JPH0683048A - Positive photosensitive resin composition - Google Patents

Abstract

PURPOSE:To provide a positive photosensitive resin compsn. excellent in compatibility with an alkali-soluble resin and showing excellent stability as a soln. or electrodeposition liquid by incorporating a specified positive photosensitive compd. as the essential component. CONSTITUTION:This positive photosensitive resin compsn. contains (a) quinone diazide phenol resin expressed by formula and (b) alkali-soluble resin as the essential components. In formula, R<1> is an alkyl group of 1-4 carbon number, R<2> is a bivalent hydrocarbon residue having 5-16 carbon number, D1, D2, D3 are hydrogen atoms or quinone diazide units. When a resin having carboxylic acid groups is used as the alkali-soluble resin, the obtd. positive photosensitive resin compsn. is suitable for an electrodeposition coating. Further, the obtd. coating film of this positive photosensitive resin by electrodepostion has excellent adhesion property to a substrate and can be formed into a fine wiring pattern.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel positive photosensitive resin composition that can be used in the production of printed wiring boards, integrated circuits, etc. More specifically, it is easy to produce and is compatible with other resins. The present invention relates to a novel positive-type photosensitive resin composition that forms a coating film having excellent compatibility with and excellent adhesion to a substrate.

[0002]

2. Description of the Related Art With the recent development of electronic equipment, a printed wiring board as a holder is required to have high density, high integration, and fine circuits. Therefore, when mounting parts on the board, A substrate surface mounting method is used in which through holes each having a small hole diameter and having a role of conduction between the front and back of the substrate are arranged. The through hole is a hole in which metal is plated on the inner wall, the front and back layer circuits are connected to each other, and mounting components are fixed.

When the printed wiring board having the through holes and fine circuit wiring is produced by etching, it is necessary to protect the metal plating layer on the inner wall of the through hole from the etching solution. However, the method of laminating a dry film as a photosensitive film which is widely used at present has a film thickness of generally 50 μm.
Since the thickness is about m, the circuit pattern formed by exposure and development is not sharp, a fine circuit pattern cannot be formed, and it is difficult to uniformly laminate the photosensitive film on the metal surface. There is a problem that the metal plating layer on the inner wall cannot be protected in the through hole portion having a small hole diameter.

Even when the resist is formed by the electrodeposition method capable of uniformly coating the etching resist, the through-hole is formed when the current negative-type electrodeposition photoresist containing a photocurable resin as a main component is used. There is a problem that it is difficult to protect the metal plating layer on the inner wall from the etching solution due to insufficient curing of the inside of the through hole because the amount of light irradiation to the inside is insufficient.

In order to overcome the above-mentioned drawbacks, a positive type electro-deposition photoresist in which an exposed part is dissolved in a developing solution and an unexposed part becomes a protective layer and can be uniformly applied to a substrate by electrodeposition coating Development is in progress and various proposals have been made. That is, in the positive photoresist, the light-irradiated portion becomes soluble in the solvent and the resist is dissolved and removed, and the unirradiated portion remains as a protective layer without being removed because it is insoluble in the solvent. It is possible to form the protective layer without irradiating the surface with light.

As the positive photoresist, a compound having a quinonediazide group is used as a photosensitizer component.
A resist using an alkaline aqueous solution as a developing solution has attracted attention because it has excellent sensitivity and resolution. When the positive photoresist having a quinonediazide group is a resin containing a group that promotes dissolution in an alkaline aqueous solution and a quinonediazide group in one resin, purification is difficult and not industrial Therefore, a resin composition of a resin or compound having a quinonediazide group and a resin that promotes dissolution in an alkaline aqueous solution is used.
In the resin composition, a resin or compound having a quinonediazide group and a resin having a group that promotes dissolution are mixed at an appropriate ratio to obtain good sensitivity and the like, and a positive photosensitive resin composition is obtained. In this case, improving the compatibility of both is the most important for achieving high resolution.

[0007]

However, at the present time,
Industrially-manufacturable quinonediazide compounds have poor compatibility with alkali-soluble resins, particularly resins having a carboxyl group, such as acrylic resins, so that the stability of positive photoresist solutions and positive photoresist electrodeposition solutions is poor. However, there is a problem that the resolution is inferior, and it does not have the performance that is practically satisfactory.

The object of the present invention is to provide a positive-type photosensitive resin composition which is excellent in compatibility between an alkali-soluble resin and a positive-type photoresist, stability in a solution or electrodeposition solution, and further excellent in resolution. To provide.

[0009]

As a result of intensive studies to solve the above problems, the present inventors have developed a positive type photosensitive resin composition containing a specific positive type photosensitive compound as an essential component. By succeeding in meeting the above issues,
The present invention has been completed.

That is, the present invention comprises (a) a quinonediazide-phenolic resin represented by the general formula 2 (hereinafter referred to as "quinonediazide-phenolic resin (1)"), and
(B) To provide a positive photosensitive resin composition characterized by containing an alkali-soluble resin (hereinafter referred to as “alkali-soluble resin (2)”) as an essential component.

[0011]

[Chemical 2]

The present invention will be described in more detail below.

The positive photosensitive resin composition of the present invention is characterized by containing a specific quinonediazide-modified phenol resin and an alkali-soluble resin as essential components.

The specific quinone diazide phenolic resin used as an essential component in the present invention is the quinone diazide phenolic resin (1) represented by the general formula 2. In the quinonediazide phenol resin (1), when R ¹ has 5 or more carbon atoms, R ² has 17 or more carbon atoms, and when m is 11 or more or n is 3 or more, the production is difficult. .

Specific examples of the quinonediazide-modified phenol resin (1) include those represented by the following structural formulas 3 to 3.
10 (in the formula, m and x represent a number of 0 to 10. Further, t ₁ , t ₂ and t ₃ are the same or different numbers, and 1 to
The number of 3 is shown. The resin and the like represented by) can be preferably mentioned.

[0016]

[Chemical 3]

[0017]

[Chemical 4]

[0018]

[Chemical 5]

[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

[Chemical 8]

[0022]

[Chemical 9]

[0023]

[Chemical 10]

To prepare the quinonediazide-modified phenol resin (1), for example, a phenol resin represented by the following general formula 11 and the following chemical formulas 12 to 14 are prepared.
(In the formula, X represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom) and can be produced by reacting with a quinonediazide compound.

[0025]

[Chemical 11]

[0026]

[Chemical 12]

[0027]

[Chemical 13]

[0028]

[Chemical 14]

The phenol resin has 5 to 1 carbon atoms having at least two carbon-carbon double bonds with a phenol represented by the following general formula 15 in the presence of a Lewis acid catalyst.
It can be produced by copolymerizing 6 with the unsaturated hydrocarbon.

[0030]

[Chemical 15]

Specific examples of the phenols that can be used as the raw material component of the phenol resin include phenol, o-cresol, m-cresol, p-cresol, t-butylphenol and 2,4-.
Preferable examples include compounds selected from the group consisting of dimethylphenol, 2,6-dimethylphenol, hydroquinone, catechol, methylhydroquinone, pyrogallol, and mixtures thereof. Particularly, the characteristics of the obtained resin, easiness of purification or From the economical point of view, it is preferable to use phenol, cresols, xylenols, and polyphenols (which may contain a substituent). Further, naphthols can be used instead of the above phenols.

The unsaturated hydrocarbon which can be used as the other raw material component of the phenol resin has 5 to 1 carbon atoms having at least two carbon-carbon double bonds.
It is not particularly limited as long as it is an unsaturated hydrocarbon of 6, but for example, chain conjugated diene compounds such as butadiene, isoprene and piperylene; cyclic conjugated diene compounds such as cyclopentadiene and methylcyclopentadiene; α
-The Diels-Alder reaction product of a compound selected from the group consisting of cyclic terpenes such as terpinene, β-terpinene, and limonene, and a mixture thereof can be preferably mentioned. Specifically, for example, the following chemical formula 16
Compounds represented by Chemical Formulas 28 to 28 are preferable, and compounds represented by Chemical Formula 19 below are particularly preferable.

[0033]

[Chemical 16]

[0034]

[Chemical 17]

[0035]

[Chemical 18]

[0036]

[Chemical 19]

[0037]

[Chemical 20]

[0038]

[Chemical 21]

[0039]

[Chemical formula 22]

[0040]

[Chemical formula 23]

[0041]

[Chemical formula 24]

[0042]

[Chemical 25]

[0043]

[Chemical formula 26]

[0044]

[Chemical 27]

[0045]

[Chemical 28]

The Diels-Alder reaction product is
All of them are intermediate raw materials or by-products of the production plant of 5-ethylidene norbornene, which is the third component of EPDM (ethylene propylene diene methylene rubber), and are compounds that can be obtained industrially at low cost.

As the unsaturated hydrocarbon, a cyclic diene compound such as cyclopentadiene or methylcyclopentadiene may be used alone or in combination of two or more kinds.

The ratio of the phenols and the unsaturated hydrocarbons charged is preferably 0.8 to 12 times the molar equivalent of the phenols with respect to the unsaturated hydrocarbons,
More preferably, it is 1 to 8 times the molar equivalent. If the charging ratio of phenols is less than 0.8 times the molar equivalent, homopolymerization of unsaturated hydrocarbons will occur simultaneously, and if it is more than 12 times the molar equivalents, much labor will be required to recover unreacted phenols. It is not preferable.

Specific examples of the Lewis acid catalyst used in the production of the phenolic resin include boron trifluoride; boron trifluoride ether complex, water complex, amine complex, phenol complex or alcohol complex. Boron fluoride complex; aluminum compounds such as aluminum trichloride and diethylaluminum monochloride; iron chloride;
Titanium tetrachloride, sulfuric acid, hydrogen fluoride, trifluoromethanesulfonic acid and the like can be preferably used, and in particular, boron trifluoride, boron trifluoride / ether complex, and trifluoride from the viewpoint of activity and easy removal of the catalyst. Boron fluoride / phenol complex, boron trifluoride / water complex, boron trifluoride / alcohol complex, boron trifluoride / amine complex are preferable,
Further, boron trifluoride and boron trifluoride / phenol complex are most preferable.

The amount of the Lewis acid catalyst used is not particularly limited and varies depending on the catalyst used. For example, in the case of boron trifluoride / phenol complex, it is 0.1-20 per 100 parts by weight of unsaturated hydrocarbon. Parts by weight, preferably 0.5-
10 parts by weight.

To prepare the phenolic resin, the reaction can be carried out with or without a solvent,
When the solvent is not used, the above phenols are equivalent or more,
It is preferable to use 3 to 12 times equivalent amount. The solvent that can be used when preparing the phenol resin is not particularly limited as long as it does not inhibit the reaction, but particularly preferable solvents are aromatic carbonization such as benzene, toluene and xylene. Examples thereof include hydrogen compounds.

The polymerization temperature at the time of producing the above-mentioned phenol resin varies depending on the kind of the Lewis acid catalyst used, but when boron trifluoride / phenol complex is used, it is generally 20 to 170 ° C., preferably 50 to 170 ° C. It is 150 ° C. When the reaction temperature exceeds 170 ° C, the catalyst is decomposed or a side reaction occurs, and when it is less than 20 ° C, the reaction is delayed and it is economically disadvantageous, which is not preferable.

In the production of the above-mentioned phenol resin, it is preferable to reduce the water content in the system as much as possible in order to make the reaction proceed smoothly.
It is preferable to keep m or less. Furthermore, when reacting the unsaturated hydrocarbon and the phenols, a method of performing polymerization while sequentially adding the unsaturated hydrocarbon,
This is a preferred method because it allows the reaction to proceed smoothly, prevents the unsaturated hydrocarbon from homopolymerizing, and removes the heat of reaction.

After completion of the copolymerization reaction of the phenols and the unsaturated hydrocarbon, after removing the Lewis acid catalyst,
A phenol resin can be obtained by concentrating. The method for removing the Lewis acid catalyst varies depending on the type of the catalyst used, but in the case of boron trifluoride / phenol complex, 1 to 10 times the molar amount of calcium hydroxide, magnesium hydroxide or the like is added. Then, after deactivating the catalyst, the catalyst can be filtered. At the time of filtration, it is desirable to improve workability by adding a solvent or performing a treatment such as raising the temperature of the filtrate.

In preparing the quinonediazide-modified phenolic resin (1) used in the present invention, the charging ratio of the quinonediazide compound to the phenolic resin is 0.1 to 0.1% of the quinonediazide compound per one hydroxyl group of the phenolic resin. The molar equivalent is 1.0 times, preferably 0.3 to 1.0 times. When the charged amount is 0.1 to 1.0 times the molar equivalent, sufficient sensitivity as a photosensitive resist cannot be obtained.

The reaction conditions for reacting the quinonediazide compound with the phenol resin are as follows: in the presence of an inert organic solvent capable of dissolving both and a base, the reaction temperature is usually 10 to 80 ° C., preferably 20 to At 60 ° C., the reaction time is usually 10 minutes to 50 hours, preferably 1 to 15 hours. Preferred examples of the inert organic solvent that can be used in this case include dioxane, acetone, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, xylene and the like. Further, as the base,
Preferable examples include alkali metal salts such as sodium carbonate, sodium hydroxide, potassium hydroxide and potassium carbonate; amines such as triethylamine, triethanolamine, tributylamine, dimethylbenzylamine and pyridine.

After completion of the reaction, the salt produced as a by-product of the reaction is removed by filtration, and then the reaction solution is dropped into a large amount of pure water to precipitate the quinonediazide phenol resin (1). It can be purified by further washing with water several times, filtering, and drying.

In the positive type photosensitive resin composition of the present invention, the alkali-soluble resin (2) used as the other essential component is not particularly limited as long as it is a resin having solubility in alkali, but specifically Can preferably include, for example, a resin having a phenolic hydroxyl group, a resin having a carboxyl group, and the like. In particular, when the resin having a carboxyl group is applied to the substrate with the positive photosensitive resin composition, electrodeposition coating is performed. It is preferable because the method can be used.

Preferred examples of the resin having a phenolic hydroxyl group include novolac phenol resin, bisphenol A type phenol resin, polyvinylphenol resin and the like.

As the resin having a carboxyl group, a (meth) acrylic resin obtained by copolymerizing acrylic acid and / or methacrylic acid with a monomer having an ethylenically unsaturated bond; maleic acid, maleic anhydride Preferable examples include maleic acid-based copolymers obtained by copolymerizing an acid, fumaric acid or a mixture thereof with a monomer having an ethylenically unsaturated bond; maleated polybutadiene and the like.

In the (meth) acrylic resin or the maleic acid copolymer, the monomer having an ethylenically unsaturated bond used as a raw material component is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, Butyl methacrylate, 2-ethylhexyl acrylate,
Alkyl (meth) acrylates such as 2-ethylhexyl methacrylate; aromatic compounds having an ethylenically unsaturated bond such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene; α-olefins such as ethylene and propylene; butadiene; A diene compound such as isoprene can be preferably used.

The (meth) acrylic resin or the maleic acid copolymer can be produced by a known polymerization method using an ordinary radical polymerization initiator. Examples of the polymerization initiator include peroxides such as benzoyl peroxide, t-butyl oxide and cumene hydroperoxide, azo compounds such as azobisisobutyronitrile and azobiscyanovaleric acid, potassium persulfate and ammonium persulfate,
Preferable examples include inorganic radical initiators such as hydrogen peroxide.

The amount of each raw material monomer charged in producing the (meth) acrylic resin or the maleic acid copolymer is not particularly limited, and is required for the positive photosensitive resin composition. Although it can be appropriately selected depending on the acid value, for example, in the case of (meth) acrylic resin, 100 to 20 parts by weight of acrylic acid and / or methacrylic acid is usually added to a monomer having an ethylenically unsaturated bond in an amount of 100 to 20.
It is desirable that the amount is 00 parts by weight, preferably 150 to 1500 parts by weight. On the other hand, in the case of a maleic acid-based copolymer, 100 to 2000 parts by weight of a monomer having an ethylenically unsaturated bond is usually added to 100 parts by weight of the maleic acid, maleic anhydride, fumaric acid or a mixture thereof, preferably 150 to It is preferably 1500 parts by weight.

When the maleic acid-based copolymer is used as the alkali-soluble resin (2), the compatibility with the quinonediazide phenol resin (1) is improved, the softening point of the coating film is increased, and the acid value is further increased. For the purpose of adjusting, a part of the acid anhydride group and / or dicarboxyl group possessed by the maleic acid-based copolymer can be used after alcohol addition, water addition and / or imidization, in which case imidization, alcohol When all the reactions of addition and water addition are performed, the order of each reaction is not particularly limited. Here, the acid anhydride group is
The ring is easily opened by water to become a dicarboxyl group, and the dicarboxyl group is easily dehydrated by heating to become an acid anhydride group.

In the imidization, a primary amine compound, for example, an amine compound containing an aromatic ring such as aniline, benzylamine, 4-methylbenzylamine and 1-aminoindene is reacted with the maleic acid copolymer. The reaction temperature is usually 0 to 300 ° C, preferably 50 to 200 ° C.

The imidization ratio of the acid anhydride group and / or dicarboxyl group by the imidization reaction can be appropriately selected according to the acid value required for the alkali-soluble resin (2), the softening point of the coating film, and the like. For example, usually 0.1 to 0.8, preferably about 0.2 to 0.7, may be imidized per one acid anhydride group and / or dicarboxyl group of the maleic acid-based copolymer.

For the alcohol addition, for example, alcohols such as methanol, ethanol, propanol, butanol and benzyl alcohol and / or cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and phenyl cellosolve are reacted with the maleic acid copolymer. It can be done by, for example. The reaction temperature of the alcohol addition reaction is usually 0 to 300 ° C., preferably 5
It is 0 to 200 ° C.

The proportion of alcohol added by the alcohol addition reaction can be appropriately selected according to the acid value required for the desired alkali-soluble resin (2), and for example, the acid anhydride contained in the maleic acid-based copolymer. Usually, 0.1 to 1.2, preferably 0.2 to 1.0 alcohol is added to each group and / or dicarboxyl group.

The imidization reaction and alcohol addition reaction are preferably carried out using a solvent which has no reactivity with each reaction component and dissolves each reaction component.
Examples of the solvent that can be used at this time include aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate; hydroxyl groups such as diethylene glycol dimethyl ether and triethylene glycol dimethyl ether. Ethers that do not have; 3 such as diacetone alcohol
Preferred examples thereof include secondary alcohols.

The above-mentioned water addition is an addition reaction in which the acid anhydride group is opened by adding water. However, water produced by imidization or alcohol addition without addition of water, It is also possible to use water added during the water dispersion described below. By the water addition reaction, all the remaining acid anhydride groups can be ring-opened to form carboxyl groups.

As the maleated polybutadiene that can be used as a resin having a carboxyl group, maleated polybutadiene and the like produced by a known method, particularly the method described in Japanese Patent Publication No. 46-11195 and the like are preferable. Can be used, and specifically, for example,
The molecular weight is usually 300 to 30,000, preferably 500.
To 50,000, iodine value is usually 50 to 500, preferably 100 to 470, and maleic acid or maleic anhydride is added to polybutadiene having a carbon-carbon double bond, usually 0.0 per 100 g of the polybutadiene.
Maleated polybutadiene reacted with 5 to 0.7 mol, preferably 0.1 to 0.5 mol can be preferably mentioned. At this time, the reaction for adding maleic acid, maleic anhydride or the like to polybutadiene is usually 100 to 3
Can be done by mixing at a temperature of 00 ° C,
Further, in order to prevent gelation during the reaction, phenylenediamines, pyrogallols, naphthols and the like can be added to the reaction system, if necessary.

If necessary, the maleated polybutadiene can be imidized, alcohol-added and / or water-added in the same manner as the maleic acid-based copolymer. At this time, the imidization ratio or the alcohol addition ratio can be appropriately selected according to the acid value required for the alkali-soluble resin (2), the softening point of the coating film, and the like. The acid anhydride group and / or succinic acid unit possessed by polybutadiene is usually 0.
1-0.8, preferably 0.2-0.7, may be imidized. In addition, for example, in the case of alcohol addition, usually 0.1 to 1.2, preferably 0.2 to 1.0 alcohol is added per acid anhydride group and / or succinic acid unit of the maleated polybutadiene. do it.

The number average molecular weight of the alkali-soluble resin (2) used as an essential component in the present invention is 500 to
10,000 is preferred. When the number average molecular weight is less than 500, the strength of the protective layer is low, and when it exceeds 10,000, the solubility of the light-irradiated portion in the developer is deteriorated, which is not preferable.

The acid value of the alkali-soluble resin (2) is preferably 40 to 250 mgKOH / g. If the acid value is less than 40 mgKOH / g, the solubility of the light-irradiated portion in the developing solution will be poor, and if it exceeds 250 mgKOH / g, the non-irradiated portion will also be dissolved in the developing solution, which is not preferable.

In the positive photosensitive resin composition of the present invention, the mixing ratio of the quinonediazide phenol resin (1) and the alkali-soluble resin (2) used as essential components is 100 parts by weight of the alkali-soluble resin (2). On the other hand, the quinonediazide-modified phenol resin (1) is usually 5 to
It is 100 parts by weight, preferably 10 to 50 parts by weight. The compounding ratio of the quinonediazide phenol resin (1) is 5
When the amount is less than weight part, the amount of carboxylic acid generated in the light irradiation part decreases, and development with a weak alkaline developer becomes difficult,
If it exceeds 100 parts by weight, cracking of the coating film is likely to occur, which is not preferable.

To use the positive type photosensitive resin composition of the present invention, for example, the positive type photosensitive resin composition is dissolved in a solvent and then coated on a substrate to form a positive type photosensitive coating film. It can be used by forming the film, then exposing the resulting film through a predetermined pattern mask, exposing it, and developing it. Solvents that can be used at this time include alcohols such as ethyl cellosolve, propyl cellosolve, butyl cellosolve and diacetone alcohol; ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone. Preferable examples thereof include esters such as ethoxyethyl acetate and phenoxyethyl acetate; amides such as methylpyrrolidone and dimethylformamide. Further, as a method for coating on the substrate, there are methods such as screen printing, spray coating, dip coating and spinner. In particular, the method using a spinner is suitable for manufacturing integrated circuits because the film thickness can be reduced and a resist having high sensitivity and excellent adhesion to a substrate can be obtained.

In the positive photosensitive resin composition of the present invention, when a resin containing a carboxyl group is used as the alkali-soluble resin (2), it is neutralized with an alkali and dispersed or dissolved in water. It can be applied as a positive type photosensitive resin aqueous solution onto the metal layer by dip coating or electrodeposition coating. At this time, the neutralization method is not particularly limited, but is usually 0.2 to 1.0 molar equivalent, preferably 0.3 to 0.8, with respect to the carboxyl group in the positive photosensitive resin composition. A method of adding a molar equivalent of an organic amine such as trimethylamine, triethylamine, dimethylethanolamine and the like to neutralize is usually used, and the neutralization temperature is not particularly limited, and it can be usually performed at 0 to 120 ° C. Is most preferred.

For the purpose of further facilitating the dispersion and dissolution in water by the above neutralization and improving the stability of the resulting aqueous solution and dispersion, the positive photosensitive resin composition which is water-soluble can be dissolved. It is also possible to add an organic solvent. Examples of the organic solvent include ethyl cellosolve, propyl cellosolve, butyl cellosolve, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diacetone alcohol, and methyl ethyl ketone. At this time, the mixing ratio of the organic solvent is usually 10 to 1 with respect to 100 parts by weight of the positive photosensitive resin composition.
It is preferably 00 parts by weight, preferably 20 to 80 parts by weight. Further, a hydrophobic organic solvent which is hydrophobic and can dissolve the positive photosensitive resin composition can be added for the purpose of improving the flowability during drying after electrodeposition. As the hydrophobic organic solvent, hexyl cellosolve, phenyl cellosolve, propylene glycol monophenyl ether, acetophenone, acetonaphthone, benzylacetone, benzyl acetate, methyl benzoate, ethyl benzoate, butyl benzoate, cyclohexanone, phenoxyethyl acetate and the like are preferable. Can be mentioned. At this time, the blending ratio of the hydrophobic organic solvent is usually 10 to 100 relative to 100 parts by weight of the positive photosensitive resin composition.
It is preferable that the amount is 15 parts by weight, preferably 15 to 80 parts by weight.

In the positive photosensitive resin composition of the present invention, in order to form an image using the positive photosensitive resin aqueous solution dispersed or dissolved in water, for example, first, the positive photosensitive resin aqueous solution is charged. It is used as a liquid for coating and is applied on the substrate by an electrodeposition coating method. Next, the formed positive type photosensitive coating film can be exposed to light through a predetermined pattern mask and then developed.

The electrodeposition coating method is carried out, for example, by immersing the substrate in which the entire surface of the substrate including through holes is coated with a conductive metal layer as an anode, immersing it in an electrodeposition solution, and applying a direct current. You can

The film thickness of the positive type photosensitive coating film can be easily controlled by the liquid temperature, the energizing time, the current density, etc., and can be set to an appropriate film thickness according to the purpose. Specifically, for example, as the electrodeposition conditions for obtaining a standard film thickness of 5 to 20 μm, the liquid temperature is 25 ° C. and the energization time is 0.05 to 10
The current density is 0.1 to 5.0 mA / cm ² (constant current).

After electrodeposition coating, the substrate is pulled up from the electrodeposition liquid, washed with water and dried. The drying temperature at this time is 50 to 12
0 ° C is preferred. If the temperature is lower than 50 ° C., it is not dried sufficiently, and if the temperature is higher than 120 ° C., decomposition of the quinonediazide group occurs, which is not preferable.

The light source that can be used for the exposure is not particularly limited as long as it can irradiate active rays such as ultraviolet rays. For example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, etc. are preferable. Can be used.

Further, the development can be carried out by spraying a weak alkaline aqueous solution with a spray, dipping in a weak alkaline aqueous solution, or the like. The weak alkaline aqueous solution is not particularly limited as long as it dissolves the exposed part and does not dissolve the unexposed part, and examples thereof include sodium carbonate, potassium carbonate, sodium metasilicate, and potassium metasilicate.
Examples thereof include sodium hydroxide, potassium hydroxide, aqueous ammonia, tetramethylammonium hydroxide, and the like, and the hydrogen ion concentration is usually pH 8 to 1
It is preferably about 3.

In the case of a normal printed wiring board, the copper foil portion exposed on the substrate is then etched with cupric chloride, ferric chloride or the like, and finally with a strong alkali such as sodium hydroxide or potassium hydroxide. A circuit pattern can be obtained by peeling off the positive photosensitive coating film in the exposed area.

[0086]

The positive-type photosensitive resin composition of the present invention is easy to purify, and has good compatibility with the alkali-soluble resin (2) regardless of the solvent, and is a quinonediazide phenol resin (1). Since it is used as a photosensitive component, it has high sensitivity. Furthermore, when a resin having a carboxylic acid group is used as the alkali-soluble resin (1), the positive photosensitive resin composition is particularly suitable for the electrodeposition coating method. Further, the electrodeposited positive photosensitive resin coating film has excellent adhesion to the substrate, can form a fine wiring pattern, and exhibits excellent long-term stability when used as an electrodeposition liquid.

[0087]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

[0088]

[Synthesis Example 1] Synthesis of phenol resin (F-1) 1500 g of phenol and 300 g of toluene were charged into a 5 liter reactor equipped with a reflux condenser and a Liebig condenser, heated to 170 ° C., and 250 g of toluene.
Was distilled off, and the water content in the system was adjusted to 60 ppm. Next, the reaction system was cooled to 80 ° C., 12 g of boron trifluoride / phenol complex was added, and then 300 g of dicyclopentadiene having a water content of 20 ppm while controlling the reaction temperature to 80 ° C.
Was gradually added dropwise over 2.5 hours. 80 ℃ after dropping
The reaction was carried out for 0.5 hours. After completion of the reaction, magnesium compound manufactured by Kyowa Chemical Industry Co., Ltd., trade name "KW-1000"
After adding 36 g and stirring for 30 minutes to deactivate the catalyst, the reaction liquid was filtered using a filter paper covered with Celite. The resulting clear filtrate was distilled under reduced pressure at 240 ° C. to give 5 parts of phenol resin (F-1) represented by the following general formula 29.
60 g was obtained. The results of various analyzes are shown below.

[0089]

[Chemical 29]

The softening point of the obtained phenol resin (F-1) was 96 ° C. Further, the content of phenolic hydroxyl groups was acetylated with acetic anhydride and then determined by back titration to find that the equivalent of phenolic hydroxyl groups was 173 g / eq.

In ¹ H-NMR analysis, δ 6.5-7.5.
Protons bound to the aromatic ring in ppm, again δ 0.8 ~
The proton of the naphthene ring was observed at 2.5 ppm, and the absorption of the proton bound to the double bond was not observed. Further, in ¹ H-NMR analysis, δ 6.5 to 8 ppm and δ
When the content of the phenolic hydroxyl group was determined from the peak area ratio of 0.8 to 2.5 ppm, the phenolic hydroxyl group equivalent was 173 g / eq, which was the same as the result of the titration. Further, in the ¹³ C-NMR analysis, a signal of 158 ppm of carbon generated when phenol was ether-added to the double bond was not observed, which shows that all the phenols are added by alkylation. Further, the number average molecular weight of this resin was determined by GPC analysis to be 430.

[0092]

[Synthesis Example 2] Synthesis of phenol resin (F-2) Except that 1600 g of o-cresol was used instead of phenol, the reaction was performed in the same manner as in Synthesis Example 1 and the phenol resin (F -2) 560 g was obtained.

[0093]

[Chemical 30]

The obtained phenol resin (F-2) had a softening point of 92 ° C. and a phenolic hydroxyl group equivalent determined by titration was 187 g / eq. ^{In 1} H-NMR analysis, absorption of protons bound to the double bond was not observed. Further, when the content of the phenolic hydroxyl group was determined from the peak area ratio, the phenolic hydroxyl group equivalent was 187 g / eq, which was the same as the result of the titration. Further GP
When the number average molecular weight of this resin was determined by C analysis, it was 4
It was 70.

[0095]

[Synthesis Example 3] Synthesis of phenol resin (F-3) 1600 g of phenol and 300 g of toluene were charged into a 5 liter reactor equipped with a reflux condenser and a Liebig condenser, heated to 170 ° C, and 250 g of toluene.
Was distilled off and the water content in the system was adjusted to 70 ppm. Next, the reaction system was cooled to 80 ° C., 28 g of boron trifluoride / phenol complex was added, and 400 g of tetrahydroindene having a water content of 20 ppm was gradually added dropwise over 2 hours while controlling the reaction temperature at 80 ° C. After completion of the dropping, the reaction was carried out at 140 ° C. for 3 hours, and after completion of the reaction, a magnesium compound manufactured by Kyowa Chemical Industry Co., Ltd., trade name “KW-1000” 78.
g was added, the catalyst was deactivated by stirring for 30 minutes, and then the reaction solution was filtered using a filter paper covered with Celite. The obtained transparent filtrate was distilled under reduced pressure at 230 ° C. to obtain 410 g of a phenol resin (F-3) represented by the following general formula 31.

[0096]

[Chemical 31]

The softening point of the obtained phenol resin (F-3) was 105 ° C. In addition, phenol resin (F-
The hydroxyl equivalent of 3) was 195 g / eq.

[0098]

[Synthesis Example 4] Synthesis of Phenolic Resin (F-4) The reaction was performed in the same manner as in Synthesis Example 3 except that vinylcyclohexene was used instead of tetrahydroindene, and the phenol resin (F- 4) 39
0 g was obtained.

[0099]

[Chemical 32]

The phenol resin (F-4) thus obtained had a softening point of 104 ° C. and a phenolic hydroxyl group equivalent of 196 g.
It was / eq.

[0101]

[Synthesis Example 5] Synthesis of phenol resin (F-5) Except that vinyl norbornene was used instead of tetrahydroindene, the reaction was performed in the same manner as in Synthesis Example 3, and the phenol resin (F- 5) 380
g was obtained.

[0102]

[Chemical 33]

The phenol resin (F-5) thus obtained had a softening point of 109 ° C. and a phenolic hydroxyl group equivalent of 200 g.
It was / eq.

[0104]

[Synthesis Example 6] Synthesis of phenol resin (F-6) The reaction was performed in the same manner as in Synthesis Example 3 except that 300 g of a Diels-Alder reaction product of butadiene and dicyclopentadiene was used in place of dicyclopentadiene, and the following reaction was performed. 560 g of a mixture (F-6) of the phenol resin represented by the general formulas 34 and 35 was obtained.

[0105]

[Chemical 34]

[0106]

[Chemical 35]

The copolymer (F-6) thus obtained had a softening point of 110 ° C. and a phenolic hydroxyl group equivalent of 205 g / eq.
Met.

[0108]

[Synthesis Example 7] The reaction was performed in the same manner as in Synthesis Example 1 except that catechol was used instead of phenol to obtain 560 g of a phenol resin (F-7) represented by the following general formula 36.

[0109]

[Chemical 36]

The obtained phenol resin (F-7) had a softening point of 115 ° C. and a phenolic hydroxyl group equivalent of 94 g / e.
It was q.

[0111]

[Synthesis Example 8] Polybutadiene (manufactured by Nippon Petrochemical Co., Ltd.,
Product name "B-1000", number average molecular weight 1000, iodine value 430, 1,2 bond 65%) 1000 g, maleic anhydride 751 g, "Antigen 6
C "(Sumitomo Chemical Co., Ltd., trade name) 5.0 g and xylene 10 g, equipped with a reflux cooling pipe and a nitrogen blowing pipe 3
Charge in a liter separable flask, under a nitrogen stream,
The reaction was carried out at 190 ° C for 5 hours. Then, unreacted maleic anhydride and xylene were distilled off to obtain a maleated polybutadiene polymer.

The total acid value of the obtained maleated polybutadiene polymer was measured and found to be 480 mgKOH / g. Then, 500 g of maleic polybutadiene having a total acid value of 480 mg KOH / g and 250 g of diethylene glycol dimethyl ether were charged into a 2 liter separable flask equipped with a reflux condenser and uniformly dissolved, and then benzylamine 148 g of 30 was added at 130 ° C. under a nitrogen stream. Dropped in minutes. After completion of the dropping, the solution was heated to 165 ° C., and the reaction was continued for 7 hours while maintaining the same temperature to obtain an alkali-soluble resin solution containing a dicarboxyl group and an imide group. The obtained resin solution had a nonvolatile content of 72% by weight and had 169 mg equivalent of carboxyl groups per 100 g of the solution.

[0113]

[Synthesis Example 9] In a 5-liter separable flask equipped with a reflux condenser, 1,2-naphthoquinonediazide-5-sulfonyl chloride (269 g), dioxane (1900 g) and the phenol resin (F-1) 216 synthesized in Synthesis Example 1 were mixed.
After g was charged and dissolved, 101 g of triethylamine was added dropwise over 2 hours while maintaining the temperature at 30 ° C.

The reaction was continued for 5 hours while maintaining the temperature at 30 ° C., and after confirming the disappearance of 1,2-naphthoquinonediazide-5-sulfonyl chloride by TLC, the hydrochloride of triethylamine was removed by filtration, and the reaction solution was diluted 20 times. The amount of pure water was added dropwise to precipitate the resin. The obtained resin was filtered, washed with water, and dried to obtain a naphthoquinonediazide-modified phenol resin (N-1) represented by the following general formula 37.

[0115]

[Chemical 37]

By IR analysis of the obtained resin, 2166c
m- ^1, 2120cm- ¹ sharp peak caused by diazide groups are observed two on, the peak attributable to the phenol OH was reduced. When the naphthoquinonediazide group was analyzed by elemental analysis of sulfur, it was found to be 2.23 mg equivalent / g.

[0117]

[Synthesis Examples 10 to 15] Synthetic Examples 10-15 except that the phenol resins (F-1) were changed to the phenol resins (F-2) to (F-7) shown in Table 1, respectively, and the charged amounts shown in Table 1 were used. Reaction and analysis were performed in the same manner as in Example 9 to obtain quinonediazide-modified phenolic resins (N-2) to (N-7) shown in Table 1, respectively. The results are shown in Table 1.

[0118]

[Table 1]

[0119]

Example 1 111 g of the alkali-soluble resin solution synthesized in Synthesis Example 8 and the photosensitive resin (N-1) synthesized in Synthesis Example 9
After mixing 20 g and 35 g of phenoxyethyl acetate and making them compatible, triethylamine 7.5 g was added and fully neutralized. Then, deionized water was added so that the solid content was 10% by weight to obtain an electrodeposition liquid of the positive photosensitive resin composition.

Next, the copper clad laminate for printed wiring having through holes was dipped in the obtained electrodeposition solution as an anode, a direct current of ² mA / cm ² was applied for 20 seconds, and after washing with water, 100 After drying at 5 ° C. for 5 minutes, an electrodeposition coating film of a positive photosensitive resin composition having a film thickness of 7 μm was obtained. Then, through a photomask having a positive pattern, ultraviolet rays having a wavelength of 365 nm and an exposure dose of 300 mJ / cm ² were irradiated using an ultra-high pressure mercury lamp, and further 30% with a 1.0 wt% sodium carbonate aqueous solution.
Spray development was carried out at 60 ° C. for 60 seconds. The line of the obtained protective layer was the same as the line width of the pattern, and pinholes and peeling or cracking of the protective layer were not observed. Then, after etching the copper with a ferric chloride solution, the protective layer was removed by immersing the copper in 4 wt% sodium metasilicate at 40 ° C. for 60 seconds, and a circuit pattern of 30 μm was obtained, and no defects were recognized. . At this time, the copper inside the through hole was protected from the etching solution and completely remained. When the electrodeposition liquid was left at room temperature for 3 months, no resin component was precipitated and no abnormality was observed even after repeated use.

[0121]

Example 2 Acrylic resin manufactured by Toagosei Co., Ltd., trade name “S-4030” (butyl cellosolve solution, solid content concentration 60% by weight) 111 g, resin synthesized in Synthesis Example 10 (N
-2) After mixing 20 g and making them compatible, triethylamine 7.5 g was added and fully neutralized. Then, the solid content is 10
Deionized water was added so as to make the weight% to obtain an electrodeposition liquid of the positive photosensitive resin composition.

Electrodeposition, exposure and development were carried out in the same manner as in Example 1. The line of the obtained protective layer was the same as the line width of the pattern, and pinholes and peeling or cracking of the protective layer were not observed. Then, after etching in the same manner as in Example 1, when the protective layer was removed by immersing in 4 wt% sodium metasilicate at 40 ° C. for 60 seconds, a circuit pattern of 30 μm was obtained and no defects were recognized. At this time,
The copper inside the through hole was protected from the etching solution and remained completely. The electrodeposition liquid was allowed to stand at room temperature for 3 months, but no resin component was precipitated and no abnormality was observed even after repeated use.

[0123]

Examples 3 to 6 Instead of the resin (N-1), the resin (N
-3) (Example 3), Resin (N-4) (Example 4), Resin (N-5) (Example 5), Resin (N-6) (Example 6) were used, respectively. An electrodeposition solution was prepared in the same manner as in Example 1. Electrodeposition was performed using the obtained electrodeposition solution in the same manner as in Example 1, followed by exposure and development.

When any of the resins (N-3) to (N-6) was used, the line of the obtained protective layer was the same as the line width of the pattern, and pinholes and peeling or cracking of the protective layer were not observed. Not observed. Then, after etching the copper with a ferric chloride solution, 60% with 4 wt% sodium metasilicate at 40 ° C.
When the protective layer was removed by immersing for 2 seconds, a circuit pattern of 30 μm was obtained, and no defect was recognized. At this time, in any case, the copper inside the through hole was protected from the etching solution and completely remained. In addition, 3 times this electrodeposition solution
After being left at room temperature for a month, none of the resin components precipitated, and no abnormality was observed even after repeated use.

[0125]

Example 7 Novolac phenolic resin (hydroxyl equivalent 1
10) 80 g, resin (N-1) 20 synthesized in Synthesis Example 9
g and 100 g of diethylene glycol dimethyl ether
Are mixed and made compatible with each other, and then coated on a silicon oxide film wafer using a spinner and then dried at 100 ° C. for 5 minutes to obtain a coating film of a positive photosensitive resin composition having a film thickness of 2 μm. It was

Then, through a photomask having a positive pattern, ultraviolet rays having a wavelength of 365 nm and an exposure amount of 100 mJ / cm ² were irradiated using an ultrahigh pressure mercury lamp, and the temperature was raised to 23 ° C. at 2.
When developed by immersing in a 38 wt% tetramethylammonium hydroxide aqueous solution for 70 seconds, 1.0
A protective layer having a line with a width of μm was obtained, and pinholes and peeling or cracking of the protective layer were not observed.

[0127]

Example 8 Novolac phenolic resin (hydroxyl equivalent 1
10) 80 g, Resin (N-7) 1 synthesized in Synthesis Example 15
After mixing 2 g and 200 g of ethyl cellosolve and making them compatible with each other, they were coated on a silicon oxide film wafer using a spinner and then dried at 100 ° C. for 5 minutes to give a film thickness of 1
A coating film of the positive photosensitive resin composition having a thickness of μm was obtained.

Then, through a photomask having a positive pattern, ultraviolet rays having a wavelength of 365 nm and an exposure amount of 70 mJ / cm ² were irradiated using an ultrahigh pressure mercury lamp, and the temperature was 2.3 ° C. at 2.3 ° C.
When development was performed by immersing in an 8 wt% tetramethylammonium hydroxide aqueous solution for 70 seconds, 1.
A protective layer of 0 μm wide lines was obtained.

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[Procedure amendment]

[Submission date] May 10, 1993

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[Chemical 11]

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location H05K 3/00 F 6921-4E

Claims (1)

[Claims] 1. A positive photosensitive resin composition comprising (a) a quinonediazide-modified phenol resin represented by the following general formula 1 and (b) an alkali-soluble resin as essential components. [Chemical 1]