JP2501505B2 - Positive photosensitive quinonediazide 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 positive photosensitive quinone diazide electrodeposition coating composition used for forming a photoresist pattern in the production of printed wiring boards and the like.

[0002]

2. Description of the Related Art Conventionally, a print-and-etching method has been commonly used as a method for manufacturing a printed wiring board. After forming a photoresist pattern on a copper clad laminate having an insulating copper foil, The exposed copper foil was removed with an etching solution to form a desired circuit pattern, and the photoresist film on the circuit was removed with a film remover to complete the wiring board. Before this photoresist, the screen printing method was the mainstream, and the etching resistant ink liquid was printed on the surface of the copper clad laminate through the screen, but the fluidity of the ink itself transferred the circuit pattern precisely. However, it was difficult to obtain a fine pattern. Therefore, photoresists have been adopted, and the entire surface of the copper foil is covered with photoresist, and after selectively exposing with a negative film having a printed circuit pattern, the resist film of unnecessary portions is developed with a developing solution. Was removed to obtain the required circuit pattern. Since this photoresist method is superior in resolution and reliability in comparison with the screen printing method, a negative photoresist has been indispensable for forming a fine pattern.

Conventionally, there are two types of photoresists for printed wiring boards, liquid ones and dry film-like ones. The liquid photoresists are applied by dip coating method, roller coating method and spin coating method. And there was an electrodeposition method. Since the liquid photoresist is dispersed as an emulsion in a solvent, a drying step is necessary after coating, and the step such as exposure has been started only after the drying. Compared with this, when using a dry film type photoresist, it is directly sandwiched between the upper and lower two layers of protective films (materials are polyester and polyether) and then thermocompression bonded, so that the next exposure step can be performed directly. I was able to proceed.

Such photoresists are classified into a positive type and a negative type due to the difference in the reaction mechanism to exposure. In the case of the positive type, the exposure produces an carboxyl group inside the photosensitive material to produce an alkaline developer. Therefore, an etching resistant pattern was formed in the non-exposed portion by providing good solubility to In the case of the negative type, a photo-curing reaction occurs in the exposed area to make it insoluble in an alkali developing solution and the non-exposed area becomes soluble, so an etching resistant pattern was formed in the exposed area and it was developed earlier. Since the negative type is more advantageous than the positive type in terms of stability and price, negative type photoresists have been widely used.

However, the negative type photoresist has a problem that it is difficult to form through holes in a good condition on a printed wiring board. Of course, the electroplating method can produce good through-holes, but the process becomes complicated, and the simple tenting method causes a problem that the photoresist suppresses oxygen inside the holes, resulting in insufficient curing. The copper foil in the tent was washed off, which was unreliable.

In contrast to this, the positive photoresist has a uniform film thickness and can completely cover the copper foil portion inside the through hole, and it is not necessary to expose the inside of the hole, which is a point of reliability. However, at the same time, there was no problem and good through holes could be completed by a simple etching method, which was advantageous in terms of process simplification. Further, since the positive photoresist is a water-soluble emulsion, the amount of organic solvent used can be reduced as compared with other photoresists, and the photoresist composition ratio is high, so that it has become preferable from the viewpoint of environmental protection.

[0007] Such an electrodeposition method is a method for applying a paint to protect the metal surface of various appliances by applying a solid component of the paint, but it is possible to form a uniform film thickness and facilitate automation. was there. Therefore, the electrodeposition method has been used for the coating of photoresists from an early stage.
Patent No. 3738835 discloses a technique of coating a negative photoresist on a metal substrate by an electrodeposition method. Further, when only one side of the metal substrate is used, the positive type photoresist is not particularly superior to the negative type photoresist, but as the demand for the copper clad laminate utilizing the two sides of the front and back increases, However, the advantages of positive photoresist over through holes have become non-negligible. Against this background,
Various positive photoresist compositions have been proposed, and JP-A-63-29747 adopts a maleic acid copolymer.
4. Japanese Patent Laid-Open No. 1-4627 employing acrylic copolymer,
Japanese Patent No. 1-90270 and US Patent No. 4681923 and the like, both of which are grafted onto a polymer loaded with a quinonediazide group as a photosensitive component to give a single-component positive photoresist, and the quinonediazide group reacts with a trace amount component inside the photoresist after exposure to generate a carboxyl group. By converting it into a group, it was dissolved in an alkali developing solution.

However, although this kind of electrodeposition photoresist is simple, its photosensitivity component is fixed to the side chain of the polymer, so that it has little activity and is inferior in photosensitivity.

In addition to the single-component photosensitive composition,
Grafted not with a polymer bearing a quinonediazide group but with a relatively small molecule, for example, US Patent No. 4673458 and European Patent No. 0265387 and the like, and the quinonediazide group is 2,3-dihydroxybenzophenone or 2,3,4
-Grafted on trihydroxybenzophenone.

This method was intended to improve the photosensitivity, but since 2,3-dihydroxybenzophenone or 2,3,4-trihydroxybenzophenone grafted to a quinonediazide group exhibits strong hydrophobicity, it is an electrodeposition emulsion. It has a drawback that it tends to precipitate in the solution, there is a problem in the stability of the photoresist electrodeposition solution, and that the photoresist film becomes thick and sharp resolution cannot be obtained.

[0011]

The present invention provides a positive-working photosensitive quinonediazide electrodeposition composition in which a quinonediazide group is grafted onto a polyester polyol to improve the photosensitivity and obtain good resolution. An object of the present invention is to provide an electrodeposition liquid using a positive-type photosensitive quinonediazide electrodeposition composition, which is free from pinholes and the like, has excellent adhesiveness to a printed wiring board, and at the same time maintains a stable emulsion state.

[0012]

Means for Solving the Problems The inventors of the present invention have:
By allowing an acrylic copolymer containing a carboxyl group and a photosensitive quinonediazide resin to exist in an aqueous solution in an emulsion state, the carboxyl group contained in the acrylic copolymer is neutralized with a low-molecular amine to obtain a charged state. As a result of repeated studies on a positive-type photosensitive quinonediazide electrodeposition composition that is highly photosensitive and does not generate pinholes and has excellent adhesion to printed wiring boards, as well as obtaining a stable photosensitive electrodeposition solution in water The invention has been reached.

That is, the present invention comprises (a) a carboxyl group-containing acrylic copolymer neutralized with a low molecular weight amine,
(B) a photosensitive quinonediazide resin represented by the following chemical formula 1,

Embedded image [In the chemical formula 1, R is a polyester having a molecular weight of 100 to 2000, n is an integer of 2 to 4, and Z is selected from the group consisting of hydrogen, the following chemical formulas 2, 3, and 4 (provided that At least one Z in the chemical formula 1 is selected from the chemical formula 2, the chemical formula 3, and the chemical formula 4.)

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Embedded image (C) A positive photosensitive quinone diazide electrodeposition coating composition obtained by mixing water mixed so that the solid content of the above (a) and (b) is 5 to 20% by weight in the whole. The purpose is to provide.

[0014]

The positive-working photosensitive quinonediazide electrodeposition coating composition of the present invention is suitable for the electrodeposition coating method and comprises an acrylic copolymer containing a carboxyl group neutralized with low molecular weight amines and a photosensitive quinonediazide resin. It exists as an emulsion in the water system, with and as the main components.

The acrylic copolymer used in the present invention includes the following unsaturated monomers, namely, carboxyl group-containing monomers such as methacrylic acid, acrylic acid, phthalic acid (meth) acrylate and succinic acid (meth). Acrylate, itaconic acid, cinnamic acid, crotonic acid, maleic acid,
β-carboxyethyl (meth) acrylate or other unsaturated monomer (α, β-ethylenically unsaturated monomer), that is, (1) hydroxyl group-containing monomer [hydroxylethyl (meth) acrylate, etc.] , (2) Alkyl group acrylic monomer [alkyl (meth) acrylate, such as methyl (meth) acrylate, butyl (meth) acrylate, etc.], (3) Amide group-containing monomer [eg (meth)
Acrylamide, diacetone acrylamide], (4) nitrile group-containing monomer (eg, acrylonitrone, etc.),
(5) Amino group-containing monomer [eg, N, N-dimethylethyl (meth) acrylate, N, N-dimethyl ether (meth) acrylate, etc.], (6) Aromatic-containing monomer (eg, benzyl acrylate, acrylic acid) (Phenoxy etc.)
Among them, it consists of those selected from (1) to (6).

The above unsaturated monomers, alone or in combination, are reacted with a carboxyl group-containing monomer to form an acrylic copolymer, which improves both the stability of the emulsion solution and the developability of the photoresist film. Therefore, it is desirable that the carboxyl group-containing monomer accounts for 3 to 30% by weight of the acrylic copolymer. And, this reaction is obtained by radically reacting the above-mentioned unsaturated monomer, but the suspension polymerization method, emulsion polymerization method or solution polymerization method can also be adopted as the method of the reaction, and the average molecular weight of the polymer. Is preferably between 2500 and 200,000.

The surface charge of the emulsion is formed by neutralizing the carboxyl group of the acrylic copolymer with low molecular weight amines. As amines that can be adopted, ammonia water, ethylamine, diethylamine, methyldiethylamine, diethanolamine, triethylamine are used. , Triethanolamine, etc., but it is preferable to use amines having a low volatility as much as possible and not to adjust the addition amount.

The photosensitive quinonediazide resin of the present invention is
A quinonediazide group, which is mainly composed of polyester and has photosensitivity, is grafted to the end of the ester.

[0019]

Embedded image [In the formula, R is a polyester having a molecular weight of 100 to 2000, n is preferably an integer of 2 to 4, Z is hydrogen,

[0020]

Embedded image

[0021]

Embedded image and

[0022]

Embedded image Selected from the group consisting of (wherein at least one Z in the molecule is

[0023]

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[0024]

Embedded image and

[0025]

Embedded image More selected)]].

There are various production methods for the photosensitive quinonediazide resin of the present invention.
-The esterification reaction with a quinonediazide sulfonic acid halide is suitable and can be easily synthesized using commercially available raw materials. The polyester polyol of the present invention can be selected from many ones, but one having a molecular weight of 3000 or less is suitable, and as a general compounding method, a divalent hydroxyl group compound (diol) and a divalent carboxyl group compound ( At the same time as an esterification reaction with dibasic acid), water as a by-product is removed by distillation. Examples of the hydroxy group compound commonly used in the esterification reaction include ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, trimethyl divalent pentane, triethylene glycol, and 1,6-2 valent. There are hexane and 1,2-divalent butane, and among them, neopentyl glycol and trimethyl divalent pentane have many side chains and can give a flexible ester. In addition, common divalent carboxyl group compounds include phthalic acid, isophthalic acid, adipic acid, oxalic acid, succinic acid, and glutaric acid. Among them, the esters synthesized from succinic acid and glutaric acid are unstable in an aqueous system. Since it easily causes a water-splitting reaction, it is not often used in the synthesis of esters.

Since the ester of the present invention is a polyester polyol, its terminal is a hydroxyl group, and when the divalent hydroxyl group compound and the divalent carboxyl group compound are combined, the divalent hydroxyl group compound becomes excessive. To produce a hydroxyl group-containing ester.

In addition to the above linear polyester polyol, esterification reaction of a low molecular weight polyester polyol and a dibasic acid gives an ester having a side chain (weakly branched polyester). Examples include trifunctional alcohols (eg, glycerol, trimethanolethane, trimethanolpropane, etc.) and tetrafunctional alcohols (eg, pentaerythritol).

Further, the polyester polyol can be synthesized by adopting a ring-opening polymerization method. For example, even if ε-caprolactone and methyl-ε-caprolactone are added to the polyester polyol, a divalent polyester or a trivalent polyester can be synthesized. .

The quinonediazide sulfonic acid halide of the present invention includes 1,2-quinone-2-diazide-5.
-Sulfonic acid salt, 1,2-naphthoquinone-2-diazide-5-sulfonic acid salt, 1,2-naphthoquinone-2-
There are diazide-4-sulfone oxide salt, 1,2-benzoquinonediazide-4-sulfone oxide salt, etc., and in the esterification reaction of polyester polyol and quinonediazide sulfonic acid halide, the equivalent of hydroxyl group and sulfonic acid halogenated group The ratio with the equivalent weight is preferably 1: 0.3 to 1. Then, the acrylic copolymer and the photosensitive quinonediazide resin are thoroughly mixed, an appropriate amount of solvent is added and stirred, and low molecular weight amines and deionized water are added to obtain a pH value of 7.0 to 8. 5
Arrange in between. The proportion of solids such as acrylic copolymer in the mixture is 5 to 20%, and the weight ratio of acrylic copolymer to photosensitive quinone diazide resin is 1: 0.1 to 1.2.
Is desirable.

Therefore, the photosensitive electrodeposition liquid prepared as described above is put in an electrodeposition tank, the wiring board is connected to the positive electrode and the stainless plate is connected to the negative electrode, and the applied voltage is 10 to 10 while the electrodeposition liquid is refluxed. Energize at 100V for 30 seconds to 5 minutes,
After forming a photoresist film on the surface of the wiring board, a circuit pattern is transferred to the photoresist by a known pattern transfer technique through a drying process. Exposure is performed with a halogen lamp or a mercury lamp, and the exposed portion is removed with an alkali developing solution. Suitable alkali developing solutions include sodium hydroxide (caustic soda), sodium silicate, sodium carbonate,
An aqueous solution such as potassium hydroxide or aqueous ammonia can be used, and an appropriate concentration range is 0.5 to 3%. Then, the exposed copper foil portion is removed with an etching solution, and an appropriate etching solution is an aqueous solution of copper chloride, iron chloride, sodium persulfate or the like. Next, the remaining photoresist film is removed, but an aqueous solution of 3 to 5% of sodium hydroxide, potassium hydroxide, methane dichloride or the like is used as a film removing agent and dissolved by immersion.

[0032]

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

Synthesis Example 1: Synthesis of Acrylic Copolymer 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. After about 11 minutes of charging 110.0 g of diethyl ketone, 45.0 g of methyl methacrylate, 40.6 g of butyl acrylate, 5
9.0 g of 2-hydroxyethyl acrylate, 85.
A mixed solution consisting of 0 g of diacetone acrylamide, 7.2 g of acrylic acid and 3.0 g of N, N'-azobisisobutyronitrile was added dropwise, and the reaction was carried out for 6 hours to obtain an acrylic copolymer having a molecular weight of 14,000. Was synthesized.

Synthesis Example 2: Synthesis of Acrylic Copolymer 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 through. 92.0 g of diethyl ketone was added, and after about 10 minutes, 38.0 g of methyl methacrylate, 64.0 g of methyl acrylate, 5
0.0 g of 2-hydroxyethyl acrylate, 11.
A mixed solution of 5 g of methacrylic acid and 1.8 g of N, N'-azobisisobutyronitrile was injected dropwise, and an acrylic copolymer having a molecular weight of 21,000 was synthesized by reacting for 6 hours.

Synthesis Example 3: Synthesis of Acrylic Copolymer A cold shrink tube, a thermometer, a feeder tube and a stir bar were inserted into a four-necked flask, and the temperature was raised to 100 ° C. while nitrogen gas was passed through the flask. After about 8 minutes of adding 83.0 g of propylene glycol monomethyl ether, 90.0 g of methyl methacrylate, 115.2
g of butyl acrylate, 43.2 g of succinic acid acrylate and 2.5 g of N, N′-azobisisobutyronitrile were added dropwise, and the reaction was carried out for 6 hours. The coalescence was synthesized.

Synthesis Example 4: Preparation of photosensitive quinonediazide resin I
Inserting a condenser, a thermometer, a feeder tube, and a stirring rod into a synthetic four-necked flask, respectively, to obtain 95.6 g of an aliphatic polyester polyol (hydroxyl group equivalent: 239 g / equivalent,
Manufactured by Taiwan King Industries), 80.6g
1,2-naphthaquinone-diazide-5-sulfone salt and 250.0 g of acetone were added and sufficiently stirred to mix, then, 33.0 g of triethylamine and 15
A mixed solution of 0.0 g of acetone was added dropwise for 1 hour, and the reaction temperature of 25 ° C. was maintained for 6 hours to complete the esterification reaction. Then, add 1% of this resin mixed solution
16% of yellowish brown photosensitive quinonediazide resin I was synthesized by washing with deionized water after separating the resinous precipitate by stirring in an aqueous hydrochloric acid solution of 1.

Synthesis Example 5: of photosensitive quinonediazide resin II
A cold shrink tube, a thermometer, a feeder tube, and a stirring rod were inserted into a synthetic four-necked flask, and 48.8 g of an aliphatic polyester polyol (hydroxyl group equivalent: 244 g / equivalent,
Manufactured by Taiwan King Industries), 32.2 g
1,2-naphthaquinone-diazide-5-sulfone salt and 120.0 g of dichloromethane were added and sufficiently stirred and mixed, and then a mixed solution of 13.3 g of triethylamine and 50.0 g of dichloromethane was added for 1 hour. It was injected dropwise and the reaction temperature of 25 ° C. was maintained for 6 hours to complete the esterification reaction. Then, this resin mixed solution was put into a 1% hydrochloric acid aqueous solution and stirred to separate a resinous precipitate, which was washed with deionized water and then vacuum dried at 40 ° C. for 20 hours to give a yellowish brown color. 76.2 g of photosensitive quinone diazide resin II was synthesized.

Synthesis Example 6: Photosensitive quinonediazide resin III
The cold shrink tube, thermometer, feeder tube, and stirring rod were inserted into a 4-necked flask, and 150.0 g of poly [1,6
-Divalent hexane-adipic acid] (hydroxyl group equivalent 5
00g / equivalent, manufactured by Taiwan Yongchun Co., Ltd.), 72.5g
1,2-naphthaquinone-2-diazide-4-sulfone salt of Example 1 and 280.0 g of dichloromethane were added and sufficiently stirred and mixed, and then a mixed solution of 27.3 g of triethylamine and 200.0 g of dichloromethane was added to 1 It was injected dropwise over time, and the reaction temperature of 25 ° C. was maintained for 6 hours to complete the esterification reaction. Then, this resin mixed solution was put into a 1% hydrochloric acid aqueous solution and stirred to separate a resinous precipitate, which was washed with deionized water and then vacuum dried at 40 ° C. for 20 hours to give a yellowish brown color. 201.1 g of photosensitive quinone diazide resin III was synthesized.

Production Example 1: Positive photosensitive electrodeposition coating composition A
Preparation of 26.0 g of photosensitive quinonediazide resin II (Synthesis example 5)
21.0 g of ethylene glycol monobutyl ether was added and completely dissolved, and then 67.6 g of an acrylic copolymer (Synthesis Example 2) was added so that the ratio of solid content in the whole was 69% by weight. Gradually add ethanol and deionized water to bring the pH value to 7.5. Further, deionized water was mixed so that the proportion of the solid content in the whole was 9% by weight to produce a positive photosensitive electrodeposition coating composition A. And this positive type photosensitive electrodeposition coating composition A
Was placed in an electrodeposition tank, and an applied voltage of 30 V was applied for 2 minutes with the wiring substrate as a positive electrode to obtain a smooth photoresist film having a film thickness of 6 μm. Therefore, the amount of energy is 350m
The circuit pattern was exposed with J / cm ² ultraviolet light, the exposed portion was removed with a 1% sodium silicate aqueous solution, and after a developing time of 60 seconds, a sharp photoresist pattern was obtained on the surface of the wiring board. Then, when the state of adhesion of the photoresist film was observed at the stage where the exposed copper foil portion was removed with the copper chloride etching solution, the adhesion to the wiring board was good and no pinholes were formed on the surface. In addition, no precipitation mutation occurred even after a storage test for 2 weeks, showing good emulsion stability.

Production Example 2: Positive type photosensitive electrodeposition coating composition B
Preparation of 34.0 g of photosensitive quinonediazide resin III (Synthesis example 6) was completely dissolved by adding 21.0 g of propylene glycol monomethyl ether, and the total solid content was adjusted to 69% by weight. 0.0 g of acrylic copolymer (Synthesis Example 3) is added, and triethylamine and deionized water are gradually added dropwise to bring the pH value to 7.8. Further, deionized water was mixed so that the proportion of the solid content in the whole was 10% by weight to produce a positive photosensitive electrodeposition coating composition B. When this positive type photosensitive electrodeposition coating composition B was placed in an electrodeposition tank and a wiring board was used as a positive electrode, an applied voltage of 35 V was energized for 2 minutes, energized for 2 minutes, and dried with hot air for 5 minutes A smooth photoresist film having a film thickness of 8 μm was obtained. Therefore, the energy amount is 350 mJ / cm ²
The circuit pattern was exposed by the ultraviolet ray of 1), the exposed portion was removed with a 1% sodium silicate aqueous solution, and after a developing time of 60 seconds, a sharp photoresist pattern was obtained on the surface of the wiring board. Then, when the state of adhesion of the photoresist film was observed at the stage where the exposed copper foil portion was removed with the copper chloride etching solution, the adhesion to the wiring board was good and no pinholes were formed on the surface. In addition, no precipitation mutation occurred even after a storage test for 2 weeks, showing good emulsion stability.

Comparative Example: US Patent No. 4673
Comparison with the US Patent No. 658 described above. 467365
No. 8 (hereinafter referred to as a known example), a comparative example with the present invention will be given. 2,3,4-tri [1,2-naphthoquinone-2-diazide- 5-sulfone base] 5.0 g of benzophenone
And 36.2 g of an acrylic copolymer having a solid content of 69% by weight are sufficiently mixed and dissolved, and triethylamine and deionized water are gradually added dropwise to a pH value of 7.5. Then, deionized water was further mixed so that the solid content was 9% by weight, but at this point, a precipitate had already started to be generated at the bottom of the emulsion solution. Since this precipitate is 2,3,4-tri [1,2-naphthoquinone-2-diazide-5-sulfonebase] benzophenone and the surface of the precipitate film lacks smoothness, it is necessary to form a photoresist film. It was inappropriate.

[0042]

As described above, the positive photosensitive quinonediazide electrodeposition coating composition of the present invention is obtained by synthesizing a photosensitive quinonediazide resin mainly composed of polyesterpolyol, and this polyesterpolyol has flexibility. Since it is a rich polymer, the photoresist film produced by exhibiting excellent flatness by heating also has good flexibility and becomes a suitable smooth surface, so a powdery non-smooth surface in the electrodeposition process. It is possible to improve the resolution of the photoresist film without forming a film and it is also excellent in adhesiveness. In addition, the positive-type photosensitive electrodeposition coating composition of the present invention is water-soluble, so that it can prevent environmental pollution, can produce a stable emulsion solution with good solubility, and can be stored for several weeks. However, since it maintains a good emulsion state, it has high industrial utility value.

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Claims (5)

(57) [Claims] 1. A positive photosensitive quinonediazide electrodeposition coating composition obtained by mixing the following components (a), (b) and (c). (A) A carboxyl group-containing acrylic copolymer neutralized with a low molecular amine (b) A photosensitive quinonediazide resin represented by the following chemical formula 1 [In the chemical formula 1, R is a polyester having a molecular weight of 100 to 2000, n is an integer of 2 to 4, and Z is selected from the group consisting of hydrogen, the following chemical formulas 2, 3, and 4 (provided that At least one Z in the chemical formula 1 is selected from the chemical formulas 2, 3, and 4)] Embedded image Embedded image (C) Water mixed so that the proportion of the solid content according to (a) and (b) above is 5 to 20% by weight. 2. The carboxyl group-containing acrylic copolymer contains the carboxyl group-containing acrylic monomer in a molar ratio of 3 to 3.
30%, other unsaturated monomers are 70-97% in molar ratio
The positive-type photosensitive quinone diazide electrodeposition coating composition according to claim 1, which is obtained by compounding in a ratio of. 3. The positive photosensitive quinonediazide electrodeposition coating composition according to claim 1, wherein the carboxyl group-containing acrylic copolymer has an average molecular weight of 3,000 to 200,000. 4. The photosensitive quinonediazide resin has an equivalent weight of 1
Reaction of hydroxy group-terminated polyester of 00 to 1000 with 1,2-quinonediazide sulfonic acid halide so that the equivalent ratio of hydroxy group to sulfonic acid halide group is 1: 0.3 to 1. The positive photosensitive quinonediazide electrodeposition coating composition according to claim 1, which is obtained by the method. 5. The weight ratio of the carboxyl group-containing acrylic copolymer to the photosensitive quinone diazide resin is 1: 0.1.
The positive type photosensitive quinonediazide electrodeposition coating composition according to claim 1, wherein