JP2010078820A - Method for producing photosensitive film, photosensitive film, photosensitive laminate, permanent pattern forming method and printed circuit board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive film which, when applied to a substrate, ensures a uniform film thickness, hardly causes surface defects such as pinholes and cissing, excels in adhesion to the substrate such as a substrate for printed wiring formation, and can efficiently form a high-definition permanent pattern, and to provide a method for producing such a photosensitive film, a photosensitive laminate, a permanent pattern forming method and a printed circuit board. <P>SOLUTION: The method for producing a photosensitive film includes: a coating liquid preparation step of preparing a coating liquid containing a photosensitive resin composition comprising (i) a compound into which a photosensitive group and an acid radical for imparting alkali developability have been introduced, (ii) a polymerizable compound and (iii) a photopolymerization initiator; a defoaming step of subjecting the coating liquid to defoaming treatment; an application step of applying the coating liquid to a support after the defoaming step; and a drying step of drying the coating liquid to form a photosensitive layer on the support. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is a photosensitive resin composition and a photosensitive film that have high sensitivity, high resolution, good sensitivity over time, film curability, and thermal shock resistance, and can efficiently form a high-definition permanent pattern. The present invention relates to a photosensitive laminate, a permanent pattern forming method, and a printed board.

  Along with the downsizing and multi-functionalization of electronic devices, printed wiring boards are now in the direction of higher density. For example, conductor circuits can be thinned, multi-layered, blind holes, through holes including interstitial via holes such as burred holes, and high-density mounting by surface mounting of small chip components.

  Conventional solder resists for printed wiring boards include, for example, heat-resistant thermosetting resins such as epoxy resins and epoxy melamine resins, thermosetting catalysts such as amines, imidazoles, and acid anhydrides, and organic solvents such as butyl cellosolve and butyl carbitol. A thermosetting solder resist prepared by blending a polymerizable monomer such as acrylic acid ester or methacrylic acid ester with a crosslinkable polymer such as epoxy acrylate or urethane acrylate, and a photosensitizer such as benzoin ethyl ether or benzophenone. And UV curing type solder resists; dual cure type solder resists in which the above-mentioned thermosetting type solder resist and each component contained in the UV type solder resist are combined.

As a method for forming a solder resist, for example, a photosensitive layer made of a photosensitive resin composition is formed on a substrate such as a copper clad laminate on which the solder resist is formed, and the photosensitive layer is exposed, Examples of the method include developing the photosensitive layer after the exposure to form a solder resist having a predetermined pattern.
As a method for forming a photosensitive layer on a substrate, a liquid type photosensitive resin composition is formed on a substrate by a screen coater, a dip coater, a bar coater or the like. Alternatively, a photosensitive resin composition is sandwiched with a polyester film or a protective film made of polyethylene to form a dry film having a three-layer structure, and this is laminated on a substrate with a roll laminator or a vacuum laminator to form a photosensitive layer, etc. Is mentioned.

  In recent years, since the density has been increased and the wiring density has been increased, the solder resist surface is required to be flattened when mounting components. The dry film type solder resist can be pressure-molded with a vacuum laminator or the like, and has a small volume shrinkage due to solvent volatilization. Therefore, the dry film type solder resist is advantageous for planarization as compared with a liquid type solder resist, and is eagerly desired. However, in the case of a dry film type solder resist, when a planar defect such as a pinhole or a repellency occurs in the film manufacturing process, it is difficult to repair this defect in the process after lamination on the substrate. In the state where planar defects such as pinholes and repellants remain in the cured film (solder resist), the insulation reliability of the printed wiring board will decrease, so how to produce a dry film with few planar defects It was an issue.

Here, Patent Document 1 proposes that a resist composition contains a surfactant in order to form a photosensitive layer having a uniform thickness.
However, the resist composition described in Patent Document 1 is intended to be applied to a substrate as a liquid type and is not intended to be used as a dry film. Further, when a surfactant is contained in the resist composition, there is a problem that the adhesion between the photosensitive layer and the substrate is deteriorated.

Japanese Examined Patent Publication No. 7-21626

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention has a uniform film thickness when applied to a substrate, is less likely to cause surface defects such as pinholes and repellency, and has excellent adhesion to a substrate such as a printed wiring board, and has high definition. It aims at providing the photosensitive film which can form a permanent pattern efficiently, the manufacturing method of a photosensitive film, the photosensitive laminated body, the permanent pattern formation method, and a printed circuit board.

Means for solving the above problems are as follows. That is,
<1> i) A coating solution containing a photosensitive resin composition containing a photosensitive group and an acid group for imparting alkali developability, ii) a polymerizable compound, and iii) a photopolymerization initiator. A coating solution preparation step,
A defoaming step of defoaming the coating solution;
After the defoaming step, an application step of applying the coating liquid to a support;
A drying step of drying the coating solution to form a photosensitive layer on the support;
It is a manufacturing method of the photosensitive film characterized by including.
<2> The method for producing a photosensitive film according to <1>, wherein the defoaming treatment is ultrasonic defoaming.
<3> The method for producing a photosensitive film according to any one of <1> to <2>, wherein the photosensitive resin composition further includes iv) a thermal crosslinking agent.
<4> The method for producing a photosensitive film according to any one of <1> to <3>, wherein the photosensitive resin composition further includes v) a filler.
<5> The method for producing a photosensitive film according to any one of <1> to <4>, wherein the viscosity of the coating solution is from 5 mPa · s to 100 mPa · s.
<6> The method for producing a photosensitive film according to <5>, wherein the coating solution has a viscosity of 10 mPa · s to 50 mPa · s.
<7> A photosensitive film produced by the production method according to any one of <1> to <6>, wherein the photosensitive film has a long shape and is wound in a roll shape. It is a film.
<8> A photosensitive laminate comprising a substrate and a photosensitive layer provided on the substrate,
The photosensitive layer is a photosensitive laminate that is transferred from a photosensitive film produced by the production method according to any one of <1> to <6>.
<9> A method for forming a permanent pattern, comprising at least an exposure step of exposing the photosensitive layer in the photosensitive laminate according to <8>.
<10> A printed circuit board comprising a permanent pattern formed by the method for forming a permanent pattern according to <9>.

  According to the present invention, the conventional problems can be solved, the object can be achieved, the film thickness when applied to the substrate is uniform, and surface defects such as pinholes and repellency are unlikely to occur. Photosensitive film having excellent adhesion to a substrate such as a printed wiring board and capable of efficiently forming a high-definition permanent pattern, a method for producing a photosensitive film, a photosensitive laminate, a permanent pattern forming method, and a printed board Can be provided.

(Method for producing photosensitive film)
The method for producing a photosensitive film of the present invention includes at least a coating liquid preparation step, a defoaming step, a coating step, and a drying step, and further includes other steps that are appropriately selected as necessary.

<Coating solution preparation process>
The coating solution preparation step is a step of preparing a coating solution containing a photosensitive resin composition described later.
A method for preparing the coating solution is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a method of dissolving, emulsifying or dispersing the photosensitive resin composition in a solvent such as water or an organic solvent. Is mentioned. Moreover, you may add a well-known surfactant.
There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably.
Ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene Glycol ethers such as glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, and acetic acid esterified products of the above glycol ethers; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; petroleum ether, petroleum naphtha, Examples thereof include, but are not limited to, petroleum solvents such as hydrogenated petroleum safsa and solvent naphtha.
There is no restriction | limiting in particular as a viscosity of the said coating liquid, Although it can select suitably according to the objective, For example, 5 mPa * s to 100 mPa * s is preferable and 10 mPa * s to 50 mPa * s is more preferable.

-Photosensitive resin composition-
The photosensitive resin composition has at least i) a compound (binder) into which an acid group for imparting a photosensitive group and alkali developability is introduced, ii) a polymerizable compound, and iii) a photopolymerization initiator. Further, it contains other components such as iv) a thermal crosslinking agent and v) a filler as necessary.

--Binder--
The binder is not particularly limited as long as it is a compound into which a photosensitive group and an acid group for imparting alkali developability are introduced, and can be appropriately selected according to the purpose. For example, two or more epoxy A polymer obtained by reacting an epoxy resin having a group with unsaturated (meth) acrylic acid and further reacting with a polybasic acid anhydride; containing a (meth) acrylic acid ester and an unsaturated group, and at least Modified copolymer obtained by adding glycidyl (meth) acrylate to some acid groups of a copolymer obtained from a compound having one acid group; carboxyl group-containing (meth) acrylic copolymer resin and fat Examples thereof include a polymer obtained by a reaction with a cyclic epoxy group-containing unsaturated compound.

  Among these, when the photosensitive resin composition is formed into a dry film to form a photosensitive layer, the tackiness is low, and therefore it contains a (meth) acrylic acid ester and an unsaturated group and has at least one acid group. A modified copolymer obtained by adding glycidyl (meth) acrylate to some acid groups of a copolymer obtained from the compound is preferable.

  5-80 mass% is preferable and, as for solid content in the said photosensitive resin composition solid content of the said binder, 30-60 mass% is more preferable. If the solid content is 5% by mass or more, developability and exposure sensitivity are good, and if it is 80% by mass or less, it is possible to prevent the adhesiveness of the photosensitive layer from becoming too strong.

--Polymerizable compound--
There is no restriction | limiting in particular as said polymeric compound, Although it can select suitably according to the objective, For example, the compound which has one or more ethylenically unsaturated bonds is preferable.

  Examples of the ethylenically unsaturated bond include (meth) acryloyl group, (meth) acrylamide group, styryl group, vinyl group such as vinyl ester and vinyl ether, allyl group such as allyl ether and allyl ester, and the like.

  The compound having one or more ethylenically unsaturated bonds is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least one selected from monomers having a (meth) acryl group is Preferably mentioned.

  There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) ) Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin Poly (functional) alcohols such as tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, etc., which are subjected to addition reaction with ethylene oxide and propylene oxide, and converted to (meth) acrylate, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50- Urethane acrylates described in JP-A-6034, JP-A-51-37193, etc .; JP-A-48-64183, JP-B-49-43191, JP-B-52-30 Polyester acrylates described in each publication of such 90 No.; and epoxy resin and (meth) polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

  5-50 mass% is preferable and, as for solid content in the said photosensitive resin composition solid content of the said polymeric compound, 10-40 mass% is more preferable. When the solid content is 5% by mass or more, developability and exposure sensitivity are good, and when the solid content is 50% by mass or less, the adhesiveness of the photosensitive layer can be prevented from becoming too strong.

-Photopolymerization initiator-
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected according to the purpose. Those having photosensitivity are preferable, and may be an activator that generates an active radical by causing some action with a photoexcited sensitizer, and is an initiator that initiates cationic polymerization according to the type of monomer. May be.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a wavelength range of about 300 to 800 nm. The wavelength is more preferably 330 to 500 nm.

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, Examples include ketone compounds, aromatic onium salts, and metallocenes. Among these, halogenated hydrocarbons having a triazine skeleton, oxime derivatives, ketone compounds, hexaarylbiimidazoles from the viewpoints of sensitivity and storage stability of the photosensitive layer, and adhesion between the photosensitive layer and the printed wiring board forming substrate. System compounds are preferred.

  Examples of the hexaarylbiimidazole include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-fluorophenyl)- 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis ( 2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (3-methoxyphenyl) ) Biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (4-methoxyphenyl) biimidazole, 2,2′-bis (4-methoxyphenyl) -4 , 4 ', , 5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-trifluoromethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, compounds described in WO00 / 52529, and the like.

  The biimidazoles are described in, for example, Bull. Chem. Soc. Japan, 33, 565 (1960); Org. It can be easily synthesized by the method disclosed in Chem, 36 (16) 2262 (1971).

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

  Wakabayashi et al., Bull. Chem. Soc. As a compound described in Japan, 42, 2924 (1969), for example, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- (4-tolyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl)- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2, 4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-n-nonyl-4,6- Bis (trichloromethyl) 1,3,5-triazine, and 2-(alpha, alpha, beta-trichloroethyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  Examples of the compound described in the British Patent 1388492 include 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4,6- Bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl)- 4-amino-6-trichloromethyl-1,3,5-triazine and the like can be mentioned.

  Examples of the compounds described in JP-A-53-133428 include 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 -(4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl]- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5- Examples include triazine and 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  Examples of the compound described in the specification of German Patent 3333724 include 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4 -Methoxystyryl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (1-naphthylvinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-thiophen-2-vinylenephenyl) -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (4-thiophene-3-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-furan-2 Vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (4-benzofuran-2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3 5-triazine etc. are mentioned.

  F. above. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964) include, for example, 2-methyl-4,6-bis (tribromomethyl) -1,3,5-triazine, 2,4,6-tris (tribromomethyl); -1,3,5-triazine, 2,4,6-tris (dibromomethyl) -1,3,5-triazine, 2-amino-4-methyl-6-tri (bromomethyl) -1,3,5- Examples include triazine and 2-methoxy-4-methyl-6-trichloromethyl-1,3,5-triazine.

  Examples of the compounds described in JP-A-62-258241 include 2- (4-phenylethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- Naphthyl-1-ethynylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-tolylethynyl) phenyl) -4,6-bis (trichloromethyl) -1 , 3,5-triazine, 2- (4- (4-methoxyphenyl) ethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-isopropylphenyl) Ethynyl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-ethylphenylethynyl) phenyl) -4,6-bis (trichloromethyl) Le) -1,3,5-triazine.

  Examples of the compound described in JP-A-5-281728 include 2- (4-trifluoromethylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2, 6-difluorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,6-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5- Examples include triazine, 2- (2,6-dibromophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  Examples of the compound described in JP-A-5-34920 include 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -1, 3,5-triazine, trihalomethyl-s-triazine compounds described in US Pat. No. 4,239,850, 2,4,6-tris (trichloromethyl) -s-triazine, 2- (4-chlorophenyl) Examples include -4,6-bis (tribromomethyl) -s-triazine.

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromomethyl-5-styryl-1,3,4 Oxadiazole and the like).

  As an oxime derivative used suitably by this invention, it represents with following General formula (1), for example.

However, in the general formula (1), R ¹ represents any ^one of a hydrogen atom, an optionally substituted acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, and an arylsulfonyl group. , R ² each independently represents a substituent. m represents an integer of 0 to 4, and in the case of 2 or more, they may be connected to each other to form a ring. A represents any of 4, 5, 6, and 7-membered rings. A is preferably either a 5- or 6-membered ring.

  Moreover, as an oxime derivative (oxime compound) used by this invention, what is represented by following General formula (2) is more preferable.

However, in the general formula (2), R ¹ represents any of a hydrogen atom, an optionally substituted acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, and an arylsulfonyl group. , R ² each independently represents a substituent. m represents an integer of 0 to 4, and in the case of 2 or more, they may be connected to each other to form a ring. X represents any of CH ₂ , O, and S. A represents either a 5- or 6-membered ring.

In the general formulas (1) and (2), the acyl group represented by R ¹ may be any of aliphatic, aromatic, and heterocyclic, and may further have a substituent.
Examples of the aliphatic group include an acetyl group, a propanoyl group, a butanoyl group, a hexanoyl group, a decanoyl group, a phenoxyacetyl group, and a chloroacetyl group. Examples of the aromatic group include a benzoyl group, a naphthoyl group, a methoxybenzoyl group, and a nitrobenzoyl group. Examples of the heterocyclic group include a furanoyl group and a thiophenoyl group.
As the substituent, any of an alkoxy group, an aryloxy group, and a halogen atom is preferable. As the acyl group, those having 2 to 30 carbon atoms are preferable, those having 2 to 20 carbon atoms are more preferable, and those having 2 to 16 carbon atoms are particularly preferable. Examples of the acyl group include acetyl group, propanoyl group, methylpropanoyl group, butanoyl group, pivaloyl group, hexanoyl group, cyclohexanecarbonyl group, octanoyl group, decanoyl group, dodecanoyl group, octadecanoyl group, benzylcarbonyl Group, phenoxyacetyl group, 2-ethylhexanoyl group, chloroacetyl group, benzoyl group, paramethoxybenzoyl group, 2,5-dibutoxybenzoyl group, 1-naphthoyl group, 2-naphthoyl group, pyridylcarbonyl group, methacryloyl group , An acryloyl group, and the like.

  The alkyloxycarbonyl group may have a substituent and is preferably an alkoxycarbonyl group having 2 to 30 carbon atoms in total, more preferably having 2 to 20 carbon atoms in total, and 2 to 16 carbon atoms in total. Those are particularly preferred. Examples of such alkoxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonylbutoxycarbonyl group, isobutyloxycarbonyl group, allyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, ethoxyethoxycarbonyl group. .

  The aryloxycarbonyl group may have a substituent and is preferably an alkoxycarbonyl group having a total carbon number of 7 to 30, more preferably a total carbon number of 7 to 20, and a total carbon number of 7 to 16. Is particularly preferred. Examples of such aryloxycarbonyl groups include phenoxycarbonyl group, 2-naphthoxycarbonyl group, paramethoxyphenoxycarbonyl group, 2,5-diethoxyphenoxycarbonyl group, parachlorophenoxycarbonyl group, paranitrophenoxycarbonyl group. And paracyanophenoxycarbonyl group.

  The alkylsulfonyl group may further have a substituent. Examples of the substituent include a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a carbamoyl group, a cyano group, a carboxylic acid group, a sulfonic acid group, and a heterocyclic group. Preferably mentioned. Particularly preferred examples of the alkylsulfonyl group include a methylsulfonyl group, a butylsulfonyl group, an octylsulfonyl group, a decylsulfonyl group, a dodecylsulfonyl group, a benzylsulfonyl group, and a trifluoromethylsulfonyl group.

  The arylsulfonyl group may further have a substituent. Examples of the substituent include a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a carbamoyl group, a cyano group, a carboxylic acid group, a sulfonic acid group, and a heterocyclic group. Preferably mentioned. Particularly preferred examples of the arylsulfonyl group include a benzenesulfonyl group, a toluenesulfonyl group, a chlorobenzenesulfonyl group, a butoxybenzenesulfonyl group, a 2,5-dibutoxybenzenesulfonyl group, a paranitrobenzenesulfonyl group, and a perfluorobenzenesulfonyl group.

In the general formulas (1) and (2), examples of the substituent represented by R ² include aliphatic, aromatic, heteroaromatic, halogen atom, —OR ³ , —SR ³ , —NR ³ R ⁴ . Can be mentioned. R ³ and R ⁴ may be linked to each other to form a ring. R ³ and R ⁴ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heteroaromatic group. When m is 2 or more and are connected to each other to form a ring, each R ² may form a ring, and a ring may be formed via at least one of R ³ and R ^4. Also good.

In the case where a ring is formed via the substituent R ² , the following structures are exemplified.

In the structural formula, Y and Z represent any one of CH ₂ , —O—, —S—, and —NR—.

Specific examples of the aliphatic group, aromatic group, and heteroaromatic group of R ² , R ³ , and R ⁴ include the same groups as those described above for R ¹ .

  Specific examples of the oxime compound represented by the general formula (1) include compounds represented by the following structural formulas (1) to (51), but the present invention is not limited thereto. .

In addition, the oxime compound used by this invention can be identified by measuring a < ¹ > H-NMR spectrum and a UV-vis absorption spectrum.

--- Method for producing oxime compound ---
As a method for producing the oxime compound, the corresponding oxime compound and acyl chloride or anhydride in the presence of a base (for example, triethylamine, pyridine) in an inert solvent such as THF, DMF, acetonitrile, It can be easily synthesized by reacting in such a basic solvent. As said reaction temperature, -10-60 degreeC is preferable.
Further, by using chloroformate, alkylsulfonyl chloride, and arylsulfonyl chloride as the acyl chloride, various corresponding oxime ester compounds can be synthesized.

  As a method for synthesizing the oxime compound used as a starting material in the production of the oxime compound, standard chemistry textbooks (for example, J. March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992), or a professional monograph For example, S. R. Sandler & W. Karo, Organic functional group preparations, Vol. 3, can be obtained by various methods described in Academic Press.

  As a particularly preferable synthesis method of the oxime compound, for example, a method of reacting an aldehyde or ketone with hydroxylamine or a salt thereof in a polar solvent such as ethanol or ethanol water can be mentioned. In this case, a base such as sodium acetate or pyridine is added to control the pH of the reaction mixture. It is well known that the reaction rate is pH dependent and the base can be added at the start or continuously during the reaction. A basic solvent such as pyridine can also be used as the base and / or solvent or cosolvent. The reaction temperature is generally preferably the reflux temperature of the mixture, that is, about 60 to 120 ° C.

Another different preferred method of synthesis of the oxime compound is by nitrosation of an “active” methylene group with nitrous acid or alkyl nitrite. See, for example, Organic Synthesis coll. Vol. VI (J. Wiley & Sons, New York, 1988), pp. 199 and 840 and alkaline conditions such as those described in Organic Synthesis coll. Vol. V, pp. 32 and 373, coll. Vol. III, pp. 191 and 513, coll. Vol. II, pp. Both acidic conditions as described in 202, 204 and 363 are suitable for the synthesis of oxime compounds used as starting materials in the present invention.
The nitrous acid is usually produced from sodium nitrite.
Examples of the alkyl nitrite include methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, and isoamyl nitrite.

  The oxime ester group may exist in two types of configuration (Z) or (E). The isomers may be separated by conventional methods, or the isomer mixture may be used as it is as a photoinitiating seed. Therefore, the oxime compound of the present invention may be a mixture of isomers on the configuration of the compounds of the structural formulas (1) to (51).

  The oxime compound has excellent storage stability and high sensitivity, and when added to the polymerizable composition, it has excellent storage stability without causing polymerization during storage, and is active when irradiated with energy rays, particularly light. It is possible to obtain a highly sensitive polymerizable composition capable of efficiently generating polymerization by generating radicals and capable of polymerizing the polymerizable compound efficiently in a short time.

  Further, as photopolymerization initiators other than the above, acridine derivatives (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine, and the like, polyhalogen compounds (for example, Carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-n-propoxycoumarin), 3,3′-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206 No., JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, etc.), amines (for example, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate) N-butyl acid, 4-dimethylaminobenzoic acid phenethyl, 4-dimethyl 2-phthalimidoethyl tilaminobenzoate, 2-methacryloyloxyethyl 4-dimethylaminobenzoate, pentamethylenebis (4-dimethylaminobenzoate), phenethyl of 3-dimethylaminobenzoic acid, pentamethylene ester, 4-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-dimethylaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine, N, N-diethyl-3-phenetidine, tribenzylamine, dibenzylphenylamine, N-methyl-N-phenylbenzylamine, 4-bromo-N, N-dimethylaniline, tridodecylamine, amino Nofluoranes (ODB, ODBII, etc.), crystal violet lactone, leuco crystal violet, etc., acylphosphine oxides (for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) ) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.).

  Further, vicinal polyketaldonyl compounds described in US Pat. No. 2,367,660, acyloin ether compounds described in US Pat. No. 2,448,828, and US Pat. No. 2,722,512 are described. An aromatic acyloin compound substituted with α-hydrocarbon, a polynuclear quinone compound described in US Pat. Nos. 3,046,127 and 2,951,758, an organoboron compound described in JP-A-2002-229194, and a radical Generator, triarylsulfonium salt (for example, salt with hexafluoroantimony or hexafluorophosphate), phosphonium salt compound (for example, (phenylthiophenyl) diphenylsulfonium salt, etc.) (effective as a cationic polymerization initiator), WO01 / 71428 Onium Such compounds.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together. Examples of the combination of two or more include, for example, a combination of hexaarylbiimidazole and 4-aminoketone described in US Pat. No. 3,549,367, a benzothiazole compound described in Japanese Patent Publication No. 51-48516, and trihalomethyl- Combinations of s-triazine compounds, combinations of aromatic ketone compounds (such as thioxanthone) and hydrogen donors (such as dialkylamino-containing compounds and phenol compounds), combinations of hexaarylbiimidazole and titanocene, and coumarins And combinations of titanocene and phenylglycines.
Particularly preferred examples of the photopolymerization initiator include halogenated carbonization having the phosphine oxides, the α-aminoalkyl ketones, and the triazine skeleton capable of supporting laser light having a wavelength of 405 nm in the exposure described later. Examples include a composite photoinitiator, a hexaarylbiimidazole compound, or titanocene, which is a combination of a hydrogen compound and an amine compound as a sensitizer described later.

  The content of the photopolymerization initiator in the photosensitive resin composition is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 0.5 to 15% by mass.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, thermal crosslinking agents, fillers, thermosetting accelerators, sensitizers, thermal polymerization inhibitors, plasticizers, and colorants. (Color pigments or dyes) and the like, and further adhesion promoters to the substrate surface and other auxiliary agents (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, Antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) may be used in combination.
By appropriately containing these components, properties such as the stability, photographic properties, and film properties of the intended photosensitive film can be adjusted.

--- Thermal crosslinking agent ---
The thermal crosslinking agent is not particularly limited and can be appropriately selected depending on the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the photosensitive film, it can be developed and the like. For example, a compound containing an epoxy compound (for example, an epoxy compound having at least two oxirane groups in one molecule) or an oxetane compound having at least two oxetanyl groups in one molecule may be used within a range that does not adversely influence. An epoxy compound having an oxirane group, an epoxy compound having an alkyl group at the β-position, an oxetane compound having an oxetanyl group, a polyisocyanate compound, a polyisocyanate and derivatives thereof as described in JP-A-2007-47729 Examples include compounds obtained by reacting isocyanate groups with blocking agents It is.

  Moreover, a melamine derivative can be used as the thermal crosslinking agent. Examples of the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, or the like). These may be used individually by 1 type and may use 2 or more types together. Among these, alkylated methylol melamine is preferable and hexamethylated methylol melamine is particularly preferable in that it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

  1 mass%-50 mass% are preferable, and, as for solid content in the said photosensitive resin composition solid content of the said thermal crosslinking agent, 3 mass%-30 mass% are more preferable. When the solid content is 1% by mass or more, the film strength of the cured film is improved, and when it is 50% by mass or less, the developability and the exposure sensitivity are improved.

  Examples of the epoxy compound include an epoxy compound having at least two oxirane groups in one molecule and an epoxy compound having at least two epoxy groups having an alkyl group at the β-position in one molecule.

  Examples of the epoxy compound having at least two oxirane groups in one molecule include, for example, a bixylenol type or biphenol type epoxy resin (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, a complex having an isocyanurate skeleton, etc. Cyclic epoxy resin (“TEPIC; manufactured by Nissan Chemical Industries, Ltd.”, “Araldite PT810; manufactured by Ciba Specialty Chemicals”, etc.), bisphenol A type epoxy resin, novolak type epoxy resin, bisphenol F type epoxy resin, water Bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin) Brominated phenol novolac type epoxy resin, etc.), allyl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP-7200"). , HP-7200H; manufactured by Dainippon Ink and Chemicals, Inc.), glycidylamine type epoxy resin (diaminodiphenylmethane type epoxy resin, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resin (phthalic acid) Diglycidyl ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) Hydantoin type epoxy resin, alicyclic epoxy resin ( , 4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “GT-300, GT-400, ZEHPE3150; Daicel Chemical Industries , Imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene Group-containing epoxy resin (naphthol aralkyl type epoxy resin, naphthol novolac type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercially available products such as “ESN-190, ESN-360; Gaku Co., Ltd. "," HP-4032, EXA-4750, EXA-4700; Dainippon Ink and Chemicals Co., Ltd. "), phenol compounds and diolefin compounds such as divinylbenzene and dicyclopentadiene Reaction product of polyphenol compound obtained by reaction and epichlorohydrin, ring-opening polymer of 4-vinylcyclohexene-1-oxide epoxidized with peracetic acid, epoxy resin having linear phosphorus-containing structure, cyclic phosphorus-containing Epoxy resin having structure, α-methylstilbene type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal epoxy resin, azophenyl type liquid crystal epoxy resin, azomethine phenyl type liquid crystal epoxy resin, binaphthyl type liquid crystal epoxy resin, azine type epoxy resin, glycidyl meta Acrylate copolymer epoxy Si resin (“CP-50S, CP-50M; manufactured by NOF Corporation”, etc.), copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis (glycidyloxy) Phenyl) adamantane type epoxy resin and the like can be mentioned, but not limited thereto. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

In addition to the epoxy compound having at least two oxirane groups in one molecule, an epoxy compound containing at least two epoxy groups having an alkyl group at the β-position can be used, and the β-position is an alkyl group. Particularly preferred is a compound containing an epoxy group substituted with a (specifically, a β-alkyl-substituted glycidyl group or the like).
In the epoxy compound containing at least an epoxy group having an alkyl group at the β-position, all of two or more epoxy groups contained in one molecule may be a β-alkyl-substituted glycidyl group, and at least one epoxy group May be a β-alkyl-substituted glycidyl group.

Examples of the oxetane compound include oxetane compounds having at least two oxetanyl groups in one molecule.
Specifically, for example, bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl- 3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers or copolymers thereof, compounds having an oxetane group; Novolac resin, poly (p-hydroxystyrene), cardo type bisphenol , Calixarenes, calixresorcinarenes, and ether compounds such as silsesquioxane and other hydroxyl group-containing resins. In addition to these, an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate A polymer etc. are also mentioned.

  Moreover, as the polyisocyanate compound, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is an aliphatic, cycloaliphatic or aromatic group containing at least two isocyanate groups. It may be derived from a group-substituted aliphatic compound. Specifically, bifunctional isocyanate (for example, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene). Diisocyanate, bis (4-isocyanate-phenyl) methane, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc.), the bifunctional isocyanate, trimethylolpropane, pentalithol tol Polyfunctional alcohols such as glycerin; alkylene oxide adducts of the polyfunctional alcohols and adducts of the bifunctional isocyanates; hexamethylene diisocyanate, hexamethylene-1,6-di Isocyanate and cyclic trimers thereof derivatives; and the like.

  As an isocyanate group blocking agent in a compound obtained by reacting a blocking agent with the polyisocyanate compound, that is, a compound obtained by reacting a blocking agent with an isocyanate group of polyisocyanate and derivatives thereof, alcohols (for example, isopropanol, tert-butanol etc.), lactams (eg ε-caprolactam etc.), phenols (eg phenol, cresol, p-tert-butylphenol, p-sec-butylphenol, p-sec-amylphenol, p-octylphenol, p -Nonylphenol, etc.), heterocyclic hydroxyl compounds (eg, 3-hydroxypyridine, 8-hydroxyquinoline, etc.), active methylene compounds (eg, dialkyl malonate, methyl ethyl ketoxy) , Acetylacetone, alkyl acetoacetate oxime, acetoxime, cyclohexanone oxime, etc.) and the like. In addition to these, compounds having at least one polymerizable double bond and at least one blocked isocyanate group in the molecule described in JP-A-6-295060 can be used.

  Examples of the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, or the like). These may be used individually by 1 type and may use 2 or more types together. Among these, alkylated methylol melamine is preferable and hexamethylated methylol melamine is particularly preferable in that it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

--- Filler ---
In the photosensitive resin composition, if necessary, for the purpose of improving the surface hardness of the permanent pattern, or keeping the coefficient of linear expansion low, or keeping the dielectric constant and dielectric loss tangent of the cured film itself low. An inorganic filler or an organic filler (organic fine particles) can be added. The inorganic filler is not particularly limited and may be appropriately selected from known ones. For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, vapor phase method silica, amorphous Examples thereof include silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica. Among these, silica is preferable from the viewpoint of thermal shock resistance. The average particle size of the inorganic filler is preferably less than 10 μm, and more preferably 3 μm or less. When the average particle diameter is less than 10 μm, it is possible to prevent the resolution from being deteriorated by light scattering.
There is no restriction | limiting in particular as said organic filler, According to the objective, it can select suitably, For example, a melamine resin, a benzoguanamine resin, a crosslinked polystyrene resin etc. are mentioned. Further, silica having an average particle diameter of 1 to 5 μm and an oil absorption of about 100 to 200 m ² / g, spherical porous fine particles made of a crosslinked resin, and the like can be used.

  The amount of the filler added is preferably 5 to 60% by mass. If the addition amount is 5% by mass or more, the linear expansion coefficient can be sufficiently reduced, and if it is 60% by mass or less, the film quality of the cured film can be improved when a cured film is formed on the surface of the photosensitive layer. When the wiring is formed using a permanent pattern, it is possible to prevent the function of the wiring as a protective film from being impaired.

--- Thermosetting accelerator ---
In order to accelerate the thermal curing of the epoxy compound or the oxetane compound as the thermal crosslinking agent, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N- Dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, , Dimethylamine, etc.), imidazole derivative bicyclic amidine compounds and salts thereof (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, -Cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (eg triphenylphosphine etc.), guanamine compounds (eg melamine, guanamine, acetoguanamine, Benzoguanamine etc.), S-triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino -S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. The epoxy resin compound or the oxetane compound is a curing catalyst, or any compound that can accelerate the reaction between the epoxy resin compound and the oxetane compound and a carboxyl group. May be.
Solid content in the said photosensitive resin composition solid content of the said epoxy compound, the said oxetane compound, and the thermosetting accelerator which can accelerate | stimulate thermosetting with these and carboxylic acid is 0.01-15 mass% normally. It is.

Moreover, in order to accelerate | stimulate the thermosetting of thermal crosslinking agents other than the epoxy compound as said thermal crosslinking agent or the said oxetane compound, as a thermosetting accelerator, for example, an amine compound (For example, dicyandiamide, benzyldimethylamine, 4- (dimethyl). Amino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (for example, triethylbenzylammonium chloride, etc.) ), Blocked isocyanate compounds (such as dimethylamine), imidazole derivative bicyclic amidine compounds and salts thereof (such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl) Imidazole, 4-fu Nylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine), guanamine compounds (eg, melamine, guanamine) , Acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4 , 6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, and the like. These may be used alone or in combination of two or more. In addition, there is no restriction | limiting in particular if the curing catalyst of the said thermal crosslinking agent or the reaction of these and a carboxyl group can be accelerated | stimulated, You may use the compound which can accelerate | stimulate thermosetting other than the above.
The solid content in the photosensitive resin composition of the thermal crosslinking agent and the thermal curing accelerator capable of accelerating thermal curing between these and a carboxylic acid is preferably 0.01 to 15% by mass.

--- Sensitizer ---
The sensitizer is not particularly limited and may be appropriately selected from known sensitizers. For example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, , Fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, Methylene blue, toluidine blue), acridines (for example, acridine orange, chloroflavin, acriflavine, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane), anthraquinones (for example, anthraquinone), squalium Kind (For example, squalium), acridones (for example, acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, 2-chloro-10-butylacridone, etc.), coumarin (Eg, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) ) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5,7-di-n-propoxycoumarin), 3,3′-carbonylbis ( 7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-fur Yl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, etc.) And thioxanthone compounds (thioxanthone, isopropyl thioxanthone, 2,4-hour ethyl thioxanthone, 1-chloro-4-propyloxythioxanthone, Quantacure QTX, etc.) and the like, as well as JP-A-5-19475 and JP-A-7-271028 No., JP-A 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, and the like. Compounds with condensed rings or heterocycles ( Ring compounds) are preferred, hetero condensed ring systems ketone compounds, and acridines are more preferred. Among the hetero-fused ketone compounds, an acridone compound and a thioxanthone compound are particularly preferable.

  Examples of the combination of the photopolymerization initiator and the sensitizer include, for example, an electron transfer start system described in JP-A-2001-305734 [(1) an electron donating initiator and a sensitizing dye, (2) A combination of an electron-accepting initiator and a sensitizing dye, (3) an electron-donating initiator, a sensitizing dye and an electron-accepting initiator (ternary initiation system)], and the like.

The content of the sensitizer is preferably 0.01 to 4% by mass, more preferably 0.02 to 2% by mass, and more preferably 0.05 to 1% with respect to all components of the photosensitive resin composition for photosensitive film. Mass% is particularly preferred.
If the said content is 0.01 mass% or more, a sensitivity will become favorable, and if it is 4 mass% or less, the shape of a pattern will become favorable.

--- Thermal polymerization inhibitor ---
The thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound in the photosensitive layer.
Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine. , Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

The content of the thermal polymerization inhibitor is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, and particularly preferably 0.01 to 1% by mass with respect to the photosensitive resin composition. .
When the content is 0.001% by mass or more, a decrease in stability during storage can be prevented, and when the content is 5% by mass or less, sensitivity to active energy rays is improved.

---- Plasticizer ---
The plasticizer may be added to control film physical properties (flexibility) of the photosensitive layer.
Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diphenyl phthalate, diallyl phthalate, octyl capryl phthalate, and the like. Phthalic acid esters: Triethylene glycol diacetate, tetraethylene glycol diacetate, dimethylglycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene glycol dicabrylate, etc. Glycol esters of tricresyl phosphate, triphenyl phosphate, etc. Acid esters; 4-toluenesulfonamide, benzenesulfonamide, Nn-butylbenzenesulfonamide, amides such as Nn-butylacetamide; diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sepacate, dioctyl Aliphatic dibasic acid esters such as sepacate, dioctyl azelate, dibutyl malate; triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, 4,5-diepoxycyclohexane-1,2-dicarboxylic acid Examples include glycols such as dioctyl acid, polyethylene glycol, and polypropylene glycol.

  The content of the plasticizer is preferably from 0.1 to 50 mass%, more preferably from 0.5 to 40 mass%, particularly preferably from 1 to 30 mass%, based on all components of the photosensitive layer.

--- Colored pigment ---
There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, Victoria pure blue BO (CI. 42595), auramine (CI. 41000), fat black HB (CI. 26150), Monolite Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow HR). Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11) Fastel Pink B Supra (CI Pigment Red 81) Monastral Fa Strike Blue (C.I. Pigment Blue 15), mono Light Fast Black B (C.I. Pigment Black 1), carbon, C. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 64 and the like. These may be used alone or in combination of two or more. Moreover, the dye suitably selected from well-known dye can be used as needed.

  The solid content in the solid content of the photosensitive resin composition of the colored pigment can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive layer during permanent pattern formation. Generally, 0.01 to 10% by mass is preferable, and 0.05 to 5% by mass is more preferable.

--- Adhesion promoter ---
In order to improve the adhesion between the layers or the adhesion between the photosensitive layer and the substrate, a known so-called adhesion promoter can be used for each layer.

  Preferable examples of the adhesion promoter include adhesion promoters described in JP-A Nos. 5-11439, 5-341532, and 6-43638. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 3-morpholino Methyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, and 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole Amino group-containing benzotriazole, silane coupling agents, and the like.

  The content of the adhesion promoter is preferably 0.001% by mass to 20% by mass, more preferably 0.01% by mass to 10% by mass, and 0.1% by mass to 5% by mass with respect to all components of the photosensitive layer. Is particularly preferred.

<Defoaming process>
The defoaming step is a step of defoaming the coating solution.
The method of defoaming treatment is not particularly limited and can be appropriately selected according to the purpose. For example, membrane defoaming using a vacuum pump, centrifugal defoaming using centrifugal force, ultrasonic defoaming device For example, ultrasonic defoaming using. Among these, ultrasonic defoaming is preferable in terms of the effect of suppressing planar defects such as pinholes and repellencies.

  The ultrasonic defoaming device is a device that promotes gas foaming by generating cavitation by ultrasonic irradiation. In other words, the liquid is degassed by the foaming or dissolution of the gas in the liquid caused by the minute pressure fluctuation that occurs locally. Although there is no restriction | limiting in particular in the pressure at the time of ultrasonic irradiation, the ultrasonic irradiation at a normal pressure is desirable from a viewpoint of gas solubility control. The control of the apparatus is the output control of the ultrasonic transducer by the voltage value. As an example, an ultrasonic transmitter connected to an ultrasonic transmitter of Nippon Alex Co., Ltd. or Honda Electronics Co., Ltd., which is installed in a pipe or a tank.

The conditions for using the ultrasonic defoaming device are not particularly limited and can be appropriately selected according to the purpose. The output is preferably 1 V or more and 200 V or less, and more preferably 10 V or more and 150 V or less. 30 V or more and 110 V or less is particularly preferable.
The conditions for using the membrane defoaming apparatus are not particularly limited and may be appropriately selected depending on the intended purpose. However, the output is preferably, for example, atmospheric pressure or lower, and preferably 0.01 atmospheric pressure or higher and 0.0. 5 atm or less is more preferable, and 0.05 atm or more and 0.15 atm or less is particularly preferable.

<Application process>
The coating step is a step of coating the coating liquid on a support after the defoaming step.
The method for applying the coating liquid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a spray method, a roll coating method, a spin coating method, a slit coating method, an extrusion coating method, a curtain coating method. And various coating methods such as a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method.

-Support-
The support is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable that the photosensitive layer is peelable and has good light transmittance, and further has a smooth surface. Is more preferable.

  The support is preferably made of synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly ( (Meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoro Various plastic films, such as ethylene, a cellulose film, and a nylon film, are mentioned, Among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular in the thickness of the said support body, Although it can select suitably according to the objective, For example, 2-150 micrometers is preferable, 5-100 micrometers is more preferable, and 8-50 micrometers is especially preferable.

  There is no restriction | limiting in particular as a shape of the said support body, Although it can select suitably according to the objective, A long shape is preferable. There is no restriction | limiting in particular in the length of the said elongate support body, For example, the thing of 10-20,000m length is mentioned.

<Drying process>
The drying step is a step of drying the coating solution to form a photosensitive layer on the support.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 to 110 ° C. for about 30 seconds to 15 minutes.

-Photosensitive layer-
If the said photosensitive layer is a layer which consists of photosensitive resin compositions, there will be no restriction | limiting in particular, According to the objective, it can select suitably.
There is no restriction | limiting in particular as thickness of the said photosensitive layer, Although it can select suitably according to the objective, For example, 1-100 micrometers is preferable, 2-50 micrometers is more preferable, and 4-30 micrometers is especially preferable.
Further, the number of laminated photosensitive layers is not particularly limited and may be appropriately selected depending on the purpose. For example, it may be one layer or two or more layers.

  According to the method for producing a photosensitive film of the present invention, since a film having few surface defects can be produced, a high-definition permanent pattern excellent in insulation (a protective film, an interlayer insulation film, a solder resist pattern, etc.) Can be obtained efficiently.

(Photosensitive film)
The photosensitive film of the present invention has at least a support and a photosensitive layer comprising the photosensitive resin composition of the present invention on the support, and further, if necessary, a thermoplastic resin layer or the like as appropriate. With other layers selected.
The structures of the support and the photosensitive layer are as described above.

<Other layers>
The other layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a protective film, a thermoplastic resin layer, a barrier layer, a release layer, an adhesive layer, a light absorbing layer, a surface protective layer, etc. Layer. The said photosensitive film may have these layers individually by 1 type, and may have 2 or more types.

<< Protective film >>
The photosensitive film may form a protective film on the photosensitive layer.
Examples of the protective film include those used for the support, paper, polyethylene, paper laminated with polypropylene, and the like. Among these, a polyethylene film and a polypropylene film are preferable.
There is no restriction | limiting in particular in the thickness of the said protective film, Although it can select suitably according to the objective, For example, 5-100 micrometers is preferable, 8-50 micrometers is more preferable, 10-30 micrometers is especially preferable.
Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. . Moreover, interlayer adhesion can be adjusted by surface-treating at least one of the support and the protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.

Moreover, 0.3-1.4 are preferable and the static friction coefficient of the said support body and the said protective film has more preferable 0.5-1.2.
If the static friction coefficient is 0.3 or more, it is possible to prevent the occurrence of winding misalignment when it is made into a roll shape due to excessive slip, and if it is 1.4 or less, it can be wound into a good roll shape. .

  For example, the photosensitive film is preferably wound around a cylindrical core, wound into a long roll, and stored. There is no restriction | limiting in particular in the length of the said elongate photosensitive film, For example, it can select suitably from the range of 10-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 to 1,000 m may be formed into a roll. In this case, it is preferable that the support is wound up so as to be the outermost side. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. From the viewpoint of protecting the end face and preventing edge fusion during storage, it is preferable to install a separator (especially moisture-proof and desiccant-containing) on the end face, and use a low moisture-permeable material for packaging. Things are preferable.

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

(Photosensitive laminate)
The photosensitive laminate includes at least a base and a photosensitive layer provided on the base, and is formed by stacking other layers appropriately selected according to the purpose.
The photosensitive layer is transferred from the photosensitive film produced by the manufacturing method described above, and has the same configuration as described above.

<Substrate>
The substrate is a substrate to be processed on which a photosensitive layer is formed, or a substrate to which at least the photosensitive layer of the photosensitive film of the present invention is transferred, and is not particularly limited, and is appropriately selected depending on the purpose. For example, it can be arbitrarily selected from those having high surface smoothness to those having a rough surface. A plate-like substrate is preferable, and a so-called substrate is used. Specific examples include known printed wiring board manufacturing substrates (printed substrates), glass plates (soda glass plates, etc.), synthetic resin films, paper, metal plates, and the like.

<Method for producing photosensitive laminate>
Examples of the method for producing the photosensitive laminate include a method in which at least the photosensitive layer in the photosensitive film of the present invention is transferred and laminated while performing at least one of heating and pressing.

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

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating, According to the objective, it can select suitably, For example, Laminator (For example, Taisei Laminator VP-II, Nichigo Morton VP130) Etc. are preferable.

  The photosensitive film and the photosensitive laminate of the present invention have a uniform film thickness and an extremely low occurrence rate of planar defects such as pinholes and repellency, so that they have excellent insulation reliability and high-definition permanent patterns (protection) Film, interlayer insulating film, solder resist pattern, etc.) can be formed efficiently. Therefore, it can be widely used for forming a high-definition permanent pattern in the field of electronic materials, and can be suitably used particularly for forming a permanent pattern on a printed circuit board.

(Permanent pattern forming method)
The permanent pattern forming method of the present invention includes at least an exposure step and further includes other steps such as a development step appropriately selected as necessary.

<Exposure process>
The said exposure process is a process of exposing with respect to the photosensitive layer in the photosensitive laminated body of this invention. The photosensitive laminate of the present invention is as described above.

  The exposure target is not particularly limited as long as it is a photosensitive layer in the photosensitive laminate, and can be appropriately selected according to the purpose. For example, as described above, a photosensitive film is formed on a substrate. It is preferably performed on a laminate formed by laminating while performing at least one of heating and pressurization.

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

<Other processes>
There is no restriction | limiting in particular as said other process, According to the objective, it can select suitably, For example, the surface treatment process of a base material, a development process, a hardening process process, a post exposure process etc. are mentioned.

<< Development process >>
The development is performed by removing an unexposed portion of the photosensitive layer.
There is no restriction | limiting in particular as the removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.

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

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

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

<< Curing treatment process >>
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed pattern after the development step is performed.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the development. By the entire surface exposure, curing of the resin in the photosensitive resin composition forming the photosensitive layer is accelerated, and the surface of the permanent pattern is cured.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

Examples of the entire surface heat treatment method include a method of heating the entire surface of the laminate on which the permanent pattern is formed after the development. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
120-250 degreeC is preferable and the heating temperature in the said whole surface heating has more preferable 120-200 degreeC. When the heating temperature is 120 ° C. or higher, the film strength is improved by heat treatment, and when the heating temperature is 250 ° C. or lower, the resin in the photosensitive resin composition is decomposed and the film quality is prevented from becoming weak and brittle. .
The heating time in the entire surface heating is preferably 10 to 120 minutes, and more preferably 15 to 60 minutes.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

When the permanent pattern forming method is a permanent pattern forming method for forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern, the permanent pattern is formed on the printed wiring board by the permanent pattern forming method. Further, soldering can be performed as follows.
That is, by the development, a hardened layer that is the permanent pattern is formed, and the metal layer is exposed on the surface of the printed wiring board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer exhibits a function as a protective film, an insulating film (interlayer insulating film), or a solder resist, and prevents external impact and conduction between adjacent electrodes.

(Printed board)
The printed circuit board of the present invention comprises at least a substrate and a permanent pattern formed by the permanent pattern forming method, and further has other configurations appropriately selected as necessary.
There is no restriction | limiting in particular as another structure, According to the objective, it can select suitably, For example, the buildup board | substrate etc. in which the insulating layer was further provided between the base material and the said permanent pattern are mentioned.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not restrict | limited to the following Example.

-Binder synthesis-
In a 1,000 mL three-necked flask, 159 g of 1-methoxy-2-propanol was placed and heated to 85 ° C. under a nitrogen stream. To this, a solution of 159 g of 1-methoxy-2-propanol containing 63.4 g of benzyl methacrylate, 72.3 g of methacrylic acid, and 3.0 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped over 2 hours. After completion of the dropwise addition, the reaction was further continued by heating for 5 hours. Subsequently, the heating was stopped to obtain a copolymer of benzyl methacrylate / methacrylic acid (ratio of 30/70 mol%).
Next, 120.0 g of the copolymer solution was transferred to a 300 mL three-necked flask, and 16.6 g of glycidyl methacrylate and 0.16 g of p-methoxyphenol were added and stirred to dissolve. After dissolution, 3.0 g of triphenylphosphine was added while performing air bubbling, heated to 100 ° C., and after 20 minutes, glycidyl methacrylate was added to perform an addition reaction. The disappearance of glycidyl methacrylate was confirmed by gas chromatography, and heating was stopped. 1-Methoxy-2-propanol was added to prepare a binder solution represented by the following structural formula (29) having a solid content of 45% by mass.
It was 30,000 as a result of measuring the mass mean molecular weight (Mw) of the obtained binder by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance. Moreover, the acid value per solid content was 2.2 meq / g from the titration using sodium hydroxide. Furthermore, the content of ethylenically unsaturated bonds per solid (C = C value) determined by iodine value titration was 2.1 meq / g.

Example 1
-Preparation of photosensitive resin composition-
Each component was mix | blended with the following quantity, and the photosensitive resin composition solution (coating liquid) was prepared.
[Each component amount of photosensitive resin composition solution]
-Binder (solid content in the 1-methoxy-2-propanol solution: 45% by mass) ... 45.51 parts by mass-Pentaerythritol tetraacrylate (polymerizable compound) ... 11.03 parts by mass Photopolymerization initiator represented by formula (26): 0.35 parts by mass / diethylthioxanthone ... 0.37 parts by mass / bis-F type epoxy resin (thermal crosslinking agent, manufactured by Toto Kasei Co., Ltd., YDF -170) ... 4.57 parts by mass-thermosetting agent (dicyandiamide) -0.08 parts by mass-Silica SO-C2 (manufactured by Admatechs) ... 7.11 parts by mass-coloring Pigment (manufactured by BASF, HELIOGEN BLUE D7086) ... 0.17 parts by mass, methyl ethyl ketone ... 16.74 parts by mass, normal propyl acetate ... 13.96 parts by mass The viscosity of the photosensitive resin composition solution Is 40 mPa It was s.

-Production of photosensitive film-
The obtained photosensitive resin composition solution was passed through an ultrasonic defoaming device (SDF), and then applied onto a PET (polyethylene terephthalate) film having a thickness of 16 μm as the support and dried to obtain a film thickness. A 30 μm photosensitive layer was formed. Next, a 20 μm-thick polypropylene film was laminated as a protective film on the photosensitive layer to produce the photosensitive film. In addition, the ultrasonic defoaming device used Nippon Alex Co., Ltd. NEOSONIC series 0833-16 as a transmitter, set the voltage value to 35V, and used the transmitter output.

<Evaluation of planar defects>
Describe the evaluation procedure / criteria. The photosensitive film produced by the above method was visually evaluated with red transmitted light. As evaluation criteria, bubbles having a diameter of 1 mm or more were repelled (large), and bubbles of 1 mm or less were repelled (small). The size of the photosensitive film was 1 m ² .

<Insulation reliability test>
It was prepared by subjecting the surface of a copper-clad laminate (L / S = 50 μm / 50 μm comb pattern, copper thickness 12 μm) on which wiring was formed as a printed circuit board to a chemical polishing treatment. A vacuum laminator (VP130, manufactured by Nichigo Morton Co., Ltd.) was peeled off on the copper-clad laminate while peeling the protective film from the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper-clad laminate. The photosensitive laminate was prepared by laminating the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) in this order. The pressure bonding conditions were a vacuum drawing time of 40 seconds, a pressure bonding temperature of 70 ° C., a pressure bonding pressure of 0.2 MPa, and a pressure application time of 10 seconds. Using this substrate, an insulation reliability test was conducted using an ion migration evaluation apparatus SIR12 manufactured by ETAC under the conditions of 130 ° C./85%/0.196Mpa/10V/200h. In addition, as for the result, 10 specimen test was done and the number which short-circuited was described. The results are shown in Table 1.

(Example 2)
A photosensitive film was produced in the same manner as in Example 1 except that the SDF condition was changed from 35 V to 70 V, and surface defects and insulation reliability were evaluated. The results are shown in Table 1.

(Example 3)
A photosensitive film was produced in the same manner as in Example 1 except that the SDF condition was changed from 35V to 100V, and surface defects and insulation reliability were evaluated. The results are shown in Table 1.

(Comparative Example 1)
A photosensitive film was produced in the same manner as in Example 1 except that the SDF condition was changed from 35 V to 0 V, and surface defects and insulation reliability were evaluated. The results are shown in Table 1.

  From Table 1, although the photosensitive film of the comparative example 1 which does not implement a defoaming process has many planar defects and insulation reliability is remarkably bad, the photosensitive film of Examples 1-3 which implemented the defoaming process It can be seen that there are very few planar defects and the insulation reliability is excellent.

The coating liquid that has been subjected to defoaming treatment in the photosensitive film of the present invention can greatly suppress the rate of occurrence of surface defects such as pinholes and repellency, so that a photosensitive film and a photosensitive laminate excellent in insulation reliability can be obtained. Can be provided. Therefore, since a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern) can be efficiently formed, it can be widely used for forming a high-definition permanent pattern in the field of electronic materials. And can be suitably used for forming a permanent pattern on a printed circuit board.
Since the method for forming a permanent pattern of the present invention uses the photosensitive film of the present invention, it can be suitably used for forming various patterns that require high-definition exposure. It can be used suitably for formation.

Claims (10)

i) a coating solution containing a photosensitive resin composition containing a photosensitive group and an acid group for imparting alkali developability, ii) a polymerizable compound, and iii) a photopolymerization initiator. A preparation process;
A defoaming step of defoaming the coating solution;
After the defoaming step, an application step of applying the coating liquid to a support;
A drying step of drying the coating solution to form a photosensitive layer on the support;
The manufacturing method of the photosensitive film characterized by including.   The method for producing a photosensitive film according to claim 1, wherein the defoaming treatment is ultrasonic defoaming.   The method for producing a photosensitive film according to claim 1, wherein the photosensitive resin composition further contains iv) a thermal crosslinking agent.   The method for producing a photosensitive film according to claim 1, wherein the photosensitive resin composition further comprises v) a filler.   The method for producing a photosensitive film according to claim 1, wherein the coating solution has a viscosity of 5 mPa · s to 100 mPa · s.   The method for producing a photosensitive film according to claim 5, wherein the coating solution has a viscosity of 10 mPa · s to 50 mPa · s. A photosensitive film produced by the production method according to claim 1,
A photosensitive film which is long and is wound into a roll. A photosensitive laminate comprising a substrate and a photosensitive layer provided on the substrate,
A photosensitive laminate, wherein the photosensitive layer is transferred from a photosensitive film produced by the production method according to claim 1.   The permanent pattern formation method characterized by including at least the exposure process which exposes with respect to the photosensitive layer in the photosensitive laminated body of Claim 8. A printed circuit board comprising a permanent pattern formed by the permanent pattern forming method according to claim 9.