JP2007328090A - Photosensitive composition, photosensitive film, pattern forming method and printed circuit board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative photosensitive composition having high sensitivity to a blue-violet laser exposure system, excellent in storage stability and plating resistance, giving a thick film suitable for forming a bump pattern, a wiring pattern or the like, and suitable for forming a high-definition bump pattern, a high-definition wiring pattern or the like with high resolution, a photosensitive film, a pattern forming method for forming a pattern such as a bump pattern or a wiring pattern, and a printed circuit board. <P>SOLUTION: The photosensitive composition comprises a phenolic hydroxyl group-containing resin, a resin containing benzyl, carboxyl and hydroxyl groups, a crosslinking agent which achieves crosslinking under an acid, and a photoacid generator having an absorption maximum at a wavelength of 350-420 nm, wherein the sensitivity of the photosensitive composition at a wavelength of 405 nm is 10-100 mJ/cm<SP>2</SP>. There are also provided the photosensitive film using the photosensitive composition, the pattern forming method using the photosensitive composition, etc., and the printed circuit board formed by the pattern forming method. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is highly sensitive to a blue-violet laser exposure system, has excellent storage stability and plating resistance, and can provide a thick film suitable for forming bump patterns, wiring patterns, etc., and has high resolution and high definition. The present invention relates to a negative photosensitive composition, a photosensitive film, a pattern formation method such as a bump pattern and a wiring pattern, and a printed circuit board which are suitable for forming a bump pattern and a wiring pattern.

In recent years, with the downsizing of electronic devices, LSI integration and ASICs are rapidly progressing, and multi-pin thin film mounting is required for mounting LSIs in electronic devices. Implementation has attracted attention. In such a multi-pin mounting method, it is necessary that a bump electrode called a bump, which is a connection terminal for an LSI, having a height of 20 μm or more be arranged on the substrate with high accuracy. Corresponding to the miniaturization, higher accuracy of bumps is becoming more necessary. Further, in order to assist the formation of the connection terminal, a design in which a wiring between the chip and the connection terminal is formed using a rewiring process is often seen. In this case, a wiring pattern is formed using a resist having a thickness of about 5 to 20 μm.
A so-called thick film photoresist is used as a bump forming material or a rewiring material used when forming such a bump. The thick film photoresist means a photoresist capable of forming a film thickness of about 5 μm or more on the substrate, and bumps are formed by a plating process using this thick film pattern as a plating mask.
As the bump forming and wiring forming materials, for example, the thick film photosensitive compositions described in Patent Documents 1 to 3 are disclosed.
However, in these conventional thick film photosensitive compositions, since the film is thick, a large amount of a reaction initiator is required to sufficiently react the entire resist film. Thus, when there is much content of a reaction initiator, there exists a possibility that compatibility will worsen and there exists a tendency for the bleed out at the time of storage to generate | occur | produce. Accordingly, there has been a demand for a reaction initiator that is excellent in storage stability of a photosensitive composition and that is highly sensitive even in a smaller amount.
In addition, when a known bump forming material is used in a blue-violet laser exposure system, there is also a problem that sensitivity is insufficient.

On the other hand, a chemically amplified resist using an acid generator is known as a highly sensitive photosensitive composition. A feature of the chemically amplified resist is that a protonic acid generated from an acid generator as a component by radiation irradiation causes an acid-catalyzed reaction to a base resin or the like in the resin composition by heat treatment after exposure. In this way, a dramatic increase in sensitivity is achieved as compared with conventional photoresists having a photoreaction efficiency (reaction per photon) of less than 1. As a typical example of the chemically amplified negative resist, L. E. Bogan et al. Describe resists that combine polyvinylphenol and melamine derivatives.
However, when a thick film is produced using these chemically amplified resists, there is a problem that cracks occur and the necessary plating resistance cannot be obtained.
In order to improve the above problems, a photosensitive composition comprising a novolac resin, a plasticizer, a crosslinking agent, and an acid generator is known (see, for example, Patent Document 4). Although such a photosensitive composition can form a resist film having high resolution and excellent plating resistance, there is a problem that flexibility and storage stability are not so good that a dry film can be formed. It was.

  Therefore, it is highly sensitive to the blue-violet laser exposure system, has good plating resistance, has excellent storage stability, and is suitable for dry film materials for forming wiring patterns, bump patterns, etc. A negative photosensitive composition suitable for forming high-definition and high-definition bump patterns and wiring patterns, photosensitive films, and patterns such as bump patterns and wiring patterns using the photosensitive composition A forming substrate and a printed circuit board on which bumps and wiring are formed by the pattern forming method have not been provided yet, and further improvement and development are desired.

JP-A-10-207057 JP 2000-39709 A JP 2000-66385 A JP 2003-43688 A SPIE Proceeding (Proceeding of SPIE), 1086, 34-47 (1989)

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention is highly sensitive to a blue-violet laser exposure system, has excellent storage stability and plating resistance, and can provide a thick film suitable for forming bump patterns, wiring patterns, etc., with high resolution. It is an object of the present invention to provide a negative photosensitive composition, a photosensitive film, a pattern forming method, and a printed board suitable for forming a high-definition bump pattern, wiring pattern, and the like.

As a result of intensive studies by the present inventors in order to solve the above-mentioned problems, (A) a phenolic hydroxyl group-containing resin, (B) a resin containing a benzyl group, a carboxyl group and a hydroxyl group, and (C) a bridge crosslinked with an acid. By using a photosensitive composition containing an agent and (D) a photoacid generator having an absorption maximum with respect to a wavelength of 350 to 420 nm and a sensitivity at a wavelength of 405 nm of 10 to 100 mJ / cm ² , High sensitivity to the laser exposure system, excellent storage stability and plating resistance, thick film suitable for forming bump patterns, wiring patterns, etc., and high-definition patterns can be formed. I found out.

The present invention is based on the above knowledge of the present inventor, and means for solving the above problems are as follows. That is,
<1> (A) phenolic hydroxyl group-containing resin, (B) resin containing benzyl group, carboxyl group and hydroxyl group, (C) crosslinking agent crosslinked with acid, and (D) absorption maximum with respect to wavelength 350-420 nm And a photoacid generator having a sensitivity of 10 to 100 mJ / cm ² at a wavelength of 405 nm.
<2> (B) The glass transition temperature (Tg) of the resin containing a benzyl group, a carboxyl group and a hydroxyl group is 240 to 300 K (−33 to 27 ° C.), the acid value is 50 to 120 mgKOH / g, and the hydroxyl group It is a photosensitive composition as described in said <1> which is a benzyl (meth) acrylate copolymer whose value is 70-180 mgKOH / g and whose mass average molecular weight is 10,000-100,000.
<3> (B) The photosensitive property according to any one of <1> to <2>, wherein the resin containing a benzyl group, a carboxyl group, and a hydroxyl group is a copolymer represented by the following general formula (I): It is a composition.
However, in said general formula (I), R < ¹ >, R < ² >, R < ³ >, R < ⁵ >, R < ⁶ >, R <^7> , R <^8> , and R < ⁹ > independently represent either a hydrogen atom or a methyl group, R ⁴ is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, and ^{-CO-R 12,, R 12} is a hydrogen atom, an alkyl group, a substituted alkyl group, vinyl group, substituted vinyl group , An alkenyl group, a substituted alkenyl group, an aryl group, and a substituted aryl group. R ¹⁰ and R ¹¹ represent any of a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. x, y, and z represent the molar composition ratio of each repeating unit, and x = 0.05-0.70, y = 0.1-0.3, z = 0.2-0.8, x + y + z = 1.
<4> (C) The crosslinking agent is at least one selected from methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, and methoxymethylated glycoluril resin. The photosensitive composition according to any one of <1> to <3>.
<5> (D) The photoacid generator according to any one of <1> to <4>, wherein the photoacid generator is an oxime sulfonate compound represented by the following general formulas (II-1) to (II-4): It is a photosensitive composition.
In the general formula (II-1) ~ (II -4), n represents an integer of 1 to 2, ^{X 0} is - _(CH 2) any m-X, and -CH = CH ₂ X represents any of an ester group, an ether group, an amide group, an imide group, a thioether group, a sulfoxide group, and a sulfonate group. m represents an integer of 2 to 6. When n is 1, R ¹ and R ⁵ represent either hydrogen or an organic group. When n is 2, R ¹ and R ⁵ represent either a direct bond or a divalent organic group. To express. . X ′ represents either a direct bond or a divalent organic group. R ³ , R ⁴ , R ⁷ and R ⁸ may be the same or different from each other, and represent either hydrogen or an organic substituent, and any one of R ³ and R ⁴ , and R ⁷ and R ⁸ May form either a benzene ring or a maleimide ring, which may be substituted together.
<6> Further comprising a neutral sensitizer, wherein the neutral sensitizer is at least one selected from 2,4-diethylthioxanthone and 1-chloro-4-propoxythioxanthone <5> The photosensitive composition according to any one of the above.

<7> A photosensitive film comprising a support and a photosensitive layer comprising the photosensitive composition according to any one of <1> to <6> on the support.
<8> The photosensitive film according to <7>, wherein the support includes a synthetic resin and is transparent.
<9> The photosensitive film according to any one of <7> to <8>, wherein the support has a long shape.
<10> The photosensitive film according to any one of <7> to <9>, which is long and wound in a roll shape.
<11> The photosensitive film according to any one of <7> to <10>, having a protective film on the photosensitive layer.
<12> The photosensitive film according to any one of <7> to <11>, wherein the photosensitive layer has a thickness of 5 to 100 μm.

<13> The photosensitive layer formed of the photosensitive composition according to any one of <1> to <6> is subjected to pattern exposure and development to form a resist pattern, and the resist pattern is masked After the plating, the method includes a method of peeling off the resist pattern.
<14> The pattern forming method according to <13>, wherein the photosensitive layer is formed of the photosensitive film according to any one of <7> to <12>.
<15> The pattern forming method according to any one of <13> to <14>, wherein the exposure is performed using a laser beam having a wavelength of 350 to 415 nm.
<16> The pattern forming method according to any one of <13> to <15>, wherein the heat treatment is performed after the exposure.
<17> The pattern forming method according to any one of <13> to <16>, wherein after the development, the photosensitive layer is subjected to a post-curing process.
<18> The pattern forming method according to <17>, wherein the post-curing process is at least one of an entire surface exposure process and an entire surface heat treatment.
<19> The pattern forming method according to any one of <13> to <18>, wherein any one of a bump pattern and a wiring pattern is formed.

  <20> A printed circuit board comprising at least one of a bump and a wiring formed by the pattern forming method according to any one of <13> to <19>.

  According to the present invention, conventional problems can be solved, high sensitivity to a blue-violet laser exposure system, excellent storage stability and plating resistance, and suitable for formation of bump patterns, wiring patterns, etc. A negative photosensitive composition, a photosensitive film, a bump pattern using the photosensitive composition, a wiring pattern, and the like suitable for forming a high-resolution and high-definition bump pattern, wiring pattern, etc. And a printed circuit board on which bumps, wirings, and the like are formed by the pattern forming method.

(Photosensitive composition)
The photosensitive composition of the present invention comprises (A) a phenolic hydroxyl group-containing resin, (B) a resin containing a benzyl group, a carboxyl group and a hydroxyl group, (C) a crosslinking agent, and (D) a photoacid generator, Further, it contains (E) a neutral sensitizer and other components appropriately selected as necessary.
The photosensitive composition of the present invention is required to have a sensitivity at a wavelength of 405 nm of 10 to 100 mJ / cm ² , and preferably 10 to 30 mJ / cm ² .

<(A) Phenolic hydroxyl group-containing resin>
Preferable examples of the phenolic hydroxyl group-containing resin include a phenol group-containing vinyl polymer (a-1) having a mass average molecular weight of 5,000 or more and a phenol group-containing condensed polymer (a-2).

-(A-1) Phenol group-containing vinyl polymer-
The phenol group-containing vinyl polymer is a polymer having a molecular weight of 5,000 or more and a phenolic hydroxyl value of 160 to 460 mgKOH / g. (1) Examples thereof include a polymer obtained and (2) a polymer obtained by reacting a polymer having a reactive functional group with a phenolic hydroxyl group-containing compound.
(1) Polymer obtained by vinyl polymerization of monomer having phenolic hydroxyl group and vinyl group in the same molecule Examples of the monomer having phenolic hydroxyl group and vinyl group in the same molecule include vinylphenols and (meth) acryloyl. Examples include aminophenols and (meth) acryloyloxyphenols.
Examples of the vinylphenols include p-vinylphenol, m-vinylphenol, o-vinylphenol, p-vinyl-o-cresol, p-vinyl-m-cresol, and the like.
Examples of the (meth) acryloylaminophenols include p- (meth) acryloylaminophenol, m- (meth) acryloylaminophenol, o- (meth) acryloylaminophenol, and the like.
Examples of the (meth) acryloyloxyphenol include p- (meth) acryloyloxyphenol, m- (meth) acryloyloxyphenol, o- (meth) acryloyloxyphenol, and the like.

The said phenol group containing polymer suitable for this invention can also contain the copolymer with other vinyl monomers, unless the monomer containing these phenol groups and a vinyl group, and alkali solubility are impaired.
The vinyl monomer is preferably selected from a group of compounds that are copolymerizable with the phenolic hydroxyl group and the vinyl group-containing monomer and do not contain a group that reacts with a carboxyl group, an amino group, or a phenolic hydroxyl group.
Examples of the compound include (meth) acrylic acid esters, (meth) acrylonitrile, (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid alkoxyalkyl ester, and styrenes.

(2) Polymer obtained by reaction of polymer having reactive functional group and phenolic hydroxyl group-containing compound Specific examples of the polymer include addition reaction products of an epoxy group-containing binder and hydroxybenzoic acid. It is done.

(A-2) Phenol group-containing condensation polymer The phenol group-containing condensation polymer is a phenol polymer obtained by polycondensation using an acidic catalyst of phenols and aldehydes, and is known as a novolak resin.
The phenol group-containing condensation polymer can be obtained, for example, by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as “phenols”) and an aldehyde in the presence of an acid catalyst.
Examples of the phenols used at this time include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3 , 4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglicinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol, etc. Can be mentioned.
Examples of the aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde, and the like.
There is no restriction | limiting in particular as a catalyst at the time of the said addition condensation reaction, According to the objective, it can select suitably, For example, hydrochloric acid, nitric acid, a sulfuric acid, formic acid, an oxalic acid, an acetic acid etc. are used as an acid catalyst. be able to.
There is no restriction | limiting in particular as a mass average molecular weight of the said phenol group containing condensation type polymer (novolak resin), According to the objective, it can select suitably, For example, 1,000-30,000 are preferable.

  As content of said (A) phenolic hydroxyl group containing resin, 50-95 mass parts is preferable with respect to 100 mass parts of total amounts of a photosensitive composition, and 65-80 mass parts is more preferable. When the content is less than 50 parts by mass, plating resistance, bump shape, and peelability may be deteriorated. When the content is more than 95 parts by mass, poor development may occur during development.

(B) Resin containing benzyl group, carboxyl group and hydroxyl group The resin containing benzyl group, carboxyl group and hydroxyl group is not particularly limited as long as it basically contains benzyl group, carboxyl group and hydroxyl group in the molecule. The glass transition temperature (Tg) is 300 K (27 ° C.) or less, the acid value is 10 to 200 mg KOH / g, and the hydroxyl value in the molecule is A benzyl (meth) acrylate copolymer of 70 to 180 mgKOH / g and a weight average molecular weight of 10,000 to 100,000 is preferable, and the glass transition temperature (Tg) is 240 to 300 K (−33 to 27 ° C.). The acid value is 50 to 120 mgKOH / g, the hydroxyl value is 70 to 180 mgKOH / g, and the mass average molecular weight is 10,000 to 1. More preferred is a benzyl (meth) acrylate copolymer of 00,000. Details of the glass transition temperature, the acid value, the hydroxyl value, and the mass average molecular weight will be described later.

Specific examples of the resin containing a benzyl group, a carboxyl group, and a hydroxyl group include a copolymer having a structure composed of a repeating unit represented by the following general formula (I).
However, in said general formula (I), R < ¹ >, R < ² >, R < ³ >, R < ⁵ >, R < ⁶ >, R <^7> , R <^8> , and R < ⁹ > independently represent either a hydrogen atom or a methyl group, R ⁴ is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, and ^{-CO-R 12,, R 12} is a hydrogen atom, an alkyl group, a substituted alkyl group, vinyl group, substituted vinyl group , An alkenyl group, a substituted alkenyl group, an aryl group, and a substituted aryl group. R ¹⁰ and R ¹¹ represent any of a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. x, y, and z represent the molar composition ratio of each repeating unit, and x = 0.05-0.70, y = 0.1-0.3, z = 0.2-0.8, x + y + z = 1.

As the first repeating unit of the general formula (I), an acrylic acid unit, a methacrylic acid unit, a crotonic acid unit, a 2,3-dimethylacrylic acid unit, or a 2,3,3-trimethylacrylic acid unit, It can be obtained by reaction with a compound having one epoxy group represented by the structural formula.
However, in said structural formula, R < ⁴ > represents the same meaning as R < ⁴ > of the said general formula (I).

The repeating unit of the general formula (I) can be obtained by polymerization of a corresponding acrylic compound, but can also be obtained by reacting with a polymer having a repeating unit represented by the following structural formula. In particular, when R ⁴ in the general formula (I) is —CO—CR ¹² ═CH ₂ , it is produced by a reaction method with the polymer.
In Structural ^Formula, R 12 ^{to R 14} represents a hydrogen atom or a methyl ^group, R 8 ^{to R 11} represent the same meaning as ^R 8 ^{to R 11} in the general formula (I) . i and j represent the molar composition ratio of each repeating unit, i = 0.8 to 0.20, j = 0.2 to 0.8, and i + j = 1.

Specific examples of the first repeating unit of the general formula (I) include 3-isopropoxy-2-hydroxypropyl (meth) acrylate, 3-n-butoxy-2-hydroxypropyl (meth) acrylate, 3-n -Hexyloxy-2-hydroxypropyl (meth) acrylate, 3-cyclohexyloxy-2-hydroxypropyl (meth) acrylate, 3-benzyloxy-2-hydroxypropyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl ( (Meth) acrylate, 3-methallyloxy-2-hydroxypropyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, 3- (2-methylphenoxy) -2-hydroxypropyl (meth) acrylate, 3- (4-methoxypheno ) -2- hydroxypropyl (meth) acrylate, 3-acetoxy-2-hydroxypropyl (meth) acrylate, 3-benzoyloxy-2-hydroxypropyl (meth) acrylate, repeat units from.
Moreover, 3- (meth) acryloyloxy-2-hydroxypropyl (meth) acrylate is mentioned as a repeating unit obtained only by a polymer reaction.
Among these, as the most preferable one as the first repeating unit, 3-phenoxy-2-hydroxypropyl (meth) acrylate, 3-benzyloxy-2-hydroxypropyl (meth) acrylate, 3-acryloyloxy-2- And hydroxypropyl (meth) acrylate.

  As the second repeating unit, a repeating unit from a monomer having a carboxylic acid group as an alkali-soluble group is preferable. Specifically, an acrylic acid unit, a methacrylic acid unit, a crotonic acid unit, a 2,3-dimethylacrylic acid unit. Or 2,3,3-trimethylacrylic acid units, and among these, (meth) acrylic acid units are most preferred.

  The third repeating unit can be included for the purpose of appropriately controlling physical and chemical properties. Examples of such radical polymerizable compounds include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxy (Meth) acrylic acid hydroxyalkyl esters such as propyl (meth) acrylate; (meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate; dicarboxylic acids such as diethyl maleate and dibutyl fumarate Diesters; vinyl group-containing aromatic compounds such as styrene and α-methylstyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitric acid such as acrylonitrile and methacrylonitrile Lil group-containing polymerizable compound, vinyl chloride, chlorine-containing polymerizable compounds such as vinylidene chloride; acrylamide, amide bond-containing polymerizable compounds such as methacrylamide, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, n-butyl acrylate, benzyl methacrylate, methyl methacrylate, and the like are particularly preferable.

Preferred combinations of x, y, and z, which are the copolymer composition ratio of each repeating unit, include the acid value, hydroxyl value, glass transition temperature (Tg), etc. of the alkali-soluble polymer represented by the general formula (I). Can be selected.
As said glass transition temperature (Tg), 300K (27 degreeC) or less is preferable, 200-300K (-73-27 degreeC) is more preferable, 240-300K (-33-27 degreeC) is still more preferable. When the glass transition temperature is less than 200K (−73 ° C.), the adhesiveness of the photosensitive layer is high and the peelability of the support may be inferior, and when it exceeds 300K (27 ° C.), the mechanical properties of the photosensitive layer are increased. Since the strength is inferior, cracks may easily occur.
As said acid value, 10-200 mgKOH / g is preferable and 50-120 mgKOH / g is more preferable. When the acid value is less than 10 mgKOH / g, the developability is inferior and sufficient peelability of the cured film may not be obtained. When the acid value exceeds 200 mgKOH / g, the remaining film ratio in the exposed area is reduced and the plating resistance is reduced. May get worse.
As said hydroxyl value, 70-180 mgKOH / g is preferable and 80-150 mgKOH / g is more preferable. When the hydroxyl value is less than 70 mgKOH / g, the compatibility with the phenol compound may be inferior, and when it exceeds 180 mgKOH / g, the water resistance of the exposed cured portion may be inferior.
The mass average molecular weight of the alkali-soluble binder is preferably 10,000 to 100,000, more preferably 10,000 to 80,000, and still more preferably 30,000 to 50,000. When the mass average molecular weight is less than 10,000, sufficient strength of the photosensitive layer cannot be obtained, and the swelling of the profile during plating and the generation of cracks may be caused. There are things to do.

Examples of the solvent used when synthesizing the resin containing the benzyl group, carboxyl group and hydroxyl group include alcohols such as ethanol and diethylene glycol; Alkyl ethers of alcohols; Alkyl ether acetates of polyhydric alcohols such as ethylene glycol ethyl ether acetate and propylene glycol methyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as acetone and methyl isobutyl ketone; Acetic acid And esters such as ethyl and butyl acetate. Among these, polyhydric alcohol alkyl ethers and polyhydric alcohol alkyl ether acetates are particularly preferred.
As the catalyst, an ordinary radical polymerization initiator can be further used. Specifically, for example, azo compounds such as 2,2′-azobisisobutyronitrile; benzoyl peroxide, di-t -Organic peroxides such as butyl peroxide.

  The content of the resin containing (B) a benzyl group, a carboxyl group and a hydroxyl group is preferably 5 to 30 parts by mass, more preferably 10 to 20 parts by mass with respect to 100 parts by mass of the total amount of the photosensitive composition. preferable. When the content is less than 5 parts by mass, the resist may float during plating and cracking may occur, and the plating resistance may decrease. When the content exceeds 30 parts by mass, the strength of the formed thick film decreases. A clear profile may not be obtained due to swelling or the like, and the resolution may be lowered.

<(C) Crosslinking agent that crosslinks with acid>
The crosslinking agent is not particularly limited as long as it is crosslinked with an acid, and can be appropriately selected according to the purpose. Examples thereof include amino compounds. Examples of the amino compound include melamine resin, urea resin, guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, ethyleneurea-formaldehyde resin, and the like. Among these, alkoxymethylated amino resins such as alkoxymethylated melamine resins and alkoxymethylated urea resins are particularly preferred.
The alkoxymethylated amino resin is obtained by, for example, condensing a condensate obtained by reacting melamine or urea with formalin in a boiling aqueous solution with a lower alcohol such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, or isopropyl alcohol. And then the reaction solution is cooled and precipitated.
Specific examples of the alkoxymethylated amino resin include methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, methoxymethylated urea resin, and ethoxymethylated urea. Examples thereof include resins, propoxymethylated urea resins, butoxymethylated urea resins and the like. As said alkoxymethylated amino resin, you may use individually by 1 type and may use 2 or more types together. Among these, an alkoxymethylated melamine resin is particularly preferable from the viewpoint of forming a stable resist pattern with a small dimensional change amount of the resist pattern with respect to a change in radiation dose. Among the alkoxymethylated melamine resins, methoxymethylated melamine resins, ethoxymethylated melamine resins, propoxymethylated melamine resins, butoxymethylated melamine resins, and methoxymethylated glycoluril resins are most preferable.

  As content of the said (C) crosslinking agent, 1-30 mass parts is preferable with respect to 100 mass parts of total amounts of the said photosensitive composition, and 5-20 mass parts is more preferable. When the content is less than 1 part by mass, plating resistance, chemical resistance, and adhesion of the obtained thick film may be reduced, and the formed bump shape may be defective. Development failure may occur during development.

<(D) Photoacid generator>
The photoacid generator (hereinafter referred to as component (D)) is particularly a compound that has an absorption maximum at a wavelength of 350 to 420 nm and generates an acid directly or indirectly by a 405 nm laser beam. There is no restriction | limiting, According to the objective, it can select suitably, From the viewpoint of a sensitivity or storage stability, the oxime sulfonates represented by the following general formula (II-1)-general formula (II-4) are suitable. It is mentioned in.
However, in said general formula (II-1)-(II-4), n represents the integer in any one of 1 and 2. X ⁰ represents any of — (CH ₂ ) m—X and —CH═CH ₂ . m represents an integer of 2, 3, 4, 5 and 6.
When n is 1, R ¹ and R ⁵ are any one of a phenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, and a heteroaryl, hydrogen (provided that R ² is not hydrogen at the same time); C ₁ -C ₁₈ alkyl group, one or more _C 3 _{-C 30} cycloalkylene group, ^{and, -O -, - S -,} - NR 9 -, - (CO) -, - O (CO) -, - S ( ^{CO) -, - NR 9 (} CO) -, - SO -, - SO 2 -, and -OSO ₂ - _{C 2 ~C 18} alkyl group which is interrupted by either, _either, C 3 -C _{It represents any of a 30} cycloalkyl group, a C ₁ -C ₈ haloalkyl group, a C ₂ -C ₁₂ alkenyl group, a C ₄ -C ₃₀ cycloalkenyl group, and a camphoryl group.
When n is 2, R ¹ and R ⁵ are a phenylene group, a naphthylene group, the following formula:
, Diphenylene group, oxydiphenylene group, and the following formula:
A direct bond, and the following formula:
Represents one of the following.
Here, except for the case where all of R ¹ are hydrogen and a direct bond, a group having either an —O—C— bond or an —O—Si— bond that is cleaved by the action of an acid, May be substituted. R ¹ is a C _{2 to} C ₁₈ alkanoyl group, optionally one or more C _{1 to} C ₁₈ alkyl groups, a C _{1 to} C ₈ haloalkyl group, a C _{3 to} C ₃₀ cycloalkyl group, a halogen group, — _{^{NO 2, -CN, -Ar 1,}} - (CO) R 10, - (CO) OR 11, - (CO) NR 12 R 13, -O (CO) R 10, -O (CO) OR 11, - O (CO) NR ¹² R ¹³ , —NR ⁹ (CO) R ¹⁰ , —NR ⁹ (CO) OR ¹¹ , —OR ¹¹ , —NR ¹² R ¹³ , —SR ⁹ , —SOR ¹⁰ , —SO ₂ R ¹⁰ , and at least a benzoyl group substituted with one of _{^{-OSO 2 R 10, NO 2,}} S (O) p C 1 ~C 18 alkyl _{group, S (O) p -C 6} ~C 12 aryl group, SO _{2 O-C} 1 _{~C 18} alkyl _{, SO 2 O-C 6 ~C} 10 aryl group and diphenyl, - represents any of phosphinoyl group.

A ¹ represents a direct bond, a C _{1 to} C ₁₈ alkylene group, —O—, —S—, —NR ⁹ —, —O (CO) —, —S (CO) —, —NR ⁹ (CO) —. _{, -SO -, - SO 2 -} , and -OSO ₂ - represents either.
A ² represents a direct bond, C _{1 to} C ₁₈ alkylene, one or more C _{3 to} C ₃₀ cycloalkylene groups, and —O—, —S—, —NR ⁹ —, — (CO) —, C interrupted by any of —O (CO) —, —S (CO) —, —NR ⁹ (CO) —, —SO—, —SO ₂ —, —OSO ₂ —, and —Ar ² —. ₂ -C ₁₈ alkylene group, _either, C 3 _{-C 30} cycloalkylene group, and an phenylene group and naphthylene group.

The p represents an integer of 1 or 2.
Said X is -O (CO) R < ¹⁴ >, -O (CO) OR < ¹¹ >, -O (CO) NR < ¹² > R < ¹³ >, -NR < ⁹ > (CO) R < ¹⁴ >, -NR < ⁹ > (CO) OR < ¹¹ >, -OR. ¹¹ , —NR ¹² R ¹³ , the following formula:
_{^{, -SR 9, -SOR 10, -SO}} 2 R 10, and represents one of -OSO ₂ R ^10.
X ′ is represented by the following formula:
Represents.
X ¹ and X ² are independently of each other, —O (CO) —, —O (CO) O—, —O (CO) NR ⁹ —, —NR ⁹ (CO) —, —NR ⁹ (CO ^{) O -, - O -,} - NR 9 -, - S -, - SO -, - SO 2 -, and -OSO ₂ - represents either. X ¹ and X ² are direct bonds, provided that both X ¹ and X ² are not direct bonds at the same time.
Wherein ^{A 3} is a phenylene group, a naphthylene group of the following formula:
, Diphenylene group, oxydiphenylene group, and the following formula:
A direct bond, and the following formula:
Represents one of the following.

R ² has ^one of the meanings indicated for R ¹ , a C _{2 to} C ₁₈ alkanoyl group, one or more C _{1 to} C ₁₈ alkyl groups, a C _{1 to} C ₈ haloalkyl group, C ₃ -C ₃₀ cycloalkyl group, a halogen _{^{group, -NO 2, -CN, -Ar 1}} , - (CO) R 10, - (CO) OR 11, - (CO) NR 12 R 13, -O (CO ) R ¹⁰ , —O (CO) OR ¹¹ , —O (CO) NR ¹² R ¹³ , —NR ⁹ (CO) R ¹⁰ , —NR ⁹ (CO) OR ¹¹ , —OR ¹¹ , —NR ¹² R ¹³ , _{^{-SR 9, -SOR 10, -SO 2}} R 10, and optionally substituted benzoyl group in one of _{^{-OSO 2 R 10, NO 2,}} S (O) p C 1 ~C 18 alkyl group, S _{(O) p -C} 6 ~C ₁₂ aryl group, S _{2 O-C} 1 _{~C 18} alkyl _{group, SO 2 O-C 6 ~C} 10 aryl group, and diphenyl - phosphinoyl represents any one group. R ¹ and R ² may be combined to form a 5-membered, 6-membered or 7-membered ring.
R ³ , R ⁴ , R ⁷ and R ⁸ are each independently hydrogen, a C _{1 to} C ₁₈ alkyl group, a C _{1 to} C ₈ haloalkyl group, a C _{3 to} C ₃₀ cycloalkyl group, and one more ^{-O -, - S -, -} NR 9 -, - O (CO) - and _{^{-NR 9 (CO) - C 3}} ~C 30 cycloalkyl group which is interrupted by either, either, a halogen _{^{group, -NO 2, -CN, -Ar 1}} , - (CO) R 10, - (CO) OR 11, - (CO) NR 12 R 13, -O (CO) R 10, -O (CO) ^{OR 11, -O (CO) NR} 12 R 13, -NR 9 (CO) R 10, -NR 9 (CO) OR 11, -OR 11, -NR 12 R 13, -SR 9, -SOR 10, - SO ₂ R ^10, and represents one of -OSO ₂ R ^10. R ³ and R ⁴ , or R ⁷ and R ⁸ are combined together to form —C (R ¹⁵ ) ═C (R ¹⁶ ) —C (R ¹⁷ ) ═C (R ¹⁸ ) —, and — Any one of (CO) NR ⁹ (CO) — may be represented.

The G represents any of —S—, —O—, —NR ⁹ —, and a group represented by any one of the following formulas Z ¹ , Z ² , Z ³ and Z ⁴ .

R ¹⁹ and R ²⁰ may have, independently of each other, one of the meanings indicated by R ³ , or R ¹⁹ and R ²⁰ together represent —CO One of -NR < ⁹ > CO- and -C (R < ¹⁵ >) = C (R < ¹⁶ >)-C (R < ¹⁷ >) = C (R < ¹⁸ >)-may be represented.
R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently hydrogen, halogen, C ₁ -C ₁₈ alkyl group, C ₁ -C ₁₈ alkoxy group, C ₁ -C ₈ haloalkyl group, CN, NO ₂ , C _{2 to} C ₁₈ alkanoyl group, benzoyl group, phenyl group, —S-phenyl group, OR ¹¹ , SR ⁹ , NR ¹² R ¹³ , C _{2 to} C ₆ alkoxycarbonyl group, phenoxycarbonyl group, S (O) _p C ₁ -C ₁₈ alkyl _group, C 1 _{-C 18} optionally substituted with an alkyl group _{S (O) p -C 6 ~C} 12 aryl _{group, SO 2 O-C 1 ~C} 18 alkyl group, SO _It represents any of ₂ O—C ₆ -C ₁₀ aryl and NHCONH ₂ .
Ar ¹ is any ^one of a phenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, and a heteroaryl group.
R ¹⁰ is a phenyl group, a naphthyl group, a C _{3 to} C ₃₀ cycloalkyl group, a C _{1 to} C ₁₈ alkyl group, a C _{1 to} C ₈ haloalkyl group, a C _{2 to} C ₁₂ alkenyl group, or a C _{4 to} C ₃₀ cyclo. or alkenyl group, _C 2 _{-C 18} alkyl radical which is interrupted by one or more -O-, one or more ^{-O -, - S -, -} NR 9 -, - O (CO) -, and ^-NR 9 (CO) - _C 3 interrupted by either _{-C 30} cycloalkyl group (all of which optionally substituted with one or more ^Ar 1, _OH, C 1 _{-C 18} alkyl group, _{C 1} -C ₈ haloalkyl _group, C 3 _{-C 30} cycloalkyl group, a halogen _{group, -NO 2, -CN, C 1} ~C 12 alkoxy group, a phenoxy group, a phenoxycarbonyl group, a phenylthio group, phenylthio group, _{^{NR 12 R 13, C 1 ~C}} 12 alkylthio _groups, C 2 _{-C 12} alkoxycarbonyl _group, C 2 -C ₈ haloalkanoyl group, halobenzoyl _group, C 1 _{-C 12} alkylsulfonyl group, phenylsulfonyl group, (4 - methylphenyl) sulfonyl _group, C 1 _{-C 12} alkylsulfonyloxy group, a phenylsulfonyloxy group, (4-methylphenyl) sulfonyloxy _group, C 2 _{-C 12} alkanoyl _group, C 2 _{-C 12} alkanoyloxy group, a benzoyl , And at least one of benzoyloxy groups), hydrogen.
R ¹¹ is a phenyl group, a naphthyl group, a C _{3 to} C ₃₀ cycloalkyl group, a C _{1 to} C ₁₈ alkyl group, a C _{1 to} C ₈ haloalkyl group, a C _{2 to} C ₁₂ alkenyl group, or a C _{4 to} C ₃₀ cyclo. or alkenyl group, _C 2 _{-C 18} alkyl radical which is interrupted by one or more -O-, one or more ^{-O -, - S -, -} NR 9 -, - O (CO) -, and ^-NR 9 (CO) - one _C 3 _{-C 30} cycloalkyl radical which is interrupted _by, C 2 _{-C 18} alkanoyl group, a benzoyl _group, C 1 _{-C 18} alkylsulfonyl group, hydrogen, phenylsulfonyl group , (4-methylphenyl) sulfonyl group, naphthylsulfonyl group, anthracylsulfonyl group, and phenanthrylsulfonyl group.
R ¹² , R ¹³ and R ⁹ are each independently a phenyl group, a naphthyl group, a C ₃ -C ₃₀ cycloalkyl group, a C ₁ -C ₁₈ alkyl group, a C ₁ -C ₈ haloalkyl group, a C _2- C ₁₂ alkenyl group, and _C 4 _{-C 30} or cycloalkenyl group, _C 2 _{-C 18} alkyl radical which is interrupted by one or more -O-, one or more -O -, - S-, ^{-NR 9 -, - O (CO} ) -, and ^-NR 9 (CO) - _C 3 interrupted by either _{-C 30} cycloalkyl _group, C 2 _{-C 18} alkanoyl group, a benzoyl group, and a C ₁ -C ₁₈ or an alkyl sulfonyl group; independently of one another, hydrogen, a phenylsulfonyl group, (4-methylphenyl) sulfonyl group, naphthylsulfonyl group, anthracyl sill sulfonyl group, and phenanthryl Either Rusuruhoniru group; represents any of. R ¹² and R ¹³ together with the nitrogen atom to which they are attached are optionally 5-membered, 6-membered and 7-membered rings interrupted by either —O— or —NR ⁹ —. Any of these may be formed.
R ¹⁴ is any one of a phenyl group, a naphthyl group, a C _{3 to} C ₃₀ cycloalkyl group, a C _{1 to} C ₁₈ alkyl group, a C _{1 to} C ₈ haloalkyl group, and a C _{4 to} C ₃₀ cycloalkenyl group, One or more —O— interrupted C ₂ -C ₁₈ alkyl groups, one or more —O—, —S—, —NR ⁹ —, —O (CO) —, and —NR ⁹ (CO). - C ₃ -C ₃₀ cycloalkyl group which is interrupted by either, represent hydrogen, one of the. R ⁹ and R ¹⁴ may form any of a 5-membered, 6-membered and 7-membered ring together with the N atom to which they are bonded.
The Q ¹ represents any of —CR ²⁰ — and —N—, and the Q ² represents any of —CH ₂ —, —S—, —O—, and —NR ⁹ —.

  Specific examples of the photoacid generator represented by the general formula (II-1) to the general formula (II-4) include compounds represented by the following names and structural formulas, D-1 to D- 9 is mentioned.

[D-1]
5- {2- (methanesulfonyl) -ethanesulfoxy} -imino-5H-thiophen-2-ylidene-o-tolyl-acetonitrile absorption maximum wavelength: 405 nm

[D-2]
5- {2- (p-toluenesulfonyl) -ethanesulfoxy} -imino-5H-thiophen-2-ylidene-o-tolyl-acetonitrile absorption maximum wavelength: 410 nm

[D-3 (CGI1397)]
5- (3-propanesulfoxy) -imino-5H-thiophen-2-ylidene-o-tolylacetonitrile absorption maximum wavelength: 405 nm

[D-4]
5- (8-Octanesulfoxy) -imino-5H-thiophen-2-ylidene-o-tolylacetonitrile absorption maximum wavelength: 405 nm

[D-5 (CGI 1380)]
5- (Camphorsulfoxy) -imino-5H-thiophen-2-ylidene-o-tolylacetonitrile absorption maximum wavelength: 405 nm

[D-6 (CGI1311)]
5- (p-Toluenesulfoxy) -imino-5H-thiophen-2-ylidene-o-tolylacetonitrile absorption maximum wavelength: 410 nm

[D-7 (PAG103)]
3- (3-propanesulfoxy) -imino-2H-thiophene-3-ylidene-o-tolylacetonitrile absorption maximum wavelength: 408 nm

[D-8 (PAG108)]
3- (8-Octanesulfoxy) -imino-2H-thiophene-3-ylidene-o-tolylacetonitrile absorption maximum wavelength: 405 nm

[D-9 (PAG121)]
3- (p-Toluenesulfoxy) -imino-2H-thiophene-3-ylidene-o-tolylacetonitrile absorption maximum wavelength: 405 nm

  As the photoacid generator (D), trihalomethyl-1,3,5-triazine represented by the following general formula (III-1), trihalomethyl- represented by the following general formula (III-2) 1,3,4-oxadiazole is preferred.

However, in the general formula (III-1) and the general formula (III-2), Ar ¹ and Ar ² may be the same as or different from each other and may be substituted. An optionally substituted aryl group, a hydroxyl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an acyloxy group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, —NR ¹ R ² group, an aromatic hydrocarbon ring optionally substituted by a halogen atom, and a heteroaromatic ring, X represents any of a fluorine atom, a chlorine atom, and a bromine atom, Y Represents either a CX ₃ group or a group represented by the following general formula (III-3). R ¹ and R ² may be the same or different and are selected from a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an acyl group, and an amide group. Is done. R ¹ and R ² may be bonded together to form a 5- to 7-membered ring with the nitrogen atom. m and n represent 0, 1, or 2.

However, the general formula ^(III-3), Ar 3 represents an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, an aryloxy group, an acyloxy group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a nitro group, a cyano group , —NR ¹ R ² group, an aromatic hydrocarbon ring optionally substituted with a halogen atom, and a heteroaromatic ring, R ¹ and R ² may be the same or different. And may be selected from a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an acyl group, and an amide group. R ¹ and R ² may be bonded together to form a 5- to 7-membered ring with the nitrogen atom. k represents one of 0, 1, and 2.

  Specific examples of the photoacid generator represented by the general formula (III-1) and the general formula (III-2) include compounds represented by the following names and structural formulas, D-10 to D- 24.

[D-10]
2,4-bis (trichloromethyl) -6-fluorenon-2-yl-1,3,5-triazine Absorption maximum wavelength: 356 nm

[D-11]
2,4-bis (trichloromethyl) -6- (3,4-methylenedioxyphenyl) -1,3,5-triazine absorption maximum wavelength: 355 nm

[D-12]
2,4-bis (trichloromethyl) -6- [4-N, N-di (ethoxycarbonylmethyl) amino-3-bromophenyl)]-1,3,5-triazine Absorption maximum wavelength: 368 nm

[D-13]
2,4-bis (trichloromethyl) -6- (1-naphthyl) -1,3,5-triazine absorption maximum wavelength: 363 nm

[D-14]
2,4-bis (trichloromethyl) -6- (4-styrylphenyl) -1,3,5-triazine absorption maximum wavelength: 374 nm

[D-15]
2,4-bis (trichloromethyl) -6- (4-ethoxy-1-naphthyl) -1,3,5-triazine Absorption maximum wavelength: 388 nm

[D-16]
2,4-bis (4-methoxystyryl) -6-trichloromethyl-1,3,5-triazine absorption maximum wavelength: 368 nm

[D-17]
2,4-bis (2-ethoxystyryl) -6-trichloromethyl-1,3,5-triazine absorption maximum wavelength: 366 nm

[D-18]
2- (4-Methoxystyryl) -4- (3-fluoro-4-methoxystyryl) -6-trichloromethyl-1,3,5-triazine Absorption maximum wavelength: 363 nm

[D-19]
2- (4-hydroxystyryl) -4-trifluoromethyl-6-trichloromethyl-1,3,5-triazine absorption maximum wavelength: 375 nm

[D-20]
2- (4-Hydroxy-3-methoxystyryl) -4-trifluoromethyl-6-trichloromethyl-1,3,5-triazine Absorption maximum wavelength: 390 nm

[D-21]
2,4-bis (trichloromethyl) -6- (4-phenyl-1,3-butadiene-1-yl) -1,3,5-triazine Absorption maximum wavelength: 378 nm

[D-22]
2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine absorption maximum wavelength: 377 nm

[D-23]
2- [2- (6-Methoxybenzofuran-2-yl) -vinyl] -5-trichloromethyl-1,3,4-oxadiazole absorption maximum wavelength: 370 nm

[D-24]
2- (4-Styrylstyryl) -5-trichloromethyl-1,3,4-oxadiazole absorption maximum wavelength: 354 nm

  The content of the (D) photoacid generator is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 1 part by mass with respect to 100 parts by mass of the total amount of the photosensitive composition. .1 to 0.5 parts by mass is particularly preferable. When the content is less than 0.01 parts by mass, crosslinking and curing by heat and light are not sufficiently performed, and the resist pattern obtained has poor plating resistance, chemical resistance and adhesion, and the formed bump shape is poor. If the amount exceeds 5 parts by mass, development failure may occur during development.

<(E) Neutral sensitizer>
The neutral sensitizer has a maximum absorption at 350 to 420 nm and is not limited as long as it is neutral. For example, a thioxanthone derivative is preferable. Specifically, for example, 2,4-diethylthioxanthone and 1-chloro-4-propoxythioxanthone are particularly preferable.
Here, the neutral sensitizer is neutral (pH = 6.4 to 7.4) when the sensitizer is dissolved in water or a solution of a solvent miscible with water. Basically, the molecule does not contain basic groups such as amino groups or acidic groups such as carboxylic acid groups and sulfonic acid groups, and even if they exist, acidic groups and basic groups in the molecule, respectively. It is selected from those neutralized by bonding with a group or by bonding with another acidic molecule or basic molecule.

  As content of the said (E) neutral sensitizer, 5 mass parts or less are preferable with respect to 100 mass parts of total amounts of the said photosensitive composition solid content, 1 mass part or less is more preferable, 0.5 mass Part or less is particularly preferable. When the content exceeds 5 parts by mass, development failure may occur during development.

(Other ingredients)
Examples of the other components include organic solvents, quenchers, surfactants, adhesion promoters, and the like.
-Organic solvent-
The organic solvent can be appropriately used for adjusting the viscosity of the photosensitive composition of the present invention. Specific examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monophenyl ether, Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate , Propylene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3- Ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3- Methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, acetone, methyl ethyl ketone , Diethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, tetrahydrofuran, cyclohexanone, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy 2-methyl, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, ethyl-3-propoxypropionate, propyl-3-methoxypropionate, Isopropyl-3-methoxypropionate, ethyl ethoxy acetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, acetic acid Soamyl, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, benzyl methyl ether, benzyl ethyl ether, dihexyl ether, acetic acid Examples include benzyl, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, benzene, toluene, xylene, cyclohexanone, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, and glycerin. . These may be used alone or in combination of two or more.
From the viewpoint of obtaining a photosensitive layer having a thickness of 20 μm or more by spin coating using the obtained photosensitive composition, the amount of the organic solvent used is such that the solid content concentration of the photosensitive composition is 65 It is preferable to add in the range of less than mass%. When the solid content concentration exceeds 65% by mass, the fluidity of the photosensitive composition is remarkably deteriorated and handling is difficult, and a uniform photosensitive layer may be difficult to obtain by spin coating.

-Quencher-
There is no restriction | limiting in particular as said quencher, According to the objective, it can select suitably, For example, secondary or tertiary amines, such as a triethylamine, a tributylamine, a dibutylamine, a triethanolamine, etc. are mentioned.

-Surfactant-
The surfactant is added for the purpose of improving the coating property, defoaming property, leveling property and the like of the photosensitive composition of the present invention.
There is no restriction | limiting in particular as said surfactant, According to the objective, it can select suitably, For example, various anionic, cationic, and nonionic surfactants are mentioned. Specifically, for example, BM-1000, BM-1100 (manufactured by BM Chemie), MegaFuck F142D, F172, F173, F183 (manufactured by Dainippon Ink and Chemicals), Florard FC-135, FC-170C, FC-430, FC-431 (manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145 (Asahi Glass ( ), SH-28PA, -190, -193, SZ-6032, SF-8428 (manufactured by Toray Silicone Co., Ltd.), and the like. be able to.
As content of the said surfactant, 5 mass parts or less are preferable with respect to 100 mass parts of (A) phenolic hydroxyl group containing resin.

-Adhesion promoter-
The adhesion promoter (hereinafter sometimes referred to as an adhesion aid) is added to improve the adhesion of the photosensitive composition of the present invention to a substrate.
There is no restriction | limiting in particular as said adhesion promoter, According to the objective, it can select suitably, For example, a functional silane coupling agent is mentioned suitably. Here, the functional silane coupling agent means a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and specifically, for example, trimethoxysilyl benzoate. Acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. .
As content of the said adhesion promoter, 20 mass parts or less are preferable with respect to 100 mass parts of (A) phenolic hydroxyl group containing resin.

In addition, from the viewpoint of finely adjusting the solubility in an alkaline developer, the photosensitive composition of the present invention includes acetic acid, propionic acid, n-butyric acid, iso-butyric acid, n-valeric acid, iso-valeric acid, Monocarboxylic acids such as benzoic acid and cinnamic acid; lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid Hydroxy monocarboxylic acids such as acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, syringic 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-cyclohexanetricarboxylic acid, trimelli Polycarboxylic acids such as toic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, succinic anhydride, citraconic anhydride, anhydrous Dodecenyl succinic acid, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hymic anhydride, 1,2,3,4, -butanetetracarboxylic acid, cyclopentanetetracarboxylic dianhydride, Acid anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitic anhydride, and glycerin tris anhydrous trimellitate can also be added.
Further, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone , Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. It is also possible to add a high boiling point solvent.
Further, the content of the compound for finely adjusting the solubility in the alkali developer can be adjusted according to the use and application method, and particularly if the photosensitive composition can be mixed uniformly. Although not limited, 60 mass% or less is preferable with respect to the photosensitive composition obtained, and 40 mass% or less is more preferable.

Furthermore, a filler, a coloring agent, a viscosity modifier, etc. can also be added to the said photosensitive composition of this invention as needed.
Examples of the filler include silica, alumina, talc, bentonite, zirconium silicate, and powdered glass.
Examples of the colorant include extender pigments such as alumina white, clay, barium carbonate, and barium sulfate; zinc white, lead white, yellow lead, red lead, ultramarine, bitumen, titanium oxide, zinc chromate, bengara, carbon black, and the like. Inorganic pigments; Brilliant Carmine 6B, Permanent Red 6B, Permanent Red R, Organic Pigments such as Benzidine Yellow, Phthalocyanine Blue, and Phthalocyanine Green; Basic Dyes such as Magenta and Rhodamine; Direct Dyes such as Direct Scarlet and Direct Orange; Roserine, Meta And acid dyes such as nil yellow.
Examples of the viscosity modifier include bentonite, silica gel, aluminum powder, and the like.
The content of these additives is preferably in a range that does not impair the essential characteristics of the photosensitive composition, and is more preferably 50% by mass or less based on the resulting composition.

Moreover, an antifoamer and another additive can be added to the said photosensitive composition of this invention as needed.
Examples of the antifoaming agent include silicone-based and fluorine-based various antifoaming agents.

  As a method for preparing the photosensitive composition of the present invention, when the filler and pigment are not added, it is only necessary to mix and stir by a usual method. When the filler and pigment are added, a dissolver is used. , Using a disperser such as a homogenizer or a three-roll mill. Moreover, you may further filter using a mesh, a membrane filter, etc. as needed.

The photosensitive composition of the present invention is suitable for forming a thick film, but its application range is not limited to this, for example, a protective film during etching of various substrates such as copper, chromium, iron, and glass substrates. It can also be used as a resist for semiconductor manufacturing. Further, in forming an FDP such as an LSI element or LCD (liquid crystal display device), a circuit board, etc., in addition to the formation of bumps, wiring and the like are also formed by plating. At this time, copper, nickel, solder and other metals are used as plating materials in addition to the electrolytic gold plating for bumps and wirings. Then, the chemically amplified negative photosensitive resin composition of the present invention is used as a resist in the step of forming such a plating with copper, nickel, solder, etc. in the plating process at the time of bump formation or wiring formation. Can also be preferably used.
When the photosensitive composition of the present invention is a photoresist film, the thickness of the photosensitive layer is preferably 5 to 100 μm, more preferably 5 to 40 μm, and more preferably 20 to 30 μm.

(Photosensitive film)
The photosensitive film has at least a support and a photosensitive layer made of the photosensitive composition of the present invention on the support, and has a protective film on the photosensitive layer according to the purpose. .

<Support>
The support is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferable that the photosensitive layer can be peeled off and has good light transmittance, and further has a smooth surface. It is more preferable that it is good.

The material of the support is preferably made of a synthetic resin and transparent. For example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester , Poly (meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, Various plastic films such as polytrifluoroethylene, cellulose-based film, nylon film and the like can be mentioned, and among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.
As the support, for example, the support described in JP-A-4-208940, JP-A-5-80503, JP-A-5-173320, JP-A-5-72724, or the like is used. You can also.

  There is no restriction | limiting in particular in the thickness of the said support body, According to the objective, it can select suitably, For example, 4-300 micrometers is preferable and 5-175 micrometers is more preferable.

  The shape of the support is not particularly limited and can be appropriately selected depending on the purpose. For example, the support is wound around a cylindrical core, wound into a long roll, and stored. Is preferred. There is no restriction | limiting in particular in the length of the said elongate photosensitive film, For example, it can select suitably from the range of 10-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 to 1,000 m may be formed into a roll. In this case, it is preferable that the support is wound up so as to be the outermost side. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. From the viewpoint of protecting the end face and preventing edge fusion during storage, it is preferable to install a separator on the end face, and it is also preferable to use a material with low moisture permeability for packaging. As the separator, those having moisture resistance and those containing a desiccant are particularly preferable.

<Photosensitive layer>
The photosensitive layer is formed using the photosensitive composition of the present invention. There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said photosensitive layer, According to the objective, it can select suitably, Usually, it laminates | stacks on the said support body.
The photosensitive layer may be a single layer or a plurality of layers.

  There is no restriction | limiting in particular in the thickness of the said photosensitive layer, According to the objective, it can select suitably, For example, 5-100 micrometers is preferable, 5-40 micrometers is more preferable, 20-30 micrometers is still more preferable.

<Protective film>
The protective film has a function of preventing and protecting the photosensitive layer from being stained and damaged.
There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said protective film, According to the objective, it can select suitably, Usually, it provides on the said photosensitive layer.
Examples of the protective film include those used for the support, silicone paper, polyethylene, paper laminated with polypropylene, polyolefin or polytetrafluoroethylene sheet, etc. Among these, polyethylene film, Polypropylene film is preferred.
There is no restriction | limiting in particular in the thickness of the said protective film, According to the objective, it can select suitably, For example, 5-100 micrometers is preferable and 8-30 micrometers is more preferable.
When the protective film is used, it is preferable that the adhesive force A between the photosensitive layer and the support and the adhesive force B between the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B.
Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. . Moreover, the relationship of the above adhesive forces can be satisfy | filled by surface-treating at least any one of a support body and a protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.

Moreover, 0.3-1.4 are preferable and the static friction coefficient of the said support body and the said protective film has more preferable 0.5-1.2.
When the coefficient of static friction is less than 0.3, slipping is excessive, so that winding deviation may occur when the roll is formed, and when it exceeds 1.4, it is difficult to wind into a good roll. Sometimes.

  The protective film may be surface-treated in order to adjust the adhesion between the protective film and the photosensitive layer. In the surface treatment, for example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol is formed on the surface of the protective film. The undercoat layer can be formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 to 150 ° C. for 1 to 30 minutes. The drying temperature is particularly preferably 50 to 120 ° C.

[Method for producing photosensitive film]
The said photosensitive film can be manufactured as follows, for example.
First, the material contained in the photosensitive composition is dissolved, emulsified or dispersed in water or a solvent to prepare a photosensitive resin composition solution for a photosensitive film.

  There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol; acetone , Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate Aromatic hydrocarbons such as toluene, xylene, benzene, and ethylbenzene; halogenated carbonization such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, and monochlorobenzene Motorui; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethers such as 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and sulfolane. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

  Next, the photosensitive resin composition solution is applied on the support and dried to form a photosensitive layer, whereby a photosensitive film can be produced.

The method for applying the photosensitive composition solution is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a spray method, a roll coating method, a spin coating method, a slit coating method, and an extrusion coating method. And various coating methods such as a curtain coating method, a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 to 110 ° C. for about 30 seconds to 15 minutes.

(Photosensitive laminate)
The photosensitive laminate is formed by laminating at least the photosensitive layer on a substrate and other layers appropriately selected according to the purpose.

<Substrate>
The substrate is not particularly limited as long as it is a substrate to be processed on which a photosensitive layer is formed or a transfer target to which at least the photosensitive layer of the photosensitive film of the present invention is transferred. can do. The substrate can be arbitrarily selected from, for example, one having a high surface smoothness to one having a rough surface, but a plate-like substrate is preferable, and a so-called substrate is used. Specific examples include a known printed wiring board (printed board), a glass plate (soda glass plate, etc.), a synthetic resin film, paper, and a metal plate.

[Method for producing photosensitive laminate]
Examples of the method for producing the photosensitive laminate include, as the first aspect, a method of applying the photosensitive composition to the surface of the substrate and drying, and as the second aspect, at least the photosensitive film of the present invention. Examples of the method include transferring and laminating the photosensitive layer while performing at least one of heating and pressing.

In the method for producing a photosensitive laminate of the first aspect, a photosensitive layer is formed by applying and drying the photosensitive composition on the substrate.
The method for applying and drying is not particularly limited and can be appropriately selected depending on the purpose. For example, the photosensitive composition is dissolved, emulsified or dispersed in water or a solvent on the surface of the substrate. And a method of laminating by preparing a photosensitive composition solution, applying the solution directly, and drying the solution.

  There is no restriction | limiting in particular as a solvent of the said photosensitive composition solution, According to the objective, it can select suitably, The same solvent as what was used for the said photosensitive film is mentioned. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

  There is no restriction | limiting in particular as said coating method and drying conditions, According to the objective, it can select suitably, It carries out by the same method and conditions as what was used for the said photosensitive film.

In the method for producing a photosensitive laminate according to the second aspect, the photosensitive film of the present invention is laminated on the surface of the substrate while performing at least one of heating and pressing. In addition, when the said photosensitive film has the said protective film, it is preferable to peel this protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base | substrate.
There is no restriction | limiting in particular in the said heating temperature, According to the objective, it can select suitably, For example, 15-180 degreeC is preferable and 60-140 degreeC is more preferable.
There is no restriction | limiting in particular in the pressure of the said pressurization, According to the objective, it can select suitably, For example, 0.1-1.0 MPa is preferable and 0.2-0.8 MPa is more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating and pressurization, According to the objective, it can select suitably, For example, Laminator (For example, Taisei Laminator VP-II, Nichigo Morton Co., Ltd.) V130) etc. are mentioned suitably.

(Pattern formation method)
The pattern forming method of the present invention includes at least an exposure process, a development process, a plating process, and a resist peeling process, and includes other appropriately selected processes such as a post-exposure heating process and a post-curing process.
Patterns such as bump patterns and wiring patterns are formed by the pattern forming method.

[Exposure process]
The exposure step is a step of performing pattern exposure on the photosensitive layer in the photosensitive laminate. Examples of the photosensitive layer in the photosensitive laminate include a photosensitive layer formed from the photosensitive composition of the present invention and a photosensitive layer transferred from the photosensitive film.

  There is no restriction | limiting in particular as said exposure, According to the objective, it can select suitably, Digital exposure, analog exposure, etc. are mentioned, Among these, digital exposure is preferable.

  The analog exposure is not particularly limited and may be appropriately selected depending on the purpose.For example, a method of performing exposure with a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, or the like through a negative mask having a predetermined pattern. Can be mentioned.

  As a means for the digital exposure, a maskless pattern exposure method (digital) that forms a two-dimensional image by exposing the photosensitive laminate by exposing it by relative scanning while modulating light based on image data. An exposure process using exposure will be mainly described.

  Digital exposure is an exposure method in which a two-dimensional image is formed by using two-dimensional spatial light modulation devices and performing relative scanning while modulating light based on image data.

  An object called a “mask” in which an image (exposure pattern; hereinafter also referred to as a pattern) is formed with a material that does not transmit or weakly transmits exposure light is disposed in the optical path of the exposure light, and the photosensitive layer is the image. In contrast to the conventional mask exposure method (also referred to as analog exposure) in which exposure is performed in a pattern corresponding to the above, a photosensitive layer is exposed in a pattern without using the “mask”.

In digital exposure, an ultra-high pressure mercury lamp or laser is used as a light source.
An ultra-high pressure mercury lamp is a discharge lamp in which mercury is enclosed in a quartz glass tube, etc., and has a high mercury vapor pressure to increase luminous efficiency (the mercury vapor pressure during lighting is approximately 5 MPa) W. Ellenbaas: Light Sources, Philips Technical Library 148-150). Of the bright line spectrum, a single exposure wavelength of 405 nm ± 40 nm is used, and h-line (405 nm) can be mainly used.

  Lasers use the phenomenon of stimulated emission that occurs in materials with an inversion distribution. Oscillators and amplifiers that produce monochromatic light with stronger coherence and directivity by amplification and oscillation of light waves, crystals, glass, liquids as excitation media, There are dyes, gases, etc. From these media, known lasers such as solid lasers (YAG lasers), liquid lasers, gas lasers (argon lasers, He-Ne lasers, carbon dioxide lasers, excimer lasers), semiconductor lasers, etc. Can be used.

  The semiconductor laser uses a light emitting diode that induces coherent light emission at the pn junction when electrons and holes flow out to the junction due to injection of an electron source, excitation by an electron beam, ionization by collision, optical excitation, and the like. It is a laser. The wavelength of the emitted coherent light is determined by the semiconductor compound. The laser wavelength is a single exposure wavelength of 405 nm ± 40 nm.

  The single exposure wavelength in the present invention refers to the dominant wavelength when using a laser, and when using an ultra-high pressure mercury lamp, the dominant wavelength is set by cutting the bright line other than 405 nm with an ND filter to a wavelength greater than 365 nm or 405 nm. This means one wavelength only.

  There is no restriction | limiting in particular as said exposure method, Although it can select suitably according to the objective, Digital exposure using a laser is preferable.

  The digital exposure means is not particularly limited and may be appropriately selected according to the purpose. For example, a light irradiation means for irradiating light described in JP-A-2005-258431 is formed. Examples include light modulation means for modulating light emitted from the light irradiation means based on pattern information.

  The digital exposure is not particularly limited and can be appropriately selected depending on the purpose.For example, a control signal is generated based on pattern formation information to be formed, and light modulated in accordance with the control signal is generated. For example, the photosensitive layer is arranged in a two-dimensional array of light irradiation means and n pieces (where n is a natural number of 2 or more) that receives and emits light from the light irradiation means. An exposure head comprising a light modulation means capable of controlling the drawing portion in accordance with pattern information, the column direction of the drawing portion relative to the scanning direction of the exposure head Using an exposure head arranged so as to form a predetermined set inclination angle θ, the exposure head is subjected to N-fold exposure (where N is (Natural number of 2 or more) Designation of a grapheme part and control of the pixel part for the exposure head so that only the picturee part designated by the use picture element part designation means is involved in exposure by the picture element part control means It is preferable that the exposure head is moved relative to the photosensitive layer in the scanning direction.

In the present invention, “N double exposure” means that the exposed surface is irradiated with a straight line parallel to the scanning direction of the exposure head in almost all of the exposed region on the exposed surface of the photosensitive layer. This means exposure by setting that intersects N light spot rows (pixel rows). Here, the “light spot array (pixel array)” has a smaller angle with the scanning direction of the exposure head in the array of light spots (pixels) as pixel units generated by the pixel unit. It shall refer to a sequence of directions. Note that the arrangement of the picture element portions is not necessarily a rectangular lattice shape, and may be, for example, an arrangement of parallelograms.
Here, “substantially all areas” of the exposure area is described as a straight line parallel to the scanning direction of the exposure head by tilting the pixel part rows at both side edges of each picture element part. Since the number of drawing element rows of the used drawing element parts to be crossed decreases, even if it is used to connect a plurality of exposure heads in such a case, it is parallel to the scanning direction due to errors in the mounting angle and arrangement of the exposure heads. The number of pixel parts in the used pixel part that intersect with a straight line may slightly increase or decrease, and the connection between the pixel parts in each used pixel part is only a fraction of the resolution. However, due to errors such as the mounting angle and the arrangement of the picture element parts, the pitch of the picture element parts along the direction orthogonal to the scanning direction does not exactly match the pitch of the picture element parts of other parts, and is parallel to the scanning direction. The number of used pixel parts that intersect with the straight line may increase or decrease within a range of ± 1. It is an order. In the following description, N multiple exposures where N is a natural number of 2 or more are collectively referred to as “multiple exposure”.
N in the N-fold exposure is not particularly limited as long as it is a natural number of 2 or more, and can be appropriately selected according to the purpose. However, a natural number of 3 to 20 is preferable, and a natural number of 3 to 7 is preferable. More preferred.

  There is no restriction | limiting in particular as a wavelength of the laser in this invention, Although it can select suitably according to the objective, 330-650 nm is preferable and 365-445 nm is preferable from the objective of aiming at shortening of the exposure time of a photosensitive composition. More preferably, 395 to 415 nm is still more preferable, and 400 to 410 nm is particularly preferable.

The beam diameter of the laser is not particularly limited, but among these, from the viewpoint of the resolution of the dark color separation barrier, the 1 / e ² value of the Gaussian beam is preferably 5 to 30 μm, and more preferably 7 to 20 μm.
Although it does not specifically limit as energy amount of a laser beam, From a viewpoint of exposure time and resolution, 1-100 mJ / cm < ² > is preferable especially and 5-20 mJ / cm < ² > is more preferable.

  In the present invention, it is necessary to spatially modulate laser light according to image data. For this purpose, it is preferable to use a digital micro device which is a spatial light modulation element described in JP-A-2005-258431 [0016] to [0047].

  As the exposure apparatus, for example, a laser direct imaging apparatus “INPREX IP-3000 (manufactured by Fuji Photo Film)” can be used, but the exposure apparatus in the present invention is not limited to this.

[Post-exposure heating process]
The post-exposure heating step is a step of performing a heat treatment (post-exposure baking, PEB) on the resist film after pattern exposure.
Examples of the PEB method include proximity bake that provides a gap between the hot plate and the substrate, and direct bake that does not have a gap, and obtains a diffusion effect by PEB without causing warpage of the substrate. Therefore, a method of performing direct baking after performing proximity baking is preferable.
In addition, 90-150 degreeC is preferable for heating temperature, and 100-140 degreeC is especially preferable.

[Development process]
The developing step is a step of exposing the photosensitive layer in the photosensitive film by the exposing step, curing the exposed region of the photosensitive layer, and developing by removing the uncured region to form a resist pattern. It is.
The developing step can be preferably performed by, for example, developing means.
The developing means is not particularly limited as long as it can be developed using a developer, and can be appropriately selected according to the purpose. For example, means for spraying the developer, means for applying the developer And means for immersing in the developer. These may be used alone or in combination of two or more.
In addition, the developing unit may include a developer replacing unit that replaces the developer, a developer supplying unit that supplies the developer, and the like.

  There is no restriction | limiting in particular as said developing solution, According to the objective, it can select suitably, For example, an alkaline solution, an aqueous developing solution, an organic solvent etc. are mentioned, Among these, weakly alkaline aqueous solution is preferable. Examples of the basic component of the weak alkaline liquid include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, phosphorus Examples include potassium acid, sodium pyrophosphate, potassium pyrophosphate, and borax.

The pH of the weak alkaline aqueous solution is, for example, preferably about 8 to 12, and more preferably about 9 to 11. Examples of the weak alkaline aqueous solution include a 0.1 to 5% by mass aqueous sodium carbonate solution or an aqueous potassium carbonate solution.
The temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and is preferably about 25 to 40 ° C., for example.

  The developer includes a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) and development. Therefore, it may be used in combination with an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.). The developer may be an aqueous developer obtained by mixing water or an aqueous alkali solution and an organic solvent, or may be an organic solvent alone.

[Post-curing process]
The photosensitive coating film (photosensitive layer) comprising the composition of the present invention can be sufficiently cured only by the above-described exposure, but depending on the application, additional exposure (hereinafter referred to as post-exposure) or It can be further cured by heating.
The post-exposure method can be carried out in the same manner as the exposure method in the pattern exposure, and the exposure amount is not particularly limited, but when using a high-pressure mercury lamp, it is 100 to 2,000 mJ / cm ^2. preferable.
As the heating method, a heating device such as a hot plate or an oven is used, and a predetermined temperature, for example, 60 to 100 ° C. for a predetermined time, for example, 5 to 30 minutes on the hot plate, in the oven. What is necessary is just to heat-process for 5 to 60 minutes.
By such a post-curing treatment step, a predetermined pattern of a cured film (resist pattern) having even better characteristics can be obtained.

[Plating process]
The plating process is a process of performing a plating process using the resist pattern as a mask to form a bump pattern or a wiring pattern.
When the bump pattern is formed, solder, nickel, gold or the like is used as the metal, and there are various methods for forming the bump pattern. Before the resist pattern is formed, electroless plating is performed on the entire surface of the substrate to form a thin electroless plating layer, and then a resist pattern is formed thereon. Then, the portion that is not covered with the formed resist pattern is electroplated. I do. Thereafter, the resist is generally peeled off by a resist peeling step described later, and the thin electroless plating layer is generally removed by soft etching.
Representative examples of the electroless plating solution include a nickel plating solution and a gold plating solution.
Examples of the electrolytic plating solution include aluminum, copper, silver, gold, nickel, palladium, and those containing the same components as those of two or more alloys thereof (for example, palladium-gold). For example, a solder plating solution, a cyan or non-cyan electrolytic gold plating solution may be used.
The conditions for the electrolytic plating vary depending on the composition of the plating solution. For example, in the case of gold plating, the temperature is usually 40 to 70 ° C, preferably 55 to 70 ° C, and the current density is usually It is 0.1-1 A / dm < ² >, and 0.2-0.8 A / dm < ² > is preferable. After plating, after washing and drying, the state and thickness of the bump pattern are observed, and electrolytic plating is performed again if necessary.
The thickness of the bump pattern is usually 5 to 50 μm, preferably 10 to 30 μm, and more preferably 15 to 25 μm.
In the case of the wiring pattern, the thickness is usually 1 to 30 μm, preferably 3 to 20 μm, more preferably 5 to 15 μm.

[Resist stripping process]
As the resist stripping step, for example, in order to strip the cured film (resist pattern) from the plated substrate, the substrate is immersed in a stripping solution at 50 to 80 ° C. for 5 to 30 minutes. Good. Examples of the stripping solution used here include an aqueous solution of a quaternary ammonium salt, and a mixed solution of a quaternary ammonium salt, dimethyl sulfoxide, and water.
A bump pattern and a wiring pattern are formed on the surface of the substrate by the resist stripping step.

[Bump formation method]
The pattern forming method of the present invention can be particularly suitably used for a bump pattern forming method. The bump forming method includes, for example, a photosensitive laminate forming process, an exposure process, a post-exposure heating process, a developing process, a post-curing process process, a plating process process, and a resist stripping process. .

[Photosensitive laminate forming step]
By applying the photosensitive composition solution of the present invention prepared as described above on a substrate having a predetermined wiring pattern in a thickness of 5 μm to 100 μm, preferably 20 to 40 μm, and removing the solvent by heating. A desired coating film (photosensitive layer) is formed.
As a method for applying the photosensitive composition solution onto the substrate to be treated, methods such as a spin coating method, a roll coating method, a screen printing method, and an applicator method can be employed. The pre-baking conditions for the coating film of the composition of the present invention vary depending on the type of each component in the composition, the blending ratio, the thickness of the coating film, etc., but usually 70 to 130 ° C, preferably 80 to 120 ° C. ~ About 60 minutes.

[Exposure process]
The photosensitive laminate obtained above is irradiated with radiation, for example, ultraviolet rays having a wavelength of 300 to 500 nm or visible light directly through a mask having a predetermined pattern or by scanning light having predetermined pattern information. By doing so, only the wiring pattern portion on which the bump is formed is exposed. As these radiation sources, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an argon gas laser, a blue-violet laser, a UV laser, or the like can be used. Here, the radiation means ultraviolet rays, visible rays, far ultraviolet rays, X-rays, electron beams, and the like. The amount of radiation irradiation varies depending on the type of each component in the composition, the blending amount, the thickness of the photosensitive layer, and the like, but is, for example, 10 to 100 mJ / cm ² when using an ultrahigh pressure mercury lamp.

[Post-exposure heating process]
After the exposure step, heating is performed using a known method, for example, the method described in the post-exposure heating step of the pattern forming method.

[Development process]
The development step is a step of dissolving and removing unnecessary portions using an alkaline aqueous solution as a developer, that is, dissolving and removing only unexposed portions of radiation.
Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, and methyldiethylamine. , Dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3 , 0] -5-nonane, and the like.
Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
The development 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 preferably 1 to 30 minutes.
Examples of the developing method include a liquid piling method, a dipping method, a paddle method, and a spray developing method. After development, washing with running water is preferably performed for 30 to 90 seconds, and air-dried using an air gun or the like, or dried in an oven.

[Post-curing process]
As the post-curing treatment step, for example, the method described in the post-curing treatment step of the pattern forming method can be used.

[Plating process]
The plating process is a process of forming a bump pattern on the substrate by plating the resist pattern, and can be performed using the method described in the plating process of the pattern forming method.

[Resist stripping process]
As the resist stripping step, for example, the method described in the resist stripping step of the pattern forming method can be used.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, parts are parts by mass and% is mass%.

<(A) Synthesis of phenolic hydroxyl group-containing resin>
-Resin A-1-
As the resin A-1, Resist Top PSF-2803 (manufactured by Gunei Chemical Co., Ltd., cresol formaldehyde novolak resin) was precipitated in water, and the obtained coagulated product was vacuum-dried at 40 ° C. for 48 hours for use.
-Resin A-2-
As the resin A-2, Marcarinka-M (manufactured by Maruzen Petrochemical Co., Ltd., poly-p-vinylphenol, mass average molecular weight is 5,000, dispersity is 2.5) was used as it was.

<(B) Synthesis of alkali-soluble resin>
According to the following synthesis examples 1 to 29, alkali-soluble resins B-1 to B-29 (hereinafter sometimes simply referred to as resins B-1 to B-29) were synthesized-synthesis example 1 (resin B-1) Synthesis)-
A flask equipped with a stirrer, a reflux device, a thermometer, and a dropping tank was purged with nitrogen, and then 200 g of propylene glycol methyl ether acetate was charged as a solvent, and stirring was started. Thereafter, the temperature of the solvent was raised to 80 ° C. A dropping tank was charged with 0.5 g of 2,2′-azobisisobutyronitrile, 50.3 g of benzyl acrylate, 35.3 g of acrylic acid, and 25.6 g of n-butyl acrylate as a polymerization solvent, and a polymerization initiator (Wako Pure Chemical Industries, Ltd.). After stirring until a product made by a company, brand name V-65) was dissolved, this solution was uniformly dropped into the flask for 3 hours, and then polymerization was carried out at 80 ° C. for 5 hours. Then, after cooling to room temperature, 42.1 g of phenyl glycidyl ether and 1.0 g of trimethylbenzylammonium chloride were added and reacted at 100 ° C. for 8 hours, whereby the following resin B-1 as a ring-opening addition reaction product was obtained. Obtained.
Table 1 shows the physical properties of the obtained resin B-1.
The numbers in the structural formula of the resin B-1 represent the monomer composition ratio, and the unit of the composition ratio is mol%. The same applies to the resins B-2 to B29.

Synthesis Examples 2 to 24 (Synthesis of Resins B-2 to B-24 for Examples)
Resins B-2 to B-24 were obtained in the same manner as in Synthesis Example 1 except that the monomers in Synthesis Example 1 were changed as shown in Table 1.
Table 1 shows the physical properties of the obtained resins B-2 to B-24, and the structural formula (composition) is shown below.

-Synthesis Examples 25 to 27 (Synthesis of Resin B-25 to B-27 for Comparative Example)-
Resins B-25 to B-27 were obtained in the same manner as in Synthesis Example 1 except that the monomers were changed as shown in Table 1 in Synthesis Example 1.
The physical properties of the obtained resins B-25 to B-27 are shown in Table 1, and the structural formula (composition) is shown below.

-Synthesis Example 28 (Synthesis of Resin B-28 for Comparative Example)-
A flask equipped with a dry ice / methanol reflux was purged with nitrogen, and then charged with 3.0 g of 2,2′-azobisisobutyronitrile as a polymerization initiator and 100.0 g of ethyl 3-ethoxypropionate as a solvent for polymerization. Stir until the initiator is dissolved. Subsequently, 75.0 g of 2-hydroxyethyl methacrylate, 60.0 g of n-butyl acrylate, and 15.0 g of 2-hexahydrophthaloyl ethyl methacrylate were charged, and then gently stirring was started. Next, the temperature of the solution was raised to 80 ° C., and polymerization was carried out at this temperature for 4 hours. Thereafter, the reaction product was dropped into a large amount of methanol to solidify the reaction product. The coagulated product was washed with water, redissolved in tetrahydrofuran having the same mass as the coagulated product, and coagulated again with a large amount of methanol. After this re-dissolution / coagulation operation was carried out three times in total, the obtained coagulated product was vacuum-dried at 40 ° C. for 48 hours to obtain the intended resin B-28.
Table 1 shows the physical properties of the obtained resin B-28, and the structural formula (composition) is shown below.

-Synthesis Example 29 (Synthesis of Resin B-29 for Comparative Example)-
A flask equipped with a stirrer, a reflux device, a thermometer, and a dropping tank was purged with nitrogen, and then 200 g of propylene glycol methyl ether acetate was charged as a solvent, and stirring was started. Thereafter, the temperature of the solvent was raised to 80 ° C. A dropping tank was charged with 0.5 g of 2,2′-azobisisobutyronitrile, 130 g of 2-methoxyethyl acrylate, 50.0 g of benzyl methacrylate and 20.0 g of acrylic acid as a polymerization solvent, and a polymerization initiator (Wako Pure Chemical Industries, Ltd.). After stirring until the product name V-65) was dissolved, this solution was uniformly dropped into the flask for 3 hours, followed by polymerization at 80 ° C. for 5 hours. Thereafter, the reaction product was cooled to room temperature, and the reaction product was added dropwise to a large amount of methanol to solidify the reaction product. The coagulated product was washed with water, redissolved in tetrahydrofuran having the same mass as the coagulated product, and coagulated again with a large amount of methanol. After this re-dissolution / coagulation operation was performed three times in total, the obtained coagulated product was vacuum-dried at 40 ° C. for 48 hours to obtain the intended resin B29.
The physical properties of the obtained resin B29 are shown in Table 1, and the structural formula (composition) is shown below.

Example 1
-Preparation of photosensitive composition solution-
A photosensitive composition solution was prepared based on the following composition.
[Composition of photosensitive composition coating solution]
(A) Resin A-1 ... 75 parts by mass (B) Alkali-soluble resin B-1 ... 15 parts by mass (C) Crosslinking agent Hexamethoxymethylated melamine (manufactured by Sanwa Chemical Co., Ltd., trade name Nicarak Mw- 100) ... 10 parts by mass (D) Photoacid generator D-7 represented by the following formula: Irgacure PAG103 (maximum absorption wavelength: 408 nm, manufactured by Ciba Specialty Chemicals) ... 0.3 parts by mass propylene Glycol methyl ether acetate (PEGMEA: solvent) 150 parts by mass After the components (A) to (E) are dissolved in the solvent propylene glycol methyl ether acetate, they are filtered using a microfilter having a pore size of 0.2 μm. Then, a photosensitive composition solution was prepared.
The characteristics evaluation shown below was performed using this photosensitive composition solution. The results are shown in Table 3.
A light absorption characteristic chart of the D-7: Irgacure PAG103 is shown in FIG.

<Evaluation of compatibility>
The photosensitive composition solution was mixed at room temperature for 12 hours and stirred, and the dissolved state immediately after stirring and 12 hours after stirring was visually observed. The dispersion state was determined according to the following evaluation criteria.
○: It was visually confirmed that the composition was uniformly dispersed after stirring for 12 hours.
(Triangle | delta): The composition disperse | distributed uniformly after 12-hour stirring, but phase-separated by standing still for a long time.
X: The composition is not uniformly dispersed after stirring for 12 hours.

-Production of photosensitive film-
A 25 μm thick polyethylene terephthalate film (Lumirror 16FB50, manufactured by Toray Industries, Inc.) is used as a support, and the photosensitive composition coating solution is dried on the support by a bar coater, so that the thickness of the photosensitive layer after drying becomes about 30 μm. And then dried in a hot air circulating drier for 30 minutes at 80 ° C., and then a polypropylene film having a thickness of 12 μm was laminated as a protective film on the photosensitive layer to produce a photosensitive film. .
The characteristics evaluation shown below was performed about the photosensitive film obtained above. The results are shown in Table 3.

<Measurement of the shortest development time>
The photosensitive film was laminated on a substrate to prepare a photosensitive laminate. The polyethylene terephthalate film (support) is peeled off from the photosensitive laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed on the entire surface of the photosensitive layer on the copper clad laminate at a pressure of 0.15 MPa. The time required from the start of spraying of the aqueous sodium solution until the photosensitive layer on the copper clad laminate was dissolved and removed was measured, and this was defined as the shortest development time (t ₀ ).

<Evaluation of storage stability>
The obtained sheet of photosensitive film was put in a light-proof moisture-proof bag (BF3X manufactured by Tokai Aluminum Foil Co., Ltd.) made of black vinyl and an aluminum foil laminated structure, and stored in a dry oven at 40 ° C. for 3 days. Thereafter, the photosensitive film sheet was taken out and laminated on the substrate, and then the above shortest development time test was performed, and the shortest development time (t ₃ ) was measured.
The time required for development was compared with the shortest development time (t ₀ ) on the photosensitive film production day. Specifically, the obtained t ₃ / t ₀ ratio value was evaluated according to the following criteria (rounded up to 2 decimal places).
-Evaluation criteria-
○: 1.0 to 1.3
Δ: 1.4 to 1.8
×: 1.9 or more

<Evaluation of sensitivity>
The above-mentioned photosensitive composition solution is applied onto a 5-inch silicon wafer to form a photosensitive layer (coating film) having a thickness of about 40 μm, and INPREX IP-, which is a 405 nm laser light irradiation device having a pattern for resolution measurement. One coated substrate was divided using 3000 (Fuji Photo Film Co., Ltd.), and each was subjected to ultraviolet exposure stepwise in the range of 10 to 200 mJ / cm ² . This was developed with a 2.38 mass% TMAH aqueous solution. Thereafter, it was washed with running water and blown with nitrogen to obtain a patterned cured product. This was observed with a microscope, a 5 μm square hole pattern was resolved, an exposure amount at which no residue was observed was measured, and a determination was made according to the following criteria.
○: exposure amount, 10 mJ / cm ² or more, of less than 30 mJ / cm ^2.
△: exposure, 30 mJ / cm ² or more, for 100 mJ / cm ² or less.
X: When the exposure amount exceeds 100 mJ / cm ² .

<Evaluation of resolution>
The photosensitive composition solution was applied onto a 5-inch silicon wafer using a spinner at 1,000 rpm for 25 seconds, and then pre-baked on a hot plate at 110 ° C. for 6 minutes to form a photosensitive layer (coating having a thickness of about 20 μm). Film). Next, using INPREX IP-3000 (manufactured by Fuji Photo Film), which is a 405 nm laser beam irradiation apparatus having a resolution measurement pattern, one coated substrate is divided, and each is in the range of 5 to 200 mJ / cm ² . And stepwise exposure. After the exposure, it was heated at 110 ° C. for 6 minutes, and developed with a 2.38 mass% TMAH aqueous solution. Thereafter, it was washed with running water and blown with nitrogen to obtain a patterned cured product. This was observed with a microscope, and the resolution was determined according to the following evaluation criteria.
○: When a hole pattern of 5 μm square is resolved at any of the above exposure amounts, no residue is observed.
Δ: When a hole pattern of 5 μm square is resolved at any of the above exposure amounts, but a residue is observed.
X: When the hole pattern of 5 μm square is not resolved.

<Evaluation of plating resistance>
Using the substrate having the patterned cured product obtained by the resolution evaluation as a test specimen, after ashing with oxygen plasma, immersing it in a non-cyanide gold sulfite plating solution at 70 ° C. for 90 minutes, washing with running water, Obtained. Using an optical microscope or an electron microscope, observe the state of the bumps and patterned cured product formed on the specimen to be processed, and the resistance of the patterned cured product to the plating solution, the shape of the formed pump, and the patterned curing The plating resistance with respect to the plating process of an object was determined according to the following evaluation criteria.
◯: There is no particular change in the state of the formed bump and the patterned cured product, and it is good.
(Triangle | delta): The pattern-like hardened | cured material has partially floated.
X: Cracks, bulges, and chips are generated in the patterned cured product, or the surface of the patterned cured product is rough.

<Evaluation of bump shape>
A specimen to be processed is obtained by the same operation as in the evaluation of the plating resistance, and the state of the formed bump and the patterned cured product is observed using an optical microscope or an electron microscope. Judgment was made based on evaluation criteria.
○: The shape of the bump follows the pattern-like cured product and is good.
Δ: Part of bump shape does not follow.
X: The shape of the pump hardly follows the patterned cured product.

<Evaluation of peelability>
A substrate having a patterned cured product obtained by the resolution evaluation was used as a test specimen, immersed in a stripping solution (Tokyo Oka Stripper 710) for 5 minutes at room temperature, washed with running water, and then patterned cured product. Was peeled off, visually observed or observed with an optical microscope, and evaluated according to the following criteria.
◯: No residue of the patterned cured product is observed.
Δ: A small amount of residue of the pattern-like cured product was observed.
X: A large amount of residue of the patterned cured product was observed.

(Example 2)
(B) As an alkali-soluble resin, as shown in Table 2, 15 parts by mass of resin B-2 was used, and (D) as a photoacid generator, D-3: Irgacure CGI1397 (absorption maximum wavelength: A photosensitive composition solution was prepared in the same manner as in Example 1 except that 0.3 part by mass of 405 nm (manufactured by Ciba Specialty Chemicals) was used, and a photosensitive film was produced. Using the composition solution and the photosensitive film, the characteristics were evaluated in the same manner as in Example 1. Table 3 shows the results.
The light absorption characteristic chart of D-3: Irgacure CGI1397 is shown in FIG.

(Example 3)
(B) As an alkali-soluble resin, as shown in Table 2, 15 parts by mass of resin B-3 was used, and (D) photoacid generator was represented by the following formula: D-8: Irgacure PAG108 (maximum absorption wavelength: A photosensitive composition solution was prepared in the same manner as in Example 1 except that 0.3 part by mass of 405 nm (manufactured by Ciba Specialty Chemicals) was used, and a photosensitive film was produced. Using the photosensitive composition solution and the photosensitive film, the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 3.
A light absorption characteristic chart of the D-8: Irgacure PAG108 is shown in FIG.

(Examples 4 to 24)
(B) As the alkali-soluble resin, as shown in Table 2, a photosensitive composition solution was prepared in the same manner as in Example 1 except that 15 parts by mass of each of the resins B-4 to B-24 was used. A photosensitive film was prepared. Using the photosensitive composition solution and the photosensitive film, the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Example 25)
(A) As phenolic hydroxyl group-containing resin, as shown in Table 2, 75 parts by mass of resin A-2: poly p-vinylphenol was used, and (D) photoacid generator was used as D-3: Irgacure CGI1397 ( Absorption maximum wavelength: 405 nm, except that 0.3 parts by mass (manufactured by Ciba Specialty Chemicals) was used, a photosensitive composition solution was prepared and a photosensitive film was prepared in the same manner as in Example 1. Using the photosensitive composition solution and the photosensitive film, the characteristics were evaluated in the same manner as in Example 1. Table 3 shows the results.

(Example 26)
(D) As shown in Table 2, as a photoacid generator, except that 0.3 parts by mass of D-8: Irgacure PAG108 (absorption maximum wavelength: 405 nm, manufactured by Ciba Specialty Chemicals) was used, In the same manner as in Example 1, a photosensitive composition solution was prepared and a photosensitive film was produced. Using the photosensitive composition solution and the photosensitive film, the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Example 27)
In Example 1, 0.1 part by mass of Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd., 2,4-diethylthioxanthone) represented by the following formula was further added as a neutral sensitizer (E) in the photosensitive composition. Except for the above, a photosensitive composition solution was prepared in the same manner as in Example 1 to prepare a photosensitive film. Using the photosensitive composition solution and the photosensitive film, the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Example 28)
In Example 1, 0.1 parts by mass of (S) SpeedCureCPTX (manufactured by The Lambson Group, 1-chloro-4-propoxythioxanthone) represented by the following formula as a neutral sensitizer in the photosensitive composition was further added. A photosensitive composition solution was prepared and a photosensitive film was prepared in the same manner as in Example 1 except that it was added. Using the photosensitive composition solution and the photosensitive film, the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Example 29)
(C) As shown in Table 2, as a cross-linking agent, Nicalak MX-270 represented by the following formula (manufactured by Sanwa Chemical Co., Ltd., except that tetramethoxymethylated glycoluril was used) was used in the same manner as in Example 1. A photosensitive composition solution was prepared to produce a photosensitive film, and the characteristics were evaluated using the photosensitive composition solution and the photosensitive film in the same manner as in Example 1. The results are shown in Table 3. Show.

(Example 30)
(D) As shown in Table 2, except that 0.3 parts by mass of D-22: TAZ-110 (absorption maximum wavelength: 377 nm, manufactured by Midori Chemical Co., Ltd.) represented by the following formula was used as the acid generator. In the same manner as in Example 1, a photosensitive composition solution was prepared to prepare a photosensitive film. Using the photosensitive composition solution and the photosensitive film, the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Example 31)
(D) As shown in Table 2, as the acid generator, D-12: (absorption maximum wavelength: 368 nm) represented by the following formula was used in the same manner as in Example 1 except that 0.3 part by mass was used. A photosensitive composition solution was prepared to produce a photosensitive film. Using the photosensitive composition solution and the photosensitive film, the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Example 32)
(D) As shown in Table 2, as the acid generator, D-24: (absorption maximum wavelength: 354 nm) represented by the following formula was used in the same manner as in Example 1 except that 0.3 part by mass was used. A photosensitive composition solution was prepared to produce a photosensitive film. Using the photosensitive composition solution and the photosensitive film, the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Comparative Examples 1-4)
(B) As the alkali-soluble resin, as shown in Table 2, a photosensitive composition solution was prepared in the same manner as in Example 1 except that 15 parts by mass of resins B-25 to B-28 were used. A photosensitive film was prepared. Using the photosensitive composition solution and the photosensitive film, the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Comparative Example 5)
(B) As alkali-soluble resin, as shown in Table 2, 15 parts by mass of resin B-29 was used, and (D) a photoacid generator was used except that a compound represented by the following formula D-25 was used. In the same manner as in Example 1, a photosensitive composition solution was prepared, and a photosensitive film was produced. Using the photosensitive composition solution and the photosensitive film, the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Comparative Example 6)
(D) As shown in Table 2, 0.3 parts by mass of D-26: Irgacure PAG203 (absorption maximum wavelength: 280 nm, manufactured by Ciba Specialty Chemicals) represented by the following formula was used as a photoacid generator. Except for this, a photosensitive composition solution was prepared in the same manner as in Example 1 to prepare a photosensitive film. Using the photosensitive composition solution and the photosensitive film, the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 3.
A light absorption characteristic chart of the D-11: Irgacure PAG203 is shown in FIG.

(Comparative Example 7)
In Example 1, as shown in Table 2, a known photoreaction started without using (B) a resin containing a benzyl group, a carboxyl group and a hydroxyl group, (C) a crosslinking agent, and (D) a photoacid generator. 15 photocatalyst obtained by reacting 1 mol of 1,2-naphthoquinonediazide-4-sulfonyl chloride with 1 mol of the compound represented by the following structural formula (1) (hereinafter referred to as NQD) 15 Except having used the mass part, it carried out similarly to Example 1, and prepared the photosensitive composition solution, and produced the photosensitive film. Using the photosensitive composition solution and the photosensitive film, the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Comparative Example 8)
(D) As an acid generator, as shown in Table 2, the following D-27: 2- (4-n-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole (absorption maximum wavelength: A photosensitive composition solution was prepared in the same manner as in Example 1 except that 0.3 part by mass of 330 nm) was used, and a photosensitive film was produced. Using the photosensitive composition solution and the photosensitive film, the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Comparative Example 9)
(D) As an acid generator, as shown in Table 2, the following D-28: 2,4-bis (trichloromethyl) -6- (4-N, N-dimethylaminostyryl) -1,3,5- A photosensitive composition solution was prepared in the same manner as in Example 1 except that 0.3 part by mass of triazine (absorption maximum wavelength: 468 nm) was used, and a photosensitive film was produced. Using the photosensitive composition solution and the photosensitive film, the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 3.

The formal names of the components indicated by abbreviations in Table 1 are as follows.
AA-GPE: 3-phenoxy-2-hydroxypropyl acrylate unit MAA-GPE: 3-phenoxy-2-hydroxypropyl methacrylate unit HEMA: 2-hydroxyethyl methacrylate unit BzA: benzyl acrylate unit BzMA: benzyl methacrylate unit AA: acrylic acid Unit HPEMA: 2-hexahydrophthaloyl ethyl methacrylate unit BA: n-butyl acrylate unit i-BA: isobutyl acrylate unit

From the results of Table 3, (A) a phenolic hydroxyl group-containing resin, (B) a resin containing a benzyl group, a carboxyl group and a hydroxyl group, (C) a crosslinking agent crosslinked with an acid, and (D) a wavelength of 350 to 420 nm Examples 1 to 32 using a photosensitive composition containing a photoacid generator having an absorption maximum and having a sensitivity at a wavelength of 405 nm of 10 to 100 mJ / cm ² have high sensitivity and high resolution, and are stable in storage. It was found that the high-definition bump pattern was able to be formed with excellent plating resistance, excellent plating resistance, bump shape and resist pattern peelability.

The photosensitive composition and photosensitive film of the present invention have high sensitivity and high resolution, good storage stability, good properties required, and high-definition patterns can be formed. For this reason, it can be particularly suitably used for forming a pattern such as a bump pattern and a wiring pattern on a printed circuit board.
Since the pattern forming method of the present invention uses the photosensitive composition and the photosensitive film of the present invention, it can be suitably used particularly for the formation of patterns such as high-definition bump patterns and wiring patterns on a printed circuit board. .

FIG. 1 is a light absorption characteristic chart of the Irgacure PAG103. FIG. 2 is a light absorption characteristic chart of Irgacure CGI1397. FIG. 3 is a light absorption characteristic chart of the Irgacure PAG108. FIG. 4 is a light absorption characteristic chart of Irgacure PAG203.

Claims (10)

(A) a phenolic hydroxyl group-containing resin, (B) a resin containing a benzyl group, a carboxyl group and a hydroxyl group, (C) a crosslinking agent crosslinked with an acid, and (D) light having an absorption maximum at a wavelength of 350 to 420 nm. A photosensitive composition containing an acid generator and having a sensitivity of 10 to 100 mJ / cm ² at a wavelength of 405 nm.   (B) The glass transition temperature (Tg) of the resin containing a benzyl group, a carboxyl group and a hydroxyl group is 240 to 300K (−33 to 27 ° C.), the acid value is 50 to 120 mgKOH / g, and the hydroxyl value is The photosensitive composition according to claim 1, which is a benzyl (meth) acrylate copolymer having a weight average molecular weight of 10,000 to 100,000 at 70 to 180 mg KOH / g. (B) The photosensitive composition in any one of Claim 1 to 2 whose resin containing a benzyl group, a carboxyl group, and a hydroxyl group is a copolymer represented by the following general formula (I).
However, in said general formula (I), R < ¹ >, R < ² >, R < ³ >, R < ⁵ >, R < ⁶ >, R <^7> , R <^8> , and R < ⁹ > independently represent either a hydrogen atom or a methyl group, R ⁴ is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, and ^{-CO-R 12,, R 12} is a hydrogen atom, an alkyl group, a substituted alkyl group, vinyl group, substituted vinyl group , An alkenyl group, a substituted alkenyl group, an aryl group, and a substituted aryl group. R ¹⁰ and R ¹¹ represent any of a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. x, y, and z represent the molar composition ratio of each repeating unit, and x = 0.05-0.70, y = 0.1-0.3, z = 0.2-0.8, x + y + z = 1.   (C) The crosslinking agent is at least one selected from methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, and methoxymethylated glycoluril resin. 4. The photosensitive composition according to any one of items 1 to 3. (D) The photosensitive composition in any one of Claim 1 to 4 whose photo-acid generator is an oxime sulfonate compound represented by the following general formula (II-1)-(II-4).
In the general formula (II-1) ~ (II -4), n represents an integer of 1 to 2, ^{X 0} is - _(CH 2) any m-X, and -CH = CH ₂ X represents any of an ester group, an ether group, an amide group, an imide group, a thioether group, a sulfoxide group, and a sulfonate group. m represents an integer of 2 to 6. When n is 1, R ¹ and R ⁵ represent either hydrogen or an organic group. When n is 2, R ¹ and R ⁵ represent either a direct bond or a divalent organic group. To express. . X ′ represents either a direct bond or a divalent organic group. R ³ , R ⁴ , R ⁷ and R ⁸ may be the same or different from each other, and represent either hydrogen or an organic substituent, and any one of R ³ and R ⁴ , and R ⁷ and R ⁸ May form either a benzene ring or a maleimide ring, which may be substituted together.   A photosensitive film comprising a support and a photosensitive layer comprising the photosensitive composition according to claim 1 on the support.   The photosensitive film according to claim 6, wherein the photosensitive layer has a thickness of 5 to 100 μm.   A photosensitive layer formed from the photosensitive composition according to any one of claims 1 to 5 is subjected to pattern exposure and development to form a resist pattern, and after plating using the resist pattern as a mask, the resist A pattern forming method comprising peeling a pattern.   The pattern forming method according to claim 8, wherein either a bump pattern or a wiring pattern is formed. A printed circuit board comprising at least one of a bump and a wiring formed by the pattern forming method according to claim 8.