JPH04279616A - Polymerization-curable resin - Google Patents

Abstract

PURPOSE:To provide the subject resin consisting of a block copolymer comprising polyurethane segments and vinyl polymer segments and having alpha,beta-ethylenic unsaturated groups, exhibiting high curability and low shrinkability and having extremely practical usefulness. CONSTITUTION:The objective resin consisting of a block copolymer which comprises polyurethane segments and vinyl polymer segments and which has alpha,beta-ethylenic unsaturated groups. The block copolymer is preferably obtained by polymerizing 98-5 pts.wt. of a polymerizable unsaturated monomer in the presence of 2-95 pts.wt. of a polymer having both units of formulas I and II (R1 is alkylene, cyclic alkylene, etc.; R2, R2' is alkylene, cyano group-having alkylene, etc.; R3 is polyol residue) and having a number-average mol.wt. of 1500-50000. The polymer having both the units of formulas I and II is obtained e.g. by condensing an azobisalkanol compound and a polyol with a polyisocynate compound.

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. More specifically, in the presence of a specific compound containing a diazo bond and a urethane bond in the main chain,
The present invention relates to a polymerization-curable resin obtained by introducing an α,β-ethylenically unsaturated bond into a block copolymer obtained by polymerizing at least one polymerizable unsaturated monomer.

[0002] The novel polymerization-curing resin of the present invention exhibits a revolutionary effect as a polymerization-curing resin for coatings, and is resistant to heat, oxidation-reduction, ultraviolet rays, X-rays, electron beams, etc. It can be hardened by

0003

[Prior Art] Examples of polymerization-curable resins include alkyd resins, side chain acrylic prepolymers, telomerized polyester acrylates, telomerized polyamide acrylates, and urethane acrylate resins.
Research has been done in the past, and there is a need for resins that have a good balance of performance such as high hardness, high appearance, flexibility, and low shrinkage. The reality is that this is not the case.

0004

[Problem to be Solved by the Invention] Therefore, 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 provide an extremely practical material that has excellent curability and high appearance, and also has excellent shrinkage resistance. The purpose of the present invention is to provide a highly polymerizable and curable resin.

[0006]

[Means for solving the problem] Therefore, the present inventors
As a result of intensive studies aimed at the problems to be solved by the invention as described above, we found that the following formulas are available: , a benzene ring or an alkylene group containing a benzene ring, R2 and R
2' 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; shall be. ] 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 each molecule, at least one
A resin in which α,β-ethylenically unsaturated groups are introduced into a block copolymer obtained by polymerizing certain polymerizable unsaturated monomers exhibits high curability and low shrinkage. After discovering that it was an extremely excellent polymerization-curing resin,
The present invention has now been completed.

That is, the present invention basically provides a block copolymer composed of a polyurethane segment and a vinyl polymer segment, which has an α,β-ethylenically unsaturated group in the block copolymer. The purpose of this invention is to provide a specific type of polymerization-curable resin.

[0008] Here, in one molecule, as shown in the above-mentioned general formulas [I] and [II], respectively,
A so-called polymeric azo initiator having both a urethane bond and a diazo bond is a compound having specific structural units represented by both of these formulas,

0009
For example, various azobisalkanol compounds such as azobiscyanopropanol, azobiscyano-n-butanol, azobisisobutanol or azobiscyanopentanol or "VA-080, VA-082
A compound having at least one diazo bond and at least two hydroxyl groups in one molecule, such as azoamide polyol such as "VA-086" [product of Wako Pure Chemical Industries, Ltd.], and a polyisocyanate compound. and those obtained by reaction with polyol compounds.

That is, such 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 functional group capable of reacting with each of these diisocyanates and various polyhydric alcohols or isocyanate groups such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol or dipentaerythritol, 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,

[0012] 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,

Alternatively, various di- or polyols such as trimethylolethane, trimethylolpropane, glycerin, pentaerythritol or hydrogenated bisphenol A, furthermore, bisphenol A or polyester polyol, as mentioned above, may be combined in one molecule. , and a compound having both at least one diazo bond and at least two hydroxyl groups, are subjected to an addition condensation reaction.

Here, the number average molecular weight of the above-mentioned di- or polyol compound is not particularly limited, but from the viewpoint of reactivity etc., 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 polymer 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.

[0017] In the reaction of these di- or polyol compounds with di- or polyisocyanate compounds, ethylenediamine, hexamethylenediamine, triethylenetetramine, tetraethylenepentamine, bisaminopropylamine or 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 or vinyltoluene;

Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate,
tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dibromopropyl (meth)acrylate, tribromophenyl (meth)acrylate or alkoxy (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 acetate, vinyl benzoate, “Beoba”
Vinyl esters such as (vinyl ester manufactured by Shell, Netherlands);

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

Alternatively, vinyl monomers having no functional group, 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 or alkoxylated N-methylolated (meth)acrylamide Vinyl monomers containing amide bonds such as;

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

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

Dialkylaminoalkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate and 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-hydroxypropyl (meth)acrylate, di-2 -Hydroxyethyl fumarate, mono-2-hydroxyethyl monobutyl fumarate,

or polypropylene glycol or polyethylene glycol mono(meth)acrylate,
Alternatively, hydroxyalkyl esters of α,β-ethylenically unsaturated carboxylic acids such as “Plaxel FM or FA monomer” (caprolactone addition monomer manufactured by Daicel Chemical Industries, Ltd.), or these and ε
- adduct with 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

00
31] Or the aforementioned α,β-ethylenically unsaturated carboxylic acid hydroxyalkyl esters, maleic acid, succinic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, various unsaturated carboxylic acids such as "Himic acid" (product of Hitachi Chemical Co., Ltd.), adducts of polycarboxylic acids such as tetrachlorophthalic acid or dodecynylsuccinic acid with anhydrides;

"Cardura E" (branched synthetic resin glycidyl ester of fatty acid manufactured by Shell), monoglycidyl ester of monovalent carboxylic acid such as coconut oil fatty acid glycidyl ester or octylic acid glycidyl ester or butyl glycidyl ether, ethylene oxide or Adducts with monoepoxy compounds such as propylene oxide, or adducts with these and ε-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 ;

Fluoroolefins such as tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, (per)fluoroalkyl trifluorovinyl ether having C1 to C18;

Alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, n-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;

[0037]2
- hydroxyl group-containing vinyl ethers such as hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether or 6-hydroxyhexyl vinyl ether;

Vinylethoxysilane, α-methacryloxypropyltrimethoxysilane, trimethylsiloxyethyl (meth)acrylate, “KR-215” (product of Shin-Etsu Chemical Co., Ltd.) or “X-22-5002” (product of the same company) ) and other silicon-based monomers.

Polymerization of the vinyl (co)polymer used in the present invention can be carried out by using the above-mentioned raw material components and making full use of known and commonly used (co)polymerization reaction methods.
At that time, azobisisobutyronitrile (AIBN),
Benzoyl peroxide (BPO), tert-butyl perbenzoate (TBPB), tert-butyl hydroperoxide, di-tert-butyl peroxide, (DTBPO), cumene hydroperoxide (CH
Even if a radical generating polymerization catalyst such as P) is used alone,
Alternatively, it goes without saying that several types may be used in combination.

[0040] Here, the α,β-ethylenically unsaturated group refers to a group selected from a (meth)acroyl group, an allyl group, a vinyl ether group, or an unsaturated fatty acid residue. It is introduced into the polyurethane segment and/or acrylic segment of the polymer.

[0041] In the block copolymer, such α, β
- As a method for introducing ethylenically unsaturated groups, a polymerizable unsaturated monomer having a functional group that reacts with the functional group of the block copolymer is added to the block copolymer containing α, A method is adopted in which the reaction is carried out under conditions that do not deactivate the β-ethylenically unsaturated group.

That is, to give a few representative examples, for hydroxyl group-containing block copolymers, isocyanate group-containing polymerizable unsaturated monomers such as isocyanate ethyl methacrylate and acyl isocyanate are used. It's a way to add body,

[0043] There is a method of introducing a hydroxyl group-containing polymerizable unsaturated monomer such as β-hydroxyethyl (meth)acrylate using diisocyanate as a medium;

004
4] A method using an esterification reaction with a carboxyl group-containing polymerizable unsaturated monomer such as (meth)acrylic acid,

Alternatively, there is a method using a dehydrochloric acid reaction with (meth)acrylic acid chloride, a method using a transesterification reaction with an ester such as methyl (meth)acrylate, etc.

For carboxyl group-containing block copolymers, esterification reactions with hydroxyl group-containing polymerizable unsaturated monomers, epoxy group-containing polymerizable unsaturated monomers,
There is a method of adding an amino group-containing polymerizable unsaturated monomer or a carbonate group-containing polymerizable unsaturated monomer.

Furthermore, there are methods of adding a carboxyl group-containing polymerizable unsaturated monomer, an amino group-containing polymerizable unsaturated monomer, etc. to the epoxy group-containing block copolymer.

For isocyanate group-containing block copolymers, there is a method of adding a hydroxyl group-containing polymerizable unsaturated monomer, and for amino group-containing block copolymers, epoxy group-containing Methods of adding a polymerizable unsaturated monomer, a carbonate group-containing polymerizable unsaturated monomer, a carboxyl group-containing polymerizable unsaturated monomer, etc. can be mentioned; It is not limited to only.

[0049] Each α, obtained in this way,
β-ethylenically unsaturated group-containing block copolymers are particularly useful as polymerization-curable coating resins, and are suitable for use with azo initiators such as azobisisobutyronitrile and benzoyl peroxide. Thermal radical polymerization reaction using organic peroxides represented by

Curing is carried out by a redox polymerization reaction using a metal oxidizing agent, an amine compound, etc. and an organic peroxide, an ultraviolet polymerization reaction using ultraviolet light, or an electron beam polymerization reaction using an electron beam.

[0051] This resin has α,
Curing is based on the polymerization of β-ethylenically unsaturated groups, and of course curing using cations, anions, etc. using metal catalysts is also possible.

[0052]

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

Reference Example 1 (Example of Preparation 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.

However, after the isocyanate group is reacted 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

Note that this target initiator solution has a nonvolatile content of 4
0%, and the Gardner viscosity (hereinafter the same) at 25° C. 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, and then heated to 20°C.
After the temperature was raised to 100% and maintained at the same temperature for 2 hours to continue the reaction, ice cooling was performed again.

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 of this polymeric azo initiator, 1.0 part of hydroquinone and 20 parts of n-butanol were added to 20 parts of the initiator at 100°C for 10 hours. Heating was continued to decompose the initiator.

The number average molecular weight of the decomposition product obtained here is 4
, 100, and the target polymeric azo initiator was found to have 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 to 140°C. The temperature was gradually raised to 220°C over 2 hours, and the reaction was carried out at the same temperature for 6 hours to obtain an acid value of 2, a hydroxyl group of 78, and a number average molecular weight of 1. 400 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 completion of the dropwise addition, the temperature was raised to 30°C and kept at the same temperature for 10 hours to continue the reaction, resulting in a number average molecular weight of 28,000, a viscosity of 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, this polyurethane polymeric azo initiator was found to have 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 dropping the solution over 2 hours, the temperature was raised to 20°C.
After continuing the reaction by maintaining the same temperature for 2 hours, ice cooling was performed 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 obtained here has a number average molecular weight of 25,000 and a viscosity of Z2.
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 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, the temperature was raised to 20°C, the temperature was maintained for 2 hours to continue the reaction, and then the temperature was increased 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.

Example 1 600 parts of toluene and 100 parts of methyl ethyl ketone were charged into a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 80°C. A mixture of 350 parts of butyl acrylate, 300 parts of β-hydroxyethyl methacrylate, and 500 parts of the polyurethane polymer azo initiator obtained in Reference Example 1 was added dropwise over 4 hours. death,
After the dropwise 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.
By charging 57 parts and 0.1 part of di-n-butyltin laurate and continuing the reaction at the same temperature for 20 hours,
A solution of a methacryloyl group-containing polyurethane-acrylic resin block copolymer having a number average molecular weight of 22,000, a nonvolatile content of 50%, and a viscosity of X was obtained.

Example 2 In a reaction vessel similar to Example 1, methyl ethyl ketone was added.
80 parts by adding 150 parts of n-butanol and 150 parts of n-butanol.
℃ and added 200 parts of methyl methacrylate, 350 parts of butyl acrylate and 150 parts of methacrylic acid.
and 750 parts of the polyurethane polymer azo initiator obtained in Reference Example 2 was added dropwise over 4 hours, and even after the addition was completed, the same temperature was maintained for 15 hours to carry out polymerization. The reaction was allowed to proceed.

Next, after cooling to 60°C, 247 parts of glycidyl methacrylate, 247 parts of toluene, p
By adding 0.1 part of -tert-butylcatechol and 0.1 part of triethylamine and continuing the reaction at the same temperature for 20 hours, a methacryloyl group-containing polyurethane-acrylic resin block copolymer with a number average molecular weight of 26,000 is produced. , the nonvolatile content is 50%, and the viscosity is Z
A solution of 1-Z2 was obtained.

Example 3 In a reaction vessel similar to Example 1, methyl ethyl ketone (6) was added.
25 parts of methyl methacrylate, 100 parts of styrene, and acrylic acid were added to the mixture and heated to 80°C.
A mixed solution consisting of 230 parts of 2-ethylhexyl, 270 parts of N,N-dimethylamino methacrylate, and 625 parts of the polyurethane polymer azo initiator obtained in Reference Example 3 was added dropwise over 4 hours, After the dropwise addition was completed, 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.
A solution of a methacryloyl group-containing polyurethane-acrylic resin block copolymer having a number average molecular weight of 24,000, a nonvolatile content of 50%, and a viscosity of Z was obtained.

Example 4 In a reaction vessel similar to Example 1, methyl ethyl ketone was added.
80 parts by charging 50 parts and 200 parts of n-butanol.
℃ and added 200 parts of methyl methacrylate, 350 parts of butyl acrylate and 150 parts of methacrylic acid.
and 750 parts of the polyurethane polymer azo initiator obtained in Reference Example 4 was added dropwise over 4 hours, and even after the addition was completed, the same temperature was maintained for 15 hours to carry out polymerization. The reaction was allowed to proceed.

[0080] Next, after cooling to 60°C, 99 parts of propylene imine was charged to carry out an addition reaction. Thereafter, 372 parts of 2,3-carbonate propyl methacrylate and 271 parts of toluene were charged and reacted for 10 hours to produce a methacryloyl group-containing polyurethane-acrylic resin block copolymer having a number average molecular weight of 20,000. A solution with a nonvolatile content of 50% and a viscosity of XY was obtained.

Example 5 In a reaction vessel similar to Example 1, methyl ethyl ketone was added.
50 parts were charged and the temperature was raised to 80°C, and thereto were added 100 parts of methyl methacrylate, 270 parts of butyl acrylate, 330 parts of isocyanate ethyl methacrylate, and the polyurethane polymer azo initiator obtained in Reference Example 5. 750
A mixed solution consisting of 50% and 50% 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 to obtain a polyurethane-acrylic resin block copolymer containing a methacroyl group having a number average molecular weight of 18,000, with a nonvolatile content of 50% and a viscosity of 50%. A solution called V-W was obtained.

Application Example 1 100 parts of the resin obtained in Example 1 and 1.5 parts of 2,2'-azobis(2-methylbutyronitrile) were blended, and then toluene/n-butanol was added. =70/30
It was diluted to 20 seconds with Ford Cup #4 and painted by air spray.

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

Application Examples 2 to 8 Coating films were prepared in the same manner as in Example 1, except that the formulation and curing conditions were changed as shown in Table 1. We also evaluated the

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

[0088] The coating film performance was evaluated in the following manner. Gloss: Murakami 60° specular reflection gloss was measured for the Bonderite-treated steel plate coated.

Appearance: Evaluated visually. Shrinkage resistance (%)...In a Teflon petri dish with a diameter of 15 cm, 30 parts of resin (non-volatile content: 50%) and 2,
One part of 2'-azobis(2-methylbutyronitrile) was added, the mixture was allowed to stand at room temperature for 2 hours, and then dried at 160°C for 2 hours, after which the rate of decrease in diameter was measured.

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

[0091]

[Table 1]

[0092]

[Table 2]

As is clear from Table 1, the polymerization-curing resin of the present invention has a high appearance and shrinkage resistance, and is extremely excellent as a polymerization-curing resin. I can know.

[0094]

[Effects of the Invention] The polymerization-curable resin of the present invention has, inter alia,
It has excellent curability and a high appearance, and also has excellent shrinkage resistance, making it extremely practical.

Claims (6)

[Claims] 1. A block copolymer consisting of a polyurethane segment and a vinyl polymer segment, characterized in that the block copolymer has an α,β-ethylenically unsaturated group; mold resin. 2. The block copolymer described above is produced by reacting at least one kind of polymerizable unsaturated monomer,
The polymerizable curable resin according to claim 1, wherein a polymerizable unsaturated group is introduced into the block copolymer. 3. The block copolymer described above is obtained by polymerizing at least one polymerizable unsaturated monomer in the molecule of the block copolymer in the presence of a polyurethane having an azo group. The polymerizable curable resin according to claim 1 or 2, which is a polymeric curable resin. 4. The block copolymer described above has the general formula [
However, R1 in the formula 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' are the same or different. It 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. ]
A structural unit represented by 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 curable resin according to claim 1 or 2. 5. The block copolymer described above has the general formula [
However, R1 in the formula 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' are the same or different. It 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. ]
A structural unit represented by 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 according to claim 1 or 2. 6. The block copolymer described above has the general formula [
However, R1 in the formula 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' are the same or different. It 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. ]
A structural unit represented by the general formula [However, R3 in the formula represents a polyol residue. ] has at least one structural unit in one molecule, and has a number average molecular weight of 1,500 to 1,500.
In the presence of 2 to 95 parts by weight of the compound 50,000,
The polymerizable curable resin according to claim 1 or 2, which is obtained by polymerizing 98 to 5 parts by weight of at least one polymerizable unsaturated monomer. 0000