JP3222573B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition containing an acrylic polymer having hydroxyl groups at both ends and having improved physical properties.

[0002]

2. Description of the Related Art A resin composition containing a polyol and a polyisocyanate as essential components has excellent mechanical properties and moldability, various foams, elastomers, various industrial parts, daily necessities and paints, adhesives, Widely used for artificial leather, synthetic leather and the like. In particular, in applications where heat resistance, wet resistance, weather resistance, light resistance, etc. are required, such as paints, artificial leather, and synthetic leather, as the polyol component, a polyol whose main chain is an acrylic polymer is used. The resin composition used is suitable.

[0003] However, the acrylic polyol containing a monomer unit having a hydroxyl group used in this resin composition has a problem that when used in a coating material, elongation and strength are not sufficient in mechanical properties. In addition, when used for artificial leather or synthetic leather, there is a problem that thermosetting is required regardless of the need for thermoplasticity. The present inventors have studied variously to solve this problem, and conventionally, an acrylic polyol generally used is an acrylic copolymer having a hydroxyl group in a side chain, which is considered to be the cause. In order to solve the above problem, it was considered that a linear acrylic polymer having hydroxyl groups at both ends may be used as the acrylic polyol.

[0004]

However, as a result of additional tests, this resin composition using an acrylic polymer having hydroxyl groups at both ends as a polyol component has a low stress-strain characteristic of a resin film obtained therefrom. Although the elongation is large, there is a problem that the stress (mechanical strength) is insufficient and the solvent resistance is low. It was also found that there is still room for improvement in drying properties, viscosity and the like.

Accordingly, the present invention provides heat resistance, wet resistance,
Excellent mechanical strength, elongation, weather resistance, light resistance, etc.
An object of the present invention is to provide a resin composition which can obtain a resin excellent in solvent resistance and the like, has high drying properties, and has a low viscosity and can be made into a high solid.

[0006]

Means for Solving the Problems In order to solve the above problems, the inventors have made various studies. As a result, if the resin composition containing an acrylic polymer having hydroxyl groups at both ends as a polyol component further contains a low-molecular weight compound having two or more active hydrogens in one molecule, the above-described problem occurs. With the idea that the point was eliminated, this was confirmed by experiments, and the present invention was completed.

Accordingly, a resin composition according to the present invention is a resin composition containing an acrylic polymer (a) and a polyisocyanate (b) as essential components, wherein the acrylic polymer (a) is provided at both ends. It is a polymer having a hydroxyl group and a number average molecular weight of 1,000 or more, and in addition to the two (a) and (b), active hydrogen is contained in one molecule.
It is characterized by containing a low molecular weight compound (c) having at least one compound as an essential component.

Hereinafter, the present invention will be described specifically. The acrylic polymer having a hydroxyl group at both terminals, which is the component (a) used in the present invention, will be described. The acrylic polymer (a) always has a hydroxyl group at both terminals, and the number of hydroxyl groups at the terminal is one or more for each terminal.

The structural unit of the acrylic polymer (a) is a vinyl monomer (d) essentially including an acrylic monomer. The vinyl monomer (d) may be composed of only an acrylic monomer, or may be composed of an acrylic monomer and another vinyl monomer copolymerizable therewith. The composition ratio of these monomer units is such that the acrylic monomer unit ranges from 40 wt% to 100 wt%,
It is preferable that the vinyl monomer unit copolymerizable with the acrylic monomer is in the range of 60 wt% to 0 wt% (however, the total of these monomer units is 100 wt%).

The acrylic monomer in the present invention is:
Although not particularly limited, for example,
5.

[0011]

Embedded image

[0012]

Embedded image

[0013]

Embedded image

[0014]

Embedded image

[0015]

Embedded image

(In the above formulas, R ⁴ and R ⁶ are H, an alkyl group, a hydroxyalkyl group, a halogenated alkyl group, an aryl group or a halogenated aryl group, and R ¹ , R ² and R ³ Is H, an alkyl group, a halogenated alkyl group, an aryl group, a halogenated aryl group or COOR ⁴ , and R ⁵ is H, an alkyl group, a halogenated alkyl group, an aryl group or a halogenated aryl group.) Acrylic Specific examples of the monomer are not particularly limited. 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, sulfur (meth) acrylate (Meth) acrylic acid alkyl esters such as tearyl; (meth) acrylic acid aryl esters such as benzyl (meth) acrylate; (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid hydroxypropyl and like (meth) ) Hydroxyalkyl acrylates; (meth) acrylic acid derivatives such as methoxyethyl (meth) acrylate and ethylene oxide adduct of (meth) acrylic acid; trifluoromethylmethyl (meth) acrylate, (meth) acrylic 2-trifluoromethylethyl acid, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, ( Perfluoromethyl (meth) acrylate, (meth) a Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-par (meth) acrylate Fluoromethyl-2-perfluoroethylmethyl, trifluoromethylmethyl (meth) acrylate, 2-perfluoroethyl-2- (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate Perfluoroalkyl esters of (meth) acrylic acid, such as 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate and perfluoroethylene; maleic anhydride;
Maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenyl Maleimide derivatives such as maleimide and cyclohexylmaleimide; acrylic monomers containing nitrile groups such as acrylonitrile and methacrylonitrile; acrylic monomers containing amide groups such as acrylamide and methacrylamide;
Silicon-containing acrylic monomers such as γ- (methacryloyloxypropyl) trimethoxysilane may be mentioned, and these may be used alone or in combination of two or more.

Specific examples of the vinyl monomer copolymerizable with the acrylic monomer are not particularly limited as long as they are conventionally known vinyl monomers copolymerizable with the acrylic monomer. For example, aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and its sodium salt; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane Monomers; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; dienes such as butadiene and isoprene; vinyl chloride and vinylidene chloride , Allyl chloride, allyl alcohol and the like.
Only the species may be used, or a plurality of species may be used in combination.

The acrylic polymer (a) has a number average molecular weight of 1,000 or more. Although not particularly limited,
Considering the reactivity of the terminal and the ease of handling (viscosity etc.),
The number average molecular weight of this polymer (a) is from 1000 to 20
A range of up to 10,000 is preferred, and a range of from 1000 to 50,000 is more preferred. Regarding the number of hydroxyl groups at the terminal of the acrylic polymer (a), one at each end
You need more than one. Having one at each end is a necessary condition for making a thermoplastic resin. Further, the average number of terminal hydroxyl groups (Fn) of the acrylic polymer (a)
When (OH)) is 2.1 or more, it becomes a thermosetting resin,
In this case, the value of Fn (OH) is selected according to the desired physical properties.

The resin composition of the present invention may contain, if necessary, other active hydrogen-containing polymer compounds in addition to the polymer (a). Other active hydrogen-containing polymer compounds that can be used are not particularly limited, and for example, active hydrogen-containing polyethers (PEG, PPG, EO
/ PO copolymer, PTMG), active hydrogen-containing polyester, active hydrogen-containing polybutadiene, active hydrogen-containing polycarbonate, active hydrogen-containing polyolefin, acrylic copolymer containing active hydrogen-containing monomer, polymer polyol, etc. More than one species is used.

Here, the active hydrogen contained in the active hydrogen-containing polymer compound is a functional group containing active hydrogen capable of reacting with an isocyanate group. As a specific example,
Although not particularly limited, examples thereof include a hydroxyl group, an amino group, an imino group, a carboxyl group, a mercapto group, and a thiocarboxyl group. Next, the low molecular weight compound (c) having two or more active hydrogens in one molecule used in the present invention will be described.

Here, the active hydrogen contained in the low molecular weight compound (c) is a functional group containing active hydrogen capable of reacting with an isocyanate group. Specific examples thereof include, but are not limited to, a hydroxyl group, an amino group, an imino group, a carboxyl group, a mercapto group, and a thiocarboxyl group. The molecular weight of the low molecular weight compound (c) is 500
Or less, and more preferably 250 or less. This is because when a compound having a molecular weight of more than 500 is used as the compound (c), the viscosity of the resin composition increases and the workability decreases.

Specific examples of the low molecular weight compound (c) include:
Although not particularly limited, for example, polyol, polyamine, polycarboxylic acid, polyimino compound, polymercapto compound, polythiocarboxylic acid and the like,
Compounds having different active hydrogens are also included. More specific examples of the low molecular weight compound (c) include, but are not particularly limited to, those listed below.

As the polyol, ethylene glycol, diethylene glycol, triethylene glycol,
Propylene glycol, 1,4-butanediol, 1,
3-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 2- Ethyl-1,3-hexanediol, 3-methyl-1,5-pentanediol, 1,8-
Aliphatic polyols such as octanediol, tripropylene glycol, cyclohexane-1,4-diol, glycerin, trimethylolpropane, trimethylolethane, hexanetriol, sorbitol, and methylglycoside; and alicyclic polyols such as 1,4-cyclohexaneglycol. , Xylylene glycol, 1,4-dihydroxyethylbenzene, aromatic polyols such as hydrogenated bisphenol A, dithiodiethanol, polyols containing sulfur atoms such as thiodiethylene glycol, polyols containing nitrogen atoms such as triethanolamine,
Other examples include 3-mol adduct of ethylenoxide of bisphenol A. Among these, in particular, molecular weight 25
A polyol of 0 or less is suitable for lowering the viscosity of the resin composition and the like.

As the polyamine, ethylenediamine,
Aliphatic polyamines such as 1,3-propylenediamine, 1,2-propylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, o- or p-phenylenediamine, 2,4- or 2,6-tolylenediamine Amines, aromatic polyamines such as 4,4′-diamino-3,3′-dimethyldiphenyl, 1,5-naphthylenediamine, tris (4-aminophenyl) methane,
Trimethylene glycol-di-p-aminobenzoate, 2,6-dichloro-p-phenylenediamine, 4,
4'-diamino-3,3'-dimethoxycarbonyldiphenylmethane, 2,2'-diaminodiphenyldithioethane, 1,2-bis (2-aminophenylthio) ethane, trimethylene glycol-di-p-aminobenzoate, Polyamines such as (methylthio) tolylenediamine, hydrazine, piperazine, N, N-diaminopiperazine, 2-methylpiperazine, 4,4′-diaminodicyclohexylmethane, isophoronediamine, methylenebisdichloroaniline, and 3,3′-dichloro- 4,
4'-diaminodiphenylmethane, methylene dianiline / NaCl complex and the like.

Examples of the polycarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid,
Pimelic acid, suberic acid, azelaic acid, sebacic acid,
Dodecane diacid, phthalic acid, terephthalic acid, maleic acid,
Fumaric acid, itaconic acid, trimellitic acid, pyromellitic acid, diphenic acid, naphthalenedicarboxylic acid, 3,3'-
And dithiodipropionic acid.

As the polymercapto compound, ethanedithiol, 1,3-propanedithiol, 1,6-hexanedithiol, dimercapto-1,8-dioxa-
3,6-octane, 2,2′-thiodietanthiol,
Ethylene glycol dithioglycolate, pentaerythritol tetrakis (thioglycolate), 1,4-butanediol dithiopropionate, trimethylolpropane tris- (β-thiopropionate), pentaerythritol tetrakis- (β-thiopropionate) ).

Examples of polythiocarboxylic acids include thioterephthalic acid. Compounds having different active hydrogens used as the low molecular weight compound (c) include:
Amino acids such as ethanolamine, diethanolamine, glycolic acid, malic acid and glutamic acid, lactic acid, mercaptoethanol, β-mercaptopropionic acid, 1-
Thioglycerol, glycerol monothioglycolate, 2-aminothiophenol, 4-aminothiophenol, thiosalicylic acid, 2-aminoethanethiol, and the like.

As the low molecular weight compound (c), one type may be used alone, or two or more types may be used in combination. The compounding ratio of the low molecular weight compound (c) in the resin composition of the present invention is preferably in the range of 0.1 to 200 parts by weight based on 100 parts by weight of the acrylic polymer (a). The content is more preferably in the range of 100 to 100 parts by weight, but may be determined as appropriate in consideration of the intended use and required physical properties of the resin obtained from this composition.

As the polyisocyanate (b) used in the present invention, any conventionally known polyisocyanate can be used, and there is no particular limitation. Examples thereof include those listed below. 1,4-phenylene diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, 4,4-diisocyanate-3,3-dimethyldiphenyl, diphenyldimethylmethane-4,4 '
-Diisocyanate, 1,3- or 1,4-cyclohexyl diisocyanate, 1,4-tetramethylene diisocyanate, bis (isocyanatomethyl) cycloxane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, Xylylene diisocyanate, meta-xylylene diisocyanate, isopropylbenzene
2,4-diisocyanate, polymethylene polyphenylisocyanate, triphenylmethane triisocyanate, tris-4-phenylisocyanate thiophosphate, 3,3 ', 4,4'diphenylmethane tetraisocyanate, polypropylene glycol or triol and tolylene diisocyanate addition reaction Product, an addition reaction product of 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate, a prepolymer of the active hydrogen-containing polymer and a polyisocyanate, cyclohexanephenylene diisocyanate, chlorophenylene diisocyanate, naphthalene-1,5-diisocyanate, hydrogen Diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate Isocyanate compounds such as over door;
Bullet polyisocyanate compound such as Sumidur N (manufactured by Sumitomo Bayer Urethane); 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.); And adduct polyisocyanate compounds. These can be used alone or in combination of two or more. Further, a blocked isocyanate may be used.

The blending amount of the polyisocyanate (b) is N
The equivalent ratio of the CO group to the active hydrogen group (NCO group / active hydrogen group) is preferably in the range of 0.5 to 3.0, more preferably in the range of 0.7 to 2.0, and most preferably in the range of 0.7 to 2.0. 8 ~
The range is 1.5, but may be determined as appropriate depending on the application. Further, if necessary,
n-butyltin dilaurate, stanna octoate,
Catalysts such as triethylenediamine, diethylenediamine, triethylamine, metal salts of naphthenic acid, metal salts of octylic acid and the like can be used.

Further, if necessary, plasticizers such as dioctyl phthalate and dibutyphthalate, modifiers such as process oil and adhesive resin, carbon black, white carbon, calcium carbonate, gypsum, vulcanized rubber powder, etc. Fillers, reinforcing agents such as carbon fiber, glass fiber, organic fiber and asbestos, oxidation stabilizers, anti-aging agents, coloring agents,
Flame retardants can also be added.

If necessary, a solvent may be used. For example, ketones such as acetone, MEK, MIBK, and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chlorobenzene, trichlene and perchrene; ethers such as THF and dioxane; cellosolve acetate; Esters such as ethyl and butyl acetate, and water. These can be used alone or in combination of two or more.
Water reacts with isocyanates and nates, so
Although it should be avoided to be mixed into the resin composition, it may be used as an aqueous two-pack resin for the purpose of environmental protection. In this case, the type of isocyanate,
The amount, catalyst, reaction temperature and reaction time must be carefully selected.

In the resin-forming step, a conventionally known one-shot method, prepolymer method or the like can be used. The order of the reaction can be arbitrarily selected. The acrylic polymer (a) used in the present invention is not particularly limited, but can be obtained, for example, by the following method A, B or C. (A) Polymerization of a vinyl monomer (d) essentially containing an acrylic monomer is carried out by polymerization of an initiator system (f) essentially containing an organic peroxide in the presence of an alcohol (e), By using the sulfonic acid compound (g) and making the reaction vessel substantially free from components other than the above four components (d), (e), (f) and (g), the acrylic A method for obtaining a polymer (a).

(B) The polymerization of the vinyl monomer (d), which essentially requires an acrylic monomer, requires hydrogen peroxide in the presence of an alcohol (h), which essentially requires a polyfunctional alcohol. By using the initiator system (i) and performing the reaction in such a manner that the components other than the above three components (d), (h) and (i) are not substantially contained in the reactor, the acrylic polymer (a) How to get).

(C) The polymerization of a vinyl monomer (d) essentially comprising an acrylic monomer is carried out in the presence of a compound (j) represented by the following general formula (I) in the presence of a radical polymerization initiator. (K)
The compound (j) is always present in the reactor at 50 mol times or more of the radical polymerization initiator (k) during the reaction, and the compound (j) is other than the above three (d), (j) and (k). A method of obtaining an acrylic polymer (a) by substantially eliminating the use of the above.

HO—R ¹ — (S) x —R ² —OH (I) [In the formula (I), R ¹ and R ² each represent a divalent organic group, and x is an integer of 2 to 5. It is. Hereinafter, these methods will be described in detail. First, the method A will be described.

The vinyl monomer (d) essentially comprising an acrylic monomer used in the method A is as described above as a structural unit of the acrylic polymer (a). The amount of the acrylic monomer which is an essential component of the vinyl monomer (d) is 4 to the total amount of the vinyl monomer (d).
The proportion is preferably 0% by weight or more. In the method A, the alcohol used for the alcohol (e) is
It 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 monofunctional alcohol and a polyfunctional alcohol may be used in combination. Examples of the monofunctional alcohol is not specifically limited, for example, ethyl alcohol, methyl alcohol, propyl alcohol, butyl alcohol, tertiary butyl alcohol, pentyl alcohol, higher alcohols C ₁₂ -C _14, methoxyethanol, ethoxyethanol, propylene One or more of oxyethanol, ethylene glycol monoacetic acid ester, cyclohexanol, benzyl alcohol, phenethyl alcohol, and the like are included. Although it does not specifically limit as a polyfunctional alcohol, For example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butane Diol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, neopentyl glycol, 1,5-pentanediol, 2,3-pentanediol, 2, Alkylene glycols such as 4-pentanediol and 1,6-hexanediol; hydroquinone diethylol ether;
Ethylene glycol derivatives such as diethylene glycol and triethylene glycol; aliphatic polyfunctional alcohols such as sorbitol, cyclohexanediol and xylylene diol; glycerol fatty acid esters such as glycerol and monoacetin, monolaurin, monoolein, monopalmitin and monostearin, and glycerol monoallyl Mono- or di-substituted derivatives of glycerol such as ether, thymil alcohol, glycerol monomethyl ether, glycerol monoether such as butyl alcohol; trimethylolpropane and its 1 or 2
Substituted derivatives; pentaerythritol, pentaerythritol 2-oleate, pentaerythritol 2-stearate, pentaerythritol 1- to 3-substituted derivatives; sorbitan fatty acid esters; erythritol, threose, ribose, arabinose, xylose, lyxose, allose, glucose, and glucose. One or more sugars such as monosaccharides such as mannose, gulose, idose, galactose, talose, fructose, apiose, rhamnose, psicose, sorbose, tagitose, ribulose, xylulose and disaccharides such as sucrose, maltose and lactose; Is mentioned. Among these alcohols (e), when a thermoplastic polymer is intended, a monofunctional alcohol is preferably used, and when a thermosetting polymer is intended, a polyfunctional alcohol is preferably used. Among the alcohols (e), use of ethylene glycol, 1,4-butanediol, trimethylolpropane, glycerol, pentaerythritol and sorbitol is particularly preferred.

The alcohols (e) are not limited to those containing only carbon, hydrogen and oxygen as constituent elements. For example, it may contain a nitrogen element or a sulfur element in addition to the three elements. The nitrogen element-containing alcohol that can be used is not particularly limited. For example, amine-based polyfunctional alcohols such as phenyldiethanolamine, triethanolamine, triisopropanolamine, diethanolamine, diisopropanolamine, and trishydroxymethylaminomethane; Cyanuric acid and the like can be mentioned.

As for the sulfur element-containing alcohol, various bonds containing a sulfur element, for example, C ＝ S bond, C—S
-C bond, SO ₂ bond, SO ₃ bond, SH bond or S
An alcohol having _n bonds (n ≧ 2) or the like can be used. Examples of the sulfur element-containing alcohol that can be used are not particularly limited. Ethyl sulfide, bishydroxyethyl sulfone, N, N-bis (2-hydroxyethyl) taurine and its metal salt, thiodiethanolamine laurylthiopropionate, ethylene oxide adduct of thioethylene glycol, bis (2-hydroxyethyl) bisphenol- S, bis (2-hydroxyethyl) tetrabromobisphenol-S, bis (2-hydroxyethyl) tetramethylbisphenol-S, Scan (2-hydroxyethyl) diphenyl bisphenol -S, bis (2-hydroxyethyl) thio-diphenol and the like.

The weight ratio of the amount of the alcohol (e) to the amount of the vinyl monomer (d) [alcohol (e): vinyl monomer (d)] is preferably from 1:20 to 20: 1
And more preferably 1:10 to 10: 1. The amount of the alcohol (e) is preferably 2 mol times or more, more preferably 50 mol times or more, with respect to the initiator system (f).

Initiator system (f) essentially comprising an organic peroxide
Although there is no particular limitation on the organic peroxide used in the above, for example, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide Ketone peroxides such as oxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane,
1-bis (t-butylperoxy) cyclohexane,
2,2-bis (t-butylperoxy) octane, n-
Peroxyketals such as butyl-4,4-bis (t-butylperoxy) valate, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, di- Isopropyl benzene hydroperoxide, 2- (4-methylcyclohexyl) -propane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide Hydroperoxides such as oxides,
Di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di Dialkyl peroxides such as (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, deca Noyl peroxide, lauroyl peroxide, 3,
5,5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide,
diacyl peroxides such as m-toluyl peroxide, di-isopropyl peroxydicarbonate,
Di-2-ethylhexylperoxydicarbonate, di-n-propylperoxydicarbonate, bis- (4
-T-butylcyclohexyl) peroxydicarbonate, dimyristyl peroxydicarbonate, di-2-
Peroxydicarbonates such as ethylhexylperoxydicarbonate, 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-butyl peroxy maleic acid, t- butyl peroxy isopropyl carbonate,
Peroxyesters such as cumylperoxyoctoate, t-hexylperoxypivalate, t-butylperoxyneohexanoate, t-hexylperoxyneohexanoate, cumylperoxyneohexanoate, 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, one kind may be used alone, or two or more kinds may be used in combination.

Examples of the initiator system (f) essentially comprising an organic peroxide used in the method A include a compound (l) capable of promoting polymerization by combining with an organic peroxide. There are a case where it is used in combination with an oxide and a case where it is used alone with an organic peroxide. Examples of the compound (l) include an organic peroxide decomposition catalyst, a reducing compound that undergoes an oxidation-reduction reaction with an organic peroxide, and a surfactant. That is, an initiator system (f) which essentially requires an organic peroxide.
May be an organic peroxide alone, or an organic peroxide as an essential component, an organic peroxide decomposition catalyst, selected from the group consisting of a reducing compound and a surfactant, polymerization. May be a mixture containing one or more compounds capable of promoting the following. less than,
The compound (l) capable of promoting polymerization by combining with an organic peroxide will be specifically described.

The organic peroxide decomposition catalyst used as the compound (l) is not particularly limited.
Metal halides such as lithium chloride and lithium bromide; metal oxides such as titanium oxide and silicon dioxide; hydrochloric acid, sulfuric acid,
Inorganic acids such as nitric acid, perchloric acid, and hydrobromic acid and their metal salts; carboxylic acids such as formic acid, acetic acid, propionic acid, lacnic acid, isoleic acid, and benzoic acid, and their metal salts and esters; pyridine, indole and its salts And heterocyclic amines such as derivatives, imidazole and its derivatives, and carbazole and its derivatives. These may be used alone or in combination of two or more.

The reducing compound that undergoes an oxidation-reduction reaction with an organic peroxide, which is used as the compound (l), is not particularly limited. For example, organometallic compounds such as ferrocene; iron, copper, nickel, cobalt, etc. Inorganic compounds such as boron trifluoride ether adduct, potassium permanganate, perchloric acid, etc., including inorganic metal compounds capable of generating metal ions; sulfur dioxide, sulfites, mono- or di-alkyl esters of sulfuric acid, sulfuric acid Sulfur-containing compounds such as mono- or di-allyl esters, bisulfites, thiosulfates, sulfoxylates, benzenesulfinic acids and their substituted products, and homologues of cyclic sulfinic acids such as paratoluenesulfinic acid; octyl mercaptan , Decyl mercaptan, dodecyl mercaptan, mercaptoethanol, α-mercap Propionic acid, thioglycolic acid,
Mercapto compounds such as thiopropionic acid, α-thiopropionate sodium sulfopropyl ester, α-thiopropionate 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.

Surfactants used as compound (l) include triethylbenzylammonium chloride, tetraethylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, Lauryl pyridinium,
Trimethylbenzyl ammonium hydroxide, tetramethyl ammonium hydroxide, trimethyl phenyl ammonium bromide, tetramethyl ammonium bromide, tetraethyl ammonium bromide, tetra-n-butyl ammonium bromide, tetra-n-butyl ammonium hydrogen sulfate, N-benzyl Quaternary ammonium salts such as picolinium chloride, tetramethylammonium iodide, tetra-n-butylammonium iodide, N-lauryl-4-picolinium chloride, N-lauryl-4-picolinium chloride; tetrabutylphosphonium chloride A sulfonium salt such as trimethylsulfonium iodide; an onium salt such as;
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 and metal salts of the sulfates Higher fatty acids such as lauric acid and stearic acid and metal salts of these higher fatty acids. These may be used alone or in combination of two or more.

Among the above surfactants, surfactants having hydroxyl groups at both ends, such as a polyoxyethylene-polypropylene oxide block copolymer, are incorporated into a crosslinked structure, and therefore, are not crosslinked. Since there is no adverse effect on toughness, weather resistance and water resistance, no purification or removal is required, which is preferable. The initiator system (f) is not limited to those described above. For example, an organic peroxide, or an organic peroxide and the above compound (l), may be used to form a radical initiator known in the art such as an azo initiator such as AIBN (azobisisobutyronitrile) or hydrogen peroxide. It can be used in combination with an agent.

The amount of the initiator system (f) to be used is naturally determined by the molecular weight of the target acrylic polymer (a). 1
Preferably, it is about 20% by weight. The organic sulfonic acid compound (g) used in the method A is not particularly limited. For example, aliphatic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and octanesulfonic acid; benzenesulfonic acid, benzene Aromatic sulfonic acids such as disulfonic acid, naphthalene sulfonic acid and naphthalenedisulfonic acid, chlorobenzenesulfonic acid, 1-naphthol-4-sulfonic acid, 2-naphthylamine-6-sulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid, etc. Examples include aromatic sulfonic acids and alicyclic sulfonic acids having a nuclear substituent. These may be used alone or in combination of two or more.

Among the above organic sulfonic acid compounds (g), methanesulfonic acid, dodecylbenzenesulfonic acid and the like are particularly preferable. In addition, organic sulfonic acid compounds having surface activity such as dodecylbenzenesulfonic acid, etc.
Especially effective. The preferred amount of the organic sulfonic acid compound (g) is 0.05 to 10% by weight based on the whole polymerization system.
It is.

In the method A, during the reaction, a vinyl monomer (d), an alcohol (e), an initiator system (f) essentially comprising an organic peroxide, an organic sulfonic acid compound ( g) Substantially no use other than the above. Specifically, vinyl monomers (d), alcohols (e),
The components other than the initiator system (f) and the organic sulfonic acid compound (g), each of which is essentially composed of an organic peroxide, are adjusted to be about 10% by weight or less of the whole. And (d), (e),
It is preferable that components other than (f) and (g) be 5% by weight or less, and most preferably (d), (e), (f),
That is, it does not contain any components other than (g).

The polymerization vessel (reactor for performing the polymerization reaction) used in the method A may be a batch type such as a general tank type reactor or a kneader, a tube type of a piston flow, Depending on the viscosity of the polymer, a continuous type such as a twin screw extruder or a continuous kneader may be used. A semi-batch reactor can be used without any problem, but the concentration ratio of each additive in the reactor can be easily controlled by adding each additive in the middle of the tube, and the residence time must be constant. From the viewpoint of good productivity and the like, it is preferable to use a tubular reactor, an extruder, a continuous kneader, or the like. Regarding the proper use of a tubular reactor, an extruder and a continuous kneader, it is preferable to use a tubular reactor for those having a low viscosity after polymerization, and to use an extruder or a continuous kneader for those having a relatively high viscosity after polymerization.

However, a suitable material should be selected for the liquid contact part of these devices.
6, 304L, Teflon, aluminum, glass and the like. Among these, Teflon, aluminum and glass are preferred, and Teflon and glass are most preferred. There are no particular restrictions on the structure of the tube reactor, and there are no particular limitations on the tube reactor known in the art, such as a single tube type, a multi-tube type, or a mixer having no moving parts (manufactured by Noritake Company or Sumitomo Sulzer). It can be used if it is a container,
From the viewpoint of mixing and heat exchange efficiency, it is preferable to use a tubular reactor using a mixer having no moving parts. Similarly, for extruders and continuous kneaders, single-shaft,
A conventionally known extruder such as a twin-screw extruder can be used, but it is preferable to use a twin-screw extruder or a continuous kneader from the viewpoint of mixing and heat exchange efficiency.

In the method A, 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 method A is not particularly limited, and there is no problem as long as it is about room temperature to 200 ° C. at which normal radical polymerization is performed. Next, the method B will be described.

The acrylic polymer (a) obtained by the method B has not only hydroxyl groups at both ends but also two or more hydroxyl groups at at least one end. The vinyl monomer (d) used in the method B is the same as the vinyl monomer (d) used in the above method A. In the method B, the polyfunctional alcohol used in the alcohols (h) which essentially require a polyfunctional alcohol is not particularly limited as long as it is a compound having at least two hydroxyl groups in one molecule. Glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol Alkylene glycols such as 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol and 1,6-hexanediol; hydroquinone dietrol Ethers; ethylene glycol derivatives such as diethylene glycol and triethylene glycol Body; aliphatic polyfunctional alcohols such as sorbitol, cyclohexanediol, xylylene diol; glycerol fatty acid esters such as glycerol and monoacetin, monolaurin, monoolein, monopalmitin, monostearin, glycerol monoallyl ether, thymil alcohol, glycerol monomethyl ether Glycerol mono-substituted derivatives such as glycerol monoether such as batyl alcohol; trimethylolpropane and its mono-substituted derivatives; pentaerythritol and pentaerythritol 2-oleate, pentaerythritol 2-stearate and pentaerythritol 2-substituted derivatives; sorbitan fatty acid esters; Erythritol, threose, ribose, arabinose, xylose, Monosaccharides such as xose, allose, artose, glucose, mannose, gulose, idose, galactose, talose, fructose, apiose, rhamnose, psicose, sorbose, tagitose, ribulose, xylulose, and disaccharides such as sucrose, maltose, lactose, etc. Is mentioned. Among these, the use of ethylene glycol, 1,4-butanediol, trimethylolpropane, glycerol, pentaerythritol and sorbitol is preferred.

The polyfunctional alcohol is not limited to those containing only carbon, hydrogen and oxygen as constituent elements. For example, it may contain a nitrogen element or a sulfur element in addition to the three elements. The nitrogen-functional polyfunctional alcohol that can be used is not particularly limited, and examples thereof include amine polyfunctional alcohols such as phenyldiethanolamine, triethanolamine, triisopropanolamine, diethanolamine, diisopropanolamine, and trishydroxymethylaminomethane; Trishydroxycyanuric acid and the like can be mentioned.

As for the polyfunctional alcohol containing a sulfur element, a polyfunctional alcohol having various bonds containing a sulfur element, for example, a C ＝ S bond, a C—S—C bond, an SO ₂ bond, an SO ₃ bond, or the like is used. Can be. However, in the method B, a polyfunctional alcohol having an SH bond or a _Sn bond (n ≧ 2) cannot be used. that is,
For the following reasons. SH bond and _Sn bond (n ≧ 2)
Since it has high reactivity to radicals, the chain transfer constant is large, and a chain transfer reaction is likely to occur. This is because it is very difficult to introduce hydroxyl groups into both ends of the polymer and to introduce two or more hydroxyl groups into at least one end. Furthermore, SH bonds and _Sn bonds are easily oxidized by hydrogen peroxide, and hydrogen peroxide is wasted, resulting in a decrease in the polymerization rate and an increase in the molecular weight.

[0056] As the sulfur element-containing polyfunctional alcohols which can be used, so long as it does not have any SH bond and S _n bond (n ≧ 2), is not particularly limited, for example, thiodiethylene glycol, ethylenebis -2 −
Hydroxyethyl sulfide, bishydroxyethyl sulfone, N, N-bis (2-hydroxyethyl) taurine and its metal salt, lauryl thiopropionic acid thiodiethanolamine salt, ethylene oxide adduct of thioethylene glycol, bis (2-hydroxyethyl) bisphenol -S, bis (2-hydroxyethyl) tetrabromobisphenol-S, bis (2-hydroxyethyl)
Tetramethylbisphenol-S, bis (2-hydroxyethyl) diphenylbisphenol-S, bis (2-
(Hydroxyethyl) thiodiphenol and the like.

As the polyfunctional alcohol, only one kind may be used, or a plurality of kinds may be used in combination. To adjust the solubility of the polyfunctional alcohol and the viscosity of the polymerization system,
It is also possible to add a monofunctional alcohol having only one hydroxyl group in the molecule. However, in this case, the amount of the monofunctional alcohol to be added is preferably less than 50% by weight in the alcohols (h) in which the polyfunctional alcohol is essential.

The polyfunctional alcohol can be used in the reaction system as an aqueous solution. In this case, the concentration of the aqueous solution is not particularly limited. However, considering the control of the molecular weight of the polymer and the control of the reaction temperature, the concentration of the polyfunctional alcohol aqueous solution is preferably 50% by weight or more. As the initiator system (i) which essentially requires hydrogen peroxide used in the method B, a compound (m) capable of promoting polymerization by combining with hydrogen peroxide is used in combination with hydrogen peroxide; A case where hydrogen peroxide is used alone is exemplified. Hydrogen peroxide is
It can be used as an industrially available aqueous solution, and its concentration is not particularly limited. Examples of the compound (m) include a hydrogen peroxide decomposition catalyst, a reducing compound that undergoes an oxidation-reduction reaction with hydrogen peroxide, and a surfactant. That is, the initiator system (i) which essentially requires hydrogen peroxide is either hydrogen peroxide alone or hydrogen peroxide as an essential component, from a hydrogen peroxide decomposition catalyst, a reducing compound and a surfactant. It is a mixture selected from the group consisting of one or more compounds capable of promoting polymerization. Hereinafter, the compound (m) capable of promoting polymerization by combining with hydrogen peroxide will be specifically described.

The hydrogen peroxide decomposition catalyst used in the method B is not particularly limited. Examples thereof include metal halides such as lithium chloride and lithium bromide; metal oxides such as titanium oxide and silicon dioxide; hydrochloric acid, sulfuric acid, Nitric acid, perchloric acid,
Inorganic acids such as hydrobromic acid and metal salts thereof; alkylbenzenesulfonic acids and metal salts thereof such as benzenesulfonic acid and p-toluenesulfonic acid; Acids and metal salts and esters thereof; pyridine, indole and derivatives thereof, imidazole and derivatives thereof, and heterocyclic amines such as carbazole and derivatives thereof.

Examples of the compound that undergoes a redox reaction with hydrogen peroxide used in the method B include organometallic compounds such as ferrocene; and inorganic metal compounds capable of generating metal ions such as iron, copper, nickel and cobalt in water. Inorganic compounds such as boron trifluoride ether adduct, potassium permanganate, perchloric acid; sulfur dioxide, sulfite, mono- or di-alkyl esters of sulfuric acid, mono- or di-allyl esters of sulfuric acid, Sulfur-containing compounds such as sulfites, thiosulfates, sulfoxylates, benzenesulfinic acid and its substituted products, and homologues of cyclic sulfinic acids such as paratoluenesulfinic acid; octylmercaptan, decylmercaptan, dodecylmercaptan, mercaptoethanol, α -Mercaptopropionic acid, thioglycolic acid, thiopropionic acid Acid, α-thiopropionate sodium sulfopropyl ester, α-thiopropionate sodium sulfoethyl ester and other mercapto compounds, hydrazine, β-hydroxyethylhydrazine, nitrogen-containing compounds such as hydroxylamine, formaldehyde, acetaldehyde, propionaldehyde, n-
Aldehydes such as butyraldehyde, isobutyraldehyde and isovalerian aldehyde, ascorbic acid and the like can be mentioned.

The surfactant used in the method B includes:
Triethylbenzylammonium chloride, tetraethylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, N-laurylpyridinium chloride, trimethylbenzylammonium hydroxide, tetramethylammonium hydroxide, odor Trimethylphenylammonium bromide, tetramethylammonium bromide, tetraethylammonium bromide, tetra-n-butylammonium bromide, tetra-n-butylammonium hydrogen sulfate,
N-benzylpicolinium chloride, tetramethylammonium iodide, tetra-n-butylammonium iodide, N-lauryl-4-picolinium chloride, N
Quaternary ammonium salts such as lauryl-4-picolinium chloride; phosphonium salts such as tetrabutylphosphonium chloride; sulfonium salts such as trimethylsulfonium iodide; onium salts such as; or p-toluenesulfonic acid, dodecylbenzenesulfone Alkylbenzene sulfonic acids such as acids and metal salts thereof; 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 and metal salts of the sulfates Lauric acid, stearic acid and other higher fatty acids, and metal salts of these higher fatty acids.
One type may be used, or a plurality of types may be used.

Among the above-mentioned surfactants, surfactants containing alkylbenzenesulfonic acid, onium salts, and phosphorus are preferred because they have an effect of promoting the decomposition of hydrogen peroxide in addition to the surface activity. Particularly, dodecylbenzenesulfonic acid is more preferred. In addition, a surfactant having a hydroxyl group at both ends itself, such as a polyoxyethylene-polypropylene oxide block copolymer, is incorporated into a crosslinked structure, so that the crosslinked product has toughness, weather resistance, and water resistance. Since no adverse effect is exerted, purification and removal are not required, which is preferable.

In the method B, during the reaction, a vinyl monomer (d), an alcohol (h) which essentially requires a polyfunctional alcohol, and an initiator system (i) which essentially requires hydrogen peroxide are placed in a reactor.
Substantially do not use anything other than Specifically, the components other than the vinyl monomer (d), the alcohol (h) which essentially requires a polyfunctional alcohol, and the initiator system (i) which essentially requires hydrogen peroxide are 10% by weight or less of the whole. To the extent. The components other than (d), (h) and (i) are preferably 5% by weight or less, and most preferably contain no components other than (d), (h) and (i). It is.

The polymerization vessel (reactor for conducting the polymerization reaction) used in the method B is the same as that used in the method A. The polymerization pressure and temperature in the method B are the same as those in the method A. Next, the method C will be described.

The vinyl monomer (d) used in the method C
Is the same as the vinyl monomer (d) used in the above methods A and B. Specific examples of the compound (j) represented by the general formula (I) include, but are not particularly limited to, for example, bis (hydroxymethyl) disulfide, bis (hydroxymethyl) trisulfide, bis (hydroxymethyl) tetrasulfide , Bis (hydroxymethyl) pentasulfide, bis (2-hydroxyethyl) disulfide, bis (2-hydroxyethyl)
Trisulfide, bis (2-hydroxyethyl) tetrasulfide, bis (2-hydroxyethyl) pentasulfide, bis (3-hydroxypropyl) disulfide, bis (3-hydroxypropyl) trisulfide,
Bis (3-hydroxypropyl) tetrasulfide, bis (2-hydroxypropyl) disulfide, bis (2
-Hydroxypropyl) trisulfide, bis (2-hydroxypropyl) tetrasulfide, bis (4-hydroxybutyl) disulfide, bis (4-hydroxybutyl) trisulfide, bis (4-hydroxybutyl)
Hydroxyalkyldi, tri, tetra or pentasulfides such as tetrasulfide, bis (8-hydroxyoctyl) disulfide, bis (8-hydroxyoctyl) trisulfide, bis (8-hydroxyoctyl) tetrasulfide and ethylene oxide addition thereof Product or propylene oxide adduct; 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,
Di, such as 2'-trithiodibenzoic acid, 2,2'-tetrathiodibenzoic acid, 2,2'-dithiodinicotinic acid, 2,2'-trithiodinicotinic acid, and 2,2'-tetrathiodinicotinic acid; Di (2-hydroxyethyl) ester (ethylene oxide adduct) or di (hydroxypropyl) ester (propylene oxide adduct) of tri- or tetrasulfidedicarboxylic acids, and the like,
These can be used alone or in combination of two or more.

The radical polymerization initiator (k) used in the method C is not particularly restricted but includes, for example, isobutyryl peroxide, cumyl peroxy neodecanoate, diisopropyloxydicarbonate, di (n-
Propyl) peroxy dicarbonate, di (2-ethoxyethyl) peroxy dicarbonate, di (2-ethylhexyl) peroxy dicarbonate, t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-hexyl peroxypivalate, t
-Butylperoxypivalate, 3,3,5-trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, cumylperoxyoctate, succinic peroxide, acetyl peroxide,
t-butyl peroxy (2-ethyl hexanate), m
-Toluoyl peroxide, benzoyl peroxide,
t-butylperoxyisobutyrate, 1,1'-bis (t-butylperoxy) cyclohexane, t-butylperoxymaleic acid, t-butylperoxylaurate, cyclohexanone peroxide, t-butylperoxyisopropyl Carbonate, 2,5-dimethyl-
2,5-di (benzoylperoxyhexane, t-butylperoxyacetate, 2,2'-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4'-bis (T-butylperoxy) valerate, di- (t-butylperoxy) isophthalate, 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-butyl peroxide, p-menthanehydroperoxide, 2,5- Dimethyl-2,5-di (t-butylperoxy) hexyne-3,1,1,3,
Organic peroxides such as 3, -tetramethylbutyl hydroperoxide, cumene hydroperoxide and t-butyl hydroperoxide; inorganic peroxides such as hydrogen peroxide, potassium persulfate, sodium persulfate and ammonium persulfate; , 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) iso Butyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2'-azobis (2-amidino Propane) 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,
Azo compounds such as 2'-azobis (2-cyanopropanol); hydrogen peroxide-Fe (II) salt, persulfate-sodium bisulfite, cumene hydroperoxide-Fe (I
I) Redox initiators such as salts and benzoyl peroxide-dimethylaniline; diacetyl, dibenzyl,
Examples thereof include photosensitizers such as acetophenone. Among them, only one type may be used, or two or more types may be used in combination.

In the method C, during the reaction, the molar ratio of the compound (j) and the radical polymerization initiator (k) ((j)
/ (K)) must always be 50 or more, more preferably 60 or more, and most preferably 100 or more. In the method C, components other than the compound (j), the vinyl monomer (d) and the radical polymerization initiator (k) are not substantially used in the polymerization process. Specifically, compound (j), vinyl monomer (d)
In addition, components other than the radical polymerization initiator (k) are adjusted to be about 10% by weight or less of the whole. And
The components other than (j), (d) and (k) are preferably 5% by weight or less, and most preferably not used at all.

In the polymerization process of the method C, during the polymerization, the molar ratio ((j) / (k)) of the compound (j) and the radical polymerization initiator (k) in the reactor is always 50 or more. As long as there is a certain method, any polymerization method may be used. For example, the compound (j), the vinyl monomer (d) and the radical polymerization initiator (k) may be charged at once from the beginning to carry out the polymerization, or the polymerization may be carried out while supplying each component to the polymerization system as needed. May be performed. First, at least a part of the required amount of the compound (j) is charged in a polymerization vessel in advance,
The polymerization may be carried out by feeding (feeding) the vinyl monomer (d) and the radical polymerization initiator (k) and, in some cases, the remaining amount of the compound (j).
In this case, considering the operability, it is preferable to supply the radical polymerization initiator (k) as a solution of the vinyl monomer (d). It is preferable to use an initiator which is sufficiently soluble in the monomer (d). When the initiator (k) is hardly soluble in the vinyl monomer (d), a solvent may be used in combination as long as the object of the present invention is not impaired. At this time, if the vinyl monomer (d) and the radical polymerization initiator (k) are continuously supplied to the compound (j), the polymerization reaction becomes milder and the control is extremely controlled. Easier to do. However, the supply of the vinyl monomer (d) and the radical polymerization initiator (k) into the compound (j) may be intermittent.

In the method C, the amount ratio of the compound (j) and the vinyl monomer (d) to be used is not particularly limited. In order to further reduce the decrease in the number of terminal hydroxyl groups Fn (OH) per polymer molecule due to a side reaction of directly adding to the vinyl monomer (d) to initiate polymerization without adding the vinyl monomer, It is preferable that the amount of the compound (j) is larger than that of the compound (d). More specifically, the weight ratio of the compound (j) to the vinyl monomer (d) (compound (j) / vinyl monomer (d)) is preferably 0.5 or more, and 1.0 or more. More preferably, it is the above.

The polymerization vessel (reactor for performing the polymerization reaction) used in the method C is the same as that used in the above methods A and B. The polymerization pressure and temperature in the method C are the same as those in the methods A and B described above.

[0071]

The resin composition containing an acrylic polymer (a) having hydroxyl groups at both ends and a polyisocyanate (b) is further mixed with a low molecular weight compound (c) having two or more active hydrogens in one molecule. When added, the viscosity of the resin composition is reduced to enable high solidification, and the drying property of the resin composition is improved, and the resin obtained from the resin composition is
The toughness, elastomeric properties, solvent resistance, etc. in stress-strain characteristics are improved.

The toughness of the resin obtained from the resin composition is improved because the addition of the low molecular weight compound (c) increases the active hydrogen and increases the crosslinking density while maintaining the distance between crosslinking points. It is estimated to be. The improvement in the elastomeric properties of the resin is due to the appropriate reaction of the low molecular weight compound (c) having two or more suitable active hydrogens in one molecule to obtain an appropriate morphology and a micro phase-separated block polymer. It is presumed that such a structure is made to some extent.

It is presumed that the reason why the solvent resistance of the resin is improved is that the addition of the low molecular weight compound (c) increases the active hydrogen and increases the crosslink density. It is presumed that the reason why the viscosity of the resin composition decreases is that the low molecular weight compound (c) serves as a reactive diluent. It is presumed that the drying property of the resin composition is improved because the low molecular weight compound (c) having two or more active hydrogens in one molecule has higher activity than the polymer having active hydrogen. . The reason why the compound (c) has a higher activity than the polymer having active hydrogen is simply because the viscosity of the low molecular weight compound (c) is low, or is it due to steric hindrance of the polymer having active hydrogen itself? It is not clear if this is for any other reason.

When the low molecular weight compound (c) having a functional group is used, the functional group can be easily introduced into the resin structure. Since the resin composition contains the acrylic polymer (a), the resin obtained from the resin composition has high heat resistance, wet resistance, weather resistance, light resistance, and the like. In the present invention, the acrylic polymer (a) having a number average molecular weight of 1,000 or more is used. If the number average molecular weight is less than 1,000, elongation of the resin obtained from the composition is reduced.

[0075]

EXAMPLES Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. In the following examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. And producing a polymer by the production examples described below manufacture of the polymer.

-Production Example A- 160 parts of ethylene glycol was charged into a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser, and the atmosphere in the flask was replaced with nitrogen. The temperature was raised to 140 ° C. After the temperature in the reaction vessel was stabilized, a mixed solution obtained by dissolving 4.4 parts of cyclohexanone peroxide in 48 parts of butyl acrylate and 72 parts of methyl methacrylate, and 2.
After a mixture of 0 parts and 40 parts of ethylene glycol was added dropwise over 1 hour, stirring was continued at 140 ° C. for 10 minutes to complete the polymerization. The polymerization rate was determined by gas chromatogram from the residual rates of butyl acrylate and methyl methacrylate to be 92%.

Subsequently, the polymer was extracted and separated from the reaction mixture using a toluene / water extraction solvent to obtain a toluene solution containing the polymer. The purified polymer A was obtained by distilling off toluene and further drying under reduced pressure at 45 ° C. Number average molecular weight (Mn) of polymer A after purification
Was 7500 as a result of measurement by standard polystyrene conversion method using gel permeation chromatography (GPC). Further, the average number of terminal hydroxyl groups (Fn (O
H)) was 4.4 (mol / mol of polymer) as a result of calculation based on the OH value 33 determined according to JIS-K-1557 and the value of the number average molecular weight measured above. .

-Production Example B- A flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser was charged with 80 parts of ethylene glycol, and the inside of the flask was purged with nitrogen. The temperature was raised to 140 ° C. After the temperature in the reaction vessel was stabilized, a mixed solution obtained by dissolving 2.0 parts of dodecylbenzenesulfonic acid in 48 parts of butyl acrylate and 72 parts of methyl methacrylate, and 5.3 parts of a 60% by weight hydrogen peroxide solution After the mixture with 40 parts of ethylene glycol was added dropwise over 1 hour, stirring was continued at 140 ° C. for 10 minutes to complete the polymerization. The polymerization rate was determined from the residual rates of butyl acrylate and methyl methacrylate by gas chromatography, and was found to be 95%.

Subsequently, the polymer was extracted and separated from the reaction mixture using a toluene / water extraction solvent to obtain a toluene solution containing the polymer. The toluene was distilled off, and the polymer was further dried at 45 ° C. under reduced pressure to obtain a purified polymer B. Number average molecular weight (Mn) of polymer B after purification
Was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
Met. Further, the average number of terminal hydroxyl groups (Fn
(OH)) is an O determined according to JIS-K-1557.
As a result of calculation based on the H value of 20 and the value of the number average molecular weight measured above, it was 3.9 (mol / mol of polymer).

-Production Example C- In a flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser, 234 parts of 2-hydroxyethyl disulfide (compound (j)) is charged, and nitrogen gas is slowly added. Heated to 100 ° C. while blowing. There, 2.50 parts of 2,2'-azobisisobutyronitrile (hereinafter abbreviated as "AIBN") (radical polymerization initiator (k)) were added with 63 parts of butyl acrylate and 103 parts of methyl methacrylate. What was dissolved in a part was dripped over 2 hours and 30 minutes. During the dropwise addition, the polymerization temperature was maintained at 105 ± 5 ° C. Compound (j) in the flask at the end of the dropping
And the molar ratio (= (j) / (k)) of the initiator (k) is 10
It was 0.

After completion of the dropping, stirring was continued at the same temperature for 1 hour and 30 minutes to complete the polymerization, thereby obtaining a dispersion of the polymer C. The polymerization rate calculated from the solid concentration of this dispersion is 90.
%Met. 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, and thus polymer C was purified.

Number average molecular weight (Mn) of polymer C after purification
Was 5,000 as a result of measurement with a vapor pressure molecular weight analyzer (VPO). The average number of terminal hydroxyl groups (Fn (OH)) of the polymer C was calculated based on the OH value 22 obtained according to JIS-K-1557 and the value of the number average molecular weight. 0 (mol / mol of polymer).

-Production Example D- A flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser was charged with 153 parts of 2-hydroxyethyl disulfide (compound (j)), and nitrogen gas was slowly added. Heated to 100 ° C. while blowing. A solution obtained by dissolving 1.64 parts of AIBN (radical polymerization initiator (k)) in 64 parts of butyl acrylate was added dropwise thereto over 30 minutes. During the dropwise addition, the polymerization temperature was maintained at 105 ± 5 ° C. The molar ratio (= (j) / (k)) between the compound (j) and the initiator (k) in the flask at the end of the dropping is 100
Met.

After completion of the dropwise addition, stirring was continued at the same temperature for another 30 minutes to complete the polymerization, whereby a dispersion of Polymer D was obtained. The polymerization rate calculated from the solid content concentration of this dispersion was 96%. Subsequently, the dispersion was transferred to a separating funnel, 100 parts of toluene was added, and the mixture was shaken well, and then allowed to stand for a while to remove a lower layer (2-hydroxyethyl disulfide) separated from two phases. Thereafter, the toluene layer was washed three times with 200 parts of ion-exchanged water. Then, 50 parts of sodium sulfate was 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 D.

Number average molecular weight (Mn) of purified polymer D
Was 3600 as measured by a vapor pressure molecular weight analyzer (VPO). Further, the average number of hydroxyl groups of the polymer D was 3 based on an OH number of 3 determined according to JIS-K-1557.
As a result of calculation based on 1 and the value of the number average molecular weight,
2.0 (mol / mol of polymer). -Production Example E-A flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser was charged with 100 parts of toluene,
The mixture was heated to 110 ° C. while gently blowing nitrogen gas into a reflux state. A solution obtained by dissolving 2.0 parts of AIBN (radical polymerization initiator (k)) in 38.4 parts of butyl acrylate, 54.0 parts of methyl methacrylate, and 7.6 parts of 2-hydroxyethyl methacrylate was added. It was added dropwise over 2 hours. During the dropwise addition, the polymerization temperature was maintained at 110 ± 5 ° C.

After completion of the dropwise addition, stirring is continued at the same temperature.
After 1 hour and 2 hours, 0.2 parts each of AIBN (radical polymerization initiator (k)) was added as a post-catalyst, and the mixture was further stirred for 2 hours to complete the polymerization, thereby obtaining a dispersion of Polymer E. . The polymerization rate calculated from the solid content concentration of this dispersion is 97
%Met. Subsequently, the toluene and the remaining monomer in this dispersion were distilled off with an evaporator to purify the polymer E.

Number average molecular weight (Mn) of polymer E after purification
Was 5700 as measured by a vapor pressure molecular weight analyzer (VPO). The average number of hydroxyl groups of the polymer E was 2 based on an OH value of 2 determined according to JIS-K-1557.
As a result of calculation based on 9 and the value of the number average molecular weight,
It was 2.9 (mol / mol of polymer). -Production Example F-A flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser was charged with 100 parts of toluene,
The mixture was heated to 110 ° C. while gently blowing nitrogen gas into a reflux state. There, 3.60 parts of AIBN (radical polymerization initiator (k)) were added to 38.5 parts of butyl acrylate.
Part, methyl methacrylate 56.3 parts and methacrylic acid 2-
What was dissolved in 5.2 parts of hydroxyethyl was added dropwise over 2 hours. During the dropwise addition, the polymerization temperature was maintained at 110 ± 5 ° C.

After completion of the dropwise addition, stirring was continued at the same temperature.
After 1 hour and 2 hours, 0.24 parts of perhexa 3M (radical polymerization initiator (k)) was added as a post-catalyst, and the mixture was further stirred for 5 hours to complete the polymerization, thereby obtaining a dispersion of polymer F. Was. The polymerization rate calculated from the solid content of this dispersion was 98%. Subsequently, the toluene and residual monomers in this dispersion were distilled off with an evaporator to purify the polymer F.

Number average molecular weight (Mn) of polymer F after purification
Was 4300 as measured by a vapor pressure molecular weight analyzer (VPO). Further, the average number of hydroxyl groups of the polymer F is an OH number of 2 determined according to JIS-K-1557.
As a result of calculation based on 0 and the value of the number average molecular weight,
It was 1.7 (mol / mol of polymer). -Production Example G-A flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser was charged with 65 parts of xylene, and heated to 140 ° C while gently blowing nitrogen gas,
Refluxed. A solution obtained by dissolving 3.60 parts of AIBN (radical polymerization initiator (k)) in 87.0 parts of butyl acrylate and 13.0 parts of 2-hydroxyethyl methacrylate was added dropwise thereto over 4 hours. During the dropwise addition, the polymerization temperature was kept at 140 ± 5 ° C.

After completion of the dropwise addition, stirring is further continued at the same temperature.
After 1 hour and 2 hours, 0.30 parts of perhexa 3M (radical polymerization initiator (k)) was added as a post-catalyst, and the mixture was further stirred for 6 hours to complete the polymerization to obtain a dispersion of polymer G. Was. The polymerization rate calculated from the solid content of this dispersion was 98%. Subsequently, xylene and residual monomers in the dispersion were distilled off with an evaporator to purify the polymer G.

Number average molecular weight (Mn) of polymer G after purification
Was 2300 as measured by a vapor pressure molecular weight analyzer (VPO). The average number of hydroxyl groups of the polymer G was determined by the OH value of 5 determined according to JIS-K-1557.
As a result of calculation based on 6 and the value of the number average molecular weight,
2.3 (mol / mol of polymer). -Production Example H-A flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser was charged with 32 parts of xylene and 33 parts of butyl acetate, and heated to 130 ° C while gently blowing nitrogen gas. Refluxed. There, 34.4 parts of butyl acrylate, 46.2 parts of methyl methacrylate, 19.3 parts of 2-hydroxyethyl acrylate and 0.1 part of acrylic acid were added to 2,2'-azobis-2-methylbutyronitrile. A solution of 5.0 parts of (radical polymerization initiator (k)) was added dropwise over 4 hours. During the dropwise addition, the polymerization temperature was kept at 130 ± 5 ° C.

After completion of the dropwise addition, stirring was continued at the same temperature.
After 1 hour and 2 hours, 0.2 parts of Perhexa 3M (radical polymerization initiator (k)) was added as a post-catalyst, and the mixture was further stirred for 5 hours to complete the polymerization, thereby obtaining a dispersion of Polymer H. Was. The polymerization rate calculated from the solid concentration of this dispersion was 99%. Subsequently, xylene, butyl acetate and residual monomers in this dispersion were distilled off with an evaporator,
Polymer H was purified.

Number average molecular weight (Mn) of polymer H after purification
Was 3,000 as a result of measurement with a vapor pressure molecular weight analyzer (VPO). The average number of hydroxyl groups of the polymer H was 9 based on an OH value of 9 determined according to JIS-K-1557.
As a result of calculation based on 4 and the value of the number average molecular weight,
It was 5.0 (mol / mol of polymer). Preparation and performance of thermosetting resin composition and resin film
Evaluation The following Examples 1 to 5 and Comparative Examples 1 to 10 were performed using the polymer produced above.

-Example 1- 4 parts of dioxane was added to a flask, and 10 parts of a 50% solution of polymer A in toluene was further added and stirred well. Next, ethylene glycol (E
G) 0.20 part was added and stirred well. Thereafter, in order to obtain a thermosetting resin composition and a resin film, Sumidur N-3500 (trimer of hexamethylene diisocyanate, manufactured by Sumitomo Bayer Urethane Co., Ltd.), which is a trifunctional isocyanate, is used as a polyisocyanate in NCO / O.
An amount by which the molar ratio of H was 1.1 was added, and 0.5 part of a 0.1% toluene solution of dibutyltin dilaurate was further added as a catalyst, and the mixture was stirred well to obtain a resin composition.

After transferring the resin composition to a petri dish, the petri dish was placed in a hot-air dryer in which humidity was kept low, and
After leaving at 0 ° C. for 8 hours, baking was performed at 80 ° C. for 3 hours to prepare a resin film. -Examples 2 to 5 and Comparative Examples 1 to 10-In Example 1, the same operation as in Example 1 was performed except that the type of the polymer and the type and amount of the low molecular weight polyol were as shown in Table 1 below. As a result, a resin composition was obtained, and a resin film was prepared from the composition. However, Comparative Examples 1 to 6
Did not use any low molecular weight polyols.

The above Examples 1 to 5 and Comparative Examples 1 to 10
The strength-elongation characteristics and the solvent resistance of the resin film obtained in the above were examined by the following methods. Strength-elongation characteristics
Evaluation was made by pulling the film by hand. Solvent resistance is measured by dropping a few drops of MEK (methyl ethyl ketone) on the film and examining changes (whitening, roughness, etc.) on the film surface.
Those that changed immediately after dropping were evaluated as “x”, those that changed after 24 hours were evaluated as “Δ”, and those that did not change after 24 hours were evaluated as “「 ”.

The results were as follows. Example 1 A tough film having high elongation and strength, improved elastomeric properties, and solvent resistance of “○”. Example 2 A tough film with high elongation and strength, improved elastomeric properties, and solvent resistance of “「 ”.

Example 3 A tough film having both large elongation and strength was obtained, and the solvent resistance was “○”. Example 4 A film having greatly improved strength, and the solvent resistance was “○”. Example 5: A film whose strength was greatly improved, and the solvent resistance was “○”.

Comparative Example 1 A very stretched film, and the solvent resistance was “Δ”. Comparative Example 2 ... A very stretched film, and the solvent resistance was "x". Comparative Example 3 is a very stretchy soft film,
The solvent resistance was "x". Comparative Example 4 ... A brittle film with low elongation and high strength, and the solvent resistance was "△".

Comparative Example 5: A film having some elongation but low strength, and having a solvent resistance of "x". Comparative Example 6: The film was small in elongation, high in strength, hard and brittle, and the solvent resistance was “○”. Comparative Example 7: The film was hardly stretched and was a brittle film having a large strength, and the solvent resistance was “○”.

Comparative Example 8: The film was hardly stretched and was a brittle film having high strength, and the solvent resistance was “○”. Comparative Example 9: A hard film having a large strength, and the solvent resistance was “」 ”. Comparative Example 10: A hard film having high strength, and the solvent resistance was “○”. The stress-strain characteristics of the resin films obtained from the resin compositions of Examples 1 and 3 and the resin films obtained from the resin compositions of Comparative Examples 1, 4, 6, 7 and 8 were examined by the following method. Was.

The resin composition was applied on a release paper with an applicator, placed in a hot air drier with low humidity, left at 30 ° C. for 8 hours, and baked at 80 ° C. for 3 hours to obtain a resin film. Obtained. Put this film in dumbbell shape 2
A test piece was prepared by punching out the sample into a shape, and a tensile tester (Model 118 manufactured by Instron) was used for the test piece.
The stress-strain characteristics were measured using 5). The tensile measurement conditions at that time were as follows: tensile speed = 10 mm / min, load =
5 kgwt, temperature = 25 ° C., relative humidity = 60%.

The results are shown in FIG. In this figure, the values in parentheses are the film thicknesses. As shown in FIG.
The resin films obtained from the resin compositions of Examples 1 and 3 were compared with those of Comparative Examples 1, 4, 6, 7, and 8,
It was confirmed that the toughness was excellent. Preparation and performance of thermoplastic resin composition and resin film
Evaluation The following Example 6 and Comparative Examples 11 to 12 were performed using the polymer produced above.

Example 6 N, N-Dimethylformamide (DMF) 2 was added to a flask.
, And 10 parts of a 50% solution of polymer D in toluene were added, followed by thorough stirring. Next, 0.24 parts of 1,4-butanediol (BD) was added as a low molecular weight polyol, and the mixture was stirred well. Thereafter, in order to obtain a thermoplastic resin composition and a resin film, Desmodur H (hexamethylene diisocyanate, manufactured by Sumitomo Bayer Urethane Co., Ltd.), which is a bifunctional isocyanate, is used as a polyisocyanate at an NCO / OH molar ratio of 1.05. Add as much as possible, and add 0.1 ml of dibutyltin dilaurate as a catalyst.
A resin composition was obtained by adding 0.5 part of a 1% toluene solution and stirring well.

After the resin composition was transferred to a petri dish, the petri dish was placed in a hot-air dryer in which the humidity was kept low, and
After leaving at 0 ° C. for 8 hours, baking was performed at 80 ° C. for 3 hours to prepare a resin film. -Comparative Example 11- In Example 6, the low molecular weight polyol 1,4-
A resin composition was obtained in the same manner as in Example 6 except that butanediol (BD) was not used at all, and a resin film was prepared from this composition.

Comparative Example 12 In Example 6, a 50% solution of polymer D in toluene 10
In the same manner as in Example 6 except that 10 parts of a 50% solution of a polymer G in toluene was used instead of parts and the amount of 1,4-butanediol (BD) as a low molecular weight polyol was changed to 0.45 parts. By performing the operation of, to obtain a resin composition,
A resin film was prepared from this composition.

With respect to the resin films produced in Example 6 and Comparative Examples 11 to 12, the strength-elongation characteristics and the solvent resistance were examined in the same manner as described above. The results were as follows. Example 6 A thermoplastic elastomeric film was formed. The solvent resistance was “○”.

Comparative Example 11: Only a very weak film having tackiness (adhesion) was formed. The solvent resistance was "x". Comparative Example 12: Gelled. The solvent resistance was “○”.

[0109]

[Table 1]

[0110]

The resin composition according to the present invention has a low viscosity so that it can be made into a high solid, and has high drying properties and good workability. From this resin composition, a resin having excellent heat resistance, wet resistance, weather resistance, and light resistance, as well as excellent toughness in stress-strain characteristics, elastomeric properties, solvent resistance, and the like can be obtained. Further, a low molecular weight compound (c) which is an essential component of the resin composition
When a compound having a functional group is used, the functional group can be easily introduced into the resin structure.

The resin composition of the present invention can be suitably used as a raw material for paints, artificial leathers, synthetic leathers, etc. by utilizing the properties of the acrylic polymer (a) contained as an essential component. Elastic wall material, floor material, waterproof coating material, adhesive, tackifier, adhesive, binder, sealing material, urethane foam (hard, semi-hard, soft), urethane RIM, UV / EB cured resin, high solid Paints, thermosetting elastomers, thermoplastic elastomers, various molding materials, microcellular, elastic fibers, fiber processing agents, plasticizers, sound absorbing materials, vibration damping materials, surfactants, gel coating agents,
As raw materials for artificial marble resin, artificial marble impact resistance agent, laminated glass resin, reactive diluent, etc.,
It is very useful as various resin additives and their raw materials.

[Brief description of the drawings]

FIG. 1 shows the results of examining the stress-strain characteristics of the resin films obtained from the resin compositions of Examples 1 and 3, and the resin films obtained from the resin compositions of Comparative Examples 1, 4, 6, 7, and 8. FIG.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroyuki Ikeuchi 5-8 Nishiburi-cho, Suita-shi, Osaka Inside Nippon Shokubai Central Research Institute, Inc. (72) Inventor Fumihide Tamura 5-8, Nishi-Maburi-cho, Suita-shi, Osaka No. Nippon Shokubai Central Research Laboratory Co., Ltd. (56) References JP-A-3-34118 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G08G 18/00-18/87

Claims (4)

(57) [Claims] 1. A resin composition containing an acrylic polymer (a) and a polyisocyanate (b) as essential components, wherein the acrylic polymer (a) has a hydroxyl group at both terminals and has a number average molecular weight of 1000 or more. A resin composition comprising, as an essential component, a low molecular weight compound (c) having two or more active hydrogens in one molecule, in addition to the polymer (a) and (b), which is a polymer. . 2. An acrylic polymer (a) is used for polymerization of a vinyl monomer (d) essentially comprising an acrylic monomer, and an organic peroxide in the presence of an alcohol (e). And an organic sulfonic acid compound (g), and the four components (d), (e),
The resin composition according to claim 1, which is obtained by a method carried out in such a manner that components (f) and (g) are not substantially contained. 3. The acrylic polymer (a) polymerizes a vinyl monomer (d) essentially comprising an acrylic monomer in the presence of an alcohol (h) essentially comprising a polyfunctional alcohol. A method in which an initiator system (i) essentially comprising hydrogen peroxide is used and the reactor is substantially free of components other than the above three components (d), (h) and (i). The resin composition according to claim 1, which is obtained by: 4. An acrylic polymer (a) is used for the polymerization of a vinyl monomer (d) having an acrylic monomer as an essential component by the polymerization of a compound (j) represented by the following general formula (I). In the presence of the radical polymerization initiator (k), the compound (j) is always present in the reactor at 50 mole times or more of the radical polymerization initiator (k) during the reaction. 2. The method according to claim 1, wherein the method is performed by using substantially no other than d), (j), and (k).
The resin composition as described in the above. HO-R ¹ - in ^{(S) x -R 2 -OH ...} (I) [Formula (I), R ¹ and R ² each represent a divalent organic group, x is an integer from 2 to 5. )