JP2006098565A - Cover film for photosensitive layer and pattern exposure method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cover film for photosensitive layer which can be applied for directly plotting by a laser exposure of 405 nm, prevents deterioration of the sensitivity of a photosensitive layer due to oxygen and has satisfactory handleability, adhesiveness and strippability, and to provide a pattern exposure method that uses the cover film for photosensitive layer. <P>SOLUTION: In the method for forming a pattern by performing exposure and development with respect to the photosensitive layer, the cover film for photosensitive layer is disposed and used on the photosensitive layer and has a total light transmittance of 70% or higher for a laser beam of wavelength 405 nm. In the pattern exposure method, exposure is performed to the photosensitive layer, on which the cover film for photosensitive layer is disposed by using a laser beam of wavelength 395 to 415 nm. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a photosensitive layer cover film that is used to prevent a decrease in sensitivity due to oxygen in a photosensitive layer during pattern formation, and a pattern exposure method using the photosensitive layer cover film.

  In recent years, high-density mounting and various types of printed circuit boards are rapidly progressing, and high density and high productivity are strongly demanded. In conventional analog exposure systems using photomasks, poor development due to photomask contamination caused by contact between the wiring pattern and through-hole land pattern due to expansion and contraction due to temperature and humidity changes of the photomask film, and contact with the photosensitive layer There are problems such as.

  Therefore, as an exposure apparatus that performs photolithography without using a photomask, laser light such as a semiconductor laser or gas laser is directly scanned on the photosensitive composition based on digital data such as a wiring pattern, and patterning is performed. There has been proposed an exposure apparatus using a laser direct imaging system (hereinafter also referred to as “LDI”). However, the exposure apparatus using LDI has a problem that it takes more time for exposure than a conventional analog exposure system and is inferior in productivity. Therefore, a high-output UV laser line head or a highly sensitive photosensitive composition is used. Development is required.

  Conventionally, in order to shorten the exposure time at the time of exposure by an exposure apparatus using a 300 nm to 700 nm ultraviolet light or visible light laser light source and to improve productivity, photo-radical polymerization type photosensitivity is used as a highly sensitive photosensitive composition. Although a photosensitive composition is known (see Patent Documents 1 and 2), in this case, there is a problem that the polymerization reaction is inhibited by the influence of oxygen during exposure, and the sensitivity of the photosensitive composition is lowered.

  Therefore, in order to prevent the influence of oxygen during exposure, a dry film resist having a support that functions as an oxygen blocking layer during exposure has been put into practical use (see Patent Document 3). However, in addition to the problem that the image formed on the photosensitive composition layer is blurred due to the influence of light scattering and refraction by the support, a high resolution cannot be obtained. Currently, a liquid resist is selected.

As a technique for preventing polymerization inhibition by oxygen in a liquid resist, a method of performing exposure in the presence of an inert gas such as nitrogen (see Patent Document 4) or a method of unevenly distributing an oxygen blocking substance on the surface of a photosensitive layer (Patent) Document 5) has been proposed.
A pattern forming method (see Patent Document 6) in which a cover coat formed of polyvinyl alcohol or the like is laminated on a photosensitive layer has also been proposed. However, the solder resist used in the LDI can be compatible with a 365 nm or 405 nm UV laser, and has high productivity (high-definition pattern drawing, high-precision pattern alignment, etc.) and high productivity by photomaskless exposure. There is no disclosure or suggestion about achieving both.

  Therefore, it can be applied to direct writing by laser exposure of 405 nm, can prevent the sensitivity of the photosensitive layer from being lowered by oxygen, and can achieve both high density in pattern formation and high productivity by photomaskless exposure. The present situation is that the layer cover film and the pattern exposure method are not yet sufficiently satisfactory.

U.S. Pat. No. 2,850,445 Japanese Patent Publication No. 44-20189 US Pat. No. 3060026 JP-A-5-265221 JP 7-168347 A Japanese Patent Laid-Open No. 7-120930

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention can be applied to direct drawing by laser exposure at 405 nm, can prevent the sensitivity of the photosensitive layer from being lowered by oxygen, and has a good handling property, adhesion and peelability. And a pattern exposure method.

Means for solving the problems are as follows. That is,
<1> In a method of forming a pattern by exposing and developing a photosensitive layer, the pattern is formed on the photosensitive layer and used, and the total light transmittance with respect to a laser beam having a wavelength of 405 nm is 70% or more. It is a photosensitive layer cover film characterized by being.
<2> The photosensitive layer cover film according to <1>, wherein an oxygen permeability during exposure is 600 mL / m ² · day · MPa or less.
<3> The photosensitive layer cover film according to any one of <1> to <2>, wherein a resist adhesion preventing layer is provided on the support for the photosensitive layer cover film. In the photosensitive layer cover film according to <3>, since the resist adhesion preventing layer is provided, adhesion of an uncured photosensitive layer can be prevented when peeling from the photosensitive layer.
<4> The antistatic agent is contained on the support for the photosensitive layer cover film, and the surface resistance of the surface is 10 ¹⁵ Ω / □ or less in an environment of a temperature of 10 ° C. and a relative humidity of 33%. The photosensitive layer cover film according to any one of <1> to <3>. In the photosensitive layer cover film according to <4>, since the antistatic agent is contained, adhesion of foreign matters due to charging can be prevented when peeling from the photosensitive layer.
<5> The photosensitive layer cover film according to any one of <1> to <4>, wherein an undercoat layer is provided between the support for the photosensitive layer cover film and the resist adhesion preventing layer. In the photosensitive layer cover film as described in <5>, since it has the said undercoat layer, it is excellent in the adhesiveness of the said support body for photosensitive layer cover films, and the said resist adhesion prevention layer.
<6> The method according to any one of <1> to <5>, wherein at least the surface of the photosensitive layer cover film on the support for the photosensitive layer cover film on which the resist adhesion preventing layer is not laminated is subjected to uneven processing. It is a photosensitive layer cover film. In the photosensitive layer cover film according to <6>, the surface on which the resist adhesion prevention layer is not laminated, that is, the surface of the surface that does not adhere to the photosensitive layer is subjected to uneven processing. Excellent adsorptivity to adsorption means such as a translucent member of the frame.
<7> The photosensitive layer cover film according to any one of <1> to <6>, wherein a protective material is laminated on the resist adhesion preventing layer in the photosensitive layer cover film.
<8> The photosensitive layer cover film according to <1> to <7>, which is long and wound in a roll shape.
<9> The photosensitive layer cover film according to <8>, wherein the photosensitive layer cover film is a multilayer formed by laminating a plurality of photosensitive layer cover films, and is used by peeling one by one.
<10> The photosensitive layer cover film according to <9> to <9>, wherein the film is disposed on the photosensitive layer and is in close contact with the photosensitive layer under reduced pressure.
<11> The photosensitive layer cover film according to <1> to <10>, wherein the exposure is performed with a laser beam having a wavelength of 395 to 415 nm having pattern information.
<12> The photosensitive layer cover film according to any one of <1> to <11>, wherein the photosensitive layer is a photosensitive layer formed by applying a photosensitive composition to a surface of a substrate and drying. is there.
<13> A photosensitive film in which a photosensitive layer includes a photosensitive layer support, and a photosensitive layer formed by applying a photosensitive composition to the surface of the photosensitive layer support and drying the photosensitive layer in this order. A photosensitive layer formed by laminating the substrate on the substrate so that the surface opposite to the substrate for the photosensitive layer is in contact with the substrate, and then peeling the substrate for the photosensitive layer. The photosensitive layer cover film according to any one of <1> to <11>.
<14> The photosensitive layer cover film according to any one of <1> to <13>, which is used when a permanent pattern is formed after development.
<15> The photosensitive layer cover film according to <14>, which is used when forming at least one of a protective film and an interlayer insulating film.
<16> The photosensitive layer cover film according to <14>, which is used when forming a wiring pattern.
<17> Using a photosensitive composition colored in at least three primary colors of R, G, and B, a photosensitive layer is sequentially formed for each color of R, G, and B in a predetermined arrangement on the surface of the substrate. The photosensitive layer cover film according to any one of <1> to <16>, which is used when a color filter is formed by repeating a step, an exposure step, and a development step.
<18> A pattern exposure method, wherein the photosensitive layer on which the photosensitive layer cover film according to any one of <1> to <17> is disposed is exposed with a laser beam having a wavelength of 395 to 415 nm. It is.
<19> A photosensitive film in which a photosensitive layer includes a support for a photosensitive layer and a photosensitive layer formed by applying a photosensitive composition to the surface of the support for the photosensitive layer and drying it in this order. Is formed by laminating the substrate on the substrate so that the surface opposite to the substrate for the photosensitive layer is in contact with the substrate, and then peeling the substrate for the photosensitive layer. > The pattern exposure method described in the above.
<20> The photosensitive layer cover film according to <18>, wherein the photosensitive layer is formed by applying a photosensitive composition to a surface of a substrate and drying.

  According to the present invention, conventional problems can be solved, and it can be applied to direct drawing by laser exposure of 405 nm, can prevent the sensitivity of the photosensitive layer from being lowered by oxygen, and has good handling properties, adhesion and peelability. A photosensitive layer cover film and a pattern exposure method using the same can be provided.

(Photosensitive layer cover film)
The photosensitive layer cover film of the present invention is used by being disposed on the photosensitive layer in a method of forming a pattern by exposing and developing the photosensitive layer.
In addition, it is preferable that after being disposed on the photosensitive layer, it is brought into close contact with the photosensitive layer under reduced pressure.
Furthermore, the photosensitive layer cover film is preferably used repeatedly at least twice.

The total light transmittance of the photosensitive layer cover film with respect to a laser beam having a wavelength of 405 nm is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more. When the total light transmittance is less than 70%, the exposure sensitivity of the photosensitive layer is lowered, and the pattern formed by scattering of laser light may be deformed or defective.
The method for measuring the total light transmittance is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an integrating sphere and a spectrophotometer capable of irradiating 405 nm light (for example, Shimadzu Corporation) And UV-2400).

The photosensitive layer cover film preferably has an oxygen permeability of at least 600 mL / m ² · day · MPa or less, and more preferably 400 mL / m ² · day · MPa or less.
If the oxygen permeability exceeds 600 mL / m ² · day · MPa, the oxygen layer may not be sufficiently blocked, and the sensitivity of the photosensitive layer may be reduced.
Here, the oxygen permeability can be measured in accordance with, for example, the method described in ASTM standards D-1434-82 (1986).

There is no restriction | limiting in particular as an aspect of the said photosensitive layer cover film, Although it can select suitably according to the objective, For example, (1) The aspect which has a resist adhesion prevention layer on the support body for photosensitive layer cover films (FIG. 38), (2) an embodiment having an undercoat layer between the support for the photosensitive layer cover film and the resist adhesion prevention layer (FIG. 39), and (3) a resist adhesion prevention layer on the support for the photosensitive layer cover film A mode having an antistatic layer containing an antistatic agent on the surface of the non-stacked surface (FIG. 40), (4) having an undercoat layer and a resist adhesion preventing layer on one side of the support for the photosensitive layer cover film An embodiment having an antistatic layer on the other surface (FIG. 41), (5) An embodiment having a resist adhesion preventing layer on a support for a photosensitive layer cover film, and having a protective material on the resist adhesion preventing layer (FIG. 41) 42) .
The photosensitive layer cover film having the resist adhesion preventing layer is laminated so that the resist adhesion preventing layer is in contact with the surface of the photosensitive layer (FIG. 44).

-Support for photosensitive layer cover film-
The support for the photosensitive layer cover film that can be used for the photosensitive layer cover film is not particularly limited as long as the photosensitive layer can be peeled off and has good light transmittance, and is appropriately selected according to the purpose. 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, Various pluses such as polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulose film, nylon film, etc. Kkufirumu. These may be used alone or in combination of two or more thereof.
Among these, a polyethylene terephthalate film is preferable from the viewpoint of mechanical strength characteristics, deterioration due to laser light, and transparency, and a biaxially stretched polyester film is particularly preferable.
Examples of the photosensitive layer support include photosensitive layers described in JP-A-4-208940, JP-A-5-80503, JP-A-5-173320, JP-A-5-72724, and the like. Supports can also be used.

The thickness of the support for the photosensitive layer cover film is not particularly limited as long as it has good adhesion following the photosensitive layer under reduced pressure and has good handling properties in the laminating step and the peeling step. However, for example, it is preferably 1 to 200 μm, more preferably 3 to 150 μm, and particularly preferably 5 to 100 μm.
When the thickness of the support for the photosensitive layer cover film is less than 1 μm, the oxygen barrier property is insufficient and the sensitivity of the photosensitive layer may be reduced. When the thickness exceeds 200 μm, scattering of exposure light increases. While the resolution of the photosensitive layer is lowered, the followability to the photosensitive layer is deteriorated, which may cause burning.

  There is no restriction | limiting in particular as a shape of the said support body for photosensitive layer cover films, According to the objective, it can select suitably, A single sheet form may be sufficient and a long form may be sufficient. In the case of the long shape, for example, a length of 10 m to 20000 m can be mentioned.

-Resist adhesion prevention layer-
The photosensitive layer cover film has a resist adhesion preventing layer on the photosensitive layer cover film support in order to prevent adhesion of an uncured photosensitive layer when peeling from the photosensitive layer after exposure. Is preferred.
The resist adhesion preventing layer is not particularly limited as long as it can prevent adhesion of an uncured photosensitive layer, and can be appropriately selected depending on the purpose, and includes, for example, a siloxane polymer and a fluorine atom-containing polymer. It is preferable that it is formed by applying a binder polymer in which these are mixed.

Examples of the siloxane polymer include polyalkylsiloxanes such as dimethylpolysiloxane, and graft polymers having a unit derived from an organic compound having a siloxane bond as a branch component.
Examples of the fluorine atom-containing polymer include fluorinated olefin polymers such as polyvinylidene fluoride and polyfluoroethylene, and graft polymers having units derived from fluorine atom-containing monomers as branch components.
Examples of the graft polymer having, as a branch component, a unit derived from an organic compound having a siloxane bond and a unit derived from the fluorine atom-containing monomer include a silicone macromonomer and a perfluoroalkyl macromonomer. As well, comb-shaped graft polymers that are synthesized by copolymerization with acrylic, urethane, polyester-based monomers, etc., each having a trunk portion that is a resin polymer and having a siloxane bond or a fluorine atom in a branch portion, etc. It is done.

  Examples of the binder polymer include urethane resins, acrylic resins, vinyl chloride resins, alkyd resins, polyester resins, vinylidene chloride resins, amino resins, melamine resins, and the like. You may use, and 2 or more types may be mixed and used for it.

  There is no restriction | limiting in particular as a ratio in the case of mixing the said graft polymer with the said binder polymer, Although it can select suitably, For example, the said graft polymer is 1-100 mass with respect to 100 mass parts of said binder polymers. Part is preferable, and 2 to 30 parts by mass is more preferable.

The resist adhesion preventing layer may contain an antistatic agent described later.
Further, for the purpose of improving the adhesion with the photosensitive layer, a known additive such as a pigment is added to the resist adhesion preventing layer within a range that does not impair transparency and does not cause significant scattering of exposure light. May be.
Furthermore, for the purpose of improving the solvent resistance of the resist adhesion preventing layer, a known thermal crosslinking agent or a photocurable resin may be blended. By improving the solvent resistance, it is possible to improve the resistance to the solvent used when cleaning the dirt and foreign matter on the photosensitive layer cover film.

  In order to improve the adhesion between the resist adhesion preventing layer and the photosensitive layer cover film support, a surface treatment of the photosensitive layer cover film support may be performed. Examples of the surface treatment include formation of an undercoat layer described later, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.

  As thickness of the said resist adhesion prevention layer, 0.05-5 micrometers is preferable and 0.1-2 micrometers is more preferable. When the thickness is less than 0.05 μm, the peelability from the photosensitive layer may be lowered, and when it exceeds 2 μm, the transparency may be lowered and the resolution may be lowered.

-Antistatic agent-
Examples of the antistatic agent include surfactants, inorganic salts, polyhydric alcohols, metal compounds, carbon, conductive metal oxide fine particles, and the like, and these may be included in the resist adhesion layer. You may form an antistatic layer by apply | coating on the said support body for photosensitive layer cover films.
The antistatic layer may be formed between the resist adhesion layer and the support for the photosensitive layer cover film, and the surface on which the resist adhesion layer is not formed on the support for the photosensitive layer cover film. It may be formed on the surface.

The surface resistance of the surface containing the antistatic agent is preferably 1 × 10 ¹⁵ Ω / □ or less, preferably 1 × 10 ¹³ Ω / □ or less in an environment of 10 ° C. and 33% RH. More preferred.

As the antistatic agent added to the resist adhesion layer, nonionic, anionic, cationic or zwitterionic compounds can be used.
Nonionic antistatic agents include, for example, ethylene oxide adducts of higher alcohols, ethylene oxide adducts of alkylphenols, esters (for example, esters of higher fatty acids and polyhydric alcohols, polyethylene glycol esters of higher fatty acids, etc.), poly And ethers and amides (for example, higher fatty acid amides, dialkylamides, dialkylamides, ethylene oxide adducts of higher fatty acid amides) and the like.
Examples of the anionic antistatic agent include alkyl allyl sulfonic acid, adipic acid, glutamic acid, alkyl sulfonates, alkyl sulfate, polyoxyethylene alkyl phosphate, fatty acid salt, alkyl benzene sulfonate, alkyl naphthalene sulfonate, and so on. Examples thereof include diasialkylsulfosuccinate.
Cationic antistatic agents include amines (eg, alkylamine phosphates, Schiff bases, amidoamines, polyethyleneimines, complexes of amidoamines and metal salts, amino acid alkyl esters, etc.), imidazolines, amine ethylene oxide additions Body, and quaternary ammonium salts.
Zwitterionic antistatic agents include N-acyl sarcosinates, aminocarboxylic acid derivatives, alanine-type metal salts, imidazoline-type metal salts, carboxylic acid-type metal salts, dicarboxylic acid-type ordered salts, diamine-type metal salts, and Examples thereof include metal salts having an ethylene chloride group.

  In addition, an inorganic electrolyte, metal powder, metal oxide, kaolin, silicate, carbon powder, carbon fiber, and the like can be added, and antistatic properties can be imparted by graft polymerization and polymer blending.

  As the antistatic layer, a coating liquid for forming an antistatic layer in which conductive metal oxide particles are dispersed in a binder composed of a polymer such as an acrylic resin, a vinyl resin, a polyurethane resin, and a polyurethane resin and a melamine compound. It is preferably formed by applying and drying by a known method. As said polymer, an acrylic resin and a polyurethane resin are preferable, and an acrylic resin is especially preferable.

Examples of the material of the conductive metal oxide particles include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO, MoO ₃ , and composite oxides thereof, and metal oxides thereof. Examples thereof include metal oxides containing different atoms in the product. As the metal oxide, ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ and MgO are preferable, ZnO, TiO ₂ , SnO ₂ and In ₂ O ₃ are more preferable, and SnO ₂ is particularly preferable. . Examples of the metal oxide containing different atoms include Al or In for ZnO, Nb or Ta for TiO ₂ , Sn for In ₂ O ₃ , and Sb, Nb for SnO ₂ , Or what doped 0.01-30 mol%, preferably 0.1-10 mol% of halogen elements is mentioned. When the amount of the different element added is within the above range, sufficient conductivity can be obtained, and blackening of the antistatic layer can be prevented.
Other preferable examples of the material of the conductive metal oxide particles include those having an oxygen defect in the crystal structure.

As content of the electroconductive metal oxide particle in the said antistatic layer, 10 to 1000 weight% is preferable with respect to the said binder, and it is preferable that it is 200 to 800 weight%.
In order to minimize light scattering, the conductive metal oxide is preferably particles having an average particle diameter of 0.001 to 0.5 μm, and preferably 0.003 to 0.2 μm. More preferred. Here, the average particle size includes not only the primary particle size of the conductive metal oxide particles but also the particle size of a higher order structure.

  When adding conductive metal oxide particles to the coating solution for forming the antistatic layer, it may be added and dispersed as it is, or dispersed in a solvent such as water (including a dispersant and a binder as necessary). The dispersion may be added. From the viewpoint of maintaining a good working environment and preventing air pollution, the polymer and the melamine compound are preferably water-soluble or used in an aqueous dispersion state such as an emulsion. The polymer preferably has a methylol group, a hydroxyl group, a carboxyl group, or a glycidyl group so that a crosslinking reaction with the melamine compound is possible, and preferably has a hydroxyl group and a carboxyl group. It is more preferable to have a group. The content of the hydroxyl group or carboxyl group in the polymer is preferably 0.01 to 40 mol% / kg, more preferably 0.1 to 25 mol% / kg.

Examples of the acrylic resin include acrylic acid esters such as acrylic acid and alkyl acrylate, methacrylic acid esters such as acrylamide, acrylonitrile, methacrylic acid and alkyl methacrylate, and monomers of any one of methacrylamide and methacrylonitrile. Examples include homopolymers and copolymers obtained by polymerization of two or more of these monomers. Among these, homopolymers of monomers of any one of acrylic acid esters such as alkyl acrylate and methacrylic acid esters such as alkyl methacrylate, and copolymer obtained by polymerization of two or more of these monomers Coalescence is preferred. For example, homopolymers of monomers of acrylic acid esters having 1 to 6 carbon atoms and methacrylic acid esters, and copolymers obtained by polymerization of two or more of these monomers It is done.
The acrylic resin uses, for example, a monomer having any group of a methylol group, a hydroxyl group, a carboxyl group, and a glycidyl group so that a crosslinking reaction with the melamine compound is possible with the composition as a main component. It is a polymer obtained in this way.

Examples of the vinyl resin include polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl holmar, polyvinyl butyral, polyvinyl methyl ether, polyolefin, ethylene / butadiene copolymer, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, and chloride. And vinyl / (meth) acrylic acid ester copolymer and ethylene / vinyl acetate copolymer (preferably, ethylene / vinyl acetate / (meth) acrylic acid ester copolymer). Among these, polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl polymer, polyolefin, ethylene / butadiene copolymer, and ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / (meth) acrylic acid ester copolymer). Polymer) is preferred.
In the polyvinyl resin, polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl holmar, polyvinyl butyral, polyvinyl methyl ether, and polyvinyl acetate so that a crosslinking reaction with a melamine compound is possible. In other polymers, for example, a polymer obtained by partially using a monomer having any one of a methylol group, a hydroxyl group, a carboxyl group, and a glycidyl group is used. .

Examples of the polyurethane resin include polyhydroxy compounds (for example, ethylene glycol, propylene glycol, glycerin, trimethylolpropane), aliphatic polyester polyols obtained by reaction of polyhydroxy compounds and polybasic acids, polyether polyols (for example, Poly (oxypropylene ether) polyol), polycarbonate-based polyol, and polyethylene terephthalate polyol, or a polyurethane derived from a mixture thereof and polyisocyanate.
In the polyurethane resin, for example, the hydroxyl group remaining unreacted after the reaction between the polyol and the polyisocyanate can be used as a functional group capable of a crosslinking reaction with the melamine compound.

Generally as said polyester resin, the polymer obtained by reaction of a polyhydroxy compound (for example, ethylene glycol, propylene glycol, glycerol, trimethylol propane) and a polybasic acid is used.
In the polyester resin, for example, a hydroxyl group and a carboxyl group remaining unreacted after the reaction between the polyol and the polybasic acid can be used as a functional group capable of a crosslinking reaction with the melamine compound. Moreover, you may add the other component which has functional groups, such as a hydroxyl group.

If necessary, a matting agent, a surfactant, a lubricant and the like may be added to the antistatic layer.
Examples of the matting agent include oxides such as silicon oxide, aluminum oxide, and magnesium oxide having a particle diameter of 0.001 to 10 μm, and polymers or copolymers such as polymethyl methacrylate and polystyrene.
Examples of the surfactant include known anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants.
Examples of the lubricant include phosphate esters of higher alcohols having 8 to 22 carbon atoms or amino salts thereof; palmitic acid, stearic acid, behenic acid, and esters thereof; silicone compounds, and the like.

It is preferable that the surface on which the coating solution for forming the antistatic layer is applied in advance with a surface treatment such as an ultraviolet treatment, a corona treatment, or a glow treatment.
The thickness of the antistatic layer is preferably from 0.01 to 1 μm, more preferably from 0.01 to 0.2 μm. If the thickness is less than 0.01 μm, the antistatic performance may be insufficient. It may not be obtained.

A surface layer may be formed on the antistatic layer in order to improve slipperiness and scratch resistance and to prevent detachment of the conductive metal oxide particles in the antistatic layer.
Examples of the surface layer include those formed by applying an organic solvent solution of a hydrophobic polymer or an aqueous latex on the antistatic layer and drying.
Examples of the hydrophobic polymer include a vinyl polymer produced from a monomer including cellulose ester (eg, nitrocellulose, cellulose acetate, etc.), vinyl chloride, vinylidene chloride and vinyl acrylate, and an organic solvent-soluble polyamide, Examples thereof include polymers such as polyester.

-Undercoat layer-
In order to improve the adhesion between the photosensitive layer cover film and the resist adhesion preventing layer, an undercoat layer may be formed between the photosensitive layer cover film and the resist adhesion preventing layer.
Examples of the method for forming the undercoat layer include those described in JP-A Nos. 51-135526, U.S. Pat. Nos. 3,143,421, 3,586,508, 2,698,235, and 356745. Vinylidene chloride copolymers, glycidyl acrylate or methacrylate-containing copolymers described in JP-A-51-58469, polyamide-epichlorohydrin resins described in JP-A-48-24923, and JP-A-50-39536 And a method of forming a hard film after applying a mixture of gelatin and a hardener, and the like.

-Protective layer-
A protective material may be provided on the surface of the photosensitive layer cover film, particularly on the resist adhesion preventing layer, in order to prevent damage or contamination during handling.
Examples of the protective material include synthetic resin films used for the support for the photosensitive layer cover film, silicone paper, paper laminated with polyethylene or polypropylene, polyolefin sheets, polytetrafluoroethylene sheets, and the like. Among these, a polyethylene film and a polypropylene film are preferable.

There is no restriction | limiting in particular as thickness of the said protective material, Although it can select suitably according to the objective, For example, 5-100 micrometers is preferable and 8-30 micrometers is more preferable.
When the protective material is used, the adhesive force A of the resist adhesion preventing layer and the support for the photosensitive layer cover film and the adhesive force B of the resist adhesion preventing layer and the protective material satisfy the relationship of adhesive force A> adhesive force B. A relationship is preferred.
Examples of the combination of the support for the photosensitive layer cover film and the protective material include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, and polyethylene terephthalate / polyethylene terephthalate. Moreover, the above-mentioned adhesive force relationship can be satisfied by surface-treating at least one of the support for the photosensitive layer cover film and the protective film.
The protective material may be surface-treated to adjust the adhesion between the protective material and the resist adhesion preventing layer. In the surface treatment, for example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol is formed on the surface of the protective material. The undercoat layer can be formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 to 150 ° C. (especially 50 to 120 ° C.) for 1 to 30 minutes.

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

  For example, the photosensitive layer cover film is preferably wound around a cylindrical core, wound into a long roll, and stored. There is no restriction | limiting in particular as the length of the said elongate photosensitive layer cover film, For example, it can select suitably from the range of 10m-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 m to 1,000 m may be formed into a roll. In this case, it is preferable to wind up such that the surface on which the resist adhesion preventing layer is not formed is on the outside.

  The roll-shaped photosensitive layer cover film may be slit into a sheet shape. Further, the slit film may be laminated to form a multi-layered shape and peeled one by one at the time of use. In the case of the multi-layered form, it is preferable to install a separator (particularly a moisture-proof one, containing a desiccant) on the end face from the viewpoint of protecting the end face and preventing edge fusion during storage. In addition, it is preferable to use a material with low moisture permeability for packaging.

Furthermore, the photosensitive layer cover film may be subjected to uneven processing on at least the surface on which the resist adhesion preventing layer is not laminated, that is, the surface not bonded to the photosensitive layer. Since the emboss is formed on the surface, when the photosensitive layer cover film is laminated on the photosensitive layer and then brought into close contact under reduced pressure, it has excellent adsorptivity to an adsorbing means such as a translucent member of a vacuum frame.
There is no restriction | limiting in particular as long as the emboss shape formed by the said uneven | corrugated process does not degrade the light transmittance and scattering property of the said photosensitive layer cover film, According to the objective, it can select suitably.
In addition, the method for forming the unevenness is not particularly limited as long as the light transmittance and scattering property of the photosensitive layer cover film are not deteriorated, and can be appropriately selected according to the purpose. For example, known embossing, And a method of forming irregularities with a protective layer made of a polymer to which a matting agent is added.

  The photosensitive layer cover film of the present invention is used by being disposed on the photosensitive layer in a method for forming a pattern by exposing and developing the photosensitive layer, and has excellent handleability, adhesion and peelability. Is good, can be applied to direct drawing by laser exposure of 405 nm, and can prevent the sensitivity of the photosensitive layer from being lowered by oxygen, so printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), color filters and columns The present invention can be widely applied to the formation of permanent patterns such as display members such as materials, rib materials, spacers, partition walls, holograms, micromachines, and proofs.

[Photosensitive layer]
The photosensitive layer is formed on the surface of the substrate using a photosensitive composition containing at least a binder, a polymerizable compound, and a photopolymerization initiator (FIG. 43).
Suitable examples of the photosensitive layer include a photosensitive layer constituting a photo solder resist layer, a photosensitive layer constituting a circuit forming photoresist layer, and a photosensitive layer constituting a color resist layer.
Preferred examples of the method for forming the photosensitive layer include the following first method and second method.
The first method is a method of forming a photosensitive layer on the surface of the substrate by applying the photosensitive composition to the surface of the substrate and drying it.

The second method comprises a photosensitive film comprising a support for a photosensitive layer and a photosensitive layer comprising a photosensitive composition, and further comprising other layers appropriately selected as necessary. The photosensitive film is laminated on the surface of the substrate so that the surface opposite to the support for the photosensitive layer and the substrate are in contact with each other. This is a method of laminating and then peeling off the support for the photosensitive layer (FIG. 45).
By peeling off the photosensitive layer support, it is possible to prevent a blurred image from being generated on the image formed on the photosensitive layer due to light scattering or refraction by the photosensitive layer support. Can be obtained with high resolution. When the said photosensitive film has a protective film mentioned later, this protective film is peeled and it laminates | stacks so that the said photosensitive layer may overlap with the said base material.

  In the first method, the coating and drying method is not particularly limited and may be appropriately selected depending on the purpose. For example, the photosensitive composition is added to the surface of the substrate with water or A method of laminating by preparing a photosensitive composition solution by dissolving, emulsifying or dispersing in a solvent, applying the solution directly, and drying it.

  There is no restriction | limiting in particular as a solvent of the said photosensitive composition solution, According to the objective, it can select suitably.

The coating method is not particularly limited and can be appropriately selected depending on the purpose. For example, using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, etc. The method of apply | coating is mentioned.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 to 110 ° C. for about 30 seconds to 15 minutes.

The thickness of the photosensitive layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the thickness of the photosensitive layer as the photo solder resist layer is preferably 1 to 150 μm, preferably 5 to 100 μm. Is more preferable, and 10 to 80 μm is particularly preferable.
The thickness of the photosensitive layer as the circuit forming photoresist layer is preferably 0.5 to 100 μm, more preferably 1 to 50 μm, and particularly preferably 2 to 10 μm. Furthermore, the thickness of the photosensitive layer as the color resist layer is preferably 0.5 to 10 μm, more preferably 0.75 to 6 μm, and particularly preferably 1 to 3 μm.

In the first method, other layers to be formed are not particularly limited and can be appropriately selected depending on the purpose. For example, a cushion layer, a release layer, an adhesive layer, a light absorption layer, a surface protective layer, and the like. Is mentioned.
There is no restriction | limiting in particular as a formation method of the said other layer, According to the objective, it can select suitably, For example, the method of laminating | stacking the other layer formed in the sheet form etc. are mentioned.

In the second method, the heating temperature is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 70 to 130 ° C, more preferably 80 to 110 ° C.
There is no restriction | limiting in particular as a pressure of the said pressurization, Although it can select suitably according to the objective, For example, 0.01-1.0 MPa is preferable and 0.05-1.0 MPa is more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating and pressurization, According to the objective, it can select suitably, For example, heat press, a heat roll laminator (For example, Taisei Laminator company make, VP-II). ), A vacuum laminator (for example, MVLP500, manufactured by Meiki Seisakusho) and the like are preferable.

  The support for the photosensitive layer is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable that the photosensitive layer can be peeled off and has good light transmittance, and further the surface. It is more preferable that the smoothness of is good.

  There is no restriction | limiting in particular as thickness of the said support body for photosensitive layers, Although it can select suitably according to the objective, For example, 4-300 micrometers is preferable, 5-175 micrometers is more preferable, 10-100 micrometers is especially preferable.

  There is no restriction | limiting in particular as a shape of the said support body for photosensitive layers, Although it can select suitably according to the objective, A long shape is preferable. There is no restriction | limiting in particular as the length of the said elongate support for photosensitive layers, For example, the length of 10 m-20000 m is mentioned.

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

  There is no restriction | limiting in particular as the thickness of the photosensitive layer in the said photosensitive film, Although it can select suitably according to the objective, For example, 3-100 micrometers is preferable, 8-50 micrometers is more preferable, 10-40 micrometers is especially preferable. .

  Formation of the photosensitive layer in the photosensitive film can be performed by the same method as the application of the photosensitive composition solution to the substrate and drying (the first method). For example, the photosensitive composition Examples of the method include applying the solution using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, or the like.

The protective film is a film having a function of preventing and protecting the photosensitive layer from being stained and damaged.
There is no restriction | limiting in particular as thickness of the said protective film, Although it can select suitably according to the objective, For example, 5-100 micrometers is preferable, 8-50 micrometers is more preferable, 10-40 micrometers is more preferable.

  There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said protective film, Although it can select suitably according to the objective, Usually, it provides on the said photosensitive layer.

  When the protective film is used, the relationship between the adhesive force A of the photosensitive layer and the support for the photosensitive layer and the adhesive force B of the photosensitive layer and the protective film is that adhesive force A> adhesive force B. Is preferred.

The coefficient of static friction between the photosensitive layer support and the protective film is preferably 0.3 to 1.4, more preferably 0.5 to 1.2.
When the coefficient of static friction is less than 0.3, slipping is excessive, so that winding deviation may occur when the roll is formed, and when it exceeds 1.4, it is difficult to wind into a good roll. Sometimes.

The protective film is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include those used for the photosensitive layer support, silicone paper, polyethylene, polypropylene laminated paper, polyolefin or Examples thereof include polytetrafluoroethylene sheets, and among these, polyethylene film, polypropylene film and the like are particularly preferable.
Examples of the combination of the photosensitive layer support and the protective film (photosensitive layer support / protective film) include, for example, polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / Examples include polyethylene terephthalate.

The protective film is preferably subjected to a surface treatment in order to adjust the adhesiveness between the protective film and the photosensitive layer in order to satisfy the above-described adhesive force relationship.
The surface treatment method for the photosensitive layer support is not particularly limited and may be appropriately selected depending on the intended purpose. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment Examples include irradiation treatment, glow discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.
As a specific example of the method for applying the undercoat layer, for example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol is formed on the surface of the protective film. The undercoat layer may be formed by applying the polymer coating solution on the surface of the protective film and then drying it at 30 to 150 ° C. (especially 50 to 120 ° C.) for 1 to 30 minutes. .

In the second method, the other layer to be formed is not particularly limited and may be appropriately selected depending on the purpose. For example, a cushion layer, a release layer, an adhesive layer, a light absorption layer, a surface protective layer Etc.
The cushion layer is a layer that has no tackiness at room temperature and softens and flows when laminated under vacuum and heating conditions.

  There is no restriction | limiting in particular as a structure of the said photosensitive film, According to the objective, it can select suitably, For example, it has the said photosensitive layer and the said protective film in this order on the said support body for photosensitive layers. The form which has the said cushion layer, the said photosensitive layer, and the said protective film in this order on the support body for the said photosensitive layer is mentioned. The photosensitive layer may be a single layer or a plurality of layers.

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

The photosensitive film can be widely used for forming a permanent pattern such as a printed wiring board, a color filter, a column material, a rib material, a spacer, a display member such as a partition wall, a hologram, a micromachine, or a proof.
In particular, since the photosensitive film has a uniform thickness, the film is more precisely laminated on the substrate when a permanent pattern is formed.

  In addition, there is no restriction | limiting in particular as an exposure method to the laminated body which has the photosensitive layer formed by the said 2nd method, According to the objective, it can select suitably, For example, it is a cushion on the support body for photosensitive layers. In the case of a film having a layer and a photosensitive layer in this order, the photosensitive layer cover film is laminated after peeling off the photosensitive layer support and the cushion layer.

<Photosensitive layer>
The photosensitive layer formed by the first method and the second method includes at least a binder, a polymerizable compound, and a photopolymerization initiator, and further includes other components that are appropriately selected as necessary. The composition is used.
The photosensitive layer preferably includes a photosensitive layer constituting a photo solder resist layer, a photosensitive layer constituting a circuit forming photoresist layer, and a photosensitive layer constituting a color resist layer.

-Photosensitive layer constituting the photo solder resist layer-
There is no restriction | limiting in particular as a photosensitive composition which forms the photosensitive layer which comprises the said photo soldering resist layer, Although it can select suitably from well-known photosensitive compositions, For example, a binder, polymeric compound, etc. And at least a photopolymerization initiator and a thermal crosslinking agent, and further containing other components such as a color pigment, an extender pigment, a thermal polymerization inhibitor, and a surfactant as necessary.

<< Binder >>
The binder contained in the photosensitive layer is preferably, for example, swellable in an alkaline aqueous solution, and more preferably soluble in an alkaline aqueous solution.
As the binder exhibiting swellability or solubility with respect to the alkaline aqueous solution, for example, those having an acidic group are preferably exemplified.

There is no restriction | limiting in particular as said acidic group, According to the objective, it can select suitably, For example, a carboxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, Among these, a carboxyl group is preferable.
Examples of the binder having a carboxyl group include a vinyl copolymer having a carboxyl group, a polyurethane resin, a polyamic acid resin, and a modified epoxy resin. Among these, the solubility in a coating solvent, the solubility in an alkali developer, and the like. A vinyl copolymer having a carboxyl group is preferable from the viewpoint of solubility, suitability for synthesis, ease of preparation of film properties, and the like.

  The vinyl copolymer having a carboxyl group can be obtained by copolymerization of at least (1) a vinyl monomer having a carboxyl group, and (2) a monomer copolymerizable therewith.

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and hydroxyl group. An addition reaction product of a monomer (for example, 2-hydroxyethyl (meth) acrylate) and a cyclic anhydride (for example, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride), ω-carboxy-polycaprolactone mono Examples include (meth) acrylate. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.
Moreover, you may use the monomer which has anhydrides, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group.

  The other copolymerizable monomer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, and maleic acid diesters. , Fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (eg, vinylpyridine, Vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, 2-acrylamido-2-methylpropanesulfonic acid, phosphoric acid mono (2-acryloyloxyethyl ester), phosphorus Acid mono (1- Chill-2-acryloyloxyethyl ester), functional groups (e.g., a urethane group, a urea group, a sulfonamide group, a phenol group and a vinyl monomer and the like having an imide group).

  Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, Dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meta ) Acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate , Polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl acrylate, Nylphenoxypolyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) Examples thereof include acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, and tribromophenyloxyethyl (meth) acrylate.

  Examples of the crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.

  Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- n-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Examples thereof include N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

  Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloro Examples include methylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, α-methylstyrene, and the like.

  Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  Examples of the method for synthesizing the vinyl monomer having a functional group include an addition reaction of an isocyanate group and a hydroxyl group or an amino group, specifically, a monomer having an isocyanate group and a compound containing one hydroxyl group. Alternatively, an addition reaction with a compound having one primary or secondary amino group, an addition reaction between a monomer having a hydroxyl group or a monomer having a primary or secondary amino group, and a monoisocyanate can be given.

  Examples of the monomer having an isocyanate group include compounds represented by the following structural formulas (1) to (3).

However, in the above structural formula (1) ~ (3), R 1 represents a hydrogen atom or a methyl group.

  Examples of the monoisocyanate include cyclohexyl isocyanate, n-butyl isocyanate, toluyl isocyanate, benzyl isocyanate, and phenyl isocyanate.

  Examples of the monomer having a hydroxyl group include compounds represented by the following structural formulas (4) to (12).

However, in the structural formulas (4) to (12), R ¹ represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more.

  Examples of the compound containing one hydroxyl group include alcohols (for example, methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-hexanol, 2-ethylhexanol). , N-decanol, n-dodecanol, n-octadecanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, etc.), phenols (eg, phenol, cresol, naphthol, etc.), and further containing substituents Examples thereof include fluoroethanol, trifluoroethanol, methoxyethanol, phenoxyethanol, chlorophenol, dichlorophenol, methoxyphenol, acetoxyphenol, and the like.

  Examples of the monomer having a primary or secondary amino group include vinylbenzylamine.

  Examples of the compound containing one primary or secondary amino group include alkylamines (methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, t-butylamine, hexyl). Amine, 2-ethylhexylamine, decylamine, dodecylamine, octadecylamine, dimethylamine, diethylamine, dibutylamine, dioctylamine), cyclic alkylamine (cyclopentylamine, cyclohexylamine, etc.), aralkylamine (benzylamine, phenethylamine, etc.), Arylamines (aniline, toluylamine, xylylamine, naphthylamine, etc.), combinations thereof (N-methyl-N-benzylamine, etc.), and amines containing substituents (trifluoroethylamino , Hexafluoro isopropyl amine, methoxyaniline, methoxypropylamine and the like) and the like.

  Examples of the other copolymerizable monomers other than those described above include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, and (meth) acrylic. Preferable examples include 2-ethylhexyl acid, styrene, chlorostyrene, bromostyrene, and hydroxystyrene.

  The said other copolymerizable monomer may be used individually by 1 type, and may use 2 or more types together.

  The vinyl copolymer can be prepared by copolymerizing the corresponding monomers by a known method according to a conventional method. For example, it can be prepared by using a method (solution polymerization method) in which the monomer is dissolved in a suitable solvent and a radical polymerization initiator is added thereto to polymerize in a solution. Moreover, it can prepare by utilizing superposition | polymerization by what is called emulsion polymerization etc. in the state which disperse | distributed the said monomer in the aqueous medium.

  The suitable solvent used in the solution polymerization method is not particularly limited and may be appropriately selected depending on the monomer used and the solubility of the copolymer to be produced. For example, methanol, ethanol, propanol, Examples include isopropanol, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene and the like. These solvents may be used alone or in combination of two or more.

  The radical polymerization initiator is not particularly limited, and examples thereof include 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile). Examples thereof include peroxides such as azo compounds and benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate.

There is no restriction | limiting in particular as content rate of the polymeric compound which has a carboxyl group in the said vinyl copolymer, Although it can select suitably according to the objective, For example, 5-50 mol% is preferable, 10-40 mol % Is more preferable, and 15 to 35 mol% is particularly preferable.
If the content is less than 5 mol%, the developability to alkaline water may be insufficient, and if it exceeds 50 mol%, the developer resistance of the cured portion (image portion) may be insufficient.

There is no restriction | limiting in particular as molecular weight of the binder which has the said carboxyl group, Although it can select suitably according to the objective, For example, 2,000-300,000 are preferable as a mass mean molecular weight, 4,000-150 1,000 is more preferable.
When the mass average molecular weight is less than 2,000, the strength of the film tends to be insufficient and stable production may be difficult, and when it exceeds 300,000, developability may be deteriorated.

  The binder which has the said carboxyl group may be used individually by 1 type, and may use 2 or more types together. Examples of the case where two or more binders are used in combination include, for example, a combination of two or more binders composed of different copolymer components, two or more binders having different mass average molecular weights, and two or more binders having different dispersities. Is mentioned.

  The binder having a carboxyl group may be partially or entirely neutralized with a basic substance. The binder may be used in combination with resins having different structures such as polyester resin, polyamide resin, polyurethane resin, epoxy resin, polyvinyl alcohol, and gelatin.

  Moreover, as the binder, a resin soluble in an alkaline aqueous solution described in Japanese Patent No. 2873889 and the like can be used.

There is no restriction | limiting in particular as content of the said binder in the said photosensitive layer, Although it can select suitably according to the objective, For example, 5-80 mass% is preferable, 10-70 mass% is more preferable, 15-15 50% by mass is particularly preferred.
When the content is less than 5% by mass, alkali developability and adhesion with a printed wiring board forming substrate (for example, a copper-clad laminate) may be deteriorated. The stability of the film and the strength of the cured film (tent film) may decrease. The content may be the total content of the binder and the polymer binder used in combination as necessary.

The acid value of the binder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 70 to 250 (mgKOH / g), more preferably 90 to 200 (mgKOH / g), 100 to 180 (mg KOH / g) is particularly preferable.
When the acid value is less than 70 (mgKOH / g), developability may be insufficient, resolution may be inferior, and permanent patterns such as wiring patterns may not be obtained with high definition. / G), at least one of the developer resistance and adhesion of the pattern deteriorates, and a permanent pattern such as a wiring pattern may not be obtained with high definition.

The binder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, JP-A 51-131706, JP-A 52-94388, JP-A 64-62375, JP-A 2 Examples thereof include epoxy acrylate compounds having acidic groups described in JP-A-97513, JP-A-3-289656, JP-A-61-2243869, JP-A-2002-296776, and the like. Specifically, phenol novolac type epoxy acrylate monotetrahydrophthalate, cresol novolac epoxy acrylate monotetrahydrophthalate, bisphenol A type epoxy acrylate monotetrahydrophthalate, etc. This is obtained by reacting a carboxyl group-containing monomer such as an acid and further adding a dibasic acid anhydride such as phthalic anhydride.
The molecular weight of the epoxy acrylate compound is preferably 1,000 to 200,000, and more preferably 2,000 to 100,000. When the molecular weight is less than 1,000, the tackiness of the surface of the photosensitive layer may become strong, and after curing of the photosensitive layer described later, the film quality may become brittle or the surface hardness may deteriorate. If it exceeds 1,000, developability may deteriorate.

An acrylic resin having at least one polymerizable group such as an acidic group and a double bond described in JP-A-6-295060 can also be used. Specifically, at least one polymerizable double bond in the molecule, for example, an acrylic group such as a (meth) acrylate group or (meth) acrylamide group, various polymerizations such as vinyl ester of carboxylic acid, vinyl ether, allyl ether Sex double bonds can be used. More specifically, acrylic resins containing carboxyl groups as acidic groups, glycidyl esters of unsaturated fatty acids such as glycidyl acrylate, glycidyl methacrylate, cinnamic acid, and epoxy groups such as cyclohexene oxide in the same molecule (meth) Examples thereof include compounds obtained by adding an epoxy group-containing polymerizable compound such as a compound having an acryloyl group. In addition, a compound obtained by adding an isocyanate group-containing polymerizable compound such as isocyanate ethyl (meth) acrylate to an acrylic resin containing an acidic group and a hydroxyl group, an acrylic resin containing an anhydride group, a hydroxyalkyl ( Examples thereof include compounds obtained by adding a polymerizable compound containing a hydroxyl group such as (meth) acrylate. As these commercially available products, for example, “Kaneka Resin AX; manufactured by Kaneka Chemical Co., Ltd.”, “Cyclomer (CYCLOMER) A-200; manufactured by Daicel Chemical Industries, Ltd.”, “CYCLOMER (M)” 200; manufactured by Daicel Chemical Industries, Ltd. "can be used.
Furthermore, a reaction product of hydroxyalkyl acrylate or hydroxyalkyl methacrylate described in JP-A No. 50-59315 and any of polycarboxylic acid anhydride and epihalohydrin can be used.

  Further, a compound obtained by adding an acid anhydride to an epoxy acrylate having a fluorene skeleton described in JP-A-5-70528, a polyamide (imide) resin described in JP-A-11-288087, and JP-A-2-097502 Styrene or a styrene derivative and an acid anhydride copolymer containing an amide group described in JP-A No. 2003-20310 and a polyimide precursor described in JP-A No. 11-282155 can be used. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The molecular weight of the acrylic resin, epoxy acrylate having a fluorene skeleton, polyamide (imide), amide group-containing styrene / acid anhydride copolymer, or polyimide precursor is preferably 3,000 to 500,000, 5,000-100,000 are more preferable. When the molecular weight is less than 3,000, the tackiness of the surface of the photosensitive layer may become strong, and after curing of the photosensitive layer described later, the film quality may become brittle or the surface hardness may be deteriorated. If it exceeds 1,000, developability may deteriorate.

  5-80 mass% is preferable and, as for solid content in the said photosensitive composition solid content of the said binder, 10-70 mass% is more preferable. When the solid content is less than 5% by mass, the film strength of the photosensitive layer tends to be weak, and the tackiness of the surface of the photosensitive layer may be deteriorated. When it exceeds 80% by mass, the exposure sensitivity is increased. May decrease.

<< polymerizable compound >>
The polymerizable compound contained in the photosensitive layer is not particularly limited and may be appropriately selected depending on the intended purpose, but has at least one addition-polymerizable group in the molecule and has a boiling point of normal pressure. The compound which is 100 degreeC or more is preferable, for example, at least 1 sort (s) selected from the monomer which has a (meth) acryl group is mentioned suitably.

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

  2-50 mass% is preferable, as for solid content in the said photosensitive composition solid content of the said polymeric compound, 4-40 mass% is more preferable, and 5-30 mass% is especially preferable. If the solid content is less than 2% by mass, problems such as deterioration in developability and reduction in exposure sensitivity may occur, and if it exceeds 50% by mass, the adhesiveness of the photosensitive layer may become too strong. Yes, not preferred.

<< photopolymerization initiator >>
The photopolymerization initiator contained in the photosensitive layer of the first aspect is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and is appropriately selected from known photopolymerization initiators. However, for example, those having photosensitivity to visible light from the ultraviolet region are preferable, and they may be activators that generate some kind of action with photoexcited sensitizers and generate active radicals. Depending on the type, an initiator that initiates cationic polymerization may be used.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), phosphine oxide, hexaarylbiimidazole, oxime derivatives, organic peroxides, Examples include thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, and the like.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3333724, F.I. C. J. Schaefer et al. Org. Chem. 29,1527 (1964), a compound described in JP-A-62-258241, a compound described in JP-A-5-281728, a compound described in JP-A-5-34920, US Pat. No. 4,221,976 And compounds described in the book.

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

Examples of the compound described in the British Patent 1388492 include 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4,6- Bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl)- 4-amino-6-trichloromethyl-1,3,5-triazine and the like can be mentioned.
Examples of the compounds described in JP-A-53-133428 include 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 -(4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl]- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5- Examples include triazine and 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

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

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

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

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

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

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloromethyl). -5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- ( 2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1 , 3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1, , 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-tripromemethyl-5-styryl-1,3,4-oxadiazole, etc. ) And the like.

  Examples of the oxime derivative suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2- ON, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

  Further, as photopolymerization initiators other than the above, acridine derivatives (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine, and the like, polyhalogen compounds (for example, Carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-n-propoxycoumarin), 3,3′-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206 No., JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, etc.), amines (for example, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate) N-butyl acid, 4-dimethylaminobenzoic acid phenethyl, 4-dimethyl 2-phthalimidoethyl tilaminobenzoate, 2-methacryloyloxyethyl 4-dimethylaminobenzoate, pentamethylenebis (4-dimethylaminobenzoate), phenethyl of 3-dimethylaminobenzoic acid, pentamethylene ester, 4-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-dimethylaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine, N, N-diethyl-3-phenetidine, tribenzylamine, dibenzylphenylamine, N-methyl-N-phenylbenzylamine, 4-bromo-N, N-dimethylaniline, tridodecylamine, amino Nofluoranes (ODB, ODBII, etc.), crystal violet lactone, leuco crystal violet, etc.), acylphosphine oxides (for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) ) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3-) (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.), JP-A-53-133428, Kosho 57-1819, 57-60 No. 96, US Pat. No. 3,615,455, and the like.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, In propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

  As content of the said photoinitiator, 0.1-30 mass% is preferable with respect to all the components in the said photosensitive composition, 0.5-20 mass% is more preferable, 0.5-15 mass % Is particularly preferred.

In addition to the photopolymerization initiator, a sensitizer can be added for the purpose of adjusting exposure sensitivity and photosensitive wavelength in exposure to the photosensitive layer described later.
The sensitizer can be appropriately selected by visible light, ultraviolet light, visible light laser, or the like as a light irradiation means described later.
The sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby generating radicals, acids, etc. It is possible to generate a useful group of

  The sensitizer is not particularly limited and may be appropriately selected from known sensitizers. For example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, , Fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, Methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg, squalium), acridones (eg, acridone, chloroacrine) Don, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl)- 7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3 '-Carbonylbis (5,7-di-n-propoxycoumarin), 3,3'-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7- Diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin Examples thereof include 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, and others, and JP-A-5-19475, JP-A-7-271028, JP-A-2002-. No. 363206, JP-A No. 2002-363207, JP-A No. 2002-363208, JP-A No. 2002-363209, and the like.

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

  As content of the said sensitizer, 0.05-30 mass% is preferable with respect to all the components in the said photosensitive composition, 0.1-20 mass% is more preferable, 0.2-10 mass% Is particularly preferred. When the content is less than 0.05% by mass, the sensitivity to active energy rays is reduced, the exposure process takes time, and productivity may be reduced. The sensitizer may be precipitated from the photosensitive layer.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
Particularly preferred examples of the photopolymerization initiator include halogenated carbonization having the phosphine oxides, the α-aminoalkyl ketones, and the triazine skeleton capable of supporting laser light having a wavelength of 405 nm in the exposure described later. Examples include a composite photoinitiator, a hexaarylbiimidazole compound, or titanocene, which is a combination of a hydrogen compound and an amine compound as a sensitizer described later.

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

<< Thermal crosslinking agent >>
The thermal crosslinking agent contained in the photosensitive layer is not particularly limited and can be appropriately selected according to the purpose, and improves the film strength after curing of the photosensitive layer formed using the photosensitive composition. Therefore, within a range that does not adversely affect developability and the like, for example, an epoxy resin compound having at least two oxirane groups in one molecule, an oxetane compound having at least two oxetanyl groups in one molecule, and a melamine resin compound Etc. can be used.
Examples of the epoxy resin compound include a bixylenol type or biphenol type epoxy resin (“YX4000; manufactured by Japan Epoxy Resin Co., Ltd.”) or a mixture thereof, a heterocyclic epoxy resin having an isocyanurate skeleton (“TEPIC; Nissan”). Chemical Industries, "Araldite PT810; Ciba Specialty Chemicals, etc.), bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy Resin, hydantoin type epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenylolethane type Poxy resin, glycidyl phthalate resin, tetraglycidyl xylenoylethane resin, naphthalene group-containing epoxy resin (“ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”, “HP-4032, EXA-4750, EXA-4700; large Nippon Ink Chemical Co., Ltd. ”), epoxy resins having a dicyclopentadiene skeleton (“ HP-7200, HP-7200H; manufactured by Dainippon Ink & Chemicals ”etc.), glycidyl methacrylate copolymer epoxy resin (“ CP -50S, CP-50M; manufactured by NOF Corporation, etc.), a copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, and the like, but is not limited thereto. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.
Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers or copolymers thereof, oxetane groups and novolak resins , Poly (p-hydroxystyrene), cardo-type bisphe And ether compounds such as hydroxyl groups, calixarenes, calixresorcinarenes, silsesquioxanes, and the like, as well as unsaturated monomers having an oxetane ring and alkyl (meth) acrylates. And copolymers thereof.
Examples of the melamine resin compound include alkylated methylol melamine and hexamethylated methylol melamine.

  1-50 mass% is preferable and, as for solid content in the said photosensitive composition solid content of the said epoxy resin compound or oxetane compound, 3-30 mass% is more preferable. When the solid content is less than 1% by mass, the hygroscopicity of the cured film is increased, resulting in deterioration of insulation, or solder heat resistance, electroless plating resistance, and the like may be reduced. If it exceeds 50% by mass, the developability may deteriorate and the exposure sensitivity may decrease, which is not preferable.

Moreover, in order to accelerate the thermosetting of the epoxy resin compound or the oxetane compound, for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethyl Amine compounds such as benzylamine and 4-methyl-N, N-dimethylbenzylamine; quaternary ammonium salt compounds such as triethylbenzylammonium chloride; blocked isocyanate compounds such as dimethylamine; imidazole, 2-methylimidazole and 2-ethylimidazole , 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc. Bicyclic amidine compounds and salts thereof; phosphorus compounds such as triphenylphosphine; guanamine compounds such as melamine, guanamine, acetoguanamine, benzoguanamine; 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2 -Vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid S-triazine derivatives such as adducts can be used. These may be used alone or in combination of two or more. The epoxy resin compound or the oxetane compound is a curing catalyst, or any compound that can accelerate the reaction between the epoxy resin compound and the oxetane compound and a carboxyl group. May be.
Solid content in the said photosensitive composition solid content of the said epoxy resin, the said oxetane compound, and the compound which can accelerate | stimulate thermosetting with these and carboxylic acid is 0.01-15 mass% normally.

  Further, as the thermal crosslinking agent, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is aliphatic, cycloaliphatic or aromatic containing at least two isocyanate groups. It may be derived from a group-substituted aliphatic compound. Specifically, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene diisocyanate, bis (4 -Isocyanate-phenyl) methane, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc .; bifunctional isocyanates, trimethylolpropane, pentalysitol, glycerin, etc. An alkylene oxide adduct of the polyfunctional alcohol and an adduct of the bifunctional isocyanate; hexamethylene diisocyanate, hexamethylene-1,6-diisocyanate Cyclic trimers, such as preparative and derivatives thereof; and the like.

Furthermore, for the purpose of improving the preservability of the photosensitive composition or the photosensitive film, a compound obtained by reacting an isocyanate group of the polyisocyanate and its derivative with a blocking agent may be used.
Examples of the isocyanate group blocking agent include isopropanol, tert. Alcohols such as butanol; lactams such as ε-caprolactam, phenol, cresol, p-tert. -Butylphenol, p-sec. -Butylphenol, p-sec. -Phenols such as amylphenol, p-octylphenol, p-nonylphenol; heterocyclic hydroxyl compounds such as 3-hydroxypyridine and 8-hydroxyquinoline; dialkylmalonate, methylethylketoxime, acetylacetone, alkylacetoacetate oxime, acetoxime, Active methylene compounds such as cyclohexanone oxime; and the like. In addition to these, compounds having at least one polymerizable double bond and at least one blocked isocyanate group in the molecule described in JP-A-6-295060 can be used.

  Moreover, an aldehyde condensation product, a resin precursor, etc. can be used. Specifically, N, N′-dimethylolurea, N, N′-dimethylolmalonamide, N, N′-dimethylolsuccinimide, trimethylolmelamine, tetramethylolmelamine, hexamethylolmelamine, 1,3-N, N'-dimethylol terephthalamide, 2,4,6-trimethylolphenol, 2,6-dimethylol-4-methyliloanisole, 1,3-dimethylol-4,6-diisopropylbenzene and the like can be mentioned. In place of these methylol compounds, the corresponding ethyl or butyl ether, or acetic acid or propionic acid ester may be used. Moreover, you may use the hexamethoxymethyl melamine which consists of a formaldehyde condensation product of a melamine and urea, the butyl ether of a melamine and a formaldehyde condensation product, etc.

  1-40 mass% is preferable, as for solid content in the said photosensitive composition solid content of the said thermal crosslinking agent, 3-30 mass% is more preferable, and 5-25 mass% is especially preferable. When the solid content is less than 1% by mass, improvement in the film strength of the cured film is not recognized, and when it exceeds 40% by mass, the developability and the exposure sensitivity may be lowered.

<< Other ingredients >>
Examples of the other components contained in the photosensitive layer include sensitizers, thermal polymerization inhibitors, plasticizers, colorants (color pigments or dyes), extender pigments, and the like. Adhesion promoters and other auxiliaries that promote adhesion (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release accelerators, antioxidants, fragrances, surface tension adjusters, chain transfer Agents), thermosetting accelerators, and the like. By appropriately containing these components, properties such as the intended photosensitive composition or the photosensitive film described later, such as stability, photographic properties, and film physical properties can be prepared.

-Sensitizer-
There is no restriction | limiting in particular as said sensitizer, According to visible light, an ultraviolet light, a visible light laser, etc. as a light irradiation means mentioned later, it can select suitably.
The sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby generating radicals, acids, etc. It is possible to generate a useful group of

  Specific examples of the sensitizer can be appropriately selected from known sensitizers. For example, known polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein) , Eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, Toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg, squalium), acridones (eg, acridone, chloroacridone, -Methylacridone, N-butylacridone, N-butyl-chloroacridone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- ( 1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonyl Bis (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-me Examples thereof include xyl-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, and others, and JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206. And coumarin compounds described in JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, and the like.

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

As content of the said sensitizer, 0.05-30 mass% is preferable with respect to all the components of a photosensitive composition, 0.1-20 mass% is more preferable, 0.2-10 mass% is especially preferable. preferable.
When the content is less than 0.05% by mass, the sensitivity to active energy rays decreases, the exposure process takes time, and the productivity may decrease. When the content exceeds 30% by mass, the photosensitive layer May precipitate during storage.

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

  As content of the said thermal-polymerization inhibitor, 0.001-5 mass% is preferable with respect to the said polymeric compound, 0.005-2 mass% is more preferable, 0.01-1 mass% is especially preferable. When the content is less than 0.001% by mass, stability during storage may be lowered, and when it exceeds 5% by mass, sensitivity to active energy rays may be lowered.

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

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

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

  The solid content in the photosensitive composition solid content of the color pigment can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive layer at the time of permanent pattern formation, depending on the type of the color pigment. Generally, 0.05 to 10% by mass is preferable, 0.075 to 8% by mass is more preferable, and 0.1 to 5% by mass is particularly preferable.

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

  5-60 mass% is preferable, as for the addition amount of the said extender, 10-50 mass% is more preferable, 15-45 mass% is especially preferable. When the addition amount is less than 5% by mass, the linear expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 60% by mass, when the cured film is formed on the photosensitive layer surface, The film quality becomes fragile, and when a wiring is formed using a permanent pattern, the function of the wiring as a protective film may be impaired.

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

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

  As content of the said adhesion promoter, 0.001 mass%-20 mass% are preferable with respect to all the components in the said photosensitive composition, 0.01-10 mass% is more preferable, 0.1 mass% ˜5% by weight is particularly preferred.

The said photosensitive composition which forms the photosensitive layer which comprises the said photo soldering resist layer can be prepared using a solvent.
The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include esters, ethers, ketones, aromatic hydrocarbons, aliphatic hydrocarbons, and petroleum solvents. Among these, those having good compatibility with the binder and not dissolving the thermal crosslinking agent are preferable.
Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, and lactic acid. 3 such as ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate -Oxypropionic acid alkyl esters, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropion Ethyl, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy-2- Methyl methyl propionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2 -Ethyl-2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like.
Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethyl carbitol acetate, Examples include butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate.
Examples of the ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
Examples of the aromatic hydrocarbons include toluene and xylene.
Examples of the aliphatic hydrocarbons include octane and decane.
Examples of the petroleum solvents include petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.
The amount of the solvent added during the preparation of the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose. The total solid concentration of the photosensitive composition is 10 to 95% by mass. Preferably, it is added so that it may become 20-92.5 mass%, It is especially preferable to add so that it may become 30-90 mass%.

-Photosensitive layer constituting photoresist layer for circuit formation-
The photosensitive composition for forming the photosensitive layer constituting the circuit forming photoresist layer is not particularly limited and can be appropriately selected from known photoresist materials. It is preferable to include a compound and a photopolymerization initiator and other components appropriately selected.
Moreover, there is no restriction | limiting in particular as the number of lamination | stacking of a 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.

<< Binder >>
The binder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the same binder as exemplified in the binder contained in the photosensitive layer constituting the photo solder resist layer may be used. Is possible.
10-90 mass% is preferable, as for solid content in the said photosensitive composition solid content of the said binder, 20-80 mass% is more preferable, and 40-80 mass% is especially preferable. When the solid content is less than 10% by mass, the film strength of the photosensitive layer tends to be weak, and the tackiness of the surface of the photosensitive layer may be deteriorated. When it exceeds 90% by mass, the exposure sensitivity is increased. May decrease.
The acid value of the binder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 70 to 250 (mgKOH / g), more preferably 90 to 200 (mgKOH / g), 100 to 180 (mg KOH / g) is particularly preferable.
When the acid value is less than 70 (mgKOH / g), developability may be insufficient, resolution may be inferior, and permanent patterns such as wiring patterns may not be obtained with high definition. / G), at least one of the developer resistance and adhesion of the pattern deteriorates, and a permanent pattern such as a wiring pattern may not be obtained with high definition.

<< polymerizable compound >>
The polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the polymerizable compound is the same as those exemplified as the polymerizable compound included in the photosensitive layer constituting the photo solder resist layer. Can be used.

If necessary, the polymerizable compound may be used in combination with a polymerizable compound (monofunctional monomer) containing one polymerizable group in the molecule.
Examples of the monofunctional monomer include the compounds exemplified as the raw material of the binder, and the dibasic mono ((meth) acryloyloxyalkyl ester) mono (halohydroxyalkyl ester) described in JP-A-6-236031. Monofunctional monomers such as γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate, etc., compounds described in Japanese Patent No. 2744443, WO00 / 52529, Japanese Patent No. 2548016, etc. Is mentioned.

As content of the polymeric compound in the said photosensitive layer, 5-90 mass% is preferable, for example, 15-60 mass% is more preferable, and 20-50 mass% is especially preferable.
If the content is 5% by mass, the strength of the tent film may be reduced, and if it exceeds 90% by mass, edge fusion during storage (exudation failure from the end of the roll) may be deteriorated. .
Moreover, as content of the polyfunctional monomer which has 2 or more of the said polymeric groups in a polymeric compound, 5-100 mass% is preferable, 20-100 mass% is more preferable, 40-100 mass% is especially preferable. .

<< photopolymerization initiator >>
The photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose.For example, the photopolymerization initiator includes those exemplified as the photopolymerization initiator contained in the photosensitive layer constituting the photosolder resist layer. Similar ones can be used.

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

  The said photoinitiator may be used individually by 1 type, and may use 2 or more types together. Examples of the combination of two or more include, for example, a combination of hexaarylbiimidazole and 4-aminoketone described in US Pat. No. 3,549,367, a benzothiazole compound described in Japanese Patent Publication No. 51-48516, and trihalomethyl- Combinations of s-triazine compounds, combinations of aromatic ketone compounds (such as thioxanthone) and hydrogen donors (such as dialkylamino-containing compounds and phenol compounds), combinations of hexaarylbiimidazole and titanocene, and coumarins And combinations of titanocene and phenylglycines.

  As content of the photoinitiator in the said photosensitive layer, 0.1-30 mass% is preferable, 0.5-20 mass% is more preferable, 0.5-15 mass% is especially preferable.

<< Other ingredients >>
Examples of the other components include sensitizers, thermal polymerization inhibitors, plasticizers, color formers, colorants, halogen compounds and the like, and adhesion promoters to the substrate surface and other auxiliary agents (for example, , Pigments, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, thermal crosslinking agents, surface tension adjusting agents, chain transfer agents, etc.) . By appropriately containing these components, it is possible to adjust properties such as stability, photographic properties, print-out properties, and film physical properties of the target photosensitive resin composition.

The sensitizer can be appropriately selected by visible light, ultraviolet light, visible light laser, or the like as a light irradiation means to be described later.
The sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby generating radicals, acids, etc. It is possible to generate a useful group of

  The sensitizer is not particularly limited and may be appropriately selected depending on the purpose. For example, the same sensitizers as those exemplified as the sensitizer contained in the photosensitive layer constituting the photo solder resist layer Can be used.

As content of the said sensitizer, 0.05-30 mass% is preferable with respect to all the components of a photosensitive composition, 0.1-20 mass% is more preferable, 0.2-10 mass% is especially preferable. preferable.
When the content is less than 0.05% by mass, the sensitivity to active energy rays decreases, the exposure process takes time, and the productivity may decrease. When the content exceeds 30% by mass, the photosensitive layer May precipitate during storage.

The thermal polymerization inhibitor can be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound in the photosensitive layer.
The thermal polymerization inhibitor is not particularly limited and may be appropriately selected depending on the purpose. For example, the thermal polymerization inhibitor is the same as that exemplified as the thermal polymerization inhibitor contained in the photosensitive layer constituting the photo solder resist layer. Can be used.
The content of the thermal polymerization inhibitor is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, and 0.01 to 1% by mass with respect to all components of the photosensitive composition. Particularly preferred.

There is no restriction | limiting in particular as said plasticizer, According to the objective, it can select suitably, For example, the thing similar to what was illustrated as a plasticizer contained in the photosensitive layer which comprises the said photo soldering resist layer is used. It is possible.
As content of the said plasticizer, 0.1-50 mass% is preferable with respect to all the components of a photosensitive composition, 0.5-40 mass% is more preferable, 1-30 mass% is especially preferable.

The color former may be added to give a visible image (printing function) to the photosensitive layer after exposure.
Examples of the color former include tris (4-dimethylaminophenyl) methane (leuco crystal violet), tris (4-diethylaminophenyl) methane, tris (4-dimethylamino-2-methylphenyl) methane, tris (4- Diethylamino-2-methylphenyl) methane, bis (4-dibutylaminophenyl)-[4- (2-cyanoethyl) methylaminophenyl] methane, bis (4-dimethylaminophenyl) -2-quinolylmethane, tris (4-di Aminotriarylmethanes such as propylaminophenyl) methane; 3,6-bis (dimethylamino) -9-phenylxanthine, 3-amino-6-dimethylamino-2-methyl-9- (2-chlorophenyl) xanthine, etc. Aminoxanthines; 3,6-bis (diethyl Aminothioxanthenes such as mino) -9- (2-ethoxycarbonylphenyl) thioxanthene and 3,6-bis (dimethylamino) thioxanthene; 3,6-bis (diethylamino) -9,10-dihydro-9- Amino-9,10-dihydroacridine such as phenylacridine, 3,6-bis (benzylamino) -9,10-dividro-9-methylacridine; aminophenoxazine such as 3,7-bis (diethylamino) phenoxazine Aminophenothiazines such as 3,7-bis (ethylamino) phenothiazone; aminodihydrophenazines such as 3,7-bis (diethylamino) -5-hexyl-5,10-dihydrophenazine; bis (4-dimethylamino) Aminophenylmethanes such as phenyl) anilinomethane; 4-amino-4 ′ Aminohydrocinnamic acids such as dimethylaminodiphenylamine, 4-amino-α, β-dicyanohydrocinnamic acid methyl ester; hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine; 1,4-bis ( Ethylamino) -2,3-dihydroanthraquinones amino-2,3-dihydroanthraquinones; phenethylanilines such as N, N-diethyl-4-phenethylaniline; 10-acetyl-3,7-bis (dimethylamino) ) An acyl derivative of a leuco dye containing basic NH such as phenothiazine; a leuco-like compound which does not have an oxidizable hydrogen such as tris (4-diethylamino-2-tolyl) ethoxycarbonylmentane but can be oxidized to a coloring compound Leucoin digoid pigment; U.S. Pat. Nos. 3,042,515 and 3,042 Organic amines that can be oxidized to a colored form as described in No. 517 (eg, 4,4′-ethylenediamine, diphenylamine, N, N-dimethylaniline, 4,4′-methylenediamine triphenylamine, N-vinylcarbazole), and among these, triarylmethane compounds such as leuco crystal violet are preferable.

Furthermore, it is generally known that the color former is combined with a halogen compound for the purpose of coloring the leuco body.
Examples of the halogen compound include halogenated hydrocarbons (for example, carbon tetrabromide, iodoform, ethylene bromide, methylene bromide, amyl bromide, isoamyl bromide, amyl iodide, isobutylene bromide, butyl iodide, Diphenylmethyl bromide, hexachloroethane, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, 1,2-dibromo-1,1,2-trichloroethane, 1,2,3 tribromopropan, 1-bromo-4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachlorocyclopropene, hexachlorocyclopentadiene, dibromocyclohexane, 1,1,1-trichloro-2,2-bis (4- Chlorophenyl) ethane); halogenated alcohol compounds (eg, 2,2,2-trichloroethanol, Bromoethanol, 1,3-dichloro-2-propanol, 1,1,1-trichloro-2-propanol, di (iodohexamethylene) aminoisopropanol, tribromo-t-butyl alcohol, 2,2,3-trichlorobutane 1,4-diol and the like; halogenated carbonyl compounds (for example, 1,1-dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, hexabromoacetone, 1,1,3,3-tetrachloroacetone, 1,1 , 1-trichloroacetone, 3,4-dibromo-2-butanone, 1,4-dichloro-2-butanone-dibromocyclohexanone, etc.); halogenated ether compounds (eg 2-bromoethyl methyl ether, 2-bromoethyl ethyl ether) Di (2-bromoethyl) ether, 1,2- Chloroethyl ethyl ether, etc.); halogenated ester compounds (eg, bromoethyl acetate, ethyl trichloroacetate, trichloroethyl trichloroacetate, homopolymers and copolymers of 2,3-dibromopropyl acrylate, trichloroethyl dibromopropionate, α, β Halogenated amide compounds (for example, chloroacetamide, bromoacetamide, dichloroacetamide, trichloroacetamide, tribromoacetamide, trichloroethyltrichloroacetamide, 2-bromoisopropionamide, 2,2,2- Trichloropropionamide, N-chlorosuccinimide, N-bromosuccinimide, etc.); a compound having sulfur or phosphorus (for example, tribromomethylphenylsulfone, 4-nitro) Phenyl tribromomethyl sulfone, 4-chlorophenyl tribromomethyl sulfone, tris (2,3-dibromopropyl) phosphate, etc.), e.g., 2,4-bis (trichloromethyl) 6- phenyltriazole and the like. As the organic halogen compound, a halogen compound having two or more halogen atoms bonded to the same carbon atom is preferable, and a halogen compound having three halogen atoms per carbon atom is more preferable. The said organic halogen compound may be used individually by 1 type, and may use 2 or more types together. Among these, tribromomethylphenyl sulfone and 2,4-bis (trichloromethyl) -6-phenyltriazole are preferable.

  The content of the color former is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and particularly preferably 0.1 to 5% by mass with respect to all components of the photosensitive layer. Further, the content of the halogen compound is preferably 0.001 to 5% by mass, more preferably 0.005 to 3% by mass, and particularly preferably 0.01 to 2% by mass with respect to all components of the photosensitive layer. .

In the photosensitive layer, a dye can be used for the purpose of coloring the photosensitive composition for improving handleability or imparting storage stability.
Examples of the dye include brilliant green (for example, sulfate thereof), eosin, ethyl violet, erythrosine B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymolphthalein. , Methyl violet 2B, quinaldine red, rose bengal, metanil-yellow, thymol sulfophthalein, xylenol blue, methyl orange, orange IV, diphenyltylocarbazone, 2,7-dichlorofluorescein, paramethyl red, congo red, benzo Purpurin 4B, α-naphthyl-red, Nile blue A, phenacetalin, methyl violet, malachite green, parafuxin, oil blue # 603 (Orien Chemical Co., Ltd.), rhodamine B, Rotamin 6G, and the like can be illustrated Victoria Pure Blue BOH, Among these cationic dyes (e.g., Malachite Green oxalate, malachite green sulfates) are preferable. The counter anion of the cationic dye may be a residue of an organic acid or an inorganic acid, for example, a residue such as bromic acid, iodic acid, sulfuric acid, phosphoric acid, oxalic acid, methanesulfonic acid, toluenesulfonic acid ( Anion) and the like.

  As content of the said dye, 0.001-10 mass% is preferable with respect to all the components of the said photosensitive layer, 0.01-5 mass% is more preferable, 0.1-2 mass% is especially preferable.

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

  The adhesion promoter is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the same adhesion promoter as exemplified as the adhesion promoter contained in the photosensitive layer constituting the photo solder resist layer Can be used.

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

  The photosensitive layer is, for example, J.I. It may contain organic sulfur compounds, peroxides, redox compounds, azo or diazo compounds, photoreducible dyes, organic halogen compounds, etc. as described in Chapter 5 of “Light Sensitive Systems” Good.

  Examples of the organic sulfur compound include di-n-butyl disulfide, dibenzyl disulfide, 2-mercaprobenzthiazole, 2-mercaptobenzoxazole, thiophenol, ethyltrichloromethanesulfenate, and 2-mercaptobenzimidazole. Etc.

  Examples of the peroxide include di-t-butyl peroxide, benzoyl peroxide, and methyl ethyl ketone peroxide.

  The redox compound is a combination of a peroxide and a reducing agent, and examples thereof include ferrous ions and persulfate ions, ferric ions and peroxides.

  Examples of the azo and diazo compounds include α, α'-azobisiributyronitrile, 2-azobis-2-methylbutyronitrile, and diazonium such as 4-aminodiphenylamine.

  Examples of the photoreducible dye include rose bengal, erythrosine, eosin, acriflavine, lipoflavin, and thionine.

The surfactant can be appropriately selected from, for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a fluorine-containing surfactant.
As content of the said surfactant, 0.001-10 mass% is preferable with respect to solid content of the photosensitive composition.
When the content is less than 0.001% by mass, the effect of improving the surface shape may not be obtained, and when it exceeds 10% by mass, the adhesion may be deteriorated.

As the surfactant, in addition to the above-mentioned surfactant, as a fluorine-based surfactant, it contains 40% by mass or more of fluorine atoms in a carbon chain of 3 to 20, and at least 3 counted from the non-bonding terminal A polymer surfactant having, as a copolymerization component, an acrylate or methacrylate having a fluoroaliphatic group in which a hydrogen atom bonded to a carbon atom is fluorine-substituted is also preferred.
By containing the surfactant, the surface unevenness of the photosensitive layer can be improved.

The photosensitive composition for forming the photosensitive layer constituting the circuit forming photoresist layer can be prepared using a solvent.
There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, in the photosensitive composition which forms the photosensitive layer which comprises the said photo solder resist, the thing similar to the illustrated solvent is used. Is possible.
There is no restriction | limiting in particular as the addition amount of the said solvent at the time of the said photosensitive composition preparation, Although it can select suitably according to the objective, The total solid content concentration of the said photosensitive composition is 5-80 mass%. It is preferable to add so that it may become, it is more preferable to add so that it may become 10-60 mass%, and it is especially preferable to add so that it may become 15-50 mass%.

-Photosensitive layer constituting the color resist layer-
The photosensitive composition for forming the photosensitive layer constituting the color resist layer includes a binder, a polymerizable compound, and a photopolymerization initiator, and includes other appropriately selected components such as a colorant. Specific examples of the photosensitive layer include a (meth) acrylic acid-containing polymer as a binder, a polymerizable compound, a photopolymerization initiator, and a colorant, and further appropriately selected other components. What comprises is mentioned suitably.

<< Binder >>
There is no restriction | limiting in particular as said binder, According to the objective, it can select suitably, For example, using the thing similar to what was illustrated as a binder contained in the photosensitive layer which comprises the said photo soldering resist layer is used. Is possible. A plurality of binders may be used in combination.

  The binder is appropriately selected from those having an acid value in the range of 50 to 300 mgKOH / 1 g and a mass average molecular weight in the range of 1000 to 300,000.

  When the acid value is less than 50 mgKOH / 1 g, the alkali developability may be greatly lowered. On the other hand, when it exceeds 300 mgKOH / 1 g, the target structure may not be obtained.

  As above-mentioned, as a mass average molecular weight of the said binder, 1000-300000 are preferable, and especially 10000-250,000 are preferable.

  When the mass average molecular weight is less than 1000, a target structure may not be obtained. On the other hand, when it exceeds 300,000, developability may be extremely lowered. In addition, a mass average molecular weight is a polystyrene conversion average molecular weight measured by GPC (gel permeation chromatography).

As content of the said binder, 10-60 mass% of the total solid of a photosensitive composition is preferable, 12.5-55 mass% is more preferable, 15-40 mass% is especially preferable.
When the content of the binder is less than 10% by mass, film formation may be difficult when the photosensitive composition is applied on a support for a photosensitive layer or the like, while when the content exceeds 60% by mass. In some cases, the content ratio of the polymerizable compound decreases, resulting in poor polymerization.

<< polymerizable compound >>
There is no restriction | limiting in particular as said polymeric compound, According to the objective, it can select suitably, For example, the thing similar to what was illustrated as a polymeric compound contained in the photosensitive layer which comprises the said photo soldering resist layer Can be used.

  As content of the said polymeric compound, 10-60 mass% of the total solid of a photosensitive composition is preferable, 15-50 mass% is more preferable, 20-40 mass% is especially preferable.

  Moreover, mass ratio of the total amount of the said polymeric compound with respect to the total amount of the below-mentioned (meth) acrylic acid containing polymer is 0.5-0.9.

  When the mass ratio is less than 0.5, curing by photopolymerization is insufficient and the hardness is insufficient. On the other hand, when it exceeds 0.9, a preferable shape cannot be obtained.

<< photopolymerization initiator >>
The photopolymerization initiator is not particularly limited and may be appropriately selected depending on the purpose. For example, the photopolymerization initiator is the same as the photopolymerization initiator included in the photosensitive layer constituting the photosolder resist layer. Can be used.

  The photopolymerization initiators may be used alone or in combination of two or more, and several compounds may be used in combination between different kinds.

  As content of the said photoinitiator, 0.1-50 mass% of the total solid of a photosensitive composition is preferable, 0.5-30 mass% is more preferable, 1-20 mass% is especially preferable.

<< Colorant >>
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably, For example, an organic pigment, an inorganic pigment, dye, etc. are mentioned.
Any one selected from dendritic branched molecules in which metal ions are coordinated as coloring agents, and dendritic branched molecules containing at least one metal particle of metal particles and alloy particles, separately or in combination with these colorants It is also possible to contain the following dendritic molecules.

  Examples of the colorant include a yellow pigment, an orange pigment, a red pigment, a violet pigment, a blue pigment, a green pigment, a brown pigment, and a black pigment. When forming a color filter, three primary colors (B, G , R) and black (K), a blue pigment, a green pigment, a red pigment, and a black pigment are preferably used.

  Examples of the yellow pigment include C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 86, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 125, C.I. I. Pigment yellow 137, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 148, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 166, C.I. I. And CI Pigment Yellow 168, Monolite Yellow GT (CI Pigment Yellow 12), and Permanent Yellow GR (CI Pigment Yellow 17).

  Examples of the orange pigment include C.I. I. Pigment orange 36, C.I. I. Pigment orange 43, C.I. I. Pigment orange 51, C.I. I. Pigment orange 55, C.I. I. Pigment orange 59, C.I. I. And CI Pigment Orange 61.

  Examples of the red pigment include C.I. I. Pigment red 9, C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 217, C.I. I. Pigment red 220, C.I. I. Pigment red 223, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 227, C.I. I. Pigment red 228, C.I. I. Pigment red 240, C.I. I. Pigment Red 48: 1, Permanent Carmine FBB (CI Pigment Red 146), Permanent Ruby FBH (CI Pigment Red 11), Fastel Pink B Spula (CI Pigment Red) 81).

  Examples of the violet pigment include C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 30, C.I. I. Pigment violet 37, C.I. I. Pigment violet 40, C.I. I. And CI Pigment Violet 50.

  Examples of the blue pigment include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment Blue 64, Victoria Pure Blue BO (C.I. 42595), and the like.

  Examples of the green pigment include C.I. I. Pigment green 7, C.I. I. And CI Pigment Green 36.

  Examples of the brown pigment include C.I. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26 and the like.

  Examples of the black pigment include Monolite First Black B (CI Pigment Black 1), C.I. I. Pigment Black 7, Fat Black HB (C.I. 26150), and the like.

  Other examples include carbon black and auramine (C.I. 41000).

  In addition, the said colorant, such as an organic pigment, an inorganic pigment, or dye, may be used individually by 1 type, or can also be used in combination of 2 or more type.

When using the colorant as described above, the particle size of the pigment or dye is preferably 1 nm to 10 ⁴ nm, more preferably 10 to 80 nm, and particularly preferably 20 to 70 nm. Preferably, it is 30 nm to 60 nm. Since the photosensitive resin layer is a thin layer, when the particle size of the pigment or the like is not in the above range, it cannot be uniformly dispersed in the resin layer, and a high-quality color filter can be manufactured. Since it becomes difficult, it is not preferable.

<< Other ingredients >>
The photosensitive composition may contain components such as a thermal crosslinking agent, a plasticizer, a surfactant, and a thermal polymerization inhibitor as other components.

  The thermal crosslinking agent and plasticizer are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include thermal crosslinking agents and plasticizers included in the photosensitive layer constituting the photo solder resist layer. It is possible to use a similar one.

  The addition amount of the thermal crosslinking agent and the plasticizer can be added within a range not impairing the effects of the present invention. The content of the thermal crosslinking agent is 0.01% of the total solid content of the photosensitive composition. 10 mass% is preferable, 0.02-5 mass% is more preferable, 0.05-3 mass% is especially preferable.

The surfactant is not particularly limited and may be appropriately selected depending on the purpose. For example, the surfactant is exemplified as the surfactant contained in the photosensitive layer constituting the circuit forming photoresist layer. Similar ones can be used.
Further, as the surfactant, the following _equation, and ^{_{C 8 F 17 SO 2 N (}} R 1) CH 2 CH 2 O (CH 2 CH 2 O n R 2) suitable surfactant represented by .
In the formula, R ¹ and R ² each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 30.
Examples of R ¹ include a methyl group, an ethyl group, and an isopropyl group, and examples of R ² include a hydrogen atom.
As said n, 10-25 are preferable and 10-20 are more preferable.
As specific examples of the surfactant represented by the above formula, Megafac F-141 (n = 5), F-142 (n = 10), F = 143 (n = 15), F-144 (n = 20) (Brand name: Dainippon Ink & Chemicals, Inc.).

Furthermore, as said surfactant, surfactant represented by following Formula (1)-(4) is mentioned suitably.
^{_{Rf 1 -X- (CH 2 CH 2}} O) n R 1 ··· (1)
^{_{Rf 1 -X- (CH 2 CH 2}} O) n R 2 ··· (2)
^{_{Rf 1 -X- (CH 2 CH 2}} O) n (CH 2 CH 2 CH 2 O) m R 1 ··· (3)
^{_{Rf 1 -X- (CH 2 CH 2}} O) n (CH 2 CH 2 CH 2 O) m Rf 2 ··· (4)

However, in the formula (1) ~ (4), R 1 and ^{R 2} are Tansomoto 18, preferably 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.
Examples of the alkyl group include a saturated alkyl group and an unsaturated alkyl group.
Examples of the structure of the alkyl group include those having a linear structure and a branched structure, and among these, those having a branched structure are preferred.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, otatadecyl group Eicosanyl group, docosanyl group, 2-chloroethyl group, 2-promoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-promopropyl group and the like. These alkyl groups may be substituted with a halogen atom, an acyl group, an amino group, a cyano group, an alkyl group, an alkoxy group, alkyl or haloalkyl, and may be substituted with an aryl group, an amide group, or the like. .

In the formulas (1) to (4), Rf ¹ and Rf ² each independently represent a perfluoro group having 1 to 18, preferably 2 to 12, and more preferably 4 to 10 carbon atoms.
Examples of the perfluoro group include a saturated perfluoro group and an unsaturated perfluoro group.
Examples of the structure of the perfluoro group include those having a linear structure and a branched structure. Among these, those having a branched structure are preferably exemplified, and at least one of Rf ¹ and Rf ² has a branched structure. What has is mentioned more suitably.
Specific examples of the perfluoro group include perfluorononenyl, perfluoromethyl, perfluoropropylene, perfluorononinel, perfluorobenzoic acid, perfluoropropylene, perfluoropropyl, perfluoro (9-methyloctyl), and perfluoromethyl. Examples include octyl, perfluorobutyl, perfluoro-3-methylbutyl, perfluorohexyl, perfluorooctyl, perfluoro-7-octylethyl, fluoroheptyl, perfluorodecyl, perfluorobutyl, and the like. These perfluoro groups may be substituted with a halogen atom, acyl group, amino group, cyano group, alkyl group, alkoxy group, alkyl or haloalkyl, or may be substituted with an aryl group, an amide group, or the like. .
Rf ¹ and Rf ² may be the same as or different from each other.
In said Formula (1)-(4), n represents the integer of 1-40, Preferably the integer of 4-25 is represented.
In said Formula (1)-(4), m represents the integer of 0-40, Preferably the integer of 0-25 is represented.
In the formula (1) ~ (4), -X- _{is, - (CH 2) l -} (l 1 to 10, preferably represents an integer of 1 to 5), - CO-O -, - O -, -NHCO-, or -NHCOO- is represented.
The surfactants represented by the formulas (1) to (4) can be used singly or in combination of two or more.

As content of the said surfactant, 0.001-10 mass% is preferable with respect to solid content of the photosensitive composition.
When the content is less than 0.001% by mass, the effect of improving the surface shape may not be obtained, and when it exceeds 10% by mass, the adhesion may be deteriorated.

  When the photosensitive composition contains the surfactant, the fluidity as a coating liquid is improved, and the adhesion of the liquid in a spin coater nozzle or pipe or container used in the coating process is improved. Since the residue remaining as dirt in the nozzle can be effectively reduced, the amount of cleaning liquid required for cleaning and the operation time when switching the coating liquid can be reduced, and the productivity of the color filter can be improved. In addition, it is possible to improve surface unevenness that occurs when the color resist layer is formed.

The thermal polymerization inhibitor is not particularly limited and may be appropriately selected depending on the purpose. For example, the thermal polymerization inhibitor is the same as that exemplified as the thermal polymerization inhibitor contained in the photosensitive layer constituting the photo solder resist layer. Can be used.
As content of the said thermal-polymerization inhibitor, 0.0001-10 mass% is preferable with respect to all the components of a photosensitive composition, 0.0005-5 mass% is more preferable, 0.001-1 mass% is Particularly preferred.

The photosensitive composition for forming the photosensitive layer constituting the color resist layer can be prepared using a solvent.
There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, in the photosensitive composition which forms the photosensitive layer which comprises the said photo soldering resist layer, the thing similar to the illustrated solvent is used. It is possible.
Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexane, ethyl carbitol acetate, butyl Preferred examples include carbitol acetate and propylene glycol methyl ether acetate. These solvents can be used alone or in combination of two or more.
There is no restriction | limiting in particular as the addition amount of the said solvent at the time of the said photosensitive composition preparation, Although it can select suitably according to the objective, The total solid content concentration of the said photosensitive composition is 5-80 mass%. It is preferable to add so that it may become, it is more preferable to add so that it may become 10-60 mass%, and it is especially preferable to add so that it may become 15-50 mass%.

  The thickness of the photosensitive layer is preferably 0.5 to 10 μm, more preferably 0.75 to 6 μm, and particularly preferably 1.0 to 3 μm.

  If the thickness is less than 0.5 μm, pinholes are likely to occur when the photosensitive resin layer coating solution is applied, and the production suitability may be reduced. May take a long time to remove

<Base material>
The base material used in the photosensitive layer forming step is not particularly limited, and includes a photo solder resist and a photo for forming a wiring pattern from known materials having a high surface smoothness to a surface having an uneven surface. Although it can be appropriately selected according to the purpose of each of the resist and the color resist, a plate-like base material (substrate) is preferable. Specifically, a known printed wiring board forming substrate (for example, a copper-clad laminate) ), Glass plates (eg, soda glass plates, glass plates sputtered with silicon oxide, quartz glass plates, etc.), synthetic resin films, paper, metal plates, and the like.

  In the base material, the photosensitive layer is formed on the base material, and by exposing the photosensitive layer, the exposed region can be cured, and a pattern can be formed by a development process described later.

[Arrangement of photosensitive layer cover film on photosensitive layer]
In the pattern exposure method, the method for laminating the photosensitive layer cover film on the photosensitive layer is not particularly limited as long as the photosensitive layer cover film is laminated so as to be in contact with the photosensitive layer. For example, it is preferable to use a vacuum baking frame, and after laminating the photosensitive layer cover film on the photosensitive layer, the pressure is reduced and adhered.
When the photosensitive layer cover film has a resist adhesion preventing layer, the photosensitive layer cover film is preferably laminated so that the photosensitive layer and the resist adhesion preventing layer are in contact with each other.

The vacuum frame includes a printing table having a sheet member on which the substrate on which the photosensitive layer is formed is placed, and an upper frame having a translucent member, between the sheet member and the translucent member. The pressure in the vacuum chamber is reduced by a vacuum pump or the like, thereby bringing the photosensitive layer and the photosensitive layer cover film laminated thereon into vacuum contact. The presence of the photosensitive layer cover film between the photosensitive layer and the translucent member can prevent contamination of the translucent member with the photosensitive layer.
Moreover, the said photosensitive layer cover film can also be used as a translucent member of the said vacuum baking frame.

[exposure]
In the pattern exposure method, the photosensitive layer on which the photosensitive layer cover film is laminated is exposed to a 395-415 nm laser beam having pattern information.

There is no restriction | limiting in particular as exposure in the said pattern exposure method, Although it can select suitably according to the objective, For example, the laser beam modulated according to the control signal produced | generated based on predetermined pattern information is used. The digital exposure performed in this manner is preferable.
Further, the exposure method is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoint of enabling high-speed exposure in a short time, the exposure light and the photosensitive layer are relatively moved. It is preferable to carry out the treatment while using the digital micromirror device (DMD).

  The exposure is performed by modulating light from the light irradiating means by light modulating means having at least n picture elements for receiving and emitting light from the light irradiating means, and then distorting the exit surface in the picture element. It is preferable to use light that has passed through a microlens array in which microlenses having aspherical surfaces capable of correcting the aberration due to the above are arranged.

In the exposure, the light emitted from the light irradiation means is preferably a laser beam that can be turned on / off in a short time and can easily control the interference of the light. It is preferable that a laser beam having a wavelength of 405 nm is particularly preferable.
In addition to laser light, for example, electromagnetic waves that activate photopolymerization initiators and sensitizers, ultraviolet to visible light, electron beams, and X-rays may be used.
There is no restriction | limiting in particular as the light irradiation method by the said light irradiation means, According to the objective, it can select suitably, For example, a semiconductor laser, LED, a high pressure mercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, a copying machine And irradiation with a known light source such as a cold cathode fluorescent lamp. In addition, it is preferable that two or more light beams from these light sources are combined and irradiated, and laser light that combines two or more light beams (hereinafter, referred to as “combined laser beam”) is irradiated. Is particularly preferred.
There is no restriction | limiting in particular as the irradiation method of the said combined laser beam, Although it can select suitably according to the objective, A laser irradiated from a several laser light source, a multimode optical fiber, and this several laser light source There is a method of forming and irradiating a combined laser beam with a collective optical system that collects light and couples it to the multimode optical fiber.

In the exposure, the method for modulating light is not particularly limited as long as it is a method for modulating light by means of light modulation means having n pixel parts for receiving and emitting light from the light irradiation means. Preferably, a method of controlling any less than n pixel parts arranged continuously from n pixel parts in accordance with the pattern information is preferable.
There is no restriction | limiting in particular as the number (n) of said picture element parts, According to the objective, it can select suitably.
The arrangement of the picture element portions in the light modulation means is not particularly limited and may be appropriately selected according to the purpose. For example, it is preferably arranged two-dimensionally and arranged in a lattice pattern. Is more preferable.
The light modulation method is not particularly limited and may be appropriately selected depending on the intended purpose. A preferable example is a method using a spatial light modulation element as the light modulation means.
The spatial light modulation element is not particularly limited and may be appropriately selected depending on the intended purpose. However, a digital micromirror device (DMD) or a MEMS (Micro Electro Mechanical Systems) type spatial light modulation element (SLM) may be used. A Special Light Modulator), an optical element that modulates transmitted light by an electro-optic effect (PLZT element), a liquid crystal light shutter (FLC), and the like. Among these, a DMD is particularly preferable.

In the exposure, the light modulated by the modulation means is allowed to pass through a microlens array in which microlenses having aspherical surfaces capable of correcting aberration due to distortion of the exit surface in the picture element portion are arranged.
The microlens arranged in the microlens array is not particularly limited as long as it has an aspheric surface, and can be appropriately selected according to the purpose. However, the microlens is a microlens having a toric surface. Preferably there is.
Furthermore, in the exposure, it is preferable that the light modulated by the modulation means is allowed to pass through an aperture array, a coupling optical system, other optical systems appropriately selected, and the like.

  Hereinafter, a pattern forming apparatus suitably used for the pattern exposure method using the photosensitive layer cover film of the present invention will be described with reference to the drawings.

FIG. 7 is a schematic perspective view showing an appearance of a pattern forming apparatus preferably used for forming the pattern.
The pattern forming apparatus including the light modulation means is stored in a vacuum frame (not shown) on the upper surface of a thick plate-like installation table 156 supported by four legs 154 as shown in FIG. A flat plate-like stage 152 that holds an exposure target 150 (hereinafter referred to as a pattern forming material) 150 in which a photosensitive layer and a photosensitive layer cover film are laminated on a substrate is held.
The stage 152 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by a guide 158 formed on the upper surface of the installation table 156 so as to be reciprocally movable. The pattern forming apparatus has a drive device (not shown) for driving the stage 152 along the guide 158.

  A downward C-shaped gate 160 is provided at the center of the installation table 156 so as to straddle the movement path of the stage 152. Each end portion of the gate 160 is fixed to both side surfaces in the longitudinal center portion of the installation table 156. A scanner 162 is provided on one side of the gate 160, and a plurality of (for example, two) detection sensors 164 that detect the front and rear ends of the pattern forming material 150 are provided on the other side. ing. The scanner 162 and the detection sensor 164 are respectively attached to the gate 160 and fixedly arranged above the moving path of the stage 152. The scanner 162 and the detection sensor 164 are connected to a controller (not shown) that controls them.

FIG. 8 is a schematic perspective view showing the configuration of the scanner. FIG. 9A is a plan view showing an exposed region formed on the photosensitive layer, and FIG. 9B is a diagram showing an arrangement of exposure areas by the exposure head.
As shown in FIGS. 8 and 9B, the scanner 162 includes a plurality of (for example, 14) exposure heads 166 arranged in a substantially matrix of m rows and n columns (for example, 3 rows and 5 columns). ing. In this example, four exposure heads 166 are arranged in the third row in relation to the width of the pattern forming material 150. In addition, when showing each exposure head arranged in the m-th row and the n-th column, it is expressed as an exposure head 166 _mn .
An exposure area 168 by the exposure head 166 has a rectangular shape with a short side in the sub-scanning direction. Accordingly, as the stage 152 moves, a strip-shaped exposed region 170 is formed in the pattern forming material 150 for each exposure head 166. In addition, when showing the exposure area by each exposure head arranged in the m-th row and the n-th column, it is expressed as an exposure area 168 _mn .

Further, as shown in FIGS. 9A and 9B, each of the exposure heads in each row arranged in a line so that the strip-shaped exposed regions 170 are arranged in the direction orthogonal to the sub-scanning direction without gaps. These are arranged with a predetermined interval (natural number times the long side of the exposure area, twice in this example) in the arrangement direction. Therefore, can not be exposed portion between the exposure area _{168 11} in the first row and the exposure area _{168 12,} it can be exposed by the second row of the exposure area _{168 21} and the exposure area _{168 31} in the third row.

FIG. 10 is a perspective view showing a schematic configuration of the exposure head.
As shown in FIG. 10, each of the exposure heads 166 _{11 to} 166 _mn serves as the light modulation means (spatial light modulation element for modulating each pixel) that modulates a light beam according to pattern information. A digital micromirror device (hereinafter also referred to as “DMD”) 50 manufactured by Instruments Co., Ltd. A fiber array light source 66 as a light irradiating means 66 provided with laser emitting portions 68 arranged in a line along a direction corresponding to the side direction, and a laser beam emitted from the fiber array light source 66 are corrected and placed on the DMD. A condensing lens system 67, a mirror 69 that reflects laser light transmitted through the lens system 67 toward the DMD 50, and a laser reflected by the DMD 50 The B, and an image forming optical system 51 forms an image on the pattern forming material 150. In FIG. 10, the lens system 67 is schematically shown.

FIG. 12 shows a controller that controls the DMD based on the pattern information.
As shown in FIG. 12, the DMD 50 is connected to a controller 302 having a data processing unit, a mirror drive control unit, and the like. The data processing unit of the controller 302 generates a control signal for driving and controlling each micromirror in the area to be controlled by the DMD 50 for each exposure head 166 based on the input pattern information. The area to be controlled will be described later. The mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 50 for each exposure head 166 based on the control signal generated by the pattern information processing unit.

FIG. 1 is a partially enlarged view showing a configuration of a digital micromirror device (DMD) as the light modulation means.
As shown in FIG. 1, in the DMD 50, a large number (for example, 1024 × 768) of micromirrors (micromirrors) 62 each constituting a pixel (pixel) are arranged on a SRAM cell (memory cell) 60 in a lattice shape. This is a mirror device arranged in a row. In each pixel, a micromirror 62 supported by a support column is provided at the top, and a material having high reflectance such as aluminum is deposited on the surface of the micromirror 62. The reflectance of the micromirror 62 is 90% or more, and the arrangement pitch is 13.7 μm as an example in both the vertical and horizontal directions. A silicon gate CMOS SRAM cell 60 manufactured in a normal semiconductor memory manufacturing line is disposed directly below the micromirror 62 via a support including a hinge and a yoke, and the entire structure is monolithic. ing.

2A and 2B are diagrams for explaining the operation of the DMD.
When a digital signal is written in the SRAM cell 60 of the DMD 50, the micromirror 62 supported by the support is tilted in a range of ± α degrees (for example, ± 12 degrees) with respect to the substrate side on which the DMD 50 is disposed with the diagonal line as the center. It is done. 2A shows a state in which the micromirror 62 is tilted to + α degrees when the micromirror 62 is in an on state, and FIG. 2B shows a state in which the micromirror 62 is tilted to −α degrees that is in an off state.
Therefore, by controlling the tilt of the micromirror 62 in each pixel of the DMD 50 according to the pattern information, the laser light incident on the DMD 50 is reflected in the tilt direction of each micromirror 62.
FIG. 1 shows an example of a state in which the micromirror 62 is controlled to + α degrees or −α degrees. On / off control of each micromirror 62 is performed by the controller 302 connected to the DMD 50. A light absorber (not shown) is arranged in the direction in which the laser beam B reflected by the micromirror 62 in the off state travels.

The DMD 50 is preferably arranged with a slight inclination so that the short side forms a predetermined angle θ (for example, 0.1 ° to 5 °) with the sub-scanning direction.
3A shows the scanning trajectory of the reflected light image (exposure beam) 53 by each micromirror when the DMD 50 is not tilted, and FIG. 3B shows the scanning trajectory of the exposure beam 53 when the DMD 50 is tilted. Show.
As shown in FIG. 3B, the DMD 50 has a plurality of micromirror arrays (for example, 756 pairs) arranged in the short direction, in which a large number (for example, 1024) of micromirrors are arranged in the longitudinal direction. and which is, by inclining the DMD 50, the pitch P ₂ of the scanning locus of the exposure beams 53 from each micromirror (scan line), it becomes narrower than the pitch P ₁ of the scanning line in the case of not tilting the DMD 50, significant resolution Can be improved. On the other hand, the inclination angle of the DMD 50 is small, the scanning width _{W 2} in the case of tilting the DMD 50, which is substantially equal to the scanning width _{W 1} when not inclined DMD 50.

Next, a method for increasing the modulation speed in the light modulation means (hereinafter sometimes referred to as “high-speed modulation”) will be described.
When the laser light B is irradiated from the fiber array light source 66 to the DMD 50, the laser light emitted from the fiber array light source 66 is turned on and off for each pixel, and the pattern forming material 150 has approximately the same number of pixels as the DMD 50 used. Exposure is performed in elementary units (exposure area 168). Further, when the pattern forming material 150 is moved at a constant speed together with the stage 152, the pattern forming material 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip-shaped exposed region 170 is provided for each exposure head 166. Is formed.
Here, the data processing speed of the entire DMD 50 is limited, and the modulation speed per line is determined in proportion to the number of pixels to be used. Therefore, one line can be obtained by using only a part of the micromirror array. The modulation speed per hit is increased. On the other hand, in the case of an exposure method in which the exposure head is continuously moved relative to the exposure surface, it is not necessary to use all the pixels in the sub-scanning direction.
In the DMD 50, 768 micromirror rows in which 1024 micromirrors are arranged in the main scanning direction are arranged in the subscanning direction, but a part of micromirror rows (eg, 1024 × 256 rows) is arranged by the controller 302. Only is controlled to drive.
4 (A) and 4 (B) are diagrams showing areas where DMD is used.
As shown in FIG. 4 (A), the DMD use area may be a micromirror array arranged at the center of the DMD 50. As shown in FIG. 4 (B), the end of the DMD 50 may be used. Arranged micromirror rows may be used. In addition, when a defect occurs in some of the micromirrors, the micromirror array to be used may be appropriately changed depending on the situation, such as using a micromirror array in which no defect has occurred.
For example, in the case of using only 384 sets out of 768 sets of micromirror arrays, the modulation can be performed twice as fast per line as compared with the case of using all 768 sets. Also, when only 256 pairs are used in the 768 sets of micromirror arrays, modulation can be performed three times faster per line than when all 768 sets are used.

  As described above, according to the pattern forming method, the micromirror array in which 1,024 micromirrors are arranged in the main scanning direction includes the DMD in which 768 sets are arranged in the subscanning direction. By controlling so that only a part of the micromirror rows are driven, the modulation rate per line becomes faster than when all the micromirror rows are driven.

  In addition, an example in which the DMD micromirror is partially driven has been described, but the length of the direction corresponding to the predetermined direction is reflected on the substrate longer than the length of the direction intersecting the predetermined direction according to the control signal. Even if a long and narrow DMD in which a large number of micromirrors capable of changing the surface angle are arranged in a two-dimensional manner is used, the number of micromirrors for controlling the angle of the reflecting surface is reduced. Can do.

As the exposure method, as shown in FIG. 5, the entire surface of the pattern forming material 150 may be exposed by a single scan in the X direction by a scanner 162.
Further, as the exposure method, as shown in FIGS. 6A and 6B, after the pattern forming material 150 is scanned in the X direction by the scanner 162, the scanner 162 is moved by one step in the Y direction. The entire surface of the pattern forming material 150 may be exposed by a plurality of scans by repeating scanning and movement, such as scanning in the direction.

  The exposure is performed on a partial area of the photosensitive layer to cure the partial area, and uncured areas other than the cured partial area are removed in a development step described later. A pattern is formed.

Next, the lens system 67 and the imaging optical system 51 will be described.
FIG. 11 is a cross-sectional view in the multiple scanning direction along the optical axis showing the details of the configuration of the exposure head in FIG.
As shown in FIG. 11, the lens system 67 includes a condensing lens 71 that condenses the laser light B as illumination light emitted from the fiber array light source 66, and a rod that is inserted in the optical path of the light that has passed through the condensing lens 71. And an imaging lens 74 disposed in front of the rod integrator 72, that is, on the mirror 69 side.
The condensing lens 71, the rod integrator 72, and the imaging lens 74 cause the laser light emitted from the fiber array light source 66 to enter the DMD 50 as a light beam that is close to parallel light and has a uniform beam cross-sectional intensity.

  The laser beam B emitted from the lens system 67 is reflected by the mirror 69 and irradiated to the DMD 50 via the TIR (total reflection) prism 70. In FIG. 10, the TIR prism 70 is omitted.

  As shown in FIG. 11, the imaging optical system 51 includes a first imaging optical system including lens systems 52 and 54, a second imaging optical system including lens systems 57 and 58, and these imaging optical systems. And an aperture array 59. The microlens array 55 is inserted between the microlens array 55 and the aperture array 59.

The microlens array 55 is formed by two-dimensionally arranging a large number of microlenses 55a corresponding to the pixels of the DMD 50. In this example, as will be described later, only 1024 × 256 rows of the 1024 × 768 rows of micromirrors of the DMD 50 are driven, and accordingly, 1024 × 256 rows of microlenses 55a are arranged.
The arrangement pitch of the micro lenses 55a is 41 μm in both the vertical direction and the horizontal direction. The focal length of the micro lens 55a is 0.19 mm, and the NA (numerical aperture) is 0.11.
Further, the microlens 55a is formed from the optical glass BK7.
The beam diameter of the laser beam B at the position of each microlens 55a is 41 μm.

  In the aperture array 59, a large number of apertures (openings) 59a corresponding to the respective microlenses 55a of the microlens array 55 are formed. The diameter of each aperture 59a is 10 μm.

The first imaging optical system forms an image on the microlens array 55 by enlarging the image by the DMD 50 three times.
The second imaging optical system enlarges the image that has passed through the microlens array 55 by 1.6 times, and forms and projects the image on the pattern forming material 150.
Accordingly, in the entire optical system, an image formed by the DMD 50 is magnified 4.8 times and formed and projected on the pattern forming material 150.

  A prism pair 73 is disposed between the second imaging optical system and the pattern forming material 150. By moving the prism pair 73 in the vertical direction in FIG. 11, an image on the pattern forming material 150 is obtained. The focus can be adjusted. In the figure, the pattern forming material 150 is sub-scanned in the direction of arrow F.

  Next, the microlens array, the aperture array, the imaging optical system, and the like will be described with reference to the drawings.

FIG. 13A is a cross-sectional view along the optical axis showing the configuration of the exposure head.
As shown in FIG. 13A, the exposure head includes a light irradiating means 144 for irradiating the DMD 50 with laser light, and a lens system (imaging optical system) 454 for enlarging the laser light reflected by the DMD 50 to form an image. 458, a microlens array 472 in which a large number of microlenses 474 are arranged corresponding to each pixel portion of the DMD 50, and an aperture array 476 in which a large number of apertures 478 are provided corresponding to each microlens of the microlens array 472. , And lens systems (imaging optical systems) 480 and 482 for forming an image of the laser beam that has passed through the aperture on the exposed surface 56.

FIG. 14 is a diagram showing a result of measuring the flatness of the reflecting surface of the micromirror 62 constituting the DMD 50.
In FIG. 14, the same height positions of the reflecting surfaces are shown connected by contour lines, and the pitch of the contour lines is 5 nm. In the drawing, the x direction and the y direction are two diagonal directions of the micromirror 62, and the micromirror 62 rotates around the rotation axis extending in the y direction as described above.
FIGS. 15A and 15B show the height position displacement of the reflecting surface of the micromirror 62 along the x direction and the y direction in FIG. 14, respectively.
As shown in FIGS. 14 and 15, there is distortion on the reflection surface of the micromirror 62, and when attention is particularly paid to the center of the mirror, distortion in one diagonal direction (y direction) is different from that in the other diagonal line. It is larger than the distortion in the direction (x direction). For this reason, the problem that the shape in the condensing position of the laser beam B condensed with the micro lens 55a of the micro lens array 55 may be distorted may occur.

FIGS. 16A and 16B are views showing the front and side shapes of the entire microlens array 55, respectively.
As shown in FIG. 16A, the microlens array 55 is configured by arranging microlenses 55a in parallel in the horizontal direction and 1024 rows and in the vertical direction corresponding to the micromirrors 62 of the DMD 50, respectively.
The long side dimension of the microlens array 55 is 50 mm, and the short side dimension is 20 mm.
In FIG. 9A, the arrangement order of the micro lenses 55a is indicated by j for the horizontal direction and k for the vertical direction.

FIGS. 17A and 17B are diagrams showing a front shape and a side shape of the microlens constituting the microlens array. Note that FIG. 17A also shows the contour lines of the microlens 55a.
As shown in FIGS. 17A and 17B, the end surface of the microlens 55a on the light emission side has an aspherical shape that corrects aberration due to distortion of the reflection surface of the micromirror 62.
Specifically, the aspherical microlens 55a is a toric lens having a radius of curvature Rx in the x direction of −0.125 mm and a radius of curvature Ry in the y direction of −0.1 mm.
FIG. 18 is a schematic diagram showing a condensing state by the microlens in one cross section (A) and another cross section (B).
As shown in FIG. 18, since a toric lens having an aspherical end surface on the light emission side is used as the microlens 55a constituting the microlens array, laser light in a cross section parallel to the x direction and the y direction is used. When the B condensing state is compared between the cross section parallel to the x direction and the cross section parallel to the y direction, the radius of curvature of the microlens 55a is smaller in the latter cross section, and the focal length is smaller. Shorter.

The shape of the microlens 55a may be a secondary aspherical shape or a higher order (4th order, 6th order,...) Aspherical shape. By adopting the higher order aspherical shape, the beam shape can be further refined.
In addition to making the end surface shape of the light exit side of the microlens 55a a toric surface, it is also possible to form a microlens array from microlenses having one of two light passing end surfaces as a spherical surface and the other as a cylindrical surface. It is.

19A, 19B, 19C, and 19D are diagrams showing the results of simulating the beam diameter in the vicinity of the condensing position (focal position) of the microlens 55a by a computer.
For comparison, FIGS. 20a, 20b, 20c, and 20d show the results of a similar simulation performed when the microlens has a spherical shape with a radius of curvature Rx = Ry = −0.1 mm. In addition, the value of z in each figure has shown the evaluation position of the focus direction of the micro lens 55a with the distance from the beam emission surface of the micro lens 55a.
The surface shape of the microlens 55a used for the simulation is calculated by the following calculation formula.

In the above formula, Cx is the curvature in the x direction (= 1 / Rx), Cy is the curvature in the y direction (= 1 / Ry), X is the distance from the lens optical axis O in the x direction, Y Indicates the distance from the lens optical axis O in the y direction, respectively.

  As apparent from comparison between FIGS. 19a to 19d and FIGS. 20a to 20d, in the pattern forming method, the microlens 55a has a focal length in a cross section parallel to the y direction that is greater than a focal length in a cross section parallel to the x direction. Since the toric lens is also small, distortion of the beam shape in the vicinity of the condensing position is suppressed. Therefore, it is possible to expose the pattern forming material 150 with a higher definition image without distortion.

  In addition, when the magnitude relation of the distortion of the center part in the x direction and the y direction of the micromirror 62 is opposite to the above, the focal length in the cross section parallel to the x direction is in the cross section parallel to the y direction. If the microlens is formed of a toric lens that is smaller than the focal length, similarly, it is possible to expose the pattern forming material 150 with a higher definition image without distortion.

The aperture array 59 is disposed in the vicinity of the light collection position of the microlens array 55. Only the light that has passed through the corresponding microlens 55 a is incident on each aperture 59 a provided in the aperture array 59. Therefore, it is possible to prevent light from the adjacent micro lens 55a not corresponding to one aperture 59a corresponding to the one micro lens 55a from entering, and to increase the extinction ratio.
If the diameter of the aperture 59a is reduced to some extent, an effect of suppressing distortion of the beam shape at the condensing position of the microlens 55a can be obtained, but the amount of light blocked by the aperture array 59 is increased, and the light utilization efficiency is reduced. . In this case, the microlens 55a having the aspherical shape prevents light from being blocked and keeps light use efficiency high.

  In addition, although the micro lens array 55 and the aperture array 59 correct the aberration due to the distortion of the reflection surface of the micro mirror 62 that constitutes the DMD 50, the pattern forming method using the spatial light modulation element other than the DMD can also be used. If there is distortion on the surface of the picture element portion of the spatial light modulator, the present invention can be applied to correct the aberration caused by the distortion and prevent the beam shape from being distorted.

  As shown in FIG. 13A, the imaging optical system includes lenses 480 and 482, and the light passing through the aperture array 59 is imaged on the exposed surface 56 by the imaging optical system.

As described above, in the pattern forming apparatus, the laser light reflected by the DMD 50 is magnified several times by the magnifying lenses 454 and 458 of the lens system and projected onto the exposed surface 56, so that the entire image area is Become wider. At this time, if the microlens array 472 and the aperture array 476 are not arranged, as shown in FIG. 13B, one pixel size (spot size) of each beam spot BS projected onto the exposed surface 56 is set. MTF (Modulation Transfer Function) characteristics representing the sharpness of the exposure area 468 are reduced depending on the size of the exposure area 468.
On the other hand, since the pattern forming apparatus includes the micro lens array 472 and the aperture array 476, the laser light reflected by the DMD 50 corresponds to each pixel part of the DMD 50 by each micro lens of the micro lens array 472. Focused. As a result, as shown in FIG. 13C, even when the exposure area is enlarged, the spot size of each beam spot BS can be reduced to a desired size (for example, 10 μm × 10 μm). It is possible to perform high-definition exposure while preventing deterioration of characteristics.
Note that the exposure area 468 is inclined because the DMD 50 is inclined and disposed in order to eliminate the gap between the pixels.
In addition, the aperture array can shape the beam so that the spot size on the surface to be exposed 56 is constant even if the beam is thick due to the aberration of the micro lens. Thus, crosstalk between adjacent picture elements can be prevented by passing through the aperture array.
Further, by using a high-intensity light source for the light irradiating means 144, the angle of the light beam incident from the lens 458 to each microlens of the microlens array 472 is reduced, so that a part of the light flux of the adjacent pixel enters. Can be prevented. That is, a high extinction ratio can be realized.

FIGS. 22A and 22B are views showing the front shape and side shape of another microlens array.
As shown in FIG. 22, as another microlens array, each microlens has a refractive index distribution for correcting aberration due to distortion of the reflection surface of the micromirror 62.
As illustrated, the external shape of the other microlens 155a is a parallel plate. The x and y directions in the figure are as described above.
FIG. 23 is a schematic view showing a condensing state of the laser beam B in the cross section parallel to the x direction and the y direction by the microlens 155a of FIG.
As shown in FIG. 23, the micro lens 155a has a refractive index distribution that gradually increases outward from the optical axis O. In FIG. 23, the broken line shown in the micro lens 155a indicates that the refractive index is light. A position changed from the axis O at a predetermined equal pitch is shown. As shown in the drawing, when comparing the cross section parallel to the x direction and the cross section parallel to the y direction, the ratio of the refractive index change of the microlens 155a is larger in the latter cross section, and the focal length is larger. It is shorter. Even when a microlens array composed of such a gradient index lens is used, it is possible to obtain the same effect as when the microlens array 55 is used.
In addition, in the microlens 55a shown in FIGS. 17 and 18, the refractive index distribution is given together, and the aberration due to the distortion of the reflecting surface of the micromirror 62 can be corrected by both the surface shape and the refractive index distribution. Is possible.

In the pattern forming method, other optical systems appropriately selected from known optical systems may be used in combination, and examples thereof include a light amount distribution correcting optical system including a pair of combination lenses.
The light amount distribution correcting optical system changes the light flux width at each exit position so that the ratio of the light flux width at the peripheral portion to the light flux width at the central portion close to the optical axis is smaller on the exit side than on the incident side. When the DMD is irradiated with the parallel light flux from the light irradiation means, the light amount distribution on the irradiated surface is corrected so as to be substantially uniform. Hereinafter, the light quantity distribution correcting optical system will be described with reference to the drawings.

FIG. 24 is an explanatory diagram showing the concept of correction by the light quantity distribution correction optical system.
As shown in FIG. 24A, the case where the entire luminous flux width (total luminous flux width) H0 and H1 is the same for the incident luminous flux and the outgoing luminous flux will be described. In FIG. 24A, the portions denoted by reference numerals 51 and 52 virtually indicate the entrance surface and the exit surface in the light amount distribution correcting optical system.
In the light quantity distribution correcting optical system, it is assumed that the light flux widths h0 and h1 of the light beam incident on the central portion near the optical axis Z1 and the light beam incident on the peripheral portion are the same (h0 = hl). The light quantity distribution correcting optical system expands the light flux width h0 of the incident light beam in the central portion with respect to the light having the same light flux widths h0 and h1 on the incident side, and conversely changes the incident light flux in the peripheral portion. On the other hand, the light beam width h1 is reduced. That is, the width h10 of the outgoing light beam at the center and the width h11 of the outgoing light beam at the periphery are set to satisfy h11 <h10. In terms of the ratio of the luminous flux width, the ratio “h11 / h10” of the luminous flux width in the peripheral portion to the luminous flux width in the central portion on the emission side is smaller than the ratio on the incident side (h1 / h0 = 1) ( (H11 / h10) <1).

  By changing the light flux width in this way, the light flux in the central part, which normally has a large light quantity distribution, can be utilized in the peripheral part where the light quantity is insufficient, and the overall light utilization efficiency is not reduced. In addition, the light quantity distribution on the irradiated surface is made substantially uniform. The degree of uniformity is, for example, such that the unevenness in the amount of light in the effective area is within 30%, preferably within 20%.

  The operations and effects of the light quantity distribution correcting optical system are the same when the entire luminous flux width is changed between the incident side and the exit side (FIGS. 24B and 24C).

  FIG. 24B shows a case where the entire light flux width H0 on the incident side is “reduced” to the width H2 and emitted (H0> H2). Even in such a case, the light quantity distribution correcting optical system has the same light beam width h0, h1 on the incident side, and the light beam width h10 in the central part is larger than that in the peripheral part on the emission side. Conversely, the luminous flux width h11 at the peripheral part is made smaller than that at the central part. Considering the reduction rate of the light beam, the reduction rate with respect to the incident light beam in the central part is made smaller than that in the peripheral part, and the reduction rate with respect to the incident light beam in the peripheral part is made larger than that in the central part. Also in this case, the ratio “H11 / H10” of the light flux width in the peripheral portion to the light flux width in the central portion is smaller than the ratio (h1 / h0 = 1) on the incident side ((h11 / h10) <1). .

  FIG. 24C shows a case where the entire light flux width H0 on the incident side is “enlarged” by a width Η3 and emitted (H0 <H3). Even in such a case, the light quantity distribution correcting optical system has the same light beam width h0, h1 on the incident side, and the light beam width h10 in the central part is larger than that in the peripheral part on the emission side. Conversely, the luminous flux width h11 at the peripheral part is made smaller than that at the central part. Considering the expansion rate of the light beam, the expansion rate for the incident light beam in the central portion is made larger than that in the peripheral portion, and the expansion rate for the incident light beam in the peripheral portion is made smaller than that in the central portion. Also in this case, the ratio “h11 / h10” of the light flux width in the peripheral portion to the light flux width in the central portion is smaller than the ratio (h1 / h0 = 1) on the incident side ((h11 / h10) <1). .

  As described above, the light quantity distribution correcting optical system changes the light beam width at each emission position, and the ratio of the light beam width in the peripheral part to the light beam width in the central part near the optical axis Z1 is larger on the outgoing side than on the incident side. Since the light having the same luminous flux width on the incident side is larger on the outgoing side, the luminous flux width in the central portion is larger than that in the peripheral portion, and the luminous flux width in the peripheral portion is smaller than that in the central portion. Become smaller. As a result, it is possible to make use of the light beam at the center part to the peripheral part, and it is possible to form a light beam cross-section with a substantially uniform light amount distribution without reducing the light use efficiency of the entire optical system.

Next, an example of specific lens data of a pair of combination lenses used as the light quantity distribution correcting optical system will be shown. In this example, lens data in the case where the light amount distribution in the cross section of the emitted light beam is a Gaussian distribution as in the case where the light irradiation means is a laser array light source is shown. When one semiconductor laser is connected to the incident end of the single mode optical fiber, the light quantity distribution of the emitted light beam from the optical fiber becomes a Gaussian distribution. The pattern forming method can be applied in such a case. Further, the present invention can be applied to a case where the light amount in the central portion near the optical axis is larger than the light amount in the peripheral portion, for example, by reducing the core diameter of the multi-mode optical fiber and approaching the configuration of the single mode optical fiber.
Table 1 below shows basic lens data.

  As can be seen from Table 1, the pair of combination lenses is composed of two rotationally symmetric aspherical lenses. If the light incident side surface of the first lens disposed on the light incident side is the first surface and the light exit side surface is the second surface, the first surface is aspherical. In addition, when the surface on the light incident side of the second lens disposed on the light emitting side is the third surface and the surface on the light emitting side is the fourth surface, the fourth surface is aspherical.

In Table 1, the surface number Si indicates the number of the i-th surface (i = 1 to 4), the curvature radius ri indicates the curvature radius of the i-th surface, and the surface interval di indicates the i-th surface and the i + 1-th surface. The distance between surfaces on the optical axis is shown. The unit of the surface interval di value is millimeter (mm). The refractive index Ni indicates the value of the refractive index with respect to the wavelength of 405 nm of the optical element having the i-th surface.
Table 2 below shows the aspheric data of the first surface and the fourth surface.

  The aspheric data is expressed by a coefficient in the following formula (A) that represents the aspheric shape.

In the above formula (A), each coefficient is defined as follows.
Z: Length of a perpendicular line (mm) drawn from a point on the aspheric surface at a height ρ from the optical axis to the tangent plane (plane perpendicular to the optical axis) of the apex of the aspheric surface
ρ: Distance from optical axis (mm)
K: Conic coefficient C: Paraxial curvature (1 / r, r: Paraxial radius of curvature)
ai: i-th order (i = 3 to 10) aspheric coefficient In the numerical values shown in Table 2, the symbol “E” indicates that the subsequent numerical value is a “power index” with 10 as the base. The numerical value represented by the exponential function with the base of 10 is multiplied by the numerical value before “E”. For example, “1.0E-02” indicates “1.0 × 10 ⁻² ”.

FIG. 26 shows a light amount distribution of illumination light obtained by the pair of combination lenses shown in Tables 1 and 2. Here, the horizontal axis represents coordinates from the optical axis, and the vertical axis represents the light amount ratio (%). For comparison, FIG. 25 shows a light amount distribution (Gaussian distribution) of illumination light when correction is not performed.
As shown in FIGS. 25 and 26, the light amount distribution correction optical system performs a correction to obtain a substantially uniform light amount distribution as compared with the case where the correction is not performed. Thereby, it is possible to perform exposure with uniform laser light without reducing the use efficiency of light, without causing any unevenness.

Next, the fiber array light source 66 as a light irradiation means will be described.
27A (A) is a perspective view showing a configuration of a fiber array light source, FIG. 27A (B) is a partially enlarged view of (A), and FIGS. 27A (C) and (D) are laser emitting portions. It is a top view which shows the arrangement | sequence of the light emission point in. FIG. 27 b is a front view showing the arrangement of the light emitting points in the laser emission part of the fiber array light source.

  As shown in FIG. 27 a, the fiber array light source 66 includes a plurality of (for example, 14) laser modules 64, and one end of the multimode optical fiber 30 is coupled to each laser module 64. An optical fiber 31 having the same core diameter as that of the multimode optical fiber 30 and a smaller cladding diameter than the multimode optical fiber 30 is coupled to the other end of the multimode optical fiber 30. As shown in detail in FIG. 27b, seven end portions of the multimode optical fiber 31 opposite to the optical fiber 30 are arranged along the main scanning direction orthogonal to the sub-scanning direction, and they are arranged in two rows to form a laser. An emission unit 68 is configured.

  As shown in FIG. 27b, the laser emitting portion 68 is sandwiched and fixed between two support plates 65 having a flat surface. In addition, a transparent protective plate such as glass is preferably disposed on the light emitting end face of the multimode optical fiber 31 for protection. The light exit end face of the multimode optical fiber 31 has high light density and is likely to collect dust and easily deteriorate. However, the protective plate as described above prevents the dust from adhering to the end face and deteriorates. Can be delayed.

  Further, in order to arrange the emission ends of the optical fibers 31 having a small cladding diameter in a row without any gaps, the multi-mode optical fibers 30 are stacked between two adjacent multi-mode optical fibers 30 in a portion having a large cladding diameter, The exit end of the optical fiber 31 coupled to the stacked multi-mode optical fiber 30 is between the two exit ends of the optical fiber 31 coupled to the two adjacent multi-mode optical fibers 30 at a portion where the cladding diameter is large. It is arranged to be sandwiched between.

  In such an optical fiber, as shown in FIG. 28, an optical fiber 31 having a length of 1 to 30 cm and having a small cladding diameter is coaxially provided at the tip of the multimode optical fiber 30 having a large cladding diameter on the laser light emission side. It can be obtained by bonding. In the two optical fibers, the incident end face of the optical fiber 31 is fused and joined to the outgoing end face of the multimode optical fiber 30 so that the central axes of both optical fibers coincide. As described above, the diameter of the core 31 a of the optical fiber 31 is the same as the diameter of the core 30 a of the multimode optical fiber 30.

  In addition, a short optical fiber in which an optical fiber having a short cladding diameter and a large cladding diameter is fused to an optical fiber having a short cladding diameter and a large cladding diameter may be coupled to the output end of the multimode optical fiber 30 via a ferrule or an optical connector. Good. By detachably coupling using a connector or the like, the tip portion can be easily replaced when an optical fiber having a small cladding diameter is broken, and the cost required for exposure head maintenance can be reduced. Hereinafter, the optical fiber 31 may be referred to as an emission end portion of the multimode optical fiber 30.

  The multimode optical fiber 30 and the optical fiber 31 may be any of a step index type optical fiber, a graded index type optical fiber, and a composite type optical fiber. For example, a step index type optical fiber manufactured by Mitsubishi Cable Industries, Ltd. can be used. In the present embodiment, the multimode optical fiber 30 and the optical fiber 31 are step index type optical fibers, and the multimode optical fiber 30 has a cladding diameter = 125 μm, a core diameter = 25 μm, NA = 0.2, an incident end face. The transmittance of the coat is 99.5% or more, and the optical fiber 31 has a cladding diameter = 60 μm, a core diameter = 25 μm, and NA = 0.2.

  In general, in laser light in the infrared region, propagation loss increases as the cladding diameter of the optical fiber is reduced. For this reason, a suitable cladding diameter is determined according to the wavelength band of the laser beam. However, the shorter the wavelength, the smaller the propagation loss. In the case of laser light having a wavelength of 405 nm emitted from a GaN-based semiconductor laser, the cladding thickness {(cladding diameter−core diameter) / 2} is set to an infrared light having a wavelength band of 800 nm. The propagation loss hardly increases even if it is about ½ of the case of propagating infrared light and about ¼ of the case of propagating infrared light in the 1.5 μm wavelength band for communication. Therefore, the cladding diameter can be reduced to 60 μm.

  However, the clad diameter of the optical fiber 31 is not limited to 60 μm. The clad diameter of the optical fiber used in the conventional fiber array light source is 125 μm, but the depth of focus becomes deeper as the clad diameter becomes smaller. More preferably, it is 40 μm or less. On the other hand, since the core diameter needs to be at least 3 to 4 μm, the cladding diameter of the optical fiber 31 is preferably 10 μm or more.

  The laser module 64 includes a combined laser light source (fiber array light source) shown in FIG. This combined laser light source includes a plurality of (for example, seven) chip-like lateral multimode or single mode GaN-based semiconductor lasers LD1, LD2, LD3, LD4, LD5, LD6, arrayed and fixed on the heat block 10. And LD7, collimator lenses 11, 12, 13, 14, 15, 16, and 17 provided corresponding to each of the GaN-based semiconductor lasers LD1 to LD7, one condenser lens 20, and one multi-lens. Mode optical fiber 30. The number of semiconductor lasers is not limited to seven. For example, as many as 20 semiconductor laser beams can be incident on a multimode optical fiber having a cladding diameter = 60 μm, a core diameter = 50 μm, and NA = 0.2. In addition, the number of optical fibers can be further reduced.

  The GaN-based semiconductor lasers LD1 to LD7 all have the same oscillation wavelength (for example, 405 nm), and the maximum output is also all the same (for example, 100 mW for the multimode laser and 30 mW for the single mode laser). As the GaN-based semiconductor lasers LD1 to LD7, lasers having an oscillation wavelength other than the above 405 nm in a wavelength range of 350 nm to 450 nm may be used.

  As shown in FIGS. 30 and 31, the combined laser light source is housed in a box-shaped package 40 having an upper opening together with other optical elements. The package 40 includes a package lid 41 created so as to close the opening thereof. After the deaeration process, a sealing gas is introduced, and the package 40 and the package lid 41 are closed by closing the opening of the package 40 with the package lid 41. 41. The combined laser light source is hermetically sealed in a closed space (sealed space) formed by 41.

  A base plate 42 is fixed to the bottom surface of the package 40, and the heat block 10, a condensing lens holder 45 that holds the condensing lens 20, and the multimode optical fiber 30 are disposed on the top surface of the base plate 42. A fiber holder 46 that holds the incident end is attached. The exit end of the multimode optical fiber 30 is drawn out of the package from an opening formed in the wall surface of the package 40.

  Further, a collimator lens holder 44 is attached to the side surface of the heat block 10, and the collimator lenses 11 to 17 are held. An opening is formed in the lateral wall surface of the package 40, and wiring 47 for supplying a driving current to the GaN-based semiconductor lasers LD1 to LD7 is drawn out of the package through the opening.

  In FIG. 31, in order to avoid complication of the figure, only the GaN-based semiconductor laser LD7 among the plurality of GaN-based semiconductor lasers is numbered, and only the collimator lens 17 among the plurality of collimator lenses is numbered. is doing.

  FIG. 32 shows the front shape of the attachment part of the collimator lenses 11-17. Each of the collimator lenses 11 to 17 is formed in a shape obtained by cutting a region including the optical axis of a circular lens having an aspherical surface into a long and narrow plane. This elongated collimator lens can be formed, for example, by molding resin or optical glass. The collimator lenses 11 to 17 are closely arranged in the arrangement direction of the light emitting points so that the length direction is orthogonal to the arrangement direction of the light emitting points of the GaN-based semiconductor lasers LD1 to LD7 (left and right direction in FIG. 32).

  On the other hand, each of the GaN-based semiconductor lasers LD1 to LD7 includes an active layer having a light emission width of 2 μm, and each of the laser beams B1 in a state parallel to the active layer and a divergence angle in a direction perpendicular to the active layer, respectively, for example A laser emitting ~ B7 is used. These GaN-based semiconductor lasers LD1 to LD7 are arranged so that the light emitting points are arranged in a line in a direction parallel to the active layer.

In the laser beams B1 to B7 emitted from the respective light emitting points, the direction in which the divergence angle is large coincides with the length direction and the direction in which the divergence angle is small with respect to the elongated collimator lenses 11 to 17 as described above. Incident light is incident in a state that coincides with the width direction (direction orthogonal to the length direction). That is, the collimator lenses 11 to 17 have a width of 1.1 mm and a length of 4.6 mm, and the horizontal and vertical beam diameters of the laser beams B1 to B7 incident thereon are 0.9 mm and 6 mm. Each of the collimator lenses 11 to 17 has a focal length f ₁ = 3 mm, NA = 0.6, and a lens arrangement pitch = 1.25 mm.

The condensing lens 20 is formed by cutting a region including the optical axis of a circular lens having an aspheric surface into a long and narrow shape in parallel planes, and is long in the arrangement direction of the collimator lenses 11 to 17, that is, in a horizontal direction and short in a direction perpendicular thereto. Is formed. This condenser lens 20 has a focal length f ₂ = 23 mm and NA = 0.2. This condensing lens 20 is also formed by molding resin or optical glass, for example.

Since the fiber array light source uses a high-intensity fiber array light source in which the emission ends of the optical fibers of the combined laser light source are arranged in an array as the light irradiating means for illuminating the DMD, it has a high output and a deep focus. A pattern forming apparatus having a depth can be realized. Furthermore, since the output of each fiber array light source is increased, the number of fiber array light sources required to obtain a desired output is reduced, and the cost of the pattern forming apparatus can be reduced.
Further, since the cladding diameter of the output end of the optical fiber is smaller than the cladding diameter of the incident end, the diameter of the light emitting portion is further reduced, and the brightness of the fiber array light source can be increased. Thereby, a pattern forming apparatus having a deeper depth of focus can be realized. For example, even in the case of ultra-high resolution exposure with a beam diameter of 1 μm or less and a resolution of 0.1 μm or less, a deep depth of focus can be obtained, and high-speed and high-definition exposure is possible. Therefore, it is suitable for a thin film transistor (TFT) exposure process that requires high resolution.

  The light irradiating means is not limited to a fiber array light source including a plurality of the combined laser light sources. For example, a single laser beam that emits laser light incident from a single semiconductor laser having one light emitting point is emitted. A fiber array light source obtained by arraying fiber light sources including optical fibers can be used.

  As the light irradiation means having a plurality of light emitting points, for example, as shown in FIG. 33, a laser array in which a plurality of (for example, seven) chip-shaped semiconductor lasers LD1 to LD7 are arranged on the heat block 100 is used. Can be used. A chip-shaped multicavity laser 110 in which a plurality of (for example, five) light emitting points 110a shown in FIG. 34A are arranged in a predetermined direction can also be used. Since the multicavity laser 110 can arrange the light emitting points with higher positional accuracy than the case where the chip-shaped semiconductor lasers are arranged, it is easy to multiplex laser beams emitted from the respective light emitting points. However, as the number of light emitting points increases, the multicavity laser 110 is likely to be bent at the time of laser manufacturing. Therefore, the number of light emitting points 110a is preferably 5 or less.

  As the light irradiation means, the multi-cavity laser 110 or a plurality of multi-cavity lasers 110 on the heat block 100 in the same direction as the arrangement direction of the light emitting points 110a of each chip as shown in FIG. An arrayed multi-cavity laser array can be used as a laser light source.

The combined laser light source is not limited to one that combines laser beams emitted from a plurality of chip-shaped semiconductor lasers.
For example, as shown in FIG. 21, a combined laser light source including a chip-shaped multicavity laser 110 having a plurality of (for example, three) light emitting points 110a can be used. This combined laser light source is configured to include a multi-cavity laser 110, one multi-mode optical fiber 130, and a condensing lens 120. The multi-cavity laser 110 can be composed of, for example, a GaN-based laser diode having an oscillation wavelength of 405 nm.

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 110 a of the multicavity laser 110 is collected by the condenser lens 120 and enters the core 130 a of the multimode optical fiber 130. The laser light incident on the core 130a propagates in the optical fiber, is combined into one, and is emitted.

  A plurality of light emitting points 110 a of the multicavity laser 110 are arranged in parallel within a width substantially equal to the core diameter of the multimode optical fiber 130, and a focal point substantially equal to the core diameter of the multimode optical fiber 130 is formed as the condenser lens 120. By using a convex lens of a distance or a rod lens that collimates the outgoing beam from the multicavity laser 110 only in a plane perpendicular to the active layer, the coupling efficiency of the laser beam B to the multimode optical fiber 130 can be increased. it can.

  As shown in FIG. 35, a multi-cavity laser 110 having a plurality of (for example, three) emission points is used, and a plurality of (for example, nine) multi-cavity lasers 110 are equidistant from each other on the heat block 111. A combined laser light source including the laser array 140 arranged in (1) can be used. The plurality of multi-cavity lasers 110 are arranged and fixed in the same direction as the arrangement direction of the light emitting points 110a of each chip.

  This combined laser light source includes a laser array 140, a plurality of lens arrays 114 arranged corresponding to each multi-cavity laser 110, and a single rod arranged between the laser array 140 and the plurality of lens arrays 114. The lens 113, one multimode optical fiber 130, and a condenser lens 120 are provided. The lens array 114 includes a plurality of microlenses corresponding to the emission points of the multicavity laser 110.

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 10a of the plurality of multi-cavity lasers 110 is collected in a predetermined direction by the rod lens 113, and then each microlens of the lens array 114. It becomes parallel light. The collimated laser beam L is condensed by the condenser lens 120 and enters the core 130a of the multimode optical fiber 130. The laser light incident on the core 130a propagates in the optical fiber, is combined into one, and is emitted.

  Furthermore, as another combined laser light source, as shown in FIGS. 36A and 36B, a heat block 182 having an L-shaped cross section in the optical axis direction is mounted on a heat block 180 having a substantially rectangular shape. A storage space is formed between the two heat blocks. On the upper surface of the L-shaped heat block 182, a plurality of (for example, two) multi-cavity lasers 110 in which a plurality of light emitting points (for example, five) are arranged in an array form the light emitting points 110a of each chip. It is arranged and fixed at equal intervals in the same direction as the arrangement direction.

  A concave portion is formed in the substantially rectangular heat block 180, and a plurality of (for example, two) light emitting points (for example, five) are arranged in an array on the upper surface of the space side of the heat block 180. The multi-cavity laser 110 is arranged such that its emission point is located on the same vertical plane as the emission point of the laser chip arranged on the upper surface of the heat block 182.

  On the laser beam emission side of the multi-cavity laser 110, a collimator lens array 184 in which collimator lenses are arranged corresponding to the light emission points 110a of the respective chips is arranged. In the collimating lens array 184, the length direction of each collimating lens coincides with the direction in which the divergence angle of the laser beam is large (fast axis direction), and the width direction of each collimating lens is in the direction in which the divergence angle is small (slow axis direction). They are arranged to match. Thus, by collimating and integrating the collimating lenses, the space utilization efficiency of the laser light can be improved, the output of the combined laser light source can be increased, and the number of parts can be reduced and the cost can be reduced. .

  Further, on the laser beam emitting side of the collimating lens array 184, there is one multimode optical fiber 130, and a condensing lens 120 that condenses and combines the laser beam at the incident end of the multimode optical fiber 130. Is arranged.

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 10a of the plurality of multicavity lasers 110 arranged on the laser blocks 180 and 182 is collimated by the collimating lens array 184 and condensed. The light is condensed by the lens 120 and enters the core 130 a of the multimode optical fiber 130. The laser light incident on the core 130a propagates in the optical fiber, is combined into one, and is emitted.

  As described above, the combined laser light source can achieve particularly high output by the multistage arrangement of multicavity lasers and the array of collimating lenses. By using this combined laser light source, a higher-intensity fiber array light source or bundle fiber light source can be formed, which is particularly suitable as a fiber light source constituting the laser light source of the pattern forming apparatus.

  It should be noted that a laser module in which each of the combined laser light sources is housed in a casing and the emission end of the multimode optical fiber 130 is pulled out from the casing can be configured.

  In addition, the other end of the multimode optical fiber of the combined laser light source is coupled with another optical fiber having the same core diameter as the multimode optical fiber and a cladding diameter smaller than the multimode optical fiber. However, for example, a multimode optical fiber having a cladding diameter of 125 μm, 80 μm, 60 μm or the like may be used without coupling another optical fiber to the emission end.

  In each exposure head 166 of the scanner 162, laser beams B1, B2, B3, B4, B5, and B6 emitted in a divergent light state from each of the GaN-based semiconductor lasers LD1 to LD7 constituting the combined laser light source of the fiber array light source 66. , And B7 are collimated by corresponding collimator lenses 11-17. The collimated laser beams B <b> 1 to B <b> 7 are collected by the condenser lens 20 and converge on the incident end face of the core 30 a of the multimode optical fiber 30.

The condensing optical system includes collimator lenses 11 to 17 and a condensing lens 20. Also, the converging optical system and the multimode optical fiber 30 constitute a multiplexing optical system.
The laser beams B1 to B7 condensed as described above by the condenser lens 20 are incident on the core 30a of the multimode optical fiber 30, propagate through the optical fiber, and are combined into one laser beam B. The light exits from the optical fiber 31 coupled to the exit end of the multimode optical fiber 30.

  In each laser module, when the coupling efficiency of the laser beams B1 to B7 to the multimode optical fiber 30 is 0.85 and each output of the GaN-based semiconductor lasers LD1 to LD7 is 30 mW, the light arranged in an array For each of the fibers 31, a combined laser beam B with an output of 180 mW (= 30 mW × 0.85 × 7) can be obtained. Therefore, the output from the laser emitting unit 68 in which the six optical fibers 31 are arranged in an array is about 1 W (= 180 mW × 6).

  In the laser emitting section 68 of the fiber array light source 66, high-luminance light emitting points are arranged in a line along the main scanning direction. A conventional fiber light source that couples laser light from a single semiconductor laser to a single optical fiber has a low output, so that a desired output cannot be obtained unless multiple rows are arranged. Since the laser light source has a high output, a desired output can be obtained even with a small number of columns, for example, one column.

For example, in a conventional fiber light source in which a semiconductor laser and an optical fiber are coupled on a one-to-one basis, a laser having an output of about 30 mW (milliwatt) is usually used as the semiconductor laser, and the core diameter is 50 μm and the cladding diameter is 125 μm. Since a multimode optical fiber having a numerical aperture (NA) of 0.2 is used, if an output of about 1 W (watt) is to be obtained, 48 multimode optical fibers (8 × 6) must be bundled. Since the area of the light emitting region is 0.62 mm ² (0.675 mm × 0.925 mm), the luminance at the laser emitting portion 68 is 1.6 × 10 ⁶ (W / m ² ) and one optical fiber is used. The luminance per hit is 3.2 × 10 ⁶ (W / m ² ).

On the other hand, when the light irradiating means is a means capable of irradiating a combined laser, an output of about 1 W can be obtained with six multimode optical fibers, and the area of the light emitting region at the laser emitting portion 68 can be obtained. Is 0.0081 mm ² (0.325 mm × 0.025 mm), the luminance at the laser emitting portion 68 is 123 × 10 ⁶ (W / m ² ), which is about 80 times higher than the conventional luminance. be able to. Further, the luminance per optical fiber is 90 × 10 ⁶ (W / m ² ), and the luminance can be increased by about 28 times compared with the conventional one.

  Here, with reference to FIGS. 37A and 37B, the difference in depth of focus between the conventional exposure head and the exposure head of the present embodiment will be described. The diameter of the light emission region of the bundled fiber light source of the conventional exposure head in the sub-scanning direction is 0.675 mm, and the diameter of the light emission region of the fiber array light source of the exposure head in the sub-scanning direction is 0.025 mm. As shown in FIG. 37A, in the conventional exposure head, since the light emitting area of the light irradiating means (bundle-shaped fiber light source) 1 is large, the angle of the light beam incident on the DMD 3 is increased, and as a result, the scanning surface 5 is moved. The angle of the incident light beam increases. For this reason, the beam diameter tends to increase with respect to the light condensing direction (shift in the focus direction).

  On the other hand, as shown in FIG. 37B, in the exposure head in the pattern forming apparatus, the diameter of the light emitting region of the fiber array light source 66 in the sub-scanning direction is small, so that the light flux that passes through the lens system 67 and enters the DMD 50 , And as a result, the angle of the light beam incident on the scanning surface 56 is reduced. That is, the depth of focus becomes deep. In this example, the diameter of the light emitting region in the sub-scanning direction is about 30 times that of the conventional one, and a depth of focus substantially corresponding to the diffraction limit can be obtained. Therefore, it is suitable for exposure of a minute spot. This effect on the depth of focus is more prominent and effective as the required light quantity of the exposure head is larger. In this example, the size of one pixel projected on the exposure surface is 10 μm × 10 μm. The DMD is a reflective spatial light modulator, but FIGS. 37A and 37B are developed views for explaining the optical relationship.

Next, the pattern forming method using the pattern forming apparatus will be described.
First, pattern information corresponding to the exposure pattern is input to a controller (not shown) connected to the DMD 50 and temporarily stored in a frame memory in the controller. This pattern information is data representing the density of each pixel constituting the image as binary values (whether or not dots are recorded).
Next, the stage 152 having the pattern forming material 150 adsorbed on the surface thereof is moved at a constant speed from the upstream side to the downstream side of the gate 160 along the guide 158 by a driving device (not shown). When the leading edge of the pattern forming material 150 is detected by the detection sensor 164 attached to the gate 160 when the stage 152 passes under the gate 160, the pattern information stored in the frame memory is sequentially read out for a plurality of lines. Then, a control signal is generated for each exposure head 166 based on the pattern information read by the data processing unit. Then, each of the micromirrors of the DMD 50 is on / off controlled for each exposure head 166 based on the generated control signal by the mirror drive control unit.
Next, when the DMD 50 is irradiated with laser light from the fiber array light source 66, the laser light reflected when the micromirrors of the DMD 50 are turned on is exposed to the exposed surface 56 of the pattern forming material 150 by the lens systems 54 and 58. Imaged on top.
In this way, the laser light emitted from the fiber array light source 66 is turned on / off for each pixel, and the pattern forming material 150 is exposed in approximately the same number of pixel units (exposure area 168) as the number of used pixel elements of the DMD 50. The
Further, when the pattern forming material 150 is moved at a constant speed together with the stage 152, the pattern forming material 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip-shaped exposed region 170 is provided for each exposure head 166. Is formed.

[Removal of photosensitive layer cover film]
The photosensitive layer cover film is peeled from the exposed photosensitive layer without being damaged.
There is no restriction | limiting in particular as a peeling method of the said photosensitive layer cover film, According to the objective, it can select suitably. For example, when the photosensitive layer and the photosensitive layer cover film are closely attached in a vacuum firing frame, the pressure in the vacuum firing frame is returned to atmospheric pressure, and then the photosensitive layer cover film is peeled off from the photosensitive layer. .
When the photosensitive layer cover film is used as a translucent member of the vacuum firing frame, the pressure in the vacuum firing frame is returned to atmospheric pressure, and then the vacuum firing frame is opened to open the photosensitive frame. A layer cover film is peeled off from the photosensitive layer.

  After peeling off the photosensitive layer cover film, the photosensitive layer may be post-baked as necessary. By performing the post-baking, the photopolymerization of the exposed portion of the photosensitive layer can be advanced to improve the developer resistance. However, in order to prevent thermal polymerization of unexposed portions of the photosensitive layer and not deteriorate developability, the post-bake is preferably performed at 50 to 100 ° C. for 1 to 60 minutes, and at 60 to 80 ° C. for 10 to 10 minutes. More preferably, it is performed for 30 minutes.

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

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

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

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

[Other processes]
In the formation of the pattern, for example, a curing process, an etching process, a plating process, and the like may be included. These may be used alone or in combination of two or more.

-Curing process-
When the pattern formation method is a pattern formation method for forming a permanent pattern such as a protective film or an interlayer insulating film or a color filter, a curing process step for performing a curing process on the photosensitive layer after the development step It is preferable to provide.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

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

Examples of the entire surface heat treatment method include a method of heating the entire surface of the laminate on which the permanent pattern is formed after the development. The entire surface heating increases the film strength of the surface of the permanent pattern.
As heating temperature in the said whole surface heating, 120-250 degreeC is preferable and 120-200 degreeC is more preferable. When the heating temperature is less than 120 ° C., the film strength may not be improved by heat treatment. When the heating temperature exceeds 250 ° C., the resin in the photosensitive composition is decomposed, and the film quality is weak and brittle. Sometimes.
The heating time in the entire surface heating is preferably 10 to 120 minutes, and more preferably 15 to 60 minutes.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

-Etching process-
The etching step can be performed by a method appropriately selected from known etching methods.
There is no restriction | limiting in particular as an etching liquid used for the said etching process, Although it can select suitably according to the objective, For example, when the said metal layer is formed with copper, a cupric chloride solution, Examples thereof include a ferric chloride solution, an alkali etching solution, and a hydrogen peroxide-based etching solution. Among these, a ferric chloride solution is preferable from the viewpoint of an etching factor. Moreover, a well-known sandblasting method can be used.
A wiring pattern can be formed on the surface of the substrate by removing the pattern after performing the etching process in the etching step.

-Plating process-
The plating step can be performed by an appropriately selected method selected from known plating processes.
Examples of the plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, and hard gold plating. And gold plating such as soft gold plating.
A metal wiring pattern can be formed on the surface of the substrate by removing the pattern after plating by the plating step and further removing unnecessary portions by a resist stripping process or the like as necessary.

  The pattern forming method can be used for forming various patterns that require prevention of sensitivity reduction of the photosensitive layer by oxygen in direct writing by laser exposure of 405 nm, and has high density and high productivity. It can be suitably used for forming a compatible pattern.

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

  In the pattern forming method, when the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, the wiring can be protected from external impact and bending, and in particular, In the case of an interlayer insulating film, it is useful for high-density mounting of semiconductors and components on, for example, a multilayer wiring board and a build-up wiring board.

-Printed wiring pattern formation method-
When the pattern forming method is a pattern forming method for forming a printed wiring pattern, the pattern can be formed at a high speed, and thus can be widely used for forming various patterns. In particular, it can be suitably used for the production of a printed wiring board having a hole portion such as a through hole or a via hole.

  As a method of manufacturing a printed wiring board having a hole portion such as the through hole or via hole by the pattern forming method, (1) a hole filling ink is formed on a printed wiring board forming substrate having a hole portion as the base material. (2) applying a photosensitive composition solution for a circuit forming photoresist (hereinafter referred to as a circuit forming liquid photoresist) and drying to form a photosensitive layer; A laminate is formed by laminating a photosensitive layer cover film on the photosensitive layer, and (3) irradiating the wiring pattern formation region and the hole portion formation region with light from the side opposite to the base material of the laminate under reduced pressure. The photosensitive layer is cured, (4) the photosensitive layer cover film is peeled off from the photosensitive layer, and (4) the photosensitive layer is developed to remove an uncured portion of the photosensitive layer. A pattern can be formed by.

  Thereafter, in order to obtain a printed wiring board, a method of etching or plating the printed wiring board forming substrate using the formed pattern (for example, a known subtractive method or additive method (for example, a semi-additive method) And the full additive method)). After the treatment, the cured resin remaining on the printed wiring board forming substrate is peeled off. In the case of the semi-additive method, a desired printed wiring board can be manufactured by further etching the copper thin film portion after peeling. it can. A multilayer printed wiring board can also be manufactured in the same manner as the printed wiring board manufacturing method.

A method for manufacturing a printed wiring board having a through hole using the circuit forming liquid photoresist will be further described.
First, a hole is formed on a double-sided metal-clad laminate by drilling a through-hole at a predetermined position with a predetermined size using a drill. A conductive plating layer is formed in the hole by a through-hole plating method, and a through-hole that is electrically connected to the conductor patterns on the front and back sides is formed. Next, after filling and filling the through hole with ink for filling the hole, excess ink for filling the hole remaining on the substrate surface is removed by mechanical polishing. The circuit forming liquid photoresist is applied to the surface of the substrate thus obtained and dried to form a photosensitive layer.

As the double-sided metal-clad laminate, for example, a copper-clad laminate in which copper foil is attached to the front and back of an insulating substrate made of epoxy resin, polyimide resin, polyester resin, etc., metal such as aluminum or iron is epoxy resin, etc. Examples thereof include a metal-based insulating substrate and a ceramic substrate that have been subjected to an insulating process.
The hole-filling ink may be either a thermosetting type that cures by evaporation of the ink solvent or a photocurable type that cures by light irradiation. Examples of the thermosetting hole filling ink include natural rosin, rosin-modified maleic acid resin, alkali-soluble resin such as styrene acrylic acid copolymer described in JP-A-4-52887, solvent, powdered foaming agent, and activity. Examples thereof include inks formed from solid powders, and inks composed of phenol resins, rosin resins, tetrahydrophthalic acid monoester acrylates, and thermal polymerization catalysts described in JP-A-6-338684. Examples of the photocurable ink for filling holes include those described in JP-A-56-8417, JP-A-60-3624, and JP-A-62-96513.
Examples of the method for filling the through hole with the hole filling ink include a dip filling method, a screen printing filling method, and a roll filling method.

The method of applying the circuit forming liquid photoresist to the substrate surface is not particularly limited as long as a uniform coating surface can be obtained. For example, offset printing, screen printing, spray coating, electrostatic The method of apply | coating with spray coating, a roll coater, a flow coater, a bar coater etc. is mentioned.
The viscosity of the circuit-forming liquid photoresist is preferably 10 to 2000 centipoise (E-type viscometer, 25 ° C.), and the solid content concentration is preferably 30 to 80% by mass.

  Next, the uncured region of the photosensitive layer on the printed wiring board forming substrate is dissolved and removed with an appropriate developer to form a pattern of the cured layer for forming the wiring pattern and the cured layer for protecting the metal layer of the through hole. And a metal layer is exposed on the surface of the printed wiring board forming substrate (developing step).

  Moreover, you may perform the process which further accelerates | stimulates the hardening reaction of a hardening part by post-heat processing or post-exposure processing as needed after image development. The development may be a wet development method as described above or a dry development method.

  Next, the metal layer exposed on the surface of the printed wiring board forming substrate is dissolved and removed with an etching solution (etching step). Since the opening of the through hole is covered with a cured resin composition (tent film), the metal plating of the through hole is predetermined without etching liquid entering the through hole and corroding the metal plating in the through hole. It will remain in the shape. Thus, a wiring pattern is formed on the printed wiring board forming substrate.

  There is no restriction | limiting in particular as said etching liquid, Although it can select suitably according to the objective, For example, when the said metal layer is formed with copper, a cupric chloride solution, a ferric chloride solution , Alkaline etching solutions, hydrogen peroxide-based etching solutions, and the like. Among these, ferric chloride solutions are preferable from the viewpoint of etching factors.

Next, it removes from the said board | substrate for printed wiring board formation by making the said hardened layer into a peeling piece with strong alkaline aqueous solution etc. (hardened | cured material removal process).
There is no restriction | limiting in particular as a base component in the said strong alkali aqueous solution, For example, sodium hydroxide, potassium hydroxide, etc. are mentioned.
As pH of the said strong alkali aqueous solution, about 12-14 are preferable, for example, and about 13-14 are more preferable.
There is no restriction | limiting in particular as said strong alkali aqueous solution, For example, 1-10 mass% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution etc. are mentioned.

The printed wiring board may be a multilayer printed wiring board or a flexible substrate.
The circuit forming liquid photoresist may be used not only in the etching process but also in a plating process. Examples of the plating method include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, and hard gold plating. And gold plating such as soft gold plating.

-Color filter formation method-
When the pattern forming method is a pattern forming method for forming a color filter using the color resist layer, the pattern forming method is used to form three primary colors on a transparent substrate such as a glass substrate as the base material. Pixels can be arranged in a mosaic or stripe. There is no restriction | limiting in particular as a dimension of each pixel, According to the objective, it can select suitably, For example, it is preferable to set it as 40-200 micrometers.
As the color filter forming method, for example, using a photosensitive composition colored in black on a transparent substrate, exposure and development are performed to form a black matrix, and then it is colored in one of the three primary colors of RGB. The three primary colors of RGB are arranged in a mosaic or stripe pattern on the transparent substrate by repeating exposure and development sequentially for each color in a predetermined arrangement with respect to the black matrix. And a method of forming a color filter.
The color filter formed by the color filter forming method can be suitably used for a video camera, a monitor, and a liquid crystal color television.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

Example 1
-Production of photosensitive layer cover film-
On one side of a 100 μm thick biaxially stretched polyethylene terephthalate film (support for photosensitive layer cover film, oxygen permeability: 143 mL / m ² · day · MPa) It was applied by a coater and dried at 90 ° C. for 2 minutes to form a 1 μm thick resist adhesion preventing layer. A 15 μm-thick polypropylene film was laminated thereon as a protective material to prepare a photosensitive layer cover film.
[Coating solution for resist adhesion prevention layer]
Acrylic polyol (Acridic A-801: manufactured by Dainippon Ink & Chemicals, Inc., solid content 50% by mass) 6.0 parts by mass Isocyanate prepolymer (Bernock D-750: manufactured by Dainippon Ink & Chemicals, Inc.) , Solid content: 75% by mass) 1.5 parts by mass. Silicone-acrylic graft polymer (LSI-60: manufactured by Soken Chemical Co., Ltd., solid content: 4)
5% by mass) 0.5 part by mass / toluene 20 parts by mass
・ Methyl ethyl ketone 20 parts by mass

-Manufacture of laminates-
Based on the following composition, a photosensitive solder resist was prepared and applied onto a substrate to be treated.
[Photosensitive solder resist composition]
・ Polybasic acid anhydride adduct of cresol novolac type epoxy-modified acrylate resin
100 parts by mass dipentaerythritol hexaacrylate 20 parts by mass 3,3 ′, 5,5′-tetramethyl-4,4′-diglycidyloxybiphenyl (Y
X4000: Japan Epoxy Resin Co., Ltd.) 50 parts by mass Barium sulfate (B-30: Sakai Chemical Industry Co., Ltd.) 90 parts by mass Diethylthioxanthone (DEX-S: Nippon Kayaku Co., Ltd.) 1 part by mass Parts, dimethylmorpholinomethyl-p-methylthiophenyl ketone (Irgacure 907: Ciba Specialty Chemicals Co., Ltd.) 15 parts by mass, dicyandiamide 0.3 parts by mass
-Phthalocyanine green 1 mass part Each said component was knead | mixed with the 3 roll mill, and the photosensitive soldering resist was prepared. This is coated on a copper-clad laminate (copper foil thickness 20 μm / resin thickness 1.4 mm) on which a wiring pattern is formed using a screen printer, and dried at 80 ° C. for 30 minutes in a hot-air circulating drying oven. A photosensitive layer having a thickness of 15 μm was formed on the copper foil and a thickness of 35 μm was formed on the resin.

On the photosensitive layer of the copper clad laminate on which the photosensitive layer was formed, the photosensitive layer cover film was overlaid so that the resist adhesion preventing layer was in contact with the photosensitive layer while peeling off the protective material.
This was placed in a vacuum frame of an exposure apparatus, depressurized at room temperature, and the photosensitive layer and the photosensitive layer cover film were brought into close contact to produce a laminate.
When the protective material on the photosensitive layer cover film was peeled off, the surface of the resist adhesion preventing layer was not tacky and could be easily peeled off.

--Exposure--
The cover layer is passed from the upper frame of the vacuum baking frame to the photosensitive layer in the laminate, and a laser beam having a wavelength of 405 nm is applied to a 15-step step wedge pattern (ΔlogE) using a pattern forming apparatus described below. = 0.15), and exposure was performed so as to obtain a pattern in which a large number of holes having different diameters were formed, and a part of the photosensitive layer was cured.

-Pattern forming device-
27 to 32 as the light irradiating means, and 768 pairs of micromirror arrays in which 1024 micromirrors are arranged in the main scanning direction shown in FIG. 4 as the light modulating means are arranged in the sub-scanning direction. Among the optical modulation means, the DMD 50 controlled to drive only 1024 × 256 rows, and the microlens array in which the microlenses whose one surface is a toric surface shown in FIG. 13 are arranged in an array A pattern forming apparatus having 472 and optical systems 480 and 482 for forming an image of light passing through the microlens array on the photosensitive layer was used.
As an appearance, a vacuum frame (not shown) in which the laminate is stored is disposed on the stage 152 of the pattern forming apparatus shown in FIG. 7, and the photosensitive layer 150 of the laminate is exposed.

  As the microlens, a toric lens 55a is used as shown in FIGS. 17 and 18, and a curvature radius Rx = −0.125 mm in a direction optically corresponding to the x direction, corresponding to the y direction. The radius of curvature Ry in the direction to travel is −0.1 mm.

  In addition, the aperture array 59 disposed in the vicinity of the condensing position of the microlens array 55 is disposed so that only light that has passed through the corresponding microlens 55a is incident on each aperture 59a.

<Development>
After the exposure, the laminated body is taken out from the vacuum baking frame and allowed to stand at room temperature for 10 minutes, and then the photosensitive layer cover film is peeled and removed, and 1% by mass sodium carbonate as an alkaline developer is formed on the entire surface of the photosensitive layer. Using an aqueous solution, shower development was performed at 30 ° C. for 60 seconds to dissolve and remove uncured regions. Thereafter, it was washed with water and dried to form a resist pattern.

[Evaluation]
The exposure sensitivity and resolution of the laminate were evaluated by the following methods. Moreover, about the said photosensitive layer cover film, the total light transmittance with respect to a 405 nm laser beam, the peelability after exposure, and the suitability of repeated use were evaluated. The results are shown in Table 4.

<Exposure sensitivity>
(1) Measuring method of shortest development time The photosensitive layer cover film is peeled off from the laminate produced in the same manner as in Example 1, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is added to the entire surface of the photosensitive layer at 1.5 kg / Spraying was performed at a pressure of cm ² , and the time required from the start of spraying of the aqueous sodium carbonate solution until the photosensitive layer was dissolved and removed was measured, and this was taken as the shortest development time.

(2) Measurement of exposure sensitivity For the photosensitive layer in the laminate produced in the same manner as in Example 1, a pattern forming apparatus having a laser light source of 405 nm as the light irradiation means from above the photosensitive layer cover film was used. Then, a 15-step step wedge (Δlog E = 0.15) pattern was exposed to light having different amounts of light energy, and a part of the photosensitive layer was cured. After leaving still for 10 minutes at room temperature, the said support body for photosensitive layers was peeled off from the said laminated body, and sodium carbonate aqueous solution (30 degreeC, 1 mass%) was sprayed on the whole surface of the photosensitive layer by 1.5 kg / cm < ² >. And sprayed for twice the shortest development time determined in (1) above, the uncured area was dissolved and removed, and the thickness of the remaining cured area was measured. Next, a sensitivity curve is obtained by plotting the relationship between the light irradiation amount and the thickness of the cured layer. From the sensitivity curve thus obtained, the amount of light energy when the thickness of the cured region reached 7 steps of 15 steps was defined as the amount of light energy necessary to cure the photosensitive layer, and this was taken as the sensitivity. As a result, the amount of light energy necessary for curing the photosensitive layer was 300 mJ / cm ² . The results are shown in Table 4.

<Resolution>
The surface of the obtained copper-clad laminate with the resist pattern formed was observed with an optical microscope, and the minimum hole diameter without any remaining film was measured in the hole portion of the resist pattern formed on the copper foil. The resolution. The smaller the numerical value, the better the resolution. As a result, the pattern of 50 μmφ or more was developed, but the pattern of 45 μm or less was not developed, so the resolution was 50 μmφ. The results are shown in Table 4.

<Total light transmittance>
Using a device incorporating an integrating sphere in a spectrophotometer (manufactured by Shimadzu Corporation, UV-2400), the total light transmittance was measured by irradiating the photosensitive layer cover film with 405 nm laser light. The results are shown in Table 4.

<Releasability of photosensitive layer cover film>
The peelability when peeling the photosensitive layer cover film from the exposed laminate was evaluated based on the following criteria. The results are shown in Table 4.
〔Evaluation criteria〕
○: There is no tackiness and can be easily peeled. ×: There is tackiness and is difficult to peel off.

<Appropriateness of reuse of photosensitive layer cover film>
Using one photosensitive layer cover film, lamination, exposure and peeling were repeated 100 times in the same manner as in Example 1. After the completion of 100 times, the photosensitive layer cover film was observed to confirm the presence or absence of resist debris. Furthermore, the number of defects generated in the pattern formed by the 100th exposure was observed. The results are shown in Table 4.

(Example 2)
In Example 1, 0.5 parts by mass of the silicone-acrylic graft polymer in the coating solution for resist adhesion preventing layer was replaced by 10 parts of fluorine-acrylic graft polymer (GF-300: manufactured by Toagosei Co., Ltd., solid content: 25% by mass). A photosensitive layer cover film and a laminate were produced in the same manner as in Example 1 except that the pattern was changed, except that the pattern was formed.
Further, in the same manner as in Example 1, the exposure sensitivity and resolution were evaluated for the laminate, and the light-sensitive layer cover film was evaluated for total light transmittance, peelability after exposure, and suitability for repeated use. went. The results are shown in Table 4.

(Example 3)
-Production of photosensitive layer cover film-
On one side of a 100 μm-thick biaxially stretched polyethylene terephthalate film (support for photosensitive layer cover film, oxygen permeability: 143 mL / m ² · day · MPa), an undercoat layer coating solution having the following composition was applied, By drying, an undercoat layer having a thickness of 0.5 μm was formed.
[Coating liquid for undercoat layer]
・ Butyl acrylate / tricyclo [5.2.1.0 ^2.6 ] dec-8-yl-methacrylate (weight ratio = 50/50) copolymer 11.0 parts by mass. Polyester resin (Acryt ER20: Taisei Kako) (Product made, solid content 40 mass%)
10 parts by mass-Methyl ethyl ketone 11.0 parts by mass-Toluene 11.0 parts by mass
・ Cyclohexanone 6.0 parts by mass

A coating solution for resist adhesion prevention layer having the following composition is coated on the undercoat layer with a bar coater and cured by irradiating with ultraviolet light with a high pressure mercury lamp for 1 to 2 seconds to prevent resist adhesion with a thickness of 1 μm. A layer was formed. A 15 μm-thick polypropylene film was laminated thereon as a protective material to prepare a photosensitive layer cover film.
[Coating solution for resist adhesion prevention layer]
Photocurable composition ^* (Iupimer UV H6000DS: manufactured by Mitsubishi Chemical Corporation, solid content = 30
85.7 parts by mass) Photopolymerization initiator (Irgacure 651: Ciba Specialty Chemicals Co., Ltd.)
0.9 parts by mass
・ Isopropyl alcohol 14.3 parts by mass *: Photo-curing property having a polymer having a quaternary ammonium base, a methacryloyl group and an organosiloxane simple substance, and a polyfunctional methacrylate having two or more methacryloyl groups in the molecule. Composition.

Using the obtained photosensitive layer cover film, a laminate was produced in the same manner as in Example 1 to form a pattern.
Further, in the same manner as in Example 1, the exposure sensitivity and resolution were evaluated for the laminate, and the light-sensitive layer cover film was evaluated for total light transmittance, peelability after exposure, and suitability for repeated use. went. The results are shown in Table 4.

Example 4
In Example 1, a laminate was produced in the same manner as in Example 1 except that a 100 μm-thick biaxially stretched polyethylene terephthalate film without forming a resist adhesion preventing layer was used as the photosensitive layer cover film, and a pattern was formed. .
Moreover, it carried out similarly to Example 1, and evaluated the exposure sensitivity and the resolution about the said laminated body, and evaluated the peelability after exposure and the suitability of repeated use about the said photosensitive layer cover film. The results are shown in Table 4.

(Example 5)
In Example 1, a photosensitive solder resist having the following composition was prepared, and a photosensitive layer cover film and a laminate were produced in the same manner as in Example 1 except that a pattern was formed in the same manner as in Example 1 except that the photosensitive solder resist was applied onto a substrate to be processed. .
Further, in the same manner as in Example 1, the exposure sensitivity and resolution were evaluated for the laminate, and the light-sensitive layer cover film was evaluated for total light transmittance, peelability after exposure, and suitability for repeated use. went. The results are shown in Table 4.
[Photosensitive solder resist composition]
・ Barium sulfate dispersion ^{* 1} 24.75 parts by mass ・ 35% by mass methyl ethyl ketone solution of styrene / maleic acid / butyl acrylate copolymer (molar ratio = 40/32/28, benzylamine 100% modified product) ^{* 2}
13.36 parts by mass. Bifunctional acrylic monomer (R712: Nippon Kayaku Co., Ltd.) 3.06 parts by mass. 4.59 parts by mass of dipentaerythritol hexaacrylate. Photopolymerization initiator (Irgacure 819: Ciba Specialty. Chemicals Co., Ltd.)
1.98 parts by mass-Fluorosurfactant (F780F: manufactured by Dainippon Ink Co., Ltd.) 30 mass% methyl ethyl ketone solution 0.066 parts by mass-hydroquinone monomethyl ether 0.024 parts by mass
8.6 parts by mass of methyl ethyl ketone * 1 is 30 parts by mass of barium sulfate (B-30: Sakai Chemical Industry Co., Ltd.), 34.29 parts by mass of * 2, and 1-methoxy-2-propyl acetate 35 After mixing with 71 parts by mass in advance, the mixture was prepared by using a motor mill M-200 (manufactured by Eiger) to disperse for 3.5 hours at a peripheral speed of 9 m / sec using zirconia beads having a diameter of 1.0 mm.

(Example 6)
-Formation of conductive layer-
A homogeneous solution was obtained by dissolving 65 parts by weight of stannic chloride hydrate and 1.5 parts by weight of antimony trichloride in 1000 parts by weight of ethanol. To this solution, a 1N aqueous sodium hydroxide solution was added dropwise until the pH reached 3, and the coprecipitate of colloidal stannic oxide and antimony oxide was allowed to stand at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate. After separating this by centrifugation, water was added to remove excess ions, and the operation of washing with water by centrifugation was repeated three times. 100 parts by weight of this precipitate was mixed with 1,000 parts by weight of water and sprayed into a baking furnace heated to 650 ° C. to give a bluish conductive substance (metal oxide fine particles) having an average particle size of 0.15 μm. Obtained. The conductive substance was dispersed for 5 hours using a paint shaker (manufactured by Toyo Seiki Seisakusho Co., Ltd.) according to the following formulation to obtain a conductive substance dispersion.
[Conductive substance dispersion]
-200 parts by weight of conductive material (metal oxide fine particles) obtained by the above method-Saran F-310 (vinylidene chloride copolymer, manufactured by Asahi Dow Co., Ltd.) 10 parts by weight
-150 parts by weight of methyl ethyl ketone A conductive layer forming coating solution having the following composition was prepared using the conductive fine particle dispersion. This was applied to a polyethylene terephthalate film (support for photosensitive layer cover film) having a thickness of 100 μm so that the dry coating amount was 1.3 g / m ² and dried at 130 ° C. for 2 minutes.
[Coating liquid for forming conductive layer]
-15 parts by weight of the conductive fine particle dispersion-Saran F-310 (vinylidene chloride copolymer, manufactured by Asahi Dow) 3 parts by weight-100 parts by weight of methyl ethyl ketone-20 parts by weight of cyclohexanone
-5 parts by weight of m-cresol Further, a hydrophobic polymer solution having the following formulation was applied onto the conductive layer so that the dry coating amount was 0.2 g / m @ 2, and dried at 130 DEG C for 1 minute. Then, a hydrophobic polymer layer was formed.
[Hydrophobic polymer solution]
-1 part by weight of cellulose triacetate-60 parts by weight of methylene dichloride-40 parts by weight of ethylene dichloride
-Erucic acid amide 0.01 part by weight Insulation resistance measuring device (VE-30 manufactured by Kawaguchi Electrode Co., Ltd.) was used to determine the surface electrical resistance value of the support for the photosensitive layer cover film on which the conductive layer and the hydrophobic polymer layer were formed. Type) was 7 × 10 ⁸ Ω in an environment of 10 ° C. and 33% RH.

  The photosensitive layer cover film support having the conductive layer and the hydrophobic polymer layer formed thereon is (a), and in (a), the conductive fine particles in the conductive layer forming coating solution. The surface resistance values of the support (b) to (e) for the photosensitive layer cover film in which the conductive layer was formed by changing the addition amount of the dispersion were measured. Table 3 shows the content of the conductive fine particle dispersion and the surface resistance value.

* Measured value in an environment of 10 ° C and 33% RH

The photosensitive layer cover film support (a) to (e) on which the conductive layer and the hydrophobic polymer layer are formed have a thickness of 0.008 μm on the surface where the conductive layer is not formed. A gelatin layer was formed, and a resist adhesion preventing layer was formed thereon in the same manner as in Example 1 to prepare a photosensitive layer cover film, and a laminate was produced to form a pattern.
Further, in the same manner as in Example 1, the exposure sensitivity and resolution were evaluated for the laminate, and the light-sensitive layer cover film was evaluated for total light transmittance, peelability after exposure, and suitability for repeated use. went. The results are shown in Table 4.

(Example 7)
A photosensitive layer cover film and a laminate were prepared in the same manner as in Example 1 except that a color resist having the following composition was prepared in Example 1, coated on a substrate to be processed, and developed by the following method. Manufactured and formed a pattern.
Further, in the same manner as in Example 1, the exposure sensitivity and resolution were evaluated for the laminate, and the light-sensitive layer cover film was evaluated for total light transmittance, peelability after exposure, and suitability for repeated use. went. The results are shown in Table 4.

-Preparation of color resist composition-
Benzyl methacrylate / methacrylic acid copolymer [copolymerization composition (molar ratio): 68/32, mass average molecular weight: 30.000, Tg: 77 ° C.] 80 parts by mass, C.I. I. Pigment Green 7 100 parts by mass, C.I. I. Each component consisting of 30 parts by mass of Pigment Yellow 185 and 500 parts by mass of propylene glycol monomethyl ether acetate was dispersed for one day in a sand mill.
Next, 80 parts by mass of dipentaerythritol hexaacrylate, 4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] 2,6-bis (trichloromethyl) -s was added to the obtained dispersion. -5 parts by weight of triazine, 2 parts by weight of 7- [4-chloro-6- (diethylamino) -s-triazin-2-ylamino] -3-phenylcoumarin, 0.01 part by weight of hydroquinone monomethyl ether, and propylene glycol monomethyl ether A color resist composition was prepared by adding a mixture of 500 parts by mass of acetate.

  The exposed photosensitive layer was allowed to stand at room temperature for 10 minutes, and then the photosensitive layer cover film was peeled off. An organic alkali developer (trade name; CD-2000-4) manufactured by Fuji Film Arch Co., Ltd. ) And paddle development for 60 seconds at room temperature to dissolve and remove uncured areas. Thereafter, it was rinsed with pure water in a spin shower for 20 seconds, further washed with pure water, and naturally dried to form a color filter pattern.

(Example 8)
Fill a through-hole with a hole-filling ink (trade name: SER1490T-3, manufactured by Sanei Chemical Co., Ltd.) on a copper-clad laminate having 500 holes with a diameter of 2.0 mm, and cure the hole-filling ink by UV irradiation. Then, the hole filling ink residue was removed by buffing to prepare a substrate. A photosensitive solder resist having the following composition was applied to the surface of the obtained substrate using a wire bar and dried at 120 ° C. for 120 seconds to form a 10 μm thick photosensitive layer.
[Photosensitive solder resist composition]
・ Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate /
Methacrylic acid copolymer (copolymer composition ratio (molar ratio)) = 40 / 26.7 / 4.5 / 28.8
, Mass average molecular weight = 90000, Tg = 50 ° C) 15 parts by mass · dodeca polypropylene glycol diacrylate 6.5 parts by mass · tetraethylene glycol dimethacrylate 1.5 parts by mass · 4,4'-bis (diethylamino) benzophenone 4 parts by mass, benzophenone 3.0 parts by mass, 4-toluenesulfonamide 0.5 parts by mass, malachite green oxalate 0.02 parts by mass, 1,2,4-triazole 0.01 parts by mass, leuco crystal violet 0 .2 parts by mass-Tribromomethylphenylsulfone 0.1 parts by mass-Methyl ethyl ketone 15 parts by mass
・ 35 parts by mass of 1-methoxy-2-propanol

A photosensitive layer cover film was prepared on the photosensitive layer in the same manner as in Example 1, a laminate was produced, and a pattern was formed.
Further, in the same manner as in Example 1, the exposure sensitivity and resolution were evaluated for the laminate, and the light-sensitive layer cover film was evaluated for total light transmittance, peelability after exposure, and suitability for repeated use. went. The results are shown in Table 4.

Furthermore, after performing laser exposure with predetermined circuit pattern information at the exposure amount required to cure up to 7 steps of 15 steps step wedge and developing the pattern, 35 Baume ferric chloride etchant is added. Then, etching was performed at 50 ° C., and the resist was peeled off using a 3% potassium hydroxide aqueous solution at 50 ° C. to produce a through-hole substrate.
No defects were found in the wiring pattern formed on the through-hole substrate and the through-hole portion.

(Comparative Example 1)
In Example 1, a laminate was prepared in the same manner as in Example 1 except that the photosensitive layer cover film was not laminated, and pattern formation was performed.
Moreover, the exposure sensitivity and the resolution were evaluated about the said laminated body like Example 1. FIG. The results are shown in Table 4.

(Comparative Example 2)
In Example 5, a laminate was prepared in the same manner as in Example 5 except that the photosensitive layer cover film was not laminated, and pattern formation was performed.
Moreover, the exposure sensitivity and the resolution were evaluated about the said laminated body like Example 1. FIG. The results are shown in Table 4.

(Comparative Example 3)
In Example 7, a laminate was prepared and a pattern was formed in the same manner as in Example 7 except that the photosensitive layer cover film was not laminated.
Moreover, the exposure sensitivity and the resolution were evaluated about the said laminated body like Example 1. FIG. The results are shown in Table 4.

(Comparative Example 4)
In Example 8, a laminate was prepared and a pattern was formed in the same manner as in Example 8, except that the photosensitive layer cover film was not laminated.
Moreover, the exposure sensitivity and the resolution were evaluated about the said laminated body like Example 1. FIG. The results are shown in Table 4.

From the results shown in Table 4, the pattern forming method using the photosensitive layer cover film of Examples 1 to 8 of the present invention prevents a decrease in sensitivity of the photosensitive layer as compared with Comparative Examples 1 to 4 that do not use the photosensitive layer cover film. However, it was found that there was no decrease in resolution.
In addition, the photosensitive layer cover film having a resist adhesion preventing layer used in Examples 1 to 3 and 4 to 8 is excellent in releasability from the photosensitive layer after exposure, and is contaminated by the resist even when used 100 times. It was found that the formed pattern can be used repeatedly because it does not cause defects in the formed pattern.

  The photosensitive layer cover film of the present invention can be applied to direct drawing by laser exposure of 405 nm, can prevent a decrease in sensitivity of the photosensitive layer due to oxygen, and has good handleability, adhesion and peelability. By using the photosensitive layer cover film of the present invention, it is possible to realize a pattern forming method that achieves both high density and high productivity, so printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), It can be widely applied to the formation of permanent patterns such as display members such as color filters, pillar materials, rib materials, spacers, partition walls, holograms, micromachines, and proofs.

FIG. 1 is an example of a partially enlarged view showing a configuration of a digital micromirror device (DMD). 2A and 2B are examples of explanatory diagrams for explaining the operation of the DMD. FIGS. 3A and 3B are examples of plan views showing the arrangement of the exposure beam and the scanning line in a case where the DMD is not inclined and in a case where the DMD is inclined. 4A and 4B are examples of diagrams illustrating examples of DMD usage areas. FIG. 5 is an example of a plan view for explaining an exposure method in which the photosensitive layer is exposed by one scanning by the scanner. 6A and 6B are examples of plan views for explaining an exposure method for exposing a photosensitive layer by a plurality of scans by a scanner. FIG. 7 is an example of a schematic perspective view illustrating an appearance of an example of the pattern forming apparatus. FIG. 8 is an example of a schematic perspective view illustrating the configuration of the scanner of the pattern forming apparatus. FIG. 9A is an example of a plan view showing an exposed region formed on the photosensitive layer, and FIG. 3B is an example of a diagram showing an array of exposure areas by each exposure head. FIG. 10 is an example of a perspective view showing a schematic configuration of an exposure head including light modulation means. FIG. 11A is an example of a sectional view in the sub-scanning direction along the optical axis showing the configuration of the exposure head shown in FIG. 10, and FIG. 11B is an example of a side view of FIG. . FIG. 12 is an example of a controller that controls DMD based on pattern information. FIG. 13A is an example of a cross-sectional view along the optical axis showing the configuration of another exposure head having a different coupling optical system, and FIG. 13B shows the exposure when a microlens array or the like is not used. FIG. 13C is an example of a plan view showing a light image projected on the surface to be exposed when a microlens array or the like is used. FIG. 14 is an example of a diagram showing the distortion of the reflection surface of the micromirror constituting the DMD with contour lines. FIG. 15 is an example of a graph showing distortion of the reflection surface of the micromirror in two diagonal directions of the mirror. FIG. 16 is an example of a front view (A) and a side view (B) of a microlens array used in the pattern forming apparatus. FIG. 17 is an example of a front view (A) and a side view (B) of the microlens constituting the microlens array. FIG. 18 is an example of a schematic diagram illustrating a condensing state by a microlens in one cross section (A) and another cross section (B). FIG. 19a is an example of a diagram showing a result of simulating the beam diameter in the vicinity of the condensing position of the microlens. FIG. 19B is an example of a diagram showing the same simulation result as that in FIG. 19A at another position. FIG. 19c is an example of a diagram showing the same simulation result as in FIG. 19a at another position. FIG. 19d is an example of a diagram showing the same simulation result as in FIG. 19a at another position. FIG. 20a is an example of a diagram showing the result of simulating the beam diameter in the vicinity of the condensing position of the microlens in the conventional pattern forming method. FIG. 20b is an example of a diagram showing the same simulation result as in FIG. 20a at another position. FIG. 20c is an example of a diagram showing the same simulation result as in FIG. 20a for another position. FIG. 20d is an example of a diagram illustrating simulation results similar to those in FIG. 20a at different positions. FIG. 21 is an example of a plan view showing another configuration of the combined laser light source. FIG. 22 shows an example of a front view (A) and an example of a side view (B) of the microlens constituting the microlens array. FIG. 23 is an example of a schematic diagram illustrating a light condensing state by the microlens of FIG. 22 in one cross section (A) and another cross section (B). FIG. 24 is an example of an explanatory diagram about the concept of correction by the light amount distribution correction optical system. FIG. 25 is an example of a graph showing the light amount distribution when the light irradiation means has a Gaussian distribution and the light amount distribution is not corrected. FIG. 26 is an example of a graph showing the light amount distribution after correction by the light amount distribution correcting optical system. 27A (A) is a perspective view showing the configuration of the fiber array light source, FIG. 27A (B) is an example of a partially enlarged view of (A), and FIGS. 27A (C) and (D) are lasers. It is an example of the top view which shows the arrangement | sequence of the light emission point in an emission part. FIG. 27 b is an example of a front view showing the arrangement of light emitting points in the laser emission part of the fiber array light source. FIG. 28 is an example of a diagram illustrating a configuration of a multimode optical fiber. FIG. 29 is an example of a plan view showing the configuration of the combined laser light source. FIG. 30 is an example of a plan view showing the configuration of the laser module. FIG. 31 is an example of a side view showing the configuration of the laser module shown in FIG. 32 is a partial side view showing the configuration of the laser module shown in FIG. FIG. 33 is an example of a perspective view showing a configuration of a laser array. FIG. 34A is an example of a perspective view showing a configuration of a multi-cavity laser, and FIG. 34B is a perspective view of a multi-cavity laser array in which the multi-cavity lasers shown in FIG. It is an example. FIG. 35 is an example of a plan view showing another configuration of the combined laser light source. FIG. 36A is an example of a plan view illustrating another configuration of the combined laser light source, and FIG. 36B is an example of a cross-sectional view along the optical axis of FIG. FIGS. 37A and 37B are examples of cross-sectional views along the optical axis showing the difference from the depth of focus in a conventional exposure apparatus. FIG. 38 is an example of a cross-sectional view of the photosensitive layer cover film of the present invention. FIG. 39 is an example of a sectional view of the photosensitive layer cover film of the present invention. FIG. 40 is an example of a cross-sectional view of the photosensitive layer cover film of the present invention. FIG. 41 is an example of a cross-sectional view of the photosensitive layer cover film of the present invention. FIG. 42 is an example of a cross-sectional view of the photosensitive layer cover film of the present invention. FIG. 43 is an example of a sectional view of a photosensitive layer on which the photosensitive layer cover film of the present invention is disposed. FIG. 44 is an example of a sectional view showing the pattern exposure method of the present invention. FIG. 45 shows an example of a method for forming a photosensitive layer in which the photosensitive layer cover film of the present invention is disposed.

Explanation of symbols

LD1-LD7 GaN-based semiconductor laser 10 Heat block 11-17 Collimator lens 20 Condensing lens 30-31 Multimode optical fiber 44 Collimator lens holder 45 Condensing lens holder 46 Fiber holder 50 Digital micromirror device (DMD)
52 Lens system 53 Reflected light image (exposure beam)
54 Lens of second imaging optical system 55 Micro lens array 56 Surface to be exposed (scanning surface)
55a Micro lens 57 Lens of second image forming optical system 58 Lens of second image forming optical system 59 Aperture array 64 Laser module 66 Fiber array light source 67 Lens system 68 Laser emitting portion 69 Mirror 70 Prism 73 Combination lens 74 Imaging lens 100 Heat block 110 Multi cavity laser 111 Heat block 113 Rod lens 120 Condensing lens 130 Multimode optical fiber 130a Core 140 Laser array 144 Light irradiation means 150 Pattern forming material 152 Stage 155a Micro lens 156 Installation table 158 Guide 160 Gate 162 Scanner 164 Sensor 166 exposure head 168 exposure area 170 exposed area 180 heat block 184 collimating lens array 302 controller Lola 304 Stage driving device 454 Lens system 468 Exposure area 472 Micro lens array 476 Aperture array 478 Aperture 480 Lens system S1 Photosensitive layer cover film support S2 Resist adhesion preventing layer S3 Undercoat layer S4 Antistatic layer S5 Protective material S6 Base Material S7 Photosensitive layer support S8 Photosensitive layer S9 Photosensitive film S10 Photosensitive layer cover film

Claims (19)

  In the method of forming a pattern by exposing and developing the photosensitive layer, the total light transmittance with respect to a laser beam having a wavelength of 405 nm is 70% or more used by being arranged on the photosensitive layer. A photosensitive layer cover film. The photosensitive layer cover film according to claim 1, wherein an oxygen transmission rate during exposure is 600 mL / m ² · day · MPa or less.   The photosensitive layer cover film according to claim 1, further comprising a resist adhesion preventing layer on the photosensitive layer cover film support. An antistatic agent is contained on the support for the photosensitive layer cover film, and the surface resistance of the surface is 10 ¹⁵ Ω / □ or less in an environment of a temperature of 10 ° C. and a relative humidity of 33%. The photosensitive layer cover film according to any one of the above.   The photosensitive layer cover film according to claim 1, further comprising an undercoat layer between the support for the photosensitive layer cover film and the resist adhesion preventing layer.   The photosensitive layer cover film according to any one of claims 1 to 5, wherein at least a surface of the photosensitive layer cover film on the support for the photosensitive layer cover film on which the resist adhesion preventing layer is not laminated is subjected to uneven processing.   The photosensitive layer cover film according to any one of claims 1 to 6, wherein a protective material is laminated on the resist adhesion preventing layer in the photosensitive layer cover film.   The photosensitive layer cover film according to claim 1, which is long and wound in a roll.   The photosensitive layer cover film according to claim 1, wherein the photosensitive layer cover film is a multilayer formed by laminating a plurality of photosensitive layer cover films, and is used after being separated one by one.   The photosensitive layer cover film according to claim 1, wherein the photosensitive layer cover film is disposed on the photosensitive layer and is in close contact with the photosensitive layer under reduced pressure.   The photosensitive layer cover film according to claim 1, wherein the exposure is performed by laser light having a wavelength of 395 to 415 nm having pattern information.   The photosensitive layer cover film according to any one of claims 1 to 11, wherein the photosensitive layer is a photosensitive layer formed by applying a photosensitive composition to a surface of a substrate and drying the photosensitive composition.   A photosensitive film comprising a photosensitive layer comprising, in this order, a photosensitive layer support; and a photosensitive layer formed by applying a photosensitive composition to the surface of the photosensitive layer support and drying the photosensitive layer; A photosensitive layer formed by laminating on a substrate such that the surface opposite to the substrate for the photosensitive layer is in contact with the substrate, and then peeling the substrate for the photosensitive layer. The photosensitive layer cover film according to any one of 1 to 11.   The photosensitive layer cover film according to claim 1, which is used when a permanent pattern is formed after development.   The photosensitive layer cover film according to claim 14, which is used when forming at least one of a protective film and an interlayer insulating film.   The photosensitive layer cover film according to claim 14, which is used when forming a wiring pattern.   Using a photosensitive composition colored in at least the three primary colors of R, G, and B, in a predetermined arrangement on the surface of the substrate, sequentially for each color of R, G, and B, a photosensitive layer forming step, exposure The photosensitive layer cover film according to claim 1, which is used when forming a color filter by repeating the steps and the development step.   18. A pattern exposure method comprising exposing a photosensitive layer on which the photosensitive layer cover film according to claim 1 is disposed with a laser beam having a wavelength of 395 to 415 nm. A photosensitive film comprising a photosensitive layer comprising, in this order, a photosensitive layer support; and a photosensitive layer formed by applying a photosensitive composition to the surface of the photosensitive layer support and drying. 19. The method according to claim 18, wherein the photosensitive layer support is formed by laminating on the substrate so that the surface opposite to the photosensitive layer support is in contact with the substrate, and then peeling the photosensitive layer support. Pattern exposure method.