JPH04239012A - New actinic radiation-curable resin composition - Google Patents

Abstract

PURPOSE:To provide an actinic radiation-curable resin having high sensitivity and excellent water resistance, solvent resistance and heat resistance by using a specified polyepoxy compound and a specified unsaturated monocarboxylic acid and a new and useful actinic radiation-curable resin composition containing this resin as an effective component. CONSTITUTION:An actinic radiation-curable resin composition comprising 100 pts.wt. resin synthesized from a tetraepoxy compound obtained by reacting a tetraphenol derivative derived from 4,4'-diacetyldiphenyl ether and a monophenol according to the usual manner, acrylic acid and tetrahydrophthalic anhydride and 3 pts.wt. 1-hydroxyhexyl phenyl ketone. This composition is excellent in curability, water resistance, solvent resistance and heat resistance, and can find wide applications such as coating materials, inks and photoresists.

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 uses, as active ingredients, a specific epoxy compound, a compound having a functional group and an unsaturated double bond that reacts with a specific epoxy group, and anhydrides of aromatic, aliphatic, and/or alicyclic polybasic acids. The present invention relates to an energy ray curable resin composition comprising an energy ray curable resin obtained by reaction with a compound.

The energy ray curable resin composition of the present invention is suitable for a wide range of uses such as coating materials, printing inks, photoresists, adhesives, etc. It is a resin composition that can be cured by energy rays.

0003

[Prior Art] Resins that can be cured by energy beams, especially resins that can be cured by radical polymerization reactions, include various types of resins such as unsaturated polyester resins, vinyl ester resins (epoxy acrylates), various oligoacrylates, and diallylphthalate prepolymers. These resins are widely used in their respective fields of application, making the most of their characteristics.

However, in recent years, as its uses have expanded,
Although demands for performance are increasing, a resin composition curable by energy rays that can satisfy all the performance requirements has not yet been obtained.

[0005]

[Problems to be Solved by the Invention] However, in view of the above-mentioned situation, the present inventors have discovered that it can be used for applications that cannot be satisfied with existing resins, and has excellent water resistance, solvent resistance, and Excellent in chemical properties, heat resistance, and curing properties.
We have been conducting extensive research into the synthesis of radical-curing resins, but we have found that a specific multifunctional epoxy compound, a compound that has both a specific functional group that can react with an epoxy group, and an unsaturated double bond. An energy ray-curable resin obtained by reaction with a compound selected from the group consisting of anhydrides of aromatic, aliphatic, and alicyclic polybasic acids can satisfy the various properties of the coating film described above. By discovering this, we have completed the present invention.

[0006]

[Means for Solving the Problems] That is, the present invention basically consists of a specific polyfunctional epoxy compound, a compound having both a functional group that reacts with an epoxy group and an unsaturated double bond in its resin skeleton, A novel energy ray curable resin composition containing a specific energy ray curable resin obtained by reacting an aromatic, aliphatic and/or alicyclic polybasic acid with an anhydride compound. This is what we provide.

[0007] Specifically, the general formula

[0008]

[C5]

[However, X in the formula is an oxygen atom or CH
2 group, R represents a hydrogen atom or a methyl group, and Y represents a general formula

0010

[C6]

(However, R1 in the formula represents a hydrogen atom or a methyl group, and R2 represents a hydrogen atom, a methyl group,
It represents a cyano group or a halogen atom, and B1 represents a residue of a polybasic acid anhydride. ), and each Z represents a group represented by the general formula, which may be the same or different.

0012

[C7]

(However, R1 in the formula represents a hydrogen atom or a methyl group, and R2 represents a hydrogen atom, a methyl group,
It represents a cyano group or a halogen atom, and B1 represents a residue of a polybasic acid anhydride. ) or expression

[0014]

[Chemical formula 8]

It represents a group represented by the following. )], a reaction product of a specific polyfunctional epoxy compound in which Y and Z are epoxy groups, and an unsaturated monocarboxylic acid, and aromatic, aliphatic and alicyclic It is an object of the present invention to provide a new and useful energy beam curable resin composition comprising as an active ingredient an energy beam curable resin obtained by reaction with a compound selected from the group consisting of anhydrides of polybasic acids. It is something to do.

[0016] Here, the energy ray curable resin [hereinafter also referred to as resin (A)] is used. ] refers to the reaction product of a specific polyfunctional epoxy compound, a reaction product with an unsaturated monocarboxylic acid, and a compound selected from anhydrides of aromatic, aliphatic, and alicyclic polybasic acids. It is something to do.

As the resin (A), of course, any resin can be used as long as it is a reaction product of the various compounds mentioned above, but only the most representative ones will be exemplified. First, a specific polyfunctional epoxy compound (hereinafter referred to as (a-1)) and an unsaturated monocarboxylic acid compound (hereinafter referred to as (a-1)) that reacts with the epoxy group. -2)) (hereinafter, this will be treated as (a-3)).
Resins obtained by reacting the compound (a-4) with anhydrides of aromatic, aliphatic, and alicyclic polybasic acids are suitable.

[0018] Among them, first of all, only representative ones are listed as the specific polyfunctional epoxy compound (a-1) for preparing the above (a-3). 4 acetyl groups and monohydric phenols are dehydrated and condensed in the presence of an acidic catalyst.
A kind of intermediate, a functional phenol derivative, is obtained, and then
In the above general formula [1] obtained from this tetrafunctional phenol derivative by a conventional method, Y and Z are respectively
Both of them are all epoxy groups.

On the other hand, particularly representative unsaturated monocarboxylic acids (a-2) that react with the epoxy group include acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid, which may be used alone. However, two or more types may be used in combination, but it is particularly desirable to use acrylic acid.

[0020] Furthermore, the anhydride of the polybasic acid (a-4
) are particularly representative of 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-potassium sulfoterephthalic acid, 2-Sodium sulfoterephthalic acid, isophthalic acid, 2-potassium sulfoisophthalic acid, 2-sodium sulfoisophthalic acid, di-lower alkyl 5-sodium sulfoisophthalate (such as dimethyl or diethyl), orthophthalic acid, 4-sulfophthalic acid ,1,1
0-decamethylene dicarboxylic acid, muconic acid, oxalic acid,
Examples include malonic acid, glutaric acid, trimellitic acid, hexahydrophthalic acid, tetrabromophthalic acid, or anhydride of cyclohexenetricarboxylic 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 itself highly sensitive and can be dissolved in an alkaline solution before curing, but after curing it has excellent water resistance, solvent resistance, chemical resistance, and It provides a film with excellent heat resistance.

[0022] The energy ray curable resin of the present invention thus obtained and the energy ray curable resin composition comprising the resin as an essential component may further be treated as necessary if necessary. known and customary additives, in particular other types of reactive diluents, to the extent that storage stability and water, solvent, chemical and heat resistance are maintained. This does not preclude the addition of organic solvents, organic solvents, etc.

[0023] A wide range of reactive diluents can be used, from monofunctional to polyfunctional ones, but to exemplify only the most representative ones, 2- Hydroxyethyl (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, ) 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 acrylate, pentaerythritol tetra(meth)acrylate or dipentaerythritol hexa(meth)acrylate.

The above-mentioned solvents include aromatic hydrocarbons such as toluene or xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; esters such as methyl acetate, ethyl acetate or butyl acetate; methanol and ethanol. , alcohols such as propanol or butanol; or aliphatic hydrocarbons such as hexane or heptane, as well as cellosolve acetate, carbitol acetate, dimethylformamide or tetrahydrofuran.

[0025] 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. When curing the resin composition of the present invention using ultraviolet rays as energy rays, the wavelength is 1,000 to 8,000.
A photo (polymerization) initiator that can be dissociated by angstrom ultraviolet rays to generate radicals should be used. As such photo (polymerization) initiators, any known and commonly used photo (polymerization) initiators can be used. Among them, the most representative ones are acetophenones, benzophenone, Michler's ketone, benzine, benzoin, benzoin benzoate, benzoin methyl ethers, benzyl dimethyl ketal, α-acyloxime ester, thioxanthone, anthracite. These include quinones and their various derivatives.

[0026] In addition, a known and commonly used photosensitizer can be used in combination with such a photo(polymerization) initiator, but
Typical examples of such photosensitizers include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds. .

The energy ray-curable resin of the present invention and the resin composition comprising the same are usually cured by irradiation with radiation or active energy rays using the energy sources listed above. good.

[0028]

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, Comparative Examples, and Applied Examples. 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,
Two acetyl groups of 4,4'-diacetyldiphenyl ether and monohydric phenol are dehydrated and condensed under an acidic catalyst to obtain a tetrafunctional phenol derivative, and 874 g of a tetrafunctional epoxy compound obtained therefrom. 1.3 g of hydroquinone monomethyl ether, 288 g of acrylic acid and 12.8 g of triphenylphosphine.
g, and at a temperature of 110°C, the epoxy equivalent was 15,
000 or more, reactant (a-3-1)
I got it.

Further, 152 g of tetrahydrophthalic anhydride was added thereto, and the reaction was carried out at 110° C. until the acid value reached 43 to obtain the desired resin. Hereinafter, this resin (A
-1).

Example 2 In a flask equipped with a thermometer, a stirrer and a reflux condenser,
1,162 g of (a-3-1) obtained in Example 1 and 304 g of tetrahydrophthalic anhydride were added, and the reaction was carried out until the acid value reached 39 to obtain the desired resin.

Hereinafter, this will be abbreviated as resin (A-2). Example 3 Except that the amount of (a-3-1) used was 1,162 g, the amount of tetrahydrophthalic anhydride was 608 g, and the reaction was carried out until the acid value reached 127.
In the same manner as in Example 1, the desired energy ray-cured resin was obtained.

Hereinafter, this will be abbreviated as resin (A-3). Application Example 1 The following components were added to the resin (A-1) obtained in Example 1, thoroughly mixed, and stirred to prepare a paint.

Resin (A-1)
100 parts 1-hydroxyhexylphenyl ketone 3 parts Then,
The obtained above paint was applied to a water-polished tin plate with a thickness of 20 μm.
It was applied to a thickness of . Next, 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 the performance evaluation tests conducted on the coated plates. Application Example 2 A paint was applied in the same manner as Application Example 1, except that the same amount of resin (A-2) obtained in Example 2 was used instead of resin (A-1). It was obtained, coated and cured.

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

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

Resin (A-1)
100 copies
1-Hydroxyhexyl phenyl ketone 3 parts Trimethylolpropane triacrylate 2
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 novolac 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 obtain an acid value of 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.
Then, 152 g of tetrahydrophthalic anhydride and 0.5 g of di-n-butyltin diacetate were added, and the reaction was carried out at a temperature of 110° C. until the acid value reached 78 to obtain an energy ray-cured resin. .

[0041] Hereinafter, this will be abbreviated as resin (C-1). Thereafter, the paint was obtained in the same manner as Application Example 1, except that the same amount of the resin (C-1) obtained here was used instead of the resin (A-1). It was applied and cured.

Similar performance evaluations were conducted for the coated plates, and the results shown in Table 1 were obtained.

[0043]

[Table 1]

[0044]Each performance was evaluated in the following manner. Curing property: After drying the applied coating in hot air at 80°C for 15 minutes, it is cured by passing it through a 15cm position at a speed of 50m/min under a high-pressure mercury lamp with an intensity of 80W/cm2. The number of times until

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
Measure the degree of decrease in film thickness after rubbing 0 times. The evaluation criteria are the same as for water resistance.

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

Heat resistance: After drying the applied coating film for 15 minutes in warm air at 80°C,
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 m2, and then placed in a heating oven at 200°C for 40 seconds, and then immediately
Gauze was pressed onto the paint film surface, and after cooling, the gauze was peeled off and changes in the paint film were visually determined.

◎: No change observed at all. ○: Some traces of gauze are left on the surface. ×: The coating film melts and peels off together with the gauze.

[0049] Alkali solubility...The applied coating film is heated to 80°C.
After drying in hot air for 15 minutes, the uncured coating was 1/1
Rub the area 30 times with gauze soaked in 0N potassium hydroxide aqueous solution to see how well the coating has dissolved.

◎: No coating remains at all. ○: Almost no paint film remains. △: Some paint film remains. ×: Paint film remains.

As is clear from the results in Table 1, the energy ray-curable resins and resin compositions of the present invention can be freely cured with energy rays at room temperature or under heating; Due to various properties based on the structure of the specific epoxy compound itself, it has excellent curing properties,
In addition, the cured coating film has excellent water resistance, solvent resistance, and chemical resistance, and also has excellent heat resistance, making it extremely useful for various applications.

[0052]

Effects of the Invention The energy ray-curable resin of the present invention and the resin composition containing the same are highly sensitive in themselves, and the cured coating film has good water resistance, solvent resistance, and chemical resistance. Since it also has excellent heat resistance, it is extremely useful in a wide range of applications, particularly as a coating agent, photoresist, printing ink, and plate-making material.

Claims (1)

[Claims] Claim 1: General formula [Formula 1] [However, in the formula, X represents an oxygen atom or a CH2 group, R represents a hydrogen atom or a methyl group, and Y represents a general formula [Formula 2] ] (However, R1 in the formula represents a hydrogen atom or a methyl group, R2 represents a hydrogen atom, a methyl group, a cyano group, or a halogen atom, and B1 represents a residue of a polybasic acid anhydride. represents a group represented by the general formula [Chemical formula 3] (wherein R1 is a hydrogen atom or a methyl group, , R2 represents a hydrogen atom, a methyl group, a cyano group, or a halogen atom, and B1 represents a residue of a polybasic acid anhydride) or a group represented by the formula [Formula 4] shall represent. )] An energy ray curable resin composition characterized by containing an energy ray curable resin represented by the following.