JPH013163A - Method for producing diazide group-containing unsaturated monomer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an unsaturated monomer containing a diazide group.
Moreover, the present invention relates to a method for producing an unsaturated monomer for forming a polymer having excellent hydrolysis resistance.

Conventionally, a method for producing a diazide group-containing unsaturated monomer involves reacting glycidyl (meth)acrylate with a hydroxycarboxylic acid, and then reacting the obtained hydroxyl group-containing reaction product with benzoquinone or naphthoquinonediazide sulfonic acid chloride. It was done.

However, this manufacturing method has complicated steps and problems such as separation and purity of the product, and the products produced by this manufacturing method have a structure in which pentuquinone or naphthoquinonediazide groups are bonded via an ester group. Because it is an unsaturated monomer with The ester group between the copolymer and the benzoquinone or naphthoquinone diazide compound is hydrolyzed and cleaved by a hydrolyzable substance such as an acid or a base, and as a result, the water-insoluble benzoquinone or naphthoquinone diazide compound is dissolved in the aqueous solution. separation,
There are problems with sedimentation, and even if the formed coating is irradiated with active energy rays, it is difficult to obtain alkaline solubility, and it has several woody defects.

As a result of extensive research in order to eliminate these drawbacks, the present inventors have developed a vinyl-based unsaturated monomer having one polymerizable unsaturated group and one secondary amino group in one molecule. It has been discovered that the process can be simplified and the diazide group can be reliably introduced into the unsaturated monomer by subjecting the monomer to an addition condensation reaction with a diazide group-containing compound, and the resulting unsaturated monomer has a structure in which a benzoquinone or naphthoquinone diazide compound is introduced via a secondary amino group, and therefore exhibits excellent hydrolysis resistance.

That is, the present invention provides one polymerizable unsaturated group and one polymerizable unsaturated group in one molecule.
Production of a diazide group-containing unsaturated monomer characterized by reacting a vinyl unsaturated monomer having secondary amino groups with a halide of benzoquinone diazide sulfonic acid and/or naphthoquinone diazide sulfonic acid. Regarding the method.

The diazide group-containing unsaturated monomer produced in the present invention is represented by the following general formula (1).

R, R3 1/ CH2=CA R2N (I)\ [In the formula, A represents an ester group or a phenylene group, and R1
represents a hydrogen atom or a methyl group, and R2 has 1 to 2 carbon atoms.
4 linear or branched alkylene groups or alkylene ether groups to 20 alkyl groups, substituted or unsubstituted phenyl groups, cycloalkyl groups, or aralkyl groups] -CH2CH2-1CR2CR2CR2-1-CH2C
)(-1-CH2CH2CH2CH2-1■ CR3 -CH2CH2CH2CH2CH2-1CR2CR2C
R2CR2CR2CR2-1CR2CR2 CH2CH2 -CH2CH20-CH2CH2-1 CH2CH2CH20CH2CH2CH2-1-CH2
CH-OCR2CH-1 CR3CR3 Among these, particularly preferred as R2 are 10 R2CR2-1-CH.

CR2CR2-1CH2CH2CH2CH2-1CH2
CH2 Also, R4 is a methyl group, ethyl group, propyl group, butyl group, octyl group, stearyl group, cyclohexyl group, t
Represents ert-butylphenyl group, benzyl group, etc.
Preferred are methyl group, ethyl group, propyl group, and butyl group.

The diazide group-containing unsaturated monomer represented by the above formula is a secondary amino group containing a benzoquinone and/or naphthoquinone diazide sulfonic acid halide (hereinafter referred to as these). (abbreviated as "quinonediazide sulfonic acid halide")) can be obtained by addition condensation reaction. in particular,
A mixture of a secondary amino group-containing unsaturated monomer, a quinonediazide sulfonic acid halide, a catalyst and, if necessary, an organic melt is added at room temperature to about 80°C, preferably at about 30°C.
The reaction can be carried out by continuing the reaction at a reaction temperature of ~50°C for about 10 minutes to about 6 hours, preferably about 1 to about 3 hours. Under the reaction conditions, the reaction temperature is about 80°C.
If the temperature is higher, the diazo group of the quinonediazide sulfonic acid halide will decompose during the reaction, so there is a drawback that it is only possible to produce a diazide group-containing unsaturated monomer with high purity. Further, the reaction is preferably carried out by dropping an organic solvent solution of a quinonediazide sulfonic acid halide into an organic solvent solution of a secondary amino group-containing unsaturated monomer in an inert gas atmosphere.

As the secondary amino group-containing unsaturated monomer, the general formula (II) R1H 1/ CH2=C-A-R2-N (II)\ [wherein A, R,, R2 and R3 are The meaning is the same as above].

As the unsaturated monomer represented by the formula (II),
Suitably, for example, H(CH3) CH2=CCOCH2CH2N CH3II
HH (CH3)
CH3CH2=CCOCH2CH2N
CHCH3II HH
(CH3) CH3CH2=
C-C-0-CH2-CH2-N-C-CH31HIQCH2CH2 and the like.

The quinonediazide sulfonic acid halide to be addition-condensed to the secondary amino group-containing unsaturated monomer is 1
Any compound having one benzoquinone and one (-8O2X, where X represents an atom such as fluorine, chlorine, or bromine, and preferably chlorine) in its molecule can be used without particular limitation. Preferred specific examples of these include, for example, 1,2-benzoquinonediazide sulfonic acid chloride, 2,2-naphthoquinonediazide 5
-sulfonic acid chloride, 1,2-benzoquinonediazide sulfonic acid bromide, 1,2-naphthoquinonediazide sulfone bromide, and the like.

The quinonediazide sulfonic acid halide can be used in an amount of about 0.01 to about 5, preferably about 0.1 to about 3, per mole of the secondary amino group-containing unsaturated monomer. If the amount used is less than about 0.01 mol, the content of quinonediazide groups in the formed coating film will be small, resulting in poor alkali developability. , the by-product (hydrogenated halide) generated in the reaction is combined with the secondary amino group-containing rli-mer, and the secondary amino group becomes inactive, resulting in an inert secondary that does not react with the quinonediazide sulfonic acid halide. As a result, the alkali developability of the formed coating film is poor, making it impossible to form a printed circuit board with excellent resolution.

The catalyst used in the reaction between the unsaturated monomer containing a secondary amino group and the quinonediazide sulfonic acid halide is, for example, an alkali such as ice-free charcoal, soda-resistant, hydrogenated lithium, charcoal-resistant, potassium-resistant, metallic sodium, etc. metal compounds;
・Alkali metal alcolades such as lium methyl-1;
Examples include quaternary ammonium chlorides such as triethylbenzylammonium chloride, tetraethylbenzylammonium chloride, and tributylbenzylammonium chloride.

The organic solvent used in the reaction between the secondary amino group-containing unsaturated monomer and the quinonediazide sulfonic acid halide dissolves the quinonediazide sulfonic acid halide and does not have functional groups such as hydroxyl groups or amide groups. Preference is given to using inert organic solvents. Specific examples include dioxanes such as dioxane and dioxolane; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and aromatic hydrocarbons such as benzene, toluene, and xylene. Among them, dioxanes are preferred because they have excellent solubility in quinonediazide sulfonic acid halides and can be easily removed (by reducing pressure or dispersing in water).

The proportion of the organic solvent to be used is not particularly limited, but is preferably in the range of about 100 to about 10.000 parts by weight based on 100 parts by weight of the quinonediazide sulfonic acid halide because it facilitates the uniform addition and condensation reaction. Can be used in

In the present invention, when a diazide group-containing unsaturated monomer solution is produced using an organic solvent, the organic solvent is removed by reducing the pressure from the solution, or the diazide group-containing unsaturated monomer solution is removed using a water-soluble organic solvent. When producing a saturated monomer solution,
After dispersing the solution in water to dissolve the aqueous organic solvent in water and precipitating the diazide group-containing unsaturated monomer component and separating the two, the precipitate is dried to reduce the solid content ioo weight%. A diazide group-containing unsaturated monomer can be obtained. Use of this material is advantageous in that a water-soluble organic solvent (particularly an alcoholic solvent) that is blended into water-based paints and the like can be used in the copolymerization reaction with other unsaturated monomers.

The unsaturated monomer obtained by the method of the present invention can be homopolymerized or copolymerized with a radical unsaturated monomer to obtain a diazide group-containing polymer. In this copolymer, the diazide group contained in the copolymer changes to carboxylic acid through ketene by active energy rays, so it is possible to improve adhesion or remove unnecessary films by neutralizing and cleaning with an alkaline substance. Therefore, it can be applied to the fields in which they are applied (for example, paints, adhesives, plastics, etc.).

Next, examples related to the present invention will be described. Parts and percentages in the examples are based on weight.

Example 1 210 parts of tert-butylaminoethyl methacrylate, 90 parts of dioxane, and 130 parts of triethylamino were placed in a four-bottle flask, heated to 40°C, and while stirring, 270 parts of orthonaphthoquinonediazide sulfonic acid chloride was dissolved in 1080 parts of dioxane. The solution was added dropwise over 1 hour, and then kept at 40°C for 3 hours.

This solution was placed in deionized water to precipitate the reactants. The precipitate was placed in a vacuum dryer to remove the solvent and the solid content was 100%.
An unsaturated monomer containing a naphthoquinone diazide group was obtained. The purity of the unsaturated monomer was 92%, which was good.

Example 2 210 parts of tert-propylaminoethylstyrene, 90 parts of dioxane, and 1 part of triethylamino in 4 flasks.
A solution of 270 parts of orthonaphthoquinonediazide sulfonic acid chloride dissolved in 200 parts of dioxane was added dropwise to the mixture over 1 hour while stirring, and the mixture was kept at 40°C for 3 hours.

This solution was placed in deionized water, and the reaction product was placed in a vacuum dryer to remove the solvent, yielding a naphthoquinonediazide group-containing unsaturated monomer with a solid content of 100%.

The purity of the unsaturated monomer was 90%, which was good.

Reference Example 1 600 parts of isopropyl alcohol was placed in a fourth flask, the temperature was raised to 60"C with stirring, and then 350 parts of unsaturated monomer l, 1-300 parts of methyl methacrylate, n
- A mixed solution of 260 parts of butyl acrylate, 60 parts of acrylic acid, and 50 parts of azobisdimethylvaleronitrile was extracted over 3 hours, kept for 1 hour, and then mixed with 70 parts of isopropyl alcohol and 5 parts of azobisdimethylvaleronitrile. The combined solution was added dropwise over 1 hour and kept for an additional 2 hours to obtain a positive photosensitive resin solution (acid value 48).

Next, 40 parts of triethylamino was added to this resin solution to sufficiently neutralize it, and then deionized water was added so that the solid content was 15% to produce an electrodeposition paint (pH 7.2).

Reference Example 2 600 parts of isopropyl alcohol was placed in a 4 flask and heated to 60°C with stirring, then 350 parts of unsaturated monomer 2, 1-300 parts of methyl methacrylate, n
- A mixed solution of 260 parts of butyl acrylate, 60 parts of acrylic acid, and 50 parts of azobismethylvaleronitrile was added dropwise over 3 hours and kept for 1 hour. l of
I! The combined solution was added dropwise over a period of time and kept for an additional 2 hours.
A positive photosensitive resin solution (acid value: 48) was produced.

Next, 40 parts of triethylamino was added to this resin solution to sufficiently neutralize it, and then deionized water was added so that the solid content was 15% to produce an electrodeposition paint (pH 7.2).

Even if the electrocoating paints produced in Reference Examples 1 and 2 were continuously stirred for 13 months at 30°C as an electrocoating bath, no sedimentation occurred in the bath.
The product was excellent, with no abnormalities such as aggregation observed. Also,
Copper-clad laminates for printed wiring with through holes in each electrodeposition coating bath obtained in Reference Examples 1 and 2 (240X170X1
．． ．． 5mm) was immersed as an anode, and the bath temperature was 25°C.
Electrodeposition coating was carried out by applying a DC current of 500 V for 3 minutes. The coating film was washed with water and dried at 50 DEG C. for 5 minutes to form a smooth, non-tacky photosensitive film with a thickness of 5p. Then, a positive film was brought into close contact with the electrodeposited surface using a vacuum device, and both surfaces were irradiated with 1 50 mJ/cm 2 using a 3KII7 ultra-high pressure mercury lamp. Next, the exposed areas were washed with a 0.1% charcoal-based aqueous solution and developed. After washing with water (ferric chloride solution), the copper foil was removed by etching, and the unexposed areas were etched with ethylene glycol monoethylene. By removing it with an ether solvent, a printed circuit board with a clean, sharp pattern was obtained, with copper foil also attached to the through holes.

Patent Applicant (+40) Kansai Paint Co., Ltd. Procedural Amendment (Method) 1. Indication of the case 1988 Patent Application No. 156760 2. Name of the invention Process for producing diazide group-containing unsaturated monomer 3. Make amendments Applicant Address: 33-1-4, Kanzaki-cho, Amagasaki-shi, Hyogo Prefecture; Date of amendment order: August 5, 1985 (Despatch date: August 25, 1988); Subject of amendment:

Claims (1)

[Claims] Reacting a vinyl unsaturated monomer having one polymerizable unsaturated group and one secondary amino group in one molecule with a halide of benzoquinonediazide sulfonic acid and/or naphthoquinonediazide sulfonic acid. A method for producing a diazide group-containing unsaturated monomer, characterized by: