JPH04283213A - Polymerizable and curable resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in appearance, curability and shrinkage resistance by mixing a specified block copolymer with a polymerization initiator. CONSTITUTION:98-5 pts.wt. at least one polymerizable unsaturated monomer is polymerized in the presence of 2-95 pts.wt. compound comprising at least one structural unit of formula I [wherein R1 is (cyclo)alkylene; an ester group- containing alkylene or benzene ring(-containing alkylene); R2 and R2' are each (cyano-containing) alkylene, amide bond-containing alkylene or alkylene containing an amide bond and a hydroxyl group] and at least one structural unit of formula II (wherein R3 is a polyol residue) and having a number-average molecular weight of 1500-50000 to obtain a block copolymer (A) comprising an alpha,beta-ethylenically unsaturated polyurethane segment and a vinyl polymer segment. 100 pts.wt. component A is mixed with 0.1-100 pts.wt. polymerization initiator.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a new and useful polymerizable curable resin composition. More specifically, α, α, Obtained by introducing a β-ethylenically unsaturated bond,
The present invention relates to a polymerization-curable resin composition comprising a specific polymerization-curing resin and a polymerization initiator as essential components.

The novel polymerization-curing resin composition of the present invention exhibits revolutionary effects as a polymerization-curing coating resin, and is resistant to heat, oxidation-reduction, ultraviolet rays, X-rays, electron beams, etc. It can be hardened by

0003

[Prior Art] Polymerization-curable resin compositions have so far been produced using alkyd resins, side-chain acroyl type acrylic prepolymers, telomerized polyester acrylates, telomerized polyamide acrylates, or urethane acrylate resins and polymerization initiators. Resin compositions consisting of reactive diluents such as polyfunctional (meth)acrylates and polyfunctional (meth)acrylates are being studied, and resin compositions with a good balance of performance such as high curability, high appearance, flexibility, and low shrinkage are being studied. The reality is that although there are demands for it, we are not necessarily getting what satisfies us.

0004

[Problem to be Solved by the Invention] However, the present inventors, based on the recognition of the current situation, fundamental solutions to various unresolved problems in the prior art, and the earnest needs of the industry, , began earnest research.

[0005] Therefore, the problem to be solved by the present invention is to develop a resin that is highly curable, has an excellent appearance, and exhibits low shrinkage, and is particularly effective as a polymerization-curable coating resin. An object of the present invention is to provide an extremely excellent polymerization-curable resin composition that exhibits the following properties.

[0006]

[Means for solving the problem] Therefore, the present inventors
As a result of intensive studies focused on the problems to be solved by the invention as described above, the general formula [However,
In the formula, R1 is an alkylene group, a cyclic alkylene group, an alkylene group having an ester group, a benzene ring, or an alkylene group containing a benzene ring, and R2 and R2' may be the same or different, respectively. , an alkylene group, an alkylene group containing a cyano group, an alkylene group containing an amide bond, or an alkylene group having both an amide bond and a hydroxyl group. ] and the general formula [However, R3 in the formula represents a polyol residue. ] In the presence of a compound each having at least one structural unit in one molecule,
A composition comprising a resin in which an α,β-ethylenically unsaturated group is introduced into a block copolymer obtained by polymerizing at least one polymerizable unsaturated monomer, and a polymerization initiator. The present invention was completed by discovering that the present invention provides an extremely excellent polymerization-curable resin composition that exhibits high curability and low shrinkage.

[0007] Here, in one molecule, as shown in the above-mentioned general formulas [I] and [II], respectively,
The so-called polymeric azo initiator having both a urethane bond and a diazo bond is a compound having specific structural units represented by these formulas [1] and [2], for example, azobis Azobisalkanol compounds such as cyanopropanol, azobiscyano-n-butanol, azobisisobutanol or azobiscyanopentanol; or “VA-080, VA-08
2 or VA-086” [Wako Pure Chemical Industries, Ltd. product]
It is obtained by reacting a compound having at least one diazo bond and at least two hydroxyl groups in one molecule, such as azoamide polyol, with a polyisocyanate compound and a polyol compound. .

That is, these types of polyurethane type polymeric polyazo initiators include, for example, isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate). ), various diisocyanates such as 1,3-di(isocyanatomethyl)cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylcyclohexane diisocyanate, tolylene diisocyanate or xylene diisocyanate;

Alternatively, a compound having a functional group capable of reacting with each of these diisocyanates and various polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol or dipentaerythritol, or an isocyanate group, for example, , a polyisocyanate compound such as an adduct with an extremely low molecular weight polyester compound having a number average molecular weight of about 500 to 1,500,

[0010] Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol,
1,4-butanediol, 1,3-butanediol, 1
, 6-hexanediol, 3-methyl-1,5-pentadiol, neopentyl glycol, cyclohexanedimethanol, 2-methyl-1,3-propanediol,
2,2-diethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2,2-dimethyl-
3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate, 12-hydroxystearyl alcohol;

or polyethylene glycol, polypropylene glycol or polyhexamethylene glycol, or various di- or polyols such as trimethylolethane, trimethylolpropane, glycerin, pentaerythritol or hydrogenated bisphenol A,

Furthermore, by carrying out an addition condensation reaction of three components such as bisphenol A or polyester polyol and the above-mentioned compound having at least one diazo bond and at least two hydroxyl groups in one molecule. can get.

The number average molecular weight of the above di- or polyol compound is not particularly limited, but from the viewpoint of reactivity, it is preferably 1,500.
It is desirable that the number is up to 1,000, more preferably up to 1,000.

Further, to exemplify only particularly representative polyester polyols, the various di- or polyol compounds as mentioned above,
Various types such as isophthalic acid, terephthalic acid, phthalic acid (anhydride), tetrahydrophthalic acid (anhydrous), hexahydrophthalic acid (anhydrous), trimellitic anhydride, pyromellitic acid, fumaric acid, maleic acid, succinic acid or azopic acid. Ring-opening polymerization of hydroxyl group-containing polyester resins (including oil-modified types) obtained by dehydration condensation with di- or polycarboxylic acids (anhydrides) and/or various lactone compounds such as ε-caprolactone or valerolactone. These are hydroxyl group-containing polyester resins obtained by the following methods, and all of them are obtained by known and commonly used reaction methods.

Here, methods for synthesizing the polymeric azo initiator include a method in which the above three components are simultaneously charged and reacted, and a method in which an isocyanate group-containing polyurethane intermediate (that is, a so-called urethane prepolymer) is first prepared;
Next, there is a method of reacting this with a compound having at least one diazo bond and at least two hydroxyl acids in one molecule, but such a synthesis method is not particularly limited.

[0016] During the reaction of these di- or polyol compounds with di- or polyisocyanate compounds, ethylenediamine, hexamethylenediamine, triethylenetetramine, tetraethylenepentamine, bisaminopropylamine may be used as a chain extender. Of course, various polyamine compounds such as 4-aminomethyl-1,8-diaminooctane may also be used.

Further, as the at least one polymerizable unsaturated monomer mentioned above, styrene, α-methylstyrene, p-ter
Aromatic vinyl monomers such as t-butylstyrene and vinyltoluene;

Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate,
t-Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dibromopropyl (meth)acrylate, tribromophenyl (meth)acrylate or alkoxy Various (meth)acrylates such as alkyl (meth)acrylates;

Diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid and monohydric alcohols; vinyl esters such as vinyl acetate, vinyl benzoate and "Beoba" (vinyl ester manufactured by Shell, Netherlands) Class;

"Viscoat 8F, 8FM, 17FM, 3
F or 3FM” [fluorine-containing acrylic monomer manufactured by Osaka Organic Chemical Co., Ltd.], perfluorocyclohexyl (
(meth)acrylate, such as di-perfluorocyclohexyl fumarate or N-i-propyl perfluorooctane sulfonamide ethyl (meth)acrylate.
Per) Fluorine-containing polymerizable compounds such as vinyl esters, vinyl ethers, (meth)acrylates or unsaturated polycarboxylic acid esters containing a fluoroalkyl group;

Alternatively, vinyl monomers without functional groups such as olefins such as (meth)acrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride or vinylidene fluoride; (meth)acrylamide, dimethyl (meth)acrylamide , N-tert-butyl (meth)acrylamide, N-octyl (meth)acrylamide, diacetone acrylamide, dimethylaminopropylacrylamide, alkoxylated N-methylolated (meth)acrylamide, and amide bond-containing vinyl monomers;

Dialkyl [(meth)acryloyloxyalkyl] phosphates or (meth)acryloyloxyalkyl acid phosphates, dialkyl [(
(meth)acryloyloxyalkyl] phosphites or (meth)acryloyloxyalkyl acid phosphites;

Furthermore, the above-mentioned (meth)acryloyloxyalkyl acid phosphates, alkylene oxide adducts of acid phosphites, epoxy group-containing vinyls such as glycidyl (meth)acrylate and methylglycidyl (meth)acrylate, etc. phosphorus atom-containing vinyl monomers such as ester compounds of phosphoric acid or phosphorous acid or acidic esters thereof, or 3-chloro-2-acid phosphoxypropyl (meth)acrylate;

Dialkylaminoalkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate or diethylaminoethyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-
Hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxy Propyl (meth)acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl monobutyl fumarate,
or polypropylene glycol, or polyethylene glycol mono(meth)acrylate, "Plaxel FM, FA Monomer" [Daicel Chemical Industries, Ltd.]
hydroxyalkyl esters of α,β-ethylenically unsaturated carboxylic acids, such as caprolactone addition monomers manufactured by A.I., or adducts of these with ε-caprolactone;

Unsaturated mono- or dicarboxylic acids such as (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid, as well as monoesters of these dicarboxylic acids and monohydric alcohols; α, β-ethylenically unsaturated carboxylic acids such as, or α, β-ethylenically unsaturated carboxylic acid hydroxyalkyl esters such as those listed above and maleic acid, succinic acid, phthalic acid, hexahydrophthalic acid, tetrahydro Various types of polycarboxylic acids such as phthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, "Himic acid" (a product of Hitachi Chemical Co., Ltd.), adducts of polycarboxylic acids with anhydrides such as tetrachlorophthalic acid or dodecynylsuccinic acid. Unsaturated carboxylic acids, "Cardura E" (glycidyl ester of branched synthetic resin fatty acids manufactured by Shell),
Adducts of monoglycidyl esters or butyl glycidyl ether of monovalent carboxylic acids such as coconut oil fatty acid glycidyl ester or octylic acid glycidyl ester, or monoepoxy compounds such as ethylene oxide or propylene oxide, or adducts thereof with ε-
Adduct with caprolactone;

2-Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3
-Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, di- α,β-unsaturated carboxylic acid hydroalkyl esters such as 2-hydroxyethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate or polyethylene glycol mono(meth)acrylate and maleic acid, succinic acid, phthalic acid, Carboxyl group-containing monomers such as adducts of polycarboxylic acids with anhydrides such as hexahydrophthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, "hymic acid", tetrachlorophthalic acid or dodecynylsuccinic acid ;

Tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, chlorotrifluoroethylene or hexafluoropropylene, or C1 ~
Fluoroolefins such as C18 (per)fluoroalkyl trifluorovinyl ether;

0028
] Methyl vinyl ether, ethyl vinyl ether, n-
butyl vinyl ether, isobutyl vinyl ether, n
- alkyl vinyl ethers such as pentyl vinyl ether, n-octyl vinyl ether or 2-ethylhexyl vinyl ether;

Cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether, methylcyclopentyl vinyl ether or methylcyclohexyl vinyl ether;

[0030]2
-Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxyethyl (meth)acrylate, 2-hydroxybutyl vinyl ether, 4-hydroxybutyl vinyl ether, 6
- hydroxyl group-containing vinyl ethers such as hydroxyhexyl vinyl ether or 2-ethoxyethyl allyl ether;

Vinylethoxysilane, α-methacryloxypropyltrimethoxysilane, trimethylsiloxyethyl (meth)acrylate, “KR-215” or “
These include silicon-based monomers such as "X-22-5002" (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0032] Vinyl type (co) used in the present invention
Polymerization can be carried out by using the various raw material components listed above and by making full use of known and commonly used copolymerization reaction methods.
BN), benzoyl peroxide (BPO), tert
- Radical-generating polymerization catalysts such as butyl perbenzoate (TBPB), tert-butyl hydroperoxide, di-tert-butyl peroxide (DTBPO), or cumene hydroperoxide (CHP), either alone or in combination Of course it's good.

The α,β-ethylenically unsaturated group introduced into the block copolymer referred to herein refers to a (meth)acroyl group, an allyl group, a vinyl ether group, or an unsaturated fatty acid residue. , which is introduced into the acrylic segment and/or urethane segment of the block copolymer.

[0034] In the block copolymer, such α, β
- As a method for introducing an ethylenically unsaturated group, into a block copolymer having a functional group, a polymerizable unsaturated monomer having a functional group that reacts with the functional group of the block copolymer is added to the α , a method is adopted in which the reaction is carried out under conditions that do not deactivate the β-ethylenically unsaturated group.

Specifically, a few particularly typical examples include a method of adding an isocyanate group-containing polymerizable unsaturated monomer such as isocyanate ethyl methacrylate or acyl isocyanate to a hydroxyl group-containing block copolymer. or methyl (meth)acrylate (
A method of transesterification with a meth)acrylic acid ester, or a method of introducing a hydroxyl group-containing polymerizable unsaturated monomer such as β-hydroxyethyl (meth)acrylate using a diisocyanate compound such as hexamethylene diisocyanate as a medium. or (
There are methods such as a dehydrochlorination reaction with an acid chloride such as meth)acrylic acid chloride, and an esterification reaction with a carboxyl group-containing polymerizable unsaturated monomer such as (meth)acrylic acid.

For carboxyl group-containing block copolymers, esterification reactions with hydroxyl group-containing polymerizable unsaturated monomers, epoxy group-containing polymerizable unsaturated monomers,
There are methods such as adding an amino group-containing polymerizable unsaturated monomer or a carbonate group-containing polymerizable unsaturated monomer.

Furthermore, to the epoxy group-containing block copolymer, there is a method of adding a carboxyl group-containing polymerizable unsaturated monomer or an amino group-containing polymerizable unsaturated monomer, etc. For copolymers, methods include adding hydroxyl group-containing polymerizable unsaturated monomers, and for amino group-containing block copolymers, adding epoxy group-containing polymerizable unsaturated monomers, carbonate, etc. Examples include a method of adding a group-containing polymerizable unsaturated monomer or a carboxyl group-containing polymerizable unsaturated monomer, but these methods of introduction are not limited to these methods. Of course, these methods may be used alone or in combination.

Further, as the polymerization initiator referred to herein, only typical examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-
methylnitrile), 2,2-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2,4
-methylvaleronitrile), 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2'-
Azobis(2-methylpropionamide), 2,2'-
Azobis[2-(5-methyl-2-imidazoline-2-
yl)propane], 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 4,4'-azobis(4-cyanopentanoic acid), 2 , an azo initiator represented by 2'-azobiscyanopropanol;

Organic peroxides represented by benzoyl peroxide, di-tert-butyl peroxide, octanoyl peroxide, lauroyl peroxide, tert-butyl peroxy acetate, tert-butyl peroxy pivalate, and methyl ethyl ketone peroxide. ;Metal acid salts represented by cobalt octenoate, cobalt naphthenate, and manganese naphthenate;

Photopolymerization initiators typified by benzoin, anthraquinone, benzophenone, naphthoquinone, 1,1-dichloroacetophenone, benzoin monomethyl ether, benzoin monobutyl ether, benzophenone amines, and N-methyldiethanolamine and triethylamine;

Amine complexes such as boron trifluoride; BF4-, ASF6-, SbCl6-, SbF
Salts of anions such as 6- or ClO4- and alkylsulfonium; salts of anions such as those listed above and alkylsulfoniums having a cyclic structure; salts of anions such as those listed above and alkylpyridinium; or salts of anions such as those listed above and quaternary ammonium. thermal cationic initiators such as salts;

Alternatively, salts of the anion as described above and triarylsulfonium; salts of the anion as described above and diaryliodonium; salts of the anion as described above and alkylselenonium; salts of the anion as described above and alkylphosphonium; active energy ray cationic polymerization initiators such as onium salts such as anion and alkylammonium salts, and the like.

In the case of curing with an electron beam, α,β-ethylenically unsaturated group-containing compounds, epoxy compounds, etc., as described below, are used as polymerization initiators. The appropriate amount to be used is 0.1 to 100 parts by weight per 100 parts by weight of the block copolymer.
Preferably, a range of 1 to 10 parts by weight is appropriate.

[0044] The α,β-ethylenically unsaturated group-containing compound mentioned here includes polymerizable resins such as alkyd resins, side chain acroyl type acrylic prepolymers, telomerized polyester acrylates, telomerized polyamide acrylates, or urethane acrylate resins. Unsaturated group-containing polymers or oligomers; the above-mentioned polymerizable unsaturated monomers represented by styrene and methyl (meth)acrylate;
Ethylene glycol di(meth)acrylate, 1,4-
Polyfunctional (meth)acrylates represented by butylene diol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; Examples include polyfunctional vinyl compounds typified by divinylbenzene.

Furthermore, the epoxy compound mentioned here is
Cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, cyclooctadiene monoepoxide, glycidyl ester of benzoic acid, p-
Glycidyl ester of tert-butylbenzoic acid, monoglycidyl ester of cyclohexanecarboxylic acid, monoglycidyl ester of versatic acid, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, Methylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, p
- glycidyl ester ether of oxybenzoic acid, diglycidyl ether of hydrogenated bisphenol A, diglycidyl phthalate, diglycidyl isophthalate, diglycidyl terephthalate, mono- or polyepoxide of unsaturated fatty acid monoalkyl ester,

or triglycidyl isocyanurate,
Butadiene diepoxide, cyclooctadiene epoxide, 3,4-epoxycyclohexyl-3',4'
- Mono- or polyepoxies such as epoxycyclohexyl carboxylate, vinylcyclohexene dioxide, bis(3,4-epoxycyclohexyl)succinate, bis(3,4-epoxycyclohexyl)adipate or tris(3,4-epoxycyclohexyl) trimellitate. monster;

Alternatively, glycidyl vinyl ether, 3
, 4-epoxycyclohexyl vinyl ether, ethylene glycol monoglycidyl monovinyl ether, triethylene glycol monoglycidyl monovinyl ether, bipropylene glycol monoglycidyl monovinyl ether, cyclohexyl vinyl ether, benzyl vinyl ether, 2-ethylhexyl vinyl ether, triethylene glycol divinyl ether, dipropylene glycol The molar ratio of divinyl ether, 1,4-bisdivinyloxymethylcyclohexane, isophorone diisocyanate and 4-hydroxybutyl vinyl ether is 1
:2, or an adduct in which the molar ratio of hydrogenated xylylene diisocyanate and 4-hydroxybutyl vinyl ether is 1:2.

The α,β-ethylenically unsaturated group-containing compound and/or the epoxy compound are not essential components, but if used as necessary, they may be added to 100 parts by weight of the block copolymer. The appropriate range is 0.5 to 1000 parts by weight, preferably 5 to 100 parts by weight.

The polymerization-curable resin composition obtained in this manner, which contains the α,β-ethylenically unsaturated group-containing block copolymer and the polymerization initiator as essential components, can be used especially as a polymerization-curable coating material. It is useful as a resin composition for use in thermal radical polymerization reactions using azo initiators, organic peroxides, etc.

[0050] A redox polymerization reaction between a metal oxidizing agent or an amine compound and an organic peroxide, or an organic amino compound and a metal salt such as lead, iron, cobalt, nickel, manganese, copper, zinc, cesium or aluminum. It is said that it is a redox polymerization reaction caused by

[0051]
Alternatively, curing is performed by an ultraviolet polymerization reaction using ultraviolet rays, an electron beam polymerization reaction using an electron beam, or a cationic polymerization reaction or anionic polymerization reaction using cations or anions using a metal catalyst or the like.

[0052] When performing curing using such curing methods, it goes without saying that the above-mentioned curing methods may be used alone or in combination. The polymerization-curable resin composition of the present invention obtained in this way has particularly high functionality and can be widely used in various applications such as textiles, molding, coatings, and medical applications. , which can be used.

[0053]

[Examples] Next, the present invention will be explained by reference examples and examples.
This will be explained in more detail. In the following, all parts and percentages are based on weight unless otherwise specified.

Reference Example 1 (Preparation Example of Polymeric Azo Initiator) Into a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 1,500 parts of methyl ethyl ketone, 424 parts of dipropylene glycol, and di-n - After charging 0.2 parts of butyltin dilaurate and raising the temperature to 80°C with stirring, 532 parts of hexamethylene diisocyanate was added.
was added dropwise over 2 hours, and the reaction was further continued at 80° C. for 5 hours.

The number average molecular weight of the obtained isocyanate group-containing polyurethane as measured by gel permeation chromatography (GPC) was 3,700 in terms of polystyrene.

[0056] However, after the isocyanate group has been subjected to a treatment of reacting with diethylamine, it is subjected to measurement by GPC. Next, 2,45% of this isocyanate group-containing polyurethane was placed in the same reaction vessel as above.
6 parts, and further added 44 parts to the polyurethane.
Add part of azobisisopropanol under ice cooling,
The temperature was raised to 30°C, and the reaction was carried out by maintaining the same temperature for 10 hours.

The number average molecular weight of the polyurethane polymer azo initiator thus obtained is 22,500, and therefore, this is a polyurethane polymer azo initiator having an average of 6.1 diazo bonds in one molecule. It is known that

[0058] This target initiator solution has a nonvolatile content of 40% and a Gardner viscosity at 25°C (
The same applies hereafter) was Z1. Reference Example 2 (same as above) In a reaction vessel similar to Reference Example 1, 1 of methyl ethyl ketone was added.
, 500 parts of azobiscyanopropanol and 0.1 part of di-n-butyltin dilaurate,
While stirring and ice-cooling, 552 parts of hexamethylene diisocyanate was added dropwise over 2 hours, the temperature was raised to 20°C, the temperature was maintained for 2 hours to continue the reaction, and then the mixture was heated again. , ice cooling was performed.

Next, 347 of dipropylene glycol
1 part and 55 parts of 3-methyl-1,5-pentanediol were added, the temperature was raised to 30°C, and the reaction was continued by maintaining the same temperature for 10 hours.

The polyurethane polymer azo initiator obtained here has a number average molecular weight of 18,500 and a viscosity of Y-Z.
And the nonvolatile content was 40%. To determine other properties for this polymeric azo initiator, 1.0 part of hydroquinone and 2
0 parts of n-butanol was added and heating continued at 100° C. for 10 hours to decompose the initiator. The number average molecular weight of the obtained decomposition product was 4,100, and it was found that the target polymeric azo initiator had an average of 4.5 diazo bonds in one molecule.

Reference Example 3 (same as above) 614 parts of adipic acid, 438 parts of neopentyl glycol, and 698 parts of isophthalic acid were charged into a reaction vessel equipped with a thermometer, a stirrer, and an air condenser, and the mixture was heated at 140°C for 1 hour. The temperature was then gradually raised to 220°C over a period of 2 hours, and the reaction was continued at the same temperature for 6 hours, resulting in an acid value of 2, a hydroxyl value of 78, and a number average molecular weight of 1,400. A polyester resin was obtained.

Next, in the same reaction vessel as in Reference Example 1, 837 parts of this polyester resin, 27 parts of azobiscyanopropanol, and 0.0 parts of di-n-butyltin dilaurate were added.
1 part of hexamethylene diisocyanate and 1,500 parts of methyl ethyl ketone were added under ice cooling.
34 parts were added dropwise over 2 hours.

After the dropwise addition was completed, the temperature was raised to 30°C and kept at the same temperature for 10 hours to continue the reaction, and the number average molecular weight was 28,000, the viscosity was W-X, and ,
A solution of the desired polyurethane polymeric azo initiator was obtained with a non-volatile content of 40%.

Note that 1.0 part of hydroquinone and n
- The polymeric azo initiator was decomposed by adding 20 parts of butanol and continuing heating at 100°C for 10 hours, and the number average molecular weight of the decomposed product was 4.
500, and therefore, it was found that this polyurethane polymer azo initiator had an average of 6.2 diazo bonds in one molecule.

Reference Example 4 (same as above) In a reaction vessel similar to Reference Example 1, 1 of methyl ethyl ketone was added.
, 400 parts, 100 parts of N-methyl-2-pyrrolidone,
42 parts of azobiscyanopropanol and 0.1 part of di-n-butyltin dilaurate were charged, and under stirring and ice-cooling, 508 parts of hexamethylene diisocyanate was added.
After 2 hours of addition, the temperature was raised to 20° C., maintained at the same temperature for 2 hours to continue the reaction, and then ice-cooled again.

Next, 2-butyl-2-ethyl-1,3
-450 parts of propanediol was added, the temperature was raised to 30°C, and the reaction was continued by maintaining the same temperature for 10 hours.

The polyurethane polymer azo initiator thus obtained had a number average molecular weight of 25,000, a viscosity of Z2, and a nonvolatile content of 40%. To determine other properties for this polymeric azo initiator, 1.0 part of hydroquinone and 20 parts of hydroquinone were added to 20 parts of the initiator.
of n-butanol was added and heating continued at 100° C. for 10 hours to decompose the initiator.

The number average molecular weight of the decomposition product obtained here is 4
, 400, and the target polymeric azo initiator was found to have an average of 5.7 diazo bonds in one molecule.

Reference Example 5 (same as above) In a reaction vessel similar to Reference Example 1, 1 of methyl ethyl ketone was added.
, 500 parts of azobiscyanopropanol and 0.1 part of di-n-butyltin dilaurate,
While stirring and ice-cooling, 350 parts of isophorone diisocyanate was added dropwise over 2 hours, then the temperature was raised to 20°C and maintained at the same temperature for 2 hours to continue the reaction, and then again. , ice cooling was performed.

Next, polypropylene glycol 400
Add 608 parts of
The reaction was allowed to continue for 0 hours. The polyurethane polymer azo initiator obtained here has a number average molecular weight of 26,000, a viscosity of U-V, and a nonvolatile content of 4.
It was 0%.

To determine other properties of this polymeric azo initiator, 1.0 parts per 20 parts of the initiator
1 part hydroquinone and 20 parts n-butanol were added and heating continued at 100° C. for 10 hours to decompose the initiator.

The number average molecular weight of the decomposition product obtained here is 4
, 800, and the target polymeric azo initiator was found to have an average of 5.4 diazo bonds in one molecule.

Reference Example 6 (Preparation Example of Block Copolymer Containing α,β-Ethylenically Unsaturated Group) Into a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 600 parts of toluene and 100 parts of methyl ethyl ketone were added. 150 parts of methyl methacrylate, 350 parts of butyl acrylate, 300 parts of -β-hydroxyethyl methacrylate, and the polyurethane polymer obtained in Reference Example 1. A mixed solution consisting of 500 parts of an azo initiator was added dropwise over 4 hours, and even after the addition was completed, the same temperature was maintained for 15 hours to continue the polymerization reaction.

Next, after cooling to 40°C, 357 parts of ethyl isocyanate methacrylate and 3 parts of toluene were added.
57 parts and 0.1 part of di-n-butyltin laurate were charged, and the reaction was continued at the same temperature for 20 hours to obtain a methacryloyl group-containing polyurethane with a number average molecular weight of 22,000.
A solution of an acrylic resin block copolymer having a nonvolatile content of 50% and a viscosity of X was obtained.

Reference Example 7 (same as above) In a reaction vessel similar to Example 1, methyl ethyl ketone was added.
00 parts and 150 parts of n-butanol were charged, and 80 parts of n-butanol were charged.
℃ and further added 200 parts of methyl methacrylate, 350 parts of butyl acrylate and 1 part of methacrylic acid.
A mixed solution consisting of 50 parts and 750 parts of the polyurethane polymer azo initiator obtained in Reference Example 2 was added dropwise over a period of 4 hours, and even after the addition was completed, the mixture was kept at the same temperature for 15 hours. The polymerization reaction was allowed to continue.

Next, after cooling to 60°C, 247 parts of glycidyl methacrylate, 247 parts of toluene, 0.1 part of p-tert-butylcatechol, and 0.1 part of triethylamine were added, and the mixture was heated at the same temperature for 20 hours. Continuing the reaction, a methacrylic group-containing polyurethane-acrylic resin block copolymer with a number average molecular weight of 26,000 has a nonvolatile content of 50% and a viscosity of Z1 - Z2
A solution was obtained.

Reference Example 8 (same as above) In a reaction vessel similar to Example 1, methyl ethyl ketone 6 was added.
25 parts of methacrylate, 100 parts of styrene, 230 parts of 2-ethylhexyl acrylate, and 270 parts of N,N-dimethylamino methacrylate were added. A mixed solution consisting of 625 parts of the polyurethane polymer azo initiator obtained in Example 3 was added dropwise over a period of 4 hours.
The same temperature was maintained for 15 hours to continue the polymerization reaction.

Next, after cooling to 40°C, 124 parts of methacrylic acid and 124 parts of n-butanol were charged, and the reaction was continued at the same temperature for 20 hours until the number average molecular weight was 2.
A solution of a methacryloyl group-containing polyurethane-acrylic resin block copolymer with a nonvolatile content of 50% and a viscosity of Z was obtained.

Reference Example 9 (same as above) In a reaction vessel similar to Example 1, methyl ethyl ketone was added.
50 parts and 200 parts of n-butanol were charged, and 80 parts of
℃ and further added 200 parts of methyl methacrylate, 350 parts of butyl acrylate and 1 part of methacrylic acid.
A mixed solution consisting of 50 parts of polyurethane polymer azo initiator and 750 parts of the polyurethane polymer azo initiator obtained in Reference Example 4 was added dropwise over a period of 4 hours, and even after the addition was completed, the mixture was kept at the same temperature for 15 hours. The polymerization reaction was allowed to continue.

[0080] After cooling to 60°C, 99 parts of propylene imine was added to carry out an addition reaction. After that, 372 parts of 2,3-carbonate propyl methacrylate and 271 parts of toluene were charged and the reaction was carried out for 10 hours, resulting in a methacryloyl group-containing polyurethane-acrylic resin block copolymer having a number average molecular weight of 20,000. , the nonvolatile content is 50%, and the viscosity is X-
A solution Y was obtained.

Reference Example 10 (same as above) In a reaction vessel similar to Example 1, 50% of methyl ethyl ketone was added.
Charge 50 parts, raise the temperature to 80 ° C., and further add 100 parts of methyl methacrylate, 270 parts of butyl acrylate, and 330 parts of ethyl isocyanate methacrylate.
7 of the polyurethane polymer azo initiator obtained in Reference Example 5
A mixed solution consisting of 50 parts was added dropwise over 4 hours, and even after the addition was completed, the same temperature was maintained for 15 hours to continue the polymerization reaction.

Next, after cooling to 60° C., 277 parts of β-hydroxyethyl methacrylate, 277 parts of toluene, and 0.1 part of dibutyltin dioctate were added to carry out an addition reaction.

Thereafter, the reaction was continued for 5 hours at the same temperature, and the nonvolatile content of the methacryloyl group-containing polyurethane-acrylic resin block copolymer having a number average molecular weight of 18,000 was 50% and the viscosity was V. -W solution was obtained.

Example 1 100 parts of the resin obtained in Example 1 and 1.5 parts of 2,2'-azobis(2-methylbutyronitrile) were blended, and toluene/n-butanol=70 The paint was diluted to 20 seconds with Ford Cup #4 using a thinner consisting of 1/30 and applied by air spray.

After coating, the coating was set for 5 minutes, and then dried in a dryer at 140° C. for 40 minutes. Next, the thus obtained coating film was evaluated under the following contents and conditions. The results are summarized in Table 1.

Examples 2 to 12 Coating films were prepared and evaluated in the same manner as in Example 1, except that the formulation and curing conditions were changed as shown in Table 1.

[0087] In the same table, "UV" means "ultraviolet light" and "EB" means "electron beam".

[0088] The evaluation of the coating film performance was carried out in the following manner. Gloss: The Murakami 60° specular reflection gloss of the painted Bonderite steel plate was measured.

Appearance: Evaluated visually. Shrinkage resistance (%)...30 parts of resin (non-volatile content: 50%) and 2,2'-
After adding 1 part of azobis(2-methylbutyronitrile) and leaving it at room temperature for 2 hours, it was dried at 160°C for 2 hours, and the rate of decrease in diameter was measured.

Gel fraction (%): The film was peeled off from the coated plate and soaked in acetone for 24 hours to measure the amount of the film insoluble in acetone.

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

[Table 3]

As is clear from Table 1, the polymerization-curable resin composition of the present invention has excellent curability, high appearance, and excellent shrinkage resistance, making it extremely useful. I know it's something.

[0095]

EFFECTS OF THE INVENTION The polymerizable curable resin composition of the present invention has particularly excellent curability, and in addition, it has a high appearance and excellent shrinkage resistance, making it extremely useful.

Claims (7)

[Claims] [Claim 1] A polymerization-curable resin composition comprising a block copolymer having an α,β-ethylenically unsaturated group and consisting of a polyurethane segment and a vinyl polymer segment, and a polymerization initiator. thing. 2. A block copolymer comprising a polyurethane segment and a vinyl polymer segment having an α,β-ethylenically unsaturated group, an α,β-ethylenically unsaturated group-containing compound and/or an epoxy compound, A polymerization-curable resin composition, characterized by containing a polymerization initiator. 3. A block copolymer comprising a polyurethane segment and a vinyl polymer segment having α,β-ethylenically unsaturated groups as described above, wherein at least one kind of polymerizable unsaturated group is present in the block copolymer. The polymerizable and curable resin composition according to claim 1 or 2, which is obtained by reacting monomers. 4. The above-mentioned block copolymer comprising a polyurethane segment and a vinyl polymer segment having an α,β-ethylenically unsaturated group contains a polyurethane having an azo group in the molecule of the block copolymer. Under,
The polymerizable and curable resin composition according to claim 1, which is obtained by polymerizing at least one kind of polymerizable unsaturated monomer. 5. The above block copolymer having an α,β-ethylenically unsaturated group and consisting of a polyurethane segment and a vinyl polymer segment has the general formula [wherein R1 is an alkylene group, a cyclic alkylene group] base,
An alkylene group having an ester group, a benzene ring, or an alkylene group containing a benzene ring, R2 and R2'
each represents an alkylene group, an alkylene group containing a cyano group, an alkylene group containing an amide bond, or an alkylene group having both an amide bond and a hydroxyl group, which may be the same or different. do. ] and the general formula [However, R3 in the formula represents a polyol residue. ] is obtained by polymerizing at least one kind of polymerizable unsaturated monomer in the presence of a compound having at least one structural unit in one molecule,
The polymerizable and curable resin composition according to claim 1, 2, or 3. 6. The block copolymer consisting of a polyurethane segment and a vinyl polymer segment having α,β-ethylenically unsaturated groups as described above has the general formula [wherein R1 is an alkylene group, a cyclic alkylene group] basis,
An alkylene group having an ester group, a benzene ring or an alkylene group containing a benzene ring, R2 and R2'
each represents an alkylene group, an alkylene group containing a cyano group, an alkylene group containing an amide bond, or an alkylene group having both an amide bond and a hydroxyl group, which may be the same or different. . ] and the general formula [However, R3 in the formula represents a polyol residue. ], in the presence of a compound having at least one structural unit in one molecule, at least one polymerizable unsaturated monomer containing a functional group-containing monomer as an essential component. The polymerizable curable resin composition according to claim 1, 2 or 3. 7. The above block copolymer having an α,β-ethylenically unsaturated group and consisting of a polyurethane segment and a vinyl polymer segment has the general formula [wherein R1 is an alkylene group, a cyclic alkylene group] basis,
An alkylene group having an ester group, a benzene ring or an alkylene group containing a benzene ring, R2 and R2'
each represents an alkylene group, an alkylene group containing a cyano group, an alkylene group containing an amide bond, or an alkylene group having both an amide bond and a hydroxyl group, which may be the same or different. . ] and the general formula [However, R3 in the formula represents a polyol residue. ] having at least one structural unit in one molecule, with a number average molecular weight of 1,500 to 50,
In the presence of 2 to 95 parts by weight of the compound 000, 98 to 95 parts by weight of the compound
4. The polymerizable and curable resin composition according to claim 1, obtained by polymerizing 5 parts by weight of at least one polymerizable unsaturated monomer. 0000