JPH10168120A - Production of active energy ray-curable resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin not containing impurities such as a chlorinated compound causing defective malfunctions in electronic parts, etc., and useful for coatings, adhesives, etc., by subjecting a carboxyl group-containing resin to the ring-opening addition polymerization reaction of a specific oxetane group-containing (meth)acryl monomer. SOLUTION: This method for producing an active energy ray-curable resin comprises subjecting (A) a carboxyl group-containing resin to the ring-opening addition polymerization reaction of (B) an oxetane group-containing (meth)acryl monomer of the formula (R1 is H, a 1-6C alkyl, F, a 1-6C fluoroalkyl, allyl, an aryl, an aralkyl, furyl, thienyl; R2 is H, methyl).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing an active energy ray-curable resin, and more specifically to a method for substantially containing contaminants such as chloro compounds which cause fatal defects such as malfunctions in electronic parts and the like. The present invention relates to a method for producing an active energy ray-curable resin which does not use the same.

[0002]

2. Description of the Related Art Due to its good workability, active energy ray-curable resins are used in a wide variety of fields, such as paints, printing inks, resists for manufacturing electronic parts, and printing plate materials. As the active energy ray-curable resin, an acrylic resin containing an unsaturated group is used in many cases.

Heretofore, as a method for producing an unsaturated group-containing acrylic resin, a method of ring-opening addition of an epoxy group-containing unsaturated monomer such as glycidyl (meth) acrylate to a carboxyl group-containing acrylic resin, and a method of producing an epoxy group-containing acrylic resin have been proposed. A method of ring-opening addition of a carboxyl group-containing unsaturated monomer such as (meth) acrylic acid to a system resin is known.

[0004] However, in the above-mentioned conventional method for producing an unsaturated group-containing acrylic resin, an epoxy group-containing unsaturated monomer or an epoxy group-containing acrylic resin is produced from epichlorohydrin as a starting material. There is a problem that a trace amount of a chloro compound remains as a contaminant in the group-containing unsaturated monomer and, when used in an electronic component or the like, causes a fatal defect such as a malfunction. In order to solve this problem, a method for producing an epoxy group-containing unsaturated monomer without using epichlorohydrin has been developed, but there is a problem that the cost is extremely high.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to develop a novel method for producing an active energy ray-curable resin which does not substantially contain foreign matter which causes fatal defects such as malfunctions in electronic parts and the like. 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 the above-mentioned disadvantages of the prior art can be solved by using a ring-opening addition reaction between an oxetane group and a carboxyl group, and have completed the present invention.

According to the present invention, the resin (A) containing a carboxyl group has the following general formula (I)

[0008]

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(Wherein R ₁ is a hydrogen atom, having 1 to 6 carbon atoms)
An oxetane group represented by 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 a hydrogen atom or a methyl group. A method for producing an active energy ray-curable resin characterized by ring-opening addition of a contained (meth) acrylic monomer (B) (hereinafter, this production method is referred to as “production method (1)”) is provided.

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

[0011]

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(Wherein R ₁ is a hydrogen atom, having 1 to 6 carbon atoms)
An oxetane functional group represented by 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). A method for producing an active energy ray-curable resin characterized by ring-opening addition of a group-containing unsaturated monomer (D) (hereinafter, this production method is referred to as “production method (2)”) is provided.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The production method (1) of the present invention will be described below.

The production method (1) of the present invention comprises the step of ring-opening addition of an oxetane group-containing (meth) acrylic monomer (B) represented by the general formula (I) to a carboxyl group-containing resin (A). It is a feature.

Resin having carboxyl group (A): The resin having carboxyl group (A) used in the method of the present invention is a resin having a carboxyl group.
The acid value is 50 to 500 mgKOH / g, preferably 80 to 300
mgKOH / g.

When the acid value of the resin (A) is less than 50 mgKOH / g, the photosensitivity of the active energy ray-curable resin obtained becomes low, and when the acid value is more than 500 mgKOH / g, it becomes difficult to dissolve in a solvent. Are not preferred. As the resin (A), for example, the following (A-1) to
(A-4).

(A-1) Half-esterifying an acid anhydride group
A vinyl polymer having a group consisting of: resin (A-1)
A vinyl polymer resin having a group obtained by half-esterifying an acid anhydride group in one molecule. Here, the group obtained by half-esterifying an acid anhydride group means a group obtained by adding a fatty monoalcohol to an acid anhydride group to open a ring (that is, half-esterifying) to obtain a carboxyl group and a carboxylic acid ester group. Means the group Hereinafter, this group may be simply referred to as a half ester group.

The resin (A-1) can be easily obtained by copolymerizing a vinyl monomer having a half ester group and another vinyl monomer by an ordinary method. Also, instead of a vinyl monomer having a half ester group, using a vinyl monomer having an acid anhydride group,
Similarly, the copolymer can be easily obtained by half-esterifying the acid anhydride group after copolymerization.

Examples of the vinyl monomer having an acid anhydride group include those having maleic anhydride, itaconic anhydride and the like. Examples of the vinyl monomer having a half ester group include those obtained by half esterifying the acid anhydride group of the vinyl monomer having the acid anhydride group.

As described above, the half esterification may be performed before or after the copolymerization reaction. As the aliphatic monoalcohol used for the half esterification, low molecular weight monoalcohols, for example, methanol, ethanol,
Isopropanol, tert-butanol, isobutanol, methyl cellosolve, ethyl cellosolve and the like. The half-esterification reaction can be carried out according to a usual method, usually at a temperature from room temperature to about 80 ° C., using a tertiary amine as a catalyst if necessary.

Other vinyl monomers include, for example, vinyl monomers having a hydroxyl group; (meth) acrylates; vinyl ethers and aryl ethers;
Olefinic compounds and diene compounds; hydrocarbon ring-containing unsaturated monomers; nitrogen-containing unsaturated monomers, and the like.

Examples of the vinyl monomer having a hydroxyl group include:
For example, 2-hydroxyethyl (meth) acrylate,
C2-C8 hydroxyalkyl esters of acrylic acid or methacrylic acid such as 3-hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate; and polyether polyols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; A) Monoesters with unsaturated carboxylic acids such as acrylic acid; monoethers with polyether polyols such as polyethylene glycol, polypropylene glycol and polybutylene glycol and hydroxyl-containing unsaturated monomers such as 2-hydroxyethyl (meth) acrylate; Monoesterified product of an unsaturated compound containing an acid anhydride group such as maleic acid or itaconic anhydride and a glycol such as ethylene glycol, 1,6-hexanediol, neopentyl glycol, etc. Is a diester product; hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether; allyl alcohol and the like; 2-hydroxypropyl (meth) acrylate; α, β-unsaturated carboxylic acid and Cardura E10 (manufactured by Shell Petrochemical Co., Ltd.) Adducts with monoepoxy compounds such as (name) and α-olefin epoxides; adducts of glycidyl (meth) acrylate with monobasic acids such as acetic acid, propionic acid, p-tert-butylbenzoic acid and fatty acids; Adducts of the above hydroxyl group-containing monomer with lactones (eg, ε-caprolactone, γ-valerolactone) and the like can be mentioned.

Examples of (meth) acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, stearyl acrylate, lauryl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n methacrylate -Butyl, isobutyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate,
C1-24 alkyl or cycloalkyl esters of acrylic acid or methacrylic acid such as stearyl methacrylate and cyclohexyl methacrylate; methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate,
Examples thereof include alkoxyalkyl esters of acrylic acid or methacrylic acid having 2 to 18 carbon atoms, such as ethoxybutyl acrylate and ethoxybutyl methacrylate.

Examples of vinyl ethers and aryl ethers include linear alkyl vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, tert-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, and octyl vinyl ether; cyclopentyl vinyl ether; Cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; aryl vinyl ethers such as phenyl vinyl ether and trivinyl ether; aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether; allyl ethers such as allyl glycidyl ether and allyl ethyl ether.

Examples of the olefinic compound and the diene compound include ethylene, propylene, butylene, vinyl chloride, butadiene, isoprene, chloroprene and the like.

Examples of the unsaturated monomer having a hydrocarbon ring include styrene, α-methylstyrene, phenyl (meth) acrylate, phenylethyl (meth) acrylate, phenylpropyl (meth) acrylate, benzyl (meth) acrylate, Phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-
Acryloyloxyethyl hydrogen phthalate, 2
-Acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2-acryloyloxypropyl tetrahydrohydrogen phthalate, esterified product of p-tert-butyl-benzoic acid and hydroxyethyl (meth) acrylate, dicyclopentenyl (Meth) acrylate and the like.

Examples of the nitrogen-containing unsaturated monomer include, for example,
N, N-dimethylaminoethyl (meth) acrylate,
N, N-diethylaminoethyl (meth) acrylate,
Nitrogen-containing alkyl (meth) acrylates such as Nt-butylaminoethyl (meth) acrylate; acrylamodo, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) Polymerizable amides such as acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide; 2-vinylpyridine, 1-vinyl-2-pyrrolidone, 4-vinylpyridine and the like Aromatic nitrogen-containing monomers; polymerizable nitriles such as acrylonitrile and methacrylonitrile; allylamine.

As the copolymerization method, a general polymerization method of a vinyl monomer can be used, but a solution-type radical polymerization method in an organic solvent is most suitable in consideration of versatility and cost. That is, aromatic solvents such as xylene and toluene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate and 3-methoxybutyl acetate; n-butanol and isopropyl alcohol By performing a copolymerization reaction in the range of about 60 to 150 ° C. in the presence of a polymerization initiator such as azobisisobutyronitrile and benzoyl peroxide in a solvent such as an alcohol solvent, the desired polymer can be easily obtained. Can be obtained.

The copolymerization amount of each of the vinyl monomer having a half ester group or an acid anhydride group and the other vinyl monomer is usually appropriate to be as follows in all the monomers. That is, from the viewpoint of curability and storage stability, the vinyl monomer having a half ester group or an acid anhydride group is about 5 to 40% by weight, preferably 10 to 30% by weight.
% By weight. It is appropriate that the other vinyl monomer accounts for about 60 to 95% by weight, preferably 70 to 90% by weight. When a vinyl monomer having an acid anhydride group is used, half-esterification is performed after polymerization as described above.

The resin (A-1) is preferably an acrylic polymer having a number average molecular weight of 2,000 to 20,000. If the number average molecular weight is less than 2,000, the physical properties of the cured coating film tend to decrease,
If it exceeds 00, the compatibility with the oxetane group-containing (meth) acrylic monomer (B) tends to decrease, and neither is preferable.

(A-2) Carboxyl group-containing vinyl heavy
Coalescence: Resin (A-2) is a vinyl polymer resin having a carboxyl group in one molecule. The number average molecular weight of the resin (A-2) is preferably in the range of 2,000 to 20,000. If the number average molecular weight is less than 2,000, the physical properties of the cured coating film tend to decrease, and if it exceeds 20,000, the compatibility with the oxetane group-containing (meth) acrylic monomer (B) tends to decrease. Are not preferred.

The resin (A-2) can be easily obtained by copolymerizing a vinyl monomer having a carboxyl group and other vinyl monomers in the same manner as in the case of the resin (A-1). .

Examples of the vinyl monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 5-carboxypentyl (meth) acrylate and the like.

As other vinyl monomers, (meth) acrylates, vinyl ethers and aryl ethers, olefinic compounds and diene compounds, unsaturated monomers containing a hydrocarbon ring, Examples thereof include a nitrogen-containing unsaturated monomer.

(A-3) Polyester Containing Carboxyl Group
Polymer: Resin (A-3) is a carboxyl group-containing polyester polymer.

The number average molecular weight of the carboxyl group-containing polyester polymer to be used is not particularly limited, but it is usually appropriate to be about 1,500 to 2,000.

The carboxyl group-containing polyester polymer includes ethylene glycol, butylene glycol, 1,6
-Can be easily obtained by a condensation reaction between a polyhydric alcohol such as hexanediol, trimethylolpropane, and pentaerythritol and a polycarboxylic acid such as adipic acid, terephthalic acid, isophthalic acid, phthalic anhydride, and hexahydrophthalic anhydride. it can. For example, a carboxyl group-containing polyester polymer can be obtained by a one-step reaction under the compounding condition of polycarboxylic acid with excess carboxyl group. After synthesizing the polyester polymer of the above, a carboxyl group-containing polyester polymer can also be obtained by post-adding an acid anhydride group-containing compound such as phthalic anhydride, hexahydrophthalic anhydride and succinic anhydride.

(A-4) Polyol and 1,2-acid anhydride
Half-ester formed by the addition reaction with
-4) is a half ester formed by a reaction between a polyol and 1,2-acid anhydride, and its number average molecular weight is
Although it is not particularly limited, it has a low molecular weight of usually about 400 to 1,000.

The half ester is composed of a polyol and 1,2-
It is obtained by reacting with an acid anhydride under conditions sufficient for a ring-opening reaction of the acid anhydride to occur and for substantially no polyesterification reaction to occur. Such reaction products have a low molecular weight and a narrow molecular weight distribution. They also exhibit a low volatile organic content in the composition and impart excellent properties in the resulting coating.

The half-esterification was carried out with a polyol and 1,2
-Acid anhydride with an inert atmosphere, for example under a nitrogen atmosphere,
It is performed in the presence of a solvent. Examples of suitable solvents include ketones such as, for example, methyl amyl ketone, diisobutyl ketone, methyl isobutyl ketone; aromatic hydrocarbons such as toluene, xylene; or other organic solvents such as dimethylformamide and N-methylpyrrolidone. Is mentioned.

The reaction temperature is preferably as low as about 150 ° C. or less. Specifically, it is usually preferably about 70 to 150C, more preferably about 90 to 120C. 150 ° C
If the temperature exceeds, the polyesterification reaction occurs, which is not desirable. If the temperature is lower than 70 ° C., a sufficient reaction rate cannot be obtained, which is not preferable.

The reaction time basically varies somewhat depending on the reaction temperature, but is usually about 10 minutes to 24 hours.

The equivalent ratio of acid anhydride: polyol is about 0.8: 1 to 1.2: 1, calculated on the assumption that the acid anhydride is monofunctional.
Within the range, the desired half ester can be obtained to the maximum.

The acid anhydride used for preparing the desired half ester has about 2 to 2 carbon atoms except for the carbon atom in the acid portion.
30. Examples of such include aliphatic, cycloaliphatic, olefinic and cyclic olefinic anhydrides and aromatic anhydrides. Substituted aliphatic and aromatic anhydrides are included in the aliphatic and aromatic anhydrides, so long as the substituents do not adversely affect the reactivity of the anhydride or the properties of the resulting half ester. . Examples of substituents include chloro, alkyl and alkoxy groups. Examples of acid anhydrides include succinic anhydride, methyl succinic anhydride, dodecenyl succinic anhydride, octadecenyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexa Hydrophthalic anhydride, alkylhexahydrophthalic anhydride (eg, methylhexahydrophthalic anhydride), tetrafluorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, itaconic anhydride, citracone Acid anhydrides and maleic anhydride.

Polyols which can be used are those having about 2 to 20 carbon atoms.
It has. Preferably, diols, triols and mixtures thereof are used. Examples of such include polyols having 2 to 20 carbon atoms. Examples of suitable are aliphatic polyols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, glycerol,
2,3-butanetriol, 1,6-hexanediol, neopentyl glycol, diethylene glycol,
Dipropylene glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, trimethylolpropane, 2,2,4-trimethylpentane-1,3-diol, pentaerythritol and 1,2,3 , 4-butanetetraol. Aromatic polyols such as bisphenol A and bis (hydroxymethyl) xylene may be used.

Oxetane group-containing (meth) acrylic monomer
-(B): The oxetane group-containing (meth) acrylic monomer (B) used in the method of the present invention has the following general formula (I)

[0047]

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(Wherein R ₁ is a hydrogen atom, having 1 to 6 carbon atoms)
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 a hydrogen atom or a methyl group). is there.

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,
Isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl and the like can be mentioned.
The "fluoroalkyl group having 1 to 6 carbon atoms" is a group in which at least one hydrogen atom of the above-mentioned alkyl group is substituted with a fluorine atom, and examples thereof include fluoropropyl, fluorobutyl, and trifluoropropyl. 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. R ₁
Among them, lower alkyl groups having 1 to 4 carbon atoms such as methyl and ethyl are particularly preferred.

Specific examples of the oxetane group-containing (meth) acrylic monomer (B) include 3- (meth) acryloxymethyl-3-methyloxetane and 3- (meth) acryloxymethyl-3-ethyloxetane. No.

In the production method (1) of the present invention, a desired active energy ray is obtained by a ring-opening addition reaction between the carboxyl group-containing resin (A) and the oxetane group-containing (meth) acrylic monomer (B). Manufacture curable resin. The ring-opening addition reaction is usually performed using a ring-opening catalyst, preferably while blowing air into the system at a reaction temperature in the range of room temperature to 120 ° C in the presence of a thermal polymerization inhibitor to suppress thermal polymerization. Do. When the reaction viscosity is high, toluene,
The reaction may be performed in a solvent such as xylene, methyl ethyl ketone, methyl isobutyl ketone, or ethyl acetate. Examples of the ring-opening catalyst include quaternary salt catalysts such as tetraethylammonium bromide, tetrabutylammonium bromide, tetraethylammonium chloride, tetrabutylphosphonium bromide, and triphenylbenzylphosphonium chloride; amines such as triethylamine and tributylamine And the like. Of these, quaternary salt catalysts are preferred. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, and the like.

The mixing ratio of the carboxyl group-containing resin (A) and the oxetane group-containing (meth) acrylic monomer (B) is particularly limited as long as the equivalent of the monomer (B) does not exceed the equivalent of the resin (A). Instead, it can be arbitrarily determined according to the characteristics of the obtained active energy ray-curable resin.

The production method (2) of the present invention will be described below.

The production method (2) of the present invention is characterized in that a carboxyl group-containing unsaturated monomer (D) is ring-opened to a resin (C) containing an oxetane functional group.

Resins (C) containing oxetane functional groups:
The resin (C) containing an oxetane functional group used in the method of the present invention has the following general formula (II):

[0056]

Embedded image

(Wherein R ₁ is a hydrogen atom, having 1 to 6 carbon atoms)
Which is 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).

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

The oxetane functional group can be formed by bonding an oxygen-containing bond such as an ether bond, an ester bond, or a urethane bond, or a resin (C) containing an oxetane functional group via a hydrocarbon group containing at least one of these bonds. It is preferable to use those bonded to the side chain or main chain of

The resin (C) containing the oxetane functional groups has an average number of oxetane functional groups of about 2 per molecule.
Or more, preferably in the range of about 2 to 10 on average,
The average molecular weight is suitably in the range of about 300 to 20,000, preferably about 500 to 10,000. When the number of oxetane functional groups is less than about 2 in one molecule on average, the obtained active energy ray-curable resin has poor active energy ray curability. When the average molecular weight is less than about 300, the physical properties of the coating film are deteriorated, while the average molecular weight is about 2
When it exceeds 000, the coating workability is inferior, so that it is not preferable.

Resins (C) Containing Oxetane Functional Groups
Can be used without any particular limitation as long as it contains an average of about 2 or more oxetane functional groups in one molecule. Specifically, for example, a polyester resin, an acrylic resin, a fluororesin, a silicon resin, an alkyd resin, a polyether resin, and modified resins thereof are included.

Representative examples of the method for introducing an oxetane functional group into the above resin are described below.

Polybasic acids such as (phthalic anhydride),
Isophthalic acid, terephthalic acid, (anhydrous) maleic acid, adipic acid, azelaic acid, etc.) and polyhydric alcohols (eg, ethylene glycol, neopentyl glycol, propylene glycol, 1,6-hexanediol, glycerin, pentaerythritol, trimethylol) A mixture of a monobasic acid and, if necessary, an esterification reaction in the presence of an esterification catalyst to produce a polycarboxylic acid polyester resin, and then the obtained resin is treated with a triol component such as trimethylolpropane. The following formula derived from the triol component in the polyester resin by esterification reaction

[0064]

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A polyester resin having a cyclic polycarbonate is produced by reacting the residue with diethyl carbonate to produce a 1,3-diol residue represented by the formula .

A triol such as trimethylolpropane is reacted with diethyl carbonate to produce a hydroxyl group-containing cyclic carbonate, which is then decarboxylated to give 3-ethyl-3 having a hydroxyl group at one end and an oxetane functional group at the other end.
-Hydroxymethyloxetane, followed by a resin having complementary functional groups (e.g., isocyanate group, methyl ester group, etc.) that reacts complementarily with the hydroxyl groups of the oxetane and does not substantially react with the oxetane functional group ( For example, an acrylic resin containing an isocyanate group, a polyester resin containing a methyl ester group, etc.).

An unsaturated monomer containing the above functional group and a radically polymerizable unsaturated group (eg, acryloyl group, methacryloyl group, vinyl group, etc.) reacting complementarily with the above 3-ethyl-3-hydroxymethyloxetane To produce an unsaturated monomer having a radically polymerizable unsaturated group at one end and an oxetane functional group at the other end, and then the unsaturated monomer and another radically polymerizable unsaturated monomer [for example, C1-C24 alkyl or cycloalkyl esters of (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate , 2-hydroxypropyl (meth)
Hydroxyalkyl esters of (meth) acrylic acid such as acrylate and caprolactone-modified hydroxyethyl (meth) acrylate; carboxyl group-containing unsaturated monomers such as (meth) acrylic acid; glycidyl (meth) acrylate, 3,4-epoxy Epoxy group-containing unsaturated monomers such as cyclohexylmethyl (meth) acrylate; aromatic unsaturated monomers such as styrene; fluorinated unsaturated such as perfluorobutylethyl (meth) acrylate and perfluoroisononylethyl (meth) acrylate Monomers (polymerizable amides such as (meth) acrylamide)].

A product obtained by reacting the above-mentioned hydroxyl group-containing cyclic carbonate with the above-mentioned resin having a functional group which reacts complementarily to introduce a cyclic carbonate into the resin, and then decarboxylating the cyclic carbonate to convert it into an oxetane functional group.

The above-mentioned hydroxyl group-containing cyclic carbonate is reacted with the above-mentioned functional group which reacts complementarily and an unsaturated monomer containing a radically polymerizable unsaturated group, so that one end has a radically polymerizable unsaturated group and the other end. To produce an unsaturated monomer having a cyclic carbonate, and then radically (co) polymerize the unsaturated monomer and the other radically polymerizable unsaturated monomer to introduce a cyclic carbonate into the (co) polymer, Next, the cyclic carbonate is converted into an oxetane functional group by decarboxylation.

Carboxyl group-containing unsaturated monomer
(D): The carboxyl group-containing unsaturated monomer (D) used in the method of the present invention is a per se known unsaturated monomer having a carboxyl group in the molecule, and specific examples thereof include acrylic acid and methacrylic acid. Acid, crotonic acid,
Examples include itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, and 5-carboxypentyl (meth) acrylate.

In the production method (2) of the present invention, the desired active energy ray curing is carried out by a ring-opening addition reaction between the resin (C) containing an oxetane functional group and the unsaturated monomer (D) containing a carboxyl group. Manufacturing mold resin. The ring-opening addition reaction can be carried out in exactly the same manner as described in the above-mentioned production method (1).

The mixing ratio of the oxetane functional group-containing resin (C) and the carboxyl group-containing unsaturated monomer (D) is such that the equivalent of the carboxyl group-containing unsaturated monomer (D) does not exceed the equivalent of the resin (C). It is not particularly limited as long as it can be determined arbitrarily according to the properties of the obtained active energy ray-curable resin.

The active energy ray-curable resin obtained by the method of the present invention can be cured by irradiating an active energy ray such as an electron beam or an ultraviolet ray. In the case of curing by ultraviolet irradiation, it is necessary to add a photopolymerization initiator to the resin 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 active energy ray-curable resin.

In order to accelerate the photopolymerization reaction by these photopolymerization initiators, a photosensitization accelerator 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 10 based on the amount of the active energy ray-curable resin.
A range of weight% is preferred.

On the other hand, when electron beam irradiation is used, it is not necessary to add the above-mentioned photopolymerization initiator or photosensitizer to the active energy ray-curable resin obtained by the method of the present invention.

When the active energy ray-curable resin is cured by irradiation with an electron beam, the electron beam source is as follows.
Cockcroft type, cockcroft walton type, van
An electron beam generator such as a de-Graaf type, a resonance transformer type, a transformer type, 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 this time vary depending on the shape, thickness, and the like of the active energy ray-curable resin obtained by the method of the present invention, but a dose in the range of 1 to 20 megarads is generally suitable.

As the 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.

[0078]

The active energy ray-curable resin obtained by the method of the present invention has the above-mentioned features and advantages, and can be used in paints, printing inks, adhesives, adhesives, resists, molding materials, and the like. Particularly useful.

[0079]

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

Example 1 A 5-liter glass flask equipped with a stirrer, a thermometer, and a condenser was charged with 553 parts of xylene and 414 parts of 3-methoxybutyl acetate.
° C, and at that temperature, a mixture of the following monomer compositions was evenly dropped over 4 hours. Incidentally, p-tert-butylperoxy-2-ethylhexanoate is a polymerization initiator.

Methanol half esterified product of maleic anhydride 288 parts (20%) n-butyl acrylate 864 parts (60%) Styrene 288 parts (20%) p-tert-butylperoxy-2-ethylhexanoate 72 parts Then, after aging for 30 minutes, 277 parts of 3-methoxybutyl acetate and p-tert-butylperoxy-
A mixture of 14.4 parts of 2-ethylhexanoate was added dropwise over 2 hours, and the mixture was aged for 2 hours.
An 8% solution of an acrylic polymer was obtained.

The polymer solid content of the obtained polymer solution was 55
%, Gardner viscosity (25 ° C.) M. The number average molecular weight of this polymer was 3,500. The acid value of this polymer was 86 mgKOH / g.

To 181.8 parts (solid content: 100 parts) of this acrylic polymer solution, 22.6 parts of 3-methacryloxymethyl-3-ethyloxetane and 0.5 part of tetraethylammonium bromide were added. Reacted for hours. When the resin acid value reached 18, the reaction was stopped to obtain a resin solution (a-1).

The polymer solid content of the obtained resin solution is 60
%, Gardner viscosity (25 ° C.) P. The number average molecular weight of this resin was 4,100.

Example 2 A 5-liter glass flask equipped with a stirrer, a thermometer, and a condenser was charged with 553 parts of xylene and 414 parts of 3-methoxybutyl acetate.
° C, and at that temperature, a mixture of the following monomer compositions was evenly dropped over 4 hours. Incidentally, p-tert-butylperoxy-2-ethylhexanoate is a polymerization initiator.

N-butyl methacrylate 432 parts (30%) isobutyl methacrylate 346 parts (24%) lauryl methacrylate 360 parts (25%) styrene 72 parts (5%) methacrylic acid 86 parts (6%) acrylic acid 144 parts (10 %) 72 parts of p-tert-butylperoxy-2-ethylhexanoate Then, after aging for 30 minutes, 277 parts of 3-methoxybutyl acetate and p-tert-butylperoxy-
A mixture of 14.4 parts of 2-ethylhexanoate was added dropwise over 2 hours, and the mixture was aged for 2 hours.
An 8% solution of an acrylic polymer was obtained.

The polymer solid content of the obtained polymer solution is 55
%, Gardner viscosity (25 ° C.) V, and the number average molecular weight of this polymer was 3,000. The acid value of this polymer was 117 mgKOH / g.

To 181.8 parts (100 parts solid content) of this acrylic polymer solution, 30.7 parts of 3-methacryloxymethyl-3-ethyloxetane and 0.6 part of tetraethylammonium bromide were added, and the mixture was added at 100 ° C. for about 1 part. Reacted for hours. When the resin acid value reached 25, the reaction was stopped to obtain a resin solution (a-2).

The polymer solid content of the obtained resin solution is 6
1.5%, Gardner viscosity (25 ° C.). The number average molecular weight of this resin was 3,600.

Example 3 A 5-liter glass flask equipped with a stirrer, a thermometer and a condenser was charged with 236 parts of 3-methyl-1,5-pentanediol, 134 parts of trimethylolpropane and 1078 parts of hexahydrophthalic anhydride. Then, 780 parts of xylene was charged, and the temperature was raised to 120 ° C. in a nitrogen atmosphere to cause a reaction. The reaction mixture was kept at this temperature for 4 hours and then cooled,
Solid content 65%, Gardner viscosity (25 ° C) R, acid value 27
A solution of 1 mg KOH / g half ester was obtained.

To 153.8 parts (100 parts of solid content) of this half ester solution, 71 parts of 3-methacryloxymethyl-3-ethyloxetane and 0.8 parts of tetraethylammonium bromide were added, and reacted at 100 ° C. for about 1 hour. . When the resin acid value reached 60, the reaction was stopped,
A resin solution (a-3) was obtained.

The polymer solid content of the obtained resin solution was 76
%, Gardner viscosity (25 ° C.) X. The number average molecular weight of this resin was 2,000.

Example 4 A 5-liter glass flask equipped with a stirrer, a thermometer and a condenser was charged with 450 parts of xylene and heated to 100 ° C. with an electric heating mantle. Was evenly dropped over 3 hours. Incidentally, azobisisobutyronitrile is a polymerization initiator.

3-methacryloxymethyl-3-ethyloxetane 184 parts n-butyl methacrylate 244 parts azobisisobutyronitrile 12 parts Then, after aging for 30 minutes, 4 parts of azobisdimethylvaleronitrile and 50 parts of xylene were added. The mixture was added dropwise over 1 hour and then aged for 30 minutes to obtain a solution of an acrylic polymer having a final conversion of 98%.

The polymer solid content of the obtained polymer solution was 45%.
% And Gardner viscosity (25 ° C.) K. The number average molecular weight of this polymer was 6,200.

To 944 parts of this acrylic polymer solution (428 parts of solid content), 72 parts of acrylic acid and 2.5 parts of tetraethylammonium bromide were added and reacted at 100 ° C. for about 1 hour. When the resin acid value became 0, the reaction was stopped to obtain a resin solution (a-4).

The polymer solid content of the obtained resin solution was 49
%, Gardner viscosity (25 ° C.) N. The number average molecular weight of this resin was about 7,000.

Example 5 A 5-liter glass flask equipped with a stirrer, a thermometer and a condenser was charged with 450 parts of xylene, heated to 100 ° C. with an electric heating mantle, and heated at that temperature to a mixture of the following monomer compositions. Was evenly dropped over 3 hours. Incidentally, azobisisobutyronitrile is a polymerization initiator.

3-methacryloxymethyl-3-ethyloxetane 184 parts n-butyl methacrylate 230 parts azobisisobutyronitrile 12 parts Then, after aging for 30 minutes, 4 parts of azobisdimethylvaleronitrile and 50 parts of xylene were added. The mixture was added dropwise over 1 hour and then aged for 30 minutes to obtain a solution of an acrylic polymer having a final conversion of 98%.

The polymer solid content of the obtained polymer solution was 4
4.5%, Gardner viscosity (25 ° C.) K The number average molecular weight of this polymer was 6,000.

86 parts of methacrylic acid and 2.5 parts of tetraethylammonium bromide were added to 930 parts of this acrylic polymer liquid (414 parts of solid content),
Reacted for hours. When the resin acid value became 0, the reaction was stopped to obtain a resin solution (a-5).

The polymer solid content of the obtained resin solution was 49
% And Gardner viscosity (25 ° C.) L. The number average molecular weight of this resin was about 7,000.

Comparative Example 1 A 5-liter glass flask equipped with a stirrer, a thermometer and a condenser was charged with 450 parts of xylene and heated to 100 ° C. with an electric heating mantle. Was evenly dropped over 3 hours. Incidentally, azobisisobutyronitrile is a polymerization initiator.

Glycidyl methacrylate 184 parts n-butyl methacrylate 244 parts Azobisisobutyronitrile 13 parts Then, after aging for 30 minutes, a mixture of 4 parts of azobisdimethyldimethylvaleronitrile and 50 parts of xylene was added dropwise over 1 hour. After aging for 30 minutes, 72 parts of acrylic acid and tetraethylammonium bromide 5
Was added and reacted at 100 ° C. for about 1 hour. When the resin acid value became 0, the reaction was stopped and the resin solution (a-
6) was obtained.

The polymer solid content of the obtained resin solution was 49
% And Gardner viscosity (25 ° C.) L. The number average molecular weight of this resin was about 7,000.

Comparative Example 2 A 5-liter glass flask equipped with a stirrer, a thermometer, and a condenser was charged with 450 parts of xylene and heated to 100 ° C. with an electric heating mantle. Was evenly dropped over 3 hours. Incidentally, azobisisobutyronitrile is a polymerization initiator.

72 parts of acrylic acid 244 parts of n-butyl methacrylate 9.5 parts of azobisisobutyronitrile Then, after aging for 30 minutes, a mixture of 3 parts of azobisdimethylvaleronitrile and 50 parts of xylene was further added for 1 hour. After dropwise addition and aging for 30 minutes, 144 parts of glycidyl methacrylate and 5 parts of tetraethylammonium bromide were added and reacted at 100 ° C. for about 1 hour. When the resin acid value becomes 0, the reaction is stopped,
A resin solution (a-7) was obtained.

The polymer solid content of the obtained resin solution was 47
%, Gardner viscosity (25 ° C.) M. The number average molecular weight of this resin was about 7,000.

The chloride ion concentrations in the resin solutions (a-1) to (a-7) obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were measured. Table 1 shows the results.

The chloride ion concentration was measured by an ordinary method using an ion chromatography system manufactured by Tosoh Corporation.

[0111]

[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] 1. A resin (A) containing a carboxyl group
In addition, 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, and R ₂ represents a hydrogen atom or a methyl group)
A ring-opening addition of an oxetane group-containing (meth) acrylic monomer (B) represented by the following formula: 2. The following general formula (II): (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,
A carboxyl group-containing unsaturated monomer (D) is ring-opened to a resin (C) containing an oxetane functional group represented by an allyl group, an aryl group, an aralkyl group, a furyl group or a phenyl group. Of producing active energy ray-curable resin.