JP2996426B2 - Curable composition - Google Patents

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, weather resistance, durability, stain resistance,
The present invention relates to an inexpensive curable composition for an elastic sealing material which is excellent in adhesion to a substrate, pastes a paint, has no surface tack, and is inexpensive.

[0002]

2. Description of the Related Art An elastic sealing material is an essential material in industries such as construction and civil engineering, and its use is increasing year by year.

At present, various types of elastic sealing materials such as silicon, modified silicon, polysulfide, acryl urethane, and polyurethane are used, but each of them has problems, and as the elastic sealing material, At present, there is no material that satisfies the required physical properties.

[0004] For example, while silicon-based materials have excellent weather resistance and heat resistance, they have major drawbacks such as insufficient adhesion to the substrate, inability to overcoat paint, and high cost. Polyurethanes have disadvantages such as poor weather resistance and tackiness on the surface, and acrylic urethanes have tackiness on the surface. Modified silicones also have drawbacks such as poor adhesion to the substrate, necessitating the selection of an overcoat, and some tackiness on the surface.

[0005]

In view of such circumstances, the present invention not only has excellent weather resistance and heat resistance, but also
An object of the present invention is to provide an inexpensive elastic sealing material which is excellent in adhesion to a base material and adhesion to an overcoating material, has excellent surface-tack-free stain resistance, and is inexpensive.

[0006]

In order to solve the above-mentioned problems, the curable composition for an elastic sealing material according to the present invention has at least one hydroxyl group at each terminal, and comprises a (meth) acrylate-based monomer. (Meth) acrylic copolymer (b) which is composed of a monomer containing a polymer as an essential component and has a number average molecular weight of 1,000 to 50,000 and a hydroxyl value of 10 to 400.
And a polyalkylene oxide (c) having a terminal isocyanate-modified as an essential component.

[0007] Here, each terminal means a starting terminal (α terminal) and a stopping terminal (ω terminal) which are referred to in ordinary vinyl polymerization, and a side chain usually contained in a vinyl monomer includes Not included.

[0008] The elastic sealer according to the present invention will be described below.
The curable composition for rubber material will be described.

First, the (meth) acrylic ester monomer which is an essential component of the (meth) acrylic copolymer (b) according to the present invention includes a conventionally known (meth) acrylic ester monomer There is no particular limitation as long as it is a body, for example, (meth) acrylic acid; methyl (meth) acrylate,
Ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acryl Alkyl (meth) acrylates such as stearyl acid; aryl (meth) acrylates such as benzyl (meth) acrylate; (meth) acrylic acid 2-
Alkyl esters containing a (meth) acrylic acid substituent such as hydroxyethyl, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, and γ- (methacryloyloxypropyl) trimethoxysilane (Meth) acrylic acid derivatives such as methoxyethyl (meth) acrylate and ethylene oxide adduct of (meth) acrylic acid; (meth)
Perfluoromethyl acrylate, perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluorooctyl (meth) acrylate, trifluoromethyl (meth) acrylate Methyl, (meth) acrylic acid 2
-Trifluoromethylethyl, diperfluoromethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, (meth) Tripafluoromethylmethyl acrylate, 2-perfluoroethyl-2- (meth) acrylate-2-perfluorobutylethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane silicon-containing (meth) acrylate-based monomers, and the like. Or a combination of a plurality of types.

Next, the hydroxyl group-containing polymerizable monomer (a) according to the present invention is not particularly limited as long as it is a conventionally known hydroxyl group-containing polymerizable monomer. -Hydroxyethyl, (meth) acrylic acid 2-
Hydroxypropyl, 3-hydroxypropyl (meth) acrylate, mono (meth) acrylate of polyethylene glycol, mono (meth) acrylate of polypropylene glycol, 2- (meth) acrylate
Hydroxyethyl modified polycaprolactone (trade name: Praxel F series (Daicel Chemical Industries, Ltd.)
Manufactured)), (meth) allyl alcohol 4-hydroxymethylstyrene and the like. One of these may be used alone, or a plurality of them may be used in combination.

In the present invention, only the above-mentioned hydroxyl-containing polymerizable monomer (a) and (meth) acrylate monomer may be used, and in addition to the above, a conventionally known vinyl monomer may be used. The body may be used in combination. Conventionally known vinyl monomers other than the hydroxyl group-containing polymerizable monomer (a) and the (meth) acrylate ester monomer include:
Although not particularly limited, for example, maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; styrene, α-methylstyrene, methylstyrene, chlorostyrene, Aromatic vinyl monomers such as styrene sulfonic acid and its sodium salt; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; trivinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane Alkyloxysilyl group-containing vinyl monomers; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmer Maleimide derivatives such as imide and cyclohexylmaleimide; vinyl monomers containing nitrile groups such as acrylonitrile and methacrylonitrile; vinyl monomers containing amide groups such as acrylamide and methacrylamide; vinyl acetate, vinyl propionate, and pivalin Vinyl esters such as vinyl acrylate, 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
A plurality of types may be used in combination.

The content of the (meth) acrylic ester monomer in the monomer constituting the (meth) acrylic copolymer (b) according to the present invention is not particularly limited unless it is 0. In order to sufficiently exhibit the characteristics such as good weather resistance of the (meth) acrylic polymer, it is necessary to use 30% by weight.
It is preferably at least 50% by weight.

Further, the content of the hydroxyl group-containing polymerizable monomer in the monomers constituting the (meth) acrylic copolymer (b) according to the present invention is as follows: (meth) acrylic copolymer (b) ) Is not particularly limited as long as the hydroxyl value is in the range of 10 to 400.

Next, the (meth) acrylic copolymer (b) according to the present invention must have a hydroxyl value in the range of 10 to 400. When the number of hydroxyl groups is less than 10, the crosslink density after curing becomes insufficient, and not only surface tack remains, but also sufficient mechanical strength cannot be obtained. If the hydroxyl value is 300 or more, the crosslink density is too high and sufficient elongation cannot be obtained.

Next, the (meth) acrylic copolymer (b) according to the present invention has a number average molecular weight of 1,000 to 5,000.
Must be in the range 0. This number average molecular weight is 10
When the molecular weight is not more than 00, the molecular weight is too small, and not only sufficient physical properties as a (meth) acrylic polymer cannot be sufficiently exhibited, but also the distance between crosslinking points after curing is too short, so that sufficient elongation cannot be obtained. On the other hand, if it is 50,000 or more, the polymer viscosity becomes too high, and sufficient workability cannot be secured.

Next, the production method of the (meth) acrylic copolymer (b) according to the present invention is not particularly limited, but it is preferable to synthesize it by the following production method. What
In addition, when synthesizing a (meth) acrylic polymer,
Polymerization initiator having an OH group (azobiscyanope)
Or a chain having an OH group as a chain transfer agent.
Using a chain transfer agent (such as 2-mercaptoethanol)
It has been known. Certainly, these OH groups
When an initiator or a chain transfer agent is used, an OH group is introduced into a polymerization terminal.
However, due to the reaction mechanism, all of these OH groups
Introduced only at the terminal, not introduced at the termination of polymerization
It is. Therefore, even if azobis
Using cyanopentanol, 2-mer as a chain transfer agent
Even if both are used together using captoethanol,
Initiator and / or chain transfer agent only at the starting terminal
(Meth) acrylic polymer with OH group derived from
OH groups are introduced at both ends.
Also, (meth) acrylic polymers cannot be obtained.

(1) General formula (I) HO-A- (S) x -B-OH (I) (wherein A and B each represent a divalent organic group;
Is an integer of 2 to 5. In the method in which the polymerization of the vinyl monomer (e) is carried out using the radical polymerization initiator (f) in the presence of the compound (d) represented by the formula (d), the compound (d) Of the radical polymerization initiator (f) 5
The above polymerization is carried out in an amount of at least 0 mole times and the amount other than the compound (d), the vinyl monomer (e) and the radical polymerization initiator (f) is within 10% by weight of the whole. A method for producing a polymer having hydroxyl groups at both ends, characterized by comprising:

The compound (d) in this production method is not particularly restricted but includes, for example, hydroxymethyl disulfide, hydroxymethyl trisulfide, hydroxymethyl tetrasulfide, 2-hydroxyethyl disulfide, 2-hydroxyethyl trisulfide, -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 pentasulfides such as hydroxyoctyl disulfide, 8-hydroxyoctyl trisulfide, 8-hydroxyoctyl tetrasulfide and ethylene oxide adducts thereof; 2,2'-dithiodiglycolic acid, 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'-trithiodioctanoic acid, 8,8'-tetrathiodioctanoic acid, 2,2'-dithiodibenzoic acid, 2,2'-
Di, tri or tetra such as trithiodibenzoic acid, 2,2'-tetrathiodinicotinic acid, 2,2'-dithiodinicotinic acid, 2,2'-trithiodinicotinic acid, 2,2'-tetrathiodinicotinic acid And di (2-hydroxyethyl) esters of sulfide dicarboxylic acids (ethylene oxide adduct).
It can be used in combinations of more than one species. The vinyl monomer (e) used in this production method includes:
There is no particular limitation as long as the (meth) acrylic acid ester monomer is essentially contained. For example, the above-mentioned hydroxyl group-containing polymerizable monomer (a), (meth) acrylic acid ester monomer and Examples of vinyl monomers other than the above can be given as they are.

The radical polymerization initiator (f) is not particularly restricted but includes, for example, isobutyryl peroxide, cumyl peroxy neodecanoate, diisopropyloxy dicarbonate, di-n-propyl peroxy dicarbonate and di-n-propyl peroxy dicarbonate. (2-ethoxyethyl) peroxy dicarbonate, di (2-ethylhexyl) peroxy dicarbonate, t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t
-Hexylperoxypivalate, t-butylperoxypivalate, 3,5,5-trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, cumylperoxyoctate, succinic 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- {methyl-2,5-} (benzoylperoxyhexane, t-butylperoxyacetate, , 2-bis ( - butylperoxy) butane, t
-Butylperoxybenzoate, 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-butylperoxy) hexane,
α, α′-bis (t-butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide, diisobutylbenzene hydroperoxide, di-t-butylperoxide, p-menthanehydroperoxide, 2,
Organics such as 5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide Peroxides; inorganic peroxides such as hydrogen peroxide, potassium persulfate, sodium persulfate, and 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'-dimethyleneisobutylamidine), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl)-
Azo compounds such as propionamide], 2,2'-azobis (isobutylamide) dihydrate, 4,4'-azobis (4-cyanopentanoic acid) and 2,2'-azobis (2-cyanopropanol); hydrogen peroxide -Fe (II)
Redox initiators such as salts, persulfate-sodium bisulfite, cumene hydroperoxide-Fe (II) salt, benzoyl peroxide-dimethylaniline; and other photosensitizers such as diacetyl, dibenzyl, acetophenone and the like. And only one of them may be used, or two or more of them may be used in combination. However, radical polymerization is considered in order to minimize side reactions such as chain transfer reaction due to hydrogen abstraction of primary radicals generated from the initiator, and in view of solubility in various monomers and the number of types that can correspond to the polymerization temperature. 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) and the radical polymerization initiator (f) in the reaction vessel during the polymerization must always be 50 or more. However, it is preferably 100 or more.

In the production method of the present invention, components other than the compound (d), the polymerizable monomer (e) and the radical polymerization initiator (f) must not be substantially used in the polymerization process. Specifically, components other than the compound (d), the polymerizable monomer (e) and the radical polymerization initiator (f) are
It must 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 polymerizable monomer (e) and the radical polymerization initiator (f) are present in an amount of more than 10% by weight, the components Side reactions such as chain transfer increase, and a polymer having no hydroxyl group at one end or both ends is by-produced. 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)) of the compound (d) and the radical polymerization initiator (f) in the reaction vessel during the polymerization is always 5
Any polymerization method may be used as long as it is 0 or more. For example, the compound (d), the polymerizable monomer (e) and the radical polymerization initiator (f) may be charged at a time to perform polymerization, or polymerization may be performed while supplying each component to the polymerization system as needed. Is also good. First, at least a part of the required amount of the compound (d) is charged in a polymerization vessel in advance,
The polymerization may be carried out by feeding (feeding) the polymerizable monomer (e) and the radical polymerization initiator (f) there. In this case, since it is good to consider supplying the radical polymerization initiator (f) as a solution of the polymerizable monomer (e) from the viewpoint of operability, the initiator (f) may be a polymerizable monomer. It is preferred to use an initiator that is sufficiently soluble in body (e). In this case, if the polymerizable monomer (e) and the radical polymerization initiator (f) are continuously supplied in the compound (d), the polymerization reaction becomes milder,
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 of a batch type such as a flask type or a kneader, a tube type of a piston flow, 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 about room temperature to 200 ° C. where ordinary radical polymerization is performed.

(2) The polymerization of the vinyl monomer (e) is carried out in the presence of an alcohol (g) which essentially requires a polyfunctional alcohol, using an initiator system (h) which essentially requires hydrogen peroxide. a method, wherein the three parties in the reaction system (e), (g),
Components other than (h) are within 10% by weight or less of the whole.
Method for producing a polymer, characterized in that that.

The polyfunctional alcohol used in the alcohol (g) in which a polyfunctional alcohol is essential 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 glycols such as hexanediol; hydroquinone diethylol ether; ethylene glycol derivatives such as diethylene glycol and triethylene glycol; sorbitol derivatives; aliphatic polyfunctional alcohols such as cyclohexanediol and xylylene diol; glycerol and monoacetin, monolaurin;
Glycerol mono-substituted derivatives such as glycerol mono-fatty acid ester such as monoolein, monopalmitin and monostearin, glycerol monoallyl ester, thymil alcohol, glycerol monomethyl ether and glycerol monoether such as batyl alcohol; trimethylol propane and its mono-substituted derivatives; Pentaerythritol 2-substituted derivatives such as pentaerythritol and pentaerythritol 2 oleate and pentaerythritol 2 stearate; sorbitan fatty acid esters; erythritol, threose, ribose, arabinose, xylose, lyxose, allose, artose, glucose, mannose, growth,
Saccharides such as monosaccharides such as idose, galactose, talose, fructose, apiose, rhamnose, psicose, sorbose, tagitose, ribulose and xylulose, and disaccharides such as sucrose, maltose and lactose. Among these, the use of ethylene glycol, propylene glycol, 1,4-butanediol, trimethylolpropane, glycerol, pentaerythritol and sorbitol is preferred.

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

(3) A method in which polymerization of a vinyl monomer (e) is carried out in the presence of an alcohol (i) by using an initiator system (j) essentially comprising an organic peroxide. organic sulfonic acid compound (k) and / or with an inorganic acid (l), the 5's reactor (e), (i),
Components other than (j), (k) and (l) are 10% by weight of the whole
A method for producing a polymer , which is within the following range .

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, higher alcohols C ₁₂ -C _14, methoxyethanol, ethoxyethanol, propylene oxy ethanol, ethylene glycol monoacetate, cyclohexanol, benzyl alcohol Phenethyl alcohol, or a mixture of two or more thereof. Although it does not specifically limit as a polyfunctional alcohol, For example, ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 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 xylylene diol; Guri Glycerol mono- or di-substituted derivatives such as glycerol monofatty acid esters such as rolls and monoacetin, monolaurin, monoolein, monopalmitin, monostearin, glycerol monoallyl ester, thymil alcohol, glycerol monomethyl ether, and butyl alcohol; tri; Methylolpropane and its 1- or 2-substituted derivatives; pentaerythritol and 1-3-substituted derivatives of pentaerythritol such as pentaerythritol 2-oleate and pentaerythritol 2-stearate; sorbitan fatty acid esters; erythritol, threose, ribose, arabinose, xylose, Lyxose, allose, artose, glucose, mannose, growth,
Saccharides such as monosaccharides such as idose, galactose, talose, fructose, apiose, rhamnose, psicose, sorbose, tagitose, ribulose and xylulose, and disaccharides such as sucrose, maltose and lactose. These alcohols (i) may be appropriately selected according to the intended use of the (meth) acrylic copolymer (b) to be obtained.

Further, among the above-mentioned 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 and the solubility of the alcohol in the reaction system decreases. 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 be one containing a nitrogen element such as ethanolamine, diethanolamine, triethanolamine or the like, or one containing a sulfur element such as mercaptoethanol, 2-hydroxyethyl disulfide or thiodiethylene glycol.

The weight ratio of the amount of the alcohol (i) to the amount of the vinyl monomer (e) [alcohol (i): vinyl monomer (e)] preferably ranges from 1:20 to 20: 1
And more preferably 1:10 to 10: 1. The amount of the alcohol (i) is preferably at least 2 moles, more preferably at least 50 moles, with respect to the initiator system (j) which essentially requires an organic peroxide.

The organic peroxide used in the initiator system (c) essentially comprising an organic peroxide used in the present invention is not particularly limited. Examples thereof include 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, Peroxy ketals such as 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, di-isopropylurobenzene hydroperoxide, 2- (4-methylcyclohexyl) -Propane hydroperoxa De, 2,5-dimethylhexane -
Hydroperoxides such as 2,5-dihydroperoxide, 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) hexine-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-isopropylperoxydicarbonate, di-2- Ethylhexyl peroxydicarbonate, di-n-propylperoxydicarbonate, bis- (4-t-butylcyclohexyl) peroxydicarbonate, dimyristyl peroxydicarbonate, di-2- Peroxydicarbonates such as tylhexylperoxydicarbonate, di-methoxyisopropylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, diallylperoxydicarbonate, t-butylperoxy Acetate, t-butyl peroxyisobutyrate, t-butyl peroxy pivalate, t-butyl peroxy neodecanoate, cumyl peroxy neodecanoate, t-butyl peroxy-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 cumylperoxyoctoate, t-hexylperoxypivalate, t-butylperoxyneohexanoate, t-hexylperoxyneohexanoate, cumylperoxyneohexanoate, and acetylcyclohexyl Sulfonyl peroxide, t-butyl peroxyallyl carbonate and the like can be mentioned. Particularly, cyclohexanone peroxide and benzoyl peroxide are preferred.
As the organic peroxide, only one kind may be used, or a plurality of kinds may be used in combination.

Examples of the initiator system (j) essentially comprising an organic peroxide used in the present invention include, for example, a compound (y) which can promote polymerization by combining with an organic peroxide. There are cases where they are used in combination with an oxide and cases where they are used alone with an organic peroxide. Compound (y)
Examples thereof include an organic peroxide decomposition catalyst, a reducing compound that performs an oxidation-reduction reaction with an organic peroxide, and the like. That is, the initiator system (j) in which an organic peroxide is essential may be an organic peroxide alone, or an organic peroxide as an essential component, and an organic peroxide decomposition catalyst and a reducing agent. It may be a mixture containing one or more compounds capable of promoting polymerization selected from the group consisting of compounds.

Hereinafter, the compound (y) capable of promoting polymerization by combining with an organic peroxide will be specifically described.

Examples of the organic peroxide decomposition catalyst which is an example of the compound (y) include, but are not particularly limited to, metal halides such as lithium chloride and lithium bromide; metal oxides such as titanium oxide and silicon dioxide; Carboxylic acids and their metal salts and esters such as formic acid, acetic acid, propionic acid, lacnic acid, isoleic acid and benzoic acid; and heterocyclic amines such as pyridine, indole and its derivatives, imidazole and its derivatives, and carbazole and its derivatives. Can be
These may be used alone or in combination of two or more.

Examples of the compound (y), which is a reducing compound that undergoes an oxidation-reduction reaction with an organic peroxide, are not particularly limited. For example, organometallic compounds such as ferrocene; iron naphthenate, copper naphthenate, Inorganic metal compounds capable of generating metal ions such as iron, copper, nickel, cobalt, and manganese exemplified by 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, thiosulfate, sulfoxylate, benzenesulfinic acid and the like Substituted or 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, α-thiopropionic acid sodium sulfoethyl ester; nitrogen-containing compounds such as hydrazine, β-hydroxyethylhydrazine, hydroxylamine; formaldehyde, acetaldehyde, propionaldehyde And aldehydes such as n-butyraldehyde, isobutyraldehyde and isovalerian aldehyde; and ascorbic acid. These may be used alone or in combination of two or more.

Initiator system (j) essentially comprising an organic peroxide
Is not limited to the above. For example, an organic peroxide or an organic peroxide and the above compound (e) are
An azo initiator such as BN (azobisisobutyronitrile) or one or more conventionally known radical initiators such as hydrogen peroxide can be used in combination.
The amount of the initiator system (j) which requires an organic peroxide is as follows:
The molecular weight of the desired (meth) acrylic copolymer (b) is naturally determined, but generally it is preferably 0.1 to 20% by weight based on the vinyl monomer (e).

The organic sulfonic acid compound (k) used in this production method is not particularly restricted but includes, for example, aliphatic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid and octanesulfonic acid; benzene Aromatic sulfonic acids such as sulfonic acid, benzenedisulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; chlorobenzenesulfonic acid, 1-naphthol-4-sulfonic acid, 2-naphthylamine-6-sulfonic acid, toluenesulfonic acid, dodecylbenzene Aromatic sulfonic acid having a nuclear substituent such as sulfonic acid; sulfonic acid having a polymerizable unsaturated group exemplified by 2-sulfoethyl (meth) acrylate, styrene sulfonic acid, vinyl sulfonic acid and the like; alicyclic sulfonic acid And the like. These may be used alone or in combination of two or more. Among the organic sulfonic acid compounds (k), methanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid and the like are particularly preferable. Organic sulfonic acid compounds having surface activity such as dodecylbenzenesulfonic acid are particularly effective.

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

The inorganic acid (l) used in this production method is not particularly restricted but includes, 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.
It can be used in a mixture of more than one species. Among them, sulfuric acid, hydrochloric acid and the like are preferable as the inorganic acid (l).

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

In this production method, during the reaction,
Substrate other than vinyl monomer (e), alcohols (i), initiator system (j) essentially including organic peroxide, organic sulfonic acid compound (k) and / or inorganic acid (l) Avoid using it.

Specifically, a vinyl monomer (e), an alcohol (i), an initiator system (j) essentially comprising an organic peroxide, an organic sulfonic acid compound (k) and / or an inorganic acid The components other than (l) should be about 10% by weight or less of the whole. And (e), (i), (j),
It is preferred that the component other than (k) and / or (l) be 5% by weight or less, and most preferably, (e),
It does not contain any components other than (i), (j), (k) and / or (l).

However, the above four (e), (i),
The use of the surfactant (z) as a component other than (j), (k) and / or (l) in an amount of less than 10% by weight, based on the total amount of components in the reactor, can be achieved by using the obtained polymer. There is no problem because the introduction of a hydroxyl group into A is improved but not reduced.

The surfactant (z) is not particularly restricted but includes, 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-butyl Ammonium hydrogen sulfate, N-benzylpicolinium chloride, tetramethylammonium iodide, tetra-iodide
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; Onium salts of: or polyoxyethylene-polypropylene oxide block copolymers; polyoxyethylene-based surfactants such as polyoxyethylene sulfate; higher alcohols such as lauryl alcohol and stearyl alcohol; and sulfates of these higher alcohols. Metal salts of the sulfates; higher fatty acids such as lauric acid and stearic acid; metal salts of these higher fatty acids; and sorbitan esters. These may be used alone or in combination of two or more.

When the surfactant (z) is used, its amount is less than 10% by weight, preferably 0.1 to 5% by weight, based on the total amount of 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 chain transfer reaction to the surfactant (z), the average number of terminal hydroxyl groups (Fn (O
H)) is undesirably reduced.

Among the above-mentioned surfactants (z), surfactants having hydroxyl groups at both ends, such as polyoxyethylene-polypropylene oxide block copolymer, are incorporated into a crosslinked structure. Since there is no adverse effect on the toughness, weather resistance and water resistance of the crosslinked product, there is no need for purification and removal, which is preferable.

In the present invention, the reaction can be carried out at normal pressure, but it is also possible to carry out the reaction under pressure in an autoclave or an extruder.

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 about room temperature to 200 ° C. at which ordinary radical polymerization is performed.

In the production method of the present invention, a step of removing excess alcohols (i) may be required after completion of the polymerization. At this time, when the alcohol (i) used and the produced polymer A are compatible, the alcohol (i) is removed by devolatilization under reduced pressure using a kettle or a twin-screw extruder. Can be removed. When the alcohols (i) and the (meth) acrylic copolymer (b) are incompatible with each other, the reaction mixture after the polymerization is left to stand as it is, or the reaction mixture is By adding a solvent in which the (meth) acrylic copolymer (b) dissolves but the alcohols (b) do not dissolve, the viscosity of the polymer layer is reduced, and then the mixture is allowed to stand for separation. After removing i), the remaining alcohols (i) can be removed by liquid-liquid extraction or devolatilization under reduced pressure.

(4) A method in which polymerization of a vinyl monomer (e) is carried out in the presence of an alcohol (i) using an initiator system (m) essentially including an azo initiator. In addition to using the organic sulfonic acid compound (k), all components other than the above-mentioned four (e), (i), (m), and (k) in the reaction system are used.
A method for producing a polymer , wherein the amount is within 10% by weight of the body.

The azo initiator used in the initiator system (m) in which an azo initiator is essential in this production method is not particularly limited. For example, 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′-dimethyleneisobutylamidine), 2,
2′-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], 2,2′-azobis (isobutylamide) dihydrate, 4,4′-azobis (4-cyanopentanoic acid), 2, 2'-azobis (2-
Cyanopropanol). Among these, 2,2'-azobisisobutyronitrile is particularly preferred. Only one type of azo initiator may be used,
Alternatively, a plurality of types may be used in combination.

An initiator system (m) in which an azo-based initiator is essential.
May be composed of only an azo-based initiator or 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 include, for example, conventionally known radical initiators such as hydrogen peroxide.

An initiator system (m) in which an azo-based initiator is essential.
The amount of (A) is determined by the molecular weight of the desired (meth) acrylic copolymer, but is generally 0.1 to 20% by weight based on the vinyl monomer (e). Is preferred.

In this production method, during the reaction,
Substantially no other than the vinyl monomer (e), the alcohols (i), the initiator system (m) essentially including the azo initiator, and the organic sulfonic acid compound (k) are used.

Specifically, the components other than the vinyl monomer (e), the alcohols (i), the initiator system (m) essentially including the azo-based initiator, and the organic sulfonic acid compound (k) are all contained. About 10% by weight or less. And
5% by weight of components other than (e), (i), (m) and (k)
And most preferably (e),
That is, it does not contain any components other than (i), (m) and (k).

(5) In the method of polymerizing a vinyl monomer (e) using hydrogen peroxide (n), a hydrogen peroxide decomposition accelerator (o) is further used, and ), (N) and 10% by weight of the components other than (o)
A method for producing a polymer, characterized by being within the following range .

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

The amount of hydrogen peroxide (n) used is determined by the molecular weight of the target (meth) acrylic copolymer, but is generally determined with respect to the vinyl monomer (e). Is preferably 0.5 to 30% by weight.

The hydrogen peroxide decomposition accelerator (o) used in this production method selectively decomposes hydrogen peroxide (n) to efficiently promote the generation of OH radicals, thereby promoting polymerization. It is a compound that can be. However, as the hydrogen peroxide decomposition accelerator (o), not all substances generally known as substances that promote the decomposition of hydrogen peroxide can be used. The reason is that a polymer having hydroxyl groups at both ends can be efficiently synthesized only when the hydrogen peroxide decomposition promoter (o) efficiently decomposes hydrogen peroxide into OH radicals. Even if it promotes the decomposition of hydrogen peroxide like sodium hydroxide,
This is because, when a substance having a low efficiency of generating radicals 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 restricted but includes, for example, 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 dodecylbenzenesulfonic acid and p-phenolsulfonic acid; and aliphatic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propylsulfonic acid, and octanesulfonic acid. Among these,
Benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid and methanesulfonic acid are preferred.
The number average molecular weight of the obtained (meth) acrylic copolymer (b) can be changed 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 and the like 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 low gel fraction based on 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 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. Among these, hydrochloric acid and sulfuric acid are preferred. However, when the inorganic acid is used in the form of an aqueous solution, the amount of accompanying water should be about 10% by weight or less based on the total amount of the components.

The onium salt is not particularly restricted but includes, 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 hydrogensulfate,
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 boron tetrafluoride and methyldiphenylsulfonium boron tetrafluoride; Among these, tetra-n-butylammonium hydrogen sulfate,
Tetrabutylphosphonium bromide, trimethylsulfonium boron tetrafluoride, and methyldiphenylsulfonium boron tetrafluoride are preferred. The effect of promoting decomposition of hydrogen peroxide by the onium salt is changed by the counter ion of the onium salt,
Particularly, hydrogen sulfate of ammonium salt, bromide of phosphonium salt, and boron tetrafluoride of sulfonium salt are very effective. The heterocyclic amine is not particularly limited, but includes, for example, one nitrogen atom such as pyrrole, indole, carbazole, oxazole, thiazole and the like.
5-membered pyrroles containing two nitrogen atoms; imidazoles containing two nitrogen atoms such as imidazole and pyrazole; and 6-membered pyridines containing one nitrogen atom such as pyridine, quinoline and isoquinoline. Alkaloids such as nicotine and quinine; Among these, pyridine, indole and carbazole are preferred.

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

In the production method of the present invention, a substance other than the vinyl monomer (e), hydrogen peroxide (n) and hydrogen peroxide decomposition accelerator (o) is substantially not used.

Specifically, the total amount of components other than the vinyl monomer (e), hydrogen peroxide (n) and the hydrogen peroxide decomposition accelerator (o) (for example, water and solvent) is the total component amount. 1 for
It should be about 0% by weight or less. And (e),
It is preferable that components other than (n) and (o) be 5% by weight or less, and most preferable that no components other than (e), (n) and (o) be used.

(6) In the method in which the vinyl monomer (e) is polymerized by using hydrogen peroxide (n), an amphiphilic compound (p) is further used, and
Components other than (n) and (p) are contained in an amount of 10% by weight or less of the whole.
A method for producing a polymer, wherein

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

The amphiphilic compound (p) is not particularly restricted but includes, for example, cyclic ethers such as dioxane and tetrahydrofuran; chain ethers such as diethyl ether, diisopropyl ether and di-n-propyl ether; Ethylene glycol monoethers (also referred to as cellosolves) such as methoxyethanol, ethoxyethanol (also referred to as ethyl cellosolve) and butoxyethanol; ethylene glycol diethers such as ethylene glycol diethyl ether; ethyl acetate, acetic acid n
Esters such as -propyl and butyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; amides such as dimethylformamide; and sulfoxides such as dimethyl sulfoxide. Among them, various ethers such as dioxane and ethylene glycol diethyl ether; and cellosolves such as ethyl cellosolve are preferable.

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

The preferred amount of the amphiphilic compound (p) is 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, a substance other than the vinyl monomer (e), hydrogen peroxide (n) and the amphiphilic compound (p) is substantially not used.

Specifically, the total amount of components other than the vinyl monomer (e), hydrogen peroxide (n) and the amphiphilic compound (p) (for example, water and solvent) is based on the total amount of the components. 10% by weight
It should be about the following. And (e), (n),
It is preferable that the components other than (p) be 5% by weight or less, and most preferable that no components other than (e), (n) and (p) be used.

(7) In a method in which the polymerization of the vinyl monomer (e) is carried out using hydrogen peroxide (n), a hydrogen peroxide decomposition accelerator (o) and an amphiphilic compound (p) are further added. And the above four (e), (n), (o), (p)
A method for producing a polymer, wherein components other than the above are contained in a range of 10% by weight or less of the whole .

In this production method, the hydrogen peroxide decomposition accelerator (o) is used in an amount of 0.01 to 20.
0% by weight, the amphiphilic compound (p) is 0.1 to 10.0% by weight based on the total amount of components, and the total thereof is 0.13 to 30.0% by weight based on the total amount of components. Like (o)
And (p) are preferably used.

When both the hydrogen peroxide decomposition promoter (o) and the amphipathic compound (p) are used, the reaction system becomes more uniform, and when the hydrogen peroxide decomposition promoter (o) is used alone, In comparison, there is an effect that the number average molecular weight of the (meth) acrylic copolymer (b) to be formed is reduced.

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

Specifically, components other than the vinyl monomer (e), hydrogen peroxide (n), a hydrogen peroxide decomposition accelerator (o), and the amphiphilic compound (p) (for example, water and solvent) ) Is about 10% by weight or less based on the total amount of the components. 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). Is not used at all.

The polyalkylene oxide (w) according to the present invention is not particularly limited as long as it is a conventionally known polyalkylene oxide having a terminal hydroxyl group. Examples thereof include butylene glycol and polyethylene glycol-polypropylene glycol block polymer, and these can be used alone or as a mixture of two or more.

Further, together with the polyalkylene oxide (w), a high molecular compound having another OH group at its terminal, for example, polyolefin polyol, polybutadiene polyol,
B. F. Good-rich OH-terminated HTBN, polyester polyols, and polycarbonate polyols can also be used.

The polyfunctional isocyanate compound (x) used in the present invention is not particularly limited as long as it is a conventionally known polyfunctional isocyanate compound. For example, tolylene diisocyanate (also referred to as “TDI”), 4,
4'-diphenylmethane diisocyanate ("MDI"
Isocyanate compounds such as hexamethylene diisocyanate, xylylene diisocyanate, meta-xylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate; Bullet polyisocyanate compound such as N (manufactured by Sumitomo Bayer Urethane Co.); Desmodur I
L, HL (manufactured by Bayer AG), Coronate EH
A polyisocyanate compound having an isocyanurate ring such as (Nippon Polyurethane Industry Co., Ltd.); an adduct polyisocyanate compound such as Sumidur L (manufactured by Sumitomo Bayer Urethane Co., Ltd.); Adduct polyisocyanate compounds and the like can be mentioned. These can be used alone or in combination of two or more. Further, a blocked isocyanate may be used. Of the present invention
In order to take advantage of the better weather resistance of the curable composition for an elastic sealing material, examples of the polyfunctional isocyanate compound include hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and Sumidur N.
It is preferable to use an isocyanate compound having no aromatic ring, such as (manufactured by Sumitomo Bayer Urethane Co., Ltd.).

Next, the polyalkylene oxide (c) having a terminal isocyanate-modified according to the present invention is obtained by reacting the above-mentioned polyfunctional isocyanate compound (x) with the terminal hydroxyl group of the above-mentioned polyalkylene oxide (w), and converting the terminal to isocyanate. There is no particular limitation so long as it is modified.
Only the species may be used, or two or more species may be used in combination.

Further, a polymer in which the terminal of the above-mentioned polymer compound having an OH group at the terminal is modified with isocyanate can be used in combination.

As described above, the polyalkylene oxide (c) having a terminal isocyanate-modified according to the present invention is mainly bifunctional or higher, but the monofunctional terminal isocyanate-terminated within a range that does not significantly inhibit the curing of the present composition. It is free to use modified polyalkylene oxides. From the viewpoints of water resistance, reactivity, and price, among the above examples, it is preferable to use polypropylene glycol (bifunctional or trifunctional) modified with a terminal TDI.

The mixing ratio of the (meth) acrylic copolymer (b) and the polyalkylene oxide (c) whose terminal is isocyanate-modified to be used in the curable composition for an elastic sealing material of the present invention is not particularly limited. , The weight ratio of (meth) acrylic copolymer (b) to polyalkylene oxide (c) with terminal isocyanate modification ((meth) acrylic copolymer (b) / polyalkylene oxide with terminal isocyanate modification ( c)) is 5 / 95-95 /
It is preferably 5 and more preferably 10/90 to 90/10.

The curable composition for an elastic sealing material of the present invention may contain, if necessary, a filler, a (meth) acrylic copolymer (b) and a polyalkylene oxide (c) having a terminal isocyanate-modified. A catalyst for accelerating the reaction can be blended, and if necessary, a plasticizer,
Pigments, antioxidants, fungicides, antioxidants, thixotropic agents and the like can also be added.

The filler used as necessary in the present invention improves the strength of the curable composition for an elastic sealing material of the present invention, and also makes the viscosity of the present composition appropriate and improves workability. Used for the purpose, for example, calcium carbonate, silica powder, talc, glass powder, magnesia, clay powder, titanium oxide and the like can be used.

The proportion of the above-mentioned filler is not particularly limited, but it is based on the resin content of the (meth) acrylic copolymer (b) and the polyalkylene oxide (c) whose terminal is modified with isocyanate. , 30 to 400% by weight, more preferably 50 to 200% by weight.

If the proportion of the filler is too low, it is difficult to obtain the required strength. On the other hand, if the proportion is too high, the elongation of the cured product is too low.

The catalyst used as required in the present invention is not particularly limited as long as it is a conventionally known catalyst for a urethane reaction. Examples thereof include dibutyltin dilaurate, monobutyltin oxide, and dioctyltin dilaurate. And metal compounds such as stannas octoate; amine compounds such as triethylenediamine, triethylenetetramine, diaminodiphenylmethane and triethylamine. The amount of the catalyst to be added is not particularly limited, but the (meth) acrylic copolymer (b) and the polyalkylene oxide (c) having a terminal isocyanate-modified are used.
Is preferably used in an amount of 0.01 to 5% by weight based on the total resin content.

It is also possible to add a silicone-based, modified silicon-based, polysulfide-based, acrylurethane-based, etc. elastic sealing agent to the curable composition for an elastic sealing material of the present invention, if necessary. is there.

[0096]

According to the curable composition for an elastic sealing material of the present invention, the (meth) acrylic copolymer (b) used in the present invention has at least one hydroxyl group at each terminal, and the terminal is isocyanate-modified. After curing with the polyalkylene oxide (c), 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.
A cured product having no surface tack is obtained.

In addition, having a hydroxyl group derived from a hydroxyl-containing polymerizable monomer in the main chain also contributes to good elongation.

Further, this cured product not only has good weather resistance, durability and heat resistance as a polyacrylic material, but also has good adhesiveness to a substrate as a urethane-based material, and a topcoat paint paste. such goodness of which have, as a resilient sealing material can exert regret without the features which can not be obtained in previous 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.

-Reference Example 1-(Production Example 1 of (meth) acrylic copolymer (b) 1) 2-Hydroxyl was placed in a flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser. 154 parts of ethyl disulfide (compound (d)) were charged and heated to 100 ° C. while gently blowing nitrogen gas. There,
2,2'-azobisisobutyronitrile (hereinafter abbreviated as "AIBN") (radical polymerization initiator (f))
A solution obtained by dissolving 1.64 parts in 60.2 parts of butyl acrylate and 3.8 parts of 2-hydroxyethyl acrylate (vinyl monomer (e)) was added dropwise over 30 minutes. During the dropwise addition, the polymerization temperature was maintained at 105 ± 5 ° C. In addition, the molar ratio (= (d) / (f)) of the compound (d) and the initiator (f) in the flask at the end of the dropping was 100.

After completion of the dropwise addition, stirring was continued at the same temperature for another 30 minutes to complete the polymerization, thereby obtaining a dispersion 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 shaken well, the mixture was allowed to stand for a while to remove the lower layer (2-hydroxyethyl disulfide) separated from the two phases. Thereafter, the toluene layer was washed three times with 200 parts of ion-exchanged water. Then, 50 parts of sodium sulfate were added to the washed toluene phase, and the toluene phase was dehydrated. Then, toluene and remaining monomers in the toluene phase were distilled off using an evaporator to purify the polymer [1].

The number average molecular weight (M
n) was 2,000 as measured by a vapor pressure molecular weight analyzer (VPO). The average number of hydroxyl groups (Fn (OH)) of the polymer [1] is determined according to JIS-K-155.
As a result of calculation based on the OH value of 84 determined according to No. 7 and the value of the number average molecular weight, it was 3.0 (mol / mol of polymer).

Reference Example 2- (Production Example 2 of (meth) acrylic copolymer (b) 2) 129 parts of 2-ethylhexyl acrylate was placed in a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser. , 10 parts of methyl methacrylate, 2 parts of 2-hydroxyethyl methacrylate, 50 parts of ethylene glycol and 3.6 parts of a 60% hydrogen peroxide solution, and the atmosphere in the flask was replaced with nitrogen. While blowing, the mixture was heated to 140 ° C., and stirring was continued at the same temperature for 10 minutes to complete the polymerization, thereby obtaining a dispersion of the polymer [2]. The polymerization rate was determined from the residual rate of the vinyl monomer by gas chromatography, and was found to be 94%.

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

The number average molecular weight (M
n) was measured by standard polystyrene conversion method using gel permeation chromatography (GPC).
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, 4.9 (mol / mol of polymer) (OH value: 1)
8 (mgKOH / g)).

Reference Example 3 Production Example 3 of ((meth) acrylic copolymer (b) 3) 280 parts of ethylene glycol was charged into a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser, and After the inside was replaced with nitrogen, the temperature was raised to 140 ° C. while gently blowing nitrogen gas. After the temperature in the reaction vessel was stabilized, 90 parts of butyl acrylate and Blemmer PE-
A mixture of 4.0 parts of cyclohexanone peroxide in 5.6 parts of 350 (manufactured by NOF CORPORATION) and a mixture of 2.8 parts of paratoluenesulfonic acid and 33 parts of ethylene glycol were simultaneously applied for 1 hour. After the dropwise addition, stirring was continued at 140 ° C. for 10 minutes to complete the polymerization. The polymerization rate was determined from the residual rate of the vinyl monomer by gas chromatography to be 92%.

Subsequently, using a toluene / water extraction solvent, the polymer was extracted and separated from the reaction mixture containing the polymer to obtain a toluene solution containing the polymer. The toluene was distilled off, and the polymer was dried at 45 ° C. under reduced pressure to obtain a purified polymer [3].

The number average molecular weight (M
n) was measured by standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 0. The average number of hydroxyl groups (Fn) of the polymer [3]
(OH)) is an 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, 6.6 (mol / mol of polymer) (OH value: 10
6 (mgKOH / g)).

-Reference Example 4-(Production Example 4 of (meth) acrylic copolymer (b) 4) 140 parts of propylene glycol and ethylene glycol monomer were placed in a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser. After charging 20 parts of ethyl ether and purging with nitrogen in the flask, the temperature was raised to 140 ° C. while gently blowing nitrogen gas. After the temperature in the reaction vessel was stabilized, 240 parts of butyl acrylate, 15 parts of styrene, 7.5 parts of acrylonitrile, and 120 parts of 2-hydroxyethyl acrylate were mixed with 2.0 parts of cyclohexanone peroxide.
Then, a mixed solution in which 0.5 parts of hydrochloric acid (35%) and 33 parts of ethylene glycol were simultaneously added dropwise over 1 hour, followed by stirring at 140 ° C. for 10 minutes to complete the polymerization. . The polymerization rate was determined from the residual rate of the vinyl monomer by gas chromatography to be 95%.

Subsequently, 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. The toluene was distilled off, and the polymer was dried at 45 ° C. under reduced pressure to obtain a purified polymer [4].

The number average molecular weight (M
n) was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
00. Further, the average number of hydroxyl groups of the polymer [4] (F
n (OH)) was calculated on the basis of the OH value obtained according to JIS-K-1557 and the value of the number average molecular weight measured above, and as a result, 89 (mol / 1 mol of polymer) (OH value: Fifteen
6 (mgKOH / g)).

Reference Example 5 (Production Example 5 of (meth) acrylic copolymer (b) 5) 70 parts of ethylene glycol and propylene glycol were placed in a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser. After 60 parts were charged and the atmosphere in the flask was replaced with nitrogen, the temperature was raised to 100 ° C. while gently blowing nitrogen gas. After the temperature in the reaction vessel was stabilized, 1.3 parts of 2,2′-azobisisobutyronitrile was dissolved in 90 parts of butyl acrylate and 12 parts of Praxel FA-5 (manufactured by Daicel Chemical Industries, Ltd.). The resulting mixed solution, a mixed solution of 1.4 parts of paratoluenesulfonic acid and 33 parts of ethylene glycol were simultaneously added dropwise over 1 hour, and then stirring was continued at 100 ° C. for 10 minutes to complete the polymerization. The polymerization rate was determined from the residual rate of the vinyl monomer by gas chromatography to be 93%.

Subsequently, using a toluene / water extraction solvent, the polymer was extracted and separated from the reaction mixture containing the polymer to obtain a toluene solution containing the polymer. The toluene was distilled off, and the residue was dried at 45 ° C. under reduced pressure to obtain a purified polymer [5].

The number average molecular weight (Mn) of the purified polymer [54] was measured by gel permeation chromatography (GPC) using a standard polystyrene conversion method.
2000. The average number of hydroxyl groups (Fn (OH)) of the polymer [5] was calculated based on the OH value obtained according to JIS-K-1557 and the value of the number average molecular weight measured above. .9 (mol / mol of polymer) (OH
Value: 23 (mgKOH / g)).

Reference Example 6- (Production Example 6 of ((meth) acrylic copolymer (b)) 98 parts of butyl acrylate and acrylic resin were placed in a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser. After charging 2 parts of 2-hydroxyethyl acid, 11 parts of dodecylbenzenesulfonic acid, and 3.9 parts of 60% hydrogen peroxide solution, the atmosphere in the flask was replaced with nitrogen, and then 140 ° C. while gently blowing nitrogen gas. And the stirring was continued at the same temperature for 10 minutes to complete the polymerization. When the polymerization rate was determined from the residual rate of the vinyl monomer by gas chromatography, 96
%Met.

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

The purified polymer [6] had a number average molecular weight (M
n) was 13,000. The average number of hydroxyl groups (Fn (OH)) of the polymer [6] was 4.0 (mol / mol of polymer) (OH value: 17 (mgKOH / g)).

-Reference Example 7- (Production Example 7 of (meth) acrylic copolymer (b)) 100 parts of 2-ethylhexyl acrylate was placed in a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser. , 20 parts of ethyl acrylate, 3 parts of 2-hydroxyethyl acrylate, 5 parts of dioxane, and 20 parts of a 60% hydrogen peroxide solution, and after purging with nitrogen in the flask, while gently blowing nitrogen gas into the flask. , And the mixture was stirred at the same temperature for 10 minutes to complete the polymerization. When the polymerization rate was determined from the residual rate of the vinyl monomer by gas chromatography, it was 98%.

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

The number average molecular weight (M
n) was 5,200. The average number of hydroxyl groups (Fn (OH)) of the polymer [7] was 3.2 (mol / mol of polymer) (OH value: 34 (mgKOH / g)).

-Reference Example 8- (Production Example 8 of (meth) acrylic copolymer (b)) A flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser was charged with 100 parts of butyl acrylate, After charging 4 parts of 2-hydroxyethyl acid, 3 parts of paratoluenesulfonic acid, 5 parts of dioxane, and 20 parts of 60% hydrogen peroxide solution, and performing nitrogen replacement in the flask, while gently blowing nitrogen gas, Heat to 130 ° C and at the same temperature
Stirring was continued for a minute to complete the polymerization. The polymerization rate was determined from the residual rate of the vinyl monomer by gas chromatography, and was found to be 99%.

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

The purified polymer [8] had a number average molecular weight (M
n) was 3000. The average number of hydroxyl groups (Fn (OH)) of the polymer [8] was 3.9 (mol / mol of polymer) (OH value: 73 (mgKOH / g)).

Comparative 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 inlet tube, a thermometer and a reflux condenser. The temperature was raised to 100 ° C. while gently 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. The solution was dropped into the flask over 2 hours. After completion of the dropwise addition, stirring was continued for 1 hour at the same temperature to complete the polymerization. When the polymerization rate was determined from the residual rate of the vinyl monomer by gas chromatography, 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 number average molecular weight (Mn) of the purified comparative polymer [1] was 5,000. In addition, the comparative polymer [1]
Has an average number of hydroxyl groups (Fn (OH)) of 3.0 (mol / mol of polymer) (OH value: 34 (mgKOH / g)).

Comparative Example 2 (Production Example of Copolymer Having Hydroxyl Group at One Terminal and Side Chain Only) Toluene was added to a flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser. The mixture was heated to 100 ° C. while gently blowing nitrogen, and 93 parts of butyl acrylate, 1.6 parts of mercaptoethanol dissolved in 7 parts of 2-hydroxyethyl acrylate, 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 completion of the dropwise addition, stirring was continued for 1 hour at the same temperature to complete the polymerization. When the polymerization rate was determined from the residual rate of the vinyl monomer by gas chromatography, it was 96%.

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

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

Examples 1 to 8 The blends shown in Table 1 were mixed and devolatilized at room temperature to obtain an elastic seal.
The curable composition for a brushing material was obtained.

The elastic sealing material thus obtained
The curable composition for use was evaluated for characteristics as an elastic sealant according to JIS-A5557. Table 2 shows the results.

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

The properties of the thus obtained comparative curable composition as an elastic sealant were evaluated according to JIS-A5557. Table 4 shows the results.

[0135]

The cured product obtained from the curable composition for an elastic sealing material of the present invention has no surface tack even though it has sufficient elongation and is soft, and has good weather resistance, durability, has heat resistance, further adhesion of the good to the substrate, and a good like also has to have an elastic sealant glue topcoats, regret no features which can not be obtained in previous commercial products Can be demonstrated.

[0136]

[Table 1]

[0137]

[Table 2]

[0138]

[Table 3]

[0139]

[Table 4]

[0140]

[Table 5]

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kenichi Toba 5-8 Nishiburi-cho, Suita-shi, Osaka Inside the Nippon Shokubai Central Research Institute, Inc. No. Nippon Shokubai Central Research Laboratory Co., Ltd. (72) Inventor Fumihide Tamura 5-8 Nishiburimachi, Suita City, Osaka Prefecture No. 8 Nippon Shokubai Central Research Laboratory Co., Ltd. (56) References JP-A-2-255784 (JP, A) JP-A-54-47735 (JP, A) JP-A-61-271306 (JP, A) ( 58) Field surveyed (Int.Cl. ⁶ , DB name) C08G 18/62 C08G 18/73 C09K 3/10

Claims (10)

(57) [Claims] 1. A monomer having at least one hydroxyl group at each terminal and essentially containing a (meth) acrylate monomer, and having a number average molecular weight of 1,000 to 5,000.
0, an elastic sheet containing a (meth) acrylic copolymer (b) having a hydroxyl value of 10 to 400 and a polyalkylene oxide (c) having a terminal isocyanate-modified as essential components
A curable composition for a ring material . 2. A monomer having at least one hydroxyl group at each terminal and essentially containing a (meth) acrylate monomer, and having a number average molecular weight of 1,000 to 5,000.
0, an elastomer containing (meth) acrylic copolymer (b) having a hydroxyl value of 10 to 400, polyalkylene oxide (w) and polyfunctional isocyanate compound (x) as essential components
A curable composition for a volatile sealing material . 3. The elastic sealing material according to claim 1, wherein the (meth) acrylic copolymer (b) contains a hydroxyl group-containing polymerizable monomer (a) as an essential component.
Use the curable composition. 4. The (meth) acrylic copolymer (b) has the general formula (I) HO-A- (S) x -B-OH (I) wherein A and B are each a divalent Represents an organic group, x
Is an integer of 2 to 5. In the method in which the polymerization of the vinyl monomer (e) is carried out using the radical polymerization initiator (f) in the presence of the compound (d) represented by the formula (d), the compound (d) Of the radical polymerization initiator (f) 5
The above polymerization is carried out in an amount of at least 0 mole times and the amount other than the compound (d), the vinyl monomer (e) and the radical polymerization initiator (f) is within 10% by weight of the whole. The curable composition for an elastic sealing material according to any one of claims 1 to 3 , wherein the curable composition is produced by a method for producing a polymer having hydroxyl groups at both ends, characterized by the following. 5. The (meth) acrylic copolymer (b) requires hydrogen peroxide in the presence of an alcohol (g) in which polymerization of the vinyl monomer (e) requires a polyfunctional alcohol. Using an initiator system (h) , wherein the components other than the three components (e), (g) and (h) in the reaction system are entirely
The curable composition for an elastic sealing material according to any one of claims 1 to 3 , wherein the curable composition is produced by a method for producing a polymer , which is within a range of 10% by weight or less . 6. An initiator system comprising a (meth) acrylic copolymer (b) and an organic peroxide as an essential component in the polymerization of a vinyl monomer (e) in the presence of an alcohol (i). j), further comprising an organic sulfonic acid compound (k)
And / or the inorganic acid (l) and the five components (e), (i), (j), (k), (l) in the reactor.
The elastic sealin according to any one of claims 1 to 3, wherein the components other than the above are in a range of 10% by weight or less based on the whole.
Curable composition for rubber material . 7. An initiator system comprising a (meth) acrylic copolymer (b) and an azo initiator in the presence of an alcohol (i) for polymerization of a vinyl monomer (e). m) wherein the organic sulfonic acid compound (k)
And the four members (e) in the reaction system,
Components other than (i), (m) and (k) are 10% by weight of the whole
2. A polymer produced by a method for producing a polymer , which is within the following range:
4. The curable composition for an elastic sealing material according to any one of items 1 to 3. 8. A method in which a (meth) acrylic copolymer (b) is used to carry out polymerization of a vinyl monomer (e) using hydrogen peroxide (n). (O) and the three parties (e), (n),
Components other than (o) should be within 10% by weight of the whole.
Elastic sheet of claim 1, wherein the that it is one produced by the production method of polymer characterized
Curable composition for sealing materials . 9. The method according to claim 1, wherein the (meth) acrylic copolymer (b) is used to polymerize the vinyl monomer (e) using hydrogen peroxide (n). ), And the components other than the above three (e), (n), and (p) are contained in a range of 10% by weight or less of the entirety. The curable composition for an elastic sealing material according to any one of claims 1 to 3, wherein 10. The (meth) acrylic copolymer (b) comprises:
In the method in which the vinyl monomer (e) is polymerized using hydrogen peroxide (n), a hydrogen peroxide decomposition promoter (o) and an amphiphilic compound (p) are further used, and (e), (n), (o), the entire component other than (p)
The curable composition for an elastic sealing material according to any one of claims 1 to 3 , wherein the curable composition is produced by a method for producing a polymer, which is within a range of 10% by weight or less .