JPH08259663A - Active energy ray-curable epoxy acrylate resin composition - Google Patents

Abstract

PURPOSE: To obtain an active energy ray-curable epoxy acrylate resin composition useful as a photopolymerizable resin such as a solder resist, high in sensitivity, and excellent in stability, electric characteristics and solder resistance, when the solvent is dried. CONSTITUTION: The active energy ray-curable epoxy acrylate resin composition contains as an essential component (C) an acid-pendant type epoxyacrylate obtained by reacting 1 mole of (A) an epoxy resin having two or more epoxy groups in the molecule with 0.1-0.8 mole of (meth)acrylic anhydride and 0.2-0.9 mole of an unsaturated monobasic acid, and subsequently reacting (A) the obtained epoxy acrylate resin with (B) a polybasic acid anhydride.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable epoxy acrylate resin composition. More specifically, it has excellent curability with respect to active energy rays such as light, ultraviolet rays, and electron beams, forms a cured film with excellent heat resistance, hardness, and electrical characteristics, and can be developed with an alkaline aqueous solution. The present invention relates to an active energy ray-curable resin composition useful for applications such as a color filter layer, a protective film for electronic devices, a permanent protective mask such as a solder resist for printed wiring boards, and an insulating layer for wiring boards.

[0002]

BACKGROUND OF THE INVENTION Unsaturated epoxy ester resins, also known as epoxy acrylates and vinyl esters, are superior in heat resistance, chemical resistance, water resistance, adhesiveness, and mechanical properties to other acrylic oligomers, and are therefore various coating materials. It is widely used as a resin for structural materials and wiring board solder resists.

Particularly with respect to the solder resist, it is expected that the pattern will be made finer as the amount of information on the substrate increases, and the solder resist by the photoengraving method is used. As a method, there is a method of developing the unexposed area ink with a solvent or a dilute alkaline solution, but the dilute alkaline solution developing type is predominant due to cost and pollution problems of the solvent.

For these dilute alkaline developing type solder resists, the hydroxyl groups of epoxy acrylate resin are reacted with acid anhydrides to make the carboxyl groups pendant.
The so-called acid pendant type epoxy acrylate resin is often used as a main component, and a method for producing the resin and a coating method using the resin are described in JP-A-61-243869 and JP-A-63-258975. It is described in the official gazette.

However, an epoxy acrylate in which a rigid novolac epoxy compound is reacted with an unsaturated carboxylic acid such as (meth) acrylic acid has a low sensitivity and requires a long exposure time, which not only lowers the workability, There is a defect that the photomask is damaged due to the temperature rise during exposure.

As a method for increasing the exposure sensitivity, a means of incorporating a polyfunctional acrylate such as pentaerythritol triacrylate or dipentaerythritol hexaacrylate into the composition is used. However, if mixed in a large amount, tack after temporary drying will occur and cause damage to the photomask, so its use is limited.

Further, in order to improve the curing rate, the polyfunctionalization of epoxy acrylate has been tried by various methods. In particular, JP-A-49-23900 and JP-B-55-120
No. 43 and Japanese Patent Application Laid-Open No. 1-161069 disclose a photocurable composition of a polyfunctional epoxy acrylate obtained by reacting an epoxy resin with anhydrous (meth) acrylic acid and (meth) acrylic acid. However, these are not suitable for pattern formation because they cannot be alkali-developed.

For the purpose of improving the water resistance and electrical characteristics of the solder resist cured film, an epoxy resin that blocks the carboxyl groups is blended in the ink and the radiant heat upon irradiation of ultraviolet rays is used, or 120 A method of forming a tough film by increasing the crosslink density by post-heating at ˜130 ° C. is used.

When an epoxy resin is blended with an acid pendant type epoxy acrylate resin to be used in ink or paint,
There are drawbacks such that the epoxy group and the carboxyl group react with each other and the viscosity increases or gelation occurs with time.

In addition, the resist ink usually blended includes
From the viewpoint of workability, a solvent or a small amount of an acrylic monomer is blended if necessary, and after the ink applied before patterning with a negative film is heated in an atmosphere of 70 to 80 ° C. to volatilize and remove the solvent, The step of patterning by exposure is taken.

If a part of the reaction between the carboxyl group and the epoxy group described above progresses in this step, the development after the exposure is often insufficient, and there are many restrictions on the composition and the temperature and time for removing the solvent. there were. Therefore, a composition having a long life as a composition or a long development life at the time of temporary drying is desired.

The fields of application in which these protective masks are used are radio, video, television, computer, control equipment, etc., but in recent years, due to the demand for outdoor use of these equipment and the mounting demand for vehicles, etc. The conditions are more severe, and as a permanent protection mask, higher electrical insulation, sensitivity, plating resistance, etc. than ever have been required are being demanded. Studies on the catalyst and epoxy acrylate resin structure during the synthesis of the epoxy acrylate have been conducted.

For example, Japanese Examined Patent Publication No. 6-23233 proposes a method using a metal salt of an organic acid as an esterification catalyst for the production of an acid pendant type epoxy acrylate. The properties such as properties are almost the same as those of the resins obtained with the conventionally used catalysts. Further, in Japanese Patent Laid-Open No. 3-100009,
Although an acid pendant type epoxy acrylate solder resist ink composition using a special epoxy compound has been proposed, similarly, performances such as sensitivity, electrical characteristics, and plating resistance are almost the same as those of conventional resins. .

[0014]

Therefore, the problems to be solved by the present invention are high sensitivity, stability in solvent drying, electrical characteristics, and plating resistance, which are useful as photopolymerizable resins such as solder resists. Another object of the present invention is to provide an active energy ray-curable epoxy acrylate resin composition having excellent properties.

[0015]

Means for Solving the Problems The inventors of the present invention have made it possible to improve the developing accuracy, the developing stability, and the sensitivity during the removal and drying of the solvent.
As a result of intensive studies on plating resistance and electric insulation, an epoxy resin obtained by reacting (meth) acrylic acid and (meth) acrylic acid with an epoxy resin having two or more epoxy groups in one molecule. An active energy ray curable epoxy acrylate resin composition comprising an acid pendant type epoxy acrylate obtained by reacting a polybasic acid anhydride with a rate resin, The inventors have found that the above problems can be solved, and have completed the present invention.

That is, according to the present invention, an epoxy resin having two or more epoxy groups in one molecule contains 0.1 to 0.8 mol of anhydrous (meth) acrylic acid per 1 mol of epoxy groups, and an unsaturated monocarboxylic acid. An acid pendant type epoxy acrylate obtained by reacting an epoxy acrylate resin (A) obtained by reacting a basic acid with 0.2 to 0.9 mol with a polybasic acid anhydride (B). -(C) as an essential component is an active energy ray-curable epoxy acrylate resin composition.

In the present invention, the polybasic acid anhydride (B) is reacted in an amount of 0.2 to 1.0 mol with respect to 1 mol of the unsaturated monobasic acid of the epoxy acrylate resin (A) reacted. The active energy ray-curable epoxy acrylate resin composition according to claim 1, further comprising an acid pendant type epoxy acrylate (C) obtained by the above process as an essential component.

In particular, the epoxy resin having two or more epoxy groups in one molecule used in the production of the epoxy acrylate resin (A) has a number average molecular weight of 700 to 3000 and a softening point of 30 ° C. to 120 ° C. Active energy comprising one or more resins
It is a radiation curable epoxy acrylate resin composition.

The present invention also provides the above-mentioned active energy ray-curable epoxy acrylate resin composition, further comprising a photopolymerization initiator (D), a photopolymerizable vinyl monomer (E) and / or an organic compound. An active energy ray curable epoxy acrylate resin composition containing a solvent and an epoxy compound (F) having at least two epoxy groups in one molecule is included.

Examples of the epoxy resin having two or more epoxy groups in one molecule of the present invention include bisphenol type epoxy resin, novolac type epoxy resin, halogenated bisphenol type epoxy resin, halogenated novolak type epoxy resin, and polycarboxylic acid. Glycidyl ester type resins of acids, linear aliphatic epoxy resins, alicyclic epoxy resins, triglycidyl isocyanurate and its derivatives, unsaturated monomers containing glycidyl group such as polyglycidyl (meth) acrylate and glycidyl (meth) acrylate
And other unsaturated monomers.

Particularly, as the epoxy resin used in the present invention, a novolac type epoxy resin is preferable from the viewpoint of heat resistance, hardness and tackiness after temporary drying, and further, the number average molecular weight is 700 to 3000, and the softening point is It is preferably composed of at least one resin having a temperature of 30 ° C. or higher and 120 ° C. or lower.

The anhydrous (meth) acrylic acid used in the present invention is obtained by reacting an acyl halide of (meth) acrylic acid with an alkali metal salt of (meth) acrylic acid or in the presence of a dehydrating agent such as thionyl chloride or phosphoryl chloride. It can be manufactured from (meth) acrylic acid by the following. It is also possible to prepare it by using dimer acid of some (meth) acrylic acid, trimer acid, unsaturated monobasic acid, and saturated monobasic acid together.

The reaction of the epoxy resin with anhydrous (meth) acrylic acid and unsaturated monobasic acid in the present invention is carried out by mixing 0.1 to 0.8 mol of anhydrous (meth) acrylic acid with 1 mol of epoxy group The monobasic acid is preferably used within the range of 0.2 to 0.9 mol.

As the unsaturated monobasic acid used in the present invention, a monobasic acid compound having an α, β-ethylenically unsaturated bond can be used, but preferably it has a (meth) acrylate group and a carboxylic acid group. The compound is preferably a acrylic acid or methacrylic acid, and a dimer and trimer acid thereof, or hydroxyethyl (meth) acrylate, as a typical example, in view of reactivity to energy rays such as ultraviolet rays.

A half ester compound of a hydroxy (meth) acrylate compound such as hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and a polybasic anhydride, or a reaction product of (meth) acrylic acid and epsilon caprolactone. Alternatively, a mixture thereof or the like can be used. Particularly, (meth) acrylic acid is preferable from the viewpoint of reactivity with the epoxy group.

The polybasic acid anhydride used in the present invention is a saturated or unsaturated acid anhydride such as maleic anhydride,
Phthalic anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride,
Examples thereof include het anhydride, methyl nadic anhydride, itaconic anhydride, and benzophenone tetracarboxylic anhydride.

Particularly when used as a mixed type composition with a polyepoxy resin, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, from the viewpoint of development life at the time of temporary drying,
Alternatively, dodecenyl succinic anhydride, methyl-substituted tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc., alkyl-substituted succinic anhydride, tetrahydrophthalic anhydride,
Hexahydrophthalic anhydride and the like are preferably used.

The esterification reaction of the epoxy group with (meth) acrylic acid anhydride and unsaturated monobasic acid is preferably carried out in the presence of a stabilizer such as an epoxy esterification catalyst, a polymerization inhibitor and an antioxidant.

As the epoxy esterification catalyst, known tertiary amines such as triethylamine, trisdimethylaminomethylphenol and benzyldimethylamine,
Trimethylpentyl ammonium chloride, quaternary ammonium salts such as ammonium hydroxide salts, imidazole compounds represented by 2-ethyl-4-methylimidazole, diethylamine hydrochloride, nitrogen compounds such as diazabiscycloundecene, Phosphorus compounds typified by phenylphosphine, organic metal salts such as chromium naphthenate, and the like can be used.

As the polymerization inhibitor, there are well-known and conventional ones such as hydroquinone, methylhydroquinone, trimethylhydroquinone, tert-butylhydroquinone, and 2,6.
-Ditertiarybutyl-4-methoxyphenol, copper salt, phenothiazine and the like can be used, and as the antioxidant, well-known and common examples such as phosphorous acid, phosphorous acid esters, and phosphorous acid diesters can be used.

In the present invention, 0.2 to 1.0 equivalent of polybasic acid anhydride is reacted with the hydroxyl group contained in the epoxy acrylate at 30 to 130 ° C., preferably 50 to 110 ° C. Esterify. Here, the hydroxyl group contained in the epoxy acrylate is the sum of the reaction mole numbers of the hydroxyl group contained in the raw material epoxy resin and the unsaturated monobasic acid.

The acid value of the acid pendant type epoxy acrylate of the present invention is 30 to 150 KOH-mg / g (per solid content), preferably 55 to 130 KOH-mg / g (as solid content) as an acid value that can be developed in an aqueous alkaline solution. (Per solid content). The end point of the reaction is the infrared spectroscopic spectrum 17
It is confirmed by acid anhydride peak of 70cm ^-1 and 1850 cm ^-1 disappeared.

Although the reaction can be carried out without a solvent, in order to improve the stirring efficiency, the reaction is carried out by adding a solvent such as benzene, toluene, xylene, butyl cellosolve acetate, cellosolve acetate, carbitol acetate. May be.

In the photosensitive resin composition of the present invention, the photopolymerizable initiator (D) is not particularly limited, and known and commonly used polymerizable photoinitiators can be used. Four
-Dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ester, alkoxyacetophenone, benzophenone and benzophenone derivatives, alkyl benzoylbenzoate, bis (4-dialkylaminophenyl) ketone, benzyl and benzyl derivatives, benzoin and benzoin derivatives,

Benzoin alkyl ether, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenoylphosphine oxide, 2-methyl-1- [4- ( Methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1
-On,

Acetophenone, 2,2-dimethoxy-2
-Phenylacetophenone, 2,2-diethoxy-2-
Acetophenones such as phenylacetophenone and 1,1-dichloroacetophenone,

Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone and 2-aluminanthraquinone,

2,4-dimethylthioxanthone, 2,4
-Thioxanthones such as diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone,

Examples include ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, and xanthones. The amount of the photopolymerization initiator used is usually 0.2 to 30 parts by weight, preferably 2 to 20 parts by weight, based on 100 parts by weight of the acid pendant type epoxy acrylate resin solid content. Such a photopolymerization initiator may be used in combination with one or more known photopolymerization accelerators.

The amount of the photopolymerization initiator (D) used is usually 100% of the acid pendant type epoxy acrylate resin (C).
0.2 to 30 parts by weight, preferably 2 to 2 parts by weight
It is in the range of 0 parts by weight. Such a photopolymerization initiator may be used in combination with one or more known photopolymerization accelerators.

The photopolymerizable vinyl monomer (E) used in the present invention is not particularly limited, and known and commonly used photopolymerizable vinyl monomers can be used, but a typical example is β-hydroxyethyl acrylate. , Β-hydroxypropyl acrylate, glycidyl acrylate, β
-Hydroxyethyl acryloyl phosphate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate,

Ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane diacrylate ,

Trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, or bis (acryloyloxyethyl).
Hydroxyethyl isocyanurate, tris (2-acryloyloxyethyl) isocyanurate, or each methacrylate to the above acrylate,

Mono-, di-, tri- or higher polyesters of polybasic acids and hydroxyalkyl (meth) acrylates, or ethylenically unsaturated diacrylates such as bisphenol A type epoxy acrylates, novolac type epoxy acrylates or urethane acrylates. Monomers and oligomers having a heavy bond may be used.

Typical examples of the organic solvent used in the present invention include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, cellosolves such as cellosolve and butyl cellosolve, carbitol and butyl carbyl. There are carbitols such as butyl carbitol such as toll, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, acetic acid esters such as butyl carbitol acetate.

The above-mentioned photopolymerizable vinyl monomer (E) and / or organic solvent may be used alone or as a mixture of two or more kinds. The preferred range of the amount used is 30 to 300 parts by weight, more preferably 50 parts by weight, relative to 100 parts by weight of the acid pendant type epoxy acrylate resin (C).
~ 200 parts by weight.

Further, as typical examples of the epoxy compound (F) having at least two epoxy groups in one molecule, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol There are epoxy compounds having two or more epoxy groups in one molecule such as novolac type epoxy resin, cresol novolac type epoxy resin, N-glycidyl type epoxy resin and alicyclic epoxy resin. Particularly, N-glycidyl type epoxy resin is preferably used.

The epoxy compound (F) having at least two epoxy groups in one molecule is used alone or as a mixture of two or more kinds, and the preferable range of use is 100 of the acid pendant type epoxy acrylate resin (C).
30 to 300 parts by weight, preferably 30
To 300 parts by weight, more preferably 50 to 200 parts by weight.

The active energy ray-curable epoxy acrylate resin composition of the present invention may further contain, if necessary, known conventional fillers such as barium sulfate, silicon oxide, talc, clay and calcium carbonate, and phthalocyanine. Known and commonly used coloring agents such as blue, phthalocyanine green, titanium oxide, and carbon black, defoaming agents, and adhesion-imparting agents may be added.

Further, known compounds such as amine compounds, imidazole compounds, dialkylureas, carboxylic acids, phenols, or methylol group-containing compounds for accelerating the reaction are added to the extent that the effects of the present invention are not impaired. By using a small amount of the epoxy curing accelerator of (1) and heating the coating film afterwards, it can be obtained by promoting the polymerization of the photocuring component, the reaction of the carboxyl group of the epoxy compound and the acid pendant type epoxy acrylate, and the reaction of the epoxy compounds. It is also possible to improve various physical properties of the resist film.

The photopolymerizable resin composition of the present invention can be used, for example,
It is applied on the entire surface by a screen printing method, a roll coater method, a curtain coater method, a spray coater method, etc. on a printed wiring board, irradiated with active energy rays to cure the necessary part, and then the unexposed part is dissolved away with a dilute alkaline aqueous solution. By further applying post-curing with heat, a target film can be formed. It can also be used as an etching resist without applying heat.

The irradiation light source for curing the active energy ray-curable epoxy acrylate resin composition of the present invention is, for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp or a metahalide. A lamp or the like is suitable, and a laser beam or the like can be used as an active energy ray for curing. When an ultraviolet ray or high-pressure mercury lamp is used as a light source, the irradiation dose is 10 mJ / cm ² or more, usually 10 to 1000 mJ / cm ²
Irradiation is sufficient.

Sensitivity, resolution and developability are important as the image (pattern) forming function of the photosensitive resin. In particular, the sensitivity can be evaluated by the amount of the residual film remaining on the pattern to form a pattern with respect to the irradiation light, and the sensitivity is higher as the pattern is formed with a lower irradiation amount. When the photosensitive polymer is exposed to light, it changes depending on the amount of light, but the reactive molecule (site)
Sensitivity changes depending on the number of particles and the solubility in the developing solution.

As a general method for measuring the sensitivity of a photosensitive resin, a gray scale method (step tablet method), a residual film yield method, an electric resistance method and the like are known. (Functional polymer series Photosensitive polymer Mototaro Nagamatsu Edited by Hideo Inui, Kodansha Scientific)

[0055]

EXAMPLES Next, the present invention will be described more specifically by way of examples and application examples. In the following, all parts and% are based on weight unless otherwise specified. The number average molecular weight was measured by high performance liquid chromatography (GPC) and shown as a polystyrene conversion value.

(Synthesis Example 1) 78.9 parts of ethyl carbitol acetate was placed in a flask equipped with a thermometer, a stirrer, and a reflux condenser, and orthocresol novolac type epoxy resin Epicron N-695 (Dainippon Ink and Chemicals) was used. Kogyo Co., Ltd., epoxy equivalent 216) 216 parts was dissolved and hydroquinone 1.3 parts was added as a thermal polymerization inhibitor, then acrylic acid 50.4 parts, anhydrous (meth) acrylic acid
49.2 parts Add 5 parts triphenylphosphine,
The esterification reaction was carried out at 120 ° C. for 12 hours while blowing air.

At this time, the acid value was 5.1 KOH-mg / g and the epoxy equivalent was 11200 g / eq. Then, 140.1 parts of ethyl carbitol acetate and 91.2 parts of tetrahydrophthalic anhydride were added and reacted at 90 ° C. for 5 hours to obtain the target acid pendant type epoxy acrylate (a-1).
I got At this time, the acid value of the system was 55 KOH-mg / g (solid content calculation 84.6 KOH-mg / g), and the epoxy equivalent was 33000 g / e.
It was q.

Synthesis Example 2 Carbitol acetate 7 was placed in a flask equipped with a thermometer, a stirrer, and a reflux condenser.
After adding 4.7 parts and dissolving 190 parts of phenol novolac type epoxy resin Epicron N-770 (manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 190) and adding 1.3 parts of hydroquinone as a thermal polymerization inhibitor, Add 43.2 parts of acrylic acid, 65.6 parts of methacrylic anhydride and 5 parts of triphenylphosphine, and add 1 while blowing air.
The esterification reaction was carried out at 20 ° C. for 12 hours.

At this time, the acid value of the system was 0.9 KOH-mg / g and the epoxy equivalent was 13200 g / eq. Then, 135.3 parts of ethyl carbitol acetate and 91.2 parts of tetrahydrophthalic anhydride were added and reacted at 90 ° C. for 5 hours,
Target acid pendant type epoxy acrylate (a-
2) was obtained. The acid value of the system at this time was 56 KOH-mg / g (solid content calculation 86.2 KOH-mg / g), and the epoxy equivalent was 34000 g.
It was / eq.

Synthesis Example 3 Carbitol acetate 7 was placed in a flask equipped with a thermometer, a stirrer, and a reflux condenser.
After adding 8.9 parts and dissolving 216 parts of cresol novolac type epoxy resin Epicron N-695 (manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 216) and adding 1.3 parts of hydroquinone as a thermal polymerization inhibitor, 50.4 parts of acrylic acid, 49.2 parts of methacrylic anhydride and 5 parts of triphenylphosphine were added, and the esterification reaction was carried out at 120 ° C. for 12 hours while blowing air.

At this time, the acid value of the system was 0.9 KOH-mg / g and the epoxy equivalent was 13200 g / eq. Then, 140.8 parts of ethyl carbitol acetate and 92.4 parts of hexahydrophthalic anhydride were added and reacted at 90 ° C. for 5 hours,
Target acid pendant type epoxy acrylate (a-
3) was obtained. At this time, the acid value of the system was 54 KOH-mg / g (solid content calculation 83 KOH-mg / g), and the epoxy equivalent was 31,500 g / e.
It was q.

(Comparative Synthesis Example 1) 72.1 parts of ethyl carbitol acetate was placed in a flask equipped with a thermometer, a stirrer, and a reflux condenser, and orthocresol novolac type epoxy resin Epicron N-695 (Dainippon Ink Co., Ltd.) was used. 216 parts of epoxy equivalent 216) manufactured by Kagaku Kogyo Co., Ltd. is dissolved, 1.3 parts of hydroquinone as a thermal polymerization inhibitor is added, then 72.4 parts of acrylic acid and 5 parts of triphenylphosphine are added, and air is blown in. Meanwhile, the esterification reaction was carried out at 120 ° C.

At this time, the acid value of the system was 0.5 KOH-mg / g and the epoxy equivalent was 12500 g / eq. Then, 132.2 parts of ethyl carbitol acetate and 152 parts of tetrahydrophthalic anhydride were added and reacted at 90 ° C. for 5 hours to prepare a comparative acid pendant type epoxy acrylate (x-
1) was obtained. The acid value of the system at this time is 57 KOH-mg / g (solid content calculation 87.7 KOH-mg / g), and the epoxy equivalent is 23000 g.
It was / eq.

(Comparative Synthesis Example 2) 190 parts of bisphenol A type epoxy resin Epicron 850 (Dainippon Ink and Chemicals, Inc., epoxy equivalent 190) was dissolved in a flask equipped with a thermometer, a stirrer, and a reflux condenser. Then, after adding 1.3 parts of hydroquinone as a thermal polymerization inhibitor, 43.4 parts of acrylic acid, 65.6 parts of methacrylic anhydride and 5 parts of triphenylphosphine were added, and the esterification reaction was carried out at 120 ° C while blowing air. Was done.

At this time, the acid value of the system was 0.4 KOH-mg / g, and the epoxy equivalent was 11,800 g / eq. Then, 161 parts of ethyl carbitol acetate was added and dissolved to obtain a comparative control epoxy acrylate (x-2).

Table 1 shows property values of the resins synthesized in Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 and 2. "Epoxy resin" in Table 1 is an epoxy resin used as a raw material of acid pendant type epoxy acrylate (A), "acrylic acid"
Is the number of moles of acrylic acid charged per mole of epoxy group,
“Anhydrous (meth) acrylic acid” represents the number of moles of methacrylic anhydride charged per mole of epoxy group, and “acid value” represents the solution acid value (nonvolatile content 65%) (KOH-mg / g).

[0067]

[Table 1]

Example 1 Irgacure 9 as a photoinitiator was added to 100 parts of the resin (a-1) prepared in the synthesis example.
3.25 parts of 07 were added and completely dissolved to prepare an ultraviolet curable composition.

Example 2 An ultraviolet curable composition was prepared in the same manner as in Example 1 except that 100 parts of the resin (a-2) prepared in Synthesis Example was used instead of (a-1). did.

Example 3 An ultraviolet curable composition was prepared in the same manner as in Example 1 except that 100 parts of the resin (a-3) prepared in Synthesis Example was used instead of (a-1). did.

Comparative Example 1 An ultraviolet curable composition was prepared in the same manner as in Example 1 except that 100 parts of the resin (x-1) prepared in the synthesis example was used in place of (a-1). did.

(Comparative Example 2) An ultraviolet curable composition was prepared in the same manner as in Example 1 except that 100 parts of the resin (x-2) prepared in Synthesis Example was used instead of (a-1). did.

Example 4 Resin (a) obtained in Example 1
-1) was mixed with the following components and kneaded with a roll mill to prepare an ink.

Resin (a-1) 53.0 parts Ethylcarbitol acetate 5.0 parts Pentaerythritol tetraacrylate 8.0 parts Irgacure 907 (Ciba-Geigy photopolymerization initiator) 2.5 parts Dicyandiamide 1.0 Part triglycidyl isocyanurate 8.0 parts barium sulfate 22.0 parts phthalocyanine green 0.5 parts

Next, this ink was applied on the entire surface of a copper-clad laminate of a glass epoxy substrate having a copper foil of 35 μm using a screen of 150 mesh to prepare a test piece.

Example 5 An ultraviolet curable composition was prepared in the same manner as in Example 1 except that 53.0 parts of the resin (a-2) prepared in the synthesis example was used in place of the resin (a-1). Was prepared and a test piece was prepared.

Example 6 An ultraviolet curable composition was prepared in the same manner as in Example 1 except that 53.0 parts of the resin (a-3) prepared in the synthesis example was used in place of (a-1). Was prepared and a test piece was prepared.

(Comparative Example 3) An ultraviolet curable composition was prepared in the same manner as in Example 1 except that 53.0 parts of the resin (x-1) prepared in Synthesis Example was used instead of (a-1). Was prepared and a test piece was prepared.

(Comparative Example 4) An ultraviolet-curable composition was prepared in the same manner as in Example 1 except that 53.0 parts of the resin (x-2) prepared in Synthesis Example was used instead of (a-1). Was prepared and a test piece was prepared.

(Application Example 1) Examples 1 to 3 and Comparative Example 1
The composition prepared in No. 2 and No. 2 was coated on a copper plate so that the dry film thickness was 30 μm. After that, this coated product at 90 ° C for 3
The solvent was dried for 0 minutes. The obtained coating film was evaluated using the gray scale method. That is, placing the Fuji Step Guide P (manufactured by Fuji Photo Film Co., Ltd.) on the resulting coating film, 120 mJ / cm ² using a high pressure mercury lamp, 200 mJ / cm ²
After irradiating it with the ultraviolet ray of No. 1, it was immersed in a 1% sodium carbonate aqueous solution for 180 seconds, and the evaluation was performed with the maximum number of steps that could not be developed by the ultraviolet ray exposure. Table 2 shows the evaluation results. The larger the number of stages, the higher the sensitivity.

[0081]

[Table 2]

(Application Example 2) (Stability test during solvent drying) The test pieces obtained in Examples 4 to 6 and Comparative Examples 3 and 4 were left in a dryer at 90 ° C. for 20 to 80 minutes. The solvent was volatilized, the product was immersed in a 1% sodium carbonate aqueous solution for 180 seconds for development, and the stability during solvent drying was visually determined. The test results obtained are shown in Table 3. The performance evaluation was carried out according to the following criteria, and those that were stable for 70 minutes or longer were regarded as acceptable.

A: No coating film remains on the laminated plate. ◯: Almost no coating film remains on the laminate. Δ: Some coating film remains on the laminated plate. X: The coating film remains on the laminate.

(Application Example 3) (Sensitivity) The test pieces obtained in Examples 4 to 6 and Comparative Examples 3 and 4 were allowed to stand in a dryer at 80 ° C. for 30 minutes to volatilize the solvent to form a coating film. Step tablet No. 2 (manufactured by Kodak Co., Ltd.) and 300mJ using a high pressure mercury lamp
/ Cm ^2, after irradiation with ultraviolet rays of 500mJ / cm ^2, 1%
It was immersed in an aqueous solution of sodium carbonate for 180 seconds and evaluated by the gray scale method.

Table 4 shows the test results obtained. The numbers in the table indicate the number of steps of the step tablet, and the higher the number, the better the curability. 300 mJ / cm ²
Under the irradiation conditions of No. 6 and above, 9 and above under the conditions of 500 mJ / cm ² were accepted.

(Application Example 4) (Gold Plating Resistance) The test pieces obtained in Examples 4 to 6 and Comparative Examples 3 and 4 were left in a dryer at 80 ° C. for 30 minutes to volatilize the solvent, and the high pressure was applied. After irradiating with ultraviolet ray of 500 mJ / cm ² using a mercury lamp, it is left in a dryer at 150 ° C. for 30 minutes for curing, pre-treatment such as degreasing and activation, and then 90% with electroless nickel plating solution. Immerse at 30 ° C for 30 minutes, wash with water, dilute hydrochloric acid to activate and then electroless gold plating solution at 90 ° C for 3 minutes.
It was immersed for 0 minutes and gold-plated.

The coating film after the gold plating treatment was subjected to a peeling test with cellophane tape, and the degree of peeling of the coating film was visually judged. Table 2 shows the results of the obtained evaluation tests. The performance evaluation was performed as follows. ◯: No peeling is observed. X: Slight peeling is recognized.

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[Table 3]

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[Table 4]

(Application Example 5) (Soldering resistance) The test pieces obtained in Examples 4 to 6 and Comparative Examples 3 and 4 were left in a dryer at 80 ° C. for 30 minutes to volatilize the solvent, and the high pressure was applied. After irradiating with an ultraviolet ray of 500 mJ / cm ² using a mercury lamp, it was left in a dryer at 150 ° C. for 30 minutes and then cured. The cured sample was immersed in molten solder at 260 ° C. for 2 minutes, and then the state of the coating film was evaluated. The results are shown in Table 5. The evaluation criteria were as follows.

◯: No abnormality in appearance of coating film Δ: Slight defects such as blistering, whitening, and peeling are observed. X: Defects such as blistering, whitening and peeling are observed.

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[Table 5]

[0093]

INDUSTRIAL APPLICABILITY The present invention is useful as a photopolymerizable resin such as a solder resist, has high sensitivity, is stable in solvent drying, has excellent electrical characteristics and resistance to plating, and has a high activity energy.
A wire-curable epoxy acrylate resin composition can be provided.

Claims (4)

[Claims] 1. An epoxy resin having two or more epoxy groups in one molecule, 0.1 to 0.8 mol of anhydrous (meth) acrylic acid and 0.1 to 0.8 mol of unsaturated monobasic acid per 1 mol of epoxy groups. The epoxy acrylate resin (A) obtained by reacting 2 to 0.9 mol with the polybasic acid anhydride (B)
Energy containing an acid pendant type epoxy acrylate (C) obtained by reacting with
Ray-curable epoxy acrylate resin composition. 2. A polybasic acid anhydride (B) is reacted in an amount of 0.2 to 1.0 mole with respect to 1 mole of the unsaturated monobasic acid of the epoxy acrylate resin (A) reacted. The active energy ray-curable epoxy acrylate resin composition according to claim 1, which contains the resulting acid pendant type epoxy acrylate (C) as an essential component. 3. A novolak in which the epoxy resin having two or more epoxy groups in one molecule used in the production of the epoxy acrylate resin (A) has a number average molecular weight of 700 to 3000 and a softening point of 30 ° C. to 120 ° C. The active energy ray-curable epoxy acrylate resin composition according to claim 1 or 2, which is composed of one or more epoxy resins. 4. The active energy ray-curable epoxy acrylate resin composition according to claim 1, further comprising a photopolymerization initiator (D) and a photopolymerizable vinyl-based resin composition. An active energy ray-curable epoxy acrylate resin composition containing a monomer (E) and / or an organic solvent and an epoxy compound (F) having at least two epoxy groups in one molecule.