JPH02268171A - Oxazoline compound containing unsaturated group, resin composition containing the same and solder resist resin composition - Google Patents

Abstract

NEW MATERIAL:The oxazoline compound containing unsaturated group and expressed by formula I {group of formula II [R1 is 1, 2-phenylene, 1, 2-(substituted) cyclohexyl, alkylene, etc.] is a dicarboxylic acid residue; R2 is 2-3C alkylene; R3 is (meth)acryloyl}. EXAMPLE:The compound of formula III. USE:A component of a solder resist resin composition. It can be developed with dilute alkaline aqueous solution and has excellent heat-resistance, adhesivity, solvent-resistance, acid-resistance, plating resistance, electrical properties, etc. The above resin composition can be produced by mixing the compound with a carboxyl-containing thermoplastic polymer binder, a photo-polymerization initiator, a diluent, etc. The composition is especially useful for the production of a printed circuit board, etc. PREPARATION:The subject novel substance can be produced by reacting a polybasic carboxylic acid anhydride with an OH-containing (meth)acrylate and reacting the resultant half-esterified product with 1,3-bis(2-oxazolin-2-yl)benzene.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a novel oxazoline compound containing an unsaturated group and a resist composition using the same, and more particularly, to a novel oxazoline compound containing an unsaturated group and a resist composition using the same. Contains carbo 7
A thermoplastic polymer binder having an acid compound and/or a carboxyl group, a photopolymerization initiator, and a diluent as essential components, and has excellent photocurability, heat resistance, solvent resistance, acid resistance, etc. In particular, the present invention relates to a solder resist resin composition that can be developed with a weak alkaline aqueous solution and is suitable for manufacturing consumer printed wiring boards, industrial printed wiring boards, and the like.

(Prior Art) In recent years, ultraviolet curable compositions have been widely used for reasons such as resource saving, energy saving, improved workability, and improved productivity. In the field of printed wiring board processing, various inks such as solder resist inks and marking inks have been shifting from conventional thermosetting compositions to ultraviolet curable compositions for the same reason. Solder resist inks quickly transitioned to UV-curable compositions.

(Problems to be Solved by the Invention) Screen printing methods have often been used to form resist patterns on printed wiring boards, but when such screen printing methods are used, bleeding, blurring, or sagging during printing often occurs. This phenomenon occurs, and as a result, it is no longer possible to cope with the recent increase in the density of printed wiring boards.

To solve these problems, there are dry film type photoresists and liquid developable resist inks, but dry film type photoresists tend to produce air bubbles during thermocompression bonding and have poor heat resistance. There are also problems such as concerns about adhesion and high price. -Currently commercially available liquid resists have problems with organic solvent resistance and acid resistance.

(Means for Solving the Problems) In order to solve the above problems, the present inventors have conducted extensive research and found that a dilute alkali resin with excellent heat resistance, adhesion, chemical resistance, plating resistance, and electrical insulation properties has been developed. Can be developed with an aqueous solution.
We have succeeded in providing a resin composition suitable for solder resist.

That is, the present invention provides: 1) a polybasic carboxylic anhydride and a hydroxyl group-containing (
An unsaturated group-containing oxazoline compound which is a reaction product of a half-esterified product and 13-bis(2-nooxazolin-2-yl)benzene, which is treated by reacting with meth)acrylate.

2) The unsaturated group-containing oxazoline compound (A
), an unsaturated group-containing carboxylic acid compound (B) and/or a thermoplastic polymer binder having a carboxyl group (C), a photopolymerization initiator (D), and a diluent (E). The present invention relates to a resist resin composition.

Unsaturated group-containing oxazoline compound (A) used in the present invention
is a polybasic carboxylic acid anhydride (e.g. maleic acid,
Anhydrides such as succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, trimellitic acid, pyromellitic acid, etc. can be mentioned. ) and hydroxyl group-containing (meth)acrylates [e.g., 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and ε-caprolactone-modified 2-hydroxyethyl (meth)acrylate Acrylate (e.g., Daicel Chemical Industries, Ltd., Plaxel FA-1, FA-2, FM-1)
etc.) etc. ], then 1
It can be obtained by reacting 3-bis(2-oxazo/-2-yl)benzene. In the reaction between polybasic carboxylic anhydride and hydroxyl group-containing (meth)acrylate, hydroxyl group-containing (meth)acrylate is reacted with 1 mole of polybasic carboxylic anhydride.
Preference is given to using 0.9 to 1.2 mol of meth)acrylate, particularly preferably 0.95 to 1.05 mol.

The reaction temperature is preferably 50 to 130°C, particularly preferably 80 to 100°C. The reaction between a half-esterified product obtained by the reaction of a polybasic carboxylic acid anhydride and a hydroxyl group-containing (meth)acrylate and 13-bis(2-oxazolin-2-yl)benzene, Preferably, 1.8 to 2.5 chemical equivalents of oxazoline groups of 13-bisque(2-oxacyly/-2-yl)be/yne are used per chemical equivalent;
Particularly preferred is a ratio of 2.1 to 2.2 chemical equivalents. The reaction temperature is preferably 50 to 1300C, especially 9
0-110°C is preferred.

Polymerization inhibitors (known to prevent polymerization during the reaction)
For example, it is preferable to use methquinone, hydroquinone, methylhydroquinone, phenothiazine, etc.).

Preferred examples of the unsaturated group-containing oxazoline compound (A) that have been improved in this way include anhydrides such as maleic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and methylhexahydrophthalic acid. and 2-
Examples include a reaction product of a half-esterified product, which is a reaction product of hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate, and 13-bis(2-oxazolin-2-yl)benzene. Among these reactants, a particularly preferred one uses a dicarboxylic acid as the polybasic carboxy7 acid anhydride, and can be represented by the following general formula.

CHt CHz R2 is an alkylene group of 02 to C1, R1 is a (meth)acryloyl group). Also, when used as a composition, the suitable range of the amount of component (A) to be used is the unsaturated group-containing carboxylic acid compound ( B) and/or
or a thermoplastic polymer binder having a carboxyl group (C
) Oxazoline group q o, i ~ of component (A) per chemical equivalent of 1 carboxyl group of )
1.1 chemical equivalent, preferably 0.4 to 1.0%
This is the ratio that is chemical equivalent. Specific examples of the unsaturated group-containing carboxylic acid compound (B) include epoxy resins (e.g., phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenolmethane triglycidyl ether, bisphenol A type epoxy resin, etc.) A compound obtained by further reacting the reaction product with (meth)acrylic acid with the polybasic carboxylic acid anhydride,
A copolymer of styrene or imbutylene and maleic anhydride (for example, SMA-1000, SM manufactured by ARCO)
A-2000, SMA-3000, etc., Kuraray Co., Ltd. type, Kuraraypan, Isopan-10, Isopan-06, Isopan-04, etc., and the reaction product of the above-mentioned hydroxyl group-containing (meth)acrylate, and the above-mentioned polybase Examples include reaction products of a hydroxyl group-containing (meth)acrylate and a hydroxyl group-containing (meth)acrylate. The thermoplastic polymer binder (C) is a carboxylic acid or acid anhydride having one unsaturated group, such as acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, propiolic acid, itaconic acid, maleic acid. acid, maleic anhydride, maleic acid half ester, etc., methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, phenoxyethyl acrylate, Esters of vinyl alcohol, such as vinyl-n-butyl ether, α
It is obtained by copolymerizing a polymerizable styrene derivative or styrene substituted at the -position or an aromatic ring.

A suitable range of the acid value of these unsaturated group-containing carboxylic acid compound (B) and/or thermoplastic polymer binder (C) is 40 to 500 mgKOH)t/g, particularly preferably 50 to 300 mgKOH /g.

Next, typical photopolymerization initiators (D) include benzoin, benzoin and its alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 22-dimethoxy-2- Acetophenones such as phenylacetophenone, 22-jethoxy-2-7enylacetophenodinone, 11-dichloroacetophenone; 2-methyla/traquinone, 2-ethylanthraquinone, 2-tajariyanthraquinone
．． Anthraquinones such as 1-chloroanthraquinone and 2-aminoanthraquinone; 24-dimethylthioxa7
Examples include thioxanthone such as 24-diethylthioxanthone, 24-diethylthioxanthone, 2-chlorotitaoxanthone, and 24-diisoprobylthioxanthone; acetophenone dimethyl ketal; and benzophenones such as benzophenone. The photopolymerization initiator (D) is one of the known and commonly used photopolymerization accelerators such as benzoic acid type or tertiary amine.
It can be used either as a species or in combination of two or more species.

The preferred range of the amount of the photopolymerization initiator (D) used is 0.2 to 30 parts by weight, particularly preferably 0.2 to 30 parts by weight, based on 100 parts by weight of the component (B) and/or the component (C). , 2~
The proportion is 20 parts by weight. Furthermore, as the diluent (E) mentioned above, a reactive monomer and/or an organic solvent can be used. Typical reactive monomers include -
The above hydroxyl group-containing (meth)acrylates, ε
Phosphate ester of droxyethyl (meth)acrylate, N-vinylpyrrolidone, acryloylmorpholine, methoxytetraethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, polyethylene glycol di(meth)acrylate,
NN-dimethylacrylamide, tripropylene glycol di(meth)acrylate, phenoxyethyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, cyclohexyl(meth)acrylate, trimethylolpropane tri(methane acrylate, trimethylolpropane triproxytri(meth)acrylate) meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(or hexa)(meth)acrylate, tris(hydroxyethyl)isocyanurate tri(meth)acrylate, etc.As the organic solvent, methyl ethyl keto/, Ketones such as cyclohexane, aromatic hydrocarbons such as toluene and xylene, cellosolve, cellosolves such as butyl cellosolve, carpitol, carpitols such as butyl carpitol, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carpitol acetate, butyl carpitol Examples include acetic acid esters such as toll acetate.The above-mentioned diluent (E) can be used alone or as a mixture of two or more kinds.The preferred range of the amount used is the above-mentioned (B). Component and/or (C) Component 1
The proportion is 30 to 400 parts by weight, particularly preferably 50 to 300 parts by weight. The thus obtained composition of the present invention may contain an epoxy resin (for example, a phenol novolac type epoxy resin,
It is also possible to use a reaction product of (bisphenol type epoxy resin, trisphenol methane triglycidyl ether, etc.) and (meth)acrylic acid, or the above epoxy resin and an epoxy curing agent such as amine compounds, imidazoles, phenols, etc. can. Also, barium sulfate, silicon oxide,
Known and commonly used fillers such as talc, clay, calcium carbonate, aluminum oxide, phthalocyanine blue; 7 Known and commonly used coloring agents such as thalocyanine green, titanium oxide, carpore black; known and commonly used pigments such as hydroquinone monomethyl ether pyrogallol, phenothiazine; Polymerization inhibitors may also be added. Suitable irradiation light sources for curing the compositions of the present invention include low pressure, medium pressure, high pressure and extra high pressure mercury lamps, xenon lamps or metal halide lamps. The composition of the present invention is particularly useful as a solder resist resin composition, but can also be used as an insulating material, an impregnating material, a surface coating material, a paint, an adhesive, and the like.

EXAMPLES Hereinafter, the present invention will be specifically explained using examples. Note that parts in the examples are parts by weight.

[Synthesis example of unsaturated group-containing oxazoline compound (A)]

Synthesis Example 1 260 parts of a half-esterified product of the following structural formula, 1,3-bis(
After charging 237 parts of 2-oxazolin-2-yl)benzene and 0.05 part of methoquinone and then reacting at 95°C for 15 hours, the resulting raw acid had an acid value of % mgKOI (/g
, viscosity (60°C) 44.3 voids, refractive index (256°C)
)1.5742.

The obtained product has the structural formula %Formula % 274 parts of a half-esterified product having the following structural formula 1.237 parts of 3-bis(2-oxacyly/-2-yl)benzene and 0.05 part of methoquinone were charged, and then 9
After reacting for 15 hours at 5°C, the product had an acid value of 2.4.
mgKOH/g, viscosity (60°C)/19 voids, and refractive index (256C) 1.5686.

The obtained product was charged with 270 parts of a half-esterified product having the structural formula shown below, 237 parts of 1.3-bis(2-oxazolin-2-yl)benzene and 0.05 parts of methoquinone, and then 95
The product obtained after reaction for 15 hours at °C has an acid value of 3.7 m
gKOI (/g, viscosity (60'C) 14.1 poise,
The refractive index (25°C) was 1.5465.

The obtained product has a structural formula (% formula %) 237 parts of benzene and 0.05 parts of methoquinone were charged, and after reacting at 95°C for 15 hours, the product obtained had an acid value of 3.
．． 5mgKOH/g, viscosity (60'C) 8.5 boise,
The refractive index (25°C) was 1.5394.

The obtained product was charged with 216 parts of a half-esterified product having the structural formula shown below, 237 parts of 1.3-bis(2-oxazolin-2-yl)benzene and 0.5 parts of methoquinone, and then 9
Obtained after reaction at 5°C for 15 hours.

The product has an acid value of 2.9 mgKOH/g and a viscosity (60°
C) 2.9 voids, refractive index (25°C) 1.5412
Met.

The obtained product is a half-esterified product 2 having the structural formula: 60 parts 13-bis(2-oxazolin-2-yl)benzene 2
37 parts and 0.05 part of methoquinone, then 95 parts
The product obtained after reaction for 15 hours at °C has an acid value of 3.1
mgKOH/g, viscosity (60°C) 67 voids, and refractive index (25°C) 1.5683.

The obtained product has the structural formula [Synthesis example of unsaturated group-containing carboxylic acid compound (B)] Synthesis example 7゜Phenol novolak type epoxy resin (epoxy equivalent: 1
80) Charge 1800 parts of acrylic acid, 720 parts of acrylic acid, 26 parts of triphenyl stibine, 1.3 g of hydroquino and 1407 parts of butyl cellosolve acetate, and then
After reacting at 95°C for 24 hours, 740.6 parts of hexahydrophthalic anhydride was charged and reacting at 90°C for 24 hours to obtain a compound having an e value of 86 mgKOH/g (excluding butyl cellosolve acetate). Ta.

Synthesis Example 8 Copolymer of styrene and maleic anhydride (manufactured by AR, SM
A-1000) 500 parts, 2-hydroxyethyl acrylate 521 parts, hydroquinone 0.5 part and butyrocellosolve acetate 436 parts were charged and heated at 90°C for 24 hours.
After reacting for a period of time, a compound having an acid value of 23 s mgKOH/g (excluding butyl cellosolve acetate) was obtained.

[Synthesis Example of Thermoplastic Polymer Binder (C)] Synthesis Example 9 Part A methacrylic acid 250 parts Methyl methacrylate 350 parts Phenoxyethyl acrylate) 450 parts Part B α,α'-azobis-in-butyronitrile 5 parts 250 parts of ethyl cellosolve acetate 1650 parts of butyrocellosolve was added to a separable flask equipped with a dropping funnel, a reflux condenser, a nitrogen introduction tube, and a stirring bar containing solutions A and B, and heated to 75°C. Next, both solutions A and B were added dropwise over a period of 3 hours, and stirring was continued while maintaining the temperature at 75°C for an additional 8 hours. Transparent acid value 155 mgKOH/
A resin solution of g (excluding solvent) was obtained.

Examples 1 to 5, Comparative Examples 1 to 2 A solder resist resin composition was blended according to the formulation shown in Table 1, and the coating was applied to a copper through-hole printed wiring board with a film thickness of 25μ by screen printing. 70°
After drying at C for 60 minutes, apply a negative film to the coating film, either directly or without contact. Then, a 5KW ultra-high pressure mercury lamp was used to irradiate ultraviolet light, and then 1.5%
The unirradiated portion of the coating film was dissolved and removed with an alkaline aqueous solution such as Na, Co, or aqueous solution. After that, use a hot air dryer for 150
JJD heat curing was performed for 130 minutes at °C, and various performance tests were conducted on each of the obtained specimens. The results are shown in Table 1.

(Developability) Ultraviolet rays were irradiated using a 5KW ultra-high pressure mercury lamp, and the unexposed portion was dissolved and removed with a 1.5% Na2CO1 aqueous solution at 30° C., and the developability was evaluated.

○・・・・・・Dissolution rate is fast.

×・・・・・・Does not dissolve or dissolves extremely slowly.

(Solder heat resistance) The state of the coating film after being immersed in molten solder at 260°C for 2 minutes was evaluated.

○・・・・・・No abnormality in the appearance of the paint film.

×・・・・・・・The coating film swells, melts, and peels off.

(Solvent Resistance) After being immersed in methylene chloride at 20° C. for 1 hour, the state and adhesion of the coating film were comprehensively evaluated.

○・・・・・・No abnormality in the appearance of the paint film.

×・・・・・・・・・The paint film swells, blisters, and falls off.

(Adhesion) 100 goblets with a size of 1 x 1 mm were cut into the coating film of the specimen, and the adhesion was evaluated after peeling off with cellophane tape.

(Pencil hardness) The highest hardness that does not cause scratches on the film is indicated using a pencil hardness tester according to the test method of JIS K-5400 when a load of 1 kg is applied.

(Acid resistance) The state and adhesion of the coating film after immersion in a 10% by weight aqueous hydrochloric acid solution at 20° C. for 30 minutes was comprehensively evaluated.

○・・・・・・・・・No change in the coating film.

×・・・・・・・・・The paint film swells and falls off.

(Gold plating resistance) Using Autoronex (made by Cellex), 'I (plating liquid), at a current density of IA/dr'r'+2, 15
After gold plating was performed for 1 minute, the coating film was subjected to a peel test using cellophane tape.

○・・・・・・・・・All (Does not peel off.

x: Part or all of the paint film peeled off.

(Insulation resistance) According to JIS Z-3197, 80°0.95%RH
The coating film was left in an atmosphere for 240 hours, and the insulation resistance of the coating film was measured.

*■SMA-1732: A100 company, reaction product of styrene and maleic anhydride copolymer with alkyl alcohol *■DETX: Nippon Kayaku ■, photopolymerization initiator, diethylthioxatone *■DPHA: Japan Manufactured by Kayaku ■, reactive monoacypentaerythritol hexa (and pen/yellow) acrylate*■EPA:8 Manufactured by Kayaku ■, photopolymerization accelerator, NN-
Dimethylbenzoic acid ester ester*■ Epoxy acrylate: A 20% diluted product of butyl cellosolve acetate, a reaction product of phenol novolank type epoxy resin (manufactured by Nippon Kayaku ■, EPPN-201) and acrylic acid.

〔Effect of the invention〕

The resin composition containing the compound of the present invention is suitable for a solder resist resin composition that can be developed with a dilute aqueous alkaline solution and has excellent heat resistance, adhesion, solvent resistance, acid resistance, plating resistance, electrical properties, etc.

Claims (1)

[Claims] 1. Polybasic carboxylic acid anhydride and hydroxyl group-containing (
An unsaturated group-containing oxazoline compound which is a reaction product of a half-esterified product obtained by reacting a meth)acrylate with 1,3-bis(2-oxazolin-2-yl)benzene. 2. Polybasic carboxylic acid anhydride and hydroxyl group-containing (
An unsaturated group-containing oxazone compound (
A resin composition containing A), an unsaturated group-containing carboxylic acid compound (B) and/or a thermoplastic polymer binder having a carboxyl group (C), a photopolymerization initiator (D), and a diluent (E). 3. Polybasic carboxylic anhydride and hydroxyl group-containing (
An unsaturated group-containing oxazoline compound (
Solder resist resin composition containing A), an unsaturated group-containing carboxylic acid compound (B) and/or a thermoplastic polymer binder having a carboxyl group (C), a photopolymerization initiator (D), and a diluent (E) thing.