JPH045281A - Unsaturated group-containing oxazoling compound, resin composition using the same compound, solder resist resin composition and cured material thereof - Google Patents

Abstract

NEW MATERIAL:An unsaturated group-containing oxazoline compound shown by the formula (R is H or CH3). USE:Solder resist ink. PREPARATION:for example, 1,3-bis(2-oxazolin-2-yl)benzene is reacted with 0.1-1.2 mol based on 1 mol oxazoline compound of (meth)acrylic acid in the presence of a polymerization inhibitor such as hydroquinone at 50-130 deg.C reaction temperature for 3-24 hours to give a compound shown by the formula. The oxazoline compound is blended with an unsaturated group-containing carboxylic acid compound and/or a carboxyl group-containing thermoplastic polymer binder, a photopolymerization initiator and a diluent to give a resin composition for solder resist.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a novel unsaturated group-containing oxidizing compound, a resin composition using the same which is particularly useful as a solder resist, and a cured product thereof. More specifically, a novel oxazoline compound containing an unsaturated group, the oxazoline compound containing an unsaturated group, a carboxylic acid compound containing an unsaturated group and/or a thermoplastic polymer binder having a carboxyl group, a photopolymerization initiator, and a diluent. Developed with a weak alkaline aqueous solution containing as an essential component, it has excellent hardening properties, heat resistance, solvent resistance, acid resistance, etc., and is particularly suitable for manufacturing consumer printed wiring boards and industrial printed wiring boards. The present invention relates to a resin composition useful as a possible solder resist resin composition and a cured product thereof.

(Prior Art) In recent years, ultraviolet curable compositions have been widely used in various fields 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. Otherwise, a phenomenon such as sag occurs, which makes it difficult to cope with the recent increase in density of prime wiring boards (which is becoming increasingly common).

To solve these problems, dry film type photoresists and liquid developable cyst inks are commercially available, but dry film type photoresists tend to produce air bubbles during thermocompression bonding. There are also concerns about heat resistance and adhesion, and there are other problems such as high price.

In addition, currently commercially available liquid resists include those that use an organic solvent as a developer and those that are developed with a dilute alkaline aqueous solution.
In addition to the problem of air pollution, solvents are generally expensive, and there are also problems with solvent resistance and acid resistance. Furthermore, those that can be developed with a dilute alkaline aqueous solution have problems because the cured product is insufficient in terms of heat resistance, chemical resistance, gold plating resistance, etc.

(Means for Solving the Problems) As a result of diligent efforts by the present inventors to solve the above-mentioned problems, the present inventors have found that storage stability is good, thermal stability during pre-drying is excellent, and photosensitivity is excellent. The cured film can be developed with an alkaline aqueous solution, and the cured film has an alkali-developable photosensitive property suitable for solder resists with excellent adhesion, electrical insulation, soldering heat resistance, chemical resistance, gold plating resistance, etc. The present invention has been completed by successfully providing a thermosetting resin composition.

That is, the present invention provides: 1) an unsaturated group-containing oxazoline compound represented by the formula [I] convex (in the formula, R is H or CH3); 2) an unsaturated group-containing oxazoline compound described in 1) above. A resin composition or solder resist resin composition containing a thermoplastic polymer binder B) having an unsaturated group-containing carboxylic acid compound and/or a carboxyl group, a photopolymerization initiator (C), and a diluent 0, 3 ) A cured product of the resin composition described in 2) above.

The unsaturated group-containing oxazoline compound of the present invention comprises 13-bis(2-oxazolin-2-ylnopenozene and (meth)
It can be obtained by reacting acrylic acid. When 13-bis(2-oxazolin-2-yl)benzene and (meth)acrylic acid are reacted, 0.9 to 1 of (meth)acrylic acid is
, 2 mol is preferably used, especially 0.95 to 1.0 mol.
Preferably, 5 mol is used. The reaction temperature is 50-13
0°C is preferred, particularly 70-110°C.

The reaction time is preferably 3 to 24 hours, preferably 5 to 15 hours for bamboo. In order to prevent polymerization during the reaction, it is preferable to use known polymerization inhibitors (eg, methoquinone, hydroquinone, methylhydroquinone, Fetch Asia, etc.).

The preferred proportion of the component used in the resin composition and solder resist resin composition of the present invention is per chemical equivalent of the carboxyl group of the thermoplastic polymer binder FB+ having an unsaturated group-containing carboxylic acid compound and/or a carboxyl group. The ratio is such that the oxazoline group of the iAl component has a chemical equivalent of 0.1 to 1.1, particularly preferably 0.4 to 1.0.
This is the ratio that is chemical equivalent.

Specific examples of the unsaturated group-containing carboxylic acid compound (Bl component) of the resin composition and solder resist resin composition of the present invention include epoxy resins (e.g., phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol A reaction product of (methane triglycidyl ether, bisphenol A type epoxy resin, etc.) and (meth)acrylic acid is further added to maleic anhydride, succinic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, endo anhydride. Compounds obtained by reacting with polybasic carboxylic anhydrides such as methylenetetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, copolymers of styrene or imbutylene and maleic anhydride (For example, A
Manufactured by RCO, SMA-1000゜SMA-2000,S
MA-3000, etc., manufactured by Kuraray Co., Ltd., Kuraray Soban, Isoba/10 + Isoba/-06, Isopan-0
4 etc.) and a hydroxyl group-containing (meth)acrylate, and a reaction product of the polybasic carboxylic acid anhydride and a hydroxyl group-containing (meth)acrylate.Hydroxyl group-containing (meth)acrylate Specific examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and ε-caprolactone-modified 2-hydroxyethyl (meth)acrylate.
Examples include acrylate.

(Specific examples of thermoplastic polymeric binders having a carboxyl group as the Bl component include carbo/acids or acid anhydrides having one unsaturated group, such as acrylic acid, methacrylic acid, fumaric acid) , cinnamic acid, crotonic acid, propiolic acid, itaconic acid, maleic acid, maleic acid hydrate, maleic acid half ester, etc., and methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethyl Hexyl acrylate, 2-ethylhexyl methacrylate, phenoxyethyl acrylate, ethers of vinyl alcohols, such as vinyl-butyl ether, polymerizable styrene derivatives monosubstituted at the α-position or in the aromatic ring, or styrene, etc. Examples include those obtained by copolymerizing one or more types.

These are thermoplastic polymers/g having an unsaturated group-containing carboxylic acid compound and/or a carboxyl group.

Photopolymerization initiators (typical examples of photopolymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc.)
and its alkyl ethers; acetopheno/,2,2-
Acetophenones such as dimethoxy-2-phenylacetophenone, 2,2-jethoxy-2-phenylacetophenone, 1,1-cycloacetophenone; 2-methylanthraquinone, 2-ethylanotraquinone, 2-tert-butylaquinone Anthraquinols such as traquinone, 1-chloroanthraquinone, 2-aminoanotraquino 7; 2,4-dimethylthioxanode/, 2,4-diethylthioxanto/, 2-chlorothioxant/, 2.
These include thioxate 7s such as 4-diisopropylthioxanthone; acetophenone dimethyl ketals; and benzophenos 7s such as be/siphenone. Such a photopolymerization initiator (C) can be used in combination with one or more known and commonly used photopolymerization accelerators such as benzoic acid type or tertiary amine. The preferred range of the amount of the photopolymerization initiator (C) used in the resin composition and solder resist resin composition of the present invention 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 Bl component. is 2 to 20 parts by weight.

As the diluent FD+, a reactive monomer and/or an organic solvent can be used. Typical reactive monomers include the above-mentioned hydroxyl group-containing (meth)acrylates,
and droxyethyl (meth)acrylate acid ester, N-vinylpyrrolidone, acryloylmorpholine,
Methoxytetraethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, polyethylene 7 glycol di(meth)acrylate, N,N-dimethylacrylamide, triprobylene glycol di(meth)acrylate, phenoxyethyl (meth)acrylate acrylate, tetrahydrofurfuryl (meth)acrylate, cyclohexyl (meth)acrylate, trimethylolpropane tri(meth)acrylate,
Trimethylolpropanotripropoxytri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(or hexa)
(meth)acrylate, tris(hydroxyethyl)incyanurate tri(meth)acrylate, etc. Typical organic solvents include methyl ethyl keto/,
Cyclohexatsunonato ketones, toluene/, aromatic hydrocarbons such as xylene, cellosolve, cellosolves such as butyl cellosolve, carpitol, carpitols such as butyl carpitol, butyl acetate, cello solder acetate, butyl cellosolve acetate, carpitol acetate , acetate esters such as butyl carpitol acetate. These may be used alone or in combination of two or more. The preferred range of the amount of the diluent (D) used in the resin composition and solder resist resin composition of the present invention is 3 parts by weight per 100 parts by weight of the diluent (Bl).
The amount is 0 to 400 parts by weight, particularly preferably 50 to 300 parts by weight.

The resin composition and solder resist resin composition of the present invention may further contain an epoxy resin (e.g., phenol-novolac type epoxy resin, bisphenol type epoxy resin, trisphenolmethane triglycidyl ether, etc.) and (meth) ) A reaction product of acrylic acid, the above-mentioned epoxy resin, and an epoxy curing agent such as amino/compounds, imidazoles, phenols, etc. can also be added. In addition, known and commonly used fillers such as barium sulfate, silicon oxide, talc, clay, calcium carbonate, and aluminum oxide; known and commonly used coloring pigments such as phthalocyania blue, phthalocyanine green, titanium oxide, and carbon black;
Various additives such as antifoaming agents, adhesion agents, or leveling agents, or known and commonly used polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, and Fetch Asia may be added.

The resin composition and solder resist resin composition of the present invention can be prepared by uniformly mixing each component.

The resin composition and solder resist resin composition of the present invention can be cured by irradiation with ultraviolet rays and further heat treatment in a conventional manner.

Suitable ultraviolet irradiation light sources include low pressure, medium pressure, high pressure, and extra high pressure mercury lamps, xeno-7 lamps, metal halide lamps, and the like. Heating can be performed with hot air, and the heating temperature is preferably 100 to 200°C. The resin 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.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples. Note that "parts" in the examples are "parts by weight."

[Example 1 of synthesis of unsaturated group-containing oxazoline compound hole
~2] Example 1 216 parts of 1.3-bis(2-oxazolin-2-yl)benzene, 76 parts of acrylic acid, and 0.146 parts of methoquinone
When the reaction was carried out at 80°C for 15 hours, a product with an acid value of 4 mgKOH/g and a viscosity (60°C) of 140 voids was obtained.

The measurement results of the obtained product by high resolution nuclear magnetic resonance (NMR) are shown below.

% Absorption frequency (Hz) Nu Absorption frequency (Hz) 1 2509.765 11 18
98,4372 2500.000 12 1
886.7183 2464.843 13
1191.4064 2021.484 14
1160,1565 1976.562 15
1126 9536 1968.750 1
6 1017,5787 1958.984
17 951.1718 1955.078
18 826.1719 1935.54
19 593,75010 1923.82
8 20 0.000 The above measurements were carried out by a proton decoupling method using tetramethylsilane as a reference substance and deuterated chloroform as a solvent.

Example 2 1.3-bis(2-oxazolin-2-yl)be797
216 parts, 90 parts of methacrylic acid and 0.15 parts of methoquinone
When the reaction was carried out at 80'C for 15 hours, a product with an acid value of 2 mgKOH/g and a viscosity (60°C) of 55 voids was obtained.

The results of NMR measurements conducted in the same manner as in Example 1 are shown below.

% Absorption frequency (Hz) Deafness Absorption frequency (Hz) 1 2519.531 11 1
886,7182 2509.7.65 12
1191.4063 2464.843
13 1158.2034 2042.96
8 14 1126.9535 2023
．． 437 15 1017.5786 1
968.750 16 951.1717
1955.078 17 826,1718
1935.546 18 593.75
09 1923.828 19 275.
39010 1896.484 20
0.000 [Synthesis Examples 1 to 2 of unsaturated group-containing carbo/acid compound fB] Synthesis Example 1 Phenol novolac 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 parts of hydroquinone 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 900C for 24 hours to obtain a compound having an acid value of 86 mgKOH/g (excluding butylcellotrubu acetate). Ta.

Synthesis Example 2 Copolymer of styrene and maleic anhydride (manufactured by ARCO,
SMA 1000) 50 ON, 2- was charged with 521 parts of nido-0-oxymethyl acrylate, 0.5 part of hydroquinone and 436 parts of butyl cellosolve acetate, and 90
Reacted at 0C for 24 hours, acid value 235 mgKOH/g
(excluding butyl cellosolve acetate) was obtained.

[Thermoplastic polymer binder having carboxyl group (B)
Synthesis Example 3] Synthesis Example 3 Liquid A methacrylic acid 250 parts Methyl methacrylate 350 parts Phenoxyethyl acrylate 450 parts Liquid B α,α'-azobisisobutyronitrile 5 parts Ethyl cellosolve acetate) 250 g Liquids A and B
Butyl cellosolve 1 is placed in a separable flask equipped with a dropping funnel containing liquid, a reflux condenser tube, a nitrogen introduction tube, and a stirring bar.
650 parts were added and heated at 75°K. Next, over a period of 3 hours, both solutions A and B were added dropwise and stirring was continued while keeping the temperature at 75°C for an additional 8 hours, resulting in a transparent acid value of 155 mgKOH/g.
A resin solution (excluding solvent) was obtained.

Examples 3 to 7, Comparative Examples 1 to 2 A solder resist resin composition was blended according to the formulation shown in Table 1, and applied to a copper through-hole printed wiring board with a film thickness of 25 μm using a slurry/printing method. membrane at 70°
After drying at C for 60 minutes, apply a negative film to the paint film without making direct contact with it. Then, it was irradiated with ultraviolet light using a 5KW ultra-high pressure mercury lamp, and then 1.5% Na, CO
The unirradiated area of the coat was removed by dissolving with an aqueous solution of 3, and the developability was evaluated as ○ if the dissolution rate was fast, and × if it did not dissolve or was extremely slow. After that, heat curing was performed at 150°C for 130 minutes in a hot air dryer, and various performance tests were conducted on each specimen (cured film) obtained, including solder heat resistance, solvent resistance, acid resistance, and alkaline earth resistance. Gold plating properties, adhesion, pencil hardness, and insulation resistance (Ω) were evaluated. The test method and evaluation method are as follows. The results are shown in Table 1.

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

O: No abnormality in the appearance of the cured film.

×...Blistering, melting, and peeling of the cured film were observed.

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

Is recognized.

(Adhesion) A hole of 1 x 1 mm in size is placed on the cured film.
Adhesion was evaluated based on the number of gobs/stitches remaining without being peeled off after peeling off with cellophane tape.

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

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

○・・・・・・No change at all in the cured film.

H×・・・・・・ Temperature measurement of the cured film, peeling is observed.

(Alkali resistance) 2500.15 in 10% by weight sodium hydroxide aqueous solution
It was immersed for a minute, and judged and evaluated in the same manner as the acid resistance test.

(Gold plating resistance) Using Autoronex CI (plating liquid) manufactured by Cellex, at a current intensity of LA/dm2 for 15 minutes,
After gold plating, a II release test of the cured film was carried out using cellophane tape.

○・・・・・・It does not peel off at all.

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

(Insulation resistance) According to JIS Z-3197, 80°C 295%RH
The specimen was left in an atmosphere for 240 hours, and the insulation resistance of the hard filament film was measured.

*■SMA-17352: ARCO company name, reaction product of copolymer of styrene and maleic anhydride with saturated aliphatic alcohol *■DETX: Manufactured by Nippon Kayaku ■, photopolymerization initiator, diethylthioquinone *■DPHA: Manufactured by Nippon Kayaku ■, reactive monomer hentaerythritol hexa (and penta)acrylate *■ EPA: Manufactured by Nippon Kayaku ■, photopolymerization accelerator,
N,N-Dimethylbenzoic acid ethyl ester *■ Epoxy acrylate: Butyl cellosolve acetate, a reaction product of phenol noporanc type epoxy resin (Nippon Kayaku Co., Ltd., EPPN-201) and acrylic acid, diluted with 20%.

〔Effect of the invention〕

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

Claims (1)

[Claims] 1. An unsaturated group-containing oxazoline compound represented by the formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is H or CH_3.) 2. The unsaturated group-containing oxazoline compound according to claim 1 (
A resin composition containing A), a thermoplastic polymer binder having an unsaturated group-containing carboxylic acid compound and/or a carboxyl group (B), a photopolymerization initiator (C), and a diluent (D). 3. A solder resist resin composition comprising the resin composition according to claim 1. 4. A cured product of the resin composition according to claim 2 or 3.