JPH0816780B2 - Photosensitive quinonediazide compound, positive photosensitive composition containing the compound, and photosensitive electrodeposition coating composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive quinonediazide compound, a positive photosensitive composition and a photosensitive electrodeposition coating composition produced from the photosensitive quinonediazide compound, and particularly to the production of printed wiring boards. When forming a photoresist pattern, the photosensitive electrodeposition has good flexibility, effectively prevents the occurrence of pinholes, has excellent compatibility with acrylic resin, and has good adhesion to metal substrates. It relates to a coating composition.

[0002]

2. Description of the Related Art IBM Patent No. 3,738,8 from IBM
No. 35 was an early disclosure of a method of applying a photoresist to a copper clad laminate by an electrodeposition coating method, which employs a negative photosensitive composition as a photoresist and uses a large amount of this composition. It was intended to stabilize each component by using a solvent. However, the negative photoresist has a defect that the light irradiation area is reduced and swells at the time of development, and the positive photoresist can obtain a resist pattern having a resolution higher than that of the negative photoresist. Has been adopted by many.

[0003] Positive type photoresists generally employ quinonediazides as a photosensitive compound, but in the emulsion state used as an electrodeposition coating composition, they are the same as the polymer in which the photosensitive portion is ionized. It can be divided into a single component type that is a molecule and a multi component type that is a molecule different from the ionized polymer. As the single component system, a maleic acid-based copolymer disclosed in JP-A-63-297473, JP-A-64-467, which is obtained by grafting a photosensitive component to an ionized polymer, is disclosed.
No. 32, JP-A 64-90270 and US Patent No. 4,673,458 disclosed acrylic copolymers,
There were phenol novolac resins and the like of US Patent No. 4,681,923.

However, since this single component system lacks flexibility, pinholes are easily generated in the process of electrodeposition coating. Further, when the photosensitive component is grafted to the ionized polymer, its photosensitivity is increased. There was a problem that was deteriorated. Therefore, a two-component system in which the photosensitive component is separated from the ionized polymer to improve the photosensitivity has been studied. For example, US Patent No.
As disclosed in 4,673,458 and European Patent No. 0265387 (corresponding Japanese patent: JP-A-61-218616), the photosensitive component is 2,4-dihydroxybenzophenone or 2,3,4-trihydroxybenzophenone. A method of forming an emulsion by mixing with an acrylic resin or a phenol resin at the same time as grafting to the above was adopted.

However, the photosensitive compound produced by this method has a drawback that its solubility in a solvent is extremely low, and its compatibility with an electrodeposition resin is poor, and a precipitation phenomenon is observed in an electrodeposition solution. Although the photosensitivity was improved, pinholes were still easily generated in the process of electrodeposition coating.

Further, the quinonediazide compound used in the publicly known positive photoresist has poor compatibility with the acrylic resin and easily precipitates when mixed with water, so that a good electrodeposition solution cannot be produced. was there.

[0007]

An object of the present invention is to provide a quinonediazide compound having excellent compatibility with an acrylic resin and good photosensitivity, and using the compound, generation of pinholes and the like. Another object is to provide a stable electrodeposition liquid that can obtain a coating film that is in close contact with the base material.

[0008]

The present inventors have synthesized a photosensitive quinonediazide compound by using polyisocyanate (raw material for polyurethane), amine phenols and 1,2-quinonediazidesulfonic acid halide. By grafting the photosensitive component contained in the photosensitive quinonediazide compound to polyisocyanates, a good compatibility with an acrylic resin is obtained, and at the same time, a positive photosensitive composition of a multi-component system of at least two components is obtained. As a result, the present invention has been achieved as a result of extensive studies on a photosensitive electrodeposition coating composition that improves the photosensitivity and improves the adhesion rate to a metal substrate.

That is, the present invention has the following chemical formula

[0010]

[Chemical 7]

A photosensitive quinonediazide compound represented by the formula (wherein R ¹ , X, Y ¹ , n and Z have the same meanings as described above), a positive type photosensitive composition mainly comprising the compound and a photosensitive electrodeposition. The main point is to provide a coating composition.

[0012]

The photosensitive composition of the present invention is suitable for producing a two-component photosensitive electrodeposition coating composition used in the electrodeposition coating method. The electrodeposition coating composition is the photosensitive composition of the present invention. That is, the photosensitive quinonediazide compound and the acrylic resin are used as the main components to be produced in an aqueous emulsion state.

The acrylic resin used in the present invention is obtained by copolymerizing a carboxyl group-containing acrylic monomer with another unsaturated monomer. , Methacrylic acid, acrylic acid, cinnamic acid, crotonic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl succinic acid, monocarboxylic acids such as 2-carboxyethyl methacrylate, itaconic acid, maleic acid, fumaric acid, etc. Unsaturated dicarboxylic acids or their monoesters.

Other unsaturated monomers to be copolymerized with the above-mentioned carboxyl group-containing acrylic monomer include hydroxyl group-containing monomers such as hydroxyethyl methacrylate, methyl methacrylate and butyl methacrylate. Such as methacrylic acid alkyl ester, amide group-containing monomer such as (methyl) acrylamide, nitrile group-containing monomer such as acrylonitrile, N, N′-dimethylaminoethyl methacrylate and N, N′-diethylaminomethacryl Examples thereof include amino group-containing monomers such as methyl acidate, aromatic-containing monomers such as benzyl acrylate and phenoxy acrylate, and the like, and these can be used alone or in combination.

As the method for synthesizing the acrylic resin in the present invention, known solution polymerization method, suspension polymerization method and emulsion polymerization method can be adopted, and the number average molecular weight of the polymer is between 2500 and 200,000. It is desirable to control to. The carboxyl group in the produced copolymer is neutralized with low molecular weight amines to form an anionic emulsion type polymer. In order to stabilize the emulsion state in the electrodeposition coating composition, it is desirable that the carboxyl group-containing acrylic monomer accounts for 3 to 30% by weight in the copolymer.

As the photosensitive compound in the present invention, a compound in which a quinonediazide group having photosensitivity to ultraviolet light is grafted to polyisocyanate which is a raw material of polyurethane is adopted, and a chemical reaction is caused to the quinonediazide group by irradiation of ultraviolet light. By causing this, nitrogen molecules are separated and a carboxyl group is generated. Since this carboxyl group has the effect of increasing the solubility of the photosensitive portion in an alkaline developer, a photoresist pattern can be formed.

The photosensitive quinonediazide compound (I) in the present invention is specifically produced by reacting a polyisocyanate, an aminophenol (II) and a 1,2-quinonediazidesulfonic acid halide. .
In this reaction, polyisocyanate first acts on aminophenols. And since polyisocyanate has a reaction selectivity for amino groups far higher than that for phenolic hydroxyl groups, the hydroxyl groups of aminophenols are retained until the sulfonic acid halide participates in the reaction, and then The quinonediazide is grafted onto the polyisocyanate by action on the acid halogen groups.

The polyisocyanate is obtained by reacting a polyhydroxyl group compound with diisocyanate, and the polyhydroxyl group compound of the present invention preferably has a hydroxyl equivalent of 50 to 500 g.
For example, it can be selected from triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, polyester glycol, polytetrahydrofuran, polycaprolactone, ethoxylated trimethylene cyclopentadiene or propoxylated trimethylene cyclopentadiene.

The diisocyanate is suitably selected from ethylmethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate (also referred to as TDI) or diphenylmethane diisocyanate, xylene diisocyanate, but within the same molecule 2
Tolylene diisocyanate and isophorone diisocyanate, in which the individual isocyanates have different activities, are optimal.

In the reaction of the polyhydroxy compound and the diisocyanate, the equivalent ratio of the hydroxyl group to the diisocyanate is preferably controlled to be 1.25 to 1: 1 and the polyhydroxy compound is gradually added to the diisocyanate. It is preferable to add in a dropping manner.

As the aminophenol compound (II) in the present invention, 4-amino-m-cresol, 6-
Amino-m-cresol, 5-amino-o-cresol, 2-amino-p-cresol, 2-amino-4-t
-Butylphenol, 2-amino-4-chlorophenol, 4-amino-2,6-dichlorophenol, 3-amino-4-octoxybenzoic acid, 4-amino-3-octoxybenzoic acid, 2-amino-4- Nitrophenol, 2-
Amino-5-nitrophenol, 4-amino-2-nitrophenol, o-aminophenol, m-aminophenol, p-aminophenol, 2-aminophenol-4-sulfonic acid, 3-amino-salicylic acid, 5-amino -Salicylic acid, p-amino-salicylic acid, 4-amino-2,3-dimethylphenol, 6-amino-2,4-
It can be selected from among dimethylphenol.
In the reaction between polyisocyanate and aminophenol, the equivalent ratio of isocyanate to amino group is preferably 1: 0.95 to 1.

Examples of quinonediazide sulfonic acid halides are 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and 1,2-benzoquinone-
It can be selected from diazide-4-sulfonyl chloride, and in the reaction of the aminophenol compound and the sulfonic acid halide, the equivalent ratio of the hydroxyl group of the aminophenol and the sulfonic acid halide is 1: 0.
It is preferably between 2 and 1.

In the electrodeposition coating composition of the present invention,
The charge of the emulsion particles is formed by the ion generation of the carboxyl group of the acrylic resin and the low molecular weight amines, and suitable low molecular weight amines (I
Examples of II) include, for example, aqueous ammonia, ethylamine,
Methylethylamine, diethylamine, methylethanolamine, diethanolamine, methyldiethylamine, triethylamine or triethanolamine are suitable, but those with a high boiling point are selected to prevent toxic amine gases from evaporating from the electrodeposition coating bath. Is desirable.

The above-mentioned acrylic resin and the photosensitive quinonediazide compound are mixed and uniformly mixed, and at the same time, a suitable solvent is added and stirred, and low-molecular amines and deionized water are gradually added dropwise to adjust the pH value. 7.0 to 8.
When the solid content is maintained at 8 to 12% and the weight ratio of the acrylic resin and the photosensitive quinonediazide compound is controlled to be between 1: 0.2 and 0.83 while maintaining the value between 0 and 0, excellent flexibility is obtained. An electrodeposition coating composition can be obtained, and a smooth and pinhole-free photoresist film can be formed after electrodeposition coating and heat drying.

When the electrodeposition coating composition of the present invention is used, it is desirable to control the temperature of the electrodeposition coating bath to 28 to 30 ° C. and the applied voltage to 5 to 100 V depending on the film thickness to be formed. And since the emulsion particles carry a negative charge, the electrodeposition-coated object becomes a positive pole,
The cathode is provided on a stainless steel plate and the energization time is 30
From 2 seconds to 3 minutes. In the printed wiring board manufacturing process, the electrodeposition-coated object is a copper clad laminated board, and after being electrodeposition coated, a photoresist layer is formed on the surface of the copper plating layer and dried by heating. A circuit pattern can be formed by a photoresist transfer technique.

[0026]

EXAMPLES Hereinafter, specific synthesis examples and production examples in the present invention will be described as examples, but the present invention is not limited to the following examples.

(1) Synthesis of Acrylic Resin A cold shrink tube, a thermometer, a feeder tube, and a stirring rod were inserted into a four-necked flask, and the temperature was raised to 100 ° C. while bubbling nitrogen gas. About 10 minutes after adding cyclohexanone, 900 g of methyl methacrylate, 102.4 g of butyl acrylate, 7
8.5 g of 2-methacryloyloxyethyl phthalic acid and 1.5 g of 2,2′-azobisisobutyronitrile were gradually added dropwise to form a mixed solution, which was reacted for 6 hours to synthesize an acrylic resin having a molecular weight of 22000. did.

(2) Synthesis of acrylic resin A cold shrink tube, a thermometer, a feeder tube, and a stirring rod were inserted into a four-necked flask, and the temperature was adjusted to 100 ° C. while bubbling nitrogen gas. About 10 minutes after adding methoxypropylene glycol, 7
3.5 g of methyl methacrylate, 113.5 g of butyl acrylate, 18.8 g of methacrylic acid and 2.50
g of 2,2'-azobisisobutyronitrile was gradually added dropwise to form a mixed solution, and the reaction was carried out for 6 hours to synthesize an acrylic resin having a molecular weight of 14000.

(3) Synthesis of Photosensitive Resin A A cold shrink tube, a thermometer, a feeder tube, and a stirring rod were inserted into a four-necked flask, and the temperature was adjusted to 40 ° C., and then 38.
3 g of tolylene diisocyanate and 50.0 g of acetone were added, and the mixture was uniformly mixed with a stirring rod. Within 1 hour, 23.3 g of tetraethylene glycol, 50.
0 g of acetone and 0.3 g of dibutyltin dilaurate were gradually added dropwise to form a mixed solution, which was cooled to room temperature after 2 hours of reaction, and 22.0 g of o-aminophenol and 100.0 g of acetone were added again. Gradually heat to 60 ° C. and maintain for 3 hours, then cool to room temperature and add 51.0 g of 1,2-naphthoquinone-2-
Diazido-5-sulfonyl chloride was added and mixed uniformly, 21.1 g of triethylamine and 100.0 g of acetone were gradually added dropwise within 1 hour, and the reaction was continued for 4 hours. % Hydrochloric acid solution, stirring and separation of the resinous precipitate were performed, and the product was washed with deionized water to obtain 125.2 g of a yellowish brown photosensitive resin A. The production rate was 93%.

(4) Synthesis of Photosensitive Resin B A cold shrink tube, a thermometer, a feeder tube, and a stirring rod were inserted into a four-necked flask, and the temperature was adjusted to 40 ° C., then 35.
Charge 3 g of 2,2-hexylmethylene diisocyanate and 50.0 g of acetone, stir uniformly with a stirring rod, and within 1 hour, 46.8 g of polypropylene glycol (molecular weight 425), 100.0 g of acetone and 0.3 g. Dibutyltin dilaurate was gradually added dropwise to form a mixed solution, which was allowed to react for 2 hours, cooled to room temperature, added again with 21.8 g of o-aminophenol and 50.0 g of acetone, and gradually heated to 60 ° C. After keeping it for 3 hours, it was cooled to room temperature and 45.6 g.
No. 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride was added and mixed uniformly, and 18.
After gradually dropping 0 g of triethylamine and 100.0 g of acetone and carrying out the reaction for 4 hours, this resin mixed solution was put into a 1% hydrochloric acid solution to carry out stirring and separation of a resinous precipitate, followed by desorption. Wash with ionized water 133.1
g of a yellowish brown photosensitive resin B was obtained. The production rate was 89%.

(5) Synthesis of Photosensitive Resin C A cold shrink tube, a thermometer, a feeder tube, and a stirring rod were inserted into a four-necked flask, and the temperature was adjusted to 40 ° C., and then 37.
0 g 2,4-tolylene diisocyanate and 50.
0 g of acetone was added, and the mixture was stirred with a stirrer uniformly, and within 1 hour, 52.6 g of aliphatic polyester diol (hydroxyl equivalent: 239 g), 100.0 g of acetone and 0.3 g of dibutyltin dilaurate were gradually added dropwise. The mixture was made into a mixed solution, cooled down to room temperature after 2 hours of reaction, added again with 21.8 g of o-aminophenol and 50.0 g of acetone, and gradually added to 60 ° C.
Heat to room temperature for 3 hours, then cool to room temperature,
51.0 g of 1,2-naphthoquinone-2-diazide-4
-Sulfonyl chloride was added and mixed homogeneously, and 19.2 g of triethylamine and 100.0 g of 1 hour were mixed.
Acetone was gradually added dropwise, and after the reaction for 4 hours, this resin mixed solution was poured into a 1% hydrochloric acid solution, and stirring and resin precipitates were separated and washed with deionized water.
3.1 g of a yellowish brown photosensitive resin C was obtained. Generation rate is 95
%Met.

(6) Preparation of photosensitive electrodeposition coating composition a After completely dissolving 17.24 g of methoxypropylene glycol and 10.00 g of butoxyethylene glycol in 12.63 g of photosensitive resin A, 36. 10 g
Acrylic resin and 3.21 g of triethylamine were added, and the mixture was thoroughly stirred and diluted with 435.00 g of deionized water to a solid content of 8% and a pH value of 7.7. Then, this emulsion was put in an electrodeposition coating bath, and the copper clad laminate was energized at 10 V for 30 seconds using the plus electrode as a positive electrode, and then the copper clad laminate was taken out and dried by heating at 90 ° C. for 10 minutes to form a film. A photoresist film having a thickness of 4 μm was obtained.
This is covered with a circuit pattern mask, exposed to ultraviolet rays of 400 mJ / cm ² energy, washed with 1% sodium silicate aqueous solution and developed to form a photoresist pattern on the copper plating layer, and then a sodium persulfate aqueous solution. Then, the copper foil was removed by etching under the temperature condition of 40 ° C. to obtain a sharp circuit pattern with a high degree of analysis. After the etching treatment, neither the film removal phenomenon nor the pinhole generation phenomenon was observed in the photoresist layer in the non-exposed area.

(7) Production of Photosensitive Electrodeposition Coating Composition b After completely dissolving 21.00 g of butoxyethylene glycol in 18.50 g of photosensitive resin B, 41.20
g of acrylic resin and 4.61 g of triethylamine were added and mixed thoroughly, and diluted with 413.00 g of deionized water to a solid content of 10% and a pH value of 7.55. Then, this emulsion was put in an electrodeposition coating bath, and the copper clad laminate was energized for 60 seconds at 15 V with the positive electrode being the copper clad laminate.
After heating and drying for 0 minutes, a photoresist film having a film thickness of 7 μm was obtained. Cover this with a circuit pattern mask to 500 mJ /
After exposing with ultraviolet light of cm ² energy amount, washing out with 1% sodium silicate aqueous solution and developing to form a photoresist pattern on the copper plating layer, copper foil is exposed to a temperature condition of 40 ° C. with sodium persulfate aqueous solution. A sharp circuit pattern with a high degree of analysis was obtained by etching and removing. After the etching treatment, neither the film removal phenomenon nor the pinhole generation phenomenon was observed in the photoresist layer in the non-exposed area.

(8) Production of Photosensitive Electrodeposition Coating Composition c After 16.30 g of methoxypropylene glycol was completely dissolved in 10.20 g of photosensitive resin C, 37.4 g was obtained.
0 g of acrylic resin and 2.85 g of triethylamine were added and mixed well, and diluted with 414.00 g of deionized water to a solid content of 8% and a pH value of 7.43. Then, this emulsion was put in an electrodeposition coating bath, and the copper clad laminate was energized for 60 seconds at 10 V using the copper clad laminate as a positive electrode.
It was heated and dried for 0 minutes to obtain a photoresist film having a film thickness of 5 μm. Cover this with a circuit pattern mask and 400 mJ /
After exposure with ultraviolet rays having an energy amount of cm ² and washing and development with a 1% sodium silicate aqueous solution to form a photoresist pattern on the copper plating layer, a sharp circuit pattern with high resolution was obtained. After the etching treatment, neither the film removal phenomenon nor the pinhole generation phenomenon was observed in the photoresist layer in the non-exposed area.

(9) Comparative Example Here, regarding the above-mentioned US Patent No. 4,673,458 (hereinafter referred to as a known example), a comparative example with the present invention will be given. ，
3,4-trihydroxybenzophenone and 1,2-
1.0 g of naphthoquinone-2-diazide-4-sulfonyl chloride was taken, and 5.0 mol of acrylic resin was used as 7 mol% methacrylic acid, 15 mol% methyl methacrylate, 25 mol% hydroxymethacrylate and 10 mol%. When butyl acrylate, 18 mol% methyl acrylate and 25 mol% diacetone acrylamide are prepared and 3.0 g of butyl cellosolve is added to react with it, triethanolamine is added to control the pH value to 7.5. , A precipitate other than the resinous precipitate was produced. It is speculated that this precipitate was formed because the compatibility between the photosensitive component of the known example and the acrylic resin was poor.

[0036]

As described above, the photosensitive quinonediazide compound of the present invention is obtained by reacting polyisocyanate, aminophenol and 1,2-quinonediazidesulfonic acid halide, and is contained in the photosensitive quinonediazide compound. It has excellent flexibility by grafting a photosensitive component to a flexible polyisocyanate, which is a raw material for polyurethane, and has good compatibility with an acrylic resin due to the large molecular weight of the photosensitive quinonediazide compound of the present invention. A multi-component positive type photosensitive composition having at least two components can be produced. Therefore, in the production of a positive-type photosensitive electrodeposition coating composition, it is possible to provide a flexible composition which is highly flexible and does not generate pinholes, and at the same time has improved photosensitivity and an improved adhesion rate to a metal substrate. Therefore, the industrial utility value is high.

Claims (4)

[Claims] 1. The following chemical formula: [Wherein R ¹ is a polyester or polyether residue having a molecular weight of 100 to 1000, X is a divalent organic group, Y ¹ is hydrogen, a hydroxyl group, a carboxyl group, an alkyl group or halogen, and n is 2 or 3, Z Is hydrogen, Embedded image And A group selected from the group consisting of (wherein, when n is 2 or 3, Z is at least one of the groups shown in Chemical formula 2, Chemical formula 3, and Chemical formula 4).]
A photosensitive quinonediazide compound represented by. 2. The photosensitive quinonediazide compound (I)
Is a polyisocyanate and has the chemical formula (Wherein Y ² represents hydrogen, a hydroxyl group, a carboxyl group, an alkyl group, a nitro group or halogen), and an aminophenol (II) represented by 1,2-quinonediazidesulfonic acid halide is reacted with What is obtained is an equivalent ratio of an isocyanate group in polyisocyanate to an amino group contained in aminophenols of 1: 0.95-1, and a hydroxyl group contained in aminophenols and 1,2-quinonediazide sulfone. The photosensitive quinonediazide compound according to claim 1, wherein the equivalent ratio to the acid halide is 1: 0.2 to 1. 3. A weight average molecular weight obtained by polymerizing 3 to 30% of a (meth) acrylic monomer containing a carboxyl group and 70 to 97% of an unsaturated monomer has a weight average molecular weight of 2500 to 2000.
A positive photosensitive composition containing, as a main component, a (meth) acrylic resin of No. 00 and the photosensitive quinonediazide compound (I) according to claim 1. 4. The positive photosensitive composition according to claim 3,
Chemical formula (In the formula, R ² , R ³ and R ⁴ may be the same or different and are selected from hydrogen, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 2 to 3 carbon atoms. ) A photosensitive electrodeposition coating composition comprising a low molecular weight amine (III) represented by