples thereof include isobutyryl peroxide, cumyl peroxyneodecanoate, diisopropyloxydicarbonate, di-n-propylperoxydicarbonate, dibutyl (2-ethoxyethyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexyl peroxyneodecanoate, t-butylperoxyneodecanoate, t
-Hexyl peroxypivalate, t-butyl peroxypivalate, 3,5,5-trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, cumyl peroxy octate, succinic acid peroxide, acetyl peroxide, t-butylperoxy (2-ethylhexanate), m-toluoyl peroxide, benzoyl peroxide, t-butylperoxyisobutyrate, 1,1-bis (t-butylperoxy) cyclohexane, t-butyl Peroxymaleic acid, t-butylperoxylaurate, cyclohexanone peroxide, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxyhexane, t-butylperoxyacetate, 2 , 2-bis ( - butylperoxy) butane, t
-Butyl peroxybenzoate, n-butyl-4,4
-Bis (t-butylperoxy) valerate, di-t-
Butyl peroxyisophthalate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butyl peroxy) hexane,
α, α′-bis (t-butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide, diisobutylbenzene hydroperoxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,
Organic substances such as 5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 1,1,3,3, -tetramethylbutylhydroperoxide, cumene hydroperoxide and t-butylhydroperoxide Peroxides: Inorganic peroxides such as hydrogen peroxide, potassium persulfate, sodium persulfate, ammonium persulfate; 2,2′-azobis (4-
Methoxy-2,4-dimethylvaleronitrile), 2,
2'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile,
2,2'-azobis (2-methylbutyronitrile),
1,1'-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2'azobis (2- Amidinopropane) dihydrochloride, 2,2'-azobis (N,
N'-dimethylene isobutylamidine), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl)-
Propionamide], azo compounds such as 2,2′-azobis (isobutyramide) dihydrate, 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis (2-cyanopropanol); hydrogen peroxide -Fe (II)
Redox initiators such as salts, persulfates-sodium hydrogen sulfite, cumene hydroperoxide-Fe (II) salts, benzoyl peroxide-dimethylaniline; and photosensitizers such as diacetyl, dibenzyl and acetophenone It is possible to use only one of them, or to use in combination of two or more. However, in order to minimize side reactions such as chain transfer reactions due to hydrogen abstraction of the primary radicals generated from the initiator, and in view of the solubility in various monomers and the large number of types that can support the polymerization temperature, radical polymerization As the initiator (f), an azo compound is preferable.

In the production method of the present invention, the molar ratio ((d) / (f)) of the compound (d) to the radical polymerization initiator (f) in the reaction vessel during polymerization must always be 50 or more. However, 100 or more is preferable.

In the production method of the present invention, components other than the compound (d), the vinyl monomer (e) and the radical polymerization initiator (f) should not be substantially used in the polymerization process. Specifically, components other than the compound (d), the vinyl-based monomer (e) and the radical polymerization initiator (f) are
It should be about 10% by weight or less of the whole. This is because, in the polymerization process, when components (for example, a solvent) other than the compound (d), the vinyl-based monomer (e) and the radical polymerization initiator (f) are present in an amount of more than 10% by weight based on the total amount, the component (d) Side reactions such as chain transfer increase, and a polymer having no hydroxyl group at either or both ends is produced as a by-product. As a result, the number of terminal hydroxyl groups (Fn (O
This is because the value of H)) decreases.

In the polymerization process of the production method of the present invention, the molar ratio ((d) / (f)) between the compound (d) and the radical polymerization initiator (f) in the reaction vessel during polymerization is always 5
Any polymerization method may be used as long as it is 0 or more. For example, compound (d), vinyl monomer (e)
The radical polymerization initiator (f) may be charged all at once to carry out the polymerization, or the polymerization may be carried out while supplying each component to the polymerization system at any time. In addition, first, at least a part of the required amount of the compound (d) is charged in a polymerization vessel in advance,
Polymerization may be carried out by a method of supplying (feeding) the vinyl-based monomer (e) and the radical polymerization initiator (f) thereto. At this time, it may be considered from the operability that the radical polymerization initiator (f) is supplied as a solution of the vinyl monomer (e) from the viewpoint of operability. It is preferable to use an initiator that is sufficiently soluble in body (e). Further, at this time, in the compound (d),
If the vinyl-based monomer (e) and the radical polymerization initiator (f) are continuously supplied, the polymerization reaction becomes milder and the control becomes very easy. However, the supply of the polymerizable monomer (e) and the radical polymerization initiator (f) into the compound (d) may be intermittent.

The polymerization vessel used in the present invention may be a batch type such as a flask type or a kneader, a piston flow tube type, or a twin-screw extruder depending on the viscosity of the polymer. A continuous type may be used. Also, a semi-batch type reactor can be used without any problem.

The polymerization temperature in the production method of the present invention is not particularly limited, and there is no problem as long as it is from room temperature to 200 ° C. at which ordinary radical polymerization is carried out.

(2) Polymerization of the vinyl-based monomer (e) is carried out in the presence of the alcohol (g) which requires a polyfunctional alcohol, and the initiator system (h) which requires hydrogen peroxide. A method, wherein the three components (e), (g),
A method for producing a polymer, which is substantially free of components other than (h).

The polyfunctional alcohol used in the alcohols (g) essentially containing a polyfunctional alcohol in this production method is not particularly limited as long as it is a compound having at least two hydroxyl groups in one molecule. For example, ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-
Butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentane Diol, 2,3-
Pentanediol, 2,4-pentanediol, 1,6
Alkylene glycol such as hexanediol; hydroquinone diethylol ether; ethylene glycol derivative such as diethylene glycol and triethylene glycol; sorbitol derivative; aliphatic polyfunctional alcohol such as cyclohexanediol and xylylenediol; glycerol and monoacetin, monolaurin,
Glycerol mono-substituted derivatives such as glycerol mono-fatty acid esters and glycerol mono-allyl esters such as monoolein, mono-palmitin and mono-stearin, glycerol mono-ether such as thymyl alcohol, glycerol mono-methyl ether and batyl alcohol; trimethylol propane and its mono-substituted derivatives; Pentaerythritol and pentaerythritol 2-oleate, pentaerythritol 2-stearate ester, pentaerythritol 2-substituted derivatives; sorbitan fatty acid ester; erythritol, threose, ribose, arabinose, xylose, lyxose, allose, altose, glucose, mannose, growth,
Examples thereof include monosaccharides such as idose, galactose, talose, fructose, apiose, rhamnose, psicose, sorbose, tagitose, ribulose and xylulose, and saccharides such as disaccharides such as sucrose, maltose and lactose. Among these, it is preferable to use ethylene glycol, propylene glycol, 1,4-butanediol, trimethylolpropane, glycerol, pentaerythritol and sorbitol.

Further, in this production method, in addition to the above three (e), (g), and (h), compounds that accelerate the decomposition of hydrogen peroxide are hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, and paratoluene sulfone. Hydrogen peroxide decomposition catalysts such as acids, benzenesulfonic acid, pyridine, reducing compounds such as various metals, amines, aldehydes, quaternary ammonium salts, quaternary phosphonium salts, surfactants such as dodecylbenzenesulfonic acid (sodium), etc. Can be used together.

(3) A method of polymerizing a vinyl monomer (e) in the presence of an alcohol (i) using an initiator system (j) which essentially requires an organic peroxide. The organic sulfonic acid compound (k) and / or the inorganic acid (l) are used, and the above five (e), (i),
A method for producing a polymer, which is characterized in that it substantially contains no components other than (j), (k) and (l).

Alcohols (i) in this production method
May be a monofunctional alcohol having only one hydroxyl group in one molecule or a polyfunctional alcohol having two or more hydroxyl groups in one molecule. Further, a polyfunctional alcohol and a monofunctional alcohol may be used in combination. The monofunctional alcohol is not particularly limited, for example,
Methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, tertiary butyl alcohol, pentyl alcohol, C12 to C14 higher alcohols, methoxyethanol, ethoxyethanol, propoxyethanol, ethylene glycol monoacetate ester, cyclohexanol, benzyl alcohol, phenethyl. Mention may be made of one or a mixture of two or more such as alcohol. The polyfunctional alcohol is not particularly limited, but for example, ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1, 4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4 -Alkylene glycols such as pentanediol and 1,6-hexanediol; hydroquinone diethylol ether; ethylene glycol derivatives such as diethylene glycol and triethylene glycol; sorbitol derivatives; aliphatic polyfunctional alcohols such as cyclohexanediol and xylylenediol; Green Rolls and glycerol 1 or 2 substituted derivatives such as glycerol monofatty acid esters such as monoacetin, monolaurin, monoolein, monopalmitin, monostearin and glycerol monoallyl esters, thymyl alcohol, glycerol monomethyl ether, glycerol monoethers such as batyl alcohol; tri Methylolpropane and its 1- or 2-substituted derivatives; 1-3-substituted derivatives of pentaerythritol, such as pentaerythritol and pentaerythritol 2-oleate, pentaerythritol 2-stearate; sorbitan fatty acid ester; erythritol, threose, ribose, arabinose, xylose, Lyxose, allose, altose, glucose, mannose, growth,
Examples thereof include monosaccharides such as idose, galactose, talose, fructose, apiose, rhamnose, psicose, sorbose, tagitose, ribulose and xylulose, and saccharides such as disaccharides such as sucrose, maltose and lactose. These alcohols (i) may be appropriately selected depending on the purpose of use of the (meth) acrylic acid ester-based copolymer (b) to be obtained.

Among the above alcohols (i), ethylene glycol, propylene glycol,
Preference is given to using 1,4-butanediol, trimethylolpropane, glycerol, pentaerythritol and sorbitol.

The molecular weight of the alcohol (i) is not particularly limited, but is preferably 300 or less. When the molecular weight exceeds 300, the viscosity of the alcohol increases, the solubility of the alcohol in the reaction system decreases, or the viscosity of the reaction system increases, and the physical properties such as the average terminal functional group number (Fn (OH)) of the produced polymer are increased. It is not preferable because it lowers.

The alcohols (i) are not limited to those containing only carbon, hydrogen and oxygen as constituent elements. For example, it may contain a nitrogen element such as ethanolamine, diethanolamine or triethanolamine, or may contain a sulfur element such as mercaptoethanol, 2-hydroxyethyl disulfide or thiodiethylene glycol.

The weight ratio [alcohols (i): vinyl monomers (e)] of the alcohols (i) and the vinyl monomers (e) used is preferably 1:20 to 20: 1
And more preferably 1:10 to 10: 1. Further, the alcohol (i) is preferably 2 times or more, and more preferably 50 times or more, the moles of the initiator system (j) which essentially requires an organic peroxide.

There are no particular restrictions on the organic peroxide used in the initiator system (j), which essentially requires the organic peroxide used in the present invention. For example, methyl ethyl ketone peroxide, cyclohexanone peroxide,
Ketone peroxides such as 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide, 1,1-bis (t-butylperoxy) -3,3,5 -Trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) valate, Peroxyketals such as 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, di-isoprouropylbenzene hydroperoxide, 2- (4-methylcyclohexyl) -Propane hydroperoxa De, 2,5-dimethylhexane -
2,5-dihydroperoxide, hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide,
t-butylcumyl peroxide, dicumyl peroxide, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2 , 5-dimethyl-
Dialkyl peroxides such as 2,5-di (t-butylperoxy) hexyne-3, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5. -Diacyl peroxides such as trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluyl peroxide, di-isopropyl peroxydicarbonate, di-2- Ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis- (4-t-butylcyclohexyl) peroxydicarbonate, dimyristyl peroxydicarbonate, di-2- Peroxydicarbonates such as tylhexyl peroxydicarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate and diallylperoxydicarbonate, t-butylperoxy Acetate, t-butylperoxyisobutyrate, t-butylperoxypivalate, t-butylperoxyneodecanoate, cumylperoxyneodecanoate, t-butylperoxy-2-ethylexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t
-Butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, Peroxyesters such as cumyl peroxy octoate, t-hexyl peroxy pivalate, t-butyl peroxy neohexanoate, t-hexyl peroxy neohexanoate, cumyl peroxy neohexanoate, acetylcyclohexyl Examples thereof include sulfonyl peroxide and t-butyl peroxyallyl carbonate. Cyclohexanone peroxide and benzoyl peroxide are particularly preferable.
The organic peroxide may be used alone or in combination of two or more.

As the initiator system (j) containing an organic peroxide as an essential component used in the present invention, for example, a compound (y) capable of promoting polymerization by combination with an organic peroxide is used. There are a case where it is used together with an oxide and a case where it is used alone with an organic peroxide. Compound (y)
Examples thereof include an organic peroxide decomposition catalyst and a reducing compound that undergoes a redox reaction with an organic peroxide. That is, the initiator system (j), which essentially requires an organic peroxide, may be an organic peroxide alone, or alternatively, an organic peroxide as an essential component which contains an organic peroxide decomposition catalyst and a reducing agent. It may be a mixture containing one or more compounds selected from the group consisting of compounds and capable of promoting polymerization.

The compound (y) capable of promoting polymerization by combining it with an organic peroxide will be specifically described below.

The organic peroxide decomposition catalyst which is an example of the compound (y) is not particularly limited, but examples thereof include metal halides such as lithium chloride and lithium bromide; metal oxides such as titanium oxide and silicon dioxide; Carboxylic acids such as formic acid, acetic acid, propionic acid, lactic acid, isolacic acid and benzoic acid and their metal salts and esters; pyridine, indole and its derivatives, imidazole and its derivatives, carbazole and its derivatives and other heterocyclic amines, etc. To be
These may use only 1 type and may use 2 or more types together.

The reducing compound which is an example of the compound (y) and which carries out a redox reaction with an organic peroxide is not particularly limited, but for example, an organometallic compound such as ferrocene; iron naphthenate, copper naphthenate, Inorganic metal compounds that can generate metal ions such as iron, copper, nickel, cobalt, and manganese such as nickel naphthenate, cobalt naphthenate, and manganese naphthenate, boron trifluoride ether adduct, potassium permanganate. Inorganic compounds such as sulfur dioxide, sulfite, mono- or di-alkyl ester of sulfuric acid, mono- or di-allyl ester of sulfuric acid, bisulfite salt, thiosulfate salt, sulfoxy acid salt, benzenesulfinic acid and the like. Substituted compounds, sulfur-containing compounds such as homologues of cyclic sulfinic acid such as paratoluenesulfinic acid; Chill mercaptan, decyl mercaptan, dodecyl mercaptan, mercaptoethanol, alpha-mercaptopropionic acid, thioglycolic acid,
Mercapto compounds such as thiopropionic acid, α-thiopropionic acid sodium sulfopropyl ester and α-thiopropionic acid sodium sulfoethyl ester; nitrogen-containing compounds such as hydrazine, β-hydroxyethylhydrazine and hydroxylamine; formaldehyde, acetaldehyde, propionaldehyde Aldehydes such as n-butyraldehyde, isobutyraldehyde and isovalerianaldehyde; and ascorbic acid. These may use only 1 type and may use 2 or more types together.

Initiator system (j) which essentially requires an organic peroxide
Are not limited to those described above. For example, an organic peroxide or an organic peroxide and the above compound (y) may be combined with AI
It may be used in combination with one or more azo initiators such as BN (azobisisobutyronitrile) and conventionally known radical initiators such as hydrogen peroxide.
The amount of the initiator system (j) that requires an organic peroxide is
The molecular weight of the desired (meth) acrylic acid ester-based copolymer (b) is naturally determined, but in general,
It is preferably 0.1 to 20% by weight based on the vinyl-based monomer (e). The organic sulfonic acid compound (k) used in this production method is not particularly limited, and examples thereof include aliphatic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid and octanesulfonic acid; benzenesulfonic acid, Aromatic sulfonic acids such as benzenedisulfonic acid, naphthalene sulfonic acid, naphthalene sulfonic acid; chlorobenzene sulfonic acid, 1-naphthol-4-sulfonic acid, 2-naphthylamine-6-sulfonic acid, toluene sulfonic acid, dodecylbenzene sulfonic acid, etc. An aromatic sulfonic acid having a nuclear substituent; a sulfonic acid having a polymerizable unsaturated group exemplified by 2-sulfoethyl (meth) acrylate, styrene sulfonic acid, vinyl sulfonic acid; and an alicyclic sulfonic acid. To be These may use only 1 type and may use 2 or more types together. Among the above organic sulfonic acid compounds (k), methanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid and the like are particularly preferable. Further, an organic sulfonic acid compound having a surface activity such as dodecylbenzene sulfonic acid is particularly effective.

The amount of the organic sulfonic acid compound (k) used is preferably 0.05 to 10% by weight based on the whole polymerization system.

The inorganic acid (l) used in this production method is not particularly limited, but for example, hydrochloric acid, hydrofluoric acid, hydroiodic acid, perchloric acid, chlorous acid, hypochlorous acid, Periodic acid, sulfuric acid, fuming sulfuric acid, nitric acid, fuming nitric acid, manganic acid, permanganic acid, chromic acid, dichromic acid, and various other solid acids can be mentioned. One or two of these can be mentioned.
It can be used in a mixture of one or more species. Among these, sulfuric acid and hydrochloric acid are preferable as the inorganic acid (l).

The preferable amount of the inorganic acid (1) used is 0.05 to 10% by weight based on the total amount of the components.

In this manufacturing method, during the reaction,
Substantially other than vinyl-based monomer (e), alcohols (i), initiator system (j) requiring organic peroxide, organic sulfonic acid compound (k) and / or inorganic acid (l) Not to use it.

Specifically, vinyl-based monomer (e), alcohols (i), initiator system (j) which essentially requires an organic peroxide, organic sulfonic acid compound (k) and / or inorganic acid. Components other than (l) should be about 10% by weight or less of the total. Then, (e), (i), (j),
The components other than (k) and / or (l) are preferably 5% by weight or less, and most preferably (e),
That is, it does not contain any components other than (i), (j), (k) and / or (l).

However, the above four persons (e), (i),
The use of the surfactant (z) as a component other than (j), (k) and / or (l) in the range of less than 10% by weight based on the total amount of the components in the reactor means that the resulting polymer is obtained. It may improve the introduction of the hydroxyl group into A but does not decrease it, so that it does not matter.

The surfactant (z) is not particularly limited, but examples thereof include triethylbenzylammonium chloride, tetraethylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride and trimethylbenzylammonium chloride. , N-laurylpyridinium chloride, trimethylbenzylammonium hydroxide, tetramethylammonium hydroxide, trimethylphenylammonium bromide, tetramethylammonium bromide, tetraethylammonium bromide, tetra-n-butylammonium bromide, tetra-n-butyl Ammonium hydrogen sulfate, N-benzylpicolinium chloride, tetramethylammonium iodide, tetraiodide-
Quaternary ammonium salts such as n-butylammonium, N-lauryl-4-picolinium chloride, N-lauryl-4-picolinium chloride; phosphonium salts such as tetrabutylphosphonium chloride; sulfonium salts such as trimethylsulfonium iodide; etc. Onium salts; or polyoxyethylene-polypropylene oxide block copolymers; polyoxyethylene-based surfactants such as polyoxyethylene sulfates; higher alcohols such as lauryl alcohol and stearyl alcohol; and sulfates of these higher alcohols Examples thereof include metal salts of sulfuric acid esters; higher fatty acids such as lauric acid and stearic acid, metal salts of these higher fatty acids, and sorbitan esters. These may use only 1 type and may use 2 or more types together.

When the surfactant (z) is used, the amount used is less than 10% by weight, preferably 0.1 to 5% by weight, based on the total amount of the components in the reactor. When the surfactant (z) is used in an amount of 10% by weight or more based on the total amount of components in the reactor,
By the side reaction such as a chain transfer reaction to the surfactant (z), the average number of terminal hydroxyl groups (Fn (O
H)) is reduced, which is not preferable.

Among the above-mentioned surfactants (z), a surfactant having hydroxyl groups at both ends itself like a polyoxyethylene-polypropylene oxide block copolymer is incorporated into a crosslinked structure. Since the adverse effects on the toughness, weather resistance and water resistance of the crosslinked product do not appear, purification and removal are not required, which is preferable.

In the present invention, the reaction can be carried out at atmospheric pressure, but it can also be carried out under pressure in an autoclave or an extruder.

The polymerization temperature in the production method of the present invention is also not particularly limited, and there is no problem as long as it is from room temperature to 200 ° C. at which ordinary radical polymerization is carried out.

The production method of the present invention may require a step of removing excess alcohols (i) after the completion of polymerization. At that time, when the used alcohols (i) and the produced polymer A are compatible with each other, the alcohols (i) are devolatized under reduced pressure using a kettle or a twin-screw extruder. Can be removed. When the alcohols (i) and the (meth) acrylic acid ester-based copolymer (b) are incompatible with each other, the reaction mixture after completion of the polymerization is allowed to stand or separate as it is, or the above reaction mixture is used. In addition, by adding a solvent that dissolves the (meth) acrylic acid ester-based copolymer (b) but not the alcohols (i) to reduce the viscosity of the polymer layer, the mixture is allowed to stand and be separated. After removing the alcohols (i), the remaining alcohols (i) can be removed by liquid-liquid extraction or devolatilization under reduced pressure.

(4) A method of polymerizing a vinyl-based monomer (e) in the presence of an alcohol (i) using an initiator system (m) which essentially requires an azo-based initiator, A polymer characterized by using an organic sulfonic acid compound (k) and substantially not containing components other than the above four components (e), (i), (m) and (k) in the reaction system. Production method.

The azo-based initiator used in the initiator system (m) which essentially requires the azo-based initiator in this production method is not particularly limited, but, for example, 2,2'-azobis (4-methoxy-). 2,4-dimethylvaleronitri,
2,2'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile,
2,2'-azobis (2-methylbutyronitrile),
1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis (2 -Amidinopropane) dihydrochloride, 2,2'-azobis (N, N'-dimethyleneisobutylamidine), 2,
2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], 2,2'-azobis (isobutyramide) dihydrate, 4,4'-azobis (4-cyanopentanoic acid), 2, 2'-azobis (2-
Cyanopropanol) and the like. Among these, 2,2'-azobisisobutyronitrile is particularly preferable. Only one kind of azo initiator may be used,
Alternatively, a plurality of types may be used together.

Initiator system (m) which essentially requires an azo initiator
May be composed of only an azo-based initiator, or may be a combination of an azo-based initiator and another initiator. Other initiators that can be used in combination with the azo-based initiator are not particularly limited, and examples thereof include conventionally known radical initiators such as hydrogen peroxide.

Initiator system (m) which requires an azo initiator
The amount used is determined by the molecular weight of the target (meth) acrylic acid ester-based copolymer (b), but is generally 0.1 to the vinyl monomer (e). 20
It is preferably in the weight%.

In this production method, during the reaction,
The vinyl monomer (e), the alcohols (i), the initiator system (m) which essentially requires an azo initiator, and the organic sulfonic acid compound (k) are not used substantially.

Specifically, the components other than the vinyl-based monomer (e), the alcohols (i), the initiator system (m) which essentially requires an azo-based initiator, and the organic sulfonic acid compound (k) are wholly contained. 10% by weight or less. And
5% by weight of components other than (e), (i), (m) and (k)
The following are preferred, and most preferably (e),
This means that it does not contain any components other than (i), (m) and (k).

(5) In the method of polymerizing the vinyl-based monomer (e) with hydrogen peroxide (n), a hydrogen peroxide decomposition accelerator (o) is further used, and ), (N), (o) other than the components are substantially not used.

The hydrogen peroxide (n) used in this production method can be used as hydrogen peroxide water which is an industrially available aqueous solution. When hydrogen peroxide water is used as hydrogen peroxide, the amount of water contained therein should be about 10% by weight or less with respect to the total amount of components.

The amount of hydrogen peroxide (n) itself used is naturally determined by the molecular weight of the desired (meth) acrylic acid ester-based copolymer (b), but generally vinyl-based monomers are used. It is preferably 0.5 to 30% by weight with respect to (e).

The hydrogen peroxide decomposition accelerator (o) used in this production method is to selectively decompose hydrogen peroxide (n) to efficiently promote generation of OH radicals, thereby promoting polymerization. It is a compound capable of However, as the hydrogen peroxide decomposition accelerator (o), not all substances generally known as substances that accelerate the decomposition of hydrogen peroxide can be used. The reason is that the hydrogen peroxide decomposition accelerator (o) can efficiently synthesize a polymer having hydroxyl groups at both ends only after efficiently decomposing hydrogen peroxide into OH radicals. Even if the decomposition of hydrogen peroxide is accelerated like sodium hydroxide, OH
This is because when a substance having a low radical generating efficiency is used as the hydrogen peroxide decomposition accelerator (o), only a polymer having a low average number of terminal hydroxyl groups can be obtained.

The hydrogen peroxide decomposition accelerator (o) that can be used in the present invention is not particularly limited.
Examples thereof include sulfonic acid compounds, inorganic acids, onium salts, and heterocyclic amines described below.

The sulfonic acid compound is not particularly limited, and examples thereof include benzenesulfonic acid, benzenedisulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, p-toluenesulfonic acid, chlorobenzenesulfonic acid, p-phenolsulfonic acid, 1-Naphthol-
4-sulfone-2-naphthylamine-6-sulfonic acid,
Aromatic sulfonic acids such as dodecylbenzene sulfonic acid and p-phenol sulfonic acid; and aliphatic sulfonic acids such as methane sulfonic acid, ethane sulfonic acid, propyl sulfonic acid, octane sulfonic acid and the like. Among these,
Benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid and methanesulfonic acid are preferred.
It is possible to change the number average molecular weight of the obtained (meth) acrylic acid ester-based copolymer (b) depending on the amount of the sulfonic acid compound used.

However, in the production method of the present invention, metal salts of sulfonic acid compounds such as potassium benzenesulfonate, sodium dodecylbenzenesulfonate, potassium m-benzenedisulfonate, sodium dioctylsulfosuccinate, etc. are not used. This is because when a metal salt of a sulfonic acid compound is used, only a polymer having a low average number of terminal hydroxyl groups and a gel fraction due to a trifunctional isocyanate described below can be obtained.

The inorganic acid is not particularly limited,
For example, hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, perchloric acid, chlorous acid, hypochlorous acid, periodic acid,
Examples thereof include sulfuric acid, fuming sulfuric acid, sulfurous acid, nitric acid, fuming nitric acid, manganic acid, permanganic acid, chromic acid, dichromic acid, various other solid acids, and gaseous acids such as hydrogen chloride and hydrogen fluoride. Of these, hydrochloric acid and sulfuric acid are preferable. However, when the inorganic acid is used in the form of an aqueous solution, the amount of accompanying water is adjusted to about 10% by weight or less based on the total amount of the components.

The onium salt is not particularly limited, but for example, triethylbenzylammonium chloride,
Tetraethylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, N-laurylpyridinium chloride, trimethylbenzylammonium hydroxide, tetramethylammonium hydroxide, trimethylphenylammonium bromide, Tetramethylammonium bromide, tetraethylammonium bromide, tetra-n-butylammonium bromide, tetra-n-butylammonium hydrogen sulfate,
Quaternary ammonium salts such as N-benzylpicolinium chloride, tetramethylammonium iodide, tetra-n-butylammonium iodide, N-lauryl-4-picolinium chloride; tetrabutylphosphonium chloride,
Phosphonium salts such as tetrabutylphosphonium bromide; sulfonium salts such as trimethylsulfonium iodide, trimethylsulfonium tetrafluoroboron salt, and methyldiphenylsulfonium tetrafluoroboron salt. Among these, tetra-n-butylammonium hydrogen sulfate,
Tetrabutylphosphonium bromide, trimethylsulfonium tetrafluoroboron salt and methyldiphenylsulfonium tetrafluoroboron salt are preferred. The effect of promoting decomposition of hydrogen peroxide by the onium salt changes depending on the counter ion of the onium salt,
Particularly, hydrogen sulfate of ammonium salt, bromide of phosphonium salt, and boron tetrafluoride salt of sulfonium salt are very effective. The heterocyclic amine is not particularly limited, but for example, a nitrogen atom such as pyrrole, indole, carbazole, oxazole or thiazole can be used.
5-membered pyrroles containing 5 nitrogen atoms; 5-membered imidazoles containing 2 nitrogen atoms such as imidazole and pyrazole; 6-membered pyridines containing 1 nitrogen atom such as pyridine, quinoline and isoquinoline And alkaloids such as nicotine and quinine. Among these, pyridine, indole and carbazole are preferable.

As the hydrogen peroxide decomposition accelerator (o), only one kind may be used, or two or more kinds may be used in combination. The hydrogen peroxide decomposition accelerator (o) is preferably used in an amount of 0.01 to 20.0% by weight, more preferably 0.01 to 10.0% by weight, and most preferably 0, based on the total amount of components. .01
~ 5.0 wt%. If the amount used is less than 0.01% by weight, no effect as a decomposition accelerator can be seen. Also,
Even if it is used in an amount of more than 20.0% by weight, the number average molecular weight is not significantly reduced, and further, the polymer is colored, and it becomes difficult to separate the polymer during the purification step and washing with water.

In the production method of the present invention, substantially nothing is used other than the vinyl-based monomer (e), hydrogen peroxide (n) and hydrogen peroxide decomposition accelerator (o).

Specifically, the total amount of components other than the vinyl-based monomer (e), hydrogen peroxide (n), and hydrogen peroxide decomposition accelerator (o) (for example, water, solvent, etc.) is the total amount of all components. Against 1
It should be about 0% by weight or less. And (e),
The components other than (n) and (o) are preferably 5% by weight or less, and most preferably, the components other than (e), (n) and (o) are not used at all.

(6) In the method of polymerizing the vinyl-based monomer (e) with hydrogen peroxide (n), the amphipathic compound (p) is further used, and the above-mentioned three (e),
A method for producing a polymer, wherein components other than (n) and (p) are not substantially used.

The amphipathic compound (p) used in this production method has an affinity for both hydrogen peroxide (n) and vinyl monomer (e), )
It is a compound that can promote polymerization by increasing the contact area between (usually used as an aqueous solution) and the vinyl-based monomer (e).

The amphipathic compound (p) is not particularly limited, but examples thereof include cyclic ethers such as dioxane and tetrahydrofuran; chain ethers such as diethyl ether, diisopropyl ether and di-n-propyl ether; Ethylene glycol monoethers such as methoxy ethanol, ethoxy ethanol (also called ethyl cellosolve), butoxy ethanol (also called cellosolves); ethylene glycol diethers such as ethylene glycol diethyl ether; ethyl acetate, acetic acid n
Examples include esters such as propyl and butyl acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; amides such as dimethylformamide; sulfoxides such as dimethyl sulfoxide. Among these, various ethers such as dioxane and ethylene glycol diethyl ether; and cellosolves such as ethyl cellosolve are preferable.

The amphipathic compound (p) may be used alone or in combination of two or more.

The amount of the amphipathic compound (p) to be used is preferably 0.1 to 10.0% by weight, more preferably 1.0 to 5.0% by weight, based on the total amount of the components.

In the production method of the present invention, substantially no components other than the vinyl-based monomer (e), hydrogen peroxide (n) and amphipathic compound (p) are used.

Specifically, the total amount of components other than the vinyl-based monomer (e), hydrogen peroxide (n) and the amphipathic compound (p) (eg, water, solvent, etc.) is based on the total amount of all components. 10% by weight
It should be below. And (e), (n),
The components other than (p) are preferably 5% by weight or less, and most preferably, the components other than (e), (n) and (p) are not used at all.

(7) In the method of polymerizing the vinyl monomer (e) using hydrogen peroxide (n), a hydrogen peroxide decomposition accelerator (o) and an amphipathic compound (p) are further added. In addition to being used, the four persons (e), (n), (o), (p)
A method for producing a polymer, characterized in that components other than the above are substantially not used.

In this production method, the hydrogen peroxide decomposition accelerator (o) was added in an amount of 0.01 to 20.
0% by weight, the amphipathic compound (p) is 0.1 to 10.0% by weight with respect to the total amount of components, and the total thereof is 0.11 to 30.0% by weight with respect to the total amount of components. Like (o)
And (p) are preferably used.

When both the hydrogen peroxide decomposition accelerator (o) and the amphipathic compound (p) are used, the reaction system becomes more uniform, and when the hydrogen peroxide decomposition accelerator (o) is used alone. In comparison, the effect of reducing the number average molecular weight of the produced (meth) acrylic acid ester-based copolymer (b) is observed.

In the production method of the present invention, a substance other than the vinyl-based monomer (e), hydrogen peroxide (n), hydrogen peroxide decomposition accelerator (o), and amphipathic compound (p) is substantially used. Avoid using it.

Specifically, components other than the vinyl-based monomer (e), hydrogen peroxide (n), hydrogen peroxide decomposition accelerator (o), and amphipathic compound (p) (for example, water or solvent). Etc.) so that the total amount thereof is about 10% by weight or less based on the total amount of all components. And, the components other than (e), (n), (o) and (p) are preferably 5% by weight or less, and most preferably other than (e), (n), (o) and (p). That is to say that the ingredient of is not used at all.

If necessary, the curable composition of the present invention may be reacted with a filler or a (meth) acrylic acid ester copolymer (b) and an isocyanate-modified polyalkylene oxide (c). A catalyst for accelerating the reaction can be added, and if necessary, a plasticizer, a pigment, an antiaging agent, an antifungal agent, an antioxidant, a thixotropic agent and the like can be added.

The filler used as necessary in the present invention is used for the purpose of improving the strength of the curable composition of the present invention, making the viscosity of the composition moderate, and improving workability. For example, calcium carbonate, silica powder, talc, glass powder, magnesia, clay powder, titanium oxide and the like can be used.

The use ratio of the above-mentioned filler is not particularly limited, but the (meth) acrylic acid ester copolymer (b) is used.
It is preferably used in an amount of 30 to 400% by weight, and more preferably 50 to 200% by weight, based on the total resin content of the polyalkylene oxide (c) whose ends are modified with isocyanate.

If the use ratio of the above-mentioned filler is too low, it is difficult to obtain the required strength, and if the use ratio is too high, the elongation of the cured product becomes too low, which is not preferable.

Next, the catalyst used as necessary in the present invention is not particularly limited as long as it is a conventionally known catalyst for urethane reaction. For example, dibutyltin dilaurate, monobutyltin oxide, dioctyltin dilaurate. Metal compounds such as stanna octoate; amine compounds such as triethylenediamine, triethylenetetramine, diaminodiphenylmethane and triethylamine can be used. The addition amount of this catalyst is not particularly limited, but is 0.01 to 0.01 parts by weight with respect to the resin component in which the (meth) acrylic acid ester-based copolymer (b) and the isocyanate-modified polyalkylene oxide (c) are combined.
It is preferable to use 5% by weight.

If desired, an elastic sealing agent such as a silicone-based, modified silicone-based, polysulfide-based, or acrylic urethane-based may be added to the curable composition of the present invention and used together.

[0096]

In the curable composition of the present invention, the (meth) acrylic acid ester-based copolymer (b) used in the present invention has at least one hydroxyl group at each terminal, and the terminal is isocyanate-modified polyalkylene oxide. After curing with (c), since there is no free end of the polymer that does not participate in the reaction and breathes on the surface or the polymer that does not participate in the cross-linking, it has sufficient elongation and is flexible, but the surface tack is A cured product that does not exist is obtained.

Further, by adding the low molecular weight compound (v) having an acid anhydride as a functional group and having a molecular weight of 500 or less, the extreme change in physical properties after heating, which is observed in the conventional sealing material (decrease in elongation) , Plasticization, extreme increase or decrease in modulus, increase in tack, etc.) can be prevented.

Furthermore, this cured product not only has good weather resistance, durability, heat resistance, etc. as a polyacrylic acid ester-based material, but also has good adhesion to a base material as a urethane-based material, and a top coating composition. It also has good glue properties, and when used as an elastic sealing material, it can fully demonstrate the features that were not obtained with conventional commercial products.

[0099]

EXAMPLES Hereinafter, specific examples of the present invention will be described together with comparative examples, but the present invention is not limited to the following examples. In the following Examples and Comparative Examples, "parts" and "%" represent "parts by weight" and "% by weight", respectively.

In the following Examples and Comparative Examples, "polymerization rate", "number average molecular weight (Mn)", "average number of hydroxyl groups (F
"n (OH))" and "gel fraction" were obtained by the following methods 1 to 4, respectively, unless otherwise specified.

1. After the completion of the polymerization, it was calculated from the residual rate of each monomer by a gas chromatogram.

2. The number average molecular weight (Mn) was determined from a calibration curve using standard polystyrene using gel permeation chromatography (GPC).

3. Average number of hydroxyl groups (Fn (OH)) OH value determined according to JIS-K-1557 (the alcohols contained in the polymer were quantified by gas chromatography to correct the OH value) and number average molecular weight (M
Calculated from n).

4. Gel fraction The obtained polymer and Sumidule N-75 (trifunctional isocyanate compound, manufactured by Sumitomo Bayer Urethane Co., Ltd.) were mixed so that the molar ratio of the isocyanate group and the hydroxyl group was 1.1 / 1, and the mixture was mixed. After preparing a 40% toluene solution, a small amount of dibutyltin dilaurate as a catalyst was added thereto, and the mixture was thoroughly stirred and reacted at 80 ° C. for 3 hours to obtain a polyurethane film. Then, after sufficiently drying this film, using tetrahydrofuran as a solvent,
After soxhlet extraction for 8 hours, it represents the weight percentage of insoluble matter that was not extracted.

Reference Example 1- (Production Example 1 of (meth) acrylic acid ester-based copolymer (b)) 2 in a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser. 154 parts of -hydroxyethyl disulfide (compound (d)) was charged and heated to 100 ° C while gently blowing nitrogen gas.
There, 1.64 parts of 2,2′-azobisisobutyronitrile (hereinafter, abbreviated as “AIBN”) (radical polymerization initiator (f)) was added to 54.2 parts of butyl acrylate,
What was dissolved in 3.2 parts of 2-hydroxyethyl acrylate (vinyl-based monomer (e)) was added dropwise over 30 minutes. During the dropping, the polymerization temperature was kept at 105 ± 5 ° C. The molar ratio (= (d) / (f)) of the compound (d) and the initiator (f) in the flask at the end of dropping was 100.

After the completion of the dropping, the polymerization was completed by continuing stirring at the same temperature for 30 minutes to obtain a dispersion liquid of the polymer [1].
The polymerization rate calculated from the solid content concentration of this dispersion was 96%.

Subsequently, this dispersion was transferred to a separating funnel,
After 100 parts of toluene was added and mixed by shaking well, the mixture was allowed to stand for a while and the lower layer (2-hydroxyethyl disulfide) separated into two phases was removed. Then, the toluene layer was washed with 200 parts of ion-exchanged water three times. Then, 50 parts of sodium sulfate was added to the washed toluene phase to dehydrate the toluene phase, and then toluene and residual monomers in the toluene phase were distilled off by an evaporator to purify the polymer [1].

The number average molecular weight of the polymer [1] after purification (M
n) was 1900 as a result of measurement with a vapor pressure molecular weight measuring device (VPO). The average number of hydroxyl groups (Fn (OH)) of this polymer [1] is JIS-K-155.
As a result of calculation based on the OH value 88 determined according to 7 and the value of the above number average molecular weight, it was 3.0 (mol / polymer 1 mol).

Reference Example 2- (Production Example 2 of (meth) acrylic acid ester-based copolymer (b)) 2-Ethylhexyl acrylate was placed in a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser. 11
6 parts, methyl methacrylate 9 parts, ethylene glycol 5
After charging 0 part and 1.4 parts of paratoluenesulfonic acid and 3.6 parts of 60% hydrogen peroxide solution and performing nitrogen substitution in the flask, while gently blowing nitrogen gas,
The mixture was heated to 0 ° C. and stirred at the same temperature for 10 minutes to complete the polymerization, thus obtaining a dispersion liquid of the polymer [2]. When the polymerization rate was calculated from the residual rate of the vinyl-based monomer on the gas chromatogram, it was 95%.

Then, the polymer [2] was extracted and separated from the reaction mixture containing the polymer [2] using a toluene / water-based extraction solvent to obtain a toluene solution containing the polymer [2]. Toluene was distilled off, and the residue was dried under reduced pressure at 45 ° C. to obtain a purified polymer [2].

The number average molecular weight of the polymer [2] after purification (M
n) was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 00. Further, the average number of hydroxyl groups of the polymer [2] (F
n (OH) is O determined according to JIS-K-1557.
As a result of calculation based on the H value and the value of the number average molecular weight measured above, 3.7 (mol / polymer 1 mol) (OH value: 1
9 (mgKOH / g)).

Reference Example 3 (Production Example 3 of (meth) acrylic acid ester-based copolymer (b)) A flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser was charged with 280 parts of ethylene glycol. After replacing the atmosphere in the flask with nitrogen, the temperature was raised to 140 ° C. while gently blowing nitrogen gas. After the temperature in the reaction vessel was stabilized, a mixed solution of cyclohexanone peroxide 4.0 parts in 81 parts of butyl acrylate and a mixed solution of 2.8 parts of paratoluenesulfonic acid and 33 parts of ethylene glycol were simultaneously prepared. After dropping for 1 hour, stirring was continued at 140 ° C. for 10 minutes to complete the polymerization. When the polymerization rate was calculated from the residual rate of the vinyl monomer by gas chromatography, it was 95%.

After completion of the polymerization, after cooling to 110 ° C., 2.8 parts of sodium hydrogencarbonate was added to the system, stirring was continued for 10 minutes at the same temperature, and after cooling to room temperature, the polymerization solution separated into two phases (upper layer : Polymer phase, lower layer: ethylene glycol phase), only the polymer phase was taken out by decantation, and devolatilized with a thin film evaporator under the conditions of 160 ° C. and 5 mmHg to obtain a purified polymer [3].

The number average molecular weight of the polymer [3] after purification (M
n) was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC), and was found to be 330.
It was 0. Further, the average number of hydroxyl groups of the polymer [3] (Fn
(OH)) is O determined according to JIS-K-1557.
As a result of calculation based on the H value and the value of the number average molecular weight measured above, 4.0 (mol / polymer 1 mol) (OH value: 68
(MgKOH / g)).

Reference Example 4- (Production Example 4 of (meth) acrylic acid ester-based copolymer (b)) 140 parts of propylene glycol and ethylene were placed in a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser. After 20 parts of glycol monoethyl ether was charged and the inside of the flask was replaced with nitrogen, the temperature was raised to 140 ° C. while gently blowing nitrogen gas. After the temperature in the reaction vessel became stable, 216 parts of butyl acrylate, 13 parts of styrene, 6.5 parts of acrylonitrile and 4.0 parts of cyclohexanone peroxide were dissolved in hydrochloric acid (3 parts).
A mixed solution of 1.1 parts of 5%) and 33 parts of ethylene glycol was simultaneously added dropwise over 1 hour, and then stirring was continued at 140 ° C. for 10 minutes to complete the polymerization. When the polymerization rate was calculated from the residual rate of the vinyl monomer by gas chromatography, it was 98%.

After the completion of the polymerization, after cooling to 110 ° C., 1.8 parts of sodium hydrogen carbonate was added to the system, and stirring was continued for 10 minutes at the same temperature, and then, a polymerization product liquid was added at 130 ° C. and 3 mmHg for 3 hours. The volatile content in the solution was removed to obtain a purified polymer [4].

The number average molecular weight of the polymer [4] after purification (M
n) was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 0. Further, the average number of hydroxyl groups of the polymer [4] (Fn
(OH)) is O determined according to JIS-K-1557.
As a result of calculation based on the H value and the value of the number average molecular weight measured above, 2.0 (mol / polymer 1 mol) (OH value: 35
(MgKOH / g)).

Reference Example 5- (Production Example 5 of (meth) acrylic acid ester-based copolymer (b)) 70 parts of ethylene glycol was added to a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser. After 60 parts of propylene glycol was charged and the inside of the flask was replaced with nitrogen, while gently blowing nitrogen gas, 10
The temperature was raised to 0 ° C. After the temperature in the reaction vessel became stable, a mixed solution of 1.3 parts of 2,2'-azobisisobutyronitrile in 99 parts of butyl acrylate, 1.4 parts of paratoluenesulfonic acid and ethylene glycol were added. The mixture with 33 parts was added dropwise over 1 hour at the same time, and then 10 minutes at 100 ° C.
The stirring was continued at to complete the polymerization. When the polymerization rate was calculated from the residual rate of the vinyl monomer by gas chromatography, it was 95%.

After completion of the polymerization, after cooling to 110 ° C., 2.8 parts of sodium hydrogencarbonate was added to the system and stirring was continued for 10 minutes at the same temperature, and then, a polymerization product solution was added at 130 ° C. and 3 mmHg for 3 hours. The volatile matter in the inside was removed to obtain a purified polymer [5].

The number average molecular weight of the polymer [5] after purification (M
n) was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC), and as a result, was 500.
It was 0. In addition, the average number of hydroxyl groups of the polymer [5] (Fn
(OH)) is O determined according to JIS-K-1557.
As a result of calculation based on the H value and the value of the number average molecular weight measured above, 3.0 (mol / polymer 1 mol) (OH value: 34
(MgKOH / g)).

Reference Example 6- (Production Example 6 of (meth) acrylic acid ester-based copolymer (b)) 110 parts of butyl acrylate were placed in a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser. And 2-hydroxyethyl acrylate 3 parts, dodecylbenzene sulfonic acid 11 parts and 60% hydrogen peroxide solution 3.9 parts were charged, and after nitrogen substitution in the flask was performed, while gently blowing nitrogen gas, Heat to 140 ℃, 10 at the same temperature
The stirring was continued for a minute to complete the polymerization. When the polymerization rate was calculated from the residual rate of the vinyl-based monomer by gas chromatogram, it was 98%.

Then, the polymer was extracted and separated from the reaction mixture containing the polymer using a toluene / water-based extraction solvent to obtain a toluene solution containing the polymer. Toluene was distilled off, and the residue was dried under reduced pressure at 45 ° C. to obtain a purified polymer [6].

The number average molecular weight of the polymer [6] after purification (M
n) was 16000. The average number of hydroxyl groups (Fn (OH)) of the polymer [6] was 4.9 (mol / polymer 1 mol) (OH value: 17 (mgKOH / g)).

Reference Example 7- (Production Example 7 of (meth) acrylic acid ester-based copolymer (b)) 2-Ethylhexyl acrylate was placed in a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser. 11
0 part, 22 parts ethyl acrylate, 5 parts dioxane, and 6 parts
After charging with 20 parts of 0% hydrogen peroxide water and performing nitrogen substitution in the flask, while gently blowing nitrogen gas,
The polymerization was completed by heating to 130 ° C. and continuing stirring at the same temperature for 10 minutes. When the polymerization rate was calculated from the residual rate of the vinyl-based monomer on the gas chromatogram, it was 97%.

Then, the polymer was extracted and separated from the reaction mixture containing the polymer using a toluene / water-based extraction solvent to obtain a toluene solution containing the polymer. Toluene was distilled off, and further dried at 45 ° C. under reduced pressure to obtain a purified polymer [7].

The number average molecular weight of the polymer [7] after purification (M
n) was 4800. The average number of hydroxyl groups (Fn (OH)) of the polymer [7] was 1.8 (mol / polymer 1 mol) (OH value: 21 (mgKOH / g)).

-Reference Example 8- (Production Example 8 of (meth) acrylic acid ester-based copolymer (b)) 110 parts of butyl acrylate were placed in a flask equipped with a stirrer, a nitrogen introducing tube, a thermometer and a reflux cooling tube. , 3 parts of paratoluenesulfonic acid, 5 parts of dioxane, and 20 parts of 60% hydrogen peroxide solution were charged, and the inside of the flask was replaced with nitrogen.
The mixture was heated to 0 ° C. and stirred at the same temperature for 10 minutes to complete the polymerization. When the polymerization rate was calculated from the residual rate of the vinyl-based monomer by a gas chromatogram, it was 96%.

Then, the polymer was extracted and separated from the reaction mixture containing the polymer using a toluene / water-based extraction solvent to obtain a toluene solution containing the polymer. Toluene was distilled off, and the residue was dried at 45 ° C. under reduced pressure to obtain a purified polymer [8].

The number average molecular weight of the polymer [8] after purification (M
n) was 3100. The average number of hydroxyl groups (Fn (OH)) of the polymer [8] was 2.0 (mol / polymer 1 mol) (OH value: 36 (mgKOH / g)).

Comparative Reference Example 1- (Production Example of Copolymer Having Hydroxyl Group Only in Side Chain) 100 parts of toluene was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux cooling tube. The temperature was raised to 100 ° C. while slowly blowing nitrogen, and 6.6 parts of 2,2′-azobisisobutyronitrile was dissolved in 93 parts of butyl acrylate and 7 parts of 2-hydroxyethyl acrylate. It dripped into the flask over 2 hours. After the dropping was completed, stirring was continued at the same temperature for 1 hour to complete the polymerization. When the polymerization rate was calculated from the residual rate of the vinyl-based monomer by a gas chromatogram, it was 96%.

Subsequently, toluene was distilled off, and the residue was dried at 45 ° C. under reduced pressure to obtain a purified comparative polymer [1].

The comparative polymer [1] after purification had a number average molecular weight (Mn) of 5,000. In addition, a comparative polymer [1]
The average number of hydroxyl groups (Fn (OH)) was 3.0 (mol / polymer 1 mol) (OH value: 34 (mgKOH / g)).

Comparative Reference Example 2- (Production Example of Copolymer Having Hydroxyl Group Only at One End and Side Chain) Toluene 100 was placed in a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser. Parts, the temperature was raised to 100 ° C. while gently blowing nitrogen, and butyl acrylate 93 parts, 2-hydroxyethyl acrylate 7 parts and mercaptoethanol 1.6 parts were dissolved and 2,2′-azo. A solution prepared by dissolving 1.6 parts of bisisobutyronitrile in 20 parts of toluene was dropped into the flask over 2 hours. After the dropping was completed, stirring was continued at the same temperature for 1 hour to complete the polymerization. When the polymerization rate was calculated from the residual rate of the vinyl-based monomer by a gas chromatogram, it was 96%.

Subsequently, toluene was distilled off, and the residue was dried at 45 ° C. under reduced pressure to obtain a purified comparative polymer [2].

The comparative polymer [2] after purification had a number average molecular weight (Mn) of 4,900. In addition, a comparative polymer [1]
The average number of hydroxyl groups (Fn (OH)) was 3.8 (mol / polymer 1 mol) (OH value: 43 (mgKOH / g)).

-Examples 1 to 8-The formulations shown in Table 1 were mixed at room temperature and devolatilized to obtain a curable composition.

The curable composition thus obtained was cured at 40 ° C. for 2 weeks, and the cured product thus obtained was further heated at 90 ° C. for 2 weeks. Then, the characteristics of the elastic sealant were evaluated. The results are shown in Table 2.

(Evaluation method) Flexibility: The cured product was pulled with both hands to give softness of 5, 4, 3, 2, 1.

Stretching: The cured product was pulled with both hands and set to 5, 4, 3, 2, 1 in order of good stretching.

Tack: The cured product was touched, and the touch was set to 5, 4, 3, 2, 1 in the order of no tack.

-Comparative Examples 1 and 2 In the same manner as in Examples 1 to 8, the compounds shown in Table 3 were mixed and devolatilized at room temperature to obtain curable compositions for comparison.

The comparative curable composition thus obtained was cured at 40 ° C. for 2 weeks, and the cured product thus obtained was further heated at 90 ° C. for 2 weeks. The characteristics of the elastic sealant were evaluated in the same manner as in 1 to 8. The results are shown in Table 4.

-Comparative Examples 3 and 4-Except that the low molecular weight compound (v) is not used in the Examples,
The same operation as in Example was carried out, the curable composition was cured at 40 ° C. for 2 weeks, and the cured product thus obtained was further heated at 90 ° C. for 2 weeks. In the same manner as in No. 8, the characteristics of the elastic sealant were evaluated. The results are shown in Table 4.

[0144]

The cured product obtained from the curable composition of the present invention has sufficient elongation and is flexible,
No surface tack, good weather resistance, durability,
It has heat resistance (no change in physical properties when heated), good adhesion to the base material, and good adhesiveness of the top-coat paint. If it is used as an elastic sealing material, it will be commercially available until now. It is possible to fully demonstrate the features that cannot be obtained with the product.

[0145]

[Table 1]

[0146]

[Table 2]

[0147]

[Table 3]

[0148]

[Table 4]

[0149]

[Table 5]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08G 18/10 NFT 18/65 NEX 18/73 NFG C08K 5/092 LHW C08L 33/14 LJE 71 / 02 LQC LQE C09K 3/10 D

Claims (10)

[Claims] 1. Having at least one hydroxyl group at each end,
The (meth) acrylic acid ester-based monomer unit is constituted as an essential repeating unit and has a number average molecular weight of 1000 to 5
0000, a (meth) acrylic acid ester-based copolymer (b) having a hydroxyl value of 10 to 400, a polyalkylene oxide (c) having an isocyanate-modified terminal and an acid anhydride as a functional group, a low molecular weight of 500 or less. A curable composition containing the compound (v) as an essential component. 2. The curable composition according to claim 1, wherein the low molecular weight compound (v) is maleic anhydride, succinic anhydride, or phthalic anhydride. 3. The curing according to claim 1, wherein the (meth) acrylic acid ester-based copolymer (b) contains the hydroxyl group-containing addition polymerizable monomer (a) as an essential repeating unit. Sex composition. 4. A (meth) acrylic acid ester-based copolymer (b) is represented by the following general formula (I): In the presence of the compound (d) represented by
Is always present in the reaction in an amount of 50 moles or more of the radical polymerization initiator (f), and substantially contains a monomer other than the vinyl monomer (e), the compound (d) and the radical polymerization initiator (f). The curable composition according to any one of claims 1 to 3, wherein the curable composition is produced by polymerizing so as not to exist. 5. The (meth) acrylic acid ester-based copolymer (b) is hydrogen peroxide in the presence of alcohols (g) in which the polyfunctional alcohol is essential for the polymerization of the vinyl-based monomer (e). The method is carried out using an initiator system (h) which essentially requires that the reactor system does not substantially contain any components other than the above three (e), (g) and (h). It is manufactured, The curable composition in any one of Claims 1-3 characterized by the above-mentioned. 6. An initiator in which a (meth) acrylic acid ester-based copolymer (b) essentially polymerizes a vinyl-based monomer (e) in the presence of an alcohol (i) and an organic peroxide. A method using system (j), further using an organic sulfonic acid compound (k) and / or an inorganic acid (l), and using the above-mentioned 5 (e), (i), (j) in a reactor. ),
The curable composition according to any one of claims 1 to 3, wherein the curable composition is produced by polymerizing so that components other than (k) and (l) are not substantially contained. . 7. An initiator in which a (meth) acrylic acid ester-based copolymer (b) essentially comprises an azo-based initiator for the polymerization of a vinyl-based monomer (e) in the presence of an alcohol (i). A method using a system (m), which further uses an organic sulfonic acid compound (k), and a component other than the above four (e), (i), (m) and (k) in the reaction system. The curable composition according to any one of claims 1 to 3, wherein the curable composition is manufactured so as not to substantially contain. 8. A method in which a (meth) acrylic acid ester-based copolymer (b) polymerizes a vinyl-based monomer (e) using hydrogen peroxide (n), and further decomposes with hydrogen peroxide. While using the accelerator (o), the above three (e),
The components other than (n) and (o) are manufactured so that they are not used substantially.
The curable composition according to any one of 1. 9. A method in which a (meth) acrylic acid ester-based copolymer (b) polymerizes a vinyl-based monomer (e) using hydrogen peroxide (n), further comprising an amphipathic compound. (P) is used, and the three parties (e), (n),
The curable composition according to any one of claims 1 to 3, wherein the curable composition is manufactured so that components other than (p) are not substantially used. 10. A method in which a (meth) acrylic acid ester-based copolymer (b) polymerizes a vinyl-based monomer (e) using hydrogen peroxide (n), and further decomposes with hydrogen peroxide. It was produced by using the accelerator (o) and the amphipathic compound (p) and substantially not using the components other than the above four (e), (n), (o) and (p). It is a thing, The curable composition in any one of Claims 1-3.