JP2824191B2 - Positive electrodeposited photoresist composition and method for producing resist pattern - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a positive electrodeposition photoresist composition and a method for producing a resist pattern using the same.

[0002]

2. Description of the Related Art As the density of circuit patterns on printed wiring boards is increased and the diameter of through holes is reduced, it is desired to improve the resolution of circuit patterns and the reliability of forming through holes. For this purpose, positive electrodeposition photoresists have received attention.

At present, a positive electrodeposition photoresist composition comprises a resin which is dissolved or dispersed in water by neutralization,
Neutralizing a composition combining a quinonediazide compound as a photosensitizer and dissolving or dispersing it in water, or dissolving or dispersing in water the same resin as described above in which a quinonediazide compound is chemically bonded to a resin. Proposed.

This composition utilizes a reaction in which a naphthoquinonediazide group is photolyzed by irradiation with ultraviolet rays to form indenecarboxylic acid via ketene.

However, this quinonediazide type product has low photosensitivity and a long exposure time, resulting in poor work efficiency. In addition, quinonediazide groups have poor stability in aqueous systems and are not preferably used for electrodeposition resists that require long-term liquid stability.

The principle of development utilizes the difference in solubility between exposed and unexposed areas. In an electrodeposited photoresist, the film-forming component itself is an aqueous solution of a basic compound which is essentially a developer. The development conditions are delicate due to dissolution or dispersion in the toner, and strict control of the development conditions is required to obtain good reproducibility. In addition, it is inevitable that the resist film in the unexposed portion partially dissolves or swells, and has disadvantages such as a decrease in the resistance of the formed pattern to an etchant and a decrease in the accuracy of the formed pattern.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a positive electrodeposition photoresist based on a novel principle which has solved the above-mentioned drawbacks of the conventional positive electrodeposition photoresist using a quinonediazide compound as a photosensitive agent. An object of the present invention is to provide a composition and a method for producing a resist pattern using the composition.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies on a method for overcoming the above-mentioned disadvantages of the positive-type photosensitive electrodeposition composition. As a result, the present inventors have found that a polymer containing a carboxyl group and a hydroxyphenyl group have been developed. An electrodeposition composition comprising a polymer containing, a polyvinyl ether compound and a compound which decomposes upon irradiation with active energy rays to generate an acid, is heated when the electrodeposition coating film formed therefrom is heated to a carboxyl group and / or
Alternatively, it is cross-linked by an addition reaction between a hydroxyphenyl group and a vinyl ether group, becomes insoluble in a solvent or an aqueous alkali solution, and is further irradiated with active energy rays, and when heated after irradiation, the cross-linked structure is formed by the catalytic action of the generated acid. The present inventors have found that a photosensitive electrodeposition composition that functions by a completely novel mechanism that is cut and the irradiated portion becomes soluble again in a solvent or an aqueous alkaline solution has been completed, thereby completing the present invention.

Thus, the present invention relates to A) a polymer containing a carboxyl group, B) a polymer containing a hydroxyphenyl group, and C) a compound containing at least two or more vinyl ether groups in one molecule. And the total amount of B) 10
5 to 150 parts by weight based on 0 parts by weight, and D) 0.1 to 40 parts by weight based on 100 parts by weight of the total amount of the compounds A), B) and C) which generate an acid upon irradiation with active energy rays. A) / B) = 90/10
10/90 (weight ratio), and the mixture of A) to D) has a carboxyl group content of 0.5 to 5.0 equivalents per kg of the mixture and a hydroxyphenyl group content of 0.5 to 7.0. A positive electrodeposition photoresist composition characterized by neutralizing a composition having 0 equivalents with a basic compound and dissolving or dispersing the composition in water, and a method for producing a pattern using the same. .

That is, according to the composition of the present invention, the unexposed portion is completely insolubilized in a developer used for development by forming a crosslinked structure, and the unexposed portion completely dissolves and swells during development. Therefore, there is no problem such as that in the conventional positive electrodeposition resist described above.

Further, the composition of the present invention does not require the use of a large amount of a functional group having a high extinction coefficient unlike a resist using quinonediazide as a photosensitizing agent, so that the transparency to active energy rays can be increased. Further, the acid generated in the irradiated portion acts as a catalyst at the time of heating and cuts the crosslinked structure in a chain, so that the sensitivity can be increased.

Further, the pattern formed by the composition of the present invention has an extremely high contrast, and is therefore very useful as a resist for a fine pattern.

Since the composition of the present invention does not contain an unstable group in an aqueous system such as quinonediazide, it is extremely stable in an aqueous system and is required to have a long-term liquid stability. Has extremely excellent properties as a resist composition,
For a long period of time, a resist film can be formed stably and highly reliably by an electrodeposition coating method.

Hereinafter, the present invention will be described in more detail.

A) Polymer Containing Carboxyl Group The present polymer A) is a film-forming polymer containing at least one carboxyl group in one molecule, and is, for example, a polymerizable unsaturated polymer containing a carboxyl group. Monomer homopolymer, copolymer of the carboxyl group-containing monomer and another copolymerizable monomer, polyester, polyurethane, polyamide having a carboxyl group in the molecular chain or at the molecular terminal And the like.

Examples of the polymerizable unsaturated monomer containing a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, and itaconic acid, and are copolymerizable with these carboxyl group-containing monomers. Examples of other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
(Meth) acrylic acid such as butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, and decyl (meth) acrylate Alkyl esters having 1 to 12 carbon atoms; hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the like. Meta)
Hydroxyalkyl esters of acrylic acid having 2 to 6 carbon atoms; vinyl aromatic compounds such as styrene, α-methylstyrene and p-tert-butylstyrene; vinyl acetate, (meth) acrylonitrile, (meth) acrylamide, vinylpyrrolidone and the like. These monomers may be used alone or in combination of two or more.

In particular, styrene, α-
Use of a vinyl aromatic compound such as methyl styrene or an alkyl-substituted styrene having 1 to 6 carbon atoms (for example, p-tert-butylstyrene) can reduce the accuracy of an image pattern to be formed and the etching resistance. It is suitable.

The carboxyl group-containing polymer A) preferably has a number average molecular weight generally in the range of about 3,000 to about 100,000, especially about 5,000 to about 30,000, The content of the carboxyl group is generally 0.5 to 10 equivalents, preferably 0.5 to 5 equivalents per kg of the polymer.
It is desirable to be within the range of 0 equivalents. When the content of the carboxyl group is less than 0.5 equivalent / kg, the degree of crosslinking of the film formed by heating before irradiation with actinic light is not sufficient, and the solubility of the exposed portion in an alkaline developing solution is low and the developing property is low. And the water solubility or dispersibility of the composition becomes insufficient, and the liquid stability of the composition becomes insufficient. On the other hand, if it exceeds 10 equivalents / kg, the workability at the time of electrodeposition coating decreases, which is not preferable.

The polymer A) preferably has a glass transition temperature (Tg) of 0 ° C. or higher, particularly in the range of 5 to 70 ° C. If the Tg is lower than 0 ° C., the coating film tends to be sticky, and it is easy for dust and dirt to adhere to the film, which tends to be difficult to handle.

B) Polymer Containing Hydroxyphenyl Group The present polymer is a polymer containing at least one hydroxyphenyl group in one molecule, for example, a monofunctional or polyfunctional phenol compound, an alkylphenol compound,
Or a condensate of a mixture thereof with a carbonyl compound such as formaldehyde or acetone; a homopolymer of a hydroxy group-containing vinyl aromatic compound such as p-hydroxystyrene, or a monomer copolymerizable with the compound and another copolymerizable monomer. And the like.

The monofunctional or polyfunctional phenol compounds include phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, 2,6
-Xylenol, 2,4-xylenol, catechol,
Resorcinol, pyrogallol, bisphenol A and the like, and examples of the alkylphenol compound include, for example, p-isopropylphenol, p-tert-butylphenol, p-tert-amylphenol, p-tert-
Octylphenol and the like.

The condensation reaction of these compounds with a carbonyl compound such as formaldehyde or acetone can be carried out by a method known per se. When condensed products are condensed with an alkali catalyst, they generally become insoluble as the condensation proceeds. A meltable resol type is obtained, and when condensed with an acid catalyst, a soluble and meltable novolak type is obtained. In the present invention, the latter novolak type phenol resin is used. The molecular weight of the novolak type phenolic resin increases as the condensation proceeds. In general, a polycondensate having a molecular weight of 500 to 2,000 can be obtained by condensing it for 1 to 3 hours.

As the other monomer copolymerizable with the hydroxyl group-containing vinyl aromatic compound, other copolymerizable monomers similar to those exemplified for the copolymer in the polymer A) may be used. Can be used.

The polymers B) containing hydroxyphenyl groups are generally from about 500 to about 100,000, in particular from about 1,
It preferably has a number average molecular weight in the range of 000 to about 30,000. The content of the hydroxyphenyl group in the polymer B) is generally 1.0 per kg of the polymer.
Conveniently it is in the range from 10 to 10 equivalents, especially 2.0 to 8.0 equivalents.

When the content of the hydroxyphenyl group is less than 1.0 equivalent / kg, the degree of crosslinking of the film formed by heating before irradiation with actinic light tends to be insufficient. Tends to be brittle.

The polymer B), like the polymer A), preferably has a glass transition temperature (Tg) of 0 ° C. or higher, particularly in the range of 5 to 70 ° C. When the Tg is lower than 0 ° C., the coating film exhibits tackiness, and tends to adhere to dirt and dust and tends to be difficult to handle.

The polymer A) and the polymer B) can be used in a weight ratio of A) / B) of generally 90/10 to 10/90, and the components A), B), C), The carboxyl group and hydroxyphenyl group of each polymer are adjusted so that the carboxyl group is 0.5 to 5.0 equivalents and the hydroxyphenyl group is 0.5 to 7.0 equivalents per 1 kg of the total weight of D). Is preferably adjusted.

C) Two or more vinyl ethers in one molecule
The compounds C) are compounds containing a group of the formula -R-O-CH = CH ₂ per molecule
Wherein R represents an alkylene group having 1 to 6 carbon atoms such as an ethylene group, a propylene group or a butylene group;
Low-molecular-weight or high-molecular-weight compounds containing, for example, polyphenol compounds such as bisphenol A, bisphenol F, bisphenol S, and phenolic resins; and ethylene glycol, propylene glycol, trimethylolpropane, trimethylolethane, and pentaerythritol. Condensates of polyols and halogenated alkyl vinyl ethers such as chloroethyl vinyl ether; reaction of polyisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate with hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether Objects and the like.

Particularly, a condensate of the above-mentioned polyphenol compound and a halogenated alkyl vinyl ether and a reaction product of a polyisocyanate compound having an aromatic ring and a hydroxyalkyl vinyl ether are preferable from the viewpoints of etching resistance, precision of a formed pattern and the like. .

The compound C) is liquid at room temperature or has a melting point or softening point of 150 ° C. or lower, particularly 130 ° C. or lower, when heated before irradiation with actinic rays, and thus the polymer A) and / or the polymer B) The compound is easily migrated, and an addition reaction between the carboxyl group of the polymer A) and / or the hydroxyphenyl group of the polymer B) and the vinyl ether group of the compound C) is preferred, which is preferable.

D) Generation of acid by irradiation with active energy rays
The compounds D) compounds are decomposed by irradiation of active energy rays to be described later, sufficient to cut a crosslinked structure formed between the polymer A) and polymer B) and the compound C) It is a compound that generates a strong acid, and includes, for example, those represented by the following formula.

[0032] _{^{Ar 2 I + · X - (}} I) ( wherein, Ar represents an aryl group such as phenyl group,
X ^- is PF ₆ ^-, SbF ₆ ^- or AsF ₆ ^- represents a. )

[0033] _{^{Ar 3 S + · X - (}} II) ( wherein, Ar and X ^- is the same as defined above.)

[0034]

Embedded image (Wherein R is an alkyl group having 1 to 12 carbon atoms or 1 carbon atom)
It represents 12 alkoxy group, n represents 0 to 3, X ^-
Has the same meaning as above. )

[0035]

Embedded image (In the formula, X ⁻ has the same meaning as described above.)

[0036]

Embedded image (In the formula, X ⁻ has the same meaning as described above.)

[0037]

Embedded image (In the formula, X ⁻ has the same meaning as described above.)

[0038]

Embedded image (In the formula, X ⁻ has the same meaning as described above.)

[0039]

Embedded image

[0040]

Embedded image (Wherein, R ₁ and R ₂ each independently have 1 to 12 carbon atoms)
Represents an alkyl group or an alkoxy group having 1 to 12 carbon atoms. )

[0041]

Embedded image

[0042]

Embedded image (In the formula, R ₁ and R ₂ have the same meaning as described above.)

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

Electrodeposited photoresist composition The electrodeposited photoresist composition of the present invention comprises the carboxyl group-containing polymer A), hydroxyphenyl group-containing polymer B), vinyl ether group-containing compound C), It contains four components of the acid generating compound D) as essential components,
It is obtained by neutralizing the carboxyl group of the polymer A) with a basic compound and dissolving or dispersing it in water. The mixing ratio of these components can be varied over a wide range depending on the use of the composition. , Carboxyl group-containing polymer A)
And the hydroxyphenyl group-containing polymer in a weight ratio of A) / B) of generally 90/10 to 10/90, especially 70/30.
And the content of the vinyl ether group-containing compound C) is based on 100 parts by weight of the total amount of the carboxyl group-containing polymer A) and the hydroxyphenyl group-containing polymer B). In contrast, generally 5 to 150
It is preferably used in an amount of 10 to 100 parts by weight, and the photoacid generating compound D) is a carboxyl group-containing polymer A), a hydroxyphenyl group-containing polymer B) and a vinyl ether group-containing compound C. ) And the total amount 10
In general, 0.1 to 40 parts by weight, especially 0.1 to 40 parts by weight, is preferably used.
It is suitable to use within the range of 2 to 20 parts by weight.

A sensitizing dye may be added to the electrodeposited photoresist composition of the present invention, if necessary. Examples of the sensitizing dye that can be used include phenothiazine, anthracene, coronene, and benzanthracene. , Perylene,
Dyes such as pyrene, merocyanine, and ketocoumarin are exemplified.

The compounding amount of these sensitizing dyes ranges from 0.1 to 10 parts by weight, preferably from 0.3 to 5 parts by weight, based on 100 parts by weight of the total amount of the carboxyl group-containing polymers A) and B). Inside is appropriate.

The composition of the present invention may contain a plasticizer such as a phthalate ester, a polyester resin,
An acrylic resin or the like may be added. The addition amount is usually a polymer A), a polymer B), a vinyl ether group-containing compound C),
50 per 100 parts by weight of the total amount of the photoacid generating compound D)
It is preferable that the amount is not more than part by weight.

The composition of the present invention may further contain, if necessary, a flow regulator, a coloring agent such as a dye or a pigment.

The electrodeposited photoresist composition of the present invention is prepared by mixing the above-mentioned components as they are or, if necessary, in a solvent, neutralizing with a basic compound, and dissolving or dispersing in water. Can be prepared.

As the solvent that can be used at this time, a solvent that can dissolve the components of the composition and is soluble in water at room temperature at 10% by weight or more is preferable. For example, ketones such as acetone and methyl ethyl ketone; methanol, ethanol, normal propanol, Alcohols such as isopropanol, secondary butanol, tertiary butanol; ethylene glycol, propylene glycol or monoethers such as methanol, ethanol, butanol, etc. of diethers thereof, or glycol ethers such as methanol, ethanol, diether of propanol; dioxane, And cyclic ethers such as tetrahydrofuran. These solvents may be used alone or in combination of two or more.

These solvents are usually used in an amount of 20 parts by weight per 100 parts by weight of the total of the carboxyl group-containing polymer A), the hydroxyphenyl group-containing polymer B), the vinyl ether group-containing compound C), and the photoacid generating compound D). It is preferable that the amount is not more than part by weight.

Further, a solvent having a solubility in water of 10% by weight or less may be used as an auxiliary for adjusting the applied voltage and the film forming property at the time of electrodeposition coating described later.

These solvents include ketones such as methyl isobutyl ketone, cyclohexanone and isophorone;
Alcohols such as normal butanol, hexanol, octanol and benzyl alcohol; ethylene glycol, propylene glycol or diethers thereof such as hexanol, octanol and phenol, and monoethers such as butanol, hexanol, octanol and phenol; toluene and xylene; Aromatic hydrocarbons such as alkylbenzene; aliphatic hydrocarbons having a boiling point of 80 ° C. or higher; These solvents may be used alone or in combination of two or more.

These solvents are usually a carboxyl group-containing polymer A), a hydroxyphenyl group-containing polymer B),
It is preferably 20 parts by weight or less based on 100 parts by weight of the total amount of the vinyl ether group-containing compound C) and the photoacid generating compound D).

Examples of the basic compound used for neutralization include amines such as triethylamine, diethylamine, dimethylethanolamine and diethanolamine; and inorganic alkalis such as caustic soda and caustic potash. These basic compounds may be used alone or in combination of two or more. Usually, these basic compounds are preferably used in the range of 0.1 to 1.0 equivalent to the carboxyl group.

The method of dissolving or dispersing in water is as follows: polymer A), polymer B), vinyl ether group-containing compound C),
Water is gradually added to the mixture obtained by mixing the components such as the photoacid generating compound D), the neutralizing agent and, if necessary, the solvent described above, with stirring. A known method such as gradually adding the mixture to stirred water may be used. The solid content concentration of the composition thus obtained is not particularly limited, but is usually 0.5 to 5%.
It is preferably 0% by weight.

Pattern Formation Pattern formation using the electrodeposited photoresist composition of the present invention can be performed as described below.

First, a substrate having a conductive surface, for example,
The composition is applied onto a substrate such as a copper foil laminate for printed wiring by an electrodeposition method so as to have a dry film thickness of about 0.5 to 15 μm. In the application by the electrodeposition method, the composition according to the present invention is placed in an electrodeposition bath, the object to be coated is used as an anode, and a direct current power supply is connected between the electrode and a counter electrode to supply electricity. Energization is performed by the constant voltage method that applies a constant voltage.
A constant current method in which a constant current density is applied, or an energization method in a combination thereof may be used. Also, a method of gradually increasing the voltage or current density at the beginning of energization to reach a predetermined value may be combined.

In the case of the constant voltage method, a voltage of 5-250 V is usually applied for 10 seconds to 5 minutes, and in the case of the constant current method, a voltage of 5 to 100 mA / dm ² is usually applied for 5 seconds to 5 minutes. Can be obtained.

The thickness of the electrodeposited coating is not strictly limited, and can be changed according to the purpose of use of the pattern to be formed.
A range of from about 15 μm to about 15 μm is suitable.

The substrate coated with the composition substantially undergoes a cross-linking reaction between the carboxyl group-containing polymer A) and / or the hydroxyphenyl group-containing polymer B) and the vinyl ether group-containing compound C). The coating is cross-linked and cured by heating at a temperature and a temperature of, for example, about 60 to about 150 ° C. for about 1 to about 30 minutes.

Next, the cured coating film on the substrate is image-selectively irradiated with active energy rays using a positive photomask, a reduction projection exposure machine, a direct drawing machine or the like. The active energy ray that can be used here is selected depending on the type of the photoacid generator compound D) blended in the photosensitive composition and the like. For example, an electron beam, a monochromatic ray having a wavelength of 200 to 600 nm or A mixed light thereof can be used.

The substrate irradiated with the active energy ray is then subjected to temperature and time conditions such that the crosslinked structure of the cured coating film is cut in the presence of the acid generated by the irradiation.
For example, heating is performed at a temperature of about 60 to about 150 ° C. for about 1 to about 30 minutes to substantially cut the crosslinked structure of the coating film on the irradiated portion.

By processing the substrate thus heat-irradiated-heat-treated with a developing solution, a pattern can be formed on the substrate. As the developer, a liquid capable of dissolving the carboxyl group-containing polymer A), for example,
Water-soluble organic bases such as hydroxyammonium salts such as alkanolamine and tetraethylammonium hydroxide; and aqueous solutions of inorganic alkalis such as caustic soda, sodium carbonate and sodium metasilicate can be used.

The substances used in these developers may be used alone or in combination of two or more. Preferably, the concentration of the developer is usually in the range of 0.05 to 10% by weight.

The development can be performed by a method known per se, such as immersing the substrate in a developing solution or spraying the developing solution on the substrate. After pattern formation, the substrate can be washed with water and / or dried by heating, if necessary.

Further, when the image pattern is formed on a substrate which can be etched, the exposed substrate portion is etched with an appropriate etching agent, and if necessary, the coating remaining on the substrate is removed with a hot alkali or a solvent. A relief image can be produced by peeling using the above-mentioned peeling agent.

The pattern formed in this manner is a very fine pattern and has excellent contrast. In particular, since the unexposed portion of the resist film has a crosslinked structure, it can be used in a conventional positive electrodeposition photoresist. Compared to this, the unexposed portion has better resistance to developing solutions and etching solutions, and the accuracy of the formed pattern is excellent, so that it can be applied to a wide range of fields such as the manufacture of fine-pattern printed circuit boards and metal fine processing. There is expected.

[0071]

The present invention will be described more specifically with reference to the following examples. “Parts” and “%” are based on weight.

Production Example 1 Synthesis of Carboxyl Group-Containing Polymer A-1 A mixture of 216 parts of acrylic acid, 500 parts of styrene, 284 parts of n-butyl methacrylate and 50 parts of azobisisobutyronitrile (AIBN) was heated to 80 ° C. The solution was added dropwise to 600 parts of stirring methoxypropanol over a period of 2 hours, and the temperature was further maintained for 2 hours to obtain a polymer A-1. Solid content: about 62.5%, carboxyl group: 3 mol / kg, aromatic ring content: 34.6 parts by weight / 100 parts by weight

Production Example 2 Synthesis of Carboxyl Group-Containing Polymer A-2 A mixture of 288 parts of acrylic acid, 300 parts of styrene, 255 parts of n-butyl acrylate, 157 parts of 2-hydroxyethyl acrylate, and 100 parts of t-butyl peroxybenzoate was heated to 110 ° C. Heated and stirred
After dropping in 1,000 parts of butoxyethanol in 2 hours, the temperature was further maintained for 2 hours to obtain a polymer A-2. Solid content about 50%, carboxyl group 4 mol / kg, aromatic ring content 20.7 parts by weight / 100 parts by weight

Production Example 3 Synthesis of Carboxyl Group-Containing Polymer A-3 A mixture of 72 parts of acrylic acid, 650 parts of styrene, 100 parts of ethyl acrylate, 178 parts of n-butyl acrylate, and 75 parts of AIBN was polymerized in exactly the same manner as in Production Example 1. hand,
Polymer A-3 was obtained. Solid content: about 62.5%, carboxyl group content: 1 mol / kg, aromatic ring content: 45 parts by weight / 1
00 parts by weight polymer

Production Example 4 Synthesis of hydroxyphenyl group-containing polymer B-1 1,490 parts of o-cresol, 30% formalin 1,
145 parts, 130 parts of deionized water, and 6.5 parts of oxalic acid were placed in a flask and heated to reflux for 60 minutes. Then add 15% hydrochloric acid to 1
3.5 parts were added and the mixture was heated under reflux for 40 minutes. Then 400 parts of deionized water at about 15 ° C. were added to keep the contents at about 75 ° C. to precipitate the resin. Next, a 35% sodium hydroxide solution was added thereto to neutralize the aqueous layer, and the aqueous layer was removed. Further, 400 parts of deionized water was added to wash the resin at 75 ° C., the aqueous layer was removed, and the same washing operation was repeated twice. Thereafter, the resultant was dried at about 120 ° C. under reduced pressure to obtain a novolak phenol resin (polymer B-1). The molecular weight was about 600.

Production Example 5 Synthesis of hydroxyphenyl group-containing polymer B-2 60 parts of tetrahydrofuran, p-hydroxystyrene 2
One part, 9 parts of n-butyl acrylate, and 3 parts of azobisisobutyronitrile were placed in a flask, and the inside of the vessel was replaced with nitrogen and heated at 100 ° C. for 2 hours with stirring. 700 ml of product
The resulting precipitate was poured into toluene and separated.
After dissolving in acetone, 700 ml was poured into toluene again. The precipitate was dried at 60 ° C. under reduced pressure to obtain a polymer B-2. Molecular weight about 14,000, n-butyl acrylate / p-hydroxystyrene = 35/65 (weight ratio)

Production Example 6 Synthesis of Hydroxyphenyl Group-Containing Polymer B-3 A homopolymer of p-hydroxystyrene was produced in exactly the same manner as in Production Example 5 except that 30 parts of p-hydroxystyrene was used as the polymerizable monomer. B-3 was obtained. Molecular weight about 3,50
0

Production Example 7 Synthesis of vinyl ether compound C-1 Bisphenol A (45.6 g), 2-chloroethyl vinyl ether (80 ml), and toluene (100 ml) were placed in a 250 ml flask, purged with nitrogen, charged with 20 g of sodium hydroxide, and heated at 80 ° C. for 30 minutes. Heated. Thereafter, a solution prepared by dissolving 4.56 g of tetrabutylammonium bromide in 20 ml of 2-chloroethyl vinyl ether was added thereto, and reacted by heating at 95 ° C. for 5 hours. After washing the reaction three times with deionized water, the oil layer was separated. The oil layer was distilled to remove unreacted 2-chloroethyl vinyl ether and toluene to obtain a vinyl ether compound C-1. One molecule contained two vinyl ether groups.

Production Example 8 Synthesis of vinyl ether compound C-2 1,490 parts of o-cresol, 30% formalin 1,
145 parts, 130 parts of deionized water, and 6.5 parts of oxalic acid were placed in a flask and heated to reflux for 60 minutes. Then add 15% hydrochloric acid to 1
3.5 parts were added and the mixture was heated under reflux for 40 minutes. Then 400 parts of deionized water at about 15 ° C. were added to keep the contents at about 75 ° C. to precipitate the resin. Next, a 35% sodium hydroxide solution was added thereto to neutralize the aqueous layer, and the aqueous layer was removed. Further, 400 parts of deionized water was added to wash the resin at 75 ° C., the aqueous layer was removed, and the same washing operation was repeated twice. Thereafter, the resultant was dried at about 120 ° C. under reduced pressure to obtain a novolak phenol resin. Molecular weight about 600
Met. A vinyl ether compound C-2 was obtained in exactly the same manner as in Production Example 8 except that 15 parts of the resin was used instead of 45.6 parts of bisphenol A. One molecule contained about 3.5 vinyl ether groups.

Production Example 9 Synthesis of vinyl ether compound C-3 75% of polyisocyanate obtained by reacting 1 mol of trimethylolpropane with 3 mol of tolylene diisocyanate
875 parts of ethylene glycol dimethyl ether solution and 2
-Hydroxyethyl vinyl ether (264 parts) was reacted at 35 ° C for 3 hours in the presence of 1 part of dibutyltin diacetate to obtain a vinyl ether compound C-3. Approx. 81 solids
%, 3 vinyl ether groups per molecule.

Example 1 Polymer A-1 (solid content 62.5%) 160 parts Polymer B-1 70 parts Vinyl ether compound C-1 70 parts Photoacid generator D-1 Note 1) 10 parts Triethylamine 20 parts Of diethylene glycol dimethyl ether 30
1,87 parts of deionized water stirring the solution dissolved in 0 parts
The resulting mixture was gradually added to 0 parts to obtain an aqueous dispersion having a solid content of about 10%.
A substrate obtained by laminating a copper foil having a thickness of 18 μm on a polyimide film is placed in an electrodeposition bath composed of the aqueous dispersion, and a direct current having a current density of 50 mA / cm ² is applied between the substrate and the counter electrode as an anode for 1 minute. And dried at 100 ° C. for 10 minutes. The thickness was 3.1 μm. This substrate has a wavelength of 356
120 nm after irradiation with ultraviolet light of nm
After heating at 20 ° C. for 20 minutes, development was performed using a 2.38% aqueous solution of tetramethylammonium hydroxide. The γ value (Note 2) obtained from the residual ratio curve of the film after development with respect to the amount of ultraviolet irradiation was 10.1 and the contrast was extremely high, and no decrease or swelling of the film in the unexposed portion was observed. After irradiating an ultraviolet ray of 365 nm at a dose of 8 mj / cm ² on the substrate prepared in the same manner using a pattern mask,
Processing exactly as described above, line / space = 2
/ 2 μm image was formed. The cross-sectional shape of the image pattern was evaluated based on the angle between the substrate surface and the image pattern wall.
The angle was 87 degrees, which was an extremely excellent pattern shape. The minimum exposure required for image formation was 6 mj / cm ² . Note 1), Photoacid generator D-1: The one having the following formula was used.

Embedded image Note 2) γ value: an index representing contrast, and the larger the value, the higher the contrast. The measurement was performed using the Photopolymer Society, Photopolymer Handbook, 101-10
3, (1989), Industrial Research Committee ".

Example 2 Polymer A-2 (50% solid content) 200 parts Polymer B-2 50 parts Vinyl ether compound C-2 25 parts Photoacid generator D-2 Note 3) 8 parts Sensitizing dye 1 Note 4) A mixture of 1 part of 15 parts of triethylamine was dissolved in 200 parts of 2-butoxyethanol and 40 parts of benzyl alcohol, and 688 was prepared in the same manner as in Example 1.
To 15 parts of deionized water to obtain an aqueous dispersion having a solid content of about 15%. Next, using a transparent electrode substrate in which indium tin oxide was vapor-deposited on a glass plate, electrodeposition coating was carried out in exactly the same manner as in Example 1 except that the current density was 20 mA / cm ² ,
Dried for minutes. The thickness was 1.3 μm. The substrate was exposed to 488 nm visible light and heated to 100% after exposure.
Except for 10 minutes at 10 ° C., exactly as in Example 1,
The γ value was determined. The contrast was extremely high at a γ value of 10.8, and no reduction or swelling of unexposed portions was observed. Next, the shape of the image pattern was evaluated in exactly the same manner as in Example 1 except that 488 nm visible light was used as the irradiation light, and a line / space = 1/1 μm photomask was used, and the exposure amount was 3 mj / cm ^2. did. The angle was 89 degrees, which was an extremely excellent pattern shape. The minimum exposure required for image formation was ² mj / cm ² . Note 3), Photoacid generator D-2: The one having the following formula was used.

Embedded image Note 4), Sensitizing dye 1: The following formula was used.

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Example 3 Polymer A-3 (solid content 62.5%) 160 parts Polymer B-3 30 parts Vinyl ether compound C-3 (solid content 81%) 20 parts Photoacid generator D-3 Note 5 5 parts of triethylamine 10 parts of a mixture of dimethoxydiethylene glycol 150 parts,
It was dissolved in 50 parts of benzyl alcohol and dispersed in 608 parts of deionized water in the same manner as in Example 1 to obtain an aqueous dispersion having a solid content of about 15%. Next, a copper foil having a thickness of 300 μm was placed in an electrodeposition bath composed of the aqueous dispersion to serve as an anode.
After applying a direct current of 5 V for 1 minute, the substrate was taken out, washed with water and dried at 110 ° C. for 10 minutes. The thickness was 2.3 μm. The γ value of this substrate was determined in exactly the same manner as in Example 1. The γ value was as high as 10.5. Then thickness 1.
Except that the voltage application time is 2.5 minutes on a double-sided copper-clad substrate (copper thickness 45 μm) having a through hole with a diameter of 0.3 to 0.6 mm in which the inner wall is copper-plated on a 6 mm glass reinforced epoxy resin plate, and A coating was formed on the substrate in exactly the same way. The thickness was 5.3 μm. On the prepared substrate, light was not transmitted through the through-hole portion, and the light amount monitored at 365 nm by an ultra-high pressure mercury lamp at 365 nm through a photomask having a pattern of line / space = 50/50 μm in portions other than the non-through-hole portion was 12 mj / After exposure to cm ^{2, the} film was heated at 100 ° C. for 15 minutes. Next, after developing with a 3% aqueous sodium carbonate solution, the exposed copper was etched using copper chloride, and then the coating on the substrate was removed with a 3% aqueous sodium hydroxide solution to obtain a relief image. The copper plating in the through hole was completely protected, and a relief pattern having an excellent shape was formed on the substrate. Note 5), Photoacid generator D-3: The one having the following formula was used.

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Example 4 Storage stability The dispersions of Examples 1 to 3 were put in a container, sealed, and left at 40 ° C. for 3 months. The dispersion after standing was good without sedimentation or separation. The tests of each example were repeated using the stored dispersion. There was almost no change in the characteristics, and good results were obtained.

Comparative Example 1 Carboxyl group-containing polymer 1 A mixture of 288 parts of acrylic acid 300 parts of styrene 300 parts of n-butyl acrylate 112 parts of 2-hydroxyethyl acrylate 100 parts of t-butyl peroxybenzoate was heated to 110 ° C. Stirring 2-
After dropping in 1,000 parts of butoxyethanol in 2 hours, the temperature was maintained for 2 hours to obtain polymer 1.
Solid content: about 50%, carboxyl group: 4 mol / kg, aromatic ring content: 20.7 parts by weight / 100 parts by weight Polymer Polymer 1 (solid content: 50%) 200 parts Photosensitive agent 1 Note 6) 30 parts Benzyl alcohol 15 parts of methoxypropanol 75 parts of triethylamine 12 parts were mixed and dissolved, and gradually added to 535 parts of stirred deionized water to obtain an aqueous dispersion having a solid content of about 15%. The γ value was measured in the same manner as in Example 1 except that the current density was set to 50 mA / cm ² . (Film thickness 2.5 μm) The γ value was 2.5. The unexposed part is about 25% when the exposed part is completely dissolved.
% Dissolved. The developer was changed to a 0.5% aqueous sodium carbonate solution for development. The γ value was 3.4. About 2% of the unexposed portion was dissolved when the exposed portion was completely dissolved. A pattern was formed on a substrate in exactly the same manner as in Example 1 except that the exposure amount was 80 mj / cm ² and a 0.5% aqueous sodium carbonate solution was used as a developing solution, and the cross section was observed. The angle between the substrate and the pattern was 79 degrees. In this example, an image could not be formed at an exposure amount of 60 mj / cm ² or less. Note 6), Photosensitive agent 1: The following formula was used.

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Comparative Example 2 Polymer 2 600 parts of o-hydroxybenzoic acid, 90 parts of o-cresol 90
0 parts, 30% formalin 1,145 parts, deionized water 1
30 parts and 6.5 parts of oxalic acid were placed in a flask and heated and refluxed for 60 minutes. Next, 13.5 parts of 15% hydrochloric acid was added and the mixture was refluxed for 40 minutes. Then 400 parts of deionized water at about 15 ° C. were added to keep the contents at about 50 ° C. to precipitate the resin. 4 more
After adding 00 parts of deionized water and washing the resin at 50 ° C., the aqueous layer was removed, and the same washing operation was repeated three times, followed by drying under reduced pressure at about 120 ° C. to obtain a novolak phenol resin. The molecular weight was about 650. Carboxyl group 2.8 mol / kg Polymer Polymer 2 100 parts Photosensitizer 1 30 parts Benzyl alcohol 100 parts Ethylene glycol monoethyl ether 100 parts Triethylamine 15 parts are mixed and dissolved, and stirred in 522 parts of deionized water. The solution was gradually added to obtain an aqueous dispersion having a solid content of about 15%. The γ value was measured in the same manner as in Example 1 except that the current density was set to 50 mA / cm ² . (Thickness: 1.8 μm) The γ value was 4.2. Unexposed area is about 6% when the exposed area is completely dissolved
Dissolved. Using a substrate prepared in the same manner,
A pattern was formed on a substrate in exactly the same manner as in Example 1 except that 0 mj / cm ^{2 was used,} and the cross section was observed. The angle between the substrate and the pattern was 82 degrees. In this example, the exposure amount is 70
An image could not be formed at mj / cm ² or less.

Comparative Example 3 Storage Stability The dispersions of Comparative Examples 1 and 2 were placed in a container, sealed and kept at 40 ° C. for 1 hour.
After storage for months, the condition was observed. In each case, a large amount of sediment and separation of the liquid were observed.

Continuation of the front page (56) References JP-A-1-106038 (JP, A) JP-A-55-12995 (JP, A) JP-A-48-89003 (JP, A) JP-A-5-39444 (JP, A) JP-A-5-100428 (JP, A) JP-A-5-100429 (JP, A) JP-A-6-161110 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB Name) G03F 7/00-7/18

Claims (2)

(57) [Claims] 1. A) a polymer containing a carboxyl group,
B) a polymer containing a hydroxyphenyl group; C) a compound containing at least two vinyl ether groups in one molecule of 5 parts per 100 parts by weight of the total of A) and B).
１５０150 parts by weight, and D) a compound capable of generating an acid upon irradiation with active energy rays having a total amount of A), B) and C) of 10
In a mixture containing 0.1 to 40 parts by weight to 0 part by weight as an essential component, A) / B) = 90/10 to 10/90 (weight ratio), and A) to D) A composition having a carboxyl group content of 0.5 to 5.0 equivalents and a hydroxyphenyl group content of 0.5 to 7.0 equivalents per 1 kg of the mixture is neutralized with a basic compound and dissolved or dispersed in water. A positive electrodeposition photoresist composition comprising: 2. A step of applying the positive electrodeposition photoresist composition according to claim 1 to a substrate having a conductive surface by an electrodeposition method, a step of heating the substrate, and selectively irradiating active energy rays. A step of heating, a step of heating the substrate after irradiation, and a step of developing with a basic developer.