JPH10147626A - Production of polyurethane resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin capable of improving curing characteristics without lowering physical properties of coated film, by reacting a specific (meth) acryl monomer with a polyisocyanate compound. SOLUTION: (A) A dihydroxy functional group-containing (meth)acryl monomer of the formula (R1 is H, a 1-6C alkyl, fluorine atom, a 1-6C fluoroalkyl, etc.; R2 is a 1-6C organic group; R3 is H or methyl) is reacted with (B) a polyisocyanate compound (e.g. 1,6-hexane diisocyanate). For example, the reaction is carried out in the ratio of <=1 equivalent of isocyanate group of the component B to 1 equivalent of hydroxyl group of the component A in a bulky state or in an organic solvent under heating at room temperature to 120 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel method for producing an unsaturated group-containing polyurethane resin, and more particularly, to a novel method for producing a polyurethane resin having an unsaturated group.
A novel process for producing an unsaturated group-containing polyurethane resin which has good active energy rays and / or thermosetting properties and can be suitably used as a coating resin capable of forming a coating film having excellent properties such as adhesion. About.

[0002]

2. Description of the Related Art Unsaturated group-containing acrylic resins and polyester resins have been widely used as photo-curing resins and thermosetting resins. Resins are being studied. As a method for producing an unsaturated group-containing polyurethane resin, for example, a method in which an unsaturated group is introduced into a molecule by reacting a diisocyanate compound, a dihydroxy compound, and a hydroxyl group-containing unsaturated monomer such as hydroxyethyl (meth) acrylate is generally used. Is being done.

However, in the above-mentioned method, since unsaturated groups can be introduced only at the terminal of the molecule, linear polyurethane resins can introduce only two unsaturated groups per molecule, Therefore, there is a problem that the curability of the resin is inferior.

In order to improve the above curability, a method of branching the polymer main chain using a triisocyanate compound or a trihydroxy compound has been developed. However, when the polyurethane resin is branched, the physical properties of the coating film deteriorate. There was a problem of doing.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to develop an unsaturated group-containing polyurethane resin which does not have the above-mentioned disadvantages, that is, an unsaturated group-containing polyurethane resin which can improve curability without deteriorating coating film properties. It was done as.

The present inventors have conducted intensive studies to solve the above-mentioned disadvantages of the prior art. As a result, they have found that by reacting a (meth) acrylic monomer containing two primary hydroxyl groups in one molecule with a polyisocyanate compound, the above-mentioned drawbacks of the prior art are solved and the object is achieved. Was. The present invention has been completed based on such new knowledge.

According to the present invention, (A) the following general formula (I)

[0008]

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(Wherein R ₁ is a hydrogen atom, having 1 to 6 carbon atoms)
Alkyl group, a fluorine atom, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, an aralkyl group, a furyl group or a thienyl group, R ₂ represents an organic group having 1 to 6 carbon atoms, R ₃ Represents a hydrogen atom or a methyl group). A process for producing an unsaturated group-containing polyurethane resin, comprising reacting a (meth) acrylic monomer containing a dihydroxy functional group represented by .

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method for producing an unsaturated group-containing polyurethane resin of the present invention will be described in detail.

Dihydroxy functional group-containing (meth) acrylic
Monomer (A): The dihydroxy functional group-containing (meth) acrylic monomer (A) used in the method of the present invention is a compound represented by the following general formula (I).

[0012]

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In the general formula (I), the “alkyl group having 1 to 6 carbon atoms” as R ₁ may be linear or branched, for example, methyl, ethyl, n-propyl Group, isopropyl group, n-butyl group, isobutyl group,
Examples thereof include a sec-butyl group, a tert-butyl group, and an n-hexyl group. The “fluoroalkyl group having 1 to 6 carbon atoms” is a group in which at least one hydrogen atom of the above alkyl group is substituted with a fluorine atom, and examples thereof include a fluoropropyl group, a fluorobutyl group, and a trifluoropropyl group. . Examples of the “aryl group” include a phenyl group, a toluyl group, a xylyl group, and the like. Examples of the “aralkyl group” include a benzyl group, a phenethyl group and the like. Among R ₁ , a lower alkyl group having 1 to 4 carbon atoms such as a methyl group and an ethyl group is particularly preferable.

In the general formula (I), the “organic group having 1 to 6 carbon atoms” as R ₂ may be linear or branched.

The dihydroxy functional group-containing (meth) acrylic monomer (A) is a carboxyl group-containing unsaturated monomer having the following general formula (II):

[0016]

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(Wherein R ₁ is a hydrogen atom, having 1 to 6 carbon atoms)
Represents an alkyl group, a fluorine atom, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, an aralkyl group, a furyl group or a phenyl group, and R ₂ represents an organic group having 1 to 6 carbon atoms). Is a compound obtained by subjecting a hydroxyoxetane compound to an addition reaction, and has two primary hydroxyl groups in one molecule. When a hydroxyoxirane group-containing compound is used instead of the hydroxyoxetane compound, one secondary hydroxyl group is necessarily generated in the resulting compound,
There is a problem that a low-molecular-weight product or the like is generated due to a difference in reactivity with an isocyanate group during polyurethane conversion.

Examples of the carboxyl group-containing unsaturated monomer include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, and 5-carboxypentyl (meth) acrylate. Can be Examples of the hydroxyoxetane compound represented by the general formula (II) include:
3-hydroxymethyloxetane, 3-methyl-3-hydroxymethyloxetane, 3-methyl-3-hydroxyethyloxetane, 3-methyl-3-hydroxypropyloxetane, 3-methyl-3-hydroxybutyloxetane, 3-methyl- 3-hydroxyoctyloxetane, 3-ethyl-3-hydroxyethyloxetane,
3-ethyl-3-hydroxypropyl oxetane, 3-
Ethyl-3-hydroxybutyl oxetane, 3-ethyl-3-hydroxyoctyl oxetane and the like can be mentioned.

The dihydroxy functional group-containing (meth) acrylic monomer (A) is obtained by mixing the above-mentioned carboxyl group-containing unsaturated monomer and the above-mentioned hydroxyoxetane compound in a bulk state or in an organic solvent, if necessary, in an amount of about 500 to 1,000 p.
pm in the presence of a radical polymerization inhibitor in the range of about 80
It can be obtained by heating and reacting at a temperature in the range of ~ 120 ° C for about 30 minutes to 5 hours. In addition, a reaction may be performed by adding a catalyst in order to shorten the reaction time. As a catalyst that can be used, a known reaction catalyst can be used. Specifically, tertiary amines such as triethylamine, tripropylamine, and tributylamine; amines of organic acids such as formic acid, acetic acid, lactic acid, and propionic acid Salts; alkali metal hydroxides such as sodium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; formic acid, acetic acid,
Lactic acid, alkaline earth metal salts of organic acids such as propionic acid; tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride;
Dimethyl diethyl ammonium chloride, tetramethyl ammonium bromide, tetraethyl ammonium bromide, tetrapropyl ammonium bromide,
Quaternary ammonium salts such as tetrabutylammonium bromide and dimethyldiethylammonium bromide; benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide Etc. 4th
Grade phosphonium salts; esterified products of sulfonic acids such as benzenesulfonic acid and dodecylbenzenesulfonic acid with alcohols such as propanol and butanol; esterified products of the sulfonic acids and epoxy group-containing compounds; mono- or diesters of phosphoric acid; Examples include esterified products of an acid and an epoxy group-containing compound.

The above-mentioned (meth) acrylic monomer having a dihydroxy functional group (A) can be easily isolated by distillation or the like.

In the present invention, the dihydroxy functional group-containing (meth) acrylic monomers (A) described above can be used alone or in combination of two or more.

Polyisocyanate compound (B): The polyisocyanate compound (B) used in the method of the present invention comprises 1
A compound having two or more isocyanate groups in the molecule, and a compound generally used for producing a polyurethane resin can be similarly used. Such polyisocyanate compounds include, for example, hexamethylene diisocyanate, trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-
Aliphatic diisocyanate compounds such as butylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, and lysine diisocyanate; isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4- (or -2,6- A) alicyclic diisocyanate compounds such as diisocyanate and 1,3- (or -1,4-) di (isocyanatomethyl) cyclohexane; xylylene diisocyanate, meta-xylylene diisocyanate, tetramethyl xylylene diisocyanate, tolylene diisocyanate; 4,4'-diphenylmethane diisocyanate, 1,5-naphthalenediisocyanate, 1,4-naphthalenediisocyanate,
4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, (m- or p-)
Aromatic diisocyanate compounds such as phenylene diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, bis (4-isocyanatophenyl) sulfone, isopropylidenebis (4-phenylisocyanate) Triphenylmethane 4,4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanatebenzene,
2,4,6-triisocyanate toluene, 4,4'-
Polyisocyanate compound having three or more isocyanate groups such as dimethyldiphenylmethane 2,2 ', 5,5'-tetraisocyanate; ethylene glycol, propylene glycol, 1,4-butylene glycol, polyalkylene glycol, trimethylolpropane, hexane Adducts obtained by reacting an amount of a polyisocyanate compound in which an isocyanate group is in excess with respect to a hydroxyl group of a polyol such as a triol; hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4
Burette type adducts such as' -diphenylmethane diisocyanate and 4,4'-methylenebis (cyclohexyl isocyanate), and isocyanuric ring type adducts.

In the present invention, an unsaturated group-containing polyurethane resin can be obtained by the reaction between the dihydroxy functional group-containing (meth) acrylic monomer (A) and the polyisocyanate compound (B) described above.

The above reaction is not particularly limited.
The isocyanate group of the polyisocyanate compound (B) is not more than 1 equivalent per one hydroxyl group of the dihydroxy functional group-containing (meth) acrylic monomer (A) in a bulk state or in an organic solvent in the range of room temperature to 120 ° C. By heating at a temperature and reacting until substantially no unreacted isocyanate groups are present, an unsaturated group-containing polyurethane resin can be produced.

In the above reaction, if necessary, a known catalyst for urethane synthesis can be used.
Further, a part of the dihydroxy functional group-containing (meth) acrylic monomer (A) can be replaced with a polyfunctional hydroxy compound containing no unsaturated group.

Known catalysts for the above urethane synthesis include, for example, bismuth nitrate, lead 2-ethylhexanoate, lead benzoate, lead oleate, sodium trichlorophenolate, sodium propionate, lithium acetate, potassium oleate , Tetrabutyltin, tributyltin chloride, dibutyltin dichloride, butyltin trichloride,
Tin chloride, tributyltin-o-phenolate, tributyltin cyanate, tin octylate, tin oleate, tin tartrate, dibutyltin di (2-ethylhexylate), dibenzyltin di (2-ethylhexylate), dibutyltin dilaurate, dibutyltin dilaurate Isooctyl maleate, dibutyltin sulfide, dibutyltin dibutoxide, dibutyltin bis (o-phenylphenolate), dibutyltin bis (acetylacetonate), di (2-ethylhexyl) tin oxide, titanium tetrachloride, dibutyltitanium dichloride, tetrabutyl titanate , Butoxytitanium trichloride, iron trichloride, iron (III) 2-ethylhexanoate, iron acetylacetone (II
I), ferrocene, antimony trichloride, antimony pentachloride, triphenylantimony dichloride, tolphenylantimony, uranium nitrate, cadmium nitrate, cadmium diethyldithiophosphate, cobalt benzoate, cobalt 2-ethylhexanoate, thorium nitrate, triphenyl Aluminum, trioctyl aluminum, aluminum oleate, diphenylmercury, zinc 2-ethylhexanoate, zinc naphthenate, nickelocene, hexacarbonylmolybdenum, cerium nitrate, vanadium trichloride, copper 2-ethylhexanoate, copper acetate, 2-ethyl Manganese hexanoate,
Metal catalysts such as zirconium 2-ethylhexanoate, zirconium naphthenate, triphenylarsenic, arsenic trichloride, boron trifluoride-diethyl ether complex, pyridine borane, calcium acetate and barium acetate; tetra-n-butyl-1,3 -Diacetyloxydistannoxane, tetra-n-propyl-1,3-diacetyloxydistannoxane, tetra-n-propyl-1-chloro-3-hydroxydistannoxane, tetra-n-butyl-1-chloro- 3-hydroxydistannoxane, tetramethyl-
1,3-diacetyloxydistannoxane, tetramethyl-1-chloro-3-acetyloxydistannoxane,
Tetra-n-butyl-1,3-diformyloxydistannoxane, tetra-n-butyl-1,3-diacryloxydistannoxane, tetra-n-butyl-1,3-dilauryloxydistannoxane, Tetra-n-butyl-
1,3-dioleyloxydistannoxane, tetra-n
-Butyl-1,3-distearyloxydistannoxane, tetra-n-butyl-1,3-diphenylacetyloxydistannoxane, tetra-n-butyl-1,3-
Diisocyanodistanoxane, tetra-n-butyl-1
-Acetyloxy-3-hydroxydistannoxane, tetra-n-propyl-1-acetyloxy-3-hydroxydistannoxane, tetramethyl-1-acetyloxy-3-hydroxydistannoxane, tetra-n-butyl-1 , 3-Dichlorodistannoxane, tetramethyl-
1,3-dichlorodistannoxane, tetra-n-butyl-1,3-dipropoxydistannoxane, tetra-n-
Propyl-1,3-dipropoxydistannoxane, tetra-n-butyl-1-propoxy-3-acetyloxydistannoxane, tetra-n-propyl-1-hydroxy-3-ethoxydistannoxane, 1,1 -Dibutyl-
Organotin compounds such as 3,3-dipropyl-1-hydroxy-3-acetyloxydistannoxane and 1,3-dipropyl-1,3-dibutyl-1-chloro-3-hydroxydistannoxane may be mentioned. it can.

The organic solvent used in the above reaction is not particularly limited as long as it does not have active hydrogen.
Any of ketone, ether and halogenated hydrocarbon solvents can be used. As a specific example, for example,
Acetone, methyl ethyl ketone, 2-pentanone, 2-
Hexanone, methyl isobutyl ketone, isophorone, cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, 3-
Methoxybutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl propionate, ethyl propionate, butyl propionate,
Dioctyl adipate, ethyl oxalate, diethyl malonate, maleate, dibutyl tartrate, tributyl citrate, sebacate, phthalate,
Ethylene glycol monoacetate, ethylene diacetate,
Cellosolve acetate, carbitol acetate, ethyl acetoacetate, diethyl ether, dipropyl ether, dibutyl ether, ethyl vinyl ether, methoxytoluene,
Diphenyl ether, dioxane, propylene oxide, acetal, glycerin ether, tetrahydrofuran, 1,2-dimethoxyethane, cellosolve, methyl cellosolve, butyl cellosolve, methyl carbitol,
2-methoxyethanol, 2-ethoxyethanol, 2
-Isopropoxyethanol, 2-butoxyethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether,
-Methoxy-2-propanol, dipropylene glycol monomethyl ether, dichloromethane, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, hexachloroethane, 1,1-dichloroethylene, 1,2-dichloroethylene, propyl chloride, chlorobenzene, p-
Examples thereof include chlorotoluene, 1,2-dibromoethane, propyl bromide, bromobenzene, fluorobenzene, trichlorofluoromethane, and trichloroethylene.

Although the molecular weight of the unsaturated group-containing polyurethane resin obtained as described above is not particularly limited, it generally ranges from about 300 to about 200,000, preferably from about 500 to about 100,000. It is preferable to have a number average molecular weight within the range.

The unsaturated group-containing polyurethane resin obtained by the method of the present invention is suitable for use as a curable resin composition. In this case, if necessary, a pigment, a solvent,
A curing catalyst, a fluidity-controlling agent and other additives can be added and used.

The use of the curable resin composition containing the unsaturated group-containing polyurethane resin obtained by the method of the present invention is not particularly limited, and may be selected from a wide range, for example, paints, prints, colorants and the like. Can be applied to the field.

The curable resin composition containing the unsaturated group-containing polyurethane resin obtained by the method of the present invention is preferably used after being dissolved or dispersed in an organic solvent.
As the organic solvent, those that do not substantially react with the curable resin composition are used. Specifically, aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone Solvents; ester solvents such as ethyl acetate, propyl acetate and butyl acetate; alcohol solvents such as butanol and ethylene glycol monobutyl ether. These can be used alone or in combination of two or more.

The mixing ratio of the organic solvent is not particularly limited, and may be used as needed. Usually, the solid content of the curable resin composition is about 1 to 95% by weight, preferably about 10 to 90% by weight.
A range of weight percent is preferred.

When the curable resin composition containing the unsaturated group-containing polyurethane resin obtained by the method of the present invention is used as a thermosetting resin composition, the curable resin composition is dissolved or dispersed in an organic solvent. The resulting material is applied to a substrate, printed, and then cured by heating at a temperature of about 40 ° C. to 250 ° C. for about 30 seconds to 120 minutes.

The substrate is not particularly limited as long as it is dissolved by an organic solvent or does not dissolve or deteriorate by heating at about 60 ° C., and a conventionally used substrate is selected and used. be able to. In particular,
Treated or untreated metals, plastics, papers, fibers, and the like, plate-like or mold-types obtained by coating these materials, and the like.

As a method of coating and printing on the substrate, for example, ordinary coating or printing means such as spray coating, brush coating, roller coating, dip coating and screen printing can be used. Preferably, the dry film thickness ranges from about 1 to 100 microns.

When the curable resin composition containing the unsaturated group-containing polyurethane resin obtained by the method of the present invention is used as an active energy ray-curable resin composition,
After the curable resin composition is applied and printed on a substrate, it is cured by irradiating it with an active energy ray. Preferably, the dry film thickness ranges from about 1 to 100 microns.

The active energy rays include ultraviolet rays and electron beams. When the composition is cured by ultraviolet irradiation, it is necessary to add a photopolymerization initiator to the composition in advance. As the photopolymerization initiator, a general photopolymerization initiator of a type that is excited by irradiation with ultraviolet rays to generate a radical is used, and examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, and benzoin isopropyl. Ether, benzoin n-butyl ether, α-hydroxyisobutylphenone, benzophenone, p-methylbenzophenone, Michler's ketone, acetophenone, 2-chlorothioxanthone, anthraquinone, 2-methylanthraquinone, phenyl disulfide, 2-nitrofluorene, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane 1,2-benzyl-2-
Dimethylamino-1- (4-morpholinophenyl) -butanone 1, 2,4,6-trithiophosphyl oxide, diethylthioxanthone and the like. These photopolymerization initiators can be used alone or as a mixture of two or more, and the compounding amount is preferably in the range of 0.1 to 10% by weight based on the amount of the unsaturated group-containing polyurethane resin.

In order to accelerate the photopolymerization reaction by these photopolymerization initiators, a photosensitizer may be used in combination with the photopolymerization initiator. As a photosensitizer that can be used in combination,
For example, triethylamine, triethanolamine, 2
-Tertiary amines such as dimethylaminoethanol; alkylphosphines such as triphenylphosphine; and thioether-based photosensitizers such as β-thiodiglycol. Each of these photosensitizers can be used alone or in combination of two or more. The compounding amount is 0.1 to 1 based on the amount of the unsaturated group-containing polyurethane resin.
A range of 0% by weight is preferred.

On the other hand, when electron beam irradiation is used, it is not necessary to incorporate the above-mentioned photopolymerization initiator or photosensitizer into the unsaturated group-containing polyurethane resin obtained by the method of the present invention.

When the above-mentioned unsaturated group-containing polyurethane resin is cured by irradiation with an electron beam, the electron beam generating sources include a Cockcroft type, a Cockcroft-Walton type, a Van de Graf type, a resonance transformer type, a transformer type, Electron beam generators such as an insulating core transformer type, a dynamitron type, a linear filament type, and a high frequency type can be used. The irradiation conditions of the electron beam at that time vary depending on the shape, thickness and the like of the unsaturated group-containing polyurethane resin obtained by the method of the present invention, but generally a dose in the range of 1 to 20 Mrad is suitable.

As an ultraviolet irradiation source, a mercury lamp, a xenon lamp, a carbon arc, a metal height lamp, sunlight and the like can be used. Irradiation conditions of the ultraviolet ray are not particularly limited, but it is preferable to irradiate a ray containing an ultraviolet ray in a range of 150 to 450 nm in air or in an inert gas atmosphere for several seconds or more. In particular, when irradiating in air, it is preferable to use a high-pressure mercury lamp.

[0042]

Industrial Applicability The unsaturated group-containing polyurethane resin obtained by the method of the present invention has good active energy rays and / or thermosetting properties, and is suitable for paints capable of forming a coating film having excellent properties such as adhesion. It can be suitably used as a resin.

[0043]

The present invention will be described more specifically below with reference to examples. “Parts” and “%” are based on weight, respectively.

Production Example 1 3-Ethyl-3-hydroxymethyloxetane 1 was placed in a 500 mL three-necked flask equipped with a stirrer and a condenser.
16 parts, acrylic acid 72 parts and tetraethylammonium bromide 0.2 part were added, and the mixture was stirred at 80 ° C. for about 5 hours to be reacted. After the reaction, the product was separated and purified on a silica gel column using chloroform as a developing solution.
The eluate is concentrated on a rotary evaporator to about 150
Parts of 1-acryloxy-2,2- (dihydroxymethyl) butane were obtained.

Production Example 2 In a 500 mL three-necked flask equipped with a stirrer and a condenser, 200 parts of 3-octyl-3-hydroxymethyloxetane, 72 parts of acrylic acid and 0.4 part of tetraethylammonium bromide were added. The mixture was stirred for about 5 hours to react. After the reaction, the product was separated and purified on a silica gel column using chloroform as a developing solution.
The eluate is concentrated on a rotary evaporator to about 250
Part of 1-acryloxy-2,2- (dihydroxymethyl) decane was obtained.

Production Example 3 3-Ethyl-3-hydroxymethyloxetane 1 was placed in a 500 mL three-necked flask equipped with a stirrer and a condenser.
16 parts, 86 parts of methacrylic acid and 0.2 parts of tetraethylammonium bromide were added, and the mixture was stirred and reacted at 80 ° C. for about 5 hours. After the reaction, the product was separated and purified on a silica gel column using chloroform as a developing solution.
The eluate is concentrated on a rotary evaporator to about 160
Parts of 1-methacryloxy-2,2- (dihydroxymethyl) butane were obtained.

Production Example 4 In a 500 mL three-necked flask equipped with a stirrer and a condenser, 200 parts of 3-octyl-3-hydroxymethyloxetane, 86 parts of methacrylic acid and 0.4 part of tetraethylammonium bromide were added. The mixture was stirred for about 5 hours to react. After the reaction, the product was separated and purified on a silica gel column using chloroform as a developing solution.
The eluate is concentrated on a rotary evaporator to about 260
Of 1-methacryloxy-2,2- (dihydroxymethyl) decane.

Example 1 165.5 parts of 1-acryloxy-2,2- (dihydroxymethyl) butane synthesized in Production Example 1 and 3 parts of di-n-butyltin dilaurate were dissolved in 500 ml of ethyl acetate, and a stirrer was used. The mixture was added to a 1-L three-necked flask equipped with a condenser and a dropping funnel, and heated to boiling with stirring in an oil bath. Next, a solution prepared by dissolving 132.7 parts of 1,6-hexanediisocyanate in 350 ml of ethyl acetate was rapidly added thereto from a dropping funnel, and the mixture was refluxed under ethyl acetate.
As a result of performing the reaction at about 77 ° C. for about 4 hours, an unsaturated group-containing polyurethane resin (a) having a number average molecular weight of about 3,000 was obtained.

Example 2 194.4 parts of 1-acryloxy-2,2- (dihydroxymethyl) decane synthesized in Production Example 2 and 3 parts of di-n-butyltin dilaurate were dissolved in 500 ml of ethyl acetate, and a stirrer was used. The mixture was added to a 1-L three-necked flask equipped with a condenser and a dropping funnel, and heated to boiling with stirring in an oil bath. Next, a solution prepared by dissolving 104.2 parts of 1,6-hexanediisocyanate in 350 ml of ethyl acetate was rapidly added thereto from a dropping funnel, and the mixture was refluxed under ethyl acetate.
As a result of performing the reaction at about 77 ° C. for about 4 hours, an unsaturated group-containing polyurethane resin (b) having a number average molecular weight of about 3,000 was obtained.

Example 3 172.0 parts of 1-methacryloxy-2,2- (dihydroxymethyl) butane synthesized in Production Example 3 and 3 parts of di-n-butyltin dilaurate were dissolved in 500 ml of ethyl acetate, and a stirrer was used. The mixture was added to a 1-L three-necked flask equipped with a condenser and a dropping funnel, and heated to boiling with stirring in an oil bath. Next, a solution prepared by dissolving 127.7 parts of 1,6-hexanediisocyanate in 350 ml of ethyl acetate was rapidly added thereto from a dropping funnel, and the mixture was refluxed under ethyl acetate.
The reaction was carried out at about 77 ° C. for about 4 hours. As a result, an unsaturated group-containing polyurethane resin (c) having a number average molecular weight of about 3,000 was obtained.

Example 4 198.8 parts of 1-methacryloxy-2,2- (dihydroxymethyl) decane synthesized in Production Example 4 and 3 parts of di-n-butyltin dilaurate were dissolved in 500 ml of ethyl acetate, and a stirrer was used. The mixture was added to a 1-L three-necked flask equipped with a condenser and a dropping funnel, and heated to boiling with stirring in an oil bath. Next, a solution prepared by dissolving 100.8 parts of 1,6-hexanediisocyanate in 350 ml of ethyl acetate was rapidly added to the mixture from a dropping funnel, and the mixture was refluxed under ethyl acetate.
As a result of performing the reaction at about 77 ° C. for about 4 hours, an unsaturated group-containing polyurethane resin (d) having a number average molecular weight of about 3,000 was obtained.

Example 5 122.0 parts of 1-acryloxy-2,2- (dihydroxymethyl) butane synthesized in Production Example 1, 29.5 parts of tetramethylene glycol, and 3 parts of di-n-butyltin dilaurate were treated with acetic acid. Dissolve in 500 ml of ethyl and add to a 1 L 3-neck flask equipped with stirrer, condenser and dropping funnel,
The mixture was heated in an oil bath with stirring and brought to a boil. next,
A solution prepared by dissolving 148.5 parts of 1,6-hexanediisocyanate in 350 ml of ethyl acetate was rapidly added from a dropping funnel, and the mixture was reacted at about 77 ° C. under reflux of ethyl acetate for about 4 hours. Average molecular weight about 3,000
(E) was obtained.

Example 6 177.1 parts of 1-acryloxy-2,2- (dihydroxymethyl) butane synthesized in Production Example 1, 13.4 parts of trimethylolpropane and 3 parts of di-n-butyltin dilaurate were treated with acetic acid. The residue was dissolved in 500 ml of ethyl, added to a 1 L three-necked flask equipped with a stirrer, a condenser and a dropping funnel, and heated to boiling with stirring in an oil bath. Next, a solution prepared by dissolving 109.5 parts of 1,6-hexanediisocyanate in 350 ml of ethyl acetate was rapidly added to the solution through a dropping funnel, and the solution was refluxed at about 77 ° C. under reflux of ethyl acetate at about 77 ° C.
As a result of performing the reaction for hours, an unsaturated group-containing polyurethane resin (f) having a number average molecular weight of about 3,000 was obtained.

Comparative Example 1 23.2 parts of hydroxyethyl acrylate, 120.3 parts of hexamethylene glycol and di-n-dilaurate
3 parts of butyltin were dissolved in 500 ml of ethyl acetate, added to a 1 L three-necked flask equipped with a stirrer, a condenser and a dropping funnel, and heated to boiling with stirring in an oil bath. Next, tetramethylene diisocyanate 10
A solution prepared by dissolving 9.5 parts in 350 ml of ethyl acetate was rapidly added from a dropping funnel, and the mixture was refluxed at about 77 ° C. under ethyl acetate.
As a result of performing the reaction for about 4 hours in the vicinity, a polyurethane resin containing a terminal unsaturated group having a number average molecular weight of about 3,000 (g)
I got Comparative Example 2 34.8 parts of hydroxyethyl acrylate, 95.6 parts of hexamethylene glycol, trimethylolpropane 1
3.4 parts and 3 parts of di-n-butyltin dilaurate are dissolved in 500 ml of ethyl acetate, added to a 1 L three-necked flask equipped with a stirrer, a condenser and a dropping funnel, and heated with stirring in an oil bath. And brought to a boil. Next, a solution prepared by dissolving 13.4 parts of tetramethylene diisocyanate in 350 ml of ethyl acetate was rapidly added thereto from a dropping funnel,
The reaction was carried out at about 77 ° C. for about 4 hours under reflux of ethyl acetate, and as a result, a branched terminal unsaturated group-containing polyurethane resin (h) having a number average molecular weight of about 3,000 was obtained.

To 100 parts of the unsaturated group-containing polyurethane resin solutions obtained in Examples 1 to 6 and Comparative Examples 1 and 2, "IRGAC
URE651 "(trade name, Ciba-Geigy, 2,2-
1.75 parts of dimethoxy-2-phenylacetophenone) was applied to a mild steel mild steel sheet, dried at 80 ° C. for 20 minutes to volatilize the solvent, and then cured by UV irradiation using a high-pressure mercury lamp. The properties and adhesion of the cured coatings were tested.

Also, 100 parts of the unsaturated group-containing polyurethane resin solutions obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were added with “Perbutyl O” (trade name, manufactured by NOF Corporation, t-butylperoxy-2-). Ethyl hexanoate (3 parts) was applied to a mild steel mild steel sheet and then baked for 20 minutes to test the curability and adhesion of the cured film.

Table 1 shows the results.

The test method in Table 1 is as follows.

Minimum UV irradiation without scratching: The minimum UV irradiation at mj / cm ² at which the cured coating surface did not change at all when wiped 10 times with gauze impregnated with xylol Express. Smaller numbers indicate better curability.

Minimum baking temperature at which no damage is caused : The minimum baking temperature at which the coating film surface did not change at all when the cured coating film surface was wiped 10 times with gauze impregnated with xylol. Smaller numbers indicate better curability.

Adhesion: JIS K-5400 8.5.
2 (1990), a 100 mm 1 mm × 1 mm Gobang pattern was formed on the coating film, an adhesive cellophane tape was adhered to the surface, and the number of Gobang pattern films remaining on the coated surface after rapidly peeling was determined. Recorded.

[0062]

[Table 1]

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Osamu Isozaki 4-171-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Kansai Paint Co., Ltd.

Claims (2)

[Claims] (A) The following general formula (I): (Wherein, R ₁ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorine atom, a fluoroalkyl group having 1 to 6 carbon atoms,
An allyl group, an aryl group, an aralkyl group, a furyl group or a phenyl group; R ₂ represents an organic group having 1 to 6 carbon atoms;
R ₃ represents a hydrogen atom or a methyl group), and a (meth) acrylic monomer containing a dihydroxy functional group represented by the formula (B):
A method for producing an unsaturated group-containing polyurethane resin, comprising reacting a polyisocyanate compound. 2. A curable resin composition containing an unsaturated group-containing polyurethane resin obtained by the method according to claim 1.