JPH04168114A - Curing type resin composition - Google Patents

Abstract

PURPOSE:To obtain the title stably producible resin having excellent curing properties, not shrinking during curing, not gelatinizing, by blending a urethane- based resin containing (meth)acryloyl and a hydrophilic polar group with a specific monomer. CONSTITUTION:(A) A urethane-based resin containing (meth)acryloyl and 0-2,000eq/10<6>g hydrophilic polar group, having 1,000-50,000 molecular weight is blended with (B) a monomer shown by formula I to formula V (R is alkyl, aryl, etc.; Y is H, halogen, etc.) in amounts to give >=10wt.% component A and <=90wt.% component B based on 100wt.% total amounts of the components A and B to give the objective composition. For example, bismethylene pyroorthocarbonate may be cited as the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a curable urethane resin that exhibits non-shrinkage properties upon curing.

(Conventional technology) Curable resins generate stress inside the material due to heat generation and shrinkage due to crosslinking reaction during the curing process, and heat shrinkage during the cooling process after curing, resulting in cracks, warpage, deformation, and reduced adhesion. The current situation is that this is the cause of various troubles during practical application. Therefore, making the curable resin non-shrinkable and reducing stress is a major challenge.

Polyurethane resins have excellent mechanical properties and are therefore widely used in various fields such as engineering plastics, paints, coatings, adhesives, and casting materials.

Also in the field of polyurethane resins, the above-mentioned non-shrinkage and low stress are major issues.

Methods for imparting non-shrinkage properties to polyurethane resins are disclosed in Japanese Patent Publication No. 57-21417 and Japanese Patent Publication No. 58-18.
There is one disclosed in Japanese Patent No. 4592. The method disclosed herein involves a reaction in which the resin branches through urethane bonds and becomes three-dimensional.

Therefore, when an attempt is made to introduce a non-shrinkable group into the side chain, the resulting resin contains gel, which poses the problem that the desired resin cannot be stably produced.

(Problems to be Solved by the Invention) The present invention solves the above-mentioned conventional problems, and its purpose is to provide a urethane-based material that has excellent curability and does not cause problems due to shrinkage and internal stress during curing. The purpose of the present invention is to provide a curable resin, and to stably impart non-shrinkage properties to a urethane resin.

(Means for Solving the Problems) The present inventors have found that by blending a non-shrinking monomer into a urethane resin, it not only has excellent curability and exhibits non-shrinking properties during curing, but also produces gel during the reaction process. Without,
We have discovered that it is possible to stably produce even high molecular weight products.

The curable resin composition of the present invention has (A) a molecular weight of 1.000 to 50.000, at least one acryloyl group and/or methacryloyl group in one molecular chain, and five hydrophilic polar groups. ~2,000e
A curable resin composition characterized by blending a urethane resin containing (1,/10'g) and (B) a monomer having a structure represented by the following formulas (1) to (■) so as to satisfy the following formula. (R represents an alkyl group, an aryl group, an unsaturated alkyl group, an ester group, an imide group, an amide group, and Y represents hydrogen, a halogen, an alkyl group, an unsaturated alkyl group, an aryl group, or a hydroxyl group. group, alkoxyl group, carboxyl group, silyl group, amino group, nitro group, or nitrile group, and when there are two or more of each in one molecule,
They may be the same or different. ) A curable resin composition characterized in that the blending ratio thereof satisfies the following formula.

A+B=100 (wt%) 10 (wt%)≦A, B≦90 (wt%) That is, in the present invention, the molecular weight is 1,000 to 50,000, and one molecule of acryloyl group and/or methacryloyl group Has at least one hydrophilic substituent in the chain and 0 to 2.000 hydrophilic substituents
It imparts non-curing shrinkage to the urethane resin containing eq, / 10''g.

In this way, a curable urethane resin having a non-shrinkable group in the side chain can be stably produced. Since the obtained urethane-based curable resin of the present invention has a non-shrinkable group in the side chain,
Its reactivity is influenced by the structure of the main chain, and exhibits excellent cationic ring-opening polymerization to give polymers. Moreover, its mechanical properties can be varied widely by selecting the backbone of the main chain.

Radical ring-opening polymerization of compound (1) can be carried out by conventional radical polymerization means, such as ultraviolet rays, heat, and electron beams. When using ultraviolet light, it is desirable to use a photoinitiator, and when using heat, it is desirable to use an initiator that generates radicals with heat.

Cationic ring-opening polymerization of compound (1) can be carried out using ultraviolet rays, heat, electron beams, etc. in the same manner as radical polymerization.

When using ultraviolet rays and electron beams, φ-N”: N pp,
When using catalysts such as diazonium salts such as e), φ-1'-φ" BF40, etc. (7) HaC' = Lamb ai, onium salts such as φ3S"BF4e, and when using heat, B
F3. It is desirable to use a catalyst such as a Lewis acid such as FeCl3+ 5nC14, an oxonium salt, a diazonium salt, or a carbonium salt of a Lewis acid.

In the present invention, the hydrophilic polar group is: , represents any of the amino groups, and R1-R
3 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aralkyl group. ) is preferable.

Furthermore, the urethane resin in the present invention includes (a) a polymerized polyester polyol, (b) a polyisocyanate compound, (C) a compound having an acryloyl group and/or methacryloyl group and an active hydrogen group in the molecule, and optionally It is a reaction product of a polyol and/or a polyamine other than (d) and (a), and (a) and/or (d) preferably contains a hydrophilic polar group.

The above-mentioned copolymerized polyester polyol (a) mainly consists of a dicarboxylic acid component and a glycol component.

Examples of dicarboxylic acid components include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and 1,5-naphthalic acid; aromatic oxycarboxylic acids such as p-oxybenzoic acid and p-(hydroxyethoxy)benzoic acid; acids, succinic acid, adipic acid, azelaic acid, sebacic acid,
Examples include aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, unsaturated aliphatic and alicyclic dicarboxylic acids such as fumaric acid, maleic acid, itaconic acid, hexahydrophthalic acid, and tetrahydrophthalic acid. If necessary, a small amount of tri- and tetracarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid may be included.

Glycol components include, for example, ethylene glycol, propylene glycol, l,3-propanediol, l,
4-butanediol, 1,5-bentanediol, 1.
8-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2.
4-) riftyl-1,3-bentanediol, l,4-
Cyclohexane dimetatool, spiroglycol, l,
4-phenylene glycol, ethylene oxide adduct of l,4-phenylene glycol, ethylene oxide adduct and propylene oxide adduct of bisphenol A, ethylene oxide adduct and propylene oxide adduct of hydrogenated bisphenol A, polyethylene glycol, polypropylene glycol and diols such as polytetramethylene glycol. Trimethylolethane, trimethylolpropane, if necessary
It may also contain small amounts of triols and tetraols such as chrycerin and pentaerythritol.

In order to obtain a copolymerized polyester polyol from such a dicarboxylic acid component and a glycol component, synthesis may be performed using an excess amount of glycol raw material with respect to the dicarboxylic acid raw material. It is desirable to synthesize the carboxyl terminal in the copolymerized BoIJ ester so that the amount is less than 50 eq./10"g. If it is more than 50 eq./106 g, the reaction with the diisocyanate compound will occur when synthesizing the urethane resin described below. If the number of inactive terminals in is too large, the desired urethane resin cannot be obtained and the radiation curability decreases.

Other examples of polyester polyols include lulactone-based polyester polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone.

As the polyisocyanate compound (b), for example, 2
．． 4-) lylene diisocyanate; 2. [i-) lylene diisocyanate, p-phenylene diisocyanate,
Diphenylmethane diisocyanate, phenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 2,4-
Naphthalene diisocyanate and 3,3'-dimethyl-4
, 4'-biphenylene diisocyanate, 4.4'-diphenylene diisocyanate, 4,4. '-diisocyanate diphenyl ether, l,5-naphthalene diisocyanate, p-xylylene diisocyanate,
Xylylene diisocyanate and diisocyanate compounds such as 1,3-diisocyanatemethylcyclohexane, 1,4-diisocyanatemethylcyclohexane, 4,4'-diisocyanatedicyclohexane, 4,4'-diisocyanatedicyclohexylmethane, inphorone diisocyanate, etc. Examples include triisocyanate compounds such as a trimer of 2.4-)lylene diisocyanate and a trimer of hexamethylene diisocyanate, which account for 7 mol% or less of the isocyanate groups.

Examples of the compound (C) having an acryloyl group and/or methacryloyl group and active hydrogen in the molecule include glycol mono(meth)acrylates such as ethylene glycol, diethylene glycol, and hexamethylene glycol, trimethylolethane, glycerin, Mono(meth)acrylates and di(meth)acrylates of triol compounds such as trimethylolethane, mono(meth)acrylates and di(meth)acrylates of polyols with a valence of 4 or more such as pentaerythritol and dipentaerythritol, (meth)acrylate, hydroxyl group-containing acrylic compounds such as glycerin monoallyl ether and glycerin diallyl ether, (meth)acrylamide,
Examples include amino group-containing acrylic compounds such as monomethylol (meth)acrylamide. Acrylate and methacrylate are referred to as (meth)acrylate, and acrylamide and methacrylamide are referred to as (meth)acrylamide.

In addition, polyols and/or polyamines (d) other than the copolymerized polyester polyol (a) used as necessary
), the above-mentioned copolymerized polyester polyol (a
) Glycols exemplified as glycol components, amino alcohols such as monoethanolamine and N-methylethanolamine, ethylenediamine, hexamethylenediamine, isophoronediamine, piperazine, 4.4'-
Examples include diamines such as diaminodiphenylmethane, water, and the like.

The urethane resin of the present invention can contain a hydrophilic polar group, but as a method for containing the hydrophilic polar group, the above-mentioned copolymerized polyester polyol (a) other than polyol and/or polyamine (d) may be used. What is necessary is just to copolymerize polyol and/or polyamine which contain a polar group partially or completely.

As a hydrophilic polar group, / (in the formula, M1 represents a hydrogen atom, an alkali metal, a tetraalkynammonium, or a tetraalkylphosphonium, and 2 represents a hydrogen atom, an alkali metal atom, a monovalent hydrocarbon group, or an amine group). and R1 to R3 represent any one of a hydrogen atom, an alkyl having 1 to 8 carbon atoms, an aryl, and an aralkyl.

The polar group-containing compounds used to introduce polar groups into the resin are as follows.

(1) -COOM Polycarboxylic acid which is the acid component of the polyester polyol (b), glyceric acid, dimethylolpropionic acid, N, diethanolglycine, oxycarboxylic acid such as hydroxyethyloxybenzoic acid, diaminopropionic acid, Aminocarboxylic acids such as diaminobenzoic acid and their derivatives.

Nitrogen-containing alcohols and derivatives thereof such as N-methylgetanolamine, 2-methyl-2-dimethylamine methyl-1,3-propanol, and 2-methyl-2-dimethylamino-1,3-propanediol.

picolinic acid, dipicolinic acid, aminopyridine, diaminopyridine, hydroxypyridine, dihydroxypyridine, aminohydroxypyridine, pyridine dimetatool,
Pyridine ring-containing compounds and derivatives thereof, such as pyridine propanediol and pyridine ethanol.

(2) -803M Polycarboxylic acids and derivatives such as 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium, sulfoisophthalic acid, sodium sulfosuccinic acid, sodium sulfohydroquinone and alkylene oxide adducts, sodium sulfobisphenol A and alkylene oxide Addenda etc.

The molecular weight of the present invention is 1,000 to 50,000, at least one acryloyl group and/or methacryloyl group is present in one molecular chain, and the hydrophilic polar group is 0' to 2,
The urethane resin containing 0OOeq, /106g was prepared by adding the above copolyester polyol (a
), polyisocyanate compound (b), compound (C) containing 7 acryloyl and/or methacryloyl groups and active hydrogen in the molecule, and polyol and/or polyamine (d) other than (a) as necessary as a solvent. or in the absence of a solvent.

When the molecular weight is t and ooo ungrooved, the distance between crosslinking points in the radiation-cured product becomes too short, and the workability and adhesion of the resulting precoated metal deteriorate. In addition, the molecular weight is 50.0
If it exceeds 0.00, the viscosity will already be too high before the pigment is mixed, requiring a large amount of solvent or reactive diluent, and when using a reactive diluent, which will be described later, the compatibility will decrease and the brightness will decrease. The image quality deteriorates.

In addition, the urethane resin of the present invention has an acryloyl group and/or
Alternatively, it is necessary to have at least one methacryloyl group in one molecular chain. If there is less than one acryloyl group and/or methacryloyl group in one molecular chain, there will be molecules that cannot participate in radiation curing, resulting in poor hardness and stain resistance of the cured coating film. If the concentration of polar groups in the urethane resin is low, sufficient adhesion cannot be ensured, and in coating compositions that use pigments, the dispersion stability becomes poor after the pigments are dispersed. In addition, the polar group concentration is 2.000 eq,
/10''g, the hydrophilicity becomes too high and the water resistance of the coating film deteriorates.

The pigments used in the coating composition of the present invention are usually
Various inorganic and organic pigments used in the color material industry are used. Inorganic pigments include pallite powder, precipitated barium sulfate, heavy calcium carbonate, precipitated calcium carbonate, talc, clay, alumina white, extender pigments such as white carbon, lead white, zinc white, zinc sulfide, lithopone, and titanium dioxide. White pigments such as ultramarine, navy blue, blue pigments such as cobalt blue, green pigments such as chromium oxide, viridian, chromium green, yellow lead, molybdade orange, cadmium pigments, titanium dilo, yellow iron oxide, red iron oxide, etc. Yellow to orange to red pigments, black pigments such as iron black and carbon black, metal powder pigments such as aluminum powder and bronze powder, lead red, zinc oxide powder, cyanamide lead, Mlo, zinc chromate, strontium chromate, and zinc. Examples include anti-rust pigments for suboxide steel, antifouling pigments, and the like. Examples of organic pigments include azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, bat pigments, and lake pigments for dyeing.

An organic solvent and/or a reactive diluent can be added to the radiation-curable coating composition of the present invention.

Organic solvents are limited to volatile ones, and most or all of them need to be volatilized by heat drying or the like before radiation curing. Usable solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as methyl acetate and ethyl acetate;
Ethers such as tetrahydrofuran, dioxane, ethylene glycol monoethyl ether, aromatic hydrocarbons such as benzene, toluene, xylene, aliphatic hydrocarbons such as hexane, heptane, alcohols such as methanol, ethanol, isopropyl alcohol, etc. There are mixtures of The reaction solvent used in the synthesis of the urethane resin A of the present invention can also be used as it is.

The reactive diluent is incorporated into the crosslinked network after radiation curing and is used to adjust the crosslink density.

A specific compound is 2-ethylhexyl (meth)
Acrylate, 2-hydroxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (
meth) acrylate, cyclohexyl (meth) acrylate, butoxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and glycidyl (meth) acrylate.
Acrylate and N,N-diethylaminoethyl (meth)
Acrylate, isobonyl (meth)acrylate, ethylene oxide-modified phosphoric acid (meth)acrylate, and N-
Monoacrylate compounds such as methylvinylpyrrolidone, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, (meth)acryloxyethyl succinate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate , 1,6-hexanethiol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and neopentyl glycol dihydroxypivalate. (meth)acrylate, dicyclopentenyl di(meth)acrylate, bisphenol A di(meth)acrylate, ethylene oxide-modified phosphoric acid di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, polyethylene Diacrylate compounds such as glycoldi(meth)acrylate, trimethylolpropane tri(
meth)acrylate, pentaerythritol tri(meth)acrylate, triacrylate compounds such as propylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritoltetra(meth)acrylate, and ditrimethylolpropanetetra(meth)acrylate
Examples include acrylate and tetrafunctional or higher functional hepta-acrylate compounds such as propionic acid-modified dipentaerythritol tetra(meth)acrylate.

These reactive diluents may be used as necessary within the scope of the invention. Generally, as the amount added increases, shrinkage occurs during the effect, so sufficient consideration must be given to the allowable amount.

In addition to the above-mentioned components, other components can be included in the radiation-curable coating composition of the present invention.

Such ingredients include various additives, catalysts, antioxidants, UV absorbers, antistatic agents, defoamers, plasticizers, desiccants, leveling agents, wetting and penetrating agents, photoinitiators, and stabilizers. and so on. These components may be used as necessary within the scope of the invention.

The radiation-curable coating composition containing the pigment of the present invention has a molecular weight of 1,000 to 50.00 (L), has at least one acryloyl group and/or methacryloyl group in one molecular chain, and has a hydrophilic polar group. 0~2,000eq./106
It is obtained by dispersing the pigment (B) in the urethane resin (mu) containing g and, if necessary, the other components mentioned above. As a dispersion method, a conventional known method is used.

Examples of dispersing machines include those commonly used in the color material industry, such as sand grind mills, ball mills, roll mills,
Attritor, Daysilver, etc. are optionally used.

The radiation-curable coating composition of the present invention thus obtained has excellent pigment dispersibility and dispersion stability.

This radiation-curable coating composition is applied to a material used for precoat metal to form a cured coating. Examples of the above-mentioned materials include steel plates such as galvanized iron plates, cold-rolled steel plates, electrogalvanized steel plates, aluminum plated steel plates, tinplate, tin-free steel, and stainless thin plates, and aluminum plates. In order to provide paint adhesion and corrosion resistance, these materials are also used after undergoing pre-treatments such as crystalline phosphate treatment, amorphous chromate treatment, and composite oxide film treatment.

The coating structure formed on the above-mentioned material using the present composition may be a single layer structure made of one type of composition, or may be a multilayer structure made of two or more layers made of different compositions.

Further, the present composition may be applied directly onto the material, or a primer may be applied onto the material and the present composition may be applied thereon.

When painting using this composition, various conventionally known methods are possible. Examples include spray coat, roller coat, curtain flow coat, and knife coat.

The coating film is cured by irradiation with radiation.

Radiation used in the present invention includes ultraviolet rays, electron beams, gamma rays, neutron beams, and the like. When using ultraviolet radiation, it is desirable to add a photoinitiator to the radiation-curable coating composition.

Photoinitiators include acetophenone, benzophenone,
benzoin ethyl ether, benzyl methyl ketal,
Benzylethyl ketal, benzoin isobutyl ketone, hydroxydimethyl phenyl ketone, l-hydroxycyclohexylphenyl ketone, 2,2-jethoxyacetophenone, Michler's ketone, 2-hydroxy-2-
Methylpropiophenone, benzyl, diethylthioxanthone, 2-chlorothioxanthone, benzoylethoxyphosphine oxide, l-trimethylbenzoyldiphenylphosphine oxide, etc. can be used.

If necessary, photosensitizers such as n-butylamine and di-n-butylaminetriethylamine may also be used.

The scanning method or curtain beam method can be used as the electron beam irradiation machine, and the absorbed dose is 1 to 20 Mrad.
Preferably 2 to 15 Mrad is good. Absorbed dose is IMr
If it is less than ad, the curing reaction will be insufficient, and if it exceeds 20 Mrad, the energy efficiency used for curing will decrease or excessive crosslinking will proceed, which is not preferable.

The laminated precoated metal according to the present invention includes (1) a top coat layer using the above radiation-curable coating composition, (1) an intermediate coat layer, (2)
It consists of an undercoat layer if necessary.

The resin used in the intermediate coating layer is appropriately selected from conventionally known thermosetting resins and radiation curable resins. Examples of thermosetting resins include amine alkyd, oil-free polyester, vinyl-modified alkyd, solution-type vinyl, organosol, plastisol, epoxy, epoxy ester, bake-type acrylic, silicone alkyd, silicone acrylic, silicone polyester, polyvinyl fluoride, Examples include polyvinylidene fluoride.

Furthermore, examples of radiation-curable resins include polyester acrylate, epoxy acrylate, polyurethane acrylate, polyether acrylate, oligoacrylate, alkyd acrylate, and polyol acrylate.

Radiation-curable coating compositions according to the invention may also be used.

The intermediate coating layer consists of the above resin and, if necessary, pigments and various additives.

As the pigment, those used in the various color material industries mentioned above are used. These blending ratios and dispersion methods may be conventionally known amounts and methods.

The undercoat layer, which is used as necessary, is mainly used to impart rust prevention properties. There are no particular restrictions on the resin as long as it achieves this purpose, but examples include acrylic resins, polyester resins with excellent processability, and epoxy resins with excellent rust prevention and chemical resistance. can give.

The laminated precoat metal according to the present invention is produced by forming an undercoat layer, if necessary, on the material used for the precoat metal, and then applying, drying, and curing the colored intermediate coating material by a conventionally known method to form a colored intermediate coating layer. Let it form. Thereafter, the radiation-curable coating composition of the present invention may be applied onto the colored intermediate coat layer. As a result, a precoated metal can be obtained that has excellent appearance, hardness, workability, and stain resistance that cannot be obtained with conventional precoated metals.

The adhesion between the top coat and intermediate coat is also very good.

(Function) The radiation-curable resin composition and coating composition according to the present invention can improve the wettability of the interface due to the hydrophilic polar groups contained in the urethane resin, and therefore can obtain excellent interlayer adhesion. be able to. In addition, the dispersibility of the pigment contained,
It has excellent dispersion stability.

Furthermore, it has radiation curability due to the acryloyl group and/or methacryloyl group. Therefore, the pre-coated metal produced using the radiation-curable coating composition according to the present invention not only has excellent interlayer adhesion, but also reduces the coloring power in the coating when pigments are used. (No color separation occurs). The precoated metal thus obtained exhibits an appearance with excellent gloss and sharpness. Furthermore, it is possible to obtain a material that satisfactorily satisfies the other performance requirements of Brehut metal, such as hardness, workability, and stain resistance.

Furthermore, a new type of laminated precoat metal can be obtained which has the above-mentioned excellent properties not found in conventional precoat metals and is also excellent in appearance and design.

(Example) Examples of the present invention will be described below. In the examples, parts simply indicate parts by weight.

(1) A thermometer on the production side of copolymerized polyester polyol,
In an autoclave equipped with a stirrer, 290 parts of dimethyl terephthalate, 290 parts of dimethyl isophthalate, 444 parts of ethylene glycol, 4 parts of neopentyl glycol
00 parts and 0.68 parts of tetrabutoxy titanate were charged, and the mixture was heated at 150 to 230°C for 120 minutes to carry out a transesterification reaction. Next, 292 parts of adipic acid was added, and the reaction was further carried out at 220 to 230°C for 1 hour. After the temperature of the reaction system was raised to 250° C. over 30 minutes, the pressure of the system was gradually reduced to 10 mHg after 45 minutes, and the reaction was continued for an additional 60 minutes. The obtained copolymerized polyester polyol a had a molecular weight of 200G and an acid value of 5eq/10''g.

■ Production side of urethane acrylate resin 8,100 parts of the copolymerized polyester polyol obtained in (1), 80 parts of toluene, and 80 parts of methyl ethyl ketone were charged into a reaction vessel equipped with a thermometer, a stirrer, and a reflux type cooler, and after dissolving. ,
24.4 parts of inphorone diisocyanate and 0.03 part of dibutyltin dilaurate were added and reacted at 70 to 80°C for 3 hours to obtain an incyanate-terminated prepolymer. The reaction vessel was cooled to 60°C, 36 parts of pentaerythritol triacrylate was added, and the mixture was reacted at 60 to 70°C for 6 hours to obtain a solution of urethane acrylate resin A having an active ingredient concentration of 50% by weight.

The molecular weight of urethane acrylate resin A was 3.000. Copolymerized polyester polyols be obtained by the same manufacturing method as above are shown in Table 1, and urethane acrylate resins B-G are shown in Table 2.

(3) Example 11 of blending and curing bismethylene spiroorthocarbonate with urethane acrylate resin 225 parts of urethane acrylate A and 3,9-
dimethylene-1,5,7,11-tetraoxaspiro [
5,5] Pour 25 parts of undehyde, attach a stirring bar and a cooling tube with a calcium chloride pipe, and add 250 parts of dry toluene, 1.5 mo1% of AIBN, and 1% of benzine sulfonium salt 3■O under a stream of dry nitrogen. The mixture was thoroughly mixed and dissolved, cast onto release paper, and cured at 80°C for 1 hour and at 120°C for 3 hours.

The volume shrinkage rate determined from the change in specific gravity was 0.5%, which was shown to be improved from 4.5x of the non-blended product.

Table 3 shows the results of a similar experiment.

The curable resin composition of the present invention can suppress shrinkage during curing, thereby preventing the occurrence of internal stress, warping, deformation, and adhesion of the cured product. It does not cause problems such as deterioration of properties, and can be used in molding materials, paints,
It is a composition useful in the fields of coating agents, adhesives, casting materials, etc.

Claims (1)

[Scope of Claims] 1. (A) has a molecular weight of 1,000 to 50,000, has at least one acryloyl group and/or methacryloyl group in one molecule, and has 0 to 2 hydrophilic polar groups; 000
eq. /10^6g of urethane resin and (B)
A monomer having the structure shown by formulas (1) to (5) ▲ Formula,
There are chemical formulas, tables, etc. ▼ (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (4) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (5) (R represents an alkyl group, an aryl group, an unsaturated alkyl group, an ester group, an imide group, or an amide group, and Y represents hydrogen, a halogen, an alkyl group, or an unsaturated alkyl group. Indicates any of a saturated alkyl group, aryl group, hydroxyl group, alkoxyl group, carboxyl group, silyl group, amino group, nitro group, or nitrile group, and when there are two or more of each in one molecule,
They may be the same or different. ) A curable resin composition characterized in that the blending ratio thereof satisfies the following formula. A+B=100 (weight%) 10 (weight%)≦A, B≦90 (weight%)