JP2006343400A - Photosensitive resin film and method for manufacturing photoresist pattern using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin film for reducing sludge during development, and to provide a method for manufacturing a resist pattern using it. <P>SOLUTION: The photosensitive resin film consists of a laminate of a layer containing a curable resin component and a photocatalystic coating layer one after the other. The photocatalystic coating preferably contains anatase crystal titania. In addition, the photocatalystic coating layer is preferably a film for applying and drying liquid for forming a titania film mixing amorphous titania and anatase crystal titania or antase crystal/amorphous mixing titania sol solution containing the precursor and an organic substance. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive resin film and a method for producing a resist pattern using the same.

Conventionally, in the field of printed wiring board production, as a resist material used for etching, plating, and the like, a photosensitive resin composition and a photosensitive element obtained by laminating a support and a protective film are widely used. The printed wiring board is formed by laminating a photosensitive element on a copper substrate, exposing the pattern, removing the unexposed portion with a developer, performing etching or plating, and forming a pattern. It is manufactured by a method of peeling off from above.
As a developer for removing the unexposed portion, an alkali developing type using a sodium hydrogen carbonate solution or the like has become the mainstream, and the developer usually has an ability to dissolve the photosensitive resin composition layer to some extent. The photosensitive resin composition is dissolved or dispersed in the developer during development.
The dissolved or dispersed photosensitive resin composition forms aggregates in the developing solution, and the generation thereof is a problem. The aggregates are dispersed in the developer, and when the developer is sprayed again with a spray pump or the like, the aggregates adhere to the developed printed wiring board and cause unnecessary defects in the subsequent etching and plating processes. Cause it to occur.
This aggregate is generally called scum. In recent years, it is considered that a photopolymerization initiator contained in a photosensitive resin composition is involved as one of the causes of scum.

JP 2002-351070 A JP 2003-248308 A JP 2003-149809 A

  The present invention has been made to solve the above-described problems, and uses a resin composition obtained by removing a photopolymerization initiator considered as one of the causes of scum generation from a photosensitive resin composition. By providing a photocatalytic coating instead of the polymerization initiator, it is an object of the present invention to provide a photosensitive resin film having low scum generation and a method for producing a photoresist pattern using the same.

The present invention relates to (1) a photosensitive resin film obtained by sequentially laminating a layer containing a curable resin component and a photocatalytic coating layer.
The curable resin component used in the present invention does not actively contain a photopolymerization initiator in order to prevent the occurrence of scum. Therefore, it is impossible to form a photoresist pattern by using a layer containing a curable resin component alone, exposing through a pattern mask, and subsequently developing. Therefore, by laminating a photocatalytic coating on the layer containing the curable resin component and exposing from the photocatalytic coating, the photocatalytic coating generates active species only in the portion irradiated with actinic rays. Is used for the reaction of the curable resin composition to form a pattern.
The present invention also relates to (2) the photosensitive resin film as described in (1) above, wherein the photocatalytic film contains anatase type crystalline titania.
The present invention also provides: (3) A liquid for forming a titania film, wherein the photocatalytic coating layer is a mixture of an anatase crystal / amorphous mixed titania sol solution containing amorphous titania and anatase crystal titania or a precursor thereof, and an organic substance. The photosensitive resin film according to (1) or (2) above, wherein the film is formed by coating and drying.
In addition, the present invention provides (4) a titania film formation in which the photocatalytic coating layer is formed by mixing an anatase crystal / amorphous mixed titania sol solution containing amorphous titania and anatase crystal titania or a precursor thereof and an organic substance. The present invention relates to the photosensitive resin film according to any one of the above (1) to (3), which is a film formed by applying and drying a liquid and exhibits organic matter resolution when irradiated with ultraviolet rays.
The present invention also provides: (5) The photocatalytic coating layer is coated on a support in advance, and a layer containing a curable resin component is laminated on the coated photocatalytic coating layer. It relates to the photosensitive resin film in any one of.
In the present invention, (6) a layer containing a curable resin component contains (A) a binder polymer and (B) a photopolymerizable compound having at least one ethylenically unsaturated group in the molecule as an essential component. The present invention relates to the photosensitive resin film according to any one of (1) to (5). In this invention, you may contain the amount of (C) photoinitiators as needed.
Moreover, this invention relates to the photosensitive resin film as described in said (6) characterized by the weight average molecular weight of (7) (A) binder polymer being 20,000 or more.
Further, the present invention provides (8) (A) the binder polymer as described in (6) or (7) above, wherein the binder polymer is a vinyl polymerization type polymer binder having an acid value of 30 to 200 mgKOH / g. The present invention relates to a photosensitive resin film.
In addition, the present invention provides (9) any one of (6) to (8) above, wherein component (A) is 40 to 80 parts by weight and component (B) is 20 to 60 parts by weight. It relates to the photosensitive resin film described. The component (C) that may be blended as necessary is preferably 0 to 10 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B).
In addition, according to the present invention, (10) after forming the photosensitive resin film according to any one of (1) to (9) above on a substrate, exposure through a pattern mask, followed by development The present invention relates to a method for manufacturing a photoresist pattern.

Occurs when using a photosensitive resin composition containing a conventional photopolymerization initiator by using a photosensitive resin film obtained by sequentially laminating a layer containing a curable resin component of the present invention and a photocatalytic coating layer. Generation of scum during development can be remarkably suppressed. As a result, the cause of generating unnecessary defects in the etching or plating process is removed, which is useful for increasing the density of printed wiring board circuits and improving the workability of manufacturing.
A pattern can be formed on a layer (resin composition layer) containing a curable resin component by providing a photocatalytic coating on a layer containing a curable resin component that does not actively contain the photopolymerization initiator of the present invention. We found a new pattern formation technique that can be done. By using this method, a pattern can be formed without using a photopolymerization initiator that is presumed to be involved in the cause of scum generation in the developer. Therefore, low scum generation can be expected, and high density of printed wiring board circuits can be expected. It is useful for improving workability in manufacturing and manufacturing.

Hereinafter, the present invention will be described in detail.
The layer containing the curable resin component used in the present invention is a component obtained by removing the photopolymerization initiator from the photosensitive resin composition. However, a photopolymerization initiator in a range that does not affect scum generation may be contained. The photosensitive resin composition preferably contains (A) a binder polymer and (B) a photopolymerizable compound having at least one ethylenically unsaturated group in the molecule. Here, the (meth) acrylic acid described later in the present invention means acrylic acid and methacrylic acid corresponding thereto, and (meth) acrylate means acrylate and methacrylate corresponding thereto.

  Examples of the (A) binder polymer in the present invention include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins. An acrylic resin is preferable from the viewpoint of alkali developability. These can be used alone or in combination of two or more binder polymers. Examples of combinations of two or more types of binder polymers include two or more types of binder polymers composed of different copolymer components, two or more types of binder polymers having different weight average molecular weights, and two or more types of binder polymers having different degrees of dispersion. Can be mentioned. A polymer having a multimode molecular weight distribution described in JP-A No. 11-327137 can also be used. In addition, the binder polymer may have a photosensitive group as necessary. The binder polymer of component (A) can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of polymerizable monomer pairs include polymerizable styrene derivatives such as styrene, vinyl toluene, α-methyl styrene, p-methyl styrene, and p-ethyl styrene, and vinyl alcohols such as acrylamide, acrylonitrile, and vinyl-n-butyl ether. Esters of (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2 , 2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) Acrylic acid, β-furyl (meth) Maleic acid monoesters such as crylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic Acid, itaconic acid, crotonic acid, propiolic acid and the like can be mentioned. These may be used alone to form a homopolymer, or two or more types may be combined to form a copolymer.

  Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth ) Hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and structural isomers thereof. These can be used alone or in combination of two or more.

  (A) The binder polymer preferably contains a carboxyl group from the viewpoint of alkali developability. For example, the binder polymer is obtained by radical polymerization of a polymerizable monomer having a carboxyl group and other polymerizable monomers. Can be manufactured. The polymerizable monomer having a carboxyl group is preferably methacrylic acid from the viewpoint of stability. (A) The acid value of the binder polymer is preferably 30 mgKOH / g or more from the viewpoint of development time, and preferably 200 mgKOH / g or less from the viewpoint of developer resistance of the photocured resist. / G is more preferable. When solvent development is performed as the development step, it is preferable to prepare a polymerizable monomer having a carboxyl group in a small amount. (A) The weight average molecular weight of the binder polymer (measured by gel permeation chromatography (GPC) and converted by a calibration curve using standard polystyrene) is preferably 20,000 or more from the viewpoint of developer resistance. From the viewpoint of development time, it is preferably 300,000 or less, more preferably 25,000 to 150,000.

  Examples of the photopolymerizable compound (B) having at least one ethylenically unsaturated group in the molecule in the present invention include bisphenol A (meth) acrylate compounds. Although there is no restriction | limiting in particular in a bisphenol A type (meth) acrylate compound, For example, it is preferable that it is a compound represented by general formula (I).

前記一般式（Ｉ）中、Ｒ^１及びＲ^２は、各々独立に水素原子又はメチル基を示す。前記一般式（Ｉ）中、Ｘ及びＹは各々独立に炭素数２〜６のアルキレン基を示し、エチレン基又はプロピレン基であることが好ましく、エチレン基であることがより好ましい。前記一般式（Ｉ）中、ｐ及びｑはｐ＋ｑ＝４〜４０となるように選ばれる正の整数であり、６〜３４であることが好ましく、８〜３０であることがより好ましく、８〜２８であることが特に好ましく、８〜２０であることが非常に好ましく、８〜１６であることが非常に特に好ましく、８〜１２であることが極めて好ましい。ｐ＋ｑが４未満では、（Ａ）成分との相溶性が低下する傾向があり、ｐ＋ｑが４０を超えると親水性が増加し硬化膜の吸水率が高くなる傾向がある。
前記炭素数２〜６のアルキレン基としては、エチレン基、プロピレン基、イソプロピレン基、ブチレン基、ペンチレン基、へキシレン基等が挙げられる。
また、前記一般式（Ｉ）中の芳香環は置換基を有していてもよく、それら置換基としては、例えば、ハロゲン原子、炭素数１〜２０のアルキル基、炭素数３〜１０のシクロアルキル基、炭素数６〜１８のアリール基、フェナシル基、アミノ基、炭素数１〜１０のアルキルアミノ基、炭素数２〜２０のジアルキルアミノ基、ニトロ基、シアノ基、カルボニル基、メルカプト基、炭素数１〜１０のアルキルメルカプト基、アリル基、水酸基、炭素数１〜２０のヒドロキシアルキル基、カルボキシル基、アルキル基の炭素数が１〜１０のカルボキシアルキル基、アルキル基の炭素数が１〜１０のアシル基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルコキシカルボニル基、炭素数２〜１０のアルキルカルボニル基、炭素数２〜１０のアルケニル基、炭素数２〜１０のＮ−アルキルカルバモイル基又は複素環を含む基、これらの置換基で置換されたアリール基等が挙げられる。上記置換基は、縮合環を形成していてもよい。また、これらの置換基中の水素原子がハロゲン原子等の上記置換基などに置換されていてもよい。また、置換基の数がそれぞれ２以上の場合、２以上の置換基は各々同一でも相違していてもよい。

In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. In the general formula (I), X and Y each independently represent an alkylene group having 2 to 6 carbon atoms, preferably an ethylene group or a propylene group, and more preferably an ethylene group. In the general formula (I), p and q are positive integers selected so that p + q = 4 to 40, preferably 6 to 34, more preferably 8 to 30, and more preferably 8 to 28 is particularly preferred, 8-20 is very preferred, 8-16 is very particularly preferred, and 8-12 is very particularly preferred. When p + q is less than 4, the compatibility with the component (A) tends to decrease, and when p + q exceeds 40, the hydrophilicity increases and the water absorption rate of the cured film tends to increase.
Examples of the alkylene group having 2 to 6 carbon atoms include an ethylene group, a propylene group, an isopropylene group, a butylene group, a pentylene group, and a hexylene group.
In addition, the aromatic ring in the general formula (I) may have a substituent, and examples of the substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a cyclohexane having 3 to 10 carbon atoms. Alkyl group, aryl group having 6 to 18 carbon atoms, phenacyl group, amino group, alkylamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, A C1-C10 alkyl mercapto group, an allyl group, a hydroxyl group, a C1-C20 hydroxyalkyl group, a carboxyl group, a C1-C10 carboxyalkyl group, and a C1-C10 alkyl group. 10 acyl groups, C1-C20 alkoxy groups, C1-C20 alkoxycarbonyl groups, C2-C10 alkylcarbonyl groups, C2-C10 alkyls Alkenyl group, N- alkylcarbamoyl group or a group containing a heterocyclic ring having 2 to 10 carbon atoms, an aryl group substituted by these substituents. The above substituents may form a condensed ring. Moreover, the hydrogen atom in these substituents may be substituted with the above substituents such as a halogen atom. When the number of substituents is 2 or more, each of the two or more substituents may be the same or different.

  Examples of the compound represented by the general formula (I) include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-((meth) acrylic). Loxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) Examples thereof include bisphenol A-based (meth) acrylate compounds such as propane.

  Examples of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonane) Xyl) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2 , 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy) Hexadecaethoxy) phenyl) propane and the like, and 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is BPE- 00 (available from Shin-Nakamura Chemical Co., Ltd., product name) and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) is BPE-1300 (Shin-Nakamura Chemical Co., Ltd.) It is commercially available as a company-made product name). These may be used alone or in combination of two or more.

  Examples of the 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptapropoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth) a) Liloxynonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxydodecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetradecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl) propane, 2,2-bis (4-((meta And acryloxyhexadecapropoxy) phenyl) propane. These may be used alone or in combination of two or more.

  Examples of the 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane. 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane and the like. . These may be used alone or in combination of two or more.

Examples of the compound similar to the bisphenol A-based (meth) acrylate compound include a compound obtained by adding acrylic acid to bisphenol A-diepoxy. Viscoat # 540 (product name, manufactured by Osaka Organic Chemical Industry Co., Ltd.) is commercially available. These may be used alone or in combination of two or more.
Examples of the photopolymerizable compound other than the bisphenol A (meth) acrylate compound include tricyclodecane dimethanol, neopentyl glycol-modified trimethylolpropane diacrylate, and, for example, polyhydric alcohol reacted with α, β-unsaturated carboxylic acid. A compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid, a urethane monomer such as a (meth) acrylate compound having a urethane bond, nonylphenyldioxylene (meth) acrylate, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β′- (Meth) acryloyloxyethyl Examples include o-phthalate, (meth) acrylic acid alkyl ester, EO-modified nonylphenyl (meth) acrylate, etc., but it is possible to use a photopolymerizable compound having one polymerizable ethylenically unsaturated bond in the molecule. preferable. These may be used alone or in combination of two or more (where EO represents ethylene oxide).

  Examples of the compound obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 2 propylene groups. 14 polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, Trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropanetetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetramethylolmethanetri (meta) ) Acrylate, tetramethylolmethane tetra (meth) acrylate, polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. It is done.

The blending amount of component (A) is preferably in the range of 40 to 80 parts by weight and more preferably 45 to 70 parts by weight with respect to 100 parts by weight of the total amount of components (A) and (B). preferable. If the blending amount is less than 40 parts by weight, the photocured product tends to be brittle and tends to be inferior in coating properties, and if it exceeds 80 parts by weight, the sensitivity tends to be insufficient.
The blending amount of the component (B) is preferably in the range of 20 to 60 parts by weight, more preferably 30 to 50 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). preferable. If the blending amount is less than 20 parts by weight, the resolution tends to decrease, and if it exceeds 60 parts by weight, edge fusion tends to occur.
The resin composition containing the essential components as described above may further include a dye such as malachite green, a photochromic agent such as tribromophenylsulfone or leucocrystal violet, a thermochromic inhibitor, p-toluenesulfonamide, if necessary. Such as plasticizers, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion-imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc. (A) About 0.01 to 20 parts by weight can be contained per 100 parts by weight of the total amount of the component and the component (B). These may be used alone or in combination of two or more.

The curable resin component used in the present invention including the above components can be obtained, for example, by uniformly kneading and mixing the blended components with a roll mill, a bead mill or the like. If necessary, it can be dissolved in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof to obtain a solid content of 30 It can be applied as a solution of about ˜60% by weight.
A photosensitive resin film obtained by sequentially laminating a layer containing a curable resin component and a photocatalytic coating layer is used in the form of an element coated with a protective film such as a polymer film such as polyethylene or polypropylene as necessary. be able to.
Next, for the element according to the present invention, that is, the element in which the photosensitive resin film formed by sequentially laminating the layer containing the curable resin component of the present invention and the photocatalytic coating layer is formed on the support, explain.
The element includes a support and the photosensitive resin film of the present invention formed thereon. As the support, for example, a polymer film such as polyethylene terephthalate, polypropylene, polyethylene, or polyester can be preferably used. The thickness of the polymer film is preferably about 1 to 100 μm. The method for forming the photosensitive resin film of the present invention on the support is not particularly limited, but by applying and drying a solution that becomes a layer containing a curable resin component, a solution that becomes a photocatalytic coating layer is also formed. It can implement preferably by laminating | stacking the layers obtained by apply | coating and drying. Although the thickness of the layer containing the curable resin component which forms the photosensitive resin film layer changes with uses, it is preferable that it is about 1-100 micrometers. The coating can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, or a bar coater. Drying can be performed at 70 to 150 ° C. for about 5 to 30 minutes. In addition, the amount of the remaining organic solvent in each layer is preferably 2% by weight or less from the viewpoint of preventing the organic solvent from diffusing in a later step. The polymer film used as a support may be used as a protective film to cover the layer surface. As the protective film, those having a smaller adhesive force between the photosensitive resin film layer and the protective film than the adhesive force between the photosensitive resin film layer and the support are preferable, and a film with a low fish eye is preferable. Furthermore, the photosensitive element may have intermediate | middle layers and protective layers, such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer other than the photosensitive resin film, a support body, and a protective film.
The manufactured element is stored, for example, as it is or by further laminating a protective film on the surface of the photosensitive resin film and winding it around a cylindrical core. In addition, it is preferable to wind up so that a support body may become an outer side at this time. An end face separator is preferably installed on the end face of the roll-shaped photosensitive element roll from the viewpoint of end face protection, and a moisture-proof end face separator is preferably installed from the viewpoint of edge fusion resistance. Moreover, as a packing method, it is preferable to wrap and package in a black sheet with low moisture permeability. Examples of the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).

The components of the photocatalytic coating layer in the present invention include amorphous titanium oxide (amorphous titania) and anatase crystalline titanium oxide (anatase crystalline titania) or anatase crystal / amorphous mixed titanium oxide sol (amorphous mixed) containing a precursor thereof. Titania sol) solution and an organic substance, which are diluted with a solvent or a dispersion medium, and subjected to coating and drying to obtain a photocatalytic coating film.
An anatase crystal / amorphous mixed titanium oxide sol solution containing amorphous titanium oxide and anatase crystal titanium oxide or a precursor thereof is obtained by the following method.
A titanium hydroxide gel called orthotitanic acid is prepared from an aqueous solution of a titanium compound selected from titanium chloride and titanium sulfate such as titanium tetrachloride and a basic solution such as ammonia and caustic soda. Subsequently, byproducts and impurities such as ammonium ions and chlorine ions are appropriately removed by decantation using water, and precipitated titanium hydroxide is separated. At this time, by-products and impurities can be appropriately removed using an ion exchange resin.
Further, hydrogen peroxide water is allowed to act to decompose and remove excess hydrogen peroxide, whereby a tan transparent viscous liquid, that is, an amorphous titanium oxide sol solution (I) can be obtained. When titanium hydroxide is reacted with hydrogen peroxide solution, heat is generated. Therefore, it is necessary to manage the liquid temperature at -5 to 40 ° C. At this time, since there is foaming, care must be taken so that the contents do not flow out of the container. As will be described later, this liquid is considered to contain peroxidized titanium hydroxide and is essentially different from a commercially available TiO ₂ sol. When this amorphous titanium oxide sol solution (I) is further heated at 65 ° C. or higher, a part of the titanium oxide crystallizes into the anatase type crystalline titanium oxide through the precursor, and a part of the titanium oxide becomes anatase crystal or a precursor thereof. An anatase crystal / amorphous mixed titanium oxide sol solution is obtained. In this case, the heating temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, so as to perform the reaction promptly. Is 95 ° C. or lower.

Alternatively, when the amorphous type titanium oxide sol solution (I) is further heated at 65 to 120 ° C. for 4 to 40 hours, anatase type titanium oxide sol solution in which a part or all of the titanium oxide becomes anatase type crystals or precursors thereof. (II) can be obtained, and the anatase type titanium oxide sol solution (I) and the anatase type titanium oxide sol solution (II) obtained above can be appropriately mixed to obtain an anatase crystal / amorphous mixed titanium oxide sol solution. The resulting anatase crystal / amorphous mixed titanium oxide sol solution and an organic substance can be mixed to obtain a photocatalytic film-forming liquid.
The titanium compound used as a raw material is preferably an inexpensive and easily handled chloride or oxalate such as titanium tetrachloride, and the basic solution for producing a precipitate of titanium hydroxide is ammonia water, caustic soda, etc. Is preferred. It is preferable to use a combination such that the salt formed as a by-product of the reaction becomes stable and harmless sodium chloride, sodium sulfate, ammonium chloride or the like.
The concentration of the titanium compound is not particularly limited, but the reaction is usually carried out with an aqueous solution obtained by diluting a commercially available aqueous solution at a concentration of 5 to 80% by weight to 0.3 to 10% by weight. If the concentration of the titanium compound is less than 0.3% by weight, it tends to take time to form a precipitate, and if it exceeds 10% by weight, it tends to be difficult to control the temperature during the formation of the precipitate. The pH for precipitation is preferably 1 to 3, more preferably about 2, and it is particularly preferable to adjust the pH so that impurities such as Fe do not coprecipitate. Moreover, it is preferable to produce | generate precipitation for 1 to 24 hours at 5-40 degreeC. The water used for decantation is preferably ion-exchanged water, and more preferably pure water using both ion exchange and distillation.

  Precipitated titanium hydroxide (sometimes called orthotitanic acid) is in a gel state polymerized by OH polymerization or hydrogen bonding, and cannot be used as a coating solution for a titanium oxide film. When hydrogen peroxide water is added to this titanium hydroxide in the gel state, a part of OH is in a peroxidized state and dissolved as a peroxotitanate ion, or becomes a kind of sol state in which the polymer chain is divided into low molecules, Excess hydrogen peroxide is decomposed into water and oxygen, and can be used as a viscous liquid for forming a titanium oxide film. Since this titanium oxide sol solution contains only oxygen and hydrogen in addition to titanium, only water and oxygen are generated when it is changed to titanium oxide by drying or firing, so carbon required for thermal decomposition methods such as sol-gel methods and sulfates. It is not necessary to remove components and halogen components, and a crystalline titanium oxide film having a relatively high density can be manufactured even at a lower temperature than conventional. Further, since the pH is weakly acidic to weakly alkaline, it is not necessary to consider the influence on the human body during use or corrosion of the base material. Furthermore, hydrogen peroxide acts not only as a solubilizer but also as a stabilizer, and is extremely stable in the room temperature range of the sol and can withstand long-term storage.

  From the viewpoint of safety, hydrogen peroxide is preferably used in an amount of 1 to 40% by weight of hydrogen peroxide, and the amount added is in a weight ratio with respect to the titanium hydroxide gel solid content, preferably titanium hydroxide / hydrogen peroxide. = 1 / 0.7 to 1 / 1.5, preferably 0.5 to 6 hours with stirring. Thereafter, pure water combined with ion exchange and distillation is added so that the concentration of titanium oxide is preferably 0.5 to 3% by weight, whereby a titanium oxide sol solution can be obtained.

  The organic substance used in the liquid for forming the photocatalytic film has a photocatalytic ability that is manifested when ultraviolet light is applied to a film obtained by coating and drying the titanium oxide sol solution containing anatase crystal / amorphous mixed titanium oxide. , A film obtained by applying and drying a titanium oxide sol solution containing anatase crystal / amorphous mixed titanium oxide used for this, and having a higher photocatalytic ability when the same ultraviolet rays are applied, or anatase crystal / amorphous mixed titanium oxide When mixed with a titanium oxide sol solution containing, the organic matter resolution that appears when UV is applied to the film formed by coating and drying, the titanium oxide sol solution containing the anatase crystal / amorphous mixed titanium oxide used for this is coated and dried It is higher than the organic matter resolution that appears when the same ultraviolet rays are applied to the film. The current value (A) generated when ultraviolet rays are applied to a film formed by coating and drying a titanium oxide sol solution containing an anatase crystal / amorphous mixed titanium oxide is used for the anatase used in this. A current value (B) generated when the same ultraviolet ray is applied to a film obtained by applying and drying a titanium oxide sol solution containing crystal / amorphous mixed titanium oxide, or an oxide containing anatase crystal / amorphous mixed titanium oxide The band gap (B) of the film formed by applying and drying the titanium oxide sol solution containing the anatase crystal / amorphous mixed titanium oxide used in the film (A) of the film formed by coating and drying the titanium sol solution. For example, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatics , Aliphatic and alicyclic alcohols, ketones, esters and ethers, heterocycle-containing compounds, amine-modified compounds, silicone-modified compounds, various polymers, and the like. It is not limited to. A band gap is an energy difference between a conduction band and a valence band. A material having a large band gap is an insulator, a material having a small band gap is a semiconductor, and a material having no band gap is a conductor.

Among these organic substances, from the viewpoint of mixing with an aqueous dispersion such as titanium oxide sol and improving wettability to a water-repellent substrate, organic substances having an alkyl silicate structure in the molecule or Those having an ether structure are preferred, and those having both an alkyl silicate structure and a polyether structure in the molecule are more preferred.
Here, the alkyl silicate structure refers to a structure in which an alkyl group is added to a silane atom of a siloxane skeleton. Specifically, those having a siloxane bond (—Si—O—) represented by polydimethylsiloxane as the main chain are suitable, but not limited thereto.
The polyether structure means a structure in which an alkylene group is bonded by an ether bond, such as polyalkylene oxide. Specifically, it has a structure such as polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide block copolymer, polyethylene polytetramethylene glycol copolymer, polytetramethylene glycol-polypropylene oxide copolymer. Things. Among them, the polyethylene oxide-polypropylene oxide block copolymer is more suitable from the viewpoint of controlling the wettability depending on the block degree and molecular weight, but is not limited thereto.

As the organic substance having both an alkyl silicate structure and a polyether structure in the molecule, specifically, polyether-modified polysiloxane-based additives such as polyether-modified polydimethylsiloxane can be used. A polyethylene oxide-polypropylene oxide block copolymer-modified polydimethylsiloxane obtained by reacting a terminal methacrylic polyethylene oxide-polypropylene oxide block copolymer with dihydropolydimethylsiloxane is preferably used.
The molecular weight of the organic substance having both the alkyl silicate structure and the polyether structure is preferably 100 to 10,000, more preferably 500 to 7,000 in terms of weight average molecular weight in terms of polystyrene by gel permeation chromatography. 000 to 4,000 is more preferable. If the molecular weight is less than 100, the wettability with the substrate tends to be poor, and if the molecular weight exceeds 10,000, the stability of the titanium sol tends to be adversely affected. As such an organic substance having both an alkyl silicate structure and a polyether structure, for example, a polyether-modified polydimethylsiloxane sold by Nippon Unicar Co., Ltd. under the trade name FZ-2161 can be used.
In any case, the organic substance mixed in the titanium oxide sol solution containing the anatase crystal / amorphous mixed titanium oxide is preferably soluble in the solvent or dispersion medium of the titanium oxide sol solution containing the anatase crystal / amorphous mixed titanium oxide.
Here, the ratio of the anatase crystal / amorphous mixed titanium oxide to the organic substance is preferably 1: 0.01 to 1:10 in the weight ratio of the former: the latter, and 1: 0.05 to 1: 2. More preferred is 1: 0.1 to 1: 0.5. When the ratio of the organic substance is less than 0.01 with respect to the anatase crystal / amorphous mixed titanium oxide 1, the wettability may be poor and it may not be applied to the base material. There is a tendency to be inferior to the improvement effect. On the other hand, when the ratio of the organic substance exceeds 10 with respect to the anatase crystal / amorphous mixed titanium oxide 1, the film forming property at normal temperature (20 to 25 ° C.) tends to be poor, or the durability of the coating film tends to be poor. There is.

Although there is no restriction | limiting in particular as a solvent or a dispersion medium used for the photocatalytic film of this invention, Water is the most preferable in the meaning of the stability of the liquid for titanium oxide film formation. From the viewpoint of excellent dispersibility of the titanium oxide sol, water, an organic solvent or a water-organic solvent mixture is preferable. The water / organic solvent mixing ratio is preferably 30 to 99% by weight of water and more preferably 40 to 95% by weight of the total amount of water and organic solvent from the viewpoint that gelation hardly occurs. Preferably, the amount of the organic solvent is preferably 1 to 70% by weight, and more preferably 5 to 60% by weight.
From the viewpoint of the stability of the titanium oxide film-forming liquid, the solvent or the dispersion medium preferably does not contain impurities such as ions. For example, ion-exchanged water is preferable, and pure water that combines ion exchange and distillation is used. Water is particularly preferred.
Examples of the organic solvent used as a solvent or dispersion medium include alcohols, cellosolves such as butyl cellosolve and ethyl cellosolve, carbitols such as methyl carbitol, ethyl carbitol, and butyl carbitol, and lactones such as γ-butyrolactone. Preferably used. The alcohol refers to a hydrocarbon compound that is liquid at room temperature and has a hydroxyl group. Examples thereof include ethanol, methanol, isopropanol, and the like, but are not limited thereto. Among the above solvents, water is suitable from the viewpoints of safety and storage stability. Among these, ethanol is suitable.

  To the above-mentioned liquid for forming a titanium oxide film, known surfactants, antifoaming agents, leveling agents, coupling agents, preservatives, dyes, pigments, fillers, etc. are added to the titanium oxide film forming liquid as needed. Can also be added. If necessary, acrylic resins other than the organic substances, polyester resins, melamine resins, urea resins, polyamide resins, polyimide resins, epoxy resins, phenol resins, ketone resins, polyurethane resins, fluorine resins, silicone resins, cellulose, etc. These polysaccharides and various resins such as silicone, amine, and epoxy-modified resin can be added to such an extent that the characteristics of the titanium oxide film are not impaired.

  The method for mixing the materials used in the present invention and producing the liquid for photocatalytic coating used in the present invention is not particularly limited as long as it is a method capable of uniformly dispersing and mixing, for example, a dissolver, a static mixer, Examples thereof include a homogenizer, a stirring device such as paint shaking.

  The photocatalytic film forming method in the present invention may be formed by applying the liquid for forming the photocatalytic film in advance on a support on which the layer containing the curable resin component is laminated, and drying the film. A layer containing a resin component may be formed on a substrate and then formed by applying or impregnating a photocatalytic coating. Although there is no particular limitation, a layer containing a photocatalytic coating-forming liquid as a support or a curable resin component After the coating or impregnation, a dense titanium oxide film having excellent adhesion can be formed by drying at 100 ° C. or lower. In this sense, the drying temperature after applying or impregnating the photocatalytic film forming liquid onto the support or the layer containing the curable resin component is preferably 10 to 100 ° C., and the drying time is the film thickness, solvent or dispersion. Although depending on the medium, 0.5 to 24 hours are preferable.

Specific coating or impregnation methods include spray coating, dip coating, flow coating, spin coating, roll coating, curtain coating, bar coating, ultrasonic coating, screen printing, and brush coating. Sponge coating or the like can be applied, but in the case of a liquid for forming a photocatalytic film having a low viscosity, a spray coating method is preferable.
The thickness of the photocatalytic film is not particularly limited, but is preferably 0.05 to 1.5 μm, more preferably 0.1 to 1.0 μm, and further preferably 0.2 to 0.5 μm. If it is less than 0.05 μm, sufficient photocatalytic ability tends to be not obtained, and if it exceeds 1.5 μm, the color of titanium oxide appears and the transparency decreases, or the adhesion to the substrate decreases. There is a tendency to be easily peeled off.

Next, a method for producing a photoresist pattern according to the present invention will be described.
First, the above-described photosensitive resin film of the present invention is laminated on a substrate (circuit forming substrate). As a lamination method, when a protective film is present prior to lamination, the film is laminated on the substrate while removing the protective film. For example, a method of laminating by heating the photosensitive resin film to about 70 to 130 ° C. and press-bonding to the circuit forming substrate with a pressure of about 0.1 to 1 MPa (about 1 to 10 kgf / cm ² ). It is also possible to laminate under reduced pressure. A circuit-forming substrate generally has a surface provided with a metal layer as a work layer, and the substrate surface on which the photosensitive resin film is laminated is usually a metal surface, but there is no particular limitation. . On the resulting substrate, a photosensitive resin film, and in some cases, a support is laminated.
After the lamination of the elements is completed, the photocatalytic coating layer in the exposed area is irradiated with light by irradiating an actinic ray in an image form. As a method of irradiating an actinic ray in an image form, an actinic ray can be radiated in an image form on the photocatalytic coating layer through a mask pattern to irradiate the photocatalytic coating layer in the exposed portion. The mask pattern may be a negative type or a positive type, and a commonly used one can be used. As the light source of actinic light, a known light source, for example, a light source that effectively emits ultraviolet light, visible light, or the like, such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, or a xenon lamp is used. Further, laser direct drawing exposure can be performed without using a mask pattern.
After exposure, the photocatalytic film layer in the unexposed area and the layer containing the curable resin component in the lower layer, and the photocatalytic film layer in the exposed area are selectively removed by development to form a layer containing the curable resin component. A resist pattern is formed, and a resist pattern laminated substrate is obtained. In the development step, when a support is present, the support is removed prior to development. Development is performed by removing the photocatalytic coating layer present in the unexposed area and the exposed area by wet development, dry development or the like using a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. It is preferable to use the alkaline aqueous solution. For example, a dilute solution of 0.1 to 5 wt% sodium carbonate, a dilute solution of 0.1 to 5 wt% potassium carbonate, a dilute solution of 0.1 to 5 wt% sodium hydroxide, and the like can be given. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the resin composition layer. Further, a surfactant, an antifoaming agent, an organic solvent, or the like may be mixed in the alkaline aqueous solution. Examples of the development method include a dip method, a spray method, brushing, and slapping.
As a process after development, a pattern formed by heat treatment at about 60 to 250 ° C. may be further cured as necessary.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples without departing from the technical idea of the present invention.
In the examples, “%” means% by weight.
The material shown in Table 1 was blended to obtain a solution that forms a layer containing a curable resin component. Moreover, the material shown in Table 2 was blended to obtain a solution for forming a photocatalytic coating layer.

※１ ＥＯ変性ビスフェノールＡジメタクリレート（日立化成工業株式会社製）
２ トリメチロールプロパントリアクリレート（新中村化学工業株式会社製品名）
３ ２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン（チバスペシャルティケミカルズ株式会社製品名）

* 1 EO-modified bisphenol A dimethacrylate (manufactured by Hitachi Chemical Co., Ltd.)
2 Trimethylolpropane triacrylate (product name of Shin-Nakamura Chemical Co., Ltd.)
3 2,2-dimethoxy-1,2-diphenylethane-1-one (Ciba Specialty Chemicals Co., Ltd. product name)

Next, the solution containing the curable resin component obtained in Table 1 was uniformly applied onto a 16 μm thick polyethylene terephthalate film, dried for 10 minutes with a 100 ° C. hot air convection dryer, and then made of polyethylene. An element was obtained by protection with a protective film (tensile strength in the film longitudinal direction: 16 MPa, tensile strength in the film width direction: 12 MPa, trade name: NF-15, manufactured by Tamapoly Co., Ltd.). The film thickness after drying of the layer containing the curable resin component was 30 μm.
The solution to be a photocatalytic coating layer obtained in Table 2 was applied with a bar coater onto a polyethylene terephthalate film having a release agent applied to a 38 μm-thick surface, and dried with a hot air convection dryer at 60 ° C. for 30 minutes. Thus, a photocatalytic coating was obtained.
On the other hand, the copper surface of a copper-clad laminate (trade name (MCL-E-67) manufactured by Hitachi Chemical Co., Ltd.), which is a glass epoxy material in which copper foil (thickness 35 μm) is laminated on both sides, is applied to a brush equivalent to # 600. Polishing was performed using a polishing machine (manufactured by Sankei Co., Ltd.), washed with water, and dried with an air flow. The obtained copper-clad laminate was heated to 80 ° C., and the layer containing the curable resin component of the element was laminated on the copper surface through a laminating roll heated to 110 ° C. while peeling off the polyethylene protective film. . Next, the polyethylene terephthalate film present on the layer containing the curable resin component was removed, and the photocatalytic coating layer was laminated on the exposed layer containing the curable resin component under the same lamination conditions. That is, the structure of the finished laminate is a copper-clad laminate, a layer containing a curable resin component, a photocatalytic coating layer, and a release polyethylene terephthalate film from the bottom.
Next, using a parallel light exposure machine (manufactured by Oak Manufacturing Co., Ltd.) EXM1201 having a high-pressure mercury lamp lamp, a negative for resolution and adhesion evaluation was adhered, and 200 mJ / cm ² , 2000 mJ / cm ² , 5000 mJ / cm ² , It was exposed in 10000mJ / cm ^2. After the exposure, the release polyethylene terephthalate film was peeled off, and a 1% by weight aqueous sodium carbonate solution was sprayed at 30 ° C. for 30 seconds to remove unexposed portions.
The amount of sludge was measured by dissolving the film in 1% by weight Na ₂ CO ₃ aqueous solution so as to be 0.6 m ² · mil / l (mil = 25.4 μm), 30 ° C./90 min, 0.6 kgf / cm ^2. The mixture was stirred under the following conditions. After stirring, 10 ml each was collected, and the precipitate from which the supernatant was removed under a condition of 2000 rpm / 10 mim by removing the supernatant was dried at 120 ° C./2 hours and weighed. These measurement results are shown in Table 3.

Evaluation of pattern formability ◎: A resist pattern is formed ○: A resist pattern is formed but resolution is inferior △: A resist pattern is partially formed ×: A resist pattern cannot be formed

From the results of Table 3, even if the layer containing the curable resin component does not contain (C) a photopolymerization initiator, a reaction occurs only in the exposed portion by forming a photocatalytic coating to form a pattern. Turned out to be. The amount of sludge has also been reduced to near the detection limit.
New pattern formation that a pattern can be formed in a layer containing a curable resin component by providing a photocatalytic coating layer on a layer containing a curable resin component that does not actively contain the photoinitiator of the present invention I found a method. By using this method, a pattern can be formed without using a photoinitiator that is presumed to be involved in the cause of scum generation in the developer. Therefore, scum generation is extremely small and the printed circuit board density is increased. And it is useful for improving the workability of manufacturing.

Claims (10)

A photosensitive resin film obtained by sequentially laminating a layer containing a curable resin component and a photocatalytic coating layer. The photosensitive resin film according to claim 1, wherein the photocatalytic film contains anatase type crystalline titania. The photocatalytic coating layer is a film formed by applying and drying a titania film forming liquid obtained by mixing an anatase crystal / amorphous mixed titania sol solution containing an amorphous titania and anatase crystal titania or a precursor thereof and an organic substance. The photosensitive resin film of Claim 1 or Claim 2 characterized by the above-mentioned. The photocatalytic coating layer is a film formed by applying and drying a titania film forming liquid obtained by mixing an anatase type crystal / amorphous mixed titania sol solution containing an amorphous type titania and anatase type crystal titania or a precursor thereof and an organic substance. The photosensitive resin film according to any one of claims 1 to 3, which exhibits organic matter resolution when irradiated with ultraviolet rays. The photosensitive resin film according to any one of claims 1 to 4, wherein the photocatalytic coating layer is coated on a support in advance, and a layer containing a curable resin component is laminated on the coated photocatalytic coating layer. The layer containing a curable resin component contains (A) a binder polymer and (B) a photopolymerizable compound having at least one ethylenically unsaturated group in the molecule as essential components. A photosensitive resin film according to any one of the above. (A) The weight average molecular weight of a binder polymer is 20,000 or more, The photosensitive resin film of Claim 6 characterized by the above-mentioned. The photosensitive resin film according to claim 6 or 7, wherein the binder polymer (A) is a vinyl polymerization type polymer binder having an acid value of 30 to 200 mgKOH / g. The photosensitive resin film according to any one of claims 6 to 8, wherein the component (A) is 40 to 80 parts by weight and the component (B) is 20 to 60 parts by weight. 10. A photoresist pattern produced by forming a photosensitive resin film according to claim 1 on a substrate, exposing through a pattern mask, and subsequent development steps. Method.