KR100497445B1 - Radiation-sensitive resin composition - Google Patents

Abstract

(A) 10 to 50% by weight of the component consisting of (a) a radically polymerizable compound having a carboxyl group,

(b) 20 to 60% by weight of a constituent consisting of a radically polymerizable compound having a cyclic alkyl group and no carboxyl group, and

(c) an alkali-soluble copolymer consisting of 5 to 40% by weight of the component consisting of other radically polymerizable compounds,

(B) a compound having at least one ethylenically unsaturated double bond, and

(C) radiation radical polymerization initiator

A radiation-sensitive resin composition comprising a.

The radiation-sensitive resin composition of the present invention has a sufficient resolution as a film thickness of 20 μm or more for developing an alkali developer, and further has excellent plating resistance, and shows good adhesion to a substrate during development and good wettability for plating. By plating, favorable lamp | ramp can be formed and the peelability of the hardening | curing agent from a board | substrate is excellent at the same time.

Description

Radiation-sensitive resin composition

TECHNICAL FIELD The present invention relates to a radiation-sensitive resin composition and a material for forming a bump using the same. More particularly, the present invention is carried out at the time of manufacturing a circuit board and mounting a semiconductor or an electronic component on a circuit board. The present invention relates to a radiation sensitive resin composition suitable for photo fabrication such as bump formation and the bump forming material using the same.

Photofabrication is an electroforming technique wherein a radiation-sensitive resin composition is applied to a workpiece surface, and the coating film is patterned by photolithography, which is mainly chemical etching, electrolytic etching or electroplating as a mask. ) Is a general term for the technology for manufacturing various precision parts by single or combination, and forms the mainstream of current precision micromachining technology.

In recent years, with the miniaturization of electronic devices, high integration and multilayering of LSIs are rapidly progressing, and many pin mounting methods are required for substrates for mounting LSIs in electronic devices, and a bare tip using a TAB method or a flip tip method is required. Attention has been paid to implementation.

In such a large number of mounting methods, it is necessary for the electrode having a height of 20 μm or more, which is called a bumper as a connection terminal, to be disposed on the substrate with high precision, and in the future, the precision of the bump is further increased in accordance with the miniaturization of the LSI. It is necessary.

As a requirement for the bump forming material used to form such a bump, it should be possible to form a film thickness of 20 μm or more, have adhesion to a substrate, and when plating to form bumps, It is required to have plating resistance and good wettability to the plated plate, and to be easily peeled off by the stripping solution after plating.

Moreover, when a resist is apply | coated to a flexible thing like a polyimide film as a board | substrate, flexibility is required for a resist so that a crack may not arise in a resist film even if a board | substrate is curved.

However, the conventional bump molding material has not been satisfied in terms of adhesion to the substrate during development in photolithography and wettability to the plating liquid.

In other words, if the adhesion to the substrate is insufficient at the time of development, as the pattern size for forming bumps becomes smaller, there is a problem of falling off from the substrate at the time of development.

In addition, when the wettability to the plating liquid is low, there is a problem that uniform plating is not formed on the substrate.

The present invention has sufficient developability with an alkali developing solution and a film thickness of 20 μm or more, and furthermore, has excellent plating solution resistance, shows adhesion to a substrate during development, and good wettability with a plating solution. It is possible to provide a radiation-sensitive resin composition which can form satisfactory bumps, and is also excellent in peelability from a cured product substrate and also suitable for bump molding having further flexibility.

The present invention,

(A) 10 to 50% by weight of the component consisting of (a) a radically polymerizable compound having a carboxyl group (-COOH),

(b) 20 to 60% by weight of a component consisting of a radically polymerizable compound having a cyclic alkyl group and no carboxyl group, and

(c) 5 to 40% by weight of components consisting of other radically polymerizable compounds

Alkali-soluble copolymers (hereinafter referred to as “copolymer (A)”),

(B) a compound having at least one ethylenically unsaturated double bond (hereinafter referred to as "polymerizable compound (B)"), and

(C) It provides a radiation sensitive resin composition characterized by containing a radiation radical polymerization initiator (henceforth "photoradical polymerization initiator (C)").

Hereinafter, the composition of this invention is demonstrated.

<Radiation Resin Composition>

Copolymer (A)

The copolymer (A) used for this invention is a copolymer which has alkali solubility.

Such a copolymer (A) is a copolymer obtained by copolymerizing the monomer and other monomer which have a substituent which gives alkali solubility to resin, for example.

Such a copolymer (A) is a radical polymerizable compound having a substituent which gives the said alkali solubility to resin especially, the radically polymerizable compound which has an alkyl group, and the other radically polymerizable compound as needed by radical copolymerization in a solvent. You can get it.

As a substituent which gives said alkali solubility to resin, a hydroxyl group, a carboxyl group, a sulfonic acid group, etc. are mentioned, for example, A carboxyl group is especially preferable.

The copolymer (A) is particularly preferably

(a) a radically polymerizable compound having a carboxyl group,

(b) a radically polymerizable compound having a cyclic alkyl group and not having a carboxyl group,

(c) other radically polymerizable compounds

It is a copolymer obtained by radical copolymerizing in a solvent.

As a radically polymerizable compound (a) which has the said carboxyl group, For example, Monocarboxylic acids, such as acrylic acid, methacrylic acid, a crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; 2-succinyloxyethyl (meth) acrylate, 2-maleoyloxyethyl (meth) acrylate, 2-phthaloyloxyethyl (meth) acrylate, 2-hexahydrophthaloyloxyethyl (meth) acrylic Methacrylic acid derivatives having a carboxyl group such as late and an ester bond; Etc. are used.

These compounds can be used individually or in combination of 2 or more types in order to suppress the grade of alkali solubility of acrylic soluble resin.

Among these, methacrylic acid and 2-hexahydrophthaloyloxyethyl methacrylate are preferable, More preferably, it is a combination of methacrylic acid and 2-hexahydrophthaloyloxyethyl methacrylate.

The component which consists of a radically polymerizable compound which has a carboxyl group contained in a copolymer (A) is 10-50 weight%, Preferably it is 20-40 weight%.

If it is less than 10% by weight, the copolymer becomes difficult to dissolve in the alkaline developer, so that residual film may occur after development, and sufficient resolution may not be obtained.

On the contrary, when it exceeds 50 weight%, the solubility of a copolymer with respect to the alkaline developing solution becomes too large and there exists a tendency for the dissolution of an exposure part, ie, a decrease of a film, to become large.

As said radically polymerizable compound (b) which has a cyclic alkyl group and does not have a carboxyl group, for example, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate , Isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like.

These compounds can be used individually or in combination of 2 or more types in order to control the alkali solubility degree of alkali-soluble resin.

Among these, dicyclopentanyl (meth) acrylate is preferable.

The structural component which consists of a radically polymerizable compound (b) which has a cyclic alkyl group and does not have a carboxyl group contained in a copolymer (A) is 20 to 60 weight%, Preferably it is 30 to 50 weight%.

If it is less than 20 weight%, the molecular weight of the copolymer obtained is not high enough, and the coating film formation of 20 micrometers or more of a radiation sensitive composition may become difficult.

On the contrary, when it exceeds 60 weight%, there exists a tendency for the solubility to the solvent of the obtained copolymer to fall.

The other radically polymerizable compound (c) is mainly used for the purpose of appropriately controlling the mechanical properties of the copolymer (A).

Here, "other" means radically polymerizable compounds other than the radically polymerizable compound.

As such another radically polymerizable compound (c), Preferably, (meth) acrylic-acid alkylesters, (meth) acrylic-acid aryl esters, dicarboxylic acid diesters, aromatic vinyls, conjugated diolefins, nitro group containing A polymeric compound, a chlorine containing polymeric compound, an amide bond containing polymeric compound, fatty acid vinyls, etc. are mentioned.

More specifically, methyl methacrylate, ethyl methacrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isopropyl (meth) acrylate, etc. (Meth) acrylic acid alkyl ester of; (Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid; Aromatic vinyls such as styrene, α-methylstyrene, meta-methylstyrene, para-methylstyrene, vinyl toluene and para-methoxystyrene; Conjugated diolefins such as 1,3-butadiene, isoprene and 1,4-dimethylbutadiene; Nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; Chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; Amide bond polymerizable compounds such as acrylamide and methacrylamide; Fatty acid vinyls, such as vinyl acetate, can be used.

These compounds can be used individually or in combination of 2 or more types, These heavy styrene, 1, 3- butadiene, isoprene, methyl methacrylate, n-butylacrylate, etc. are especially preferable compounds.

In addition, in particular, when forming a resist film on a flexible substrate such as polyimide, it is necessary to give flexibility to the resist itself. However, in order to soften the resist film, the following formula (A) and It is effective to use the compound represented by (b).

Where

R ₁ is hydrogen, a methyl group,

R ₂ is hydrogen, an alkyl group of C ₁ to C ₄ ,

n is a number satisfying 2 ≦ n ≦ 25.

The formula (a) and (b) of n represents a natural number of not more than 2 more than 25, R ₁ is a hydrogen or a methyl group, R ₂ represents an alkyl group of hydrogen or C ₁ to C _4, specifically, a methyl group , Ethyl group, n-propyl group, n-butyl group, tert-butyl group and the like. Among these, methyl group is mentioned as preferable R <_2> .

More specifically, examples of the compound represented by the formula (A) include methoxydiethylene glycol (meth) acrylate (n = 2), ethoxydiethylene glycol (meth) acrylate (n = 2) and methoxy tree Ethylene glycol (meth) acrylate (n = 3), methoxy tetraethylene glycol (meth) acrylate (n = 4), methoxy nona ethylene glycol (meth) acrylate (n = 9), etc. are mentioned, Preferably they are methoxy triethylene glycol (meth) acrylate (n = 3) and methoxy tetraethylene glycol (meth) acrylate (n = 4).

Moreover, as a specific example, as a compound represented by the said Formula (B), methoxy dipropylene glycol (meth) acrylate (n = 2), methoxy tripropylene glycol (meth) acrylate (n = 3), methoxy Tetrapropylene glycol (meth) acrylate (n = 4) etc. are mentioned, Preferably it is methoxydipropylene glycol (meth) acrylate (n = 2).

These compounds can be used individually or in combination of 2 or more types.

The component of the other radically polymerizable compound (c) contained in the copolymer (A) is 5 to 40% by weight, preferably 10 to 35% by weight.

As a polymerization solvent used when synthesize | combining a copolymer (A), For example, Alcohol, such as methanol, ethanol, ethylene glycol, diethylene glycol, propylene glycol; Cyclic ethers such as tetrahydrofuran and dioxane; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Alkyl ethers of polyhydric alcohols such as diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; Alkyl ether acetates of polyhydric alcohols such as ethylene glycol ethyl ether acetate, diethylene glycol ethyl ether acetate, and propylene glycol methyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and diacetone alcohol; Ethyl acetate, butyl acetate, 2-hydroxypropionate ethyl, 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetic acid, ethyl hydroxyacetate, 2-hydroxy- Ester, such as 3-methyl butyrate methyl, 3-methoxy propionate methyl, 3-methoxy ethyl propionate, 3-ethoxy ethyl propionate, and 3-ethoxy propionate methyl, is mentioned.

Among these, cyclic ethers, alkyl ethers of polyhydric alcohols, alkyl ether acetates of polyhydric alcohols, ketones, esters and the like are preferable.

In addition, as a polymerization catalyst in radical copolymerization, a normal radical polymerization initiator is used. For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- dimethylvaleronitrile), 2,2'- azobis- (4-methoxy-2- Azo compounds such as dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, tert-butylperoxy pivalate, 1,1'-bis- (tert-butylperoxy) cyclohexane, and the like.

When using a peroxide for a radical polymerization initiator, you may use it as a redox type initiator in combination with a reducing agent.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") of the copolymer (A) of the present invention is 5,000 to 50,000, preferably 10,000 to 30,000.

When Mw is 5,000 or more, it has sufficient film strength as a resist, and when Mw is 50,000 or less, uniform coating film formation is possible without the roughness of the abnormal film | membrane at the time of application | coating.

Polymerizable Compound (B)

The polymeric compound which comprises the composition of this invention is a compound thermally polymerized or photopolymerized, For example,

Acrylate compounds and methacrylate compounds having at least one ethylenically unsaturated double bond,

Bis (meth) acrylic acid ester compound, which is a compound having two ethylenically unsaturated double bonds,

Tris (meth) acrylic acid ester compound which is a compound having three ethylenically unsaturated double bonds,

The polyvalent (meth) acrylic acid ester compound etc. which are compounds which have four or more ethylenically unsaturated double bonds are mentioned.

More specifically, it is a polyfunctional compound which can be polymerized or crosslinked by irradiation, for example, an acrylate compound and a methacrylate compound having at least two ethylenically unsaturated double bonds (hereinafter referred to as “poly (meth)) Acrylate ”).

As said polyvalent (meth) acrylate, the bis (meth) acrylic acid ester compound which is a compound which has two ethylenically unsaturated double bonds, and the tris (meth) acrylic acid ester which is a compound which has three ethylenically unsaturated double bonds, for example The compound and the polyvalent (meth) acrylic acid ester compound which is a compound which has four or more ethylenically unsaturated double bond are mentioned, Specifically, the compound of the following general formula (1)-(6) and (8) is mentioned. .

Where

A is an acryloxy group (CH ₂ = CHCOO-) or a methacryloxy group (CH ₂ = C (CH ₃ ) COO-),

n and m are each 0 to 8,

R ¹ is a hydrogen atom or a methyl group.

AR ² -A ...... (2)

Where

A is an acryloxy group (CH ₂ = CHCOO-) or a methacryloxy group (CH ₂ = C (CH ₃ ) COO-),

R ² represents a 1 to 10 repeated group of an oxyalylene group, an oligooxyalkylene group, an ethylene glycol residue and / or a propylene glycol residue having 2 to 8 carbon atoms.

A- (MN) _n -MA ..... (3)

Where

A is an acryloxy group (CH ₂ = CHCOO-) or a methacryloxy group (CH ₂ = C (CH ₃ ) COO-),

M is a divalent alcohol residue,

N is a divalent basic acid residue,

n is a number from 0 to 1.

Where

A is an acryloxy group (CH ₂ = CHCOO-) or a methacryloxy group (CH ₂ = C (CH ₃ ) COO-),

n is a number from 0 to 8,

R ³ is a hydrogen atom, a hydroxyl group or a methyl group.

Where

A is an acryloxy group (CH ₂ = CHCOO-) or a methacryloxy group (CH ₂ = C (CH ₃ ) COO-),

R ⁴ is an oxygen atom or a methyl group.

Where

A is an acryloxy group (CH ₂ = CHCOO-) or a methacryloxy group (CH ₂ = C (CH ₃ ) COO-),

A plurality of X may be different from each other,

X is a trivalent or higher alcohol residue,

A plurality of Y may be different from each other,

Y is a divalent or higher basic acid residue,

n is a number from 0 to 15.

Where

B is an acryloxy group (CH ₂ = CHCOO-), methacryloxy group (CH ₂ = C (CH ₃ ) COO-), CH ₂ = CHCO [O (CH ₂ ) ₅ ] _m CO- (where m is Integers of 1 to 4) or CH ₂ = C (CH ₃ ) CO [O (CH ₂ ) ₅ ] _m CO—, where m is an integer of 1 to 4,

Among the plurality of B present, a represents an acryloxy group (CH ₂ = CHCOO-) or a methacryloxy group (CH ₂ = C (CH ₃ ) COO-), and b represents CH ₂ = CHCO [O (CH ₂ ) ₅ ] _m CO-, where m is an integer from 1 to 4 or CH ₂ = C (CH ₃ ) CO [O (CH ₂ ) ₅ ] _m CO-, where m is an integer from 1 to 4 , Where a is a number from 2 to 6, b is a number from 0 to 4, a + b is 6,

Z is a hexavalent organic group or a hexavalent group represented by the following formula (8).

Among these polyvalent (meth) acrylates, compounds having two ethylenically unsaturated bonds and compounds having three or more ethylenically unsaturated double bonds are preferable, and the above formulas (3), (4) and ( The compound represented by 6) is mentioned.

Specific examples of the compound represented by formula (1) include commercially available aronix M-210 (n = about 2, m = about 2, A = methacryloxy group) (Toagosei Kagaku Kogyo Co., Ltd.) KAYARAD R-551 (n + m = about 4, A = methacryloxy group), copper R-712 (n + m = about 4, A = methacryloxy group) (made by Nippon Kayaku Co., Ltd.) ), And the like.

Specific examples of the compound represented by the formula (2) include commercially available aronix M-240 (R ² =-(CH ₂ CH ₂ O) _n- , n = about 4), and M-245 (R ²⁾ =-(CH ₂ CH ₂ O) _n- , n = about 9) (above, manufactured by Toagosei Chemical Industries, Ltd.), KAYARAD HDDA (R ² =-(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ O)-), copper NPGDA (R ² =-(CH ₂ C (CH ₂ ) ₂ CH ₂ O)-), copper TPDGA (R ² =-(CH ₂ CH (CH ₃ ) O)-), copper PEG400DA (R ² =-(CH ₂ CH ₂ O) _n- , n = about 8), copper MANDA (R ² =-(CH ₂ C (CH ₃ ) ₂ CH ₂ O)-), copper HX-220 (R ² =-(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ O) _m -CH ₂ -C (CH ₃ ) ₂ COOCH ₂ C (CH ₃ ) ₂ CH ₂ O (COCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ O ) _n =, m + n = 2), copper HX-620 (R ² =-(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ O) _m -CH ₂ -C (CH ₃ ) ₂ , COOCH ₂ C (CH ₃₎ a _{2 CH 2 O (COCH 2 CH} 2 CH 2 CH 2 O) n-, m + n = 4) ( or more, Nippon how yakku (Ltd.)), and the like.

Specific examples of the compound represented by the above formula (3) include oligoester acrylate and commercially available aronix M-6100, copper M-6200, copper M-6250, copper M-6300, copper M-6400, copper M And -6500 (above, manufactured by Toagosei Kagaku Kogyo Co., Ltd.).

Moreover, R-604 (made by Nippon Kayaku Co., Ltd.), V260, V312 which is a commercial item, for example of the compound which has two ethylenically unsaturated double bonds other than said Formula (1), (2) and (3) And V335HP (above, manufactured by Osaka Organic Chemical Industries, Ltd.).

Specific examples of the compound represented by the formula (4) include commercially available aronix M-309 (n = 0, R ³ = OH) and M-310 (n = about 1, R ³ = CH ₃ ) ( The above is made by Toagosei Kagaku Kogyo Co., Ltd., KAYARAD TMPTA (n = 0, R ³ = CH ₃ ), (Nippon Kayak Co., Ltd.), V-295 (n = O, R ³ = CH) ₃ ) and V-300 (n = O, R < ³ > OH) (above, the Osaka Organic Chemical Industries, Ltd. make) etc. are mentioned.

As a specific example of the compound represented by said formula (5), Aronix M-400 (made by Toagosei Chemical Industries, Ltd.) which is a commercial item is mentioned.

Specific examples of the compound represented by the formula (6) include commercially available aronix M-7100, M-8030, M-8060, M-8100, M-9050 (Toagosei Kagaku Kogyo Co., Ltd.) Note)) etc. can be mentioned.

As a specific example of the compound represented by the said Formula (7), KAYARAD DPCA-20 which is a commercial item (Z is the same as Formula (8), m = average 1, a = average 2, b = average 4), the same DPCA -30 (Z is the same as formula (8), m = average 1, a = average 3, b = average 3), DPCA-60 (Z is the same as formula (8), m = average 1, a = Average 6, b = average 0), the same DPCA-120 (Z is the same as formula (8), m = average 2, a = average 6, b = average 0) (above, Nippon Kayaku Co., Ltd.) ), V-360, V-GPT, V-3PA, and V-400 (above, manufactured by Osaka Organic Chemical Industries, Ltd.).

Of the commercially available products exemplified above, the compound represented by the formula (6) is preferable, and Aronix M-8060 is particularly preferable.

The said polymeric compound (B) may be used individually or in mixture of 2 or more types, and the use ratio with respect to a copolymer (A) is 30-30-a polymeric compound (B) with respect to 100 weight part of copolymers (A) normally. 150 parts by weight, preferably 40 to 100 parts by weight.

The use rate of a polymeric compound (B) is 30 weight part or more, and has sufficient sensitivity with respect to X-ray irradiation, On the other hand, when it is 150 weight part or less, a roughness of a film | membrane on the coating film surface after coating film formation of the composition for X-ray flatbed printing. This doesn't happen.

The radiation sensitive composition of this invention can be used by substituting a part of said polymeric compound (B) by the compound which has one ethylenically unsaturated double bond as needed again. As a compound which has one such ethylenically unsaturated double bond, for example, the radically polymerizable compound (a) which has the said carboxyl group, the radically polymerizable compound (b) which has a cyclic alkyl group, and does not have a carboxyl group, another radical polymerization The compound represented by a cyclic compound (c) and following formula (9) is mentioned.

Where

n is a number from 0 to 8,

R ¹ is a hydrogen atom or an alkyl group having 1 to 9 carbon atoms.

Specific examples of the compound represented by the above (9) include commercially available aronix M-101 (n = about 2, R ¹ = H), copper M-102 (n = about 4, R ¹ = H), and copper M -111 (n = about 1, R ¹ = nC ₉ H ₁₉ ), M-113 (n = about 4, R ¹ = nC ₈ H ₁₉ ), M-114 (n = about 8, R ¹ = nC ₉ H _19), the same M-117 (n = 2.5, R 1 = nC 9 H 19) [ or more, even Iowa Gosei the cultivating ohgyo (Note)], KAYARAD R-564 ( n = about 2.3, R ¹ = H [Nippon Kayak Co., Ltd.] etc. are mentioned.

Moreover, as a compound which has one ethylenically unsaturated bond other than the compound represented by the said Formula (9), it is a commercial item KAYARAD TC-110S, copper TC-120S [above, Nippon Kayaku Co., Ltd. product], V-158 And V-2311 (above, made by Osaka Organic Chemical Industries, Ltd.).

Moreover, unsaturated carboxylic acid diesters, such as dimethyl maleate and diethyl maleate, can also be used.

The polymerizable compound (B) may be used singly or in combination of two or more, and is preferably 30 to 150 parts by weight, more preferably 50 to 100 parts by weight based on 100 parts by weight of the copolymer (A). If it is less than 30 weight part, the sensitivity at the time of exposure will fall easily, and when it exceeds 150 weight part, compatibility with a copolymer (A) will deteriorate and the film | membrane roughness may arise in the coating film surface after coating film formation.

Radical photopolymerization initiator (C)

The radical photopolymerization initiator (c) used in the present invention polymerizes the polymerizable compound (B).

As an optical radical polymerization initiator, For example, (alpha)-diketones, such as benzyl and diacetyl; Acyl phosphorus such as benzoin; Acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; Thioxanthone, 2,4-diethyl thioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzo Benzophenones such as phenone; Acetophenone, para-dimethylaminoacetophenone, α, α'-dimethoxyacetoxybenzophenone, 2,2'-dimethoxy-2-phenylacetophenone, para-methoxyacetophenone, 2-methyl [4- ( Acetophenones, such as methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Quinones such as anthraquinone and 1,4-naphthoquinone; Halogen compounds such as phenacyl chloride, tribromomethylphenyl sulfone and tris (trichloromethyl) -s-triazine; Peroxides such as di-tert-butylperoxide; And acylphosphine oxides such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide. Moreover, as a commercial item, Ilgacua 184, 651, 500, 907, CG1369, CG24-61 (made by Shiba Gaigi Co., Ltd.), Lucillin LR 8728, TPO (made by BASF Corporation), Darocua 1116, 1173 (Melk) Co., Ltd.), uvecryl P36 (made by UCB Corporation), etc. are mentioned.

Preferred compounds among the various radical photopolymerization initiators described above include 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propaneone, 2-benzyl-2-dimethylamino-1- (4 Acetophenones such as -morpholinophenyl) -butan-1-one or phenacyl chloride, tribromomethylphenyl sulfone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and the like.

These compounds can be used individually or in combination.

The amount used is preferably 1 to 50 parts by weight, particularly preferably 10 to 40 parts by weight based on 100 parts by weight of the copolymer (A). If it is less than 1 part by weight, it is easy to be affected by the loss of activity of radicals due to oxygen (decrease in sensitivity). If it exceeds 50 parts by weight, compatibility tends to deteriorate or storage stability tends to decrease.

Moreover, this radical photopolymerization initiator and a radiosensitizer can be used together.

Various additives

In this invention, various additives can be mixed and added to the composition which consists of a copolymer (A), a polymeric compound (B), and a radical polymerization initiator (C) mentioned above as needed.

(1) epoxy compound

An epoxy compound can be mix | blended with the composition of this invention for the purpose of improving heat resistance, hardness, etc.

Such epoxy compounds are not limited as long as they do not affect compatibility, but preferably bisphenol-A epoxy resins, phenol novolak-type epoxy resins, cresol novolak-type epoxy resins, cyclic aliphatic epoxy resins, and glycidyl ester types. Epoxy resin, glycidyl amine type | mold epoxy resin, heterocyclic epoxy resin, polyglycidyl methacrylate, etc. are mentioned.

Among these, bisphenyl-A epoxy resin, cresol novolak-type epoxy resin, glycidyl ester-type epoxy resin, etc. are especially preferable.

The usage-amount of these epoxy compounds becomes like this. Preferably it is 100 weight part or less with respect to 100 weight part of copolymers (A).

(2) thermal polymerization inhibitor

In order to suppress the fall of developability by exposure to the heat at the time of prebaking, the heat polymerization inhibitor can be added to the composition of this invention.

As such a thermal polymerization inhibitor, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether , 4,4 '-[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] diphenol, 1,1,3-tris (2,5-dimethyl- 4-hydroxyphenyl) -3-phenylpropane etc. are mentioned.

The usage-amount of these compounds becomes like this. Preferably it is 5 weight part or less with respect to 100 weight part of copolymers (A).

(3) surfactant

Surfactant can be mix | blended with the composition of this invention for the purpose of improving applicability | paintability, antifoaming property, leveling, etc.

As surfactant, for example, BM-1000, BM-1100 (made by BM Chemical Co., Ltd.), Mekapec F-1420, copper F172, copper F173, copper F183 (made by Dainippon Ink & Chemicals Co., Ltd.), Florad FC -135, East FC-170C, East FC-430, East FC-431 (made by Sumitomo Triem Co., Ltd.), Saffron S-112, East S-113, East S-131, East S-141, East S Fluorine-based surfactants sold under the names of -145 (manufactured by Asahi Glass Co., Ltd.), SH-28PA, copper-190, copper-193, SZ-6032, SF-8428 (manufactured by Toray Silicone Co., Ltd.) Can be used.

The usage-amount of these surfactant becomes like this. Preferably it is 5 weight part with respect to 100 weight part of copolymers (A).

(4) adhesion aid

An adhesive adjuvant can be used for the composition of this invention in order to improve adhesiveness with a board | substrate.

As the adhesion aid to be used, a functional silane coupling agent is effective.

Here, the functional silane coupling agent means a silane coupling agent having reactive substituents such as carboxyl group, methacryloyl group, isocyanate group and epoxy group, and specific examples thereof include trimethoxysilyl benzoic acid and v-methacryloxy propyl tree. Methoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, v-isocyanate propyltriethoxysilane, v-glycidoxy propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimeth Oxysilane, etc. are mentioned.

As for these compounding quantities, 20 weight part or less is preferable per 100 weight part of copolymers (A).

(5) other additives

A carboxylic acid compound can also be added to the composition of this invention in order to perform the fine adjustment of the solubility with respect to alkaline developing solution.

Specific examples of such compounds include monocarboxylic acids such as acetic acid, propionic acid, n-butyl acid, iso-butyl acid, n-valeric acid, iso-valeric acid, benzoic acid and cinnamic acid; Lactic acid, 2-hydroxybutyl acid, 3-hydroxybutyl acid, salicylic acid, beta-hydroxybenzoic acid, para-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid Hydroxy monocarboxylic acids such as 5-hydroxyphthalic acid and silinic acid; Oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricar Polyhydric carboxylic acids such as acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; Itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanylic acid anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic acid anhydride, 1,2,3,4- Butane tetracarboxylic acid, cyclopentane tetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic acid, ethylene glycol bis (anhydrous trimellitate), glycerin truss ( Acid anhydrides, such as anhydrous trimellitate), are mentioned.

Moreover, a filler, a coloring agent, a viscosity modifier, etc. can also be added to the composition of this invention as needed.

Examples of the filler include silica, alumina, talc, bentonite, zirconium silicate, powder glass, and the like.

As a coloring agent, extender pigments, such as alumina white, clay, barium carbonate, and barium sulfate; Inorganic pigments such as zinc oxide, lead white, sulfur lead, photoluminescent, prussian blue, ultramarine blue, titanium oxide, zinc chromate, red oxide, and carbon black; Organic pigments such as brilliant carmine 6B, permanent red 6B, permanent red R, benzidine yellow, phthalocyanine blue and phthalocyanine green; Basic dyes such as magenta and rhodamine, direct dyes such as direct scarlet and direct orange; Acid dyes, such as roserine and metinine yellow, are mentioned.

Moreover, bentonite, a silica gel, aluminum powder etc. are mentioned as a viscosity modifier.

These additives are in a range which does not impair the essential properties of the composition, and are preferably 50% by weight or less with respect to the obtained composition.

When the filler and the pigment are not added, the preparation of the composition of the present invention may be performed by mixing and stirring in a conventional manner, and when adding the filler and the pigment, a dissolver, a homogenizer, a three roll mill, and the like. It is good to disperse | distribute and mix using the disperser of a Moreover, you may filter using a mesh, a membrane filter, etc. again as needed.

solvent

In the present invention, the copolymer (A), the polymerizable compound (B), the photosensitive radical polymerization initiator (C) and various additives mixed and added as necessary can be diluted with an organic solvent for the purpose of uniformly mixing. have.

As a solvent used, the copolymer (A) and each component can be melt | dissolved uniformly, and what does not react with each component is used.

As such a solvent, the same solvent as the polymerization solvent used when synthesizing the copolymer (A) can be used, and N-methylformamide, N, N-dimethylformamide, N-methylformanilide and N- Methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, capronic acid, caprylic acid, 1-octanol, High-boiling solvents such as 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, v-butyrolactone, ethylene carbonate, propylene carbonate, and phenylcellosolve acetate may be added. .

Among these solvents, alkyl ethers of polyhydric alcohols such as ethylene glycol monoethyl ether and diethylene glycol monomethyl ether, in view of solubility, reactivity with each component, and ease of formation of a coating film; Alkyl ether acetates of polyhydric alcohols such as ethyl cellosolve acetate; Esters such as 3-epoxypropionate ethyl, 2-methoxy methyl propionate and 2-hydroxyethyl propionate; Ketones such as diacetone alcohol are suitable.

The usage-amount of the said solvent can be suitably determined according to a use, a coating method, etc.

<Bump Formation Method>

Next, the formation method of the bump using the composition of this invention is demonstrated.

1. Formation method of coating film

In this invention, a desired coating film can be formed by apply | coating the composition solution mentioned above on the board | substrate which has a predetermined | prescribed wiring pattern, heating as needed, drying, and removing a solvent.

As a coating method on a to-be-processed substrate, methods, such as a spin coat method, the roll coat method, the screen printing method, the applicator method, can be employ | adopted.

In addition, although the drying conditions of the coating film of the composition of this invention differ with the kind, compounding ratio, coating film thickness, etc. of each component in a composition, it is about 5 to 20 minutes at 70-120 degreeC normally, Preferably it is 80-100 ℃.

If the drying time is too short, the adhesion state at the time of development worsens, while if the drying time is too long, the resolution decreases due to the shaking of heat.

2. Irradiation method

By irradiating the ultraviolet-ray or visible light with a wavelength of 300-500 nm through the obtained coating film through the mask of a predetermined pattern, only a part other than the wiring pattern part which forms a bump can be photocured.

As a source of these radiations, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a halogenated metal lamp, an argon gas laser, or the like can be used. Radiation means ultraviolet rays, visible rays, far ultraviolet rays, X rays, an electron beam, etc. here.

The radiation dose varies depending on the type of each component in the composition, the compounding amount, the film thickness of the coating film, and the like, but is, for example, 100-500 mJ / cm ² in the case of using an ultrahigh pressure mercury lamp.

3. Developing Method

As a developing method after irradiation with radiation, an alkaline aqueous solution is used as a developing solution, and unnecessary portions are dissolved and removed, leaving only the irradiation portions.

As a developing solution, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine , Dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1, Alkali aqueous solution, such as 5-diazabicyclo [4,3,0] -5-nonene, can be used.

Moreover, the aqueous solution which added an appropriate amount of water-soluble organic solvents, such as methanol and ethanol, and surfactant to the said aqueous alkali solution can be used as a developing solution.

The developing time varies depending on the type of each component of the composition, the blending ratio, and the dry film thickness of the composition, but is usually 30 to 360 seconds, and the developing method is any method such as a liquid immersion method, a dipping method, a paddle method, a spray developing method, Also good.

After the development, washing with running water is performed for 30 to 90 seconds and dried by wind using an air conditioner or the like, or dried in an oven.

4. Post-treatment

Although the composition of this invention can harden | cure sufficiently even by said radiation irradiation only, it can further harden by further radiation irradiation (henceforth a post exposure) and heating according to a use.

As post-exposure, it can carry out by the method similar to the said irradiation method, and the irradiation amount is not specifically limited, When using a high pressure mercury lamp, 100-1,000 mJ / cm <^2> is preferable.

In addition, the method of heating uses heating apparatuses, such as a hotplate and oven, for 5 to 60 minutes at predetermined temperature, for example, 100-200 degreeC, for a predetermined time, for example, on a hot plate, and 30 to 30 in an oven. It is good to heat-process for 90 minutes.

By this post-treatment, the cured product in a pattern having more favorable characteristics can be obtained.

5. Plating

The substrate subjected to the post-treatment is immersed in various plating solutions for electroplating, and the plating is performed by setting the current value and the energization time so as to have a desired plating thickness.

6. Peeling treatment

As a method of peeling the hardened | cured material of the composition of this invention from the board | substrate which plated, it hardens | cures by the radiation sensitive resin composition of this invention by immersing this board | substrate in 5 to 30 minutes in peeling liquid stirring under 50-80 degreeC. The film can be peeled off.

As a peeling liquid used at this time, the mixed solution of a quaternary ammonium salt, dimethyl sulfoxide, and water can be used.

Example

Although an Example demonstrates this invention further more concretely below, this invention is not limited to this. Unless otherwise specified, parts are parts by weight, and% represents% by weight.

Synthesis of Copolymer (A)

① Synthesis Example 1

After nitrogen-substituting the flask with a dry ice / methanol reflux group, 4 g of 2,2'-azobis isobutyronitrile was used as a polymerization initiator, 100 g of diethylene glycol dimethyl ether and 50 g of ethylene glycol monomethyl ether were used as a solvent. It injected | thrown-in and stirred until the polymerization initiator dissolved.

Subsequently, as a polymeric compound which comprises a copolymer (A), 20 g of methacrylic acid, 15 g of 2-hexahydrophthaloyl oxyethyl methacrylate, 45 g of dicyclopentanyl methacrylates, 15 g of styrene, and After adding 5 g of 1,3-butadiene, stirring was gradually started.

Then, the temperature of the solution was raised to 80 degreeC and superposition | polymerization was performed at this temperature for 4 hours.

Thereafter, the reaction product was added dropwise to a large amount of methanol to solidify the reaction product.

After the coagulum was washed with water, the coagulum was redissolved in the same amount of tetrahydrofuran and solidified with a large amount of methanol.

After performing this redissolution-solidification operation in total three times, the obtained coagulated product was vacuum dried at 40 ° C. for 48 hours to obtain a desired copolymer ①.

② Synthesis Example 2

4 g of 2,2'-azobis-2,4-dimethylvaleronitrile as a polymerization initiator, 100 g of diethylene-glycoldiethyl ether as a solvent, 150 g of ethyl 2-hydroxypropionate, copolymer (A) Except for using 25 g of methacrylic acid, 10 g of 2-hexahydrophthaloyl oxyethyl methacrylate, 50 g of dicyclopentanyl methacrylate, 10 g of styrene and 5 g of 1,3-butadiene as the polymerizable compound to be used. The same operation as in Synthesis Example ① was performed to obtain a copolymer ②.

③ Synthesis Example 3

As a polymerization initiator, 4 g of 2,2'- azobis isobutyronitrile, 150 g of diacetone alcohol as a solvent, 15 g of acrylic acid as a polymeric compound which comprises copolymer (A), 2-hexahydrophthaloyl oxy A copolymer (3) was obtained in the same manner as in Synthesis Example (1) except that 25 g of ethylene methacrylate, 40 g of dicyclopentanyl methacrylate, 10 g of styrene, and 10 g of 1,3-butadiene were used.

④ Synthesis Example 4

4 g of 2,2'-azobis-2,4-dimethylvaleronitrile as a polymerization initiator, 150 g of ethyl 3-ethoxypropionate as a solvent, 30 g of methacrylic acid as a polymerizable compound constituting the copolymer (A) The same operation as in Synthesis Example (1) was carried out except that 10 g of 2-hexahydrophthaloyloxyethyl methacrylate, 40 g of dicyclopentanyl methacrylate, 10 g of styrene, and 10 g of 1,3-butadiene were used. Copolymer (4) was obtained.

⑤ Synthesis Example 5

As the polymerization initiator, 4 g of 2,2'-azobis-isobutyronitrile, 150 g of methyl 3-methoxypropionate as a solvent, 25 g of methacrylic acid as a polymerizable compound constituting the copolymer (A), 2- A copolymer ⑤ was carried out in the same manner as in Synthesis Example ①, except that 7.5 g of hexahydrophthaloyloxyethyl methacrylate, 47.5 g of dicyclopentanyl methacrylate, 10 g of styrene, and 10 g of 1,3-butadiene were used. Got.

⑥ Synthesis Example 6

4 g of 2,2'-azobis-isobutyronitrile as a polymerization initiator, 150 g of methyl 3-methoxypropionate as a solvent, 20 g of methacrylic acid as a polymerizable compound constituting the copolymer (A), 2- Except for using 15 g of hexahydrophthaloyloxyethyl methacrylate, 45 g of dicyclopentanyl methacrylate, 12 g of n-butyl acrylate, and 8 g of isoprene, the same operations as in Synthesis Example ① were performed to obtain a copolymer ⑥. Got.

⑦ Synthesis Example 7

4 g of 2,2'-azobis-isobutyronitrile as a polymerization initiator, 150 g of 2-ethoxyethyl acetate as a solvent, 25 g of methacrylic acid as a polymerizable compound constituting the copolymer (A), dicyclopentanyl Except having used 40 g of methacrylates, 25 g of n-butylacrylates, and 10 g of isoprene, operation similar to the synthesis example (1) was performed and copolymer (7) was obtained.

⑧ Synthesis Example 8

4 g of 2,2'-azobis-isobutyronitrile as a polymerization initiator, 150 g of methyl 3-methoxypropionate as a solvent, 25 g of methacrylic acid as a polymerizable compound constituting the copolymer (A), methoxy tree A copolymer (8) was obtained in the same manner as in Synthesis Example (1) except that 20 g of ethylene glycol acrylate, 40 g of dicyclopentanyl methacrylate, 10 g of n-butyl acrylate, and 5 g of isoprene were used.

⑨ Synthesis Example 9

4 g of 2,2'-azobis-isobutyronitrile as a polymerization initiator, 150 g of methyl 2-hydroxypropionate as a solvent, 25 g of methacrylic acid as a polymerizable compound constituting the copolymer (A), methoxydipropylene The same procedure as in Synthesis Example ① was performed except that 10 g of glycol acrylate, 40 g of dicyclopentanyl methacrylate, 20 g of n-butyl acrylate and 5 g of 1,3-butadiene were used to obtain a copolymer ⑨. .

⑩ Synthesis Example 10

As a polymerization initiator, 4 g of 2,2'- azobis-isobutyronitrile, 150 g of ethyl 3-ethoxypropionate as a solvent, 20 g of methacrylic acid as a polymeric compound which comprises a copolymer (A), methoxydi Except having used 35 g of propylene glycol acrylates, 42 g of dicyclopentanyl methacrylates, and 3 g of isoprene, operation similar to the synthesis example (1) was performed and copolymer (B) was obtained.

⑪ Synthesis Example 11 (Comparative Example)

4 g of 2,2'-azobis-isobutyronitrile as a polymerization initiator, 150 g of methyl 3-methoxypropionate as a solvent, 20 g of methacrylic acid as a polymerizable compound constituting the copolymer, 2-hexahydrophthal Except having used 15 g of oxyethyl methacrylate, 50 g of styrene, and 15 g of 1, 3- butadiene, operation similar to the synthesis example (1) was performed and the copolymer (V) for a comparative examination was obtained.

Example 1

(1) Preparation of Composition

10 g of the copolymer ① obtained in Synthesis Example 1 was dissolved in 10 g of methyl 3-methoxypropionate, and 2,4,6-trimethylbenzoyl diphenylphosphine oxide (made by BASF, Lucirin TPO) 2 was used as a radical photopolymerization initiator. g and Ilgacua 651 (manufactured by Ciba-Geigy Co., Ltd.), 4 g of aronix M8060 (manufactured by Toagosei Chemical Industries, Ltd.) as the polymerizable compound (B), and v-glycidoxypropyltrime as an adhesion aid. 0.05 g of oxysilane, 0.03 g of BM-1000 (manufactured by BM Chemical Co., Ltd.) as a surfactant, and 0.2 g of 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane as a thermal polymerization inhibitor Was dissolved and kneaded with a three roll mill to make a uniform composition solution.

Table 1 shows the content of (A) component, (B) component, and (C) component.

(2) evaluation of characteristics

① Evaluation of resolution

After using a spinner on a Nikel substrate, the composition was applied at 1,000 rpm for 20 seconds, and then prebaked at 90 ° C. for 5 minutes on a hot plate to form a coating film having a film thickness of 55 μm.

Next, 300 mJ / cm <^2> ultraviolet-rays were exposed using the ultrahigh pressure mercury lamp (USH-250D by Usio) via the pattern mask for resolution measurement.

This was developed with 0.5% aqueous tetramethylammonium hydroxy solution. Thereafter, the mixture was washed with running water, and nitrogen was blown to obtain a patterned cured product. This was observed with the optical microscope and the resolution was measured. Moreover, the film thickness after image development was measured and the residual film ratio (%) was calculated | required. Here, the residual film ratio is a value obtained by dividing the film thickness after development by the film thickness after prebaking and multiplying by 100. The results are shown in Table 2.

② Plating Resistance

The board | substrate which has the patterned hardened | cured material obtained by (1) was heated on a hotplate at 100 degreeC for 5 minutes, and it was set as the test body.

Thereafter, the test body was immersed in the plating solution at 60 ° C. for 60 minutes, washed with running water to obtain a test target object. As the plating solution, microfabric Au 100 (manufactured by Tanaku-Kokujo Co., Ltd.) (hereinafter referred to as "plating solution A") and Soldaron NF (Nippon Lironal Co., Ltd.) (hereinafter referred to as "plating solution B") Used.

The to-be-tested test body was observed with the scanning electron microscope, the state of the patterned hardened | cured material was observed, and the tolerance of the plating liquid was evaluated. The results are shown in Table 2.

The case where the state of a patterned hardened | cured material is favorable was represented by "(circle)", and the case where a crack generate | occur | produced in a patterned hardened | cured material was represented by "X".

③ Plating

On the Nikel substrate, a coating film having a thickness of 55 탆 was formed in the same manner as in?

Subsequently, a square and a circle engraved on one side or a diameter of 50 to 100 μm and 10 μm were drawn, and an ultraviolet light of 300 mJ / cm ² was obtained using an ultra-high pressure mercury lamp (USH-250D manufactured by Ushio) through a mask made as a pattern. Was exposed.

This was developed and washed with the same method as in (1), and after obtaining a patterned hardened | cured material, it heated on the hotplate at 100 degreeC for 5 minutes, and used as the test body.

Plating was conducted by conducting the plating solution A and the plating solution B for 10 minutes at a current value of 1 to 10 A / 100 cm ² at room temperature to evaluate the wettability of the patterned cured product after the completion of plating and adhesion to the substrate. The results are shown in Table 2.

In the wettability evaluation of the plating solution, the case where plating was performed uniformly in a 50 μm square pattern was indicated by “○”, and the case where plating was performed unevenly was indicated by “X”. In addition, evaluation of adhesiveness with a board | substrate shows the case where a plating liquid does not penetrate between a patterned hardened | cured material and a board | substrate with "(circle)", and the case where a plating liquid penetrates between a patterned hardened | cured material and a board | substrate is shown. It is marked with "X".

④ Peelability

In order to peel off the patterned hardened | cured material from the test body to which the plating obtained in (3) was carried out, it removed to the stripping liquid [0.5 wt% of dimethylsulfoxide solution (1.5 wt% function) of tetramethylammonium hydroxide in stirring] at 50 degreeC. The test body was immersed for 5 minutes, and the patterned hardened | cured material was peeled off and the 50 micrometer x 50 micrometer plating part formed on the board | substrate was observed with the scanning electron microscope. The results are shown in Table 2.

The case where the residue of a patterned hardened | cured material was not confirmed was represented by "(circle)", and the case where a residue was confirmed was represented by "X".

⑤ Crack resistance at bending deformation

The resist was applied to a polyimide film having a thickness of 50 μm and baked in an oven at 100 ° C. for 20 minutes. The resist-coated polyimide film was rolled up to 60 mm, 30 mm, and 10 mm diameter glass rods and visually observed whether cracks occurred in the resist film.

The case where no crack has occurred is indicated by "○" and the case where a crack has occurred as "X".

Examples 2 to 9 and Comparative Examples 1 to 3

The compositions of Examples 2 to 9 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 1 except that the copolymer (A), the photopolymerizable compound (B) and the radical photopolymerization initiator shown in Table 1 were used. .

Then, the characteristic evaluation was performed like Example 1 using each composition. The results are shown in Table 2.

Examples 10-12 and Comparative Examples 4-5

Using the compositions shown in Table 1, crack resistance at bending deformation was evaluated.

The evaluation results are shown in Table 3.

Table 1

TABLE 2

TABLE 3

The radiation-sensitive resin composition of the present invention has sufficient resolution with developability to an alkali developer and a film thickness of 20 µm or more, and furthermore, excellent plating resistance and development.

Adhesiveness with the board | substrate at the time and favorable wettability with respect to a plating liquid are shown, the favorable bump by plating can be formed, and at the same time, the peelability of the hardened | cured material from a board | substrate is excellent.

Claims (4)

(A) (a) 10 to 50% by weight of the component consisting of a radically polymerizable compound having a carboxyl group (-COOH), (b) 20 to 60% by weight of a constituent consisting of a radically polymerizable compound having a cyclic alkyl group and no carboxyl group, and (c) 5 to 40% by weight of the component consisting of radically polymerizable compounds other than (a) and (b) Alkali-soluble copolymer consisting of, (B) a compound having at least one ethylenically unsaturated double bond, and (C) radiation radical polymerization initiator A radiation-sensitive resin composition comprising a.  The method of claim 1, (A) Component (c) which comprises alkali-soluble copolymer The radically polymerizable compound other than said (a) and (b) contains the compound represented by following formula (A), The radiation sensitive resin composition characterized by the above-mentioned. . Where R ₁ is hydrogen or a methyl group, R ₂ hydrogen or C ₁ -C ₄ alkyl group, n is a number satisfying 2 ≦ n ≦ 25. The component (c) which comprises an alkali-soluble copolymer, The radically polymerizable compound other than said (a) and (b) contains the compound represented by following formula (b), The radiation-sensitive radiation of Claim 1 characterized by the above-mentioned. Resin composition. In the above formula R ₁ is hydrogen or a methyl group, R ₂ is hydrogen or a C ₁ -C ₄ alkyl group, n is a number satisfying 2 ≦ n ≦ 125. The bump forming material which consists of a radiation sensitive resin composition of Claim 1.