JP3019429B2 - Manufacturing method of new energy ray-curable resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a novel and useful energy ray-curable resin. More specifically, the present invention is characterized in that, as an active ingredient, an oxirane ring compound having a specific structure and a specific oxirane ring-containing group, an unsaturated monocarboxylic acid compound, and an anhydride of a polybasic acid are reacted. And a method for producing an energy ray-curable resin.

[0002] The energy ray-curable resin of the present invention is suitable for a wide range of uses such as coating materials, printing inks, adhesives and photoresists. Can be cured by

[0003]

2. Description of the Related Art Resins which can be cured by energy rays, in particular, resins which are cured by a radical polymerization reaction, include unsaturated polyester resins, vinyl ester resins (epoxy-acrylates), various oligoacrylates and diallyl phthalate prepolymers. There are various types,
The features are utilized in each application field, and they are directed to a wide range of applications.

[0004] However, in recent years, with the spread of applications, demands for the performance of each application have been increasing, and a resin composition curable by energy rays capable of satisfying such various application performances. The fact is that it has not yet been obtained.

[0005]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, the present inventors have found that existing resins can be used even in applications that cannot be completely satisfied.
For the synthesis of radical-curable resins with excellent water resistance, solvent resistance, chemical resistance, heat resistance and curability,
Research has begun.

[0006] That is, the problem to be solved by the present invention is, in part, an energy beam curing which is excellent in water resistance, solvent resistance, chemical resistance, heat resistance, curability and the like, and is extremely useful. It is to provide a mold resin composition.

[0007]

Means for Solving the Problems Accordingly, the present inventors have:
Aiming at the problem to be solved by the invention as described above, as a result of diligent and repeated studies, an oxirane ring-containing compound having a specific structure, an unsaturated monocarboxylic acid compound, and an anhydride of a polybasic acid The present invention has been completed by knowing that the energy ray-curable resin obtained by the above reaction can satisfy various properties of the coating film as described above.

That is, the present invention is basically very useful as an essential film-forming component obtained by reacting an oxirane ring-containing compound having a specific structure with an unsaturated monocarboxylic acid compound and a polybasic acid anhydride. It is intended to provide a method for producing an energy ray-curable resin having a high value.

[0009] Specifically, the general formula

[0010]

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Wherein W, X, Y and Z in the formula are
A hydrogen atom or a formula which may be the same or different,

[0012]

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## STR1 ## wherein W,
This excludes the case where all of X, Y or Z are hydrogen atoms. A so-called oxirane ring-containing compound wherein each of W, X, Y or Z in the compound is
Those having a specific structure such as a glycidyl ether group or a hydrogen atom (however, as described above, this is excluded only when all of W, X, Y or Z are hydrogen atoms). And a reaction between an unsaturated monocarboxylic acid compound and an anhydride of a polybasic acid.

Here, first, the above-mentioned energy ray-curable resin [hereinafter also referred to as resin (A)]. ] Refers to a product obtained by reacting an oxirane ring-containing compound having a specific structure with an unsaturated monocarboxylic acid and a polybasic acid anhydride.

As the resin (A), of course, any resin can be used as long as it is obtained by reacting the above-mentioned various compounds. Among them, only typical ones are exemplified. If it does so, first, it contains an oxirane group having a specific structure [hereinafter, this is treated as (a-1). ] And an unsaturated monocarboxylic acid compound [hereinafter, this is treated as (a-2)]. And a specific reactant obtained through at least one or more oxirane ring-containing groups and a carboxyl group in the compound (a-1) [hereinafter, this is treated as (a-3)] ] At least one aromatic, aliphatic and / or
Or an anhydride of an alicyclic polybasic acid [hereinafter referred to as (a-
4). And the like.

Among them, representative compounds represented by the above-mentioned general formula [1] and having an oxirane ring-containing compound (a-1) used for preparing the compound (a-3) If only to mention only, 2,7-dihydroxynaphthalene alone or in combination with some β-naphthol, methylol groups generated by reacting formalin under an acid catalyst are dehydrated and condensed, and dimerized. The obtained polyfunctional hydroxyl compound may be obtained by reacting epichlorohydrin in the presence of an alkali compound. W, X, Y or Z of the compound represented by the general formula [1] may be a glycidyl ether group. Or an oxirane ring-containing compound having a hydrogen atom (however,
Excluded only when all of W, X, Y and Z are hydrogen atoms. ).

On the other hand, only typical examples of the unsaturated monocarboxylic acids (a-2) which react with the oxirane ring-containing group include acrylic acid, methacrylic acid, crotonic acid and cinnamic acid. These may be used as a mixture of two or more kinds, but the use of acrylic acid is particularly preferable.

Further, the above-mentioned anhydride of polybasic acid (a-
If only typical examples among 4) are exemplified, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, hetonic acid, hymic acid,
Chlorendic acid, dimer acid, adipic acid, succinic acid, alkenyl succinic acid, sebacic acid, azelaic acid,
2,2,4-trimethyladipic acid, terephthalic acid, 2
-5-sodium-sulfoisophthalic acid represented by potassium sulfoterephthalic acid, 2-sodium sulfoterephthalic acid, isophthalic acid, 2-potassium sulfoisophthalic acid, 2-sodium sulfoisophthalic acid, dimethyl- or diethyl ester, etc. Lower alkyl ester, orthophthalic acid, 4-sulfophthalic acid, 1,1
0-decamethylene dicarboxylic acid, muconic acid, oxalic acid,
Malonic acid, glutaric acid, trimellitic acid, hexahydrophthalic acid, tetrabromophthalic acid, anhydride of methylcyclohexentricarboxylic acid or pyromellitic acid. These may be used alone or in combination of two or more.

The energy-ray-curable resin thus obtained has high sensitivity per se, and gives a film having excellent water resistance, solvent resistance, chemical resistance and heat resistance after curing. Becomes

The energy ray-curable resin composition of the present invention comprising the thus obtained energy ray-curable resin as an essential component may further comprise, if necessary, within the scope not departing from the object of the present invention. In particular, within the range that can maintain various properties such as storage stability and water resistance, solvent resistance, chemical resistance and heat resistance, known and conventional additives, especially other types of reactive diluents and It does not hinder the addition of an organic solvent or the like.

As such reactive diluents, monofunctional ones to polyfunctional ones are widely used. Of those, particularly representative ones are exemplified by 2-hydroxy. Ethyl (meth) acrylate, 2-
Hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, N-vinylpyrrolidone, 1-vinylimidazole, isobornyl (meth) acrylate, tetrahydrofurphyryl (meth) acrylate, carbitol (meth) acrylate, phenoxyethyl ( (Meth) acrylate, dicyclopentadiene (meth) acrylate, 1,3-butanedi (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalic acid ester neopentyl glycol di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate Others dipentaerythritol hexa (meth) acrylate and the like.

Further, only typical solvents are exemplified as aromatic hydrocarbons such as toluene or xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; methyl acetate, ethyl acetate or Esters such as butyl acetate; alcohols such as methanol, ethanol, propanol or butanol; aliphatic hydrocarbons such as hexane and heptane; cellosolve acetate, carbitol acetate, dimethylformamide, and tetrahydrofuran.

The energy ray referred to in the present invention is a general term for ionizing radiation and light, such as electron beam, α-ray, β-ray, γ-ray, X-ray, neutron beam or ultraviolet ray.
In the present invention, when the resin composition of the present invention is cured by using ultraviolet rays as such energy rays, light (polymerization) which is dissociated by ultraviolet rays having a wavelength of 1,000 to 8,000 angstroms to generate radicals. ) Initiators should be used.

As such a photo (polymerization) initiator, of course, any known and commonly used one can be used. Of those, particularly representative examples are acetophenones, benzophenone, Michler's ketone, and the like. Benzine, benzoin benzoate, benzoin, benzoin methyl ethers, benzyl dimethyl ketal, α-acyloxime ester, thioxanthones, anthraquinones and various derivatives thereof.

A known and commonly used photosensitizer can be used in combination with such a photo (polymerization) initiator, but only typical photosensitizers are exemplified. , Amines, ureas, sulfur-containing compounds, phosphorus-containing compounds,
Examples include chlorine-containing compounds or nitriles or other nitrogen-containing compounds.

The energy ray-curable resin-containing resin composition of the present invention may be cured by irradiating it with radiation or active energy rays by using various energy sources as described above. .

Example 1 In a flask equipped with a thermometer, a stirrer and a reflux condenser,
Oxalic acid and formalin were added to 2,7-dihydroxynaphthalene and reacted to obtain an average tetrafunctional dimer hydroxy compound. 556 g of a tetrafunctional epoxy compound obtained by reacting with epichlorohydrin and epoxidizing it
(Epoxy equivalent: 138 g / eq.) And 1.3 g of hydroquinone monomethyl ether, and 288 g of acrylic acid and 12.8 g of triphenylphosphone.
Was added and reacted at a temperature of 110 ° C. until the epoxy equivalent became 15,000 or more, and the reaction product (a-3-
1) was obtained.

Example 1 In a flask equipped with a thermometer, a stirrer and a reflux condenser,
Using 2,7-dihydroxynaphthalene alone or in combination with β-naphthol, 556 g of a tetrafunctional epoxy compound obtained through its dimerization
And 1.3 g of hydroquinone monomethyl ether, 288 g of acrylic acid and 12.8 g of triphenylphosphine were further added, and reacted at a temperature of 110 ° C. until the epoxy equivalent became 15,000 or more. The reaction product (a-3-1) was obtained.

Further, 152 g of tetrahydrophthalic anhydride was added thereto and reacted at 110 ° C. until the acid value reached 57, to obtain a desired reactant. Hereinafter, this is abbreviated as resin (A-2).

Example 2 In a flask equipped with a thermometer, a stirrer and a reflux condenser,
844 g of (a-3-1) obtained in Example 1 and 304 g of tetrahydrophthalic anhydride were charged and reacted at 110 ° C. until the acid value reached 98 to obtain a reaction product. Hereinafter, this is abbreviated as resin (A-2).

Example 3 In a flask equipped with a thermometer, a stirrer and a reflux condenser,
844 g of (a-3-1) obtained in Example 1 and 608 g of tetrahydrophthalic anhydride were charged and reacted at 110 ° C. until the acid value became 155, to obtain a reaction product. Hereinafter, this is abbreviated as resin (A-3).

Application Example 1 Various components as described below were mixed with the resin (A-1) obtained in Example 1, mixed well, and stirred to prepare a coating.

Resin (A-1) 100 parts 1-Hydroxyhexyl phenyl ketone 3 parts Next, the coating material thus obtained was applied to a water-sharpened tin plate with a thickness of 20 μm.

Thereafter, this was irradiated with ultraviolet rays from a height of 15 cm for 60 seconds with a high-pressure mercury lamp of 80 W to be cured. Table 1 shows the results of various performance evaluation tests performed on each coated plate.

Application Example 2 A coating material was prepared in the same manner as in Application Example 1, except that the same amount of the resin (A-2) obtained in Example 2 was used instead of the resin (A-1). Was obtained, applied and cured.

When the same performance evaluation was performed on the coated plate, the results shown in Table 1 were obtained. Application Example 3 A coating material was obtained in the same manner as in Application Example 1, except that the same amount of the resin (A-3) obtained in Example 3 was used instead of the resin (A-1). Coated and cured.

When the same performance evaluation was performed on the coated plate, the results shown in Table 1 were obtained. Application Example 4 The resin (A-3) obtained in Example 3 was mixed with various components as described below, mixed well, and stirred to prepare a coating material.

Resin (A-3) 100 parts 1-hydroxyhexyl phenyl ketone 3 parts Trimethylolpropane triacrylate 20 parts Thereafter, in the same manner as in Application Example 1, a coating material was obtained, applied, and cured.

When the same performance evaluation was performed on the coated plate, the results shown in Table 1 were obtained. Comparative Example 1 In a flask equipped with a thermometer, a stirrer and a reflux condenser,
"Epiclon N-695" with an epoxy equivalent of 213
426 g of [Cresol / Novolak-type epoxy compound manufactured by Dainippon Ink and Chemicals, Inc.] and 1.3 g of hydroquinone monomethyl ether were added, and 144 g of acrylic acid was added, so that the acid value became 3 or less. Until the reaction product (c-3-
1) was obtained.

Then, 570 g of (c-3-1) was added to a flask newly equipped with a thermometer, a stirrer and a reflux condenser.
And 152 g of tetrahydrophthalic anhydride,
Further, 0.5 g of di-n-butyltin diacetate was added, and the reaction was carried out at a temperature of 110 ° C. until the acid value reached 50 to obtain a control energy ray-curable resin. Hereinafter, this is abbreviated as resin (C-1).

Comparative Application Example 1 The resin (A-1) was replaced with the same amount of the resin (C-1) obtained in Comparative Example 1 except that the same amount was used.
A paint was obtained, applied, and cured in the same manner as in Application Example 1.

When the same performance evaluation was performed on the coated plate, the results shown in Table 1 were obtained. The evaluation of each performance was performed in the following manner.

Curability: The applied coating film is
80 W / cm ² after drying for 15 minutes in warm air of
Under a high-pressure mercury lamp of
It was passed at a speed of 0 m / min, and the number of times until it was cured was measured.

Water resistance: The gauze is immersed in ion-exchanged water, and the cured film is rubbed 40 times. ◎: less than 5 μm ：: 5 μm or more and less than 10 μm Δ: 10 μm or more and less than 15 μm ×: 15 μm or more Solvent resistance: Acetone was immersed in gauze and the cured coating film was rubbed 40 times. The degree of decrease in the thickness of the film is measured. Evaluation criteria are the same as water resistance.

Alkali resistance: A 10% aqueous solution of sodium hydroxide is immersed in gauze, and the cured film is rubbed 40 times, and the degree of decrease in film thickness is measured. Evaluation criteria are the same as those for water resistance.

Heat resistance ...........
80 W / cm ² after drying for 15 minutes in warm air of
Under a high-pressure mercury lamp of
The cured coating film passed 10 times at a speed of 0 m / min
The gauze was immediately pressed on the surface of the coating film after being placed in a heating furnace at 00 ° C. for 40 seconds, and the gauze was peeled off after cooling, and the change in the coating film was visually determined.

◎: No change observed at all ○: Some traces of gauze on surface ×: Melting of coating film and peeling off together with gauze Alkali solubility: 80 ° C. After drying in warm air for 15 minutes, the uncured coating film was rubbed 30 times with a gauze soaked with a 1 / 10N aqueous potassium hydroxide solution to observe the dissolution condition of the coating film.

◎: No coating film left at all ○: Little coating film remaining Δ: Slight coating film ×: Film coating remaining

[0049]

[Table 1]

As is clear from the results shown in Table 1, the energy ray-curable resin of the present invention can be freely cured at room temperature or under heating, and the specific oxirane ring-containing compound By various properties obtained based on the structure from, especially, excellent curability, the resulting cured coating also has water resistance, solvent resistance and chemical resistance, and also has excellent heat resistance, It is extremely useful for various applications.

[0051]

The energy ray-curable resin obtained by the present invention is itself highly sensitive, and the cured coating film is excellent in water resistance, solvent resistance, chemical resistance and heat resistance. From where they are, especially coatings,
They are extremely useful in a wide range as printing inks and adhesives.

Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C09D 163/10 C09D 163/10 C09J 163/10 C09J 163/10 (56) References JP-A-4-246409 (JP, A) JP-A-Hei. 1-6014 (JP, A) JP-A-2-97513 (JP, A) JP-A-2-209912 (JP, A) JP-A-3-143911 (JP, A) JP-A-4-46968 (JP, A A) JP-A-4-239012 (JP, A) JP-A-4-248883 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 59/17 C07C 69/593 C08F 2 / 46-2/50 C08F 290/00-290/14 C08F 299/00-299/08 C09D 1/00-201/10 C09J 1/00-201/10

Claims (2)

(57) [Claims] 1. A compound of the general formula [1] [Where W, X, Y and Z in the formulas may be the same or different, and each represents a hydrogen atom or a formula Wherein W, X, Y and Z
Except that all are hydrogen atoms. At least one oxirane ring-containing group of the compound represented by the formula: and an anhydride of an unsaturated monocarboxylic acid compound and a polybasic acid.
A method for producing an energy ray-curable resin. 2. A compound of the general formula Wherein W, X, Y and Z are each a hydrogen atom or a formula Wherein W, X, Y and Z
Except that all are hydrogen atoms. At least one oxirane ring-containing group of the compound represented by the general formula: [However, in the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents any one of a hydrogen atom, a methyl group, a cyano group, and a halogen atom. And the other oxirane ring-containing group is a hydrogen atom or a compound represented by the formula: Or a group represented by the general formula: Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents any of a hydrogen atom, a methyl group, a cyano group and a halogen atom, and B ₁ represents a residue of a polybasic acid. Shall be expressed. And / or a general formula: [However, the R ₁ in the formula is a hydrogen atom or a methyl group, R ₂
Represents a hydrogen atom, a methyl group, a cyano group or a halogen atom. The method for producing an energy ray-curable resin according to claim 1, wherein the resin is substituted with a group represented by the formula :