JPH04255710A - New resin composition curable with energy ray - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent water-resistance and solvent-resistance and useful as adhesive, etc., by reacting a specific com pound containing oxirane ring, a specific compound having unsaturated double bond and a functional group reactive with oxirane group and a polybasic acid anhydride. CONSTITUTION:The objective composition is produced by reacting (A) a compound of formula I (W, X, Y and Z are H or group of formula II and are not H at the same time), e.g. glycidyl-containing compound of 2,7-hydroxynaphthalene with (B) a compound [e.g. (meth)acrylic acid] having unsaturated double bond and a group reactive with at least one of the oxirane-containing groups of the compound A and reacting the reaction product with (C) a polybasic acid anhydride such as maleic anhydride.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a new and useful energy ray curable resin composition. In more detail,
The present invention deals with the reaction of an oxirane ring-containing compound with a specific structure, a compound having both a functional group that reacts with the specific oxirane ring-containing group, and an unsaturated double bond, and an anhydride of a polybasic acid, as active ingredients. The present invention relates to an energy ray curable resin composition comprising an energy ray curable resin obtained by.

The energy ray-curable resin composition of the present invention is suitable for a wide range of uses such as coating materials, printing inks, adhesives, and photoresists.
It can be cured using so-called energy rays, such as ultraviolet rays and electron beams, which are extremely useful.

0003

[Prior Art] Resins that can be cured by energy rays, especially resins that can be cured by radical polymerization reactions, include unsaturated polyester resins, vinyl ester resins (epoxy
acrylate), various oligoacrylates, and diallyl phthalate prepolymers, each of which has characteristics that are utilized in its application field and is being used in a wide range of applications.

[0004] However, in recent years, as its uses have expanded, demands for performance in each use have been increasing.
The reality is that a resin composition that can be cured by energy rays has not yet been obtained.

[0005]

[Problems to be Solved by the Invention] In view of the various situations described above, the present inventors have developed a method that can be used even in applications where existing resins cannot be completely satisfied.
We are actively researching the synthesis of radical-curing resins with excellent water resistance, solvent resistance, chemical resistance, heat resistance, and curability.
Started research.

In other words, the problem to be solved by the present invention is to provide an extremely useful energy beam curing method that is particularly excellent in water resistance, solvent resistance, chemical resistance, heat resistance, and curing properties. An object of the present invention is to provide a mold resin composition.

[0007]

[Means for solving the problem] Therefore, the present inventors
As a result of intensive studies aimed at the problems to be solved by the invention as described above, we hereby found that a polyfunctional oxirane ring-containing compound having a specific structure reacts with a specific oxirane ring-containing group. An energy ray-curable resin obtained by reacting a compound having both a functional group and an unsaturated double bond with an anhydride of a polybasic acid can satisfy all of the coating film properties described above. By discovering this, we have completed the present invention.

That is, the present invention basically consists of a polyfunctional oxirane ring-containing compound having a specific structure, and a compound having both a functional group capable of reacting with the oxirane ring-containing group and an unsaturated double bond in its skeleton. and an anhydride of a polybasic acid.

Specifically, the general formula

0010

[Chemical formula 9]

[However, W, X, Y and Z in the formula are
Hydrogen atoms or formulas that may be the same or different, respectively

0012

[Chemical formula 10]

[0013] represents a group shown by W, X
, Y and Z are all hydrogen atoms. ] So-called oxirane ring-containing compounds [those with a specific structure in which each of W, X, Y, and Z in the compound is a glycidyl ether group or a hydrogen atom (however, as described above, The case in which all of these W, X, Y, and Z are all hydrogen atoms is excluded. The present invention provides an energy ray curable resin composition comprising the obtained energy ray curable resin as an active ingredient.

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

As the resin (A), of course, any resin can be used as long as it is made by reacting the various compounds mentioned above, but only the most representative ones are exemplified. First, we need to prepare an oxirane ring-containing compound with a specific structure [hereinafter referred to as (a
-1). ] and an unsaturated monocarboxylic acid compound [hereinafter, this will be treated as (a-2). ], at least one of the compounds (a-1)
A specific reactant obtained via one or more oxirane ring-containing groups and a carboxyl group [hereinafter, this will be treated as (a-3). ], at least one aromatic, aliphatic and/or alicyclic polybasic acid anhydride [hereinafter, this shall be treated as (a-4). ] and the like.

Among them, the polyfunctional oxirane ring-containing compound (a-1
), to mention only the most representative ones:
2,7-dihydroxynaphthalene used alone or in combination with β-naphthol to form an oxirane ring-containing compound through its dimerization, and is represented by the general formula [1]. An oxirane ring-containing compound in which W, X, Y, and Z of the compound shown are each a glycidyl ether group or a hydrogen atom (however, each of W, X, Y, and Z is a hydrogen atom) ), etc.

On the other hand, typical examples of the unsaturated monocarboxylic acids (a-2) that react with the oxirane ring-containing group include acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid. Although two or more of these may be used in combination, it is particularly desirable to use acrylic acid.

[0018] Furthermore, the anhydride of the polybasic acid (a-4
) Among the most representative examples, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, het acid, hymic acid, chlorendic acid, dimer acid, adipic acid, Succinic acid, alkenylsuccinic acid, sebacic acid, azelaic acid, 2
, 2,4-trimethyladipic acid, terephthalic acid, 2-
5 such as potassium sulfoterephthalate, 2-sodium sulfoterephthalate, isophthalic acid, 2-potassium sulfoisophthalate, 2-sodium sulfoisophthalate, dimethyl or diethyl ester, etc.
-Sodium-sulfoisophthalic acid di-lower alkyl ester, orthophthalic acid, 4-sulfophthalic acid, 1,10
- Anhydrides of decamethylene dicarboxylic acid, muconic acid, oxalic acid, malonic acid, glutaric acid, trimellitic acid, hexahydrophthalic acid, tetrabromophthalic acid, methylcyclohexentricarboxylic acid or pyromellitic acid. Of course, these may be used alone or in combination of two or more.

The energy ray-curable resin thus obtained is highly sensitive in itself, and after curing, provides a film with excellent water resistance, solvent resistance, chemical resistance, heat resistance, etc. becomes.

The energy ray curable resin composition of the present invention, which contains the energy ray curable resin thus obtained as an essential component, may further contain, if necessary, within the scope of the purpose of the present invention. In particular, known and commonly used additives, such as other types of reactive diluents and This does not preclude the addition of organic solvents or the like.

[0021] As such reactive diluents, a wide range of monofunctional to polyfunctional ones are used, but among them, only the most representative ones are exemplified. 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-butane di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, trimethylolpropane Tri(meth)acrylate, pentaerythritol tri(
meth)acrylate, pentaerythritol tetra(meth)acrylate or dipentaerythritol hexa(meth)acrylate.

[0022] Further, to exemplify only typical solvents, 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, heptane, as well as cellosolve acetate, carbitol acetate, dimethylformamide, or tetrahydrofuran.

[0023] The energy ray as used in the present invention is a general term for ionizing radiation and light such as electron beams, α rays, β rays, γ rays, X rays, neutron beams, and ultraviolet rays. In the present invention, when the resin composition of the present invention is cured using ultraviolet rays as energy rays, it is preferable to use ultraviolet rays with a wavelength of 1,000 to 8,000 angstroms to dissociate and generate radicals (polymerization ) an initiator should be used.

As such photo (polymerization) initiators, of course, any known and commonly used ones can be used, but among them, representative examples include acetophenones, benzophenone, Michler's ketone, Benzine, benzoin benzoate, benzoin, benzoin methyl ethers, benzyl dimethyl ketal,
These include α-acyloxime esters, thioxanthones, anthraquinones, and various derivatives thereof.

[0025] In addition, a known and commonly used photosensitizer can also be used in combination with such a photo(polymerization) initiator, but only typical examples of such photosensitizers are listed below. , amines, ureas, sulfur-containing compounds, phosphorus-containing compounds,
These include chlorine-containing compounds, nitriles, and other nitrogen-containing compounds.

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

[0027]

[Examples] Next, the present invention will be explained by examples and application examples.
This will be explained in more detail. In the following, all parts and percentages are based on weight unless otherwise specified.

Example 1 In a flask equipped with a thermometer, a stirrer and a reflux condenser,
556 g of a tetrafunctional epoxy compound obtained through dimerization using 2,7-dihydroxynaphthalene alone or in combination with β-naphthol, and 1.3 g of hydroquinone monomethyl ether. Further, 288 g of acrylic acid and 12.8 g of triphenylphosphine were added, and the reaction was carried out at a temperature of 110° C. until the epoxy equivalent became 15,000 or more. I got it.

Further, 152 g of tetrahydrophthalic anhydride was added thereto, and the mixture was reacted at 110° C. until the acid value reached 57 to obtain the desired reaction product. Hereinafter, this will be abbreviated as resin (A-1).

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 the reaction was carried out at 110° C. until the acid value reached 98 to obtain a reaction product. Hereinafter, this will be abbreviated as resin (A-2).

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

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

Resin (A-1)
100 copies
1-hydroxyhexylphenyl ketone
Three parts of the above paint thus obtained were then applied to a thickness of 20 μm on a wet-sanded tin plate.

Thereafter, this was cured by irradiating it with ultraviolet rays for 60 seconds from a height of 15 cm using an 80 W high pressure mercury lamp. Table 1 shows the results of various performance evaluation tests conducted on each coated plate.

Application Example 2 Instead of resin (A-1), the resin (A-1) obtained in Example 2 was used.
A paint was obtained, applied, and cured in the same manner as in Application Example 1, except that the same amount of A-2) was used.

Similar performance evaluations were conducted for the coated plates, and the results shown in Table 1 were obtained. Application example 3 Instead of resin (A-1), resin (A-1) obtained in Example 3 was used.
A paint was obtained, applied, and cured in the same manner as in Application Example 1, except that the same amount of A-3) was used.

Similar performance evaluations were conducted for the coated plates, and the results shown in Table 1 were obtained. Application Example 4 Various components as described below were added to the resin (A-3) obtained in Example 3, thoroughly mixed, and stirred to prepare a paint.

Resin (A-3)
100 copies
1-hydroxyhexylphenyl ketone
3 parts trimethylolpropane triacrylate After 20 parts, a coating material was obtained, applied, and cured in the same manner as in Application Example 1.

Similar performance evaluations were conducted for the coated plates, and the results shown in Table 1 were obtained. Comparative Example 1 In a flask equipped with a thermometer, a stirrer, and a reflux condenser,
"Epicron N-695" with an epoxy equivalent of 213
426 g of ``cresol novolak type epoxy compound manufactured by Dainippon Ink & Chemicals Co., Ltd.'' and 1.3 g of hydroquinone monomethyl ether were added, and 144 g of acrylic acid was also added to make the acid value 3 or less. The reaction was carried out at a temperature of 110°C until the reaction product (c-3-1
) was obtained.

Next, 570 g of (c-3-1) was added to a flask newly equipped with a thermometer, stirrer, and reflux condenser.
and charged 152g of tetrahydrophthalic anhydride.
Furthermore, 0.5 g of di-n-butyltin diacetate was also 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-cured resin. Hereinafter, this will be abbreviated as resin (C-1).

Comparative Application Example 1 Except for using the same amount of resin (C-1) obtained in Comparative Example 1 instead of using resin (A-1),
A paint was obtained, applied, and cured in the same manner as in Application Example 1.

Similar performance evaluations were conducted for the coated plates, and the results shown in Table 1 were obtained. Note that the evaluation of each performance was performed in the following manner.

[0043] Curability: The applied coating film is cured at 80%
80W/cm2 after drying in warm air at ℃ for 15 minutes.
The sample was passed through a 15 cm position at a speed of 50 m/min under a high-pressure mercury lamp with an intensity of 15 cm, and the number of times it took to harden was measured.

Water resistance: Gauze is soaked in ion-exchanged water and the cured coating is rubbed 40 times, after which the degree of decrease in film thickness is measured. ◎: Less than 5 μm ○: 5 μm or more and less than 10 μm △: 10 μm or more and less than 15 μm The degree of decrease in film thickness is then measured. The evaluation criteria are the same as for water resistance.

Alkali resistance: Gauze is immersed in a 10% aqueous sodium hydroxide solution and the cured coating is rubbed 40 times, after which the degree of decrease in film thickness is measured. The evaluation criteria are the same as for water resistance.

[0046] Heat resistance......The applied coating film was
80W/cm2 after drying in warm air at ℃ for 15 minutes.
The cured coating was passed through a 15 cm position 10 times at a speed of 50 m/min under a high-pressure mercury lamp with an intensity of
Immediately after placing in a heating oven at 200° C. for 40 seconds, gauze was pressed onto the coated film surface, and after cooling, the gauze was peeled off and changes in the coated film were visually determined.

◎: No change observed at all ○: Some traces of gauze on the surface ×: The coating film melts and peels off together with the gauze Alkali-soluble...The applied coating film was heated at 80°C. After drying in hot air for 15 minutes, rub the uncured paint film 30 times with gauze soaked in 1/10N potassium hydroxide aqueous solution to observe the degree of dissolution of the paint film.

◎: No paint film left at all ○: Hardly any paint film left △: Some paint film remains ×: Some paint film remains

[0049]

[Table 1]

As is clear from the results in Table 1, the energy ray-curable resin composition of the present invention can be freely cured with energy rays at room temperature or under heating. Due to the various properties obtained based on the structure of the contained compounds, it has excellent curability, and the resulting cured coating film has water resistance, solvent resistance, and chemical resistance, and is also excellent in heat resistance. It is a thing,
It is extremely useful for various uses.

[0051]

Effects of the Invention: The energy ray-curable resin composition of the present invention itself is highly sensitive, and the cured coating film has excellent water resistance, solvent resistance, chemical resistance, and heat resistance. This makes them extremely useful in a wide range of applications, including as coating agents, printing inks, photoresists, and adhesives, among others.

Claims (2)

[Claims] Claim 1: General formula [Formula 1] [However, W, X, Y and Z in the formula are each a hydrogen atom or a group represented by the formula [Formula 2], which may be the same or different. , where W, X, Y and Z
shall be excluded if all of them are hydrogen atoms. ] A reaction product of a compound represented by the above, a compound having both a group capable of reacting with at least one oxirane ring-containing group and an unsaturated double bond, and an anhydride of a polybasic acid. characterized by containing a resin that
Energy ray curable resin composition. [Claim 2] General formula [Formula 3] [However, W, X, Y and Z in the formula each represent a hydrogen atom or a group represented by the formula [Formula 4], but W, , Y and Z
shall be excluded if all of them are hydrogen atoms. ] At least one oxirane ring-containing group of the compound represented by the general formula: / or represents a halogen atom, and B1 is
It represents the residue of a basic acid. ], and the remaining oxirane ring-containing group is a hydrogen atom or a group represented by the formula [Chemical formula 6], or a group represented by the general formula [Chemical formula 7] [However, R1 in the formula is a hydrogen atom or a methyl group, R2 represents a hydrogen atom, a methyl group, a cyano group and/or a halogen atom, and B1 represents a residue of a polybasic acid. ] and/or a group represented by the general formula [Formula 8] [However, R1 in the formula represents a hydrogen atom or a methyl group,
R2 represents a hydrogen atom, a methyl group, a cyano group and/or a halogen atom. ] The energy ray-curable resin composition according to claim 1, which is substituted with a group represented by the following.