JP2002244293A - Resin composition for alkali developable resist, dry film and resist comprising their cured body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for an alkali developable resist excellent in heat, printing and wear resistances while retaining sensitivity and resolution and capable of exhibiting superior dielectric property and to provide a dry film and a resist comprising their cured body. SOLUTION: The resin composition contains a copolymer (A) consisting of repeating structural units of formula (1) and repeating structural units having an acid group and a polymerizable monomer (B). In the formula, X1 is a 3-8C branched alkyl or substituted branched alkyl or a 4-8C cycloalkyl or substituted cycloalkyl and Y1 a 3-8C branched alkyl or substituted branched alkyl or a 4-8C cycloalkyl or substituted cycloalkyl.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for an alkali-developable resist which is cured by, for example, irradiation with active energy rays, a dry film obtained by using the same, and a resist which is a cured product thereof.
In particular, the present invention relates to a resin composition for an alkali developable resist having excellent sensitivity and resolution, and excellent heat resistance, printing durability, abrasion resistance and dielectric properties.

[0002]

2. Description of the Related Art A method of forming a fine image on various materials by using a photoresist using a photosensitive resin composition is widely used in fields such as printing plates, electronic materials, and metal working.

[0003] Examples of uses of a permanent resist that leaves an image of a photoresist formed by exposure and development as a film include the following two applications. That is, (1) Photosensitive printing plate resist used for various printings, (2) A film is formed on the entire surface of the circuit conductor other than the part to be soldered, which is used in the previous process of soldering electronic components to the printed wiring board This is the solder resist to be used.

In the technical field of the photosensitive printing plate resist, there is a demand for further improving the printing durability and abrasion resistance. Furthermore, in the solder resist technical field, low dielectric constant and low dielectric constant are required in order to cope with further improvement of heat resistance to cope with lead-free soldering, higher frequency, and higher signal propagation speed. Tangentization is required.

At the beginning of the development of the above-mentioned permanent resists, solvent developable ones were mainly used. However, in order to reduce the cost of treating the waste liquid of the solvent and to cope with environmental problems in the workplace and the region, the permanent resist is currently used. Alkali-developable ones are mainly used.

Various resin compositions have been proposed for use in such alkali developable resists. For example, those containing a polymer having an unsaturated bond and a carboxyl group (JP-A-5-202330), and those containing a polymer composed of a novolak-type epoxy resin and a reaction product of an anhydride of acrylic acid and polybasic acid (JP-A-3-71137) has been proposed. Further, those containing a reaction product of a hydantoin epoxy resin and acrylic acid with a polybasic acid (JP-A-4-345608) and those containing a styrene monomer and a carboxylic acid-containing monomer ( For example, JP-A-10-26829 and JP-A-10-10
No. 734).

[0007]

According to these prior arts, the required performance (heat resistance, printing durability, abrasion resistance, etc.) of the above-mentioned resin composition for an alkali developable resist in various applications.
For this reason, some improvements have been made to low dielectric constant and low dielectric loss tangent. However, in the above prior art, since the base resin is an acrylic resin, sufficient heat resistance, printing durability, abrasion resistance, and dielectric properties such as low dielectric constant and low dielectric loss tangent are sufficiently achieved. There was a problem that it could not be demonstrated.

The present invention has been made by focusing on the problems existing in the prior art as described above. The objective is to provide a resin composition for an alkali-developable resist capable of exhibiting excellent dielectric properties, while maintaining excellent sensitivity and resolution while maintaining excellent heat resistance, printing durability and abrasion resistance, and a dry film. And a resist made of a cured product thereof.

[0009]

In order to achieve the above object, a resin composition for an alkali developable resist according to a first aspect of the present invention comprises a repeating structural unit represented by the following general formula (1): It contains a copolymer (A) composed of a repeating structural unit having an acid group, and a polymerizable monomer (B).

[0010]

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(Where X ¹ in the formula is a branched alkyl group having 3 to 8 carbon atoms or a substituted branched alkyl group;
Represents a cycloalkyl group or a substituted cycloalkyl group having 8 to 8 carbon atoms, and Y ¹ represents a branched alkyl group or a substituted branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl group or a substituted cycloalkyl group having 4 to 8 carbon atoms. The resin composition for an alkali developable resist according to the second invention,
In the first invention, the repeating structural unit having an acid group contained in the copolymer (A) is represented by the following general formula (2):
It is at least one selected from the group consisting of the repeating structural units represented by (3) and (4).

[0012]

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(Where D represents a benzyl group;
Represents a hydrogen atom or a methyl group, and n represents 0 or 1. )

[0014]

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[0015]

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(Wherein F in the formula represents a methylene group;
Represents 0 or 1. The resin composition for an alkali-developable resist according to the third invention,
In the first or second invention, the polymerizable monomer (B)
Is a polymerizable monomer represented by the following general formula (5) and a polymerizable monomer having a polymerizable monomer represented by the following general formula (6) as an essential component.

[0017]

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(Provided that X ² in the formula is a branched alkyl group having 3 to 8 carbon atoms or a substituted branched alkyl group,
Represents a cycloalkyl group or a substituted cycloalkyl group having 8 to 8 carbon atoms, and Y ² represents a branched alkyl group or a substituted branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl group or a substituted cycloalkyl group having 4 to 8 carbon atoms. )

[0019]

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(Wherein Z ¹ represents a branched alkyl group having 3 to 8 carbon atoms or a substituted branched alkyl group;
To 8 represent a cycloalkyl group or a substituted cycloalkyl group, and n and p represent 0 or 1. The resin composition for an alkali-developable resist according to the fourth invention comprises:
In the third invention, the polymerizable monomer represented by the general formula (6) is an alkyl vinyl ether represented by the following general formula (7), an alkyl vinyl ester represented by the general formula (8), And at least one selected from the group consisting of alkyl allyl esters represented by the general formula (9).

Z ² —O—CH ＝ CH ₂ (7) (wherein Z ² is a branched or substituted branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl having 4 to 8 carbon atoms) An alkyl group or a substituted cycloalkyl group.) Z ³ —COO—CH ＝ CH ₂ (8) (wherein Z ³ is a branched alkyl group having 3 to 8 carbon atoms or a substituted branched alkyl group, Or a cycloalkyl group having 4 to 8 carbon atoms or a substituted cycloalkyl group.) Z ⁴ —COO—CH ₂ —CH ＝ CH ₂ (9) (wherein, Z ^{4 in} the formula has 3 to 8 carbon atoms) 8 represents a branched alkyl group or a substituted branched alkyl group, or a cycloalkyl group or a substituted cycloalkyl group having 4 to 8 carbon atoms.) The dry film for an alkali-developable resist according to the fifth aspect of the present invention includes the first to fourth groups. Alkali of any invention Coating of the image resist resin composition is one which is formed on a transparent film.

The resist of the sixth invention is an alkali-developable resist obtained by applying the resin composition for an alkali-developable resist of any one of the first to fourth inventions on a substrate or a transparent film. After the dry film is attached to the substrate, it is irradiated with active energy rays through a photomask in the form of a circuit pattern, and then subjected to alkali development to form a negative pattern of the circuit, and then post-cured. It is made of a cured product.

[0023]

Embodiments of the present invention will be described below in detail. The resin composition for an alkali developable resist of the present invention comprises a copolymer (A) comprising a repeating structural unit represented by the following general formula (1) and a repeating structural unit having an acid group, and a polymerizable monomer. (B).

[0024]

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(Where X ¹ in the formula is a branched or substituted branched alkyl group having 3 to 8 carbon atoms,
Represents a cycloalkyl group or a substituted cycloalkyl group having 8 to 8 carbon atoms, and Y ¹ represents a branched alkyl group or a substituted branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl group or a substituted cycloalkyl group having 4 to 8 carbon atoms. The copolymer (A) is used as a base resin in a resin composition for an alkali developable resist. When the copolymer (A) is composed of a repeating structural unit represented by the general formula (1) and a repeating structural unit having an acid group, the copolymer (A) can be used to prepare a resist from a resin composition for an alkali developable resist. Good alkali developability can be exhibited.

The repeating structural unit having an acid group contained in the copolymer (A) is a repeating structural unit having an acid group such as a carboxyl group and a vinyl residue. As the repeating structural unit having an acid group, the following general formula (2):
At least one selected from the group consisting of the repeating structural units represented by (3) and (4) is preferable in that it has excellent alkali developability.

[0027]

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(Where D in the formula represents a benzyl group;
Represents a hydrogen atom or a methyl group, and n represents 0 or 1. )

[0029]

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[0030]

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(Wherein F in the formula represents a methylene group;
Represents 0 or 1. The polymerizable monomer for forming the copolymer (A) is
As the fumaric acid diester represented by the following general formula (5) and a monomer having an acid group, preferably a monomer having an acid group, the following general formula (10), (11) or (12)
Is a monomer having a carboxyl group represented by This is because these polymerizable monomers have excellent alkali solubility, that is, they have high solubility in an aqueous alkali solution.

In order to balance various properties such as heat resistance and processability, other polymerizable monomers may be contained in addition to the fumaric acid diester and the monomer having an acid group. good.

[0033]

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(Where X ² in the formula is a branched or substituted branched alkyl group having 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms, or 4 to 8 carbon atoms, and preferably 4 to 8 carbon atoms.
6 represents a cycloalkyl group or a substituted cycloalkyl group, and Y ² represents a branched alkyl group or a substituted branched alkyl group having 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms, or 4 to 8 carbon atoms, preferably a carbon number. And represents 4 to 6 cycloalkyl groups or substituted cycloalkyl groups. )

[0035]

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(Where G in the formula represents a benzyl group;
Represents a hydrogen atom or a methyl group, and n represents 0 or 1. )

[0037]

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[0038]

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(Wherein F in the formula represents a methylene group;
Represents 0 or 1. Specific examples of the fumaric acid diester include diisopropyl fumarate, di-sec-butyl fumarate, and di-te
rt-butyl fumarate, diisobutyl fumarate, di-tert-amyl fumarate, di-4-methyl-2-
Pentyl fumarate, di-sec-amyl fumarate,
Di-3-pentyl fumarate, bis (2,4-dimethyl-3-pentyl) fumarate, isopropyl-sec-butyl fumarate, tert-butyl-4-methyl-2-methyl
Pentyl fumarate, isopropyl-tert-butyl fumarate, sec-butyl-tert-butyl fumarate, sec-butyl-tert-amyl fumarate,
Di-4-methyl-pentyl fumarate, tert-butyl-isoamyl fumarate and the like.

Specific examples of the fumaric acid diester having X ² as an alkyl group and Y ² as a cycloalkyl group include isopropyl-cyclobutyl fumarate, 1-chloro-2-
Propyl-cyclopentyl fumarate, 1,3-dichloro-2-propyl-cyclohexyl fumarate, sec
-Butyl-cyclohexyl fumarate, 3-chloro-2
-Propyl-cyclohexyl fumarate, tert-butyl-cyclopentyl fumarate, tert-butyl cyclohexyl fumarate, sec-amyl-cyclohexyl fumarate, 3-pentyl-bornyl fumarate,
2,3-dimethyl-3-pentyl-adamantyl fumarate, tert-amyl-cyclohexyl fumarate,
Neopentyl-cyclopentyl fumarate, 4-methyl-2-pentyl-cyclohexyl fumarate, 2-ethylhexyl-cyclohexyl fumarate and the like can be mentioned.

Specific examples of the monomer having an acid group are described below. (1) Monomers having a carboxyl group represented by the general formulas (10), (11) and (12) are exemplified. Specific examples of the monomer having a carboxyl group represented by the general formula (10) include acrylic acid, methacrylic acid, β-
Methacryloyloxyethyl hydrogen succinate, β-acryloyloxyethyl hydrogen succinate, 4-vinylphenylacetic acid and the like can be mentioned.

Specific examples of the monomer having a carboxyl group represented by the general formula (11) include fumaric acid, maleic acid, citraconic acid, and mesaconic acid.
In addition, specific examples of the monomer having a carboxyl group represented by the general formula (12) include itaconic acid. (2) Others, maleic anhydride, itaconic anhydride,
And unsaturated acid anhydrides such as citraconic anhydride and 4-methacryloxytrimellitic anhydride. (3) Further, hydroxyphenoxyethyl methacrylate, hydroxyphenoxyethyl acrylate, the addition mole number of ethylene glycol is 2-90 hydroxyphenoxy polyethylene glycol methacrylate, the addition mole number of ethylene glycol is 2-90 hydroxyphenoxy polyethylene glycol acrylate, propylene Hydroxyphenoxy polypropylene glycol methacrylate having an addition mole number of glycol of 2-90, hydroxyphenoxy polypropylene glycol acrylate having an addition mole number of propylene glycol of 2-90,
Monomers having a phenol group, such as vinylphenol and hydroxyphenylmaleimide, may be mentioned. (4) Further, monomers having a sulfonic acid group such as sulfoethyl methacrylate, sulfoethyl acrylate, styrenesulfonic acid, acrylamide-t-butylsulfonic acid, and methallylsulfonic acid are exemplified. (5) In addition, there may be mentioned phosphoric acid group-containing monomers such as mono-2-methacryloyloxyethyl acid phosphate and mono-2-acryloyloxyethyl acid phosphate.

Among these monomers having an acid group, a monomer having a carboxyl group (1) having high solubility in an aqueous alkali solution is preferable. As the copolymer (A), those having a weight average molecular weight in the entire range can be used as long as the resin composition for an alkali developable resist of the present invention can be obtained. Desirably, it is 200,000. When the weight average molecular weight is in such a range, the resolution and developability of the resin composition for an alkali-developable resist and the electrical, mechanical, and adhesive properties of the resist can be favorably maintained. Weight average molecular weight of 5.0
If it is less than 00, both the part irradiated with the active energy ray and the unirradiated part dissolve in the developing solution, and if it exceeds 200,000, both the irradiated part and the non-irradiated part of the active energy ray are hardly dissolved in the solvent, and both are hardly developed. This makes it difficult to form an image.

As the structure of the copolymer (A), various structures such as a random structure, a block structure, a graft structure and a ladder structure are possible, but it is preferable to have a random structure. When the copolymer (A) has a random structure,
Since the copolymer composition in the polymer chain is almost uniform,
The developability and resolution of the resin composition for an alkali-developable resist and the electrical and mechanical properties of the resist can be favorably maintained.

The heat resistance and printing durability of the copolymer (A)
From the viewpoint of electrical insulation and the like, the molar fraction of each polymerizable monomer charged when forming the polymer is determined. That is, the molar fraction of the fumaric acid diester is usually 50 to 95 mol%, preferably 55 to 90 mol%. The mole fraction of the monomer having an acid group is usually 5 to 50 mol%, preferably 10 to 45 mol%. Further, the mole fraction of the other polymerizable monomer is usually 0 to 30 mol%, preferably 0 to 20 mol%.

When the molar fraction of the fumaric acid diester is less than 50%, the heat resistance, printing durability and electric insulation of the copolymer (A) tend to decrease. When the mole fraction of the monomer having an acid group is less than 5 mol%, the alkali solubility of the copolymer (A) and the alkali developability of the resin composition for resist tend to decrease. Further, when the mole fraction of the other polymerizable monomer exceeds 30 mole%, the mole fraction of the fumaric acid diester and the monomer having an acid group becomes relatively small, and the resin for an alkali developable resist is reduced. The alkali developability of the composition tends to decrease.

Next, a method for producing the copolymer (A) will be described. That is, in a mixture of the fumaric acid diester and the monomer having an acid group, a polymerization initiator that generates a radical thermally is added, and bulk polymerization is directly performed, or a water-soluble polymer or an inorganic dispersant is contained. It is produced by dispersing in an aqueous solution to be subjected to suspension polymerization or by performing solution polymerization in an organic solvent that dissolves the copolymer (A). Examples of the polymerization initiator include azo organic compounds such as 2,2′-azobisisobutyronitrile (AIBN) and 2,2′-azobiscyclohexanecarbonitrile (ACN), and dibenzoyl peroxide (BPO). , Tert-
Butyl hydroperoxide (TBHP), di-tert
Organic peroxides such as -butyl peroxide (DtBP), dicumyl peroxide (DCP) are used.

The copolymer (A) is used as a base resin in a resin composition for an alkali developable resist, and its content is preferably 20 to 80% by weight, more preferably 40 to 70% by weight in the composition. It is.

Next, the polymerizable monomer (B) will be described in detail. This is a monomer that is polymerized by irradiation with heat or active energy rays, and commonly known monomers can be used. As the polymerizable monomer (B), for example, monofunctional radical polymerizable monomers (a) to (j) and polyfunctional radical polymerizable monomers (k) to (n) shown below Is mentioned. One of these monomers may be used alone, or two or more of them may be used as a mixture. (A) C1-C1 such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octadecyl acrylate, docosyl acrylate, etc.
An acrylate ester having 22 alkyl groups. (B) methyl methacrylate, ethyl methacrylate,
Methacrylic acid esters having an alkyl group having 1 to 22 carbon atoms, such as propyl methacrylate, butyl methacrylate, octadecyl methacrylate, and docosyl methacrylate. (C) dimethyl fumarate, diethyl fumarate, diisobutyl fumarate, di-sec-butyl fumarate,
Fumaric acid esters such as di-t-butyl fumarate and dicyclohexyl fumarate; (D) dimethyl itaconate, diethyl itaconate,
Itaconic esters such as diisobutyl itaconate, di-sec-butyl itaconate, di-t-butyl itaconate and dicyclohexyl itaconate. (E) Styrene derivatives such as styrene, α-methylstyrene and chlorostyrene. (F) Unsaturated ketones such as methyl vinyl ketone and butyl vinyl ketone. (G) Vinyl esters such as vinyl acetate and vinyl butyrate. (H) methyl vinyl ether, butyl vinyl ether,
Vinyl ethers such as cyclohexyl vinyl ether. (I) Allyl compounds such as phenyl allyl ether, methyl allyl ether, cyclohexyl allyl ether, allyl propionate, allyl myristate, allyl cyclohexyl propionate. (J) N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide. (K) hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol ester hydroxypivalate di (meth) acrylate, diglycidyl of 1,6-hexanediol Acrylic acid adduct of ether, di (meth) acrylate of acetalized product of hydroxypivalaldehyde and trimethylolpropane, 2,2-bis [4- (acryloyloxy) phenyl] propane, hydrogenated bisphenol A
Di (meth) acrylate of ethylene oxide adduct,
Tricyclodecane dimethanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
Trimethylolpropane propylene oxide adduct tri (meth) acrylate, glycerin propylene oxide adduct tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, lower fatty acid of dipentaerythritol and acrylic Acid ester, tris (acryloyloxyethyl) isocyanate, (meth) acrylate of caprolactone adduct of dipentaerythritol, dipentaerythritol pentapropionate penta (meth) acrylate, caprolactone of neopentyl glycol di (meth) acrylate hydroxypivalate Multifunctional (meth) acrylates such as adducts. (L) Polyfunctional vinyl esters such as divinyl adipate and divinyl phthalate. (M) cyclohexyl dimethanol divinyl ether,
Polyfunctional vinyl ethers such as hexanediol divinyl ether, butanediol divinyl ether, ethylene glycol divinyl ether, and diethylene glycol divinyl ether. (N) Polyfunctional allyl compounds such as diallyl isophthalate, diallyl terephthalate, diallyl adipate, cyclohexyl dimethanol diallyl ether, hexanediol diallyl ether, butanediol diallyl ether, ethylene glycol diallyl ether, and diethylene glycol diallyl ether.

Among these polymerizable monomers (B), the fumaric acid ester (c) or the itaconic acid ester (d) and (g), (h), (i), (l), (m) ),
The polymerizable monomer (n) with a vinyl ester, a vinyl ether or an allyl compound is preferred in view of dielectric properties.

Next, a polymerization initiator for initiating polymerization by an active energy ray can be added to the resin composition for an alkali developable resist, if necessary. This has the function of hardening only the irradiated portion by irradiating active energy rays through a photomask corresponding to the image to be formed, thereby enhancing the effect of giving a difference in solubility of the developing solution from the unirradiated portion. If necessary, a polymerization initiator for initiating polymerization by heat can be blended. Thereby, post-curing for completely curing the resist coating film after development can be promoted.

These polymerization initiators have appropriate thermal stability during processing such as mixing, coating and drying of the resist resin composition, and are necessary for initiating polymerization or curing of the polymerizable monomer. Any radical can be used as long as it generates a radical by exposure to active energy rays or heat. As the polymerization initiator, conventionally known (a) photopolymerization initiators or (b) thermal polymerization initiators can be used, and examples thereof include the following. One of these polymerization initiators can be used alone, or two or more of them can be used as a mixture. (A) photopolymerization initiator diethylthioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone,
Benzoin isopropyl ether, benzoin ethyl ether, benzophenone, benzophenone methyl ether, 2-ethylanthraquinone, 2,4-dimethylthioxanthone, 2,2-dimethoxy-2-phenylacetophenone, pt-butyltrichloroacetophenone,
Hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one,
2,2-dimethoxy-1,2-diphenylethane-1-
On, 2,4,6-trimethylbenzoyldiphenylphosphine oxide. (B) Thermal polymerization initiator Ketone peroxide such as methyl ethyl ketone peroxide, cyclohexane peroxide, acetylacetone peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane,
1-bis (t-butylperoxy) cyclohexane,
Peroxyketals such as 2,2-bis (t-butylperoxy) butane, hydroperoxides such as t-butyl peroxide, cumyl hydroperoxide and p-mentha hydroperoxide, di-t-butyl peroxide , T-butyl cumyl peroxide,
Dialkyl peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, diacyl peroxides such as dioctanoyl peroxide and dilauroyl peroxide, diisopropylperoxydicarbonate, and dimyristilper Oxydicarbonate, peroxydicarbonate such as di-2-ethylhexylperoxydicarbonate, t-butylperoxyacetate, t-butylperoxypivalate,
Organic peroxides such as peroxyesters such as t-butylperoxylaurate, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), azobis (2 4-dimethylvaleronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (isobutyric acid) dimethyl, 2,2′-azobis (2,4-dimethylvaleronitrile), etc. Azo compounds.

Among these, those having good sensitivity to active energy rays, that is, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone,
2,2-dimethoxy-1,2-diphenylethane-1-
On, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like are preferred. Also,
A thermal polymerization initiator that is relatively stable around room temperature and decomposes rapidly when heated to about 100 ° C., ie, methyl ethyl ketone peroxide, 1,1-
Bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, diisopropylbenzene hydroperoxide and the like are preferred.

The content of the polymerization initiator for initiating polymerization by the active energy ray or heat is usually 0.1 to 20% by weight in the composition from the viewpoint of rapid curability by the active energy ray or heat. Preferably it is 0.3 to 15% by weight.

The resin composition for an alkali-developable resist may contain, if necessary, a photosensitizer such as thioxanthone, anthracene, or perylene, a polymerization inhibitor such as phenothiazine or hydroquinone, an antioxidant, a thermosetting catalyst, a dye or a pigment. A thixotropic agent, a plasticizer, a surfactant and the like may be included.

Further, a thermosetting resin such as a phenol resin, a melamine resin, and a polyimide; a polyolefin resin;
A thermoplastic resin such as a polystyrene resin, a nylon resin, polyethylene terephthalate, and polycarbonate may be added. By blending these resins, various physical properties such as heat resistance and workability can be balanced.

By mixing the components described above,
A resin composition for an alkali developable resist can be prepared. When using this, benzene, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethyl lactate, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, By dissolving or dispersing in a solvent such as water, the viscosity and the applicability can be adjusted.

Hereinafter, a method for producing a dry film and a resist formed from the resin composition for an alkali developable resist and its use will be described. Alkaline developable resist resin composition, when used, transfer, bar coater, roll coater, spin coater, screen printing, gravure printing, etc., commercially available glass epoxy substrate copper-coated on both sides or one side, polyphenylene ether It is applied to an adherend such as a (PPE, PPO) substrate, a BT resin substrate, a fluororesin (Teflon (registered trademark)) substrate, a glass substrate, and an aluminum alloy substrate.

After the application or attachment, the resist resin composition is cured by irradiating an active energy ray such as an ultraviolet ray, an electron beam, an X-ray, or a γ-ray through a photomask. After that, by developing and removing the unirradiated part,
A photomask-shaped image is formed. The development is usually carried out using an aqueous alkali solution such as sodium carbonate, sodium hydrogen carbonate, tetramethylammonium hydroxide or the like at a temperature of 80 ° C. or lower. Further, in order to further promote the polymerization of the polymerizable monomer remaining in the resist after the development, post-curing is usually performed at a temperature of 80 ° C. or higher, whereby a cured resist can be obtained.

<Application of Resin Composition for Alkali Developable Resist> The resin composition for an alkali developable resist is used for printing plate resists such as PS plates (presensitize plates and plate printing plates), solder resists and the like. Can be used.

<Application Method for Each Use> (Printing plate resist) A 0.3 mm thick 2S material aluminum plate was treated with 10% sodium triphosphate maintained at 80 ° C.
The aluminum plate is degreased by immersion in a 30% by weight aqueous solution for 30 seconds, and rubbed with a nylon brush while flowing a bumish slurry (a kind of abrasive) on the aluminum plate to form a grain. Then
Etch with sodium aluminate at 60 ° C. for 10 seconds, followed by washing with a 3% aqueous solution of sodium hydrogen sulfate. This aluminum plate is subjected to a current density of 2 A in 20% sulfuric acid.
/ Dm ^{2 for} 2 minutes, then 2.5% of 70 ° C
Treat with an aqueous solution of sodium silicate for 1 minute, wash with water and dry.
Thereafter, the resin composition for an alkali developable resist is applied by a bar coater and dried to form a coating (coating) of about several tens of μm to form a photosensitive lithographic printing plate.

The photosensitive lithographic printing plate is irradiated with ultraviolet light through a negative mask. Next, Fuji Photo Film Co., Ltd.
Is developed using a PS processor 400S manufactured by Toshiba Corporation to produce a lithographic printing plate. (Solder resist) A resin composition for an alkali developable resist is applied to a substrate by a curtain coater so that the film thickness when dried is about several tens of μm, and the solvent is dried to form a smooth coating film (coating). I do. Next, after irradiating ultraviolet rays through a photomask on which a circuit diagram is printed, the unirradiated portions are removed by developing with an alkaline aqueous solution, thereby forming a film having an image according to the circuit pattern. The film on which the image is formed is post-cured to form a solder resist film.

The effects exerted by the above embodiments will be summarized below. According to the resin composition for an alkali-developable resist of the embodiment, the copolymer (A) contains the repeating structural unit represented by the general formula (1). Therefore, based on the repeating structural unit represented by the general formula (1), the obtained resist has heat resistance, printing durability, abrasion resistance,
Further, the dielectric properties can be improved. In other words, when used as a permanent resist such as a printing plate resist or a solder resist by a photoresist method, a clear image with good sensitivity to active energy rays can be obtained, and the resist obtained therefrom has heat resistance and printing durability. It has excellent chemical resistance, adhesion and low moisture absorption in addition to abrasion resistance and dielectric properties. Further, the dielectric properties are particularly excellent at frequencies in the quasi-microwave band.

The repeating structural unit having an acid group contained in the copolymer (A) is at least selected from the group consisting of the repeating structural units represented by the general formulas (2), (3) and (4). When the number is one, the solubility in an aqueous alkali solution is high, and the alkali developability can be improved.

The polymerizable monomer (B) is a polymerizable monomer containing the polymerizable monomer represented by the general formula (5) and the polymerizable monomer represented by the general formula (6) as essential components. By being a monomer, the heat resistance and the dielectric properties of the film formed of the resin composition for an alkali developable resist can be improved.

The polymerizable monomer represented by the general formula (6) is an alkyl vinyl ether represented by the general formula (7), an alkyl vinyl ester represented by the general formula (8),
And at least one selected from the group consisting of alkyl allyl esters represented by the general formula (9). This makes it possible to further improve the heat resistance and the dielectric properties of the obtained coating.

The dry film for an alkali-developable resist in which a coating of the resin composition for an alkali-developable resist is formed on a transparent film can have better workability than a liquid resist.

[0068]

Next, the above embodiment will be described more specifically with reference examples, examples and comparative examples. Parts and% in each example are based on weight unless otherwise specified.

The analytical values of the copolymers used in the examples were obtained by the following methods. (Weight average molecular weight Mw) A 1% by weight tetrahydrofuran (THF) solution of each polymer isolated in the test of solid content was prepared, and this was used as a sample, and the mobile phase was THF (SEC) (size exclusion% chromatograph). It is a polystyrene conversion value measured by the method. (Reference Example 1, Production of Copolymer 1) Thermometer, reflux condenser,
A four-necked flask equipped with a stirrer was charged with a mixture of 80 g of dicyclohexyl fumarate, 20 g of 4-vinylphenylacetic acid, and 100 g of ethyl acetate. After the air in the reactor was replaced with nitrogen under stirring, the temperature was raised to 40 ° C. did. Next, 1 g of diisopropyl peroxydicarbonate (Perloyl IPP manufactured by NOF Corporation) was charged, and the mixture was heated at 40 ° C.
, And cooled to room temperature to obtain a solution of Copolymer 1.

Next, the solution of the copolymer 1 was purified by reprecipitation using methanol as a precipitant, and then dried under vacuum at 60 ° C. for 5 hours to obtain the copolymer 1 in a yield of 93%. The weight average molecular weight was measured by the method described above. Table 1 shows the results.
It was shown to. Reference Example 2 Production of Fumaric Acid Derivative Fumaric acid 11 was placed in a four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer.
7.1 g, isobutyl vinyl ether 202.1 g and phosphoric acid ester (AP-8 manufactured by Daihachi Chemical Industry Co., Ltd.)
2 g of the mixture was charged and stirred under reflux (80 to 100 ° C). The reaction was terminated when the acid value of the mixture became 2 or less, and a fumaric acid derivative was obtained with a yield of 95%. Reference Example 3, Production of Copolymer Precursor 1 A mixture of 70 g of dicyclohexyl fumarate, 66.6 g of fumaric acid derivative and 50 g of ethyl acetate was charged into a four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer. After the air in the reactor was replaced with nitrogen under stirring, the temperature was raised to 40 ° C. Next, 1 g of diisopropyl peroxydicarbonate (Perloyl IPP manufactured by NOF Corporation) was charged, and the mixture was heated at 40 ° C.
And then cooled to room temperature to obtain a solution of copolymer precursor 1.

Next, the solution of the copolymer precursor 1 was subjected to reprecipitation purification using methanol as a precipitant.
For 5 hours to obtain a copolymer precursor 1 in a yield of 93%. (Reference Example 4, Production of Copolymer 2) Thermometer, reflux condenser,
In a four-necked flask equipped with a stirrer, copolymer precursor 16 was added.
7.5 g, dioxane 155.6 g, concentrated hydrochloric acid 0.675
After charging g, the temperature was raised to 80 ° C., kept at 80 ° C. for 4 hours, and then cooled to room temperature to obtain a solution of copolymer 2. Next, the solution of the copolymer 2 was purified by reprecipitation using water as a precipitating agent, and then dried under vacuum at 60 ° C. for 5 hours to give a yield of 95%.
% Of the copolymer 2 was obtained. The weight average molecular weight was measured by the method described above. The results are shown in Table 1. (Reference Examples 5 and 9 to 13) Reference Example 1 except that the charged composition of the polymerizable monomer was changed as shown in Tables 1 and 2.
A copolymer was synthesized in the same manner as described above. The results are shown in Tables 1 and 2. (Reference Example 6, Production of itaconic acid derivative) Itaconic acid 7 was placed in a four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer.
0.2 g, 108.2 g of isobutyl vinyl ether and phosphoric acid ester (AP-8 manufactured by Daihachi Chemical Industry Co., Ltd.)
05 g of the mixture was charged and stirred under reflux (80 to 100 ° C). The reaction was terminated when the acid value of the mixture became 2 or less, and an itaconic acid derivative was obtained in a yield of 96%. Reference Example 7, Production of Copolymer Precursor 2 70 g of dicyclohexyl fumarate, 10 g of di-t-amyl fumarate and 13.3 g of fumaric acid derivative were placed in a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer. , Itaconic acid derivative 21 g, vinyl-t-butylbenzoic acid 10 g and toluene 66.7
g of the mixture was charged, the air in the reactor was replaced with nitrogen under stirring, and the temperature was raised to 40 ° C. Next, 1 g of diisopropyl peroxydicarbonate (Perloyl IPP manufactured by NOF Corporation) was charged and kept at 40 ° C. for 25 hours, and then cooled to room temperature to obtain a solution of copolymer precursor 2.

Next, the solution of the copolymer precursor 2 was subjected to reprecipitation purification using methanol as a precipitant.
For 5 hours to obtain a copolymer precursor 2 in a yield of 93%. The results are shown in Table 1. (Reference Example 8, Production of Copolymer 4) Thermometer, reflux condenser,
In a four-necked flask equipped with a stirrer, copolymer precursor 26 was added.
7.5 g, dioxane 155.6 g, concentrated hydrochloric acid 0.675
After charging g, the temperature was raised to 80 ° C., kept at 80 ° C. for 4 hours, and then cooled to room temperature to obtain a polyfumarate solution.
Next, after reprecipitation purification of the copolymer 4 solution was performed using water as a precipitant, vacuum drying was performed at 60 ° C. for 5 hours to obtain a yield of 95.
% Of the copolymer 4 was obtained. The weight average molecular weight was measured by the method described above. The results are shown in Table 1.

The abbreviations in Table 1, Table 2, Table 3, and Table 6 are as follows. DiPF: diisopropyl fumarate, DcHF: dicyclohexyl fumarate, DiBF: di-isobutyl fumarate, DsBF: di-sec butyl fumarate, D
tBF: di-tertbutyl fumarate, StV: vinyl stearate, DtAF: di-tert amyl fumarate, CHVE: cyclohexyl vinyl ether, sB
AES: sec butyl allyl ester, iPVE: isopropyl vinyl ether, VtBB: vinyl-tert
Butyl benzoate, St: styrene, EHVE: 2-
Ethylhexyl vinyl ether, DAP: diallyl phthalate, 907: 2-methyl-1- [4- (methylthio) phenyl] -2-morphfurinopropanone (Irgacure 907, Ciba-Geigy), 819: (Irgacure 819, Ciba-Geigy), 651: 2 2-dimethoxy-1,2-diphenylethan-1-one (Irgacure 651 manufactured by Ciba-Geigy), 1173: 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173 manufactured by Ciba-Geigy), DiAF: diisoamyl fumarate, VPAA: 4-vinylphenylacetic acid, FA: fumaric acid, IA: itaconic acid, AA: acrylic acid, MAA: methacrylic acid, DiBVEBF: fumaric acid derivative, DiBVEBI: itaconic acid derivative, TM
PTA: triacrylate of a 6 mol ethylene oxide adduct of trimethylolpropane, TEGDA: tetraethylene glycol diacrylate.

[0074]

[Table 1]

[0075]

[Table 2]

Example 1 2.4 g of diisopropyl fumarate (DiPF) as a polymerizable monomer was added to 12.0 g of an ethyl acetate solution of copolymer 1 (solid content: 50.1%).
0.6 g of cyclohexyl vinyl ether (CHVE)
And 0.12 g of Darocure 1173 as a polymerization initiator for initiating polymerization by active energy rays. Then, the mixture was stirred at room temperature for 10 minutes to prepare a resin composition for an alkali developable resist. Furthermore, the basic properties (sensitivity and resolution) of the resist and the properties (dielectric properties, solder heat resistance, chemical resistance, adhesion, and water absorption) when used as a solder resist were examined in the following manner, and the resin composition for the resist was examined. The product and the solder resist were evaluated. The results are shown in Tables 4 and 5. <Sensitivity> (1) A resin composition for a solder resist was applied to an aluminum plate having a grained surface on a surface thereof using a spin coater ASS-300 manufactured by Able Co., Ltd. to a film thickness of 10 μm. (2) The solvent was removed by drying in a hot air dryer at 100 ° C. for 10 minutes. (3) Exposure was performed for 10 seconds using a 20 mW / cm ultra-high pressure mercury lamp in air through a gray scale (Photographic Step Tablet No. 2 manufactured by Eastman Kodak Company). (4) performs a spray development with a pressure of 0.29MPa a 1% sodium carbonate aqueous solution of the coating film after exposure at the gas-liquid mixing method (3 kg / cm ^2), was carried out to remove the unexposed portions. (5) 1 at 150 ° C
Time post-cure was performed. The maximum number of gray scale steps of the remaining resist film was determined and used as the sensitivity.

In Table 4, a large number of stages indicates that the sensitivity is high. <Resolution> In (3) of the sensitivity test, exposure, development and post cure were performed in the same manner as in the sensitivity test, except that exposure was performed through a photomask having a line and space of 2 to 40 μm instead of gray scale. went. The size of the line and space in the minimum portion where the image of the line and space of the photomask was missing was defined as the resolution (μm).

In Table 4, a smaller value of the resolution indicates a higher resolution. <Dielectric properties> Internal dimensions are 120mm long and 50m wide
m, put the resin composition for solder resist in a glass container having a thickness of 1 mm, and cast 1 m by air drying.
An m-thick film was produced. This film was directly exposed in air using a 20 mW / cm ultra-high pressure mercury lamp for 60 seconds. Next, post-curing was performed at 150 ° C. for 1 hour. A film of the obtained resin composition for a solder resist was prepared to have a length of 100 mm, a width of 2 mm, and a thickness of 1.2.
A test piece having a size of 1 mm was cut out and subjected to 1 GH by a perturbation method.
z, permittivity ε at 2 GHz, 5 GHz and 10 GHz
And the dielectric loss tangent tan δ were measured, and the Q value which was the reciprocal of tan δ was calculated. Table 5 shows the results. <Solder heat resistance> Conducted according to the method of JIS-6481. In the sensitivity test, the coating film on the substrate after the exposure-development-post-curing was immersed in a 260 ° C. solder bath for 2 minutes, and the appearance of the sample was visually observed. The presence or absence was observed. The appearance of the sample after the test was visually observed. When the coating film did not swell or peel off, it was evaluated as ○, and when the coating film swelled or peeled off, it was evaluated as ×. <Chemical resistance> The coating film on the substrate after exposure-development-post-curing in the sensitivity test was treated with a 10 vol% sulfuric acid aqueous solution (described as sulfuric acid in the table) or trichloroethane (described in the table) at a temperature of 25 ° C. The coating film was visually observed after immersion for 1 hour in trichloride. The case where there was no change compared with the one before immersion was evaluated as ○, and the case where the coating film was destroyed was evaluated as ×. (Adhesion) A double-sided copper-clad polyphenylene ether (PPE) substrate (CS3376C) manufactured by Risho Kogyo Co., Ltd. was used in place of the aluminum plate whose surface was grained, and a resin composition for a solder resist was formed thereon. And apply
A cured film was prepared in the same manner as in the sensitivity test, except that exposure was performed directly from a light source without going through a gray scale, and development was not performed. JIS for this cured film
A cross-cut peel test was performed according to the K5400 method. 1
The number (numerator) of the cells remaining without peeling out of the 00 cells (denominator) was shown. <Water absorption> A film of a resin composition for a solder resist (length 1
20 mm, width 70 mm and thickness 1 mm). Next, a length of 50 mm, a width of 50 mm and a thickness of 1.0
A test piece having a size of mm was cut out. Using this test piece, the water absorption (%) was measured according to the method of JIS6481. (Examples 2 to 4) The type and amount of the copolymer (A), the type and amount of the polymerizable monomer mixture (B), and the type and amount of the polymerization initiator were changed as shown in Table 3. Other than
A resin composition for an alkali-developable resist was prepared in the same manner as in Example 1, and evaluated as a resin composition for a resist and a solder resist. The results are shown in Tables 4 and 5. (Example 5) Type and amount of copolymer (A) and polymerizable monomer (B) of resin composition for resist of Example 1 in Table 3
Table 3 shows the types and addition amounts of
Was applied as described above, and was uniformly applied on a biaxially stretched polyethylene terephthalate film having a thickness of 25 μm, and dried with a hot air dryer at 100 ° C. for 10 minutes. The thickness after drying was about 10 μm. On the surface of the photosensitive layer,
A 35 μm-thick polyethylene terephthalate film was laminated as a protective film to prepare a photosensitive dry film. Next, the photosensitive film from which the protective film had been removed was laminated on an aluminum plate having a surface grained while being heated to 130 ° C.

Except that the photosensitive resist layer was formed by the above method, the sensitivity, resolution,
The dielectric properties, solder heat resistance, chemical resistance, and adhesion were examined, and the resin composition for resist and a solder resist were evaluated. The results are shown in Tables 4 and 5. (Comparative Example 1) A toluene solution of the copolymer (9) (solid content: 6
4.9%) 8.0 g, trimethylolylpropane triacrylate 2.5 g, tetraethylene glycol diacrylate 1.17 g, benzophenone 0.03 g, Victoria blue 0.02 g, hydroquinone 0.01 g
And 4.4 g of toluene were mixed. And 10 at room temperature
After stirring for minutes, a resin composition for solder resist was prepared. Next, evaluation as a resist resin composition and a solder resist was performed in the same manner as in Example 1. The results are shown in Tables 4 and 5.

[0080]

[Table 3]

(Comparative Example 2) P on the surface of an aluminum plate having a grained surface treated with P
SR-4000 (acrylate resin composition)
Was applied to a film thickness of 10 μm using a bar coater. Next, the film was dried in a hot air dryer at 80 ° C. for 20 minutes to remove the solvent, thereby obtaining a solder resist film. The sensitivity was measured by the following method, and the resolution, dielectric properties, solder heat resistance, chemical resistance, adhesion, and water absorption were measured in accordance with Example 1. The results are shown in Tables 4 and 5.

[0082]

[Table 4]

[0083]

[Table 5]

Example 6 A 2S aluminum plate having a thickness of 0.3 mm was immersed in a 10% aqueous solution of sodium triphosphate maintained at 80 ° C. for 30 seconds to be degreased. And rubbed with a nylon brush to make a grain. Subsequently, the substrate was etched with sodium aluminate at 60 ° C. for 10 seconds, and subsequently washed with a 3% aqueous solution of sodium hydrogen sulfate. The aluminum plate was placed in a 20% sulfuric acid solution at a current density of 2 A / dm ² .
Anodizing was performed for 1 minute, followed by treatment with a 2.5% aqueous solution of sodium silicate at 70 ° C. for 1 minute, followed by washing with water and drying.

Ethyl acetate solution of copolymer 5 (solid content 7
1.5%) to 8.4 g, 1.3 g of diisobutyl fumarate (DiBF) as a polymerizable monomer, 0.2 g of s-butylallyl ester (sBAES), and 6 mol ethylene oxide adduct of trimethylolpropane And 1.5 g of Irgacure 819 as a polymerization initiator for initiating polymerization by active energy rays.
g. Then, the mixture was stirred at room temperature for 10 minutes to prepare a resin composition for an alkali developable resist. Next, this resin composition was applied by a bar coater and dried to form a coating film of several tens of μm to form a photosensitive lithographic printing plate.

Further, the basic characteristics (sensitivity and resolution) of the resist of the obtained photosensitive lithographic printing plate were evaluated in the same manner as in Example 1 (3) and thereafter. Further, performance evaluation as a photosensitive lithographic printing plate was performed by the following method.

The photosensitive lithographic printing plate was irradiated with ultraviolet light through a negative mask. Next, Fuji Photo Film Co., Ltd.
Was developed for 30 seconds using a developer having the following composition using PS Processor 400S manufactured by Toshiba Corporation. After washing with water, 14
° Be 'gum arabic solution was applied to the plate surface and buff dried to prepare a lithographic printing plate. After storing the printing plate thus completed for 7 days, Heidelberg G.P. T. O. It was attached to a printing press and printed. After printing, the number of prints (the number of prints) until the ink density reached a predetermined density and the number of prints (the number of printings) until the ink density was reduced due to wear of the printing plate were recorded.

Table 7 shows the basic characteristics and the results of performance evaluation as a photosensitive lithographic printing plate. Benzyl alcohol 10 g Monoethanolamine 1 g Triethanolamine 10 g Sodium isopropylnaphthalenesulfonate 2 g Pure water 1000 ml (Examples 7 and 8) Example 6 except that the resin composition for an alkali developable resist was changed as shown in Table 6. The basic characteristics and the performance as a photosensitive lithographic printing plate were evaluated in the same manner as described above. Table 7 shows the results.

[0089]

[Table 6]

Comparative Example 4 As a resin composition for an alkali-developable resist, 48 g of methyl methacrylate / methacrylic acid (molar ratio: 85/15, weight average molecular weight Mw: 15,000),
48 g of trimethylolpropane triacrylate, 3-
Methyl-2-benzoylmethylene naphtho [1.2-d]
5 g of thiazole, phthalocyanine blue (CI.
e # 15) Basic properties and photosensitivity were obtained in the same manner as in Example 6, except that 3 g, 500 g of ethylene dichloride and 500 g of methyl cellosolve acetate were mixed and prepared by stirring at room temperature for 10 minutes. Performance evaluation as a lithographic printing plate was performed. Table 7 shows the results.

[0091]

[Table 7]

As is clear from Tables 4, 5 and 7, the resin compositions for alkali-developable resists of Examples 1 to 8 all exhibited excellent sensitivity and resolution. In addition, when the cured product is used as a solder resist in Examples 1 to 5, all have excellent solder heat resistance,
It exhibited chemical resistance, adhesion and dielectric properties. further,
When the cured product was used as a photosensitive lithographic printing plate in Examples 6 to 8, excellent inking properties and printing durability were exhibited.

On the other hand, the solder resist of Comparative Example 1 using a copolymer (9) containing styrene or acrylic acid as a main component as an alkali-developable base resin or BMR which is a commercially available acrylic resin-based solder resist C-10
In Comparative Example 2 using No. 00, the dielectric properties were inferior.

Further, the photosensitive lithographic printing plate of Comparative Example 4 using a copolymer containing methyl methacrylate or methacrylic acid as a main component as an alkali developable base resin was inferior in printing durability.

The technical ideas grasped from the above embodiment will be described below. The resin composition for an alkali developable resist according to any one of claims 1 to 4, wherein the copolymer (A) has a random structure. In this case, since the copolymer composition in the polymer chain of the copolymer (A) is substantially uniform, the developability and resolution of the resin composition for an alkali developable resist and the electrical properties of the resist are improved. And good mechanical properties can be maintained.

The copolymer (A) is 50 to 95 mol%
The resin composition for an alkali-developable resist according to any one of claims 1 to 4, wherein the resin composition is formed by copolymerization of a fumaric acid diester of the above with a monomer having an acid group of 5 to 50 mol%. object. With such a configuration, it is possible to improve physical properties such as heat resistance, printing durability, and electrical insulation of a resist obtained from the resin composition for an alkali developable resist.

The copolymer (A) is 50 to 95 mol%
3. The composition of claim 1, which is formed by copolymerization of a fumaric acid diester of the formula, a monomer having an acid group of 5 to 50 mol%, and 30 mol% or less of another polymerizable monomer. 5. The resin composition for an alkali developable resist according to any one of 4. When configured in this way, it is possible to improve the physical properties such as heat resistance, printing durability and electrical insulation properties of the resist obtained from the resin composition for an alkali-developable resist, as well as various physical properties such as heat resistance and workability. Can be balanced.

[0098]

As described above, according to the present invention, the following effects can be obtained. ADVANTAGE OF THE INVENTION According to the resin composition for alkali developable resists of 1st invention, while maintaining sensitivity and resolution, it is excellent in heat resistance, printing durability, and abrasion resistance, and can exhibit excellent dielectric properties.

According to the resin composition for an alkali developable resist of the second invention, in addition to the effects of the first invention, the alkali developability can be improved. According to the resin composition for an alkali-developable resist of the third invention, the first or second resin is used.
In addition to the effects of the invention of (1), the heat resistance and the dielectric properties of the film formed by the resin composition for an alkali developable resist can be improved.

According to the resin composition for an alkali-developable resist of the fourth invention, in addition to the effects of the third invention, the heat resistance and the dielectric properties of the obtained film can be further improved.

According to the dry film for an alkali developable resist of the fifth invention, in addition to the effects of any of the first to fourth inventions, the workability can be improved as compared with a liquid resist. .

According to the dry film for an alkali developable resist of the sixth invention, a resist such as a solder resist can be easily obtained by using the resin composition for an alkali developable resist of any of the first to fourth inventions. Thus, the resist can exhibit the effects of any of the first to fourth inventions.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H05K 3/00 H05K 3/00 FF Term (Reference) 2H025 AA01 AA02 AA10 AA12 AA13 AB03 AB11 AC01 AD01 BC18 BC38 CB10 CB41 CB43 FA17 4J011 QA03 QA08 QA09 QA12 QA13 QA15 QA16 QA18 QA19 QA20 QA21 QA23 QA24 QA36 QA38 QA39 QB14 QB16 RA03 RA10 RA11 RA12 RA17 SA04 SA05 SA06 SA15 SA16 SA17 SA19 SA03 SA01 SA03 SA01 SA22 SA01 SA19 SA01 SA22 SA01 SA19 SA23 SA01 SA23 SA01 SA19 SA19 AA43 AA48 AA50 AA53 AA54 AA55 AA62 AA63 AC15 AC16 AC23 AC33 BA05 BA06 BA08 BA12 BA16 BA17 BA19 BA20 BA26 BA27 BA28 BA36 BA38 BA39 BA40 BA50 BB01 BB02 BB03 DA02 DA03 DA05 DA07 DA12 DA15 DB15 DB32 DB36 FA05

Claims (6)

[Claims] 1. A copolymer comprising a repeating unit represented by the following general formula (1) and a repeating unit having an acid group (A), and a polymerizable monomer (B). And a resin composition for an alkali developable resist. Embedded image (However, X ¹ in the formula represents a branched alkyl group or a substituted branched alkyl group, or a cycloalkyl group or substituted cycloalkyl group having 4 to 8 carbon atoms having 3 to 8 carbon atoms, Y ¹
Represents a branched or substituted branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl or substituted cycloalkyl group having 4 to 8 carbon atoms. ) 2. The copolymer (A) wherein the repeating structural unit having an acid group contained in the copolymer (A) is represented by the following general formulas (2) and (3):
The resin composition for an alkali developable resist according to claim 1, wherein the resin composition is at least one selected from the group consisting of repeating structural units represented by (4) and (4). Embedded image (Where D represents a benzyl group, E represents a hydrogen atom or a methyl group, and n represents 0 or 1). Embedded image (However, F in the formula represents a methylene group, and m represents 0 or 1.) 3. The polymerizable monomer (B) represented by the following general formula (5) and the polymerizable monomer (B) represented by the following general formula (6):
The resin composition for an alkali developable resist according to claim 1, wherein the resin composition is a polymerizable monomer containing a polymerizable monomer represented by the following as an essential component. Embedded image (However, X ² in the formula represents a branched alkyl group or a substituted branched alkyl group, or a cycloalkyl group or substituted cycloalkyl group having 4 to 8 carbon atoms having 3 to 8 carbon atoms, Y ²
Represents a branched or substituted branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl or substituted cycloalkyl group having 4 to 8 carbon atoms. ) (However, Z ¹ is branched alkyl group or a substituted branched alkyl group having 3 to 8 carbon atoms in the formula, or a cycloalkyl group or substituted cycloalkyl group of 4-8 carbon atoms, n and p are 0 or 1 Represents.) 4. The polymerizable monomer represented by the general formula (6) is an alkyl vinyl ether represented by the following general formula (7), an alkyl vinyl ester represented by the following general formula (8), The resin composition for an alkali developable resist according to claim 3, wherein the resin composition is at least one selected from the group consisting of alkyl allyl esters represented by the general formula (9). Z ² —O—CH ＝ CH ₂ (7) (wherein Z ² is a branched alkyl group having 3 to 8 carbon atoms or a substituted branched alkyl group, or a cycloalkyl group having 4 to 8 carbon atoms or Represents a substituted cycloalkyl group) Z ³ —COO—CH ＝ CH ₂ (8) (wherein, Z ³ represents a branched alkyl group having 3 to 8 carbon atoms or a substituted branched alkyl group, or a carbon atom having 3 to 8 carbon atoms) Represents a cycloalkyl group or a substituted cycloalkyl group having 4 to 8) Z ⁴ —COO—CH ₂ —CH ＝ CH ₂ (9) (however, Z ^{4 in} the formula is a branch having 3 to 8 carbon atoms) Represents an alkyl group or a substituted branched alkyl group, or a cycloalkyl group or a substituted cycloalkyl group having 4 to 8 carbon atoms.) 5. A dry film for an alkali-developable resist, wherein a coating of the resin composition for an alkali-developable resist according to any one of claims 1 to 4 is formed on a transparent film. 6. A dry film for an alkali developable resist obtained by applying the resin composition for an alkali developable resist according to any one of claims 1 to 4 on a substrate or a transparent film. After sticking on the substrate, it is made of a cured product obtained by irradiating active energy rays through a photomask in the form of a circuit pattern, further performing alkali development to form a negative pattern of the circuit, and then post-curing. Resist.