KR20100035106A - Manufacturing method for photosensitive film, photosensitive film, photosensitive laminate, method for forming permanent pattern and printed board - Google Patents

Abstract

PURPOSE: A photosensitive film is provided to prevent in-plane defects such as pinhole due to uniform film thickness and to form highly fine persistent pattern due to excellent adhesion with a substrate for forming a printed wire. CONSTITUTION: A method for manufacturing a photosensitive film comprises: a coating preparation step for preparing a coating solution containing a photosensitive resin composition, wherein the photosensitive resin composition includes a compound introduced with a photosensitive group and an acid group for imparting alkali development, a polymerizable compound, and a photopolymerization initiator; a de-aeration step; a coating step; and a drying step for forming a photosensitive layer on a supporter.

Description

Manufacturing method of photosensitive film, photosensitive film, photosensitive laminate, permanent pattern forming method, and printed circuit board {MANUFACTURING METHOD FOR PHOTOSENSITIVE FILM, PHOTOSENSITIVE FILM, PHOTOSENSITIVE LAMINATE, METHOD FOR FORMING PERMANENT PATTERN AND PRINTED BOARD}

The present invention provides a photosensitive resin composition, a photosensitive film, a photosensitive laminate, a permanent pattern forming method, and a printed circuit board, which have high sensitivity and high resolution, and are capable of efficiently forming a high-definition permanent pattern due to their good aging stability, film hardenability, and thermal shock resistance. It is about.

BACKGROUND ART With the miniaturization and multifunctionalization of electronic devices, printed wiring boards are currently progressing toward higher densities. For example, thinning of a through-circuit, high-layering of a conductor circuit, a small diameter of the through hole containing interstitial via holes, such as a blind hole and a buried hole, high density mounting by surface mounting of a small chip component, etc. are mentioned.

Conventional solder resists for printed wiring boards include, for example, thermosetting catalysts such as amines, imidazoles, and acid anhydrides, and organic solvents such as butyl cellosolve and butyl carbitol in heat-resistant thermosetting resins such as epoxy resins and epoxy melamine resins. Combined thermosetting solder resists; Ultraviolet curable soldering resists formed by blending polymerizable monomers such as acrylic acid esters and methacrylic acid esters with crosslinkable polymers such as epoxy acrylate and urethane acrylate, and photosensitizers such as benzoin ethyl ether and benzophenone; The ducure curing type solder resist etc. which combined each component contained in the said thermosetting soldering resist and an ultraviolet curing soldering resist are mentioned.

As a formation method of a soldering resist, for example, the photosensitive layer which consists of a photosensitive resin composition is formed on base materials, such as a copper clad laminated board in which the said soldering resist is formed, it exposes to the said photosensitive layer, and after the said exposure, the said photosensitive layer The method of developing and forming the soldering resist which has a predetermined pattern is mentioned.

And as a method of forming a photosensitive layer on a base | substrate, the liquid-type photosensitive resin composition is apply | coated and formed on a base | substrate with a screen coater, a dip coater, a bar coater, etc. Alternatively, the photosensitive resin composition is sandwiched with a protective film made of a polyester film or polyethylene to form a dry film having a three-layer structure, which is laminated on a substrate with a roll laminator or a vacuum laminator to form a photosensitive layer.

In recent years, since the densification has progressed and the wiring density has increased, planarization of the solder resist surface at the time of component mounting is calculated | required. Dry film type solder resist can be press-molded by a vacuum laminator or the like, and furthermore, since the volume shrinkage due to volatilization of solvent is small, it is advantageous for flattening compared with the liquid type solder resist. However, in the case of a dry film-type soldering resist, when surface defects, such as pinholes and agglomeration, arise in a film manufacturing process, it is difficult to repair this defect in the process after lamination to a gas phase. Since the insulation reliability of a printed wiring board falls in the state in which planar defects, such as a pinhole and agglomeration, remain in the cured film (solder resist), the subject of how to manufacture the dry film with few planar defects has become a subject.

Here, Japanese Patent Laid-Open No. 7-21626 proposes to include a surfactant in the resist composition in order to form a photosensitive layer having a uniform film thickness.

However, the resist composition described in Japanese Patent Application Laid-open No. Hei 7-21626 is intended to be applied to a substrate as a liquid type, and is not intended to be used as a dry film. Moreover, when surfactant is contained in a resist composition, there exists a problem that the adhesiveness of a photosensitive layer and a base worsens.

This invention solves all the problems in the said prior art, and makes it a subject to achieve the following objectives. That is, the present invention has a uniform film thickness when applied to a substrate, so that surface defects such as pinholes and agglomerations are less likely to occur. Furthermore, the present invention has excellent adhesion to substrates such as substrates for forming printed wirings, and thus provides high-definition permanent patterns efficiently. It is an object to provide a formable photosensitive film, a method for producing a photosensitive film, a photosensitive laminate, a permanent pattern forming method, and a printed board.

Means for solving the above problems are as follows.

<1> Coating liquid preparation process which prepares the coating liquid containing the photosensitive group and the compound which introduce | transduced the acidic radical for imparting alkali developability, ii) polymeric compound, and iii) photosensitive resin composition containing a photoinitiator;

A defoaming step of performing a defoaming treatment to the coating liquid;

A coating step of applying the coating solution to a support after the defoaming step; And

It is a manufacturing method of the photosensitive film characterized by including the drying process of drying the said coating liquid and forming a photosensitive layer on the said support body.

<2> The said defoaming process is a manufacturing method of the photosensitive film as described in said <1> which is ultrasonic defoaming.

<3> The said photosensitive resin composition is a manufacturing method of the photosensitive film as described in said <1> or <2> which further contains iv) a thermal crosslinking agent.

<4> The said photosensitive resin composition is a manufacturing method of the photosensitive film in any one of said <1> to <3> which further contains v) filler.

<5> The viscosity of the said coating liquid is 5 mPa * s-100 mPa * s, It is a manufacturing method of the photosensitive film in any one of said <1> to <4> characterized by the above-mentioned.

The viscosity of a <6> above-mentioned coating liquid is 10 mPa * s-50 mPa * s, It is a manufacturing method of the photosensitive film as described in said <5> characterized by the above-mentioned.

<7> It is the photosensitive film produced by the manufacturing method in any one of said <1> to <6>, is long, and is wound in roll shape.

A photosensitive laminate comprising a <8> substrate and a photosensitive layer formed on the substrate, wherein the photosensitive layer is transferred from a photosensitive film produced by the production method according to any one of <1> to <6>. It is a photosensitive laminated body.

<9> It is a permanent pattern formation method characterized by including the exposure process which exposes to the photosensitive layer in the photosensitive laminated body as described in said <8>.

<10> It is a printed circuit board provided with the permanent pattern formed by the permanent pattern formation method as described in said <9>.

According to the present invention, all the problems in the prior art can be solved, and the above object can be attained. The film thickness when applied to the substrate is uniform, so that surface defects such as pinholes and agglomerations are less likely to occur. A photosensitive film, a method for producing a photosensitive film, a photosensitive laminate, a permanent pattern forming method, and a printed circuit board, which are excellent in adhesion with a substrate such as a substrate for use and can efficiently form a high-definition permanent pattern, can be provided.

(Method for Producing Photosensitive Film)

The manufacturing method of the photosensitive film of this invention contains at least a coating liquid preparation process, a defoaming process, a coating process, and a drying process, and also contains other processes suitably selected as needed.

<Coating solution preparation process>

The said coating liquid preparation process is a process of preparing the coating liquid containing the photosensitive resin composition mentioned later.

There is no restriction | limiting in particular as a method of preparing the said coating liquid, According to the objective, it can select suitably, For example, the method of melt | dissolving, emulsifying, or dispersing the said photosensitive resin composition in 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, tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether Glycol ethers such as these; Esters such as ethyl acetate, butyl acetate, and acetate esters of the above glycol ethers; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Although petroleum solvents, such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha, can be mentioned, It is not limited to this.

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-100 mPa * s are preferable, and 10 mPa * s-50 mPa * s are more preferable.

Photosensitive resin composition

The photosensitive resin composition comprises at least i) a compound (binder) incorporating a photosensitive group and an acid group for imparting alkali developability, ii) a polymerizable compound, and iii) a photoinitiator. It consists of other components, such as a crosslinking agent and v) filler.

--bookbinder--

There is no restriction | limiting in particular if it is a compound which introduce | transduced the photosensitive group and the acidic radical for providing alkali developability as said binder, According to the objective, it can select suitably, For example, the epoxy resin which has two or more epoxy groups, and unsaturated (meth Polymer obtained by making acrylic acid react, and then making polybasic acid anhydride further react; A modified copolymer in which glycidyl (meth) acrylate is added to an acid group of a part of a copolymer obtained from a compound containing a (meth) acrylic acid ester and an unsaturated group and having at least one acid group; The polymer etc. which are obtained by reaction of a carboxyl group-containing (meth) acrylic-type copolymer resin and an alicyclic epoxy group containing unsaturated compound are mentioned.

Among these, when the photosensitive resin composition is made into a dry film and used as a photosensitive layer, since adhesiveness is low, it is glycy to the acid group of one part of the copolymer obtained from the compound containing a (meth) acrylic acid ester and an unsaturated group, and having at least 1 acid group. Preferred is a modified copolymer to which di (meth) acrylate is added.

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 said solid content is 5 mass% or more, developability and exposure sensitivity will become favorable, and if it is 80 mass% or less, the adhesiveness of a photosensitive layer can be prevented 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 bond is preferable.

Examples of the ethylenically unsaturated bonds include (meth) acryloyl groups, (meth) acrylamide groups, styryl groups, vinyl groups such as vinyl esters and vinyl ethers, allyl groups such as allyl ethers and allyl esters, and the like. .

There is no restriction | limiting in particular as a compound which has one or more of said ethylenically unsaturated bonds, Although it can select suitably according to the objective, For example, at least 1 sort (s) chosen from the monomer which has a (meth) acryl group is mentioned preferably.

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 ( Monofunctional acrylates and monofunctional methacrylates such as meth) acrylate; Polyethylene glycol di (meth) arcacrylate, polypropylene glycol di (meth) acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, trimethylol propane diacrylate, neopentyl glycol di (meth) acrylate Pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylol Propane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, trimethylolpropane or glycerin, (Meth) acrylate after addition reaction of ethylene oxide and propylene oxide to polyfunctional alcohols, such as bisphenol Urethane acrylates described in each publication such as yttrate, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, and Japanese Patent Publication No. 51-37193; Polyester acrylates described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490; Polyfunctional acrylates, methacrylates, etc., such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid, are mentioned. 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. If the said solid content is 5 mass% or more, developability and exposure sensitivity will become favorable, and if it is 50 mass% or less, it can prevent that the adhesiveness of a photosensitive layer becomes too strong.

Photopolymerization initiator

As said photoinitiator, there is no restriction | limiting in particular as long as it has the ability to start superposition | polymerization of the said polymeric compound, Although it can select suitably according to the objective, For example, it is preferable to have photosensitivity with respect to visible light from an ultraviolet range, It may be an activator which generates an active radical by generating any action with the sensitizer excited, or may be an initiator that initiates cationic polymerization depending on the type of monomer.

The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 in a range of about 300 to 800 nm in wavelength. As for the said wavelength, 330-500 nm is more preferable.

As said photoinitiator, a halogenated hydrocarbon derivative (for example, having a triazine skeleton, having an oxadiazole skeleton, etc.), hexaaryl biimidazole, an oxime derivative, an organic peroxide, a thio compound, a ketone compound , Aromatic onium salts, metallocenes, and the like. Among these, halogenated hydrocarbons, oxime derivatives, ketone compounds, and hexaarylbiimidazole-based compounds having a triazine skeleton are preferable from the viewpoints of the sensitivity, the storage properties of the photosensitive layer, and the adhesion between the photosensitive layer and the substrate for forming a printed wiring board.

As said hexaaryl biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (o-fluorine, for example) Rophenyl) -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 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4' , 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-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'-tetraphenylbiimi Dazoles, compounds described in WO 00/52529, and the like.

The biimidazoles are, for example, Bull. Chem. Soc. Japan, 33, 565 (1960) and J. 0rg. It can be readily synthesized by the method disclosed in Chem, 36 (16) 2262 (1971).

As a halogenated hydrocarbon compound which has a triazine frame | skeleton, Wakabayashi et al., Bull. Chem. Soc. J. Japanese, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in Japanese Patent Application Laid-Open No. 53-133428, a compound described in German Patent No. 3337024, FC Schaefer et al. 0rg. Chem .; 29, 1527 (1964), a compound of JP-A-62-58241, a compound of JP-A-5-281728, a compound of JP-A 5-34920, United States The compound described in the specification of patent 4212976, etc. are mentioned.

Wakabayashi et al., Bull. Chem. Soc. As the 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-tolylphenyl) -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- (α, α, β-trichloroethyl) -4,6- Bis (trichloromethyl) -1,3,5-triazine and the like.

As a compound of the said British patent 1388492 specification, for example, 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine and 2- (4-methylstyryl) -4 , 6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyrene) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl))-4-amino-6-trichloromethyl-1,3,5-triazine and the like.

As a compound of the said Unexamined-Japanese-Patent No. 53-133428, 2- (4-methoxy- naphtho- 1-yl) -4, 6-bis (trichloromethyl) -1,3,5 is mentioned, for example. -Triazine, 2- (4-ethoxynaphtho-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl ) -Naphtho-1-yl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphtho-1-yl) -4, 6-bis (trichloromethyl) -1,3,5-triazine and 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine and the like This is listed.

As a compound of the said German patent 3337024 specification, for example, 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 (trichloro Methyl) -1,3,5-triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-thiophen-2-vinyl Phenylphenyl) -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-benzo Furan-2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine and the like.

J. 0rg. By F. C. Schaefer et al. Chem .; Examples of the compound described in 29, 1527 (1964) include 2-methyl-4,6-bis (tribromomethyl) -1,3,5-triazine, 2,4,6-tris (tribromo Methyl) -1,3,5-triazine, 2,4,6-tris (dibromomethyl) -1,3,5-triazine, 2-amino-4-methyl-6-tri (bromomethyl ) -1,3,5-triazine, 2-methoxy-4-methyl-6-trichloromethyl-1,3,5-triazine and the like.

As a compound of the said Unexamined-Japanese-Patent No. 62-58241, 2- (4-phenylethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2, for example -(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-isopropylphenylethynyl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4- Ethylphenylethynyl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine and the like.

As a compound of the said Unexamined-Japanese-Patent No. 5-281728, for example, 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 (trichloro Romethyl) -1,3,5-triazine, 2- (2,6-dibromophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine and the like.

As said JP-A-5-34920-based compound, for example, 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromo Phenyl] -1,3,5-triazine, trihalomethyl-s-triazine compounds described in US Pat. No. 4,239,850, and also 2,4,6-tris (trichloromethyl) -s-tri Azine, 2- (4-chlorophenyl) -4,6-bis (tribromomethyl) -s-triazine, and the like.

As a compound described in the said U.S. Pat.No.4212976, for example, a compound 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-tribromo Methyl-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 -Tribromomethyl-5-styryl-1,3,4-oxadiazole and the like).

As an oxime derivative used preferably by this invention, it is represented by following General formula (1), for example.

However, in General Formula (1), R ¹ represents any ^one of a hydrogen atom, an acyl group which may have a substituent, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, and an arylsulfonyl group, and R ² is each independently A substituent is shown. m represents the integer of 0-4, and in the case of 2 or more, you may connect with each other and form a ring. A represents any of 4, 5, 6, and a 7-membered ring. Moreover, it is preferable that A is either 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 General Formula (2), R ¹ represents any ^one of a hydrogen atom, an acyl group which may have a substituent, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group and an arylsulfonyl group, and R ² is each independently a substituent Indicates. m represents the integer of 0-4, and in the case of 2 or more, you may mutually connect and form a ring. X represents any one of CH ₂ , O and S. A represents either 5 or 6 membered ring.

As an acyl group represented by R <^1> in the said General formula (1) and (2), any of an aliphatic, an aromatic, and a heterocyclic ring may be sufficient, and you may have a substituent further.

Examples of the aliphatic group include acetyl group, propanoyl group, butanoyl group, hexanoyl group, decanoyl group, phenoxyacetyl group, and chloroacetyl group. Examples of the aromatic group include a benzoyl group, naphthoyl group, methoxy benzoyl group, nitrobenzoyl group and the like. Examples of the heterocyclic group include furanoyl group and thiophenoyl group.

As a substituent, any one of an alkoxy group, an aryloxy group, and a halogen atom is preferable. As an acyl group, the thing of 2-30 total carbons is preferable, The thing of 2-20 total carbons is more preferable, The thing of 2-16 total carbons is especially preferable. As such an acyl group, for example, an acetyl group, propanoyl group, methyl propanoyl 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, pyridyl Carbonyl group, methacryloyl group, acryloyl group, etc. are mentioned.

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

As an aryloxycarbonyl group, you may have a substituent, the alkoxycarbonyl group of 7-30 total carbons is preferable, The thing of 7-20 total carbons is more preferable, The thing of 7-16 total carbons is especially preferable. Examples of such aryloxycarbonyl groups include phenoxycarbonyl groups, 2-naphthoxycarbonyl groups, paramethoxyphenoxycarbonyl groups, 2,5-diethoxyphenoxycarbonyl groups, parachlorophenoxycarbonyl groups, paranitrophenoxycarbonyl groups, and paracyano. Phenoxycarbonyl groups are listed.

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

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

Examples of the substituent represented by R ² in General Formulas (1) and (2) include aliphatic, aromatic, heteroaromatic, halogen atoms, —OR ³ , —SR ³ , and —NR ³ R ⁴ . R ³ and R ⁴ may be connected to each other to form a ring. R ³ and R ⁴ each independently represent a hydrogen atom or an aliphatic group, an aromatic group, or a heteroaromatic group. When m is two or more and mutually connects and forms a ring, independent R <^{2> may} mutually form a ring, and may form a ring through at least one of R <^3> and R <^4> .

When forming a ring through the said substituent R <^2> , the following structures are enumerated.

Y and Z in the above formula represent any one of CH ₂ , -O-, -S-, and -NR-.

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

Although the compound represented by following structural formula (1)-(51) is mentioned as a specific example of the oxime compound represented by the said General formula (1), This invention is not limited to these.

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 the method for preparing the oxime compound, the reaction is carried out in an inert solvent such as THF, DMF, acetonitrile, or in a basic solvent such as pyridine in the presence of a base (for example triethylamine, pyridine) of a corresponding oxime compound and an acyl chloride or anhydride. It can synthesize | combine easily by making it. As said reaction temperature, -10-60 degreeC is preferable.

In addition, by using chloroform acid ester, 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 preparing the oxime compound, a standard chemistry textbook (e.g., J. March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992), or a professional monograph, e.g. See, for example, SR Sandler & W. Karo, Organic functional group preparations, Vol. It can be obtained by various methods described in 3, Academic Press.

Particularly preferred methods for synthesizing the oxime compound include, for example, a method of reacting an aldehyde or a ketone with a hydroxylamine or a salt thereof in a polar solvent such as ethanol or ethanol water. 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 rate of reaction is pH dependent and that bases can be added continuously at the start or between reactions. Basic solvents such as pyridine may also be used as the base and / or solvent or co-solvent. Generally as said reaction temperature, the reflux temperature of a mixture, ie, about 60-120 degreeC, is preferable.

As another preferable synthesis | combining method of the said oxime compound, the method by nitrosation of the "active" methylene group by nitrous acid or alkyl nitrite is mentioned. For example, Organic Syntheses coll. Vol. Alkaline conditions as described in VI (J. Wiley & Sons, New York, 1988), pp. 199 and 840, for example in Organic Synthesis coll. Vol. V, pp. 32 and 373, coll. Vol. III, pp. 191 and 513, coll. Vol. II, pp. Both of acidic conditions as described in 202, 204 and 363 are preferred for the synthesis of oxime compounds used as starting materials in the present invention.

As said nitrous acid, it is normally produced from sodium nitrite.

Examples of the alkyl nitrite include methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite or amyl nitrite.

As said oxime ester group, what exists in two types of three-dimensional arrangement (Z) or (E) may be sufficient. The isomer may be separated by a conventional method, or the isomer mixture may be used as it is as a species of photoinitiation. Accordingly, the oxime compound of the present invention may be a mixture of three-dimensionally arranged isomers of the compounds of the above structural formulas (1) to (51).

The oxime compound is excellent in storage stability and is highly sensitive, and thus, by adding to the polymerizable composition, the oxime compound is excellent in storage stability without generating polymerization at the time of storage, and generates active radicals by irradiation with energy rays, especially light, and efficiently polymerization. It is possible to obtain a highly sensitive polymerizable composition in which the polymerizable compound can be efficiently polymerized in a short time.

Moreover, as a photoinitiator of that excepting the above, an acridine derivative (for example, 9-phenylacridine, 1,7-bis (9, 9'-acridinyl) heptane, etc.), N-phenylglycine, etc., Polyhalogen compounds (e.g. carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethyl ketone, etc.), coumarins (e.g. 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- Diethylamino coumarin), 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-ylcou Lin also discloses Japanese Patent Application Laid-Open No. 5-19475, Japanese Patent Application Laid-Open No. 7-271028, Japanese Patent Publication 2002-363206, Japanese Patent Publication 2002-363207, Japanese Patent Publication 2002-363208, Japanese Patent Publication 2002- Coumarin compounds and the like described in Japanese Patent No. 363209 and the like, and amines (for example, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid n-butyl, 4-dimethylaminobenzoic acid phenethyl, 4-dimethylaminobenzoic acid 2-phthalimide Ethyl, 4-dimethylaminobenzoic acid 2-methacryloyloxyethyl, pentamethylenebis (4-dimethylaminobenzoate), phenethyl, pentamethylene ester of 3-dimethylaminobenzoic acid, 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, Benzylphenylamine, N-methyl-N-phenylbenzylamine, 4-bromine-N, N-dimethylaniline, tridodecylamine, aminofluorans (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-pentylphenylforce) Pinoxide, Lucirin TPO and the like).

In addition, the bisinal polyketaldonyl compound described in US Patent No. 2367660, the acyloin ether compound described in US Patent No. 2448828, and the α-hydrocarbon described in US Patent No. 2722512 Substituted aromatic acyl phosphorus compounds, polynuclear quinone compounds described in US Pat. No. 3046127 and 2951758, organic boron compounds described in Japanese Patent Application Laid-Open No. 2002-229194, radical generators, triarylsulfonium salts (e.g. For example, salts with hexafluoroantimony or hexafluorophosphate), phosphonium salt compounds (for example, (phenylthiophenyl) diphenylsulfonium salts, etc.) (effective as cationic polymerization initiator), WO 01/71428 Listed onium salt compounds and the like.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together. As two or more types of combinations, for example, the combination of the hexaaryl biimidazole and 4-amino ketones described in US Pat. No. 3549367, the benzothiazole compound and trihalomethyl described in Japanese Patent Publication No. 51-48516 combinations of -s-triazine compounds, also combinations of aromatic ketone compounds (e.g. thioxanthones) with hydrogen donors (e.g. dialkylamino containing compounds, phenolic compounds, etc.), hexaarylbiimidazoles A combination of titanocene, coumarins, a combination of titanocene and phenylglycines, and the like.

Particularly preferred examples of the photopolymerization initiator include the halogenated hydrocarbon compounds having the phosphine oxides, the α-aminoalkylketones, and the triazine skeletons, which are compatible with laser light having a wavelength of 405 nm in the exposure described below, as sensitizers described below. The complex photoinitiator which combined the amine compound, the hexaaryl biimidazole compound, titanocene, etc. are mentioned.

0.1-30 mass% is preferable, as for content in the said photosensitive resin composition of the said photoinitiator, 0.5-20 mass% is more preferable, 0.5-15 mass% is especially preferable.

--Other Ingredients--

There is no restriction | limiting in particular as said other components, According to the objective, it can select suitably, For example, a heat crosslinking agent, a filler, a thermosetting accelerator, a sensitizer, a thermal polymerization inhibitor, a plasticizer, a coloring agent (colored pigment or dye), etc. These include adhesion promoters to the substrate surface and other preparations (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, flavoring agents, surface tension modifiers, chain transfer agents, etc.) You may also

By appropriately including these components, properties such as stability, photographic properties, film properties, and the like of the intended photosensitive film can be adjusted.

--- Thermosphere ---

There is no restriction | limiting in particular as a thermal crosslinking agent, According to the objective, in order to improve the film strength after hardening of the photosensitive layer formed using the said photosensitive film, in the range which does not adversely affect developability etc., for example, A compound containing an epoxy compound (for example, an epoxy compound having at least two oxirane groups in one molecule), and an oxetane compound having at least two oxetanyl groups in one molecule can be used. A blocking agent is reacted with an isocyanate group of 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 Japanese Patent No. 47729. The compound etc. which are obtained by making it carry out are mentioned.

In addition, a melamine derivative may be used as the thermal crosslinking agent. Examples of the melamine derivatives include methylolmelamine, alkylated methylolmelamine (compounds obtained by etherification of methylol with methyl, ethyl, butyl, etc.) and the like. These may be used individually by 1 type and may use 2 or more types together. Among them, alkylated methylolmelamine is preferred, and hexamethylated methylolmelamine is particularly preferable because it has good storage stability, and is effective for 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. The film strength of a cured film improves that the said solid content is 1 mass% or more, and developability and exposure sensitivity will become favorable when it is 50 mass% or less.

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

As an epoxy compound which has at least two oxirane groups in the said one molecule, For example, bixylenol type or a biphenol type epoxy resin ("made by YX4000 Japan Epoxy Resins Co., Ltd."), or a mixture thereof, isocyanur Heterocyclic epoxy resin (late TECPIC; Nissan Chemical Industries, Ltd. make, Araldite PT 810; Chiba Specialty Chemicals KK make), etc. which have a rate frame | skeleton etc., a bisphenol-A epoxy resin, a novolak-type epoxy resin, Bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin) , Brominated phenol novolac epoxy resins), allyl group-containing bisphenol A epoxy resin, trisphenol methane epoxy resin, diphenyl dimethanol epoxy G, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP-7200, HP-7200H; Dainippon Ink and Chemical Corporation", etc.), glycidylamine type epoxy resin (diaminodiphenylmethane type) Epoxy resin, diglycidyl aniline, triglycidylaminophenol, etc., glycidyl ester type epoxy resin (phthalic acid diglycidyl ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, Dimeric acid diglycidyl ester) hydantoin type epoxy resin, alicyclic epoxy resin (3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclo) Hexylmethyl) adipate, dicyclopentadiene diepoxide, `` GT-300, GT-400, ZEHPE 3150; manufactured by Daicel Chemical Industries, Ltd. '', etc.), imide alicyclic epoxy resin, trihydroxyphenylmethane type epoxy Resins, Bisphenol A Novolac Epoxy Resin, tetraphenylol ethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group containing epoxy resin (naphthol aralkyl type epoxy resin, naphthol novolak type epoxy resin, tetrafunctional naphthalene type epoxy) As resin and a commercial item, it is "ESN-190 and ESN-360; Nippon Steel Chemical Co., Ltd. Production ”,“ HP-4032, EXA-4750, EXA-4700; Dainippon Ink and Chemical Corporation "), the reaction product of the polyphenol compound and epichlorohydrin obtained by addition reaction of a phenolic compound and diolefin compounds, such as divinylbenzene and dicyclopentadiene, 4-vinyl cyclohexene- Epoxidized ring-opening polymer of 1-oxide with peracetic acid, etc., epoxy resin with linear phosphorus containing structure, epoxy resin with cyclic phosphorus containing structure, α-methylstilbene type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal Epoxy resin, azophenyl type liquid crystal epoxy resin, azomethinephenyl type liquid crystal epoxy resin, vinaphthyl type liquid crystal epoxy resin, azine type epoxy resin, glycidyl methacrylate copolymer type epoxy resin ("CP-50S, CP-50M; NOF Corporation production "etc.), copolymerization epoxy resin of cyclohexyl maleimide and glycidyl methacrylate, bis (glycidyl oxyphenyl) fluorene type epoxy Although resin, bis (glycidyloxyphenyl) adamantane type epoxy resin etc. are mentioned, It is not limited to these. 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 two epoxy groups in at least one molecule having an alkyl group at the β-position can be used, and the β-position is an epoxy group substituted with an alkyl group (more Specifically, the compound containing (beta) -alkyl substituted glycidyl group etc.) is especially preferable.

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, or at least one epoxy group may be a β-alkyl substituted glycidyl group. good.

As said oxetane compound, the oxetane compound which has at least 2 oxetanyl group in 1 molecule is mentioned, for example.

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) methylacrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or In addition to polyfunctional oxetanes, such as these oligomers or copolymers, the compound which has an oxetane group, novolak resin, poly (p-hydroxy styrene), a cardo type bisphenol, carlix arene, and carlis resorcinar arene Ether compounds with resins, such as resin which has hydroxyl groups, such as a silsesquioxane, are mentioned, In addition, the copolymer of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate, etc. are mentioned.

As the polyisocyanate compound, a polyisocyanate compound of Japanese Patent Application Laid-Open No. 5-9407 can be used, and the polyisocyanate compound is derived from an aliphatic, cyclic aliphatic or aromatic group substituted aliphatic compound containing at least two isocyanate groups. You may be. Specifically, difunctional isocyanates (for example, a mixture of 1,3-phenylenediisocyanate and 1,4-phenylenediisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4) Xylylene diisocyanate, bis (4-isocyanate-phenyl) methane, bis (4-isocyanatecyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc.), the bifunctional isocyanate and trimethyl Polyfunctional alcohols such as olpropane, pentaerythritol, glycerin and the like; An adduct of an alkylene oxide adduct of the polyfunctional alcohol and the difunctional isocyanate; Cyclic trimers such as hexamethylene diisocyanate, hexamethylene-1,6-diisocyanate and derivatives thereof; And the like.

As the isocyanate group blocking agent in the 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 its derivatives, alcohols (for example, isopropanol, tert-butanol and the like) ), Lactams (e.g. ε-caprolactam), phenols (e.g. phenol, cresol, p-tert-butylphenol, p-sec-butylphenol, p-sec-amylphenol, p-octylphenol , p-nonylphenol, etc.), heterocyclic hydroxyl compounds (e.g., 3-hydroxypyridine, 8-hydroxyquinoline, etc.), active methylene compounds (e.g., dialkylmaronates, methylethylketoxime, Acetylacetone, alkyl acetoacetate oxime, acetooxime, cyclohexanone oxime and the like). Besides these, compounds having at least one polymerizable double bond and at least one block isocyanate group in the molecule of JP-A-6-295060 can be used.

Examples of the melamine derivatives include methylolmelamine, alkylated methylolmelamine (compounds obtained by etherification of methylol with methyl, ethyl, butyl, etc.) and the like. These may be used individually by 1 type and may use 2 or more types together. Among them, alkylated methylolmelamine is preferred, and hexamethylated methylolmelamine is particularly preferable because of its good storage stability, and the effect of improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

---filler---

In the said photosensitive resin composition, an inorganic filler or an organic filler (organic filler) is used for the purpose of improving the surface hardness of a permanent pattern, or restraining a linear expansion coefficient low, or restraining the dielectric constant and dielectric loss of the cured film itself as needed. Fine particles) can be added. There is no restriction | limiting in particular as said inorganic filler, It can select from a well-known thing suitably, For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, fine powder silicon oxide, vapor phase silica, amorphous silica, crystalline silica, Fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica and the like. Among these, silica is preferable from the viewpoint of cold shock test resistance. The average particle diameter of the said inorganic filler is less than 10 micrometers, and its 3 micrometers or less are more preferable. If the said average particle diameter is less than 100 micrometers, it can prevent that resolution deteriorates 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, benzoguanamine resin, crosslinked polystyrene resin, etc. are mentioned. Moreover, the spherical porous microparticles | fine-particles which consist of a silica of about 0.3-5 micrometers of average particle diameters, oil absorption amount of about 100-20Om <^2> / g, crosslinking resin, etc. can be used.

As for the addition amount of the said filler, 5-60 mass% is preferable. When the addition amount is 5% by mass or more, the coefficient of linear expansion can be sufficiently reduced, and when the amount is 60% by mass or less, when the cured film is formed on the surface of the photosensitive layer, the film quality of the cured film is suppressed and the permanent pattern is suppressed. In the case of forming the wiring by use, it is possible to avoid the loss of the function as the protective film of the wiring.

--- Thermosetting Accelerators ---

In order to promote the thermosetting of the epoxy compound and the oxetane compound as the thermal crosslinking agent, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N as a thermosetting accelerator) , N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc., quaternary ammonium salt compounds (e.g., triethylbenzyl ammonium chloride, etc.) , Block isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives bicyclic amidine compounds and salts thereof (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl 4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4 -Methylimidazole, etc.), phosphorus compounds (for example, triphenylphosphine, etc.), guanamine compounds (for example, melamine, guanamine, acetoguanamine, benzogu Anamine, etc.), S-triazine derivatives (eg 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid And the like) can be used. These may be used individually by 1 type and may use 2 or more types together. In addition, as long as it can accelerate | stimulate reaction of the said hardening catalyst of the said epoxy resin compound, the said oxetane compound, or these, and a carboxyl group, there is no restriction | limiting in particular, You may use the compound which can promote the thermosetting of that excepting the above.

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 promote thermosetting of these and a carboxylic acid is 0.01-15 mass% normally.

Moreover, in order to promote the thermosetting of the epoxy compound as the said thermal crosslinking agent and the thermal crosslinking agents other than the said oxetane compound, as a thermosetting accelerator, for example, an amine compound (for example, dicyandiamide, benzyl dimethylamine, 4). -(Dimethylamino) -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 (e.g., dimethylamine, etc.), imidazole derivative bicyclic amidine compounds and salts thereof (e.g., imidazole, 2-methylimidazole, 2-ethyl Imidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl ) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (for example, triphenylphosphine, etc.), guanamine compounds (for example, melamine, guana , Acetoguanamine, benzoguanamine and the like, 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-tri Azine, isocyanuric acid adduct, etc. can be used. These may be used individually by 1 type and may use 2 or more types together. There is no restriction | limiting in particular as long as it can accelerate | stimulate reaction of the hardening catalyst of the said thermal crosslinking agent, or these and a carboxyl group, You may use the compound which can accelerate | stimulate thermosetting other than the above.

As for solid content in the said photosensitive resin composition of the said thermal crosslinking agent and the thermosetting accelerator which can promote thermosetting of these and carboxylic acid, 0.01-15 mass% is preferable.

--- Sensitizer ---

There is no restriction | limiting in particular as said sensitizer, Although it can select suitably from well-known sensitizers, For example, well-known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, , Fluorescein, eosin, erythrosin, rhodamine B, rose bengal), cyanines (e.g., indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (e.g., Merocyanine, carbomerocyanine), thiazines (e.g. thionine, methylene blue, toluidine blue), acridines (e.g. acridine orange, chloroflavin, acriflavin, 9 -Phenylacridine, 1,7-bis (9,9'-acridinyl) heptane), anthraquinones (e.g., anthraquinone), squaryliums (e.g., squarylium), Credons (e.g., acridon, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, 2-chloro -10-butylacridone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-blood) Lolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylamino coumarin, 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, and the like, and thioxanthone compounds (thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 1-chloro-4-propyl jade) Citioxanthone, Quantacure QTX, etc.), and the like, Japanese Patent Laid-Open No. 5-19475, Japanese Patent Laid-Open No. 7-271028, Japanese Patent Laid-Open No. 2002-363206 , Coumarin compounds described in Japanese Patent Application Laid-Open No. 2002-363207, Japanese Patent Application Laid-Open No. 2002-363208, Japanese Patent Application Laid-Open No. 2002-363209, etc.), among which a compound in which an aromatic ring and a heterocycle are condensed (Cyclic compound) is preferable, and heterocyclic ring-type ketone compound and acridines are more preferable. Among the heterocyclic ring-type ketone compounds, an acridon compound and a thioxanthone compound are particularly preferable.

As a combination of the photoinitiator and the sensitizer, for example, the electron transfer initiator described in Japanese Patent Application Laid-Open No. 2001-305734 [(1) electron supply initiator and sensitizing dye, (2) electron accepting initiator and sensitizing dye , (3) electron supplying initiator, sensitizing dye, and electron accepting initiator (three-way initiator)].

As for content of the said sensitizer, 0.01-4 mass% is preferable with respect to the all components of the photosensitive resin composition for photosensitive films, 0.02-2 mass% is more preferable, 0.05-1 mass% is especially preferable.

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 ---

You may add the said thermal polymerization inhibitor in order to prevent thermal superposition | polymerization or time-lapse superposition | polymerization of the said polymeric compound in the said photosensitive layer.

Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, and 4-methoxy-2-hydride. Roxybenzophenone, cuprous chloride, phenothiazine, chloranyl, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2'-methylenebis (4-methyl-6 t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, nitroso compound and Al Chelates and the like.

As for content of the said thermal polymerization inhibitor, 0.001-5 mass% is preferable with respect to the said photosensitive resin composition, 0.005-2 mass% is more preferable, 0.01-1 mass% is especially preferable.

If the said content is 0.001 mass% or more, the fall of stability at the time of storage can be prevented, and if it is 5 mass% or less, the sensitivity with respect to an active energy ray will become favorable.

--- plasticizer ---

The plasticizer may be added in order to control the film 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, Phthalic acid esters such as diallyl phthalate and octyl capryl phthalate; Glycol esters, such as triethylene glycol diacetate, tetraethylene glycol diacetate, dimethyl glycophthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, and triethylene glycol dicaprylic acid ester ; Phosphoric acid esters such as tricresyl phosphate and triphenyl phosphate; Amides such as 4-toluenesulfonamide, benzenesulfonamide, N-n-butylbenzenesulfonamide and N-n-butylacetoamide; Aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioctyl sebacate, dioctyl azelate and dibutyl maleate; Glycols such as polyethylene glycol and polypropylene glycol, such as triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, and 4,5-diepoxycyclohexane-1,2-dicarboxylic acid dioctyl Listed.

As for content of the said plasticizer, 0.1-50 mass% is preferable with respect to the all components of the said photosensitive layer, 0.5-40 mass% is more preferable, 1-30 mass% is especially preferable.

--- Coloring 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), Oramine (CI41000), Fat black HB (CI26150), Mono light yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hosta Bombred ESB (CI Pigment) Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Pastel Pink B Spura (CI Pigment Red 81), Monastral Fast Blue (CI Pigment Blue 15), Monolight Fast Black B (CI Pigment Black) 1), carbon, CI Pigment Red 97, C.I. Pigment Red 122, C.I. Pigment Red 149, C.I. Pigment Red 168, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 215, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Blue 15: 1, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 64, and the like. These may be used individually by 1 type and may use 2 or more types together. Moreover, the dye suitably selected from well-known dye can be used as needed.

Solid content in the said photosensitive resin composition solid content of the said coloring pigment can be determined in consideration of exposure sensitivity, resolution, etc. of the photosensitive layer at the time of permanent pattern formation, and it changes with kinds of the said coloring pigment, but is generally 0.01-10 Mass% is preferable and 0.05-5 mass% is more preferable.

--- Adhesive Promoter ---

In order to improve the adhesiveness between each layer, or the adhesiveness of a photosensitive layer and gas, a well-known so-called adhesion promoter can be used for each layer.

As said adhesion promoter, the adhesion promoter described in Unexamined-Japanese-Patent No. 5-11439, Unexamined-Japanese-Patent No. 5-34153132, Unexamined-Japanese-Patent No. 6-43638, etc. is mentioned preferably, for example. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl Triazole-2-thione, 3-morpholinomethyl-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 agent, etc. are mentioned.

0.001 mass%-20 mass% are preferable with respect to the all components of the said photosensitive layer, as for content of the said adhesion promoter, 0.01-10 mass% is more preferable, 0.1 mass%-5 mass% are especially preferable.

<Degassing process>

The defoaming step is a step of performing a defoaming treatment on the coating liquid.

There is no restriction | limiting in particular as a method of defoaming treatment, According to the objective, it can select suitably, For example, membrane defoaming using a vacuum pump, centrifugal defoaming using a centrifugal force, ultrasonic defoaming using an ultrasonic defoaming apparatus, etc. are mentioned. Especially, ultrasonic defoaming is preferable at the point of the effect which suppresses surface defects, such as a pinhole and agglomeration.

The said ultrasonic defoaming apparatus is an apparatus which promotes foaming of gas by generating a cavitation by ultrasonic irradiation. That is, defoaming of liquid is performed by foaming and dissolution of gas in liquid by the micro pressure fluctuation which generate | occur | produced locally. Although there is no restriction | limiting in particular in the pressure at the time of ultrasonic irradiation, Ultrasound irradiation at normal pressure is preferable from a viewpoint of gas solubility control. The control of the apparatus is controlling the output of the ultrasonic vibrator by the voltage value. Examples include connecting an ultrasonic vibrator to an ultrasonic transmitter from Alex Corporation or Honda Electronics in a pipe or tank.

There is no restriction | limiting in particular as conditions in the case of using the said ultrasonic defoaming apparatus, Although it can select suitably according to the objective, As an output, for example, 1V or more and 200V or less are preferable, 10V or more and 150V or less are more preferable, 30V or more and 110V or less The following is especially preferable.

There is no restriction | limiting in particular as conditions in the case of using a film | membrane degassing apparatus, Although it can select suitably according to the objective, As an output, for example, below atmospheric pressure is preferable, 0.01 atmosphere or more and 0.5 atmosphere or less are more preferable, 0.05 Particular preference is given to at least 0.15 atm.

<Application process>

The said coating process is a process of apply | coating the said coating liquid to a support body after the said defoaming process.

There is no restriction | limiting in particular as a coating method of the said coating liquid, According to the objective, it can select suitably, For example, the spray method, the roll coating method, the rotary coating method, the slit coat method, the extrusion coating method, the curtain coating method, Various coating methods, such as a die coat method, the gravure coat method, the wire bar coat method, the knife coat method, are mentioned.

Support

There is no restriction | limiting in particular as said support body, Although it can select suitably according to the objective, it is preferable that the said photosensitive layer is peelable, and that light transmittance is favorable, and that surface smoothness is more preferable.

The support is made of synthetic resin and is preferably 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 and vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoro Various plastic films, such as ethylene, a cellulose film, and a nylon film, are mentioned, A polyethylene terephthalate is especially preferable among these. These may be used individually by 1 type and may use 2 or more types together.

Although the thickness of the said support body does not have a restriction | limiting in particular, According to the objective, it can select suitably, For example, 2-150 micrometers is preferable, 5-100 micrometers is more preferable, 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, the elongate phase is preferable. There is no restriction | limiting in particular in the length of the said elongate support body, For example, the thing of the length of 10-20,000m is mentioned.

<Drying process>

The drying step is a step of drying the coating liquid to form a photosensitive layer on the support.

As said drying conditions, although it changes also with each component, a kind of solvent, a use ratio, etc., it is about 30 to 15 minutes normally at the temperature of 60-110 degreeC.

Photosensitive layer

There is no restriction | limiting in particular if the said photosensitive layer is a layer which consists of a photosensitive resin composition, 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, 4-30 micrometers is especially preferable.

There is no restriction | limiting in particular as lamination number of the said photosensitive layer, According to the objective, it can select suitably, For example, one layer may be sufficient and two or more layers may be sufficient.

According to the manufacturing method of the photosensitive film of this invention, since the film with few surface defects can be manufactured, the high-definition permanent pattern (protective film, an interlayer insulation film, a soldering resist pattern, etc.) excellent in insulation can be obtained efficiently.

(Photosensitive film)

The photosensitive film of this invention has a photosensitive layer which consists of a photosensitive resin composition of this invention on at least a support body and the said support body, and also has other layers suitably selected, such as a thermoplastic resin layer as needed.

The configuration of the support and the photosensitive layer is as described above.

<Other floors>

There is no restriction | limiting in particular as said other layer, According to the objective, it can select suitably, For example, layers, such as a protective film, a thermoplastic resin layer, a barrier layer, a peeling layer, an adhesive layer, a light absorption layer, a surface protective layer, are mentioned. The said photosensitive film may have these layers individually by 1 type, and may have 2 or more types.

<< protective film >>

The said photosensitive film may form a protective film on the said photosensitive layer.

As said protective film, what is used for the said support body, paper, the paper laminated | stacked polyethylene, a polypropylene, etc. are mentioned, for example, Among these, a polyethylene film and a polypropylene film are preferable.

Although the thickness of the said protective film does not have a restriction | limiting in particular, According to the objective, it can select suitably, For example, 5-100 micrometers is preferable, 8-50 micrometers is more preferable, 10-30 micrometers is especially preferable. .

As a combination (support / protective film) of the said support body and a protective film, it is polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, for example. And the like. Moreover, interlayer adhesive force can be adjusted by surface-treating at least any one of a support body and a protective film. The surface treatment of the support may be carried out in order to increase the adhesive force with the photosensitive layer, and for example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow discharge irradiation treatment, active plasma Irradiation treatment, laser beam irradiation treatment, and the like.

Moreover, 0.3-1.4 are preferable and, as for the static friction coefficient of the said support body and the said protective film, 0.5-1.2 are more preferable.

If the said static friction coefficient is 0.3 or more, it will become too smooth and it can prevent that a winding shift arises when it is set as a roll, and if it is 1.4 or less, it can wind up in a favorable roll shape.

It is preferable to wind the said photosensitive film, for example, by winding it in a cylindrical core and to roll it in the shape of a long picture. 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. Moreover, you may slit process so that a user may use it, and you may make the elongate body of the range of 100-1, OOm in roll shape. In this case, it is preferable that the support is wound up to the outermost side. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. In storage, it is preferable to provide a separator (particularly moisture-proof and desiccant-containing) on the end face from the viewpoint of protecting the end face and preventing edge fusion, and it is preferable to use a material having a low moisture permeability for packing.

You may surface-treat the said protective film in order to adjust the adhesiveness of the said protective film and the said photosensitive layer. The said surface treatment forms the primer layer which consists of polymers, such as a polyorganosiloxane, a fluorinated polyolefin, polyfluoroethylene, polyvinyl alcohol, on the surface of the said protective film, for example. Formation of the said primer layer can be formed by apply | coating the coating liquid of the said polymer to the surface of the said protective film, and then drying at 30-150 degreeC for 1 to 30 minutes. As for the temperature at the time of the said drying, 50-120 degreeC is especially preferable.

(Photosensitive laminated body)

The said photosensitive laminated body consists of at least base | substrate and the photosensitive layer formed on the said base | substrate, and consists of laminating | stacking the other layer suitably selected according to the objective.

The photosensitive layer is transferred from the photosensitive film produced by the above production method, and has the same configuration as above.

<Gas>

The substrate is a substrate to be formed on which the photosensitive layer is formed or a transfer target to which at least the photosensitive layer of the photosensitive film of the present invention is transferred. There is no particular limitation, and the base can be appropriately selected according to the purpose. It can be arbitrarily selected from those having high smoothness to those having uneven surfaces. A plate-shaped gas is preferable and a so-called substrate is used. Specifically, the substrate (print substrate), glass plate (soda glass plate, etc.) for manufacturing a well-known printed wiring board, a synthetic resin film, paper, a metal plate, etc. are mentioned.

<Method for Producing Photosensitive Laminate>

As a manufacturing method of the said photosensitive laminated body, the method of transferring and laminating | stacking at least any one of heating and pressurizing at least the photosensitive layer in the photosensitive film of this invention is mentioned.

The manufacturing method of the photosensitive laminated body is laminated | stacked on the surface of the said base, performing the photosensitive film of this invention at least any one of heating and pressurization. In addition, when the said photosensitive film has the said protective film, it is preferable to peel off the said protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base | substrate.

There is no restriction | limiting in particular in the said heating temperature, According to the objective, it can select suitably, For example, 15-180 degreeC is preferable and 60-140 degreeC is more preferable.

There is no restriction | limiting in particular in the pressure of the said pressurization, According to the objective, it can select suitably, For example, 0.1-1.0 MPa is preferable and 0.2-0.8 MPa is more preferable.

There is no restriction | limiting in particular as an apparatus which performs at least one of the said heating, According to the objective, it can select suitably, For example, a laminator (for example, VP-II by Taisei Laminator Co., Ltd., Nichigo-Morton Co. Ltd.). , VP 130, Ltd.).

Since the photosensitive film and the photosensitive laminate of the present invention have a uniform film thickness and an extremely low occurrence rate of surface defects such as pinholes and agglomeration, the photosensitive film has excellent insulation reliability and high-definition permanent patterns (protective film, interlayer insulating film, and solder). Resist patterns, 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 used especially for permanent pattern formation of a printed circuit board.

(Permanent pattern formation method)

The permanent pattern formation method of this invention includes an exposure process at least, and also contains other processes, such as a development process suitably selected as needed.

Exposure process

The said exposure process is a process of exposing to the photosensitive layer in the photosensitive laminated body of this invention. The photosensitive laminated body of this invention is as above-mentioned.

There is no restriction | limiting in particular as an object of the said exposure as long as it is a photosensitive layer in the said photosensitive laminated body, According to the objective, it can select suitably, For example, as mentioned above, heating and pressurizing a photosensitive film on a base material It is preferable to carry out about the laminated body formed by laminating | stacking while performing at least one.

There is no restriction | limiting in particular as said exposure, According to the objective, it can select suitably, Digital exposure, analog exposure, etc. are enumerated, 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, the image development process, the hardening process process, a post exposure process, etc. are mentioned.

<< Development process >>

The development is performed by removing the unexposed portion of the photosensitive layer.

There is no restriction | limiting in particular as a removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method of removing using a developing solution, etc. 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, a slightly alkaline aqueous solution is preferable. As a base component of the said weak alkaline aqueous solution, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate, pyrroline acid Sodium, potassium pyrrolate, borax and the like.

About 8-12 are preferable, for example, and, as for pH of the said weakly alkaline aqueous solution, about 9-11 are more preferable. As said weakly alkaline aqueous solution, 0.1-5 mass% sodium carbonate aqueous solution or potassium carbonate aqueous solution etc. are mentioned, for example.

Although the temperature of the said developing solution can be suitably selected according to the developability of the said photosensitive layer, about 25-40 degreeC is preferable, for example.

The developing solution may be a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.), or development. In order to make it, it may use together with an organic solvent (for example, alcohol, ketones, ester, ether, amide, lactone, etc.). The developing solution may be an aqueous developing solution obtained by mixing water or an alkali aqueous solution with an organic solvent, or may be an organic solvent alone.

<< hardening process >>

The said hardening process process is a process of performing hardening process with respect to the photosensitive layer in the formed pattern after the said image development process is performed.

There is no restriction | limiting in particular as said hardening process process, Although it can select suitably according to the objective, For example, a front surface exposure process, a front surface heat treatment, etc. are mentioned preferably.

As a method of the said front surface exposure process, the method of exposing the whole surface on the said laminated body in which the said permanent pattern was formed after the said image development is mentioned, for example. By the said front surface exposure, hardening of resin in the photosensitive resin composition which forms the said photosensitive layer is accelerated | stimulated, and the surface of the said permanent pattern is hardened.

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 preferably.

As a method of the said front surface heat processing, the method of heating the whole surface on the said laminated body in which the said permanent pattern was formed after the said image development is mentioned. By the front surface heating, the film strength of the surface of the permanent pattern is increased.

120-250 degreeC is preferable and, as for the heating temperature in the said front heating, 120-200 degreeC is more preferable. When the said heating temperature is 120 degreeC or more, a film | membrane intensity | strength improves by heat processing, and when it is 250 degrees C or less, decomposition | disassembly of resin in the said photosensitive resin composition will arise, and film | membrane quality can be prevented from falling back.

10-120 minutes are preferable and, as for the heat time in the said front heating, 15-60 minutes are more preferable.

There is no restriction | limiting in particular as an apparatus which performs said whole surface heating, It can select suitably from a well-known apparatus according to the objective, For example, a dry oven, a hotplate, an 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, a permanent pattern is formed on the printed wiring board by the permanent pattern forming method. Soldering can be performed as follows.

That is, by the said development, the hardened layer which is the said permanent pattern is formed, and a metal layer is exposed on the surface of the said printed wiring board. After plating with gold on the site | part of the metal layer exposed to the surface of the said printed wiring board, soldering is performed. Then, a semiconductor, a component, or the like is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer functions as a protective film or an insulating film (interlayer insulating film) and a solder resist, and the impact from the outside and the conduction of electrodes between neighbors are prevented.

(Printed board)

The printed board of this invention has at least a base | substrate and the permanent pattern formed by the said permanent pattern formation method, and has the other structure suitably selected as needed.

There is no restriction | limiting in particular as other structures, According to the objective, it can select suitably, For example, the buildup board | substrate etc. with which the insulating layer was formed between the base material and the said permanent pattern are mentioned.

(Example)

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Synthesis of Binder

159 g of 1-methoxy-2-propanol was put into a 1,000 mL three neck flask, and it heated to 85 degreeC under nitrogen stream. 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.) 3.0 g of 1-methoxy-2-propanol solution were added dropwise over 2 hours. After completion of the dropwise addition, the mixture was heated for 5 hours and further reacted. Then, heating was stopped and the copolymer of benzyl methacrylate / methacrylic acid (30/70 mol% ratio) was obtained.

Subsequently, 120.0 g of the copolymer solution was transferred to a 30 mL three-necked flask, 16.6 g of glycidyl methacrylate and 0.16 g of p-methoxyphenol were added, stirred, and dissolved. After dissolving, 3.0 g of triphenylphosphine was added while performing air bubbling, heating at 100 ° C., and after 20 minutes, glycidyl methacrylate was added to carry out addition reaction. The disappearance of glycidyl methacrylate was confirmed by gas chromatography and the heating was stopped. 1-methoxy-2-propanol was added and the solution of the binder represented by following structural formula (29) of 45 mass% of solid content was prepared.

It was 30,000 when the mass average molecular weight (Mw) of the obtained binder was measured by the gel permeation chromatography method (GPC) which made polystyrene the reference material. In addition, the acid value of solid sugar was 2.2 meq / g from the titration using sodium hydroxide. In addition, content (C = C value) of the ethylenically unsaturated bond of solid sugar calculated | required by iodine titration was 2.1 meq / g.

(Example 1)

Preparation of Photosensitive Resin Composition

Each component was mix | blended in the following quantity and the photosensitive resin composition solution (coating liquid) was prepared.

[Each component amount of photosensitive resin composition solution]

The binder (45 mass% of solid content mass in the 1-methoxy-2-propanol solution). 45.51 parts by mass

Pentaerythritol tetraacrylate (polymerizable compound). 11.03 parts by mass

-Photoinitiator represented by Structural formula (26). 0.35 parts by mass

Diethyl thioxanthone; 0.37 parts by mass

Bis F-type epoxy resin (thermal crosslinker, manufactured by Tohto Kasei Co., Ltd., YDF-170)

                                                  … 4.57 parts by mass

Thermosetting agent (dicyandiamide). 0.08 parts by mass

Silica SO-C2 (manufactured by Admatechs Co., Ltd.). 7.11 parts by mass

Color pigment (BASF, HELIOGEN BLUE D7086). 17 parts by mass

Methyl ethyl ketone. 16.74 parts by mass

Acetic acid normal profile… 13.96 parts by mass

In addition, the viscosity of the photosensitive resin composition solution was 40 mPa * s.

Production of Photosensitive Film

After passing the obtained photosensitive resin composition solution through the ultrasonic defoaming apparatus (SDF), it apply | coated on PET (polyethylene terephthalate) film of thickness of 16 micrometers as the said support body, and dried, and formed the photosensitive layer with a film thickness of 30 micrometers. Subsequently, the said photosensitive film was manufactured by laminating | stacking the polypropylene film of 20 micrometers thickness as said protective film on the said photosensitive layer. In addition, the ultrasonic defoaming apparatus used NEOSONIC series 0833-16 by Alex Corporation as a transmitter, the voltage value was set to 35V, and it adjusted and used the transmission output.

<Evaluation of surface defects>

Describe the evaluation order / standards. The photosensitive film produced by the above method was visually evaluated with red transmitted light. As an evaluation criterion, the bubble of 1 mm or more in diameter was aggregated (large), and 1 mm or less was called the aggregation (small). In addition, the size of the photosensitive film was 1 m <^2> .

Insulation Reliability Test

As a printed board, the chemical polishing process was performed and prepared on the surface of the copper clad laminated board (L / S-50micrometer / 50micrometer comb pattern, copper thickness 12micrometer) of completion of wiring formation. Lamination | stacking using the vacuum laminator (manufactured by Nichigo-Morton Co., Ltd., VP130) while peeling the protective film in the said photosensitive film so that the photosensitive layer of the said photosensitive film may contact the said copper clad laminated board on the said copper clad laminated board. The photosensitive laminated body by which the said copper clad laminated board, the said photosensitive layer, and the said polyethylene terephthalate film (support) were laminated | stacked in this order was prepared. The crimping conditions were 40 seconds of the vacuum process, 70 degreeC of crimping temperature, 0.2MPa of crimping pressure, and 10 second of pressurization time. Using this board | substrate, insulation reliability test was done using ETAC production and ion migration evaluation apparatus SIR12 on condition of 130 degreeC / 85% / 0.196 Mpa / 10V / 20Oh. In addition, the result described the number of the short-circuiting which carried out the 10 sample test. The results are shown in Table 1.

(Example 2)

Except having changed the conditions of SDF from 35V to 70V, it carried out similarly to Example 1, and manufactured the photosensitive film, and evaluated the surface defect and insulation reliability. The results are shown in Table 1.

(Example 3)

Except having changed the conditions of SDF from 35V to 100V, it carried out similarly to Example 1, and produced the photosensitive film, and evaluated the surface defect and insulation reliability. The results are shown in Table 1.

(Comparative Example 1)

Except having changed the conditions of SDF from 35V to 0V, it carried out similarly to Example 1, and produced the photosensitive film, and evaluated the surface defect and insulation reliability. The results are shown in Table 1.

A flaw Insulation Reliability Test Short Circuit Ratio Bundle bed (pcs / m2) Agglomeration station (pcs / m2) Example 1 6 487 3/10 Example 2 7 149 1/10 Example 3 2 37 0/10 Comparative Example 1 1212 > 500 10/10

The photosensitive film of the comparative example 1 which does not perform a defoaming process from Table 1 has many surface defects, and its insulation reliability is remarkably bad, whereas the photosensitive films of Examples 1-3 which performed the defoaming process have very few surface defects, and are excellent in insulation reliability. It is confirmed that it is excellent.

Since the coating liquid which performed the defoaming process in the photosensitive film of this invention can suppress the generation | occurrence | production rate of surface defects, such as a pinhole and agglomeration large, the photosensitive film excellent in insulation reliability, and the photosensitive laminated body can be provided. Therefore, since high-definition permanent patterns (protective film, interlayer insulating film, solder resist pattern, etc.) can be efficiently formed, they can be widely used for forming high-definition permanent patterns in the field of electronic materials. It can be used suitably for permanent pattern formation.

Since the permanent pattern forming method of the present invention uses the photosensitive film of the present invention, the permanent pattern forming method can be suitably used for forming various patterns requiring high-definition exposure, and in particular, it can be suitably used for permanent pattern formation of a printed board. .

Claims (10)

a coating liquid preparation step of preparing a coating liquid containing i) a photosensitive group and an acid group for imparting alkali developability, ii) a polymerizable compound, and iii) a photosensitive resin composition containing a photopolymerization initiator; A defoaming step of performing a defoaming treatment to the coating liquid; A coating step of applying the coating solution to a support after the defoaming step; And And drying the coating liquid to form a photosensitive layer on the support. The method of claim 1, The defoaming treatment is an ultrasonic defoaming method of producing a photosensitive film. The method of claim 1, The photosensitive resin composition further comprises iv) a thermal crosslinking agent. The method of claim 1, The said photosensitive resin composition contains the v) filler further, The manufacturing method of the photosensitive film characterized by the above-mentioned. The method of claim 1, The viscosity of the said coating liquid is 5 mPa * s-100 mPa * s, The manufacturing method of the photosensitive film characterized by the above-mentioned. The method of claim 5, The viscosity of the said coating liquid is 10 mPa * s-50 mPa * s, The manufacturing method of the photosensitive film characterized by the above-mentioned. a coating liquid preparation step of preparing a coating liquid containing i) a photosensitive group and an acid group for imparting alkali developability, ii) a polymerizable compound, and iii) a photosensitive resin composition containing a photopolymerization initiator; A defoaming step of performing a defoaming treatment to the coating liquid; A coating step of applying the coating solution to a support after the defoaming step; And As a photosensitive film produced by the method for producing a photosensitive film comprising a drying step of drying the coating solution to form a photosensitive layer on the support: It is elongate and is wound up in roll shape, The photosensitive film characterized by the above-mentioned. A photosensitive laminate comprising a substrate and a photosensitive layer formed on the substrate: The said photosensitive layer is a coating liquid preparation process which prepares the coating liquid containing the photosensitive group and the photosensitive resin composition containing the acid group for imparting alkali developability, ii) polymeric compound, and iii) photoinitiator. ; A defoaming step of performing a defoaming treatment to the coating liquid; A coating step of applying the coating solution to a support after the defoaming step; And A photosensitive laminated body, which is transferred from a photosensitive film produced by a method for producing a photosensitive film comprising a drying step of drying the coating liquid to form a photosensitive layer on the support. A photosensitive laminate comprising a substrate and a photosensitive layer formed on the substrate, the photosensitive layer comprising i) a compound having a photosensitive group and an acid group for imparting alkali developability, ii) a polymerizable compound, and iii) a photopolymerization initiator. Coating liquid preparation process which prepares the coating liquid containing the photosensitive resin composition to contain, The defoaming process of performing the defoaming process to the said coating liquid, The coating process of apply | coating the said coating liquid to a support body after the said defoaming process, and the said coating liquid At least an exposure step of performing exposure to the photosensitive layer in the photosensitive laminate transferred from the photosensitive film produced by the method for producing a photosensitive film by drying the photosensitive layer to form a photosensitive layer on the support. Permanent pattern formation method characterized by. A photosensitive laminate comprising a substrate and a photosensitive layer formed on the substrate, the photosensitive layer comprising i) a compound having a photosensitive group and an acid group for imparting alkali developability, ii) a polymerizable compound, and iii) a photopolymerization initiator. A coating liquid preparation step of preparing a coating liquid containing a photosensitive resin composition to contain, a degassing step of degassing the coating liquid, a coating step of applying the coating liquid to a support after the degassing step, and the coating liquid Permanent pattern which includes at least the exposure process which exposes the photosensitive layer in the photosensitive laminated body transferred from the photosensitive film produced by the manufacturing method of the photosensitive film including the drying process which forms a photosensitive layer on the said support body. A printed circuit board comprising a permanent pattern formed by a forming method.