JPH03199227A - Manufacture of curable resin - Google Patents

Abstract

PURPOSE: To provide a process for preparing a curable resin which can be easily cured, can yield a cured coating possessing excellent flexibility, solvent resistance, contamination resistance and other properties possesses excellent adhesion to plastics and rubbers, and is suitable for paints and the like by reacting a polyisocyanate with a polyol and a plurality of specified compd.

CONSTITUTION: At least two compds. selected from among a polyisocyanate (pref., 2,4-tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate or the like), a polyol (pref., a diol prepd. by reacting polypropylene glycol or the like with adipic acid), and a compd. represented by formula I [R¹ represents H or methyl; R² represents formula II (x is 1 to 30; y is 3 to 10; m is 1 to 20; and n is 0 to 20)] are reacted with each other to obtain the curable resin.

COPYRIGHT: (C)1991,JPO

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing a curable resin, and more specifically, a curable resin that is easily cured and suitable for use in paints, coatings, lining agents, adhesives, etc. The present invention relates to a method for producing a synthetic resin.

[Conventional technology]

In recent years, liquid curable resins that are cured by irradiation with electron beams, ultraviolet rays, etc. have been used in a wide range of fields such as paints, coating agents, lining agents, and adhesives. This is because liquid curable resin has advantages such as reducing the amount of solvent used and improving the pot life of the resin, and also simplifies the manufacturing process, reduces energy consumption, and is non-polluting, resource-saving, and energy-saving. This is because it is expected to be effective in meeting the demands of the times.

Conventionally, liquid curable resins include unsaturated polyesters having ethylenically unsaturated groups in their molecules, polyurethane (meth)acrylates, epoxy (meth)acrylates, polyester (meth)acrylates, etc. (generally known).

Among these, polyurethane (meth)acrylate in particular is widely used because it can form a strong coating film due to the intermolecular force of urethane bonds and has excellent adhesion to metals and glass, but recently it has become more popular. There is a growing demand for polyurethane (meth)acrylates that have flexibility. Polyurethane (meth)acrylate having such flexibility can be obtained by using a polyol with a low glass transition temperature. However, although polyurethane (meth)acrylates made from polyols with low glass transition temperatures have flexibility, they have low hardness, insufficient solvent resistance, stain resistance, etc., and have practical problems. there were.

[Problem to be solved by the invention]

An object of the present invention is to provide a method for producing a curable resin that provides polyurethane (meth)acrylate that has excellent flexibility and excellent solvent resistance, stain resistance, and the like.

[Means to solve the problem]

That is, the present invention provides (A) polyisocyanate (B) polyol, (C) the following general formula (I) CH,=CR'COOR2...(1) [wherein R' is a hydrogen atom or a methyl group, R2 (X is a number from 1 to 30,
y is a number from 3 to 10, m is a number from 1 to 20, and n is a number from 0 to 20. The present invention provides a method for producing a curable resin.

Polyisocyanate used in the present invention (hereinafter referred to as “(A)
2. 4-) lylene diisocyanate, 2. 6-) lylene diisocyanate, 4.
4'-diphenylmethane diisocyanate, m-phenylene diisocyanate, xylylene diisocyanate,
Tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, 1.
4-cyclohexylene diisocyanate, 4.・4'-
dicyclohexylmethane diisocyanate), 3.3'-
dimethyl-4,4'-biphenylene diisocyanate,
3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3. 3'-cyclo-4.4'-biphenylene diisocyanate, 1.5-naphthalene diisocyanate, 1.5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, 2. 2.
4-) dimethylhexamethylene diisocyanate, preferably 2.4-) lylene diisocyanate, 4.4
'diphenylmethane diisocyanate), 4. Examples include 4' dicyclohexylmethane diisocyanate.

These can be used alone or in combination of two or more.

Polyol used in the present invention (hereinafter referred to as "component (B)")
Examples of the diol include polyester diol, polyether diol, polycaprolactone diol, and polycarbonate diol.

Examples of polyester diols (hereinafter referred to as "diol-1") include general formula (II-1) 0 (wherein R3 is an alkylene group having 2 to 10 carbon atoms,
R4 is a residue of a polybasic acid described later, h is an integer of 1 to 30, and X is an integer of 1 to 10), and specific examples include ethylene glycol, polyethylene glycol, propylene. Polyhydric alcohols such as glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-benzenediol, neopentyl glycol, 1,4-cyclobenzenedimetatool, geltaric acid, phthalic acid,
Examples include diols obtained by reacting with polybasic acids such as isophthalic acid, terephthalic acid, maleic acid, fumaric acid, speric acid, adipic acid, methyladipic acid, sepatic acid, and oxalic acid.

Diol-1 is also available as a commercial product, such as "Niraporan 4009", "Niraporan 4002", "
Niraporan 4010J, "Niraporan 4040J," Niraporan 4032J, "Niraporan 4042J," Niraporan 4060J, "Niraporan 4070J,""Niraporan143","Niraporan 150J, r Nituporan 5
018J.

Examples include "Nilaporan 5019J" and "Nilaporan 5035J (manufactured by Nippon Polyurethane ■).

Among the above diol-1, polypropylene glycol,
Diols obtained by reacting polytetramethylene glycol etc. with adipic acid are preferred, and corresponding commercial products include "Niraporan 4009" and "Niraporan 400".
24 etc. are mentioned.

In addition, polyether diol (hereinafter referred to as "diol-2")
Examples of the compound represented by the general formula (II-2) HO-fR30h H(II-2) (wherein R3 is the same as above and i represents an integer of 1 to 50) can be mentioned. , specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like.

Diol-2 is also available commercially, e.g.
lf r PBG# 200 J, r PBG#300
J, r PBG #4 D OJ, r PBG #6
00J, r Fil! G#1000J, rD-400J
, rD-700J, rD-1000J, rD-1200
J, rD-2000J (manufactured by NOF Corporation), r
PTMG650” (manufactured by DuPont), rPTMGl
ooo", 1'TMG2000", rPTMG3000
", (all manufactured by Mitsubishi Chemical Industries), etc.

Among these diols, polytetramethylene glycol, polyethylene glycol, etc. are commercially available as rP.
TMG3000”, r PTMGl 000J, r
PHG#400. J, r PBG#200" etc. are preferred.

Furthermore, as polycaprolactone diol (hereinafter referred to as "diol-3"), for example, general formula (n-3) (wherein R3 and X are the same as above, j and jo
each represents an integer from 1 to 30). This diol-3 can be obtained, for example, by reacting caprolactone with polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or the like.

Diol-3 is also available as a commercial product, such as "Plaxel 203ALJ, rPlaxel 203", "
Examples include "Plaxel 205", "Plaxel 205ALJ", "Plaxel 212", "Plaxel 212ALJ", "Plaxel 220", "Plaxel 220ALJ" (manufactured by Daicel Chemical Industries, Ltd.), among which "Plaxel 205ALJ", "Plaxel 212", etc. etc. are preferred.

Examples of polycarbonate diols (hereinafter referred to as "diol-4") include DN-980゜DN-981,
Examples include polycarbonate diols represented by trade names such as DN-982, DN-983 (Japan Polyurethane 4ml), and PC-8 (100 (manufactured by PPG, USA)).

In the present invention, at least one diol selected from diol-1, diol-2, diol-3, and diol-4 is used in an amount of 5 to 99 mol%, particularly 5 to 95 mol% in component (B). It is preferable to do so. If this value is less than 5 mol%, the coating film obtained by applying and curing the resulting curable resin tends to lose flexibility, and 99 mol%
If it exceeds this amount, the resulting coating film tends to lose its curability.

(B) For tL, the following (
Polyols listed in 1) to (4) can be used. These polyols have (B) a molecular weight usually 0 to 7.
0% by weight used.

(1) A polyol having a polar group such as a carboxylic acid group, a carboxylic acid metal base, a sulfonic acid group, a sulfonic acid metal base, or a phosphoric acid group in the molecule. Here, the polar group contained in the obtained prepolymer is preferably less than 1X10-' equivalent/g.

(2) Diol having multiple (meth)acryloyl groups in the molecule. For example, diols represented by general formula (n-4) can be exemplified.

HD-CHCll, 0-R5-C11, CHOH(II
-4) CH.

[In the formula, R5 is +CH, CH2O+k, -(-CH2C
HL (k represents an integer from 1 to 20) Ha (However, W and W゛CH.

is independently -CH2CH- or 113CHCH2-) or 113, and R6 represents a hydrogen atom or a methyl group] These diols can be obtained manually as commercial products, such as "Epoxy Ester 40BAJ, "Epoxy Ester 70PAJ, rEpoxy Ester 200PAJ,"Epoxy Ester 80 MFA J,"Epoxy Ester 3
002MJ, r-epoxy ester 3002AJ (manufactured by Kyoeisha Yushi Co., Ltd.), and the like.

(3) A diol that is a (poly)oxyalkylene bisphenol derivative. For example, (poly)oxyethylene bisphenol A ether represented by general formula (n-5), (
Examples include poly)oxypropylene bisphenol A ether.

Propylene oxide adduct of glycerin (wherein R1 and R8 may be the same or different and are alkylene groups having 2 or 3 carbon atoms, l and p may be the same or different, and 1 (representing an integer of ~20) These are commercially available, for example rDA-
350FJ, rDA-400J, rDB-900J,
Examples include rDB-400J and rDA-1000J (both manufactured by NOF Corporation).

(4) Ethylene glycol, propylene glycol, tetramethylene glycol, glycerin, 2-methylpropane-1,2,3-triol, 3-methylpentane-1,3,5-triol, 1,2゜6-hexane Triol, the following general formula (II-6') Cll.

(In the formula, R9 represents a hydrogen atom or a methyl group, and qSq
' and qll may be the same or different, and 1 to 2
(represents an integer of 0), a propylene oxide adduct of ethylenediamine represented by the following general formula (n-7) (in the formula, rSr・r・′ and r... may be the same or different, and are 1 to 20 ), 4-[
Bis(2-hydroxyethyl)]-]2-hydroxypentane 1-bis(2-hydroxyethyl)amino-2-
Propatool, 1.2.3-pentatriol, 1. ．．
Low molecular weight polyols such as 2,3-butanetriol and 1,6-hexamethylene glycol.

In addition, in the present invention, in addition to these (B) JijE components,
Ethylenediamine, tetramethylenediamine, hexamethylenediamine, paraphenylenediamine, 4.4'-
A polyamine such as diaminodiphenylmethane may be used in combination. These polyamines are usually 0 to 50 in component (8).
% by weight used.

Next, a compound represented by the general formula (I) (hereinafter r(
Component C) includes hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, hydroxydecyl (meth)acrylate, polyethylene glycol (meth)acrylate. , polypropylene glycol (meth)acrylate, polytetramethylene glycol (meth)acrylate, lactone-modified hydroxyethyl (meth)acrylate represented by the following general formula (III), and the like.

(In the formula, R1 and y are the same as above, and S is 1-2
(indicates the number of 0) Among these (C), the preferred one is 2.
-Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, lactone-modified hydroxyethyl (meth)acrylate, and the like. These are available as commercial products, such as "Plaxel FMJ" and "Plaxel FAJ" (manufactured by Daicel Chemical Industries, Ltd.).

The molecular weight of the compound represented by general formula (1) is 100 to 3
000 is preferable, and particularly preferably 100 to 2000. If the molecular weight exceeds 3,000, the problem arises that the mechanical strength of the coating film obtained by applying and curing the composition decreases significantly, which is not preferable.

In the present invention, by using at least two types of compounds selected from the compounds represented by the general formula (I), the desired polyurethane having excellent flexibility, solvent resistance, and stain resistance can be obtained. You can get acrylate. If there is only one type of polyurethane acrylate, the solvent resistance and stain resistance will be lowered, which poses a practical problem if the flexibility of the polyurethane acrylate is to be maintained. Preferred combinations of component (C) include combinations of 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate and lactone-modified hydroxyethyl (meth)acrylate.

In the method for producing a curable resin of the present invention, (A) to (C)
Although the order in which the tL portions are reacted is not particularly limited, it can be produced, for example, by the following production method.

In the first step, component (8) and component (B) are reacted. In this first step, component (8) is converted to (B) lff
It is used in a 1 to 1.5 times molar excess, more preferably a 1 to 1.1 times molar excess, per 1 minute of &mff1, and the two are bonded through a urethane bond to produce a polyurethane having an isocyanate group at the end of the molecule. .

Next, in the second step, component (C) is reacted with the polyurethane produced in the first step at a ratio of approximately 0.5 to 2 equivalents per equivalent of isocyanate groups possessed by the polyurethane. Through this second step, the component (C) is bonded to the terminal end of the polyurethane via a urethane bond, and the desired curable resin is obtained.

In addition, in this method, part of the component (B) and (
It is also possible to produce an intermediate by reacting a part of component C), and then react the intermediate with a product obtained by reacting component (A) with the remainder of components (B) and (C).

The first step is usually carried out using a catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, n-butyltin laurate, or triethylamine. These catalysts are preferably used in an amount of about 0.01 to 1 part by weight based on 100 parts by weight of the total amount of starting materials used in the first step. Moreover, the reaction temperature is usually 30 to 80°C.

Moreover, the second step can be carried out in the presence of the same catalyst as above. The catalyst is preferably used in an amount of 0.01 to 1 part by weight per 100 parts by weight of the polyurethane formed in the first step. The reaction in the second step is preferably 30 to 80
Conducted at °C.

Here, the first and second steps can be performed sequentially without isolating the product of each step.

In addition, when carrying out the reaction of each step, a solvent such as methyl ethyl ketone, cyclohexanone, toluene, tetrahydrofuran, methyl isobutyl ketone, dioxane, etc. can be used as necessary.

The number average molecular weight of the curable resin obtained as described above is about 2.000 to 500,000, particularly about 3.000.
~100,000 is preferred. Number average molecular weight is approximately 2.0
If it is less than 00, the cured coating film tends to lose flexibility, and if it exceeds 500,000, the viscosity increases, making it difficult to handle.

These curable resins are generally blended in an amount of 10 to 100% by weight, preferably 30 to 100% by weight, in the total composition.

In order to use the curable resin of the present invention as a paint, coating agent, adhesive, etc., other curable polymer reactive diluents and additives may be added as necessary to the extent that the effects of the present invention are not impaired. It can be a thing.

Other curable polymers include urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, and polyamide (meth)acrylate other than those listed above.
Examples include acrylates, diene polymers having (meth)acryloyloxy groups, and siloxane polymers having (meth)acryloyloxy groups.

As a reactive diluent, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, butoxyethyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, stearyl (meth)acrylate Acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate , diethylene glycol (meth)
Acrylate, ethoxydiethylene glycol (meth)
Acrylate, benzyl (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, alkylphenoxyethyl (meth)acrylate, alkylphenoxypolyalkylene glycol (meth)acrylate, 2
-Hydroxy-3-phenyloxypropyl (meth)acrylate, tetrahydrofurfuryloxypolyalkylene glycol (meth)acrylate, dicyclopentenyloxypolyalkylene glycol (meth)acrylate, 2-hydroxyalkyl (meth)acryloyl phosphate, polyfluoro Alkyl (meth)acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, diacetone (meth)acrylamide, isobutoxymethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, t-octyl (meth)acrylamide, dialkylamino ethyl (meth)acrylate,
Vinyl acetate, ethylene glycol di(methane acrylate, propanediol di(meth)acrylate), 1.4
-butanediol di(meth)acrylate, trimethylolpropane di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1.5-hexane di(meth)acrylate, polyallene glycol di(meth)acrylate, Polypropyleph glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane trioxyethyl(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dicyclopentadiene di(meth)acrylate ) acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di(meth)acrylate of ethylene oxide adduct of bisphenol A, and the like.

In addition, additives include polyamide, polyamideimide, polyurethane, polybutadiene, chloroprene, polyether, polyester, pentadiene derivatives, styrene/butadiene copolymer, polyvinyl chloride, petroleum resin,
Examples include various polymers and oligomers such as xylene resins, epoxy resins, ketone resins, fluorine-based oligomers, silicone-based oligomers, and polysulfide-based oligomers. Furthermore, antioxidants, colorants, ultraviolet absorbers,
Silane coupling agent, thermal polymerization inhibitor, leveling agent,
Storage stabilizers, plasticizers, lubricants, dispersants, abrasives, surfactants, antistatic agents, rust preventives, light stabilizers, solvents, fillers,
Anti-aging agents, coating surface improving agents, etc. can be added as necessary.

The curable resin of the present invention is cured by heat and/or radiation. Radiation herein refers to ionizing radiation such as ultraviolet rays, electron beams, X-rays, α-rays, β-rays, and T-rays.

When thermosetting the curable resin of the present invention, a radical polymerization initiator is usually used, and examples of the radical polymerization initiator include peroxides such as benzoyl peroxide and di-t-butyl peroxide, and azobis Isobutyronitrile is mentioned.

The amount added is preferably 0.1 to IO parts by weight per 100 parts by weight of the curable resin of the present invention.

When the curable resin of the present invention is cured by ultraviolet rays, a photopolymerization initiator and, if necessary, a photosensitizer are added to the curable resin of the present invention.

Here, as the photopolymerization initiator, benzophenone, benzoin, benzoin isobutyl ether, benzyl, benzoin ethyl ether, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone,
-chlorobenzophenone, triphenylamine, carbazole, 3-methylacetophenone, 4.4'-dimethoxybenzophenone, 4.4'-diaminobenzophenone, Michler's ketone, benzoinpropyl ether,
Acetophenone diethyl ketal, benzoin ethyl ether, l-hydroxycyclohexylphenyl ketone, 4'-isopropyl-2-hydroxy-2-methyl-
Propiophenone, 2-hydroxy-2-methyl-propiophenone, α,α′-dichloro-4-phenoxyacetophenone, benzyl dimethyl ketal, 2,2-jethoxyacetophenone, chlorothioxanthone, 2-
Isopropylthioxanthone, diethylthioxanthone, 3,3-dimethyl-4-methoxybenzophenone, 2
-Methyl-1-[4-(methylthio)phenyl2-
Radical photopolymerization initiators such as morpholinopropanone, α-hydroxycyclohexyl phenyl ketone, Juvecryl P36 (high molecular weight benzophenone manufactured by UCB), 2°4.6-trimethylbenzoyldiphenylphosphine oxide, 2.5 -Jethoxy-4-(p-)lylmerkabut)benzenediazonium PF5- 2.4.6
-) IJ Rio.

Benzenediazonium PF6-. Examples include ionic photopolymerization initiators such as 4-dimethylaminonaphthalenediazonium PP6- and cyclopentadienylferrocenium PP6-. The amount of the photopolymerization initiator added is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the curable resin of the present invention. In addition, as photosensitizers, amines, ureas,
Examples include phosphorus compounds, sulfur compounds, nitriles, etc., including triethylamine, diethylamine, diethylaminoethyl methacrylate, N-methylgetanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4.4'bis. Diethylaminobenzophenone, Jubecryl P104 (manufactured by UCB,
Particularly preferred are high molecular weight tertiary amine compounds), camphorquinone, and the like.

These photopolymerization initiators and photosensitizers can be used alone or in combination of two or more.

The total amount of the photopolymerization initiator and photosensitizer used is preferably 0.01 to 10 parts by weight, particularly 0.05 to 8 parts by weight, based on 100 parts by weight of the curable resin of the present invention.

When curing the curable resin of the present invention with an electron beam, an electron beam accelerator with an accelerating voltage of 100 to 750 kV is used in view of penetrating power, and the electron beam absorbed dose of the resin is 0.5 to 30 megarads. It is preferable to irradiate with an electron beam.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

In addition, in the following Examples and Comparative Examples, the molecular weight is a value determined by an osmotic pressure method.

In addition, the solution viscosity of the curable resin is the value (centipoise, cp) measured at 25°C using a B-type viscometer manufactured by Tokyo Keiki Co., Ltd. for a 40% by weight solution in the solvent used during the synthesis of the curable resin. be.

Example 1 (1) In a flask equipped with a thermometer, stirrer, reflux condenser, and dropping funnel, 152.6 g of 4,4'-dicyclohexylmethane diisocyanate, 1.2 g of dibutyltin dilauret, and methyl ethyl ketone and cyclohexanone were mixed. Solvent (volume ratio 50:50) (hereinafter referred to as “
200 g of "solvent A") was added and heated to 60°C. To this, polyester diol (manufactured by Nippon Polyurethane Co., Ltd., Niraporan 4009, hereinafter referred to as polyester diol (1)), which is a copolymer of adipic acid and butanediol, was added through the dropping funnel while being careful not to raise the temperature of the system. ) 93.8g polyoxyethylene bisphenol A ether (DA-:350F manufactured by NOF Corporation) 134.
A uniform mixture of 3 g and 400 g of solvent A was added dropwise, and after the dropwise addition was completed, the reaction was carried out at 60° C. for 4 hours.

Next, ε-caprolactone modified 2- having a structure represented by the following formula is added to this.
13.8 g of hydroxyethyl acrylate (manufactured by Daicel Chemical Co., Ltd., Plaxel FA-5, Molecular Placement Koma 686) was added, and the mixture was further reacted at 60° C. for 2 hours. Finally, 5.5 g of glycerin was added dropwise, and the mixture was further reacted at 60° C. for 2 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (1-a).

(2) Into the same flask as used in (1), add 4.4'
-dicyclohexylmethane diisocyanate 31.3
g.

dibutyltin dilaure) 0.05g and solvent A30
g was added thereto, and the mixture was heated to 40°C. Add 13.8 g of 2-hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd.) to this while being careful not to raise the temperature of the system from the dropping funnel.
was added dropwise together with 30 g of solvent A.

After the dropwise addition was completed, the reaction was carried out at 40° C. until the amount of isocyanate groups in the system became half of the initial amount. The amount of isocyanate groups was determined by titration using a potentiometric titrator. The reaction product thus obtained is referred to as reaction product (1-b).

(3) 72.7 g of reactant (1-b) was added dropwise to 1'000 g of the solution of polymer (1-a) obtained in (1), and after the dropwise addition was completed, the reaction was carried out at 60° C. for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The curable resin thus obtained is referred to as prepolymer (1). The molecular weight of prepolymer (1) is 4
．． 5X10', solution viscosity was 20.800 cp.

Example 2 (1) In a flask similar to Example 1 (1), 102.0 g of 2,4-toluene diisocyanate, 1.2 g of dibutyltin laurate, and 200 g of tetrahydrofuran.
was added and heated to 60°C. To this, add polytetramethylene glycol (manufactured by Mitsubishi Chemical Industries, Ltd., PTMG 100) from the dropping funnel, being careful not to raise the temperature of the system.
0) 146.6 g, polyoxyalkylene bisphenol A ether (manufactured by NOF Corporation, DA-400)
A uniform mixture of 54.6 g and 350 g of tetrahydrofuran was added dropwise, and after the dropwise addition was completed, the mixture was reacted at 60° C. for 2 hours. Next, add 9.1 g of ethylene glycol to this.
was dissolved in 50 g of tetrahydrofuran and added dropwise.
After the dropwise addition was completed, the reaction was allowed to proceed for 2 hours. Finally, 17.0 g of 2-hydroxyethyl acrylate and the main structure of formula C
Il, =CHC0-fcH2cH20te, 'IH1
Add 66.7 g of the compound represented by 1 and further heat at 60°C.
The mixture was allowed to react for 4 hours.

After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The curable resin thus obtained is referred to as prepolymer (2). The molecular weight of prepolymer (2) is 3.0 x 104, and the solution viscosity is 1.
It was 4.700 cp.

Example 3 (1) 89.6 g of 2,4-)luene diisocyanate, 1.2 g of dibutyltin laurate, and 200 g of tetrahydrofuran were added to the same flask as in Example 1 (1), and the mixture was heated to 60°C. Polytetramethylene glycol (PTMG 2000 manufactured by Mitsubishi Chemical Industries, Ltd.) 17 was added to this through the dropping funnel, being careful not to raise the temperature of the system.
A homogeneous mixture of 1.7 g of an acrylic acid adduct of bisphenol octa-alkylene oxide derivative (manufactured by Kyoeisha Yushi Co., Ltd., Epoxy Ester 3002 AHO, 3.0 g, and 400 g of tetrahydrofuran was added dropwise, and after the addition was completed, the mixture was reacted at 60°C for 4 hours. Then, 2-hydroxyethyl acrylate (manufactured by Kyoeisha Yushi Co., Ltd., HEA)19.
9 g was added dropwise, and the reaction was further carried out at 60° C. for 2 hours. Finally, 15.8 g of glycene was added dropwise, and the reaction was further carried out at 60°C for 2 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (3-a).

(2) In a flask similar to Example 1 (1), 6.35 g of 2,4-toluene diisocyanate, 0.05 g of dibutyltin laurate, and 50 g of tetrahydrofuran.
was added and heated to 40°C. Add 16.7 g of ε-caprolactone-modified 2-hydroxyethyl acrylate (manufactured by Daicel Chemical Co., Ltd., Plaxel FA-3, molecular weight 458) while being careful not to raise the temperature of the system from the dropping funnel.
was added dropwise, and after completion of the dropwise addition, the reaction was carried out at 40° C. until the amount of incyanate groups in the system became half of the initial amount. The amount of isocyanate groups was determined by titration using a potentiometric titrator. The reaction product thus obtained is referred to as reaction product (3-b).

(3) 48.0 g of reactant (3-b), the polymer obtained in (1), and 1000 g of a solution of (3-a) were added dropwise, and after the addition was completed, the mixture was reacted at 60° C. for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The curable resin thus obtained is referred to as prepolymer (3). Prepolymer (3) had a molecular weight of 4.7×10′ and a solution viscosity of 21,500 cp.

Example 4 (1) Solution 257 of prepolymer (1) obtained in Example 1
polyethylene glycol nonyl phenoxy acrylate (manufactured by Toagosei Kagaku Co., Ltd., Aronix M-11)
3) 5g and 1-hydroxycyclohexylphenyl ketone (manufactured by Ciba Geigy, Irgacure 184) 4
．． 2g was added and stirred for about 1 hour. The curable resin thus obtained is referred to as prepolymer (4).

Example 5 (1) Solution 250 of prepolymer (2) obtained in Example 2
5 g of phenoxyethyl acrylate (light acrylate PO-A, manufactured by Kyoeisha Yushi Co., Ltd.) and 4.2 g of 1-hydroxycyclohexylphenyl ketone were added to the mixture and stirred for about 1 hour. The curable resin thus obtained is referred to as prepolymer (5).

Comparative Example 1 (1) In a flask similar to Example 1 (1), 66.8 g of 4,4'-dicyclohexylmethane diisocyanate,
200 g of dibutyltin laurate dolphuran was added and heated to 60°C. Add polytetramethylene glycol (manufactured by Mitsubishi Chemical Industries, Ltd.,
PTMG 3000) 191.1g1 Polypropylene glycol (PPG1000 manufactured by Asahi Glass Co., Ltd.) 127.4
A homogeneous mixture of g and 400 g of tetrahydrofuran was added dropwise thereto, and after the dropwise addition was completed, the mixture was reacted at 60° C. for 3 hours. Then, to this, 2-hydroxyethyl acrylate 1
4.8 g was added dropwise, and after the dropwise addition was completed, the reaction was further carried out at 60° C. for 2 hours.

After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The prepolymer thus obtained is referred to as prepolymer (6). The molecular weight of prepolymer [6] was 2.6 x 104, and the solution viscosity was 13.200 cp.

Comparative Example 2 (1) In a flask similar to Example 1 (1), 2.4'-
) 45.9 g of luene diisocyanate, 1.2 g of dibutyltin dilaurate and 200 g of tetrahydrofuran.
was added and heated to 60°C. Add polytetramethylene glycol (manufactured by Mitsubishi Chemical Industries, Ltd., PTMG 2000) to this using a dropping funnel, being careful not to raise the temperature of the system.
) 131.8 g, polyester diol (1) 1
A uniform mixture of 31.8 g and 400 g of tetrahydrofuran was added dropwise, and after the dropwise addition was completed, the mixture was reacted at 60° C. for 3 hours. Next, 15.1 g of 2-hydroxyethyl acrylate was added dropwise to this, and after the completion of the addition, an additional 60 g of 2-hydroxyethyl acrylate was added dropwise.
The reaction was carried out at ℃ for 2 hours.

After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The prepolymer thus obtained is referred to as prepolymer (7). The molecular weight of prepolymer [7] was 2.3 x 104, and the solution viscosity was 11.000 cp.

Test Examples 1 to 5, Comparative Test Examples 1 to 2 The prepolymers (1) to (7) obtained in Examples 1 to 5 and Comparative Examples 1 to 2 were coated on a polyester film with a thickness of 40 to 50 μm. After drying at room temperature overnight, the coating was cured by the following method to obtain a cured coating film.

Curing method (1): Dry coatings of prepolymers (1) to (3), (6), and (7) are irradiated with an electron beam at an accelerating voltage of 160 kilovolts and an absorbed dose of 5 megarads to form a coating film. hardened.

Curing method (2): The dried coating films of prepolymers (4) and (5) were cured by irradiating ultraviolet rays with a total irradiation energy of 5 J/m'' using a metal halide lamp.

In order to evaluate the properties of the obtained cured coating film, the following (
Tests 1) to (4) were conducted. The results are shown in Table 1.

(1) Breaking strength, elongation and initial modulus test: A strip-shaped test piece (0.5cm x 10ct
nX 40-60 μm) was cut out and incubated at 50% at room temperature.
Measurements were made at a tensile speed of 50 m/min under relative humidity.

(2) Flexibility test: Conducted according to JIS K5400. However, the board is a chrome-plated copper plate with an epoxy-based brusher applied to a thickness of 2~2~
A material coated to a thickness of 3 μm was used, and a mandrel with a diameter of 2 mrnφ was used.

The evaluation was rated as ○ if there was no cracking or peeling of the paint film, and × if there was cracking or peeling of the paint film.

(3) Solvent resistance test: The cured paint film was rubbed 100 times using xylene, toluene, methyl ethyl ketone, and hexane as solvents, and the change in the state of the paint film was evaluated. ○ indicates that the coating film has dissolved and swelled, △ indicates that the coating film has dissolved and swelled, and × indicates that the coating film has completely dissolved.

(4) Stain resistance test: A red felt-tip pen was applied on the cured coating film, and after standing at room temperature for 24 hours, the state of the coating film was evaluated when wiped with methanol. The evaluation was rated ◯ if the felt-tip pen marks were completely removed and there was no change in the coating film, △ if the felt-tip pen stains remained, and × if the felt-tip pen did not come off.

Margins below [Effects of the Invention] According to the present invention, it is possible to produce a curable resin that is excellent in flexibility and provides a cured coating film that is excellent in solvent resistance, stain resistance, and the like. Moreover, the resulting cured coating has excellent adhesion not only to metals and glass, but also to plastics and rubber.
It is suitable for paints, coating agents, lining agents, adhesives, etc.

that's all

Claims (1)

[Claims] 1. (A) polyisocyanate (B) polyol, (C) the following general formula (I) CH_2=CR^1COOR^2...(I) [In the formula, R^1 is a hydrogen atom Or methyl group, R^2 is a formula ▲ Numerical formula, chemical formula, table, etc. ▼ (X is a number from 1 to 30, y is a number from 3 to 10, m is 1 to 20
, n is a number from 0 to 20)] A method for producing a curable resin, comprising reacting at least two types of compounds selected from the following: