TW201701070A - Photosensitive resin composition - Google Patents

Abstract

A photosensitive resin composition comprises an alkali-soluble polymer, a compound having an ethylenically unsaturated bond and a photopolymerization initiator, and has such a property that, when a photosensitive resin layer made from the photosensitive resin composition is formed on the surface of a substrate, then the photosensitive resin layer is exposed to light and is developed to form a resist pattern, and then the resist pattern is treated with a chemical solution for chemical solution resistance evaluation use, the smallest line width of the cured resist lines is 17 [mu]m or less.

Description

Photosensitive resin composition

The present invention relates to a photosensitive resin composition and the like.

Previously, printed wiring boards were usually manufactured by photolithography. In the photolithography method, first, a photosensitive resin composition layer laminated on a substrate is subjected to pattern exposure. The exposed portion of the photosensitive resin composition is subjected to polymerization hardening (in the case of a negative type) or to a developing solution (in the case of a positive type). Next, a resist pattern is formed on the substrate by removing the unexposed portion (in the case of a negative type) or the exposed portion (in the case of a positive type) with a developing solution. Further, after the etching or plating treatment is performed to form a conductor pattern, the resist pattern is removed from the substrate. By performing the steps, a conductor pattern is formed on the substrate.

In the photolithography method, generally, when the photosensitive resin composition is applied onto a substrate, any one of the following methods is used: a method of applying a solution of the photosensitive resin composition to a substrate and drying the solution; Or a photosensitive resin laminate obtained by sequentially laminating a support, a layer containing a photosensitive resin composition (hereinafter also referred to as "photosensitive resin layer"), and optionally a protective layer (hereinafter also referred to as A method of laminating a "dry film resist" on a substrate. The latter is mostly used in the manufacture of printed wiring boards.

With the miniaturization of wiring intervals of printed wiring boards in recent years, various characteristics are constantly required for dry film resists. For example, in order to improve the adhesion and resolution of the resist pattern, and to prevent the resist pattern covering the via hole from being broken at the stage before the development step, the following photosensitive resin compositions are proposed, each of which has a (meth) acrylate compound derived from a skeleton of dipentaerythritol as a compound having an ethylenically unsaturated bond, and A pyrazoline compound is used as a photosensitizer (Patent Document 1).

In order to improve the adhesion and resolution of the resist pattern and to suppress the generation of the residue at the bottom of the resist pattern in the development step, the company also proposes a photosensitive resin composition containing a skeleton derived from dipentaerythritol, respectively. A (meth) acrylate compound and a bis(meth) acrylate compound having a bisphenol A type skeleton and an alkylene oxide chain (Patent Document 2).

In the conductor pattern forming step of etching or plating the substrate on which the resist pattern is formed, or before the step, the resist pattern and the substrate are washed by a chemical liquid such as a degreasing liquid. In the comparison before and after the contact with the chemical solution, it is required to suppress the change in the shape of the resist pattern.

However, from the viewpoint of chemical resistance of the resist pattern, etc., the photosensitive resin compositions described in Patent Documents 1 and 2 have room for improvement.

Further, in order to improve the characteristics of the resist, various photosensitive resin compositions have been proposed (Patent Documents 3 to 6).

In Patent Document 3, the photosensitive resin composition containing pentaerythritol polyalkoxytetramethacrylate as a pentaerythritol polyalkoxy tetramethacrylate is studied from the viewpoint of the shape of the pendulum under the resist pattern, the resolution, and the residual film ratio. A compound having an ethylenically unsaturated bond.

In Patent Document 4, in the viewpoint of the shape of the pendulum under the resist pattern, the resolution, the adhesion, the minimum development time, and the bleed out, the industry is studying the epoxy as a monomer in the photosensitive resin composition. A combination of pentaerythritol tetra(meth)acrylate modified with ethane, di(meth)acrylate obtained by modifying bisphenol A with alkylene oxide, and dipentaerythritol (meth)acrylate.

Patent Literatures 5 and 6 describe a photosensitive resin composition containing an alkali-soluble polymer having a glass transition temperature of more than 106 °C.

However, in the production of a printed wiring board or the like, when the hardness of the hardened resist is too high, the resist pattern is broken due to a physical impact during development or during transport, and as a result, the yield of the wiring pattern is deteriorated. After that. Therefore, in order to maintain close contact with the substrate, The hardened resist is expected to have good flexibility. Further, although the dry film resist is stored in a roll shape and stored, the constituent components of a plurality of film resists adhere to the surface of the support film by oozing out, and it is difficult to produce a stable wiring pattern.

However, the photosensitive resin composition described in the patent documents 3 to 6 has a viewpoint of improving the flexibility of the resist pattern, improving the adhesion, and suppressing the bleeding of the constituent components of the dry film resist. Room for improvement.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-048202

[Patent Document 2] International Publication No. 2015/012272

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2013-156369

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2014-081440

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2013-117716

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2014-191318

The present invention has been made in view of the above-described background art, and a problem to be solved by the present invention is to provide a photosensitive resin composition which is excellent in at least one of adhesion, resolution, and storage stability.

The inventors have found that the above problems can be solved by the following technical methods.

[1]

A photosensitive resin composition comprising: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; and (C) a photopolymerization initiator; The photosensitive resin layer containing the photosensitive resin composition is formed on the surface of the substrate, and the resist pattern obtained by exposure and development is treated with a chemical liquid evaluated by the drug resistance liquid, and the minimum line of the resist line is hardened. The width is 17 μm or less.

[2]

The photosensitive resin composition as described in [1], wherein the photosensitive resin layer is formed on the surface of the substrate, and the Stouffer 41-segment staged exposure meter is used as a mask, and then exposed. The exposure amount of the highest residual film segment during development is 15 segments, and when the photosensitive resin layer is exposed, it is exposed in FT-IR (Fourier Transform Infrared Radiation) measurement. The peak height at the previous wave number of 810 cm ^-1 is P, and the reaction rate of the above-mentioned (B) ethylenic double bond in the compound having an ethylenically unsaturated bond is set to Q, and the above-mentioned photosensitivity is obtained. When the film thickness of the resin layer is R, the value of P × Q / R is 0.21 or more.

[3]

The photosensitive resin composition as described in [1] or [2], wherein the weight average Tg _total of the glass transition temperature Tg of the (A) alkali-soluble polymer is 110 ° C or less.

[4]

The photosensitive resin composition according to any one of the above aspects, wherein the compound having (B) an ethylenically unsaturated bond has a weight average molecular weight of 760 or more.

[5]

The photosensitive resin composition of any one of the above-mentioned (B) of the compound which has the ethylenic unsaturated bond in the compound (B) is the density of the methacryl oxime group of 0.20mol / 100g or more.

[6]

The photosensitive resin composition as described in any one of the above-mentioned [B], wherein the (B) compound having an ethylenic unsaturated bond has an ethylene oxide unit concentration of 0.80 mol/100. g or more.

[7]

The photosensitive resin composition as described in any one of [1] to [6] which contains the hexaarylbiimidazole compound as the (C) photopolymerization initiator.

[8]

A photosensitive resin composition comprising the following components: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; and (C) a photopolymerization initiator; and the above (A) alkali-soluble the molecular weight of the glass transition temperature Tg higher than the average Tg _Total 110 ℃, and comprises a three or more ethylenic unsaturated bonds of the (meth) acrylate compound as the above-mentioned compound (B) having the ethylenically unsaturated bond .

[9]

The photosensitive resin composition as described in [8] which contains the (meth)acrylate compound which has five or more ethylenic unsaturated bonds, and has an alkylene oxide chain as the above (B) has ethylation unsaturated. The compound of the bond.

[10]

The photosensitive resin composition as described in [8] or [9] wherein the (A) alkali-soluble polymer has an acid equivalent weight of from 100 to 600 and a weight average molecular weight of from 5,000 to 500,000, and has a fragrance at a side chain thereof. Family base.

[11]

The photosensitive resin composition as described in any one of [8] to [10] which contains the (meth)acrylate compound which has five or more ethylenic unsaturated bonds, and has an ethylene- (B) A compound having an ethylenically unsaturated bond.

[12]

The photosensitive resin composition as described in any one of [8] which contains the (meth)acrylate compound which has an ethylene oxide chain and a dipentaerythritol skeleton as the above (B) A compound that saturates the bond.

[13]

The photosensitive resin composition as described in any one of the following [8], further comprising the compound represented by the following formula (H) as the (B) compound having an ethylenically unsaturated bond,

In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , and n ₁ and n ₃ are each independently an integer from 1 to 39, and n ₁ + n ₃ is an integer of 2 to 40, n ₂ and n ₄ are each independently an integer of 0 to 29, and n ₂ + n ₄ is an integer of 0 to 30, and repeating units of -(AO)- and -(BO)- The arrangement may be random or block, and in the case of a block, either -(AO)- and -(BO)- may be a biphenyl side}.

[14]

The photosensitive resin composition as described in any one of the following [8], further comprising the compound represented by the following formula (I) as the compound (B) having an ethylenically unsaturated bond,

In the formula, R ₃ to R ₆ each independently represent an alkyl group having 1 to 4 carbon atoms, X represents an alkylene group having 2 to 6 carbon atoms, and m ₁ , m ₂ , m ₃ and m ₄ are independently 0 to 40, respectively. The integer, m ₁ + m ₂ + m ₃ + m ₄ is 1 to 40, and when m ₁ + m ₂ + m ₃ + m ₄ is 2 or more, the plurality of Xs may be the same or different from each other}.

[15]

The photosensitive resin composition as described in any one of [8] to [14] which contains the hexaarylbiimidazole compound as the (C) photopolymerization initiator.

[16]

The photosensitive resin composition as described in any one of [8] to [15] which contains a pyrazoline compound as the (C) photopolymerization initiator.

[17]

The photosensitive resin composition as described in any one of [8] to [16] which is used for direct imaging exposure.

[18]

The photosensitive resin composition as described in [8], wherein the weight average Tg _total of the glass transition temperature Tg of the (A) alkali-soluble polymer is 105 ° C or less, and is relative to the photosensitive resin composition. a compound having at least 3 methacryl fluorenyl groups as the above (B) compound having an ethylenically unsaturated bond, and the above (b) a compound having at least 3 methacryl fluorenyl groups, in a total amount of the solid content component of more than 0% by mass and not more than 16% by mass or less B) 70% by mass or more of the compound having an ethylenically unsaturated bond is a compound having a weight average molecular weight of 500 or more.

[19]

The photosensitive resin composition as described in [18], wherein the compound (b1) having at least three methacryl fluorenyl groups has a weight average molecular weight of 500 or more.

[20]

The photosensitive resin composition as described in [18] or [19] which contains (b2) the compound which has a butylene oxide chain and one or two (meth) propylene group as the above (B). A compound of ethylenically unsaturated bonds.

[twenty one]

The photosensitive resin composition as described in [20], wherein the compound (b2) having a butylene oxide chain and one or two (meth)acryl fluorenyl groups has a weight average molecular weight of 500 or more.

According to the invention, it is possible to provide a photosensitive resin composition which is excellent in at least one of adhesion, resolution and storage stability.

Hereinafter, the form for carrying out the present invention (hereinafter, simply referred to as "this embodiment") will be specifically described.

<Photosensitive Resin Composition>

In the present embodiment, the photosensitive resin composition contains (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator. Photosensitive resin group The compound may further contain other components such as (D) additives as needed.

The first aspect of the present invention is a photosensitive resin composition which is designed by forming a photosensitive resin layer containing a photosensitive resin composition on a surface of a substrate, and performing resisting for exposure and development. After the pattern is treated with the chemical liquid of the drug resistance liquid evaluation, the minimum line width of the hardened resist line is 17 μm or less. When such a photosensitive resin composition is used, when a wiring pattern is formed by plating, a short circuit can be suppressed. Further, by suppressing the plating penetration, a wiring pattern excellent in linearity can be obtained. That is, the photosensitive resin composition of the present invention is excellent in adhesion and/or resolution. The minimum line width of the hardened resist line is preferably 16 μm or less, more preferably 15 μm or less, further preferably 12 μm or less, particularly preferably 10 μm or less, and most preferably 8 μm or less. The method and conditions for measuring the minimum line width of the hardened resist line are described in the evaluation of the drug resistance liquidity of the examples.

The second aspect of the present invention is a photosensitive resin composition, wherein (A) the glass transition temperature Tg of the alkali-soluble polymer has a weight average Tg _total of 110 ° C or less and contains three or more ethylenically unsaturated bonds. The (meth) acrylate compound is (B) a compound having an ethylenically unsaturated bond. By including an (A) alkali-soluble polymer having a Tg _total of 110 ° C or less and a (meth) acrylate compound having three or more ethylenically unsaturated bonds, the reaction rate can be increased, and the crosslinking density is increased. The component (B) which is unreacted is not easily left, and as a result, the photosensitive resin composition tends to provide a resist pattern which is excellent in at least one of adhesion, resolution, and storage stability.

A photosensitive resin layer containing the photosensitive resin composition of the present embodiment is formed on the surface of the substrate, and the Stuart 41-segment staged exposure meter is used as a mask to expose the film, and then the highest residual film segment is developed. When the photosensitive resin layer is exposed, the photosensitive resin layer preferably satisfies the relationship represented by the following formula, P × Q / R ≧ 0.21.

In the formula, in the FT-IR measurement, P represents the peak height at a wave number of 810 cm ^-1 before exposure, and Q represents (B) an ethylene double in a compound having an ethylenically unsaturated bond. The bond is subjected to a reaction rate after exposure, and R represents a film thickness}. The value represented by the above formula P × Q / R is more preferably 0.22 or more, 0.23 or more, 0.24 or more, 0.25 or more, or 0.27 or more. The measurement method and conditions of the values represented by the formula P × Q / R are described in the examples.

(A) alkali soluble polymer

(A) An alkali-soluble polymer is a polymer which can be dissolved in a basic substance. In the present embodiment, the photosensitive resin composition preferably has a carboxyl group from the viewpoint of alkali developability, and more preferably a copolymer containing a carboxyl group-containing monomer as a copolymerization component.

In the present embodiment, the photosensitive resin composition has a high resolution of the resist pattern and a shape of the hem portion, and further relates to (A) from the viewpoint of chemical resistance of the resist pattern. The alkali-soluble polymer preferably contains a copolymer having an aromatic group, and more preferably a copolymer having an aromatic group in a side chain. Further, examples of such an aromatic group include a substituted or unsubstituted phenyl group or a substituted or unsubstituted aralkyl group.

The ratio of the copolymer having an aromatic group to the component (A) is preferably 50% by mass or more, preferably 60% by mass or more, preferably 70% by mass or more, and more preferably 80% by mass or more. It is preferably 90% by mass or more, and may be 100% by mass.

Further, from the viewpoint of the high resolution of the resist pattern and the shape of the hem portion, the aromatic group is also used as the aromatic group in the viewpoint of the chemical resistance of the resist pattern. The copolymerization ratio of the comonomer is preferably 20% by mass or more, preferably 30% by mass or more, preferably 40% by mass or more, preferably 50% by mass or more, preferably 60% by mass or more, preferably It is 70% by mass or more, preferably 80% by mass or more. The upper limit of the copolymerization ratio is not particularly limited, and is preferably 95% by mass or less, and more preferably 90% by mass or less from the viewpoint of maintaining alkali solubility.

Examples of the comonomer having an aromatic group include a monomer having an aralkyl group, styrene, and a styrene derivative capable of being polymerized (for example, methyl styrene, Vinyl toluene, tert-butoxystyrene, ethoxylated styrene, 4-vinylbenzoic acid, styrene dimer, styrene terpolymer, etc.). Among them, a monomer having an aralkyl group or styrene is preferred, and a monomer having an aralkyl group is more preferred.

The aralkyl group may, for example, be a substituted or unsubstituted phenylalkyl group (other than a benzyl group), a substituted or unsubstituted benzyl group or the like, and a substituted or unsubstituted benzyl group is preferred.

Examples of the comonomer having a phenylalkyl group include phenylethyl (meth)acrylate.

Examples of the comonomer having a benzyl group include a (meth) acrylate having a benzyl group, for example, benzyl (meth)acrylate, chlorobenzyl (meth)acrylate, and the like; a vinyl monomer having a benzyl group; For example, vinylbenzyl chloride, vinylbenzyl alcohol, and the like. Among them, benzyl (meth)acrylate is preferred.

The copolymer having an aromatic group (particularly preferably a benzyl group) in the side chain is preferably a monomer which has an aromatic group and at least one of the following first monomers and/or a second monomer described below At least one type is obtained by polymerization.

The (A) alkali-soluble polymer other than the copolymer having an aromatic group in the side chain is preferably obtained by polymerizing at least one of the following first monomers, and more preferably by using the first monomer. At least one type is obtained by copolymerizing at least one of the following second monomers.

A monomer having a carboxyl group in the first single system molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic anhydride. Acid half ester and the like. Among these, (meth)acrylic acid is preferred.

In the present specification, the term "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the term "(meth)acryloyl fluorenyl group" means acryl fluorenyl group or methacryl fluorenyl group, and so-called "(A) "Acrylate" means "acrylate" or "methacrylate".

The copolymerization ratio of the first monomer is based on the total mass of all the monomer components. It is preferably 10 to 50% by mass. From the viewpoint of exhibiting good developability, controlling edge meltability, and the like, it is preferred to set the copolymerization ratio to 10% by mass or more. From the viewpoint of the high resolution of the resist pattern and the shape of the hem portion, it is preferable that the copolymerization ratio is 50% by mass or less from the viewpoint of chemical resistance of the resist pattern. The viewpoint is more preferably 30% by mass or less, further preferably 25% by mass or less, particularly preferably 22% by mass or less, and most preferably 20% by mass or less.

The second monomer is non-acidic and is a monomer having at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid ring (meth)acrylates such as hexyl ester and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile. Among them, preferred are methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate.

In the present embodiment, the (A) alkali-soluble polymer can be produced by subjecting the singular or plural monomers described above to a known polymerization method, preferably addition polymerization, and more preferably The polymerization is carried out by radical polymerization.

From the viewpoint of chemical resistance, adhesion, high resolution, or shape of the hem portion of the resist pattern, a monomer having an aralkyl group and or containing styrene as a monomer are preferable, for example, Preferably, it comprises a copolymer of methacrylic acid, benzyl methacrylate and styrene, a copolymer comprising methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene.

The glass transition temperature of the (A) alkali-soluble polymer obtained by the Fox method from the viewpoint of the chemical resistance, the adhesion, the high resolution, or the shape of the hem portion of the resist pattern (at (A) When the component contains a plurality of copolymers, the glass transition temperature Tg of the entire mixture, that is, the weight average value Tg _{total of the} glass transition temperature is preferably 110 ° C or less, more preferably 107 ° C or less and 105 ° C or less. , 100 ° C or less, 95 ° C or less, 90 ° C or less or 80 ° C or less. (A) The lower limit of the glass transition temperature (Tg) of the alkali-soluble polymer is not limited, and from the viewpoint of controlling edge meltability, it is preferably 30 ° C or higher, more preferably 50 ° C or higher, and further preferably Above 60 °C.

(A) Acid equivalent of the alkali-soluble polymer (in the case where the component (A) contains a plurality of copolymers, the acid equivalent of the entire mixture), the development resistance of the photosensitive resin layer, and the resist pattern The viewpoint of the resolution and the adhesion is preferably 100 or more, and is preferably 600 or less from the viewpoint of developability and releasability of the photosensitive resin layer. The acid equivalent of the (A) alkali-soluble polymer is more preferably from 200 to 500, still more preferably from 250 to 450.

(A) The weight average molecular weight of the alkali-soluble polymer (when the component (A) contains a plurality of copolymers, the weight average molecular weight of the entire mixture) is preferably 5,000 to 500,000. The weight average molecular weight of the (A) alkali-soluble polymer is such that the thickness of the dry film resist is uniformly maintained, and from the viewpoint of obtaining resistance to the developer, it is preferably 5,000 or more, and the dry film resist is maintained. From the viewpoint of the developability, the high resolution of the resist pattern, the shape of the hem portion, and the chemical resistance of the resist pattern, it is preferably 500,000 or less. The weight average molecular weight of the (A) alkali-soluble polymer is more preferably from 10,000 to 200,000, further preferably from 20,000 to 130,000, particularly preferably from 30,000 to 100,000, most preferably from 40,000 to 70,000. (A) The dispersibility of the alkali-soluble polymer is preferably from 1.0 to 6.0.

In the present embodiment, the content of the (A) alkali-soluble polymer in the photosensitive resin composition is based on the total amount of the solid content of the photosensitive resin composition (hereinafter, unless otherwise specified, in each of the contained components) Similarly, it is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, still more preferably 40% by mass to 60% by mass. The content of the (A) alkali-soluble polymer is preferably 10% by mass or more from the viewpoint of maintaining the alkali developability of the photosensitive resin layer, and the resist pattern formed by exposure is sufficiently exhibited as a resist. The viewpoint of the performance of the agent material, the high resolution of the resist pattern, the shape of the hem portion, and the chemical resistance of the resist pattern are preferably 90% by mass. Hereinafter, it is more preferably 70% by mass or less, further preferably 60% by mass or less.

(B) a compound having an ethylenically unsaturated bond

(B) A compound having an ethylenically unsaturated bond is a compound having polymerizability by having an ethylenically unsaturated group in its structure.

The photosensitive resin composition of the present embodiment preferably contains three or more ethylenically unsaturated bonds from the viewpoint of chemical resistance, adhesion, high resolution, or hem shape of the resist pattern. A methyl acrylate compound is (B) a compound having an ethylenically unsaturated bond. In this case, the ethylenically unsaturated bond is more preferably derived from a methacryloyl group.

The (meth) acrylate compound having three or more ethylenically unsaturated bonds is, for example, a (meth) acrylate compound having an ethylene oxide chain and a dipentaerythritol skeleton, or (b1) having at least 3 methacrylic compounds. The compounds of the thiol group are described below.

The photosensitive resin composition of the present embodiment preferably contains five or more ethylenically unsaturated bonds, and the photosensitive resin composition of the present embodiment has a chemical resistance, an adhesive property, a high resolution, or a shape of a hem portion. A (meth) acrylate compound having an alkylene oxide chain as (B) a compound having an ethylenically unsaturated bond. In this case, the ethylenically unsaturated bond is more preferably derived from a methacrylonitrile group, and the alkylene oxide chain is more preferably an ethylene oxide chain.

A (meth) acrylate compound having 5 or more ethylenically unsaturated bonds and having an alkylene oxide chain is, for example, a (meth) acrylate compound having an ethylene oxide chain and a dipentaerythritol skeleton, and is hereinafter Description.

The concentration of the (meth)methacrylic acid group in the compound having an ethylenically unsaturated bond is preferably 0.20 from the viewpoint of chemical resistance, adhesion, high resolution, or shape of the hem portion of the resist pattern. The mol/100 g or more is more preferably 0.30 mol/100 g or more, further preferably 0.35 mol/100 g or more, and particularly preferably 0.40 mol/100 g or more. The upper limit of the concentration of the methacrylonitrile group is not particularly limited as long as the polymerizability and the alkali developability are ensured, and may be, for example, 0.90 mol/100 g or less or 0.80 mol/100 g or less.

From the same point of view, (B) a methyl group in a compound having an ethylenically unsaturated bond The concentration of the acrylonitrile group / the concentration of the (methacryl oxime group + the concentration of the acryl oxime group) is preferably 0.50 or more, more preferably 0.60 or more, further preferably 0.80 or more, and particularly preferably 0.90 or more. It is 0.95 or more.

The concentration of the ethylene oxide unit in the compound having an ethylenically unsaturated bond (B) is preferably 0.80 from the viewpoint of chemical resistance, adhesion, high resolution, or shape of the hem portion of the resist pattern. The mol/100 g or more is more preferably 0.90 mol/100 g or more, further preferably 1.00 mol/100 g or more, and particularly preferably 1.10 mol/100 g or more. The upper limit of the concentration of the ethylene oxide unit is not particularly limited as long as the chemical resistance, adhesion, and resolution of the resist pattern are ensured, and may be, for example, 1.60 mol/100 g or less and 1.50 mol/100 g. Hereinafter, it is 1.45 mol/100 g or less or 1.40 mol/100 g or less.

In the present embodiment, the photosensitive resin composition preferably contains an alkylene oxide chain and a dipentaerythritol skeleton from the viewpoint of chemical resistance, adhesion, high resolution, or shape of the hem portion of the resist pattern. The (meth) acrylate compound is (B) a compound having an ethylenically unsaturated bond. Examples of the alkylene oxide chain include an ethylene oxide chain, a propylene oxide chain, a butylene oxide chain, an epoxy pentanyl chain, and a hexylene oxide chain. In the case where the photosensitive resin composition contains a plurality of alkylene oxide chains, the mutually different ones may be the same or different. In view of the above, the alkylene oxide chain is more preferably an ethylene oxide chain, a propylene oxide chain, or a butylene oxide chain, and further preferably an ethylene oxide chain or a propylene oxide chain. Jia is an ethylene oxide chain.

In the photosensitive resin composition, the (A) alkali-soluble polymer and the (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton are used in combination, and the chemical resistance and adhesion of the resist pattern are maintained. And the tendency to balance the resolution.

The (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton refers to an ester of dipentaerythritol compound and (meth)acrylic acid obtained by modifying at least one of a plurality of hydroxyl groups by using an alkyleneoxy group. . The six hydroxyl groups of the dipentaerythritol skeleton can also be modified with an alkyleneoxy group. The number of ester bonds in one molecule of the ester may range from 1 to 6, preferably 6.

As a (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton, For example, hexa(meth)acrylate having an alkylene oxide average of 4 to 30 moles, an average of 6 to 24 moles, or an average of 10 to 14 moles may be added to dipentaerythritol.

Specifically, as a (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton, from the viewpoints of chemical resistance, adhesion, high resolution, or hem shape of the resist pattern, Preferred is a compound represented by the following formula (III),

In the formula, R independently represents a hydrogen atom or a methyl group, and n is an integer of 0 to 30, and the total value of all n is 1 or more}.

In the general formula (III), it is preferred that the average value of all n is 4 or more, or n is 1 or more. As R, a methyl group is preferred.

The content of the (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton in the photosensitive resin composition is preferably from 1% by mass to 50% by mass in terms of chemical resistance of the resist pattern. More preferably, it is 5% by mass to 40% by mass, and further preferably in the range of 7% by mass to 30% by mass.

In the present embodiment, in order to suppress the bleed out of the constituent components of the dry film resist and improve the storage stability, (B) the total amount of the solid content of the compound having an ethylenically unsaturated bond is used as a reference, and (B) has ethylene. 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 100% by mass of the compound of the unsaturated bond is a compound having a weight average molecular weight of 500 or more. (B) the weight of the compound having an ethylenically unsaturated bond, from the viewpoint of suppressing the chemical resistance of the bleeding and the resist pattern The average molecular weight is preferably 760 or more, more preferably 800 or more, still more preferably 830 or more, and still more preferably 900 or more. (B) The weight average molecular weight of the compound having an ethylenically unsaturated bond was measured by the method described in the examples.

In order to improve the flexibility of the resist pattern and improve the adhesion, and to suppress the bleeding of the constituent components of the dry film resist, the photosensitive resin composition preferably contains (b1) a compound having at least 3 methacryl groups. (B) A compound having an ethylenically unsaturated bond.

From the viewpoint of suppressing bleeding, (b1) the compound having at least 3 methacryl fluorenyl groups has a weight average molecular weight of preferably 500 or more, more preferably 700 or more, still more preferably 900 or more.

Regarding (b1) a compound having at least 3 methacryl fluorenyl groups, the number of methacryl fluorenyl groups is preferably 4 or more, 5 or more or 6 or more. The compound having at least 3 methacryl fluorenyl groups may also have an alkylene oxide chain, such as an ethylene oxide chain, a propylene oxide chain, or a combination thereof.

As (b1) a compound having at least 3 methacryl groups, a trimethacrylate such as ethoxylated glycerol trimethacrylate or ethoxylated isocyanuric acid trimethacrylate may be mentioned. Ester, pentaerythritol trimethacrylate, trimethylolpropane trimethacrylate (for example, in terms of flexibility, adhesion, and inhibition of bleeding, it is preferred to add to trimethylolpropane) An average of 21 moles of ethylene oxide trimethacrylate or trimethylolpropane plus an average of 30 moles of ethylene oxide trimethacrylate); tetramethacrylate For example, di-trimethylolpropane tetramethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, etc.; pentamethyl acrylate, such as dipentaerythritol pentamethyl acrylate; hexamethyl An acrylate such as dipentaerythritol hexamethacrylate or the like. Among these, tetra-, penta- or hexamethacrylate is preferred.

As the tetramethacrylate, pentaerythritol tetramethacrylate is preferred. Pentaerythritol tetramethacrylate can be added to the four ends of pentaerythritol by a total of 1 to 40 moles A tetraalkyl methacrylate or the like.

The tetramethacrylate is more preferably a tetramethacrylate compound represented by the following formula (I).

In the formula, R ₃ to R ₆ each independently represent an alkyl group having 1 to 4 carbon atoms, X represents an alkylene group having 2 to 6 carbon atoms, and m ₁ , m ₂ , m ₃ and m ₄ are independently 0 to 40, respectively. The integer, m ₁ + m ₂ + m ₃ + m ₄ is 1 to 40, and when m ₁ + m ₂ + m ₃ + m ₄ is 2 or more, the plurality of Xs may be the same or different from each other}.

Although not desirably limited to theory, it is considered that the tetramethacrylate compound represented by the general formula (I) has a radical of from R ₃ to R ₆ and has a moiety of H ₂ C=CH-CO-O- Compared with acrylate, it inhibits hydrolysis in an alkaline solution. It is preferable to use the inclusion of the general formula (I) in terms of improving the resolution of the resist pattern, in detail, the line shape, more specifically, the shape of the under-line portion and the adhesion of the resist. A photosensitive resin composition of the tetramethacrylate compound shown.

In the general formula (the I), R is preferably a group of at least ₃ ~ R ₆ is a methyl group, and more preferably all of R ₃ ~ R ₆ is the methyl group.

With respect to the resist pattern, from the viewpoint of obtaining desired resolution, hem shape, and residual film ratio, in the general formula (I), X is preferably -CH ₂ -CH ₂ -.

With respect to the resist pattern, in view of obtaining the desired resolution, the shape of the hem portion, and the residual film ratio, in the general formula (I), m ₁ , m ₂ , m ₃ and m _{4 are} preferably independent of each other. It is an integer from 1 to 20, more preferably an integer from 2 to 10. Further, in the formula (I), m ₁ + m ₂ + m ₃ + m _{4 is} preferably from 1 to 36 or from 4 to 36.

Examples of the compound represented by the formula (I) include pentaerythritol (poly) alkoxy tetramethacrylate and the like. Further, in the present specification, "pentaerythritol (poly)alkoxytetramethacrylate" is included in the above formula (I), and m ₁ + m ₂ + m ₃ + m ₄ =1 "pentaerythritol alkoxy group""Tetramethacrylate" and "pentaerythritol polyalkoxytetramethacrylate" of m ₁ + m ₂ + m ₃ + m ₄ = 2 to 40. Examples of the compound represented by the formula (I) include a compound listed in JP-A-2013-156369, for example, pentaerythritol (poly) alkoxytetramethacrylate.

As the hexamethyl acrylate compound, it is preferred to add a total of 1 to 24 moles of ethylene oxide hexamethacrylate to the 6 terminal ends of dipentaerythritol and a total of 6 terminal additions of dipentaerythritol. 1 to 10 moles of ε-caprolactone hexamethyl acrylate.

The content of the compound having at least three methacryl fluorenyl groups in (b1) is preferably more than 0% by mass and not more than 16% by mass based on the total amount of the solid content of the photosensitive resin composition. When the content is more than 0% by mass, the resolution tends to be improved. When the content is more than 16% by mass, the flexibility of the cured resist is improved, and the peeling time tends to be shortened. The content is more preferably 2% by mass or more and 15% by mass or less, and still more preferably 4% by mass or more and 12% by mass or less.

The photosensitive resin composition preferably contains (b2) a compound having a butylene oxide chain and one or two (meth)acrylonium groups as (B) a compound having an ethylenically unsaturated bond.

From the viewpoint of suppressing bleeding, (b2) the compound having a butylene oxide chain and one or two (meth) acrylonitrile groups is preferably 500 or more, more preferably 700 or more, and still more preferably 1,000. The above molecular weight.

As (b2) a compound having a butylene oxide chain and one or two (meth) acrylonitrile groups, Examples thereof include polytetramethylene glycol (meth) acrylate and polytetramethylene glycol di (meth) acrylate.

Specifically, (b2) the compound having a butylene oxide chain and one or two (meth)acryl fluorenyl groups is preferably from 1 to 20, more preferably from 4 to 15, more preferably 6 to 12 (meth) acrylate or di(meth) acrylate of C ₄ H ₈ O.

The content of the compound having a butylene oxide chain and one or two (meth)acryl fluorenyl groups in (b2) is preferably more than 0% by mass and is 20% based on the total amount of the solid content of the photosensitive resin composition. Below mass%.

The photosensitive resin composition may contain (b3) a compound having an aromatic ring and an ethylenically unsaturated bond as (B) a compound having an ethylenically unsaturated bond.

(b3) The compound having an aromatic ring and an ethylenically unsaturated bond may further have an alkylene oxide chain. The aromatic ring is preferably incorporated into the compound as a divalent skeleton derived from bisphenol A, a divalent skeleton derived from naphthalene, a diphenyl group such as a phenylene group or a methylphenyl group. The alkylene oxide chain can be an ethylene oxide chain, a propylene oxide chain, or a combination thereof. The ethylenically unsaturated bond is preferably incorporated into the compound as a (meth) acrylonitrile group.

Specifically, as the compound (b3) having an aromatic ring and an ethylenically unsaturated bond, a compound represented by the following formula (II) can be used.

In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , and n ₁ and n ₃ are each independently an integer from 1 to 39, and n ₁ + n ₃ is an integer of 2 to 40, n ₂ and n ₄ are each independently an integer of 0 to 29, and n ₂ + n ₄ is an integer of 0 to 30, and repeating units of -(AO)- and -(BO)- The arrangement may be random or block, and in the case of a block, either -(AO)- and -(BO)- may be a biphenyl side}.

From the viewpoints of resolution and adhesion, for example, it is preferred to separately add a diethylene glycol of polyethylene glycol having an average of 5 moles of ethylene oxide to both ends of bisphenol A, Diethylene glycol of polyethylene glycol having an average of 2 moles of ethylene oxide is added to both ends of bisphenol A, and an average of 1 mole is added to both ends of bisphenol A. Diethylene glycol of polyethylene oxide, etc.

Further, as the compound having an aromatic ring, an alkylene oxide chain or an ethylenically unsaturated bond, a compound having a hetero atom and/or a substituent in the aromatic ring in the above formula (II) can also be used.

Examples of the hetero atom include a halogen atom and the like, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, and benzamidine. Methyl, amine, alkylamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, fluorenyl group, alkyl group having 1 to 10 carbon atoms, aromatic a hydroxy group having 1 to 20 carbon atoms, a carboxyl group or an alkyl group having 1 to 10 carbon atoms, a carboxy group having 1 to 10 carbon atoms in the alkyl group, and an alkyl group having 1 to 20 carbon atoms An oxy group, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylamine carbenyl group having 2 to 10 carbon atoms or containing impurities a group of a ring, or an aryl group substituted with the substituents, and the like. These substituents may also form a condensed ring, or the hydrogen atom in the substituent may be substituted with a hetero atom such as a halogen atom. In the case where the aromatic ring in the formula (II) has a plurality of substituents, the plurality of substituents may be the same or different.

The content of the compound having an aromatic ring and an ethylenically unsaturated bond in (b3) is preferably more than 0% by mass and not more than 50% by mass based on the total amount of the solid content of the photosensitive resin composition. If the content exceeds 0% by mass, there is a tendency to improve the resolution and the adhesion. From the viewpoint of shadow time and edge melting, it is preferably 50% by mass or less.

The (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton described above and the (b1) to (b3) compounds may be used independently or in combination. The photosensitive resin composition may contain not only a (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton but also a compound (b1) to (b3) as (B) a compound having an ethylenically unsaturated bond, and may contain Other compounds are as (B) compounds having an ethylenically unsaturated bond.

Examples of the other compound include an acrylate compound having at least one (meth)acryl fluorenyl group, a (meth) acrylate having a urethane bond, and an α,β-unsaturated carboxylic acid and a polyhydric alcohol. A compound obtained by carrying out the reaction, a compound obtained by reacting an α,β-unsaturated carboxylic acid and a glycidyl group-containing compound, a phthalic acid-based compound or the like. Among them, from the viewpoints of resolution, adhesion, and peeling time, an acrylate compound having at least two (meth) acrylonitrile groups is preferred. The acrylate compound having at least two (meth) acrylonitrile groups may be di, tri, tetra, penta, hexa (meth) acrylate or the like. From the viewpoints of flexibility, resolution, adhesion, and the like, for example, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, having ethylene oxide and polyepoxy are preferable. Two (meth) acrylates of propane (for example, "FA-023M, FA-024M, FA-027M, product name, manufactured by Hitachi Chemical Co., Ltd.").

Further, from the viewpoint of the releasability or the flexibility of the cured film, it is preferred to contain 4-n-decylphenoxy octaethylene glycol acrylate, 4-n-nonylphenoxytetraethylene glycol acrylate, and adjacent a compound having one ethylenically unsaturated bond such as γ-chloro-β-hydroxypropyl-β'-methacryloxyethyl phthalate, in terms of sensitivity, resolution, or adhesion It is also preferred to include γ-chloro-β-hydroxypropyl-β'-methacryloxyethyl phthalate.

In the present embodiment, the photosensitive resin combination is improved from the viewpoint of improving the adhesion of the resist pattern and suppressing the hardening of the resist pattern, the delay of the development time, the cold flow or the bleeding, or the peeling delay of the hardened resist. All (B) in the substance have ethylenic unsaturated bonds The total content of the compound is preferably from 1% by mass to 70% by mass, more preferably from 2% by mass to 60% by mass, even more preferably from 4% by mass to 50% by mass.

(C) Photopolymerization initiator

(C) A photopolymerization initiator is a compound which polymerizes a monomer by light. The photosensitive resin composition contains a compound generally known in the art as (C) a photopolymerization initiator.

The total content of the (C) photopolymerization initiator in the photosensitive resin composition is preferably from 0.01 to 20% by mass, more preferably from 0.05% by mass to 10% by mass, still more preferably from 0.1% by mass to 7% by mass, It is particularly preferably in the range of 0.1% by mass to 6% by mass. The total content of the (C) photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and the light is sufficiently transmitted to the bottom surface of the resist to obtain good high resolution. From the viewpoint, it is preferably 20% by mass or less.

Examples of the (C) photopolymerization initiator include anthraquinones, aromatic ketones, acetophenones, fluorenylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, and 9-oxosulfur And dialkylamino benzoate, oxime ester, acridine (for example, in terms of sensitivity, resolution, and adhesion), for example, 9-phenyl acridine or bisacridinyl is preferred. Heptane, 9-(p-methylphenyl) acridine, 9-(m-methylphenyl)acridine), and further, hexaarylbiimidazole, pyrazoline compound, hydrazine compound (in terms of sensitivity, solution) From the viewpoints of image and adhesion, for example, preferred are 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 9,10-diphenylanthracene), coumarin compound ( From the viewpoints of sensitivity, resolution, and adhesion, for example, 7-diethylamino-4-methylcoumarin, N-arylamino acid or an ester compound thereof (in terms of sensitivity) From the viewpoints of resolution and adhesion, for example, N-phenylglycine (for example) and a halogen compound (for example, tribromomethylphenylhydrazine) are preferable. These may be used alone or in combination of two or more. In addition, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-(4-methylthienyl)-2-morpholine can also be used. Propane-1-one, 2,4,6-trimethylbenzylidene-diphenylphosphine oxide, triphenylphosphine oxide, and the like.

Examples of the aromatic ketones include benzophenone, rice ketone [4,4'-bis(dimethylamino)benzophenone], and 4,4'-bis(diethylamine). Benzo) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone. These may be used alone or in combination of two or more. Among these, from the viewpoint of adhesion, 4,4'-bis(diethylamino)benzophenone is preferred. Furthermore, the content of the aromatic ketone in the photosensitive resin composition is preferably from 0.01% by mass to 0.5% by mass, and more preferably from 0.02% by mass to 0.3% by mass, from the viewpoint of the transmittance.

Examples of the hexaarylbiimidazole include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole and 2,2',5-tris-(o-chlorophenyl)-4-( 3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl )-diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-di Methoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'- Bis-(2,4-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5- Difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4 , 4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5 , 5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-four -(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetra-(3-A Oxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxy Phenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-linked Imidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2 , 2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, and 2,2 '-Bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, etc. They may be used alone or in combination of two or more. From the viewpoint of high sensitivity, resolution and adhesion, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred.

In the present embodiment, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably from 0.05% by mass to 7% by mass, from the viewpoint of improving the peeling property and/or sensitivity of the photosensitive resin layer. It is more preferably 0.1% by mass to 6% by mass, and still more preferably 1% by mass to 4% by mass.

The photosensitive resin composition preferably further contains a pyrazoline compound as a photosensitizer from the viewpoint of the peeling property, sensitivity, resolution, and adhesion of the photosensitive resin layer.

As the pyrazoline compound, from the above viewpoint, for example, 1-phenyl-3-(4-t-butyl-styryl)-5-(4-t-butyl-phenyl)- is preferable. Pyrazoline, 1-(4-(benzo) Zin-2-yl)phenyl)-3-(4-t-butyl-styryl)-5-(4-t-butyl-phenyl)-pyrazoline, 1-phenyl-3- (4-biphenyl)-5-(4-t-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-t-octyl -phenyl)-pyrazoline, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, 1-phenyl-3- (4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-(3,5-dimethoxystyryl)-5- (3,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxybenzene -Pyrazoline, 1-phenyl-3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-benzene 3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,3-di Methoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,4-dimethoxystyryl)-5- (2,4-dimethoxyphenyl)-pyrazoline or the like, more preferably 1-phenyl-3-(4-biphenyl)-5-(4-t-butyl-phenyl)- Pyrazoline.

The photosensitive resin composition may contain one or two or more pyrazoline compounds as a photosensitizer.

In the present embodiment, the content of the photosensitizer in the photosensitive resin composition is preferably from 0.05% by mass to 5% by mass, more preferably from the viewpoint of improving the peeling property and/or sensitivity of the photosensitive resin layer. Within the range of %% to 3% by mass.

(D) Additives

The photosensitive resin composition may contain a dye, a plasticizer, an antioxidant, and a stabilizer as needed. Additives and other additives. For example, the additives listed in Japanese Patent Laid-Open Publication No. 2013-156369 can be used.

The photosensitive resin composition preferably contains tris(4-dimethylaminophenyl)methane [leuco crystal violet] and/or diamond green (Hodogaya) from the viewpoints of coloring property, hue stability, and exposure contrast. Aizen (registered trademark) DIAMOND GREEN GH manufactured by Chemical Co., Ltd. as a dye.

In the present embodiment, the content of the dye in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, more preferably 0.01% by mass to 2% by mass, still more preferably 0.02% by mass to 1% by mass. Within the scope. The content of the dye is preferably 0.001% by mass or more from the viewpoint of obtaining good coloring properties, and is preferably 3% by mass or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.

The photosensitive resin composition preferably contains a radical polymerization inhibitor, for example, a nitrosophenylhydroxylamine aluminum salt, a p-methoxy group, from the viewpoint of thermal stability or storage stability of the photosensitive resin composition. Phenol, 4-tert-butyl catechol, 4-ethyl-6-tert-butylphenol, etc.; benzotriazoles, such as 1-(2-di-n-butylaminomethyl) a 1:1 mixture of 5-carboxybenzotriazole with 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole; etc.; carboxybenzotriazoles such as 4-carboxyl -1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, 6-carboxy-1,2,3-benzotriazole, etc.; and a ring having a glycidyl group At least one of a group consisting of an oxane compound, for example, neopentyl glycol diglycidyl ether, is used as a stabilizer. In addition, 2-mercaptobenzimidazole, 1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 2-amino-5-mercapto-1,3,4-thiadiene may also be contained. Oxazole, 3-amino-5-mercapto-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-mercaptotriazole, 4,5-diphenyl-1,3 - Diazol-2-yl, 5-amino-1H-tetrazole, and the like.

In the present embodiment, the total content of all the stabilizers in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, more preferably 0.01% by mass to 1% by mass, still more preferably 0.05% by mass to 0.7% by mass. Within the range of mass %. Regarding the total content of the stabilizer, it is sensitive to The resin composition is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability, and is preferably 3% by mass or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.

The additives described above may be used alone or in combination of two or more.

<Photosensitive Resin Composition Blending Liquid>

In the present embodiment, a photosensitive resin composition preparation liquid can be formed by adding a solvent to the photosensitive resin composition. Examples of suitable solvents include ketones such as methyl ethyl ketone (MEK) and the like, and alcohols such as methanol, ethanol, and isopropanol. Preferably, the viscosity of the photosensitive resin composition preparation liquid is 500 mPa at 25 ° C. Sec~4000mPa. In a sec manner, a solvent is added to the photosensitive resin composition.

<Photosensitive Resin Laminate>

In the present embodiment, a photosensitive resin laminate having a support and a photosensitive resin layer containing the photosensitive resin composition laminated on the support can be provided. The photosensitive resin laminate may have a protective layer on the side opposite to the support side of the photosensitive resin layer as needed.

The support is not particularly limited, and is preferably a transparent one that transmits light emitted from the exposure light source. Examples of such a support include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, and a vinylidene chloride copolymer film. A polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. These films may also be extended as needed. The haze is preferably from 0.01% to 5.0%, more preferably from 0.01% to 2.5%, still more preferably from 0.01% to 1.0%. Although the thickness of the film is more advantageous in terms of image formation and economy, it is preferably 10 μm to 30 μm in order to maintain strength.

Further, an important characteristic of the protective layer used in the photosensitive resin laminate is as follows: the adhesion to the photosensitive resin layer is smaller than that of the support, and can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film or the like is preferable. For example, you can use Japan. A film excellent in peelability described in JP-A-59-202457. The film thickness of the protective layer is preferably from 10 μm to 100 μm, more preferably from 10 μm to 50 μm.

In the present embodiment, the thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably from 5 μm to 100 μm, more preferably from 7 μm to 60 μm. The smaller the thickness of the photosensitive resin layer is, the more the resolution of the resist pattern is improved. On the other hand, the thickness of the photosensitive resin layer is increased as the thickness of the cured resin layer is increased. Therefore, it can be selected according to the use.

As a method of producing a photosensitive resin laminate by sequentially laminating a support, a photosensitive resin layer, and an optional protective layer, a known method can be used.

For example, the photosensitive resin composition preparation liquid is prepared, and then applied to a support by a bar coater or a roll coater, and dried, and a photosensitive resin composition preparation liquid is laminated on the support. Photosensitive resin layer. Further, if necessary, a protective layer is laminated on the photosensitive resin layer, whereby a photosensitive resin laminate can be produced.

<Resist pattern forming method>

Preferably, the method for forming a resist pattern comprises the steps of: a laminating step of laminating a photosensitive resin layer comprising the photosensitive resin composition on a support; and an exposing step of exposing the photosensitive resin layer; And a developing step of developing the exposed photosensitive resin layer. In the present embodiment, one of specific methods for forming a resist pattern is exemplified below.

First, in the laminating step, a photosensitive resin layer is formed on a substrate using a laminator. Specifically, when the photosensitive resin laminate has a protective layer, after the protective layer is peeled off, the photosensitive resin layer is heat-pressure-bonded to the surface of the substrate by a bonding machine to be laminated. Examples of the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and the like.

In the present embodiment, the photosensitive resin layer may be laminated only on one surface of the substrate surface or, if necessary, on both sides. The heating temperature during lamination is usually from 40 ° C to 160 ° C. Moreover, by performing the thermocompression bonding at the time of lamination two or more times, the obtained resist can be improved. The adhesion of the pattern to the substrate. In the case of thermocompression bonding, a two-stage laminator having two rolls may be used, or the laminate of the substrate and the photosensitive resin layer may be repeatedly passed through a roll to be pressure-bonded.

Next, in the exposure step, the photosensitive resin group layer is exposed to active light using an exposure machine. Exposure can be performed after peeling off the support as needed. In the case of exposure using a photomask, the exposure amount is determined according to the illuminance of the light source and the exposure time, and may be measured using a photometer. Direct imaging exposure can also be performed during the exposure step. In direct imaging exposure, exposure is performed on the substrate using a direct drawing device without using a photomask. As the light source, a semiconductor laser or an ultrahigh pressure mercury lamp having a wavelength of 350 nm to 410 nm can be used. When the drawing pattern is controlled by a computer, the exposure amount is determined according to the illuminance of the exposure light source and the moving speed of the substrate. Exposure can also be performed by projecting the image of the reticle through the lens.

Next, in the developing step, the unexposed portion or the exposed portion of the exposed photosensitive resin layer is removed by a developing solution using a developing device. After the exposure, when a support is present on the photosensitive resin layer, it is removed. Then, the unexposed portion or the exposed portion is developed and removed using a developing solution containing an alkaline aqueous solution to obtain a resist image.

As the alkaline aqueous solution, an aqueous solution of Na ₂ CO ₃ , K ₂ CO ₃ or the like is preferable. The alkaline aqueous solution is selected depending on the characteristics of the photosensitive resin layer, and a Na ₂ CO ₃ aqueous solution having a concentration of 0.2% by mass to 2% by mass is usually used. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed. The temperature of the developer in the developing step is preferably kept constant in the range of 20 ° C to 40 ° C.

The resist pattern can be obtained by the above steps, and the heating step can be further carried out at 100 ° C to 300 ° C as needed. By performing this heating step, the chemical resistance of the resist pattern can be improved. A heating furnace using hot air, infrared rays, or far infrared rays can be used in the heating step.

The photosensitive resin composition of the present embodiment can be suitably used to form a circuit for a printed substrate. Generally, as a circuit forming method of a printed substrate, a subtractive method and a semi-additive method are used. (SAP).

The subtractive method is a method of forming a circuit by etching only a non-circuit portion from a conductor disposed on the entire surface of the substrate.

SAP is a method in which only a circuit portion is formed by plating after forming a resist on a non-circuit portion of a conductor seed layer disposed on the entire surface of the substrate.

In the present embodiment, the photosensitive resin composition is more preferably used for SAP.

<Cured product of photosensitive resin composition>

In the present embodiment, in order to improve the flexibility of the resist pattern, the elongation of the cured product of the photosensitive resin composition is preferably 1 mm or more, more preferably 2 mm or more, still more preferably 3 mm or more.

The elongation of the cured product was measured by exposing the photosensitive resin laminate produced by the photosensitive resin composition to a rectangular mask of 5 mm × 40 mm, and further doubling the minimum development time. The development was carried out, and the obtained hardened resist was stretched at a speed of 100 mm/min by a tensile tester (RTM-500 manufactured by Orientec Co., Ltd.).

In the present embodiment, the Young's modulus of the cured product of the photosensitive resin composition is preferably 1.5 GPa or more and less than 8 GPa from the viewpoint of the resolution and flexibility of the resist pattern. In the present specification, the "Young's modulus" can be measured by a nanoindenter DCM manufactured by Toyo Technica Co., Ltd. and by a nanoindentation method. Specifically, the "Young's modulus" is obtained by laminating a resin composition to be measured on a substrate, exposing it, and developing it, and using the surface of the photosensitive resin composition on the obtained substrate by Toyo Technica Co., Ltd. The nanoindenter DCM was measured. As a method of measurement, DCM Basic Hardness, Modulus, Tip Cal, Load Control.msm (MultiLoad Unload Method, MultiLoad Method) was used, and the parameters of the press-in test were set to Percent To Unload = 90%, maximum load ( Maximum Load) = 1gf, load ratio and unload ratio (Load Rate Multiple For Unload Rate) = 1, Number Of Times to Load = 5, Peak Hold Time = 10 s, Time To Load = 15 s, Poisson's ratio = 0.25. The Young's modulus is set to the value of "Modulas At Max Load".

<Method of Manufacturing Conductor Pattern>

Preferably, the method for producing a conductor pattern comprises the steps of: laminating step of laminating a photosensitive resin layer containing the photosensitive resin composition on a substrate such as a metal plate or a metal film insulating plate; and an exposure step for photosensitivity The resin layer is exposed; the developing step is performed by removing the unexposed portion or the exposed portion of the exposed photosensitive resin layer by using a developing solution to obtain a substrate on which the resist pattern is formed; and a conductor pattern forming step, which is resistant to formation The substrate of the etched pattern is etched or plated.

In the present embodiment, the method of manufacturing the conductor pattern is performed by forming a resist pattern by the above-described resist pattern forming method by using a metal plate or a metal film insulating plate as a substrate, and then performing a conductor patterning step. In the conductor pattern forming step, a conductor pattern is formed on a surface (for example, a copper surface) of a substrate exposed by development using a known etching method or plating method.

Further, the present invention is suitably applied to, for example, the following uses.

<Manufacturing method of wiring board>

After the conductor pattern is produced by the method for producing a conductor pattern, a peeling step of peeling off the resist pattern from the substrate by using an aqueous solution having a stronger alkalinity than the developer is performed, whereby a desired wiring pattern can be obtained. Wiring board (such as printed wiring board).

In the production of the wiring board, a laminate of an insulating resin layer and a copper layer or a flexible substrate is used as the substrate. In order to carry out SAP, it is preferred to use a laminate of an insulating resin layer and a copper layer. Regarding SAP, the copper layer is preferably an electroless copper plating layer containing palladium as a catalyst. Regarding SAP, it is also preferred to carry out the conductor pattern forming step by a known plating method. In order to carry out the modified semi-additive method (MSAP), the substrate is preferably a laminate of an insulating resin layer and a copper foil. The body is more preferably a copper foil laminate.

The alkaline aqueous solution for peeling (hereinafter also referred to as "peeling liquid") is not particularly limited, and an aqueous solution of NaOH or KOH having a concentration of 2% by mass to 5% by mass or an organic amine-based peeling liquid is usually used. A small amount of a water-soluble solvent can be added to the stripping solution. Examples of the water-soluble solvent include alcohols and the like. The temperature of the stripping liquid in the stripping step is preferably in the range of 40 ° C to 70 ° C.

In order to carry out the SAP, the method of manufacturing the wiring board preferably further includes the step of removing palladium from the obtained wiring board.

<Manufacture of lead frame>

A metal plate such as copper, a copper alloy, or an iron-based alloy is used as a substrate, and a resist pattern is formed by a resist pattern forming method, and then a lead frame can be manufactured through the following steps. First, a step of etching a substrate exposed by development to form a conductor pattern is performed. Thereafter, a peeling step of peeling off the resist pattern by the same method as the method of manufacturing the wiring board is performed, whereby a desired lead frame can be obtained.

<Manufacture of Substrate with Concavo-Concave Pattern>

The resist pattern formed by the resist pattern forming method can be used as a protective mask member when the substrate is processed by a sand blast method. In this case, examples of the substrate include glass, tantalum wafer, amorphous tantalum, polycrystalline germanium, ceramics, sapphire, and metal materials. A resist pattern is formed on the substrates by the same method as the resist pattern forming method. Thereafter, a blasting step of blowing the blast material onto the formed resist pattern and cutting to a target depth may be performed; and a peeling step of removing the resist pattern portion remaining on the substrate from the substrate by using an alkaline stripping solution or the like A substrate having a fine concavo-convex pattern on a substrate is produced.

In the blasting step, a known blasting material can be used. For example, fine particles having a particle diameter of 2 μm to 100 μm including SiC, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO, glass, stainless steel or the like are usually used.

<Manufacture of Semiconductor Package>

A wafer in which a large-scale integrated circuit (LSI) is formed is used as a substrate, and a resist pattern is formed on the wafer by a resist pattern forming method, and then a semiconductor package can be manufactured by the following steps. First, a step of forming a conductor pattern by performing columnar plating of copper, solder, or the like on the opening exposed by development is performed. Thereafter, a peeling step of peeling off the resist pattern by the same method as the method of manufacturing the wiring board is performed, and further, a step of removing a thin metal layer other than the columnar plating layer by etching is performed. The required semiconductor package.

In the present embodiment, the photosensitive resin composition can be used for the production of a printed wiring board, an IC (Integrated Circuit) wafer mounting lead frame, a metal foil manufacturing process such as metal mask fabrication, and a ball grid array (BGA). Manufacturing of packages such as wafer size packaging (CSP); fabrication of tape substrates such as film-on-film (COF), tape-and-tape automated bonding (TAB); fabrication of semiconductor bumps; and ITO electrodes, address electrodes, and electromagnetic shielding Manufacture of partition walls of flat panel displays such as covers.

Further, the values of the respective parameters described above were measured in accordance with the measurement methods in the following examples unless otherwise specified.

[Examples]

The measurement of the physical property value of the polymer, the calculation of the glass transition temperature of the polymer, and the production method of the sample for evaluation of the examples and the comparative examples will be described. Next, the evaluation method for the obtained sample and the evaluation result thereof will be described.

(1) Determination or calculation of physical property values

<Measurement of Weight Average Molecular Weight or Number Average Molecular Weight of Polymer>

The weight average molecular weight or the number average molecular weight of the polymer is a gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580, column: Shodex manufactured by Showa Denko Co., Ltd.) (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) 4 series, flowing layer solvent: tetrahydrofuran, use The polystyrene standard sample (calibration curve of Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd.) was used in the form of polystyrene.

Further, the degree of dispersion of the polymer is calculated as a ratio of a weight average molecular weight to a number average molecular weight (weight average molecular weight / number average molecular weight).

<acid equivalent>

In the present specification, the acid equivalent means a mass (gram) of a polymer having 1 equivalent of a carboxyl group in a molecule. The acid equivalent was measured by potentiometric titration using a 0.1 mol/L sodium hydroxide aqueous solution using a Pinggna automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.

<glass transition temperature>

The glass transition temperature of the alkali-soluble polymer is a value obtained by the following formula (Fox formula).

In the formula, W _i is the mass of each of the comonomers constituting the alkali-soluble polymer, and Tg _i is the glass transition temperature when each of the comonomers constituting the alkali-soluble polymer is a homopolymer, and W _total is The total mass of the alkali-soluble polymer, and n is the number of types of comonomers constituting the alkali-soluble polymer}.

Here, when the glass transition temperature Tg _i is determined, the glass transition temperature of the homopolymer including the comonomer forming the corresponding alkali-soluble polymer is set to "Polymer" by Brandrup, J. Immergut, EH. Handbook, Third Edition, John Wiley & Sons, 1989, p. 209 Chapter VI "Glass transition temperatures of polymers". Furthermore, embodiments will be used for calculation of the respective comonomers comprising the homopolymer of Tg _i is shown in Table 1.

<(B) Weight average molecular weight of a compound having an ethylenically unsaturated bond>

In Examples I-1 to I-16 and Comparative Examples I-1 to I-3, the molecular weight was determined based on the molecular structure of the compound (B) having an ethylenically unsaturated bond. In the case where a plurality of (B) compounds having an ethylenically unsaturated bond are present, they are obtained by weight-averaging the molecular weight utilization ratio of each compound.

Further, in Examples II-1 to II-6 and Comparative Examples II-1 to II-5, the weight average molecular weight of the compound having an ethylenically unsaturated bond is a gel permeation layer manufactured by JASCO Corporation Analyzer (GPC) (pump: Gulliver, PU-1580, column: Shodex (registered trademark) (K-801, K-801, K-802, KF-802.5) manufactured by Showa Denko Co., Ltd. The fluidized bed solvent: tetrahydrofuran, which was obtained in the form of polystyrene using a calibration curve using a polystyrene standard sample (TSK standard POLYSTYRENE manufactured by Tosoh Co., Ltd.).

<(B) Concentration of methacrylinyl group in a compound having an ethylenically unsaturated bond>

It was determined by calculating the molar number of the methacryl fluorenyl group relative to (B) the compound having an ethylenically unsaturated bond of 100 g.

<B) Concentration of ethylene oxide (EO) units in compounds having ethylenic unsaturated bonds >

It was determined by calculating the number of moles of the ethylene oxide (EO) unit relative to (B) the compound having an ethylenically unsaturated bond of 100 g.

(2) Method for producing sample for evaluation

The sample for evaluation was produced as follows.

<Production of Photosensitive Resin Laminate>

The components shown in the following Tables 2 to 5 (wherein the number of each component indicates the amount (parts by mass) based on the solid content) and the solvent are sufficiently stirred and mixed to obtain a photosensitive resin composition preparation liquid. . The names of the ingredients indicated in the abbreviations in Tables 2 and 4 are shown in Tables 3 and 5 below, respectively. A 16 μm thick polyethylene terephthalate film (FB-40 manufactured by Toray Co., Ltd.) was used as a support film, and the blending solution was uniformly coated using a bar coater. The film was coated on the surface and dried in a dryer at 95 ° C for 2.5 minutes to form a photosensitive resin composition layer. The dried thickness of the photosensitive resin composition layer was 25 μm.

Then, a 19 μm thick polyethylene film (GF-818 manufactured by Tamapoly Co., Ltd.) was attached as a protective layer on the surface of the side of the uncoated polyethylene terephthalate film of the photosensitive resin composition layer. A photosensitive resin laminate was obtained.

<substrate surface>

In Examples I-1 to I-16 and Comparative Examples I-1 to I-3, as a substrate for evaluation of sensitivity, image properties, adhesion, and drug resistance, a soft etchant (Lingjiang Chemical Co., Ltd.) was used. CPE-900 manufactured) A 0.4 mm thick copper foil laminate having a laminated copper foil of 35 μm was treated, and the surface of the substrate was washed with 10% by mass of H ₂ SO ₄ .

Further, in Examples II-1 to II-6 and Comparative Examples II-1 to II-5, a grinding material (Sakurundum R (registered trademark #220) manufactured by Carlit Corporation of Japan) was used, and the laminate was rolled at 35 μm. A 0.4 mm-thick copper foil laminate of copper foil was subjected to sand blasting and polishing at a spray pressure of 0.2 MPa to prepare a substrate for evaluation.

<Lamination>

The polyethylene film of the photosensitive resin laminate was peeled off, and the surface was subjected to cleaning and trimming on a copper foil laminate which was preheated to 60 ° C, and a heat roller laminator (AL-700 manufactured by Asahi Kasei Co., Ltd.) was used. The photosensitive resin laminate was laminated at a roll temperature of 105 ° C to obtain a test piece. The air pressure system was set to 0.35 MPa, and the laminating speed was set to 1.5 m/min.

<exposure>

In Examples I-1 to I-16 and Comparative Examples I-1 to I-3, a direct drawing exposure machine (manufactured by Hitachi Via Mechanics Co., Ltd., DE-1DH, light source: GaN blue-violet diode, main The wavelength was 405 ± 5 nm), and exposure was performed under the conditions of an illuminance of 85 mW/cm ² using a Stuart 41-segment staged exposure meter or a specific direct imaging (DI) exposure mask pattern. The exposure system was performed by exposing and developing the above-mentioned Stuffer 41-segment staged exposure meter as a mask to the exposure amount of the maximum residual film segment of 15 segments.

Further, in Examples II-1 to II-6 and Comparative Examples II-1 to II-5, a chrome glass mask was used, and a parallel light exposure machine (HMW-801 manufactured by Oak Co., Ltd.) was used. The exposure amount shown in Table 4 was exposed.

<development>

In Examples I-1 to I-16 and Comparative Examples I-1 to I-3, the polyethylene terephthalate film of the exposed evaluation substrate was peeled off, and then an alkaline developing machine (manufactured by FUJI KIKO) was used. The dry film developing machine was sprayed with a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C for a specific period of time to dissolve and remove the unexposed portion of the photosensitive resin layer. At this time, development was performed twice as long as the minimum development time, and a hardened resist pattern was produced. Further, the minimum development time means the time required for the photosensitive resin layer of the unexposed portion to be completely dissolved.

Further, in the examples II-1 to II-6 and the comparative examples II-1 to II-5, the polyethylene terephthalate film was peeled off from the photosensitive resin laminate, and then manufactured by FUJI KIKO Co., Ltd. The developing device uses a full cone type nozzle to spray a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C for a specific time and develops it under a developing spray pressure of 0.15 MPa, and the photosensitive resin layer is not dried. The exposed portion is dissolved and removed. At this time, the minimum time required to completely dissolve the photosensitive resin layer in the unexposed portion was measured as the minimum development time, and development was performed at twice the minimum development time to prepare a resist pattern. At this time, the water washing step was carried out by using a flat type nozzle at the same time as the development step at a water spray pressure of 0.15 MPa.

(3) Evaluation method of samples

<sensitivity evaluation>

The substrate for the sensitivity evaluation after 15 minutes of lamination was exposed through a mask of a Stuttgart 41-segment staged exposure meter. The development was performed at twice the minimum development time, and the exposure amount of the highest residual film segment number was 15 steps, which was classified by the following criteria.

○ (good): The maximum residual film segment number becomes 15 segments and the exposure amount is less than 70 mJ/cm ² .

× (defect): The maximum residual film segment number is 15 m cells and the exposure amount is 70 mJ/cm ² or more.

<resolution>

The substrate for the resolution evaluation after 15 minutes of lamination was exposed using a drawing material having a line pattern in which the width of the exposed portion and the unexposed portion was 1:1. Development is performed at a development time twice the minimum development time to form a hardened resist line.

In Examples I-1 to I-16 and Comparative Examples I-1 to I-3, the minimum line width of the normally formed hardened resist line was set to the value of the resolution and classified by the following criteria.

○ (good): The resolution is 12 μm or less.

△ (allowed): The value of the resolution exceeds 12 μm and is 17 μm or less.

× (bad): The resolution value exceeds 17 μm.

Further, in Examples II-1 to II-6 and Comparative Examples II-1 to II-5, the minimum line width of the normally formed hardened resist line was set to the value of the resolution and classified by the following criteria.

◎ (very good): The resolution is 7.5 μm or less.

○ (good): The value of the resolution is more than 7.5 μm and is 9 μm or less.

△ (allowed): The value of the resolution exceeds 9 μm.

<FT-IR measurement>

After the polyethylene film of the photosensitive resin laminate was peeled off, FT-IR (NICOLET 380 manufactured by Thermo SCIENTIFIC) was measured.

The peak height P at a wave number of 810 cm ^-1 was determined by measuring the absorbance by FT-IR before exposure. In the case where the peak overlaps with other peaks, the rising points on both sides of the peak are connected by a line, and the highest height from the line is measured.

The reaction rate Q of the ethylenic double bond was determined by the following method. A direct drawing exposure machine is used on the polyethylene terephthalate film (support layer) side of the photosensitive resin laminate (manufactured by Hitachi Via Mechanics Co., Ltd., DE-1DH, light source: GaN blue-violet diode (main wavelength) 405 ± 5 nm)), exposure was performed. The illuminance at the time of exposure was set to 85 mW/cm ² . With respect to the exposure amount at this time, exposure was carried out by using the Stuffer 41-segment staged exposure meter as a mask by the above method, and then the maximum residual film segment number at the time of development was 15 minutes. The reaction rate Q of the ethylenic double bond of the hardened resist obtained by the above operation was calculated, and the disappearance rate (%) of the ethylenic double bond group was calculated from the peak height before and after the exposure of the wave number of 810 cm ^-1 . The reaction rate Q (%) was obtained.

R is the film thickness (μm) of the photosensitive resin layer, and P × Q / R is calculated by calculation.

<Adhesiveness>

In the examples I-1 to I-16 and the comparative examples I-1 to I-3, the substrate for the resolution evaluation after 15 minutes of lamination was used, and the width of the exposed portion and the unexposed portion was set to 1: Exposure is performed on the drawing of the line pattern of the ratio of 400. The development was performed at a development time twice the minimum development time, and the minimum line width of the normally formed hardened resist line was set to the value of the adhesion, and classification was performed by the following criteria.

○ (very good): The value of the adhesion is 12 μm or less.

○ Δ (good): The value of the adhesion is more than 12 μm and 13 μm or less.

△ (allowed): The value of the adhesion is more than 13 μm and 15 μm or less.

× (bad): The value of the adhesion is more than 15 μm.

Further, in Examples II-1 to II-6 and Comparative Examples II-1 to II-5, the substrate for evaluation which was passed for 15 minutes after lamination was passed through the width of the exposed portion and the unexposed portion to be 1:100. The chrome glass mask of the line pattern of the ratio is exposed. The development was performed at twice the minimum development time, and the minimum line width of the normally formed hardened resist line was set to the value of the adhesion, and classification was carried out in the following manner.

◎ (very good): The value of the adhesion is 7.5 μm or less.

○ (good): The value of the adhesion was more than 7.5 μm and 9 μm or less.

△ (allowed): The value of the adhesion is more than 9 μm and less than 10 μm.

× (bad): The value of the adhesion is 10 μm or more.

<Drug resistance liquidity evaluation>

100 kPa of CupraPro S2 manufactured by Atotech Japan Co., Ltd., 60 mL of 98% sulfuric acid, and 840 mL of pure water were mixed to prepare a chemical solution. The substrate for the resolution evaluation after 15 minutes of lamination was exposed using a drawing material having a line pattern having a ratio of the exposed portion to the unexposed portion at a ratio of 1:400. Development was carried out at a development time twice the minimum development time, and immersed in a beaker for 5 minutes in a chemical solution heated to 40 °C. After the immersion, it was washed with pure water, and the minimum line width of the normally formed hardened resist line was obtained as the value of the resistant liquid property. In addition, in Table 2, only the case where the value of the drug-resistant liquid property exceeds 17 μm is represented as "x (bad)".

<exudative>

The photosensitive resin laminate which was taken up in a roll shape was stored under a light-shielding condition at 23° C., and the time before the adhesion of the surface of the support film (excluding the outermost layer of the roll) due to bleeding occurred was classified as follows. Evaluation of exudation.

○ (good): The time before the adhesion of the support film surface is 1 month or longer

× (bad): the time before the adhesion of the support film surface is less than 1 month

(4) Evaluation results

The evaluation results are shown in Tables 2 to 5 below. The photosensitive resin composition designed to have a drug-resistant liquid property of 17 μm or less has excellent adhesion, resolution, and balance of the shape of the hem portion. Moreover, when such a photosensitive resin composition is used, when a wiring pattern is formed by plating, a short circuit can be suppressed. Copper plating was performed after the evaluation of the resistance liquidity, and as a result, a short circuit was observed in the portion of the line width of the hardened resist of 15 μm by the composition of Comparative Example I-1, but the composition of Example I-1 was not observed. To the short circuit, it is estimated that the defect is reduced.

Claims (24)

A photosensitive resin composition comprising: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; and (C) a photopolymerization initiator; and forming the photosensitive layer on the surface of the substrate After the resist pattern obtained by exposure and development of the photosensitive resin layer of the resin composition is treated with the chemical liquid of the drug resistance liquid evaluation, the minimum line width of the cured resist line is 17 μm or less. The photosensitive resin composition of claim 1, wherein the photosensitive resin layer is formed on the surface of the substrate, and the Stuart 41-segment staged exposure meter is used as a mask to expose the film, and then the highest level of development is performed. When the photosensitive resin layer is exposed, the peak height of the wavelength of 810 cm ^-1 before exposure is P, and it is performed in the FT-IR measurement. The reaction rate of the ethylenic double bond in the compound (B) having an ethylenically unsaturated bond after the exposure is Q, and the P×Q/R when the film thickness of the photosensitive resin layer is R is The value is 0.21 or more. The photosensitive resin composition of claim 1 or 2, wherein the weight average Tg _total of the glass transition temperature Tg of the (A) alkali-soluble polymer is 110 ° C or less. The photosensitive resin composition according to any one of claims 1 to 3, wherein the (B) compound having an ethylenically unsaturated bond has a weight average molecular weight of 760 or more. The photosensitive resin composition according to any one of claims 1 to 4, wherein the concentration of the methacrylinyl group in the compound (B) having an ethylenically unsaturated bond is 0.20 mol/100 g or more. The photosensitive resin composition according to any one of claims 1 to 5, wherein the concentration of the ethylene oxide unit in the compound (B) having an ethylenically unsaturated bond is 0.80. Mol / 100g or more. The photosensitive resin composition according to any one of claims 1 to 6, which comprises a hexaarylbisimidazole compound as the above (C) photopolymerization initiator. A photosensitive resin composition comprising: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; and (C) a photopolymerization initiator; and (A) an alkali-soluble polymer weight average glass transition temperature Tg of the Tg or less _Total 110 ℃, and comprises a three or more ethylenic unsaturated bonds of the (meth) acrylate compound as a compound having an ethylenically unsaturated bond having the above-mentioned (B). The photosensitive resin composition of claim 8, which comprises a (meth) acrylate compound having 5 or more ethylenically unsaturated bonds and having an alkylene oxide chain as the above (B) compound having an ethylenically unsaturated bond . The photosensitive resin composition according to claim 8 or 9, wherein the (A) alkali-soluble polymer has an acid equivalent weight of from 100 to 600 and a weight average molecular weight of from 5,000 to 500,000, and has an aromatic group in a side chain thereof. The photosensitive resin composition according to any one of claims 8 to 10, which comprises a (meth) acrylate compound having 5 or more ethylenically unsaturated bonds and having an ethylene oxide chain as (B) A compound of ethylenically unsaturated bonds. The photosensitive resin composition according to any one of claims 8 to 11, which comprises a (meth) acrylate compound having an ethylene oxide chain and a dipentaerythritol skeleton as the above (B) compound having an ethylenically unsaturated bond . The photosensitive resin composition according to any one of claims 8 to 12, further comprising a compound represented by the following formula (II) as the compound (B) having an ethylenically unsaturated bond, In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , and n ₁ and n ₃ are each independently an integer from 1 to 39, and n ₁ + n ₃ is an integer of 2 to 40, n ₂ and n ₄ are each independently an integer of 0 to 29, and n ₂ + n ₄ is an integer of 0 to 30, and repeating units of -(AO)- and -(BO)- The arrangement may be random or block, and in the case of a block, -(AO)- and -(BO)- may also be a biphenyl side}. The photosensitive resin composition according to any one of claims 8 to 13, further comprising a compound represented by the following formula (I) as the compound (B) having an ethylenically unsaturated bond, In the formula, R ₃ to R ₆ each independently represent an alkyl group having 1 to 4 carbon atoms, X represents an alkylene group having 2 to 6 carbon atoms, and m ₁ , m ₂ , m ₃ and m ₄ are independently 0 to 40, respectively. The integer, m ₁ + m ₂ + m ₃ + m ₄ is 1 to 40, and when m ₁ + m ₂ + m ₃ + m ₄ is 2 or more, the plurality of Xs may be the same or different from each other}. The photosensitive resin composition according to any one of claims 8 to 14, which comprises a hexaarylbisimidazole compound as the above (C) photopolymerization initiator. The photosensitive resin composition according to any one of claims 8 to 15, which comprises a pyrazoline compound as the above (C) photopolymerization initiator. The photosensitive resin composition according to any one of claims 8 to 16, which is for direct imagewise exposure. The photosensitive resin composition of claim 8, wherein the weight average Tg _total of the glass transition temperature Tg of the (A) alkali-soluble polymer is 105 ° C or less, and the total solid content of the photosensitive resin composition is (b1) a compound having at least 3 methacryl fluorenyl groups as the above (B) compound having an ethylenically unsaturated bond, and the above (B) having ethylene, in an amount of more than 0% by mass and not more than 16% by mass 70% by mass or more of the compound of the unsaturated bond is a compound having a weight average molecular weight of 500 or more. The photosensitive resin composition of claim 18, wherein the compound (b1) having at least 3 methacryl fluorenyl groups has a weight average molecular weight of 500 or more. The photosensitive resin composition of claim 18 or 19, which comprises (b2) a compound having a butylene oxide chain and one or two (meth) acrylonitrile groups as the above (B) having an ethylenically unsaturated bond Compound. The photosensitive resin composition of claim 20, wherein the compound (b2) having a butylene oxide chain and one or two (meth)acryl fluorenyl groups has a weight average molecular weight of 500 or more. The photosensitive resin composition according to any one of claims 18 to 21, which is a semi-additive method Used by (SAP). A method of forming a resist pattern, comprising the steps of: laminating a layer of a photosensitive resin comprising the photosensitive resin composition according to any one of claims 1 to 22 on a support; and an exposing step Exposing the photosensitive resin layer; and developing a step of developing the exposed photosensitive resin layer. A method of producing a wiring board, comprising the steps of: laminating a layer of a photosensitive resin comprising the photosensitive resin composition according to any one of claims 1 to 22 on a substrate; and an exposing step of The photosensitive resin layer is exposed; a developing step of developing the exposed photosensitive resin layer to obtain a substrate on which a resist pattern is formed; and a conductor pattern forming step of etching the substrate on which the resist pattern is formed Or plating; and a stripping step of stripping the resist pattern.