JP2005106991A - Blue-violet semiconductor laser sensitive image forming material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming material, suitable for direct pattern formation using blue-violet semiconductor laser of 390-430 nm wavelength and which is superior in sensitivity and resolution. <P>SOLUTION: The image forming material has at least a blue-violet semiconductor laser sensitive resin composition layer on a substrate to be worked, where the ratio S[400 nm]/S[420 nm] between the minimum light exposure S[400 nm] (mJ/cm<SP>2</SP>) realizing formation of an image upon exposure with a light source of 400 nm wavelength, and the minimum light exposure S[420 nm] (mJ/cm<SP>2</SP>) realizing formation of an image upon exposure with a light source of 420 nm wavelength is 0.47-1.53. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  INDUSTRIAL APPLICABILITY The present invention is useful for forming fine electronic circuits such as printed wiring boards, plasma display wiring boards, liquid crystal display wiring boards, large-scale integrated circuits, thin transistors, and semiconductor packages, and particularly suitable for exposure with a blue-violet semiconductor laser. The present invention relates to an image forming material and an image forming method using the same.

  Conventionally, for forming fine electronic circuits such as printed wiring boards, plasma display wiring boards, liquid crystal display wiring boards, large-scale integrated circuits, thin transistors, semiconductor packages, etc., for example, a photosensitive resist material on a substrate to be processed The photosensitive resist material layer of the image forming material having a layer and, if necessary, a protective layer thereon is exposed by ultraviolet irradiation through a mask film or the like, and then the mask film is removed, and a protective layer is further formed. If it has, remove the protective layer, develop using the difference in solubility in the developer between the exposed and unexposed areas to form a pattern, and use this pattern layer as a mask to etch or plate the substrate to be processed A lithography method for forming a circuit pattern on a substrate to be processed by performing such processing is widely used.

  In recent years, by using laser light as an exposure light source, a laser direct drawing method that directly forms an image from digital information such as a computer without using a mask film can improve resolution and positional accuracy. It is also attracting attention because of cost reduction by unmasking.

As a laser light source used in the laser direct drawing method, various sources that oscillate light in the ultraviolet to infrared region are known, but those that can be used for image exposure include output, stability, photosensitive ability, and In terms of cost, UV solid state laser (350-380nm), blue-violet semiconductor laser (390-430nm), argon ion laser (488nm), FD-YAG laser (532nm), near infrared semiconductor laser (832nm), YAG Lasers (1064nm) are considered promising. For example, an argon ion laser with a wavelength of 488 nm and an FD-YAG laser with a wavelength of 532 nm have been put into practical use, but these use a photosensitive resist material that is sensitive to visible light, so they are safe light under yellow light. In other words, there is a restriction that it is necessary to work in a dark room environment such as red light illumination. On the other hand, UV lasers (wavelengths of about 350 to 365 nm) that can be used in bright room environments such as yellow light illumination are also being put into practical use, but they cannot handle high-resolution patterns (30 to 50μm line / space is the limit), and it is in an unfinished state.

On the other hand, due to significant progress in laser technology in recent years, the lifetime of the light source is long (10,000 to 20,000 hours), the beam diameter can be narrowed down to 10 μm or less, and the wavelength of 390 to 430 nm that enables operation under a yellow light The use of semiconductor lasers that can oscillate stably in the blue-violet region is being put into practical use particularly in the field of lithographic printing plates.

  Conventionally, blue-violet semiconductor lasers with a laser element output of several to several tens of mW have been used. However, due to recent technological advances and demands for improving throughput during exposure, laser elements have been used. Laser light sources with several to several tens connected to increase the output and exposure machines that carry a plurality of them and perform exposure in parallel have been developed. In addition, Nichia Industrial Chemical Co., Ltd., one of the manufacturers, has also announced that the center wavelength of lasers oscillated from individual laser elements has individual differences of 400 to 420 nm.

In view of these matters, it is not possible to use only a laser element whose oscillation wavelength is limited to 405 nm, for example, as a high-power laser light source used in a lithography exposure machine using these blue-violet semiconductor lasers. Since the apparatus cost is very disadvantageous, it is conceivable that laser elements having different oscillation wavelengths in the wavelength range of 400 to 420 nm are used, and as a result, a laser light source having a relatively wide oscillation wavelength distribution or a different one is provided. Furthermore, there is a possibility that a plurality of laser light sources may be mounted on one exposure machine for the purpose of improving the throughput. In this case, a plurality of laser light sources having different central oscillation wavelengths and distributions are placed in the same exposure machine. It can be installed. In other words, in an exposure machine equipped with a high-power blue-violet semiconductor laser light source, exposure is performed with a laser light source having a different wavelength or wavelength distribution for each exposure machine, or for each exposure area when multiple laser light sources are installed. May be performed.

On the other hand, as a blue-violet semiconductor laser photosensitive composition, for example, JP 2002-296764 A,
Although technologies related to blue-violet semiconductor laser photosensitive lithographic printing plates have been disclosed, in the conventionally known technology, it is assumed that the exposure machine used is a single laser element, and exposure in a wide wavelength range. A photosensitive composition that focuses on or can cope with the above has not been known so far.

  In view of the above situation, an object of the present invention is to provide an image forming material that can cope with exposure at any wavelength of 400 to 420 nm, in other words, even if an exposure machine such as that described above is used, An object of the present invention is to provide an image forming material that can form a uniform image on the entire exposed surface without depending on the above.

  As a result of intensive studies on the above problems, the present inventors have found that the above object can be achieved by using a photosensitive resin composition having specific properties, and have completed the present invention. That is, the gist of the present invention is as follows.

1. An image forming material having at least a blue-violet semiconductor laser photosensitive resin composition layer on a substrate to be processed, which satisfies the following (1): (1) Exposure by a light source having a wavelength of 400 nm Minimum exposure dose S [400 nm] (mJ / cm ²
) And the minimum exposure S (420nm) that can form an image by exposure with a light source with a wavelength of 420nm (
mJ / cm ² ) The ratio S [400 nm] / S [420 nm] is 0.47 or more and 1.53 or less 2 and further satisfies the following (2) or (3): (2) Minimum exposure amount S [405nm] (mJ / cm) capable of forming an image by exposure with a light source with a wavelength of 405nm
² ) and the minimum exposure S (450nm) that allows image formation by exposure with a light source with a wavelength of 450nm
(mJ / cm ²⁾ the ratio of the S [405nm] / S [450nm ] is, is 0.2 or less and (3) the S [405nm] (mJ / cm 2) according to each wavelength of the light source wavelength 450~650nm By exposure
Ratio S [405nm] / S [450-6] with minimum exposure S (450-650nm) (mJ / cm ² ) capable of image formation
50nm] is 0.2 or less

  The image forming material of the present invention can provide an image forming material excellent in sensitivity and resolution suitable for direct drawing with a blue-violet semiconductor laser having a wavelength of 390 to 430 nm.

Hereinafter, the present invention will be described in detail.
The image forming material of the present invention is an image forming material having at least a blue-violet semiconductor laser photosensitive resin composition layer on a substrate to be processed, which is exposed with a blue-violet semiconductor laser having a wavelength of 390 to 430 nm, and then an alkaline developer. Development is performed to form an image pattern.

As described above, the gist of the present invention is to provide an image forming material capable of performing the same image formation using a light source having any wavelength or wavelength distribution in the wavelength range of 400 to 420 nm. This image forming material must satisfy the following (1).
(1) Minimum exposure amount S [400 nm] (mJ / cm ² ) capable of image formation by exposure with a light source having a wavelength of 400 nm
) And the minimum exposure S (420nm) that can form an image by exposure with a light source with a wavelength of 420nm (
mJ / cm ²⁾ the ratio of the S [400nm] / S [420nm ] is 0.47 or more, is 1.53 or less

  Here, the minimum exposure amount capable of forming an image by exposure with a light source of each wavelength can be measured by using a diffraction spectroscopic irradiation apparatus, as will be described in the examples described later. Since the ratio of so-called “sensitivity” relating to image formation at 400 nm and 420 nm is important, there is no problem even if it is obtained by another method.

The most preferable value of S [400nm] / S [420nm] is 1, that is, it is best that there is no difference in sensitivity at wavelengths of 400nm and 420nm, but even if there is some acceptable difference in practice. The range is usually 0.47 or more and 1.53 or less, more preferably 0.70 or more, and a preferable upper limit is 1.40. If S [400nm] / S [420nm] is less than or above the above, the difference in "sensitivity" between wavelength 400nm and wavelength 420nm is too large. Problems are likely to occur, which is not preferable.

The image forming material of the present invention preferably satisfies the following (2) or (3).
(2) Minimum exposure amount S [405nm] (mJ / cm) capable of forming an image by exposure with a light source with a wavelength of 405nm
² ) and the minimum exposure S (450nm) that allows image formation by exposure with a light source with a wavelength of 450nm
(mJ / cm ²⁾ the ratio of the S [405nm] / S [450nm ] is, is 0.2 or less and (3) the S [405nm] (mJ / cm 2) according to each wavelength of the light source wavelength 450~650nm By exposure
Ratio S [405nm] / S [450-6] with minimum exposure S (450-650nm) (mJ / cm ² ) capable of image formation
50nm] is 0.2 or less

S [405nm] / S [450nm] and S [405nm] / S [450-650nm] means that the smaller the value, the lower the sensitivity at wavelengths 450nm and 450-650nm, and as a result, under yellow light, That is, it is preferable because the handleability is excellent in an environment including light having a wavelength of around 500 nm. On the contrary, if it exceeds the above, there is a possibility of being exposed even under a yellow light, which is not preferable. The upper limit of S [405 nm] / S [450 nm] is preferably 0.15 or less, and the upper limit of S [405 nm] / S [450-650 nm] is preferably 0.15 or less. The lower limit of each of the above values is preferably as small as possible, but in practice it is usually 0.03 or more.

The image forming material of the present invention, (4) sensitivity to blue-violet semiconductor laser having a wavelength of 405nm is preferably at 30 mJ / cm ² or less, more preferably 25 mJ / cm ² or less, it is 20 mJ / cm ² or less Is particularly preferred. Exceeding the sensitivity is not preferable because the exposure time becomes longer and the productivity becomes worse. The practical, preferably 1.5 mJ / cm ² or more, 2 mJ / cm ² or more is more preferable.

As a specific method satisfying the above conditions (1) to (4),
(A) Method for appropriately selecting the type and amount of components in the photosensitive composition, particularly sensitizing dye (B) Oxygen blocking layer and / or light transmission which may be provided on the photosensitive resin composition layer Method of adjusting the absorption wavelength of the layer for adjusting the property (c) Wavelength of the layer including the oxygen blocking layer and / or the light transmission adjusting layer and the photosensitive resin composition layer of 400 nm
And the ratio of absorbance at 420 nm (respectively ABS [400 nm] and ABS [420 nm]) ABS [400 nm] / A
Examples include a method of adjusting BS [420 nm] to be 0.5 or more and 2 or less.

<<< Photosensitive resin composition >>>
The photosensitive resin composition of the present invention is not particularly limited as long as it satisfies the above conditions. For example, photopolymerization type, chemically amplified negative type, or chemically amplified positive type photosensitivity A resin composition can be mentioned.

<< Sensitizing dye >>
The photosensitive resin composition of the present invention, when exposed with a blue-violet semiconductor laser having a wavelength of 390 to 430 nm, efficiently absorbs the laser beam to express the image forming ability of each photosensitive resin composition. (D) Sensitizing dye having spectral sensitivity at a wavelength of 390 to 430 nm (hereinafter sometimes simply referred to as sensitizing dye)
It is preferable to contain. Here, “having spectral sensitivity” means that, for example, an image can be obtained by a method using a diffraction spectroscopic irradiation apparatus shown in an embodiment described later. Such a sensitizing dye can be selected from known sensitizing dyes, and dialkylaminobenzene compounds, triarylamine compounds, acridone compounds, imidazole / oxazole / thiazole compounds and the like are particularly preferable. A plurality of these sensitizing dyes may be used in combination.

<Sensitizing dye: Dialkylaminobenzene compound>
As particularly preferred dialkylaminobenzene compounds, the following general formula (I),
What is represented by (II) and (III) is mentioned.

[In the formulas (I), (II) and (III), R ^{1 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom,
An optionally substituted (halo) alkyl group or (halo) aryl group, R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ may each independently form a nitrogen-containing heterocycle (in the present invention, the heterocycle means a heterocycle in a broad sense, that is, includes an alicyclic compound). Y represents a sulfur atom, an oxygen atom, or an optionally substituted nitrogen atom. ]

Here, R ¹ is preferably a haloalkyl group, particularly preferably a fluorine-substituted alkyl group. As the (halo) alkyl group of R ^{2 to} R ¹⁰ , those having 1 to 12 carbon atoms are preferable, and carbon number 1
More preferred are ˜8. R ¹⁰ is preferably a haloalkyl group or a (halo) aryl group. Among the compounds represented by the general formula (II), a compound in which a substituent on the benzene ring and an amino group form a 5- to 7-membered nitrogen-containing heterocycle is particularly preferable. As Y,
An oxygen atom or an optionally substituted nitrogen atom is preferred. Specific examples of the compounds represented by the general formulas (I), (II) and (III) include compounds having the following structures.

<Sensitizing dye: Triarylamine compound>
Particularly preferable triarylamine compounds include those represented by the following general formula (IV).

[In Formula (IV), A to C each independently represent an aromatic hydrocarbon ring group or an aromatic heterocyclic group which may have a substituent. ]

  Here, examples of the aromatic hydrocarbon ring group A to C include aryl groups such as phenyl group and tolyl group, and examples of the aromatic heterocyclic group include nitrogen-containing groups such as pyridyl group and quinolinyl group. Although a heterocyclic group etc. are mentioned, an aryl group is preferable. These aromatic heterocyclic groups may have a substituent such as a (halo) alkyl group or a (halo) aryl group, and among these, the aromatic heterocyclic group directly or ( Particularly preferred is a compound further having an amino group having an aromatic heterocyclic group which may have a substituent via an aza) alkylene group, an (aza) alkynylene group or an arylene group. Specific examples of the compound represented by the general formula (IV) include compounds having the following structure.

<Sensitizing dye: Acridone compound>
Particularly preferred examples of the acridone compounds include those represented by the following general formula (V).

[In the formula (V), R ^{11 to} R ¹⁹ each independently represents a hydrogen atom, a halogen atom, or an optionally substituted (halo) alkyl group, and groups adjacent to each other are bonded to form a ring. May be. ]

Here, the (halo) alkyl group R ¹¹ to R ^19, preferably those having 1 to 12 carbon atoms, more preferably those having 1 to 8 carbon atoms. Examples of the halogen atom of R ^{11 to} R ¹⁹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom and a chlorine atom are preferable. Specific examples of the compound represented by the general formula (V) include 9 (10H) -acridone (V-1) and 10-butyl-2-chloro-9 (10H) -acridone (V-2). I can list.

<Sensitizing dye: imidazole / oxazole / thiazole compound>
Particularly preferred examples of the imidazole / oxazole / thiazole compound include those represented by the following general formula (VI).

[In the formula (VI), R ^{20 to} R ²² each independently represents an optionally substituted (halo) alkyl group or (halo) aryl group. Y represents a sulfur atom, an oxygen atom or an optionally substituted nitrogen atom. R ²⁰ and R ²¹ , R ²¹ and R ²² , and R ²² and Y may be independently bonded to each other to form a ring. Z represents an optionally substituted alkylene group, alkynylene group, or arylene group. ]

Here, as the alkyl group for R ²⁰ , one having 1 to 12 carbon atoms is preferable, and one having 1 to 8 carbon atoms is more preferable. R ²¹ and R ²² are preferably bonded to each other to form an aromatic heterocyclic ring or an aromatic hydrocarbon ring, and more preferably a condensed benzene ring. Y is preferably a sulfur atom or an oxygen atom. Z is preferably an alkylene group which may be substituted, and more preferably one having a sulfur atom or an oxygen atom in the substituent. Specific examples of the compound represented by the general formula (VI) include compounds having the following structure.

尚、本明細書において、（ハロ）アルキル、（ハロ）アリールは、ハロゲン原子で置換されていてもよいアルキル又はアリールを意味する。
尚、本明細書において（ハロ）アルキル、（ハロ）アリールは、夫々、ハロゲン原子で置換されていてもよいアルキル基又はアリール基を意味する。

In the present specification, (halo) alkyl and (halo) aryl mean alkyl or aryl which may be substituted with a halogen atom.
In the present specification, (halo) alkyl and (halo) aryl each mean an alkyl group or an aryl group which may be substituted with a halogen atom.

<< Photopolymerization type photosensitive resin composition >>
Among the photosensitive resin compositions of the present invention, the photopolymerizable type includes (N-1) a polymer having a carboxyl group, (N-2) an ethylenically unsaturated compound, and (N-3) a photopolymerization initiator. The composition containing can be mentioned.

<(N-1) Polymer having carboxyl group>
(N-1) As the polymer having a carboxyl group, from the viewpoint of alkali developability and the like, an ethylenic resin of a carboxyl group-containing vinyl resin or an epoxy resin containing at least a constitutional repeating unit derived from an ethylenically unsaturated carboxylic acid is used. It is preferably an unsaturated group- and carboxyl group-containing epoxy resin obtained by adding a polyvalent carboxylic acid or an anhydride thereof to a saturated carboxylic acid adduct, and particularly at least a structural repeating unit derived from an ethylenically unsaturated carboxylic acid. A carboxyl group-containing vinyl resin is preferable. A mixture of two or more of these can also be used.

(Carboxyl group-containing vinyl resin containing at least a constitutional repeating unit derived from ethylenically unsaturated carboxylic acid)
Examples of the carboxyl group-containing vinyl resin containing at least a constitutional repeating unit derived from an ethylenically unsaturated carboxylic acid include a copolymer of an ethylenically unsaturated carboxylic acid and another monomer copolymerizable therewith. These can be synthesized by a conventionally known method.

  Here, examples of the ethylenically unsaturated carboxylic acid in the copolymer include monocarboxylic acids such as (meth) acrylic acid and crotonic acid, and dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid. Acids, mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as mono [2- (meth) acryloyloxyethyl] oxalate, mono [2- (meth) acryloyloxyethyl] phthalate, ω- Examples include carboxypolycaprolactone mono (meth) acrylates and other polymer mono (meth) acrylates having a carboxyl group and a hydroxyl group at both ends, and these may be used alone or in combination of two or more. May be used. Among these, (meth) acrylic acid is preferable from the viewpoints of copolymerization reactivity and solubility of the photopolymerization type photosensitive composition layer as an image forming material in an alkali developer after exposure. The proportion of the structural repeating unit derived from these ethylenically unsaturated carboxylic acids is preferably 5 to 30% by weight based on the total amount of the copolymer. When the proportion of the constitutional repeating unit derived from the ethylenically unsaturated carboxylic acid is less than the above range, the solubility of the photopolymerization type photosensitive composition layer as an image forming material in an alkali developer after exposure tends to decrease, whereas If the range is exceeded, the solubility becomes excessive, and in any case, good image formation becomes difficult.

Other copolymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) Alkyl esters on (meth) acrylic acid chain such as 2-ethylhexyl acrylate, cyclohexyl (meth) acrylate, 2-ethylcyclohexyl (meth) acrylate, (meth)
(Meth) acrylic acid alicyclic esters such as isobornyl acrylate, (meth) acrylic acid aryl esters such as phenyl (meth) acrylate, (meth) acrylic acid aralkyl esters such as benzyl (meth) acrylate, Dialkyl dialkyl esters such as diethyl maleate, diethyl fumarate and diethyl itaconate; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; Such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 7,8-epoxy [tricyclo [5.2.1.0] dec-2-yl] methyl (meth) acrylate, etc. (Meth) acrylic acid epoxy group-containing alkyl esters, styrene, α-methyls Vinyl aromatic compounds such as len, m-methylstyrene, p-methylstyrene and p-methoxystyrene, conjugated diene compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene, (Meth) acrylonitrile, (
Examples include other vinyl compounds such as (meth) acrylamide, vinyl chloride, vinylidene chloride, vinyl acetate, p-vinylbenzylglycidyl ether, etc., and these may be used alone or in combination of two or more. It may be. Among these, from the aspects of copolymerization reactivity, solubility of the photopolymerization type photosensitive composition layer as an image forming material in an alkali developer after exposure, and adhesion of a fine line image to be formed, ) Alkyl esters on (meth) acrylic acid chains such as methyl acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic such as 2-hydroxyethyl (meth) acrylate Preferred are vinyl aromatic compounds such as acid hydroxyalkyl esters, styrene, and α-methylstyrene. The content of these other copolymerizable monomers is such that the alkyl ester on the (meth) acrylic acid chain is 30 to 93% by weight and the hydroxyalkyl ester of (meth) acrylic acid is 1 with respect to the entire copolymer. It is preferable that it is -20 weight% and vinyl aromatic compounds are 1-20 weight%.

Since the acid value of the carboxyl group-containing vinyl resin containing at least a constitutional repeating unit derived from an ethylenically unsaturated carboxylic acid is too low, the development is poor, and when it is too high, damage to the resist during development increases. ˜300 mg KOH / g is preferred, and 80 to 250 mg KOH / g is particularly preferred. Also, if the molecular weight is too small, the strength when the photosensitive resin composition is made into a film becomes weak, and problems such as instability of developability are seen. Since the viscosity of the photosensitive solution becomes too large, causing problems such as handling problems, the polystyrene equivalent weight average molecular weight Mw by gel permeation chromatography (hereinafter GPC) is preferably 10,000 to 200,000. 20,000 to 120,000 is particularly preferable. The ratio Mw / Mn of Mw to number average molecular weight Mn is preferably 1 to 3, and more preferably 1.2 to 2.5.

(Unsaturated group and carboxyl group-containing epoxy resin)
In addition, an unsaturated group and carboxyl group-containing epoxy resin obtained by adding a polyvalent carboxylic acid or its anhydride to an ethylenically unsaturated carboxylic acid adduct of an epoxy resin, specifically, an ethylene group is added to the epoxy group of the epoxy resin. An ethylenically unsaturated bond is added via an ester bond (-COO-) formed by ring-opening addition of a carboxyl group of an unsaturated carboxylic acid, and a part of the resulting hydroxyl group is polyvalent. The remaining carboxyl group is added via an ester bond formed by the reaction of a carboxyl group of carboxylic acid or its anhydride, and can be synthesized by a conventionally known method.

Specific examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, and the like. Among them, phenol novolac epoxy resin or cresol novolac Epoxy resins are particularly preferred. Specific examples of the ethylenically unsaturated carboxylic acid include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and the like. Acrylic acid is particularly preferred. Specific examples of the polycarboxylic acid or anhydride thereof include oxalic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendo Examples include methylenetetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, and anhydrides thereof, among which maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferable, Tetrahydrophthalic anhydride is particularly preferred.

Among the unsaturated group- and carboxyl group-containing epoxy resins described above, in the present invention, the epoxy resin is a phenol novolac epoxy in terms of sensitivity, resolution, adhesion to a substrate, etc. as a photopolymerizable photosensitive composition. A resin or a cresol novolac epoxy resin, in which the ethylenically unsaturated carboxylic acid is (meth) acrylic acid, and the polyvalent carboxylic acid or anhydride thereof is tetrahydrophthalic anhydride is particularly preferable. Further, those having an acid value of 50 to 300 mgKOH / g are preferable, and 80 to 250 mgKOH / g is particularly preferable. Further, those having a polystyrene-equivalent weight average molecular weight Mw by GPC of 1,000 to 300,000 are preferable, and 2,000 to 200,000 are particularly preferable. The ratio Mw / Mn is preferably 1 to 3, and more preferably 1.2 to 2.5.

<(N-2) ethylenically unsaturated compound>
As the (N-2) ethylenically unsaturated compound in the present invention, an acrylate compound in which an unsaturated bond is derived from a (meth) acryloyloxy group is particularly preferable. Specific examples include bisphenol A polyoxyethylene di (meth) acrylates (having 2 to 14 ethyleneoxy groups), bisphenol A polyoxypropylene di (meth) acrylates (having 2 propyleneoxy groups). 14), polyethylene glycol di (meth) acrylates (having 2 to 14 ethyleneoxy groups), polypropylene glycol di (meth) acrylates (having 2 to 14 propyleneoxy groups), and the like Dialcohols such as di (meth) acrylate, trimethylolpropane di or tri (meth) acrylate, pentaerythritol tri, tetra or penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate (Meth) acrylates and the same A compound obtained by adding an α, β-unsaturated carboxylic acid to a glycidyl group-containing compound such as a modified product of ethylene oxide or propylene oxide, trimethylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether acrylate, (2-hydroxyethyl) mono- or di (meth) acrylate polyalkyl carboxylic acid hydroxyalkyl esters mono- or di (meth) acrylates, phenoxyethyl (meth) acrylate, nonylphenol ethylene oxide adduct (
Aryloxy group-containing mono (meth) acrylates such as (meth) acrylate, hexamethylene diisocyanate, 1,3,6-hexamethylene triisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, tris (isocyanate phenylmethane), etc. Examples thereof include a reaction product of an isocyanate compound and a hydroxyalkyl (meth) acrylate (so-called urethane-based ethylenically unsaturated compound). Of these, di (meth) acrylates of dialcohols are preferred, and dimethacrylates of dialcohols are more preferred. You may mix and use these.

<(N-3) Photopolymerization initiator>
The (N-3) photopolymerization initiator in the present invention generates an active radical directly or upon receiving light excitation energy of a sensitizing dye when irradiated with light, and the (N-2) ethylenically unsaturated compound Examples of radical generators that lead to polymerization include hexaarylbiimidazole compounds, titanocene compounds, halogenated hydrocarbon derivatives, diaryliodonium salts, organic borates, and organic peroxides. Of these, hexaarylbiimidazole compounds, titanocene compounds, and organoborates are preferred from the standpoints of sensitivity as a photosensitive resin composition, adhesion to a substrate, and storage stability, and hexaarylbiimidazole compounds are particularly preferred. preferable.

Specific examples of the hexaarylbiimidazole compound include 2,2 ′.
-Bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-methyl) Phenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-methoxyphenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4
, 4 ′, 5,5′-tetra (p-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-chlorophenyl) biimidazole Etc. Among them, a hexaphenylbiimidazole compound is preferable, and a compound in which the o-position of the benzene ring bonded to the 2,2′-position on the imidazole ring is substituted with a halogen atom is more preferable. Particularly preferred are those in which the benzene ring bonded to the 4 ′, 5,5′-position is unsubstituted or substituted with a halogen atom or an alkoxycarbonyl group.

Specific examples of the titanocene compound include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,6-difluorophenyl), and dicyclopenta. And dienyltitanium bis [2,6-difluoro-3- (1-pyrrolyl) phenyl]. Among them, a titanocene compound having a dicyclopentadienyl structure and a bisphenyl structure is preferable, and a compound in which the o-position of the bisphenyl ring is substituted with a halogen atom is particularly preferable.

Examples of the organic borates include organic boron ammonium complexes, organic boron phosphonium complexes, organic boron sulfonium complexes or organic boron oxosulfonium complexes, organic boron iodonium complexes, and organic boron transition metal coordination complexes. Examples of the organic boron anion include n-butyl-triphenyl boron anion, n-butyl-tris (p-methoxyphenyl) boron anion, n-butyl-tris (p-fluorophenyl) boron anion, n-butyl- Alkyl-triphenyl boron anions such as tris (2,6-difluoro-3-pyrrolylphenyl) -boron anion are preferred, and the counter cations include onium compounds such as ammonium cation, phosphonium cation, sulfonium cation and iodonium cation. Is preferred, tetraalkyl Organic ammonium cations such as ammonium are particularly preferred.

<Composition of photopolymerization type photosensitive resin composition>
In the photopolymerizable photosensitive resin composition of the present invention, (N-1) a polymer having a carboxyl group, (N-2) an ethylenically unsaturated compound, and (N-3) a photopolymerization initiator, (D) Each content ratio of the composition containing the dye is from the viewpoint of sensitivity and image forming property as a photopolymerization type photosensitive resin composition, with respect to 100 parts by weight of the polymer having (N-1) carboxyl group, (N-2) ethylenically unsaturated compound is usually 1 to 150 parts, preferably 5 to 120 parts by weight, (N-3) photopolymerization initiator is usually 1 to 30 parts, preferably 3 to 20 parts by weight, ( D) A sensitizing dye is usually used in an amount of 0.01 to 30 parts by weight, preferably 0.05 to 20 parts by weight. The ratio of (D) sensitizing dye to (N-3) photopolymerization initiator is usually 0.001 to 50 parts by weight, preferably 0.01 to 30 parts by weight. When the amount of the sensitizing dye is less than this range, the sensitivity tends to be low. When the amount of the sensitizing agent is more than this range, the resist pattern is deteriorated due to a decrease in the transparency of the resist film due to the sensitizing dye. Tends to be inverted trapezoidal and cause a decrease in resolution.

<Other ingredients>
In addition to the components (N-1), (N-2), (N-3) and (D), the photopolymerization type photosensitive resin composition of the present invention aims to improve the photopolymerization initiation ability, etc. Polymerization accelerators, amine compounds for the purpose of improving the storage stability of photosensitive resin compositions, polymerization accelerators, polymerization prohibition contained in (N-2) ethylenically unsaturated compounds that are usually commercially available Additives such as additives, colorants such as plasticizers, dyes and pigments, exposure visible paints, surfactants, adhesion improvers, heat resistance or chemical resistance imparting agents may be contained. The content ratio of these components may be in a range that does not impair the performance of the photosensitive resin composition, but is usually 20% by weight or less, preferably 15% by weight or less, and more preferably based on the entire composition. 10% by weight or less.

<< Chemically Amplified Negative Photosensitive Resin Composition >>
Among the photosensitive resin compositions of the present invention, those of the chemically amplified negative type include (CN-1) alkali-soluble resin, (CN-2) a crosslinking agent that acts on the alkali-soluble resin under acidic conditions, and (CN- 3) A composition containing an acid generator can be mentioned.

<(CN-1) alkali-soluble resin>
The (CN-1) alkali-soluble resin in the chemically amplified negative photosensitive resin composition of the present invention is not particularly limited as long as the unexposed part becomes alkali-soluble during development and can be eluted in an alkali developer, Usually, novolak resins, resole resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, polymers containing acrylic acid, vinyl alcohol or vinyl phenol as monomer units, or derivatives thereof Is used. Among these, those containing polymer units having a phenolic hydroxyl group are particularly preferred, and novolak resins or polyvinylphenols are particularly preferred. Moreover, you may mix and use these.

More preferably, the novolak resin is o-cresol, m-cresol, p-
Novolac resin obtained by polycondensation of at least one phenol selected from cresol, 2,5-xylenol, 3,5-xylenol, and resorcin with at least one selected from aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, and the like. Is mentioned. Among these, the mixing ratio of m-cresol: p-cresol: 2,5-xylenol: 3,5-xylenol: resorcin is 70-100: 0-30: 0-20: 0-20-20-20 in molar ratio. A novolak resin which is a polycondensate of phenols and aldehydes is preferred. Among the aldehydes, formaldehyde is particularly preferable. Such novolak resin may be partially hydrogenated to reduce the absorbance of the resin. In order to control the alkali solubility of the resin, a phenolic hydroxyl group partially protected with a substituted alkyl group, silyl group, t-butoxycarbonyl group, pyranyl group, furanyl group, etc. You may use what gave the crosslinked structure to resin. As the novolak resin, those having a weight average molecular weight Mw in terms of polystyrene by GPC of 1,000 to 15,000, preferably 1,500 to 10,000 are used. Mw / Mn is preferably 1 to 3, and more preferably 1.2 to 2.5.

The polyvinylphenols include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2- (o-hydroxyphenyl) propylene, 2- (m-
Examples thereof include hydroxystyrenes such as hydroxyphenyl) propylene and 2- (p-hydroxyphenyl) propylene alone or in combination of two or more polymers. Hydroxystyrenes may be substituted on the aromatic ring with a halogen such as chlorine, bromine, iodine or fluorine, or a substituent such as an alkyl group having 1 to 4 carbon atoms. Therefore, as polyvinylphenols, The polyvinylphenol which may have a substituent of a C1-C4 alkyl group is mentioned. Polyvinylphenols can be obtained by a conventionally known radical polymerization method or cationic polymerization method. Such polyvinylphenols may be partially hydrogenated to reduce the absorbance of the resin. In addition, in order to control the alkali solubility of the resin, some hydroxyl groups of polyvinylphenols are protected with a substituted alkyl group, silyl group, t-butoxycarbonyl group, pyranyl group, furanyl group, etc. You may use what gave the crosslinked structure to polyvinylphenols with the compound. As the polyvinylphenols, those having a weight average molecular weight Mw in terms of polystyrene by GPC of 1,000 to 100,000, preferably 1,500 to 50,000 are used. Mw / Mn is preferably 1 to 3, and more preferably 1.2 to 2.5.

  If the molecular weight of such an alkali-soluble resin is less than the above range, a sufficient coating film as a photosensitive composition cannot be obtained, and if it exceeds the above range, the solubility of an unexposed part in an alkaline developer is reduced. There is a tendency that a resist pattern cannot be obtained.

<(CN-2) Crosslinking agent acting on alkali-soluble resin under acidic conditions>
In the chemically amplified negative photosensitive resin composition of the present invention, (CN-2) the crosslinking agent that acts on the alkali-soluble resin under acidic conditions may be any compound that can undergo a crosslinking reaction with the alkali-soluble resin under acidic conditions. Examples include, but are not limited to, compounds obtained by allowing formalin to act on melamine, benzoguanamine, glycoluril, or urea, or alkyl-modified compounds thereof, epoxy compounds, resole compounds, and the like. Moreover, you may mix and use these.

Specifically, Cymel (registered trademark) 300 series manufactured by Mitsui Cyanamid Co., Ltd., Nikalac (registered trademark) E-2151, MW-100LM, MX-750LM manufactured by Sanwa Chemical Co., Ltd., a compound obtained by allowing formalin to act on melamine, or a compound thereof Examples of alkyl-modified products are mentioned. Moreover, Cymel (registered trademark) 1123, 1125, and 1128 can be mentioned as examples of compounds obtained by allowing formalin to act on benzoguanamine or alkyl modified products thereof. Cymel (registered trademark) 1170, 1171, 1174, 1172 and Nicarak (registered trademark) MX-270 can be mentioned as examples of a compound obtained by allowing formalin to act on glycoluril or an alkyl modified product thereof. Examples of a compound obtained by allowing formalin to act on urea or an alkyl-modified product thereof include UFR (registered trademark) 65 and 300 and Nicalac (registered trademark) MX-290 manufactured by Mitsui Cyamide.

  Examples of epoxy compounds include novolak epoxy resins, amine epoxy resins, bisphenol A epoxy resins, (poly) glycerol (poly) glycidyl ether, pentaerythritol (poly) glycidyl ether, triglycidyl trishydroxyethyl isocyanurate, glycidyl phthalimide, ( And poly) ethylene glycol glycidyl ether.

Among these, particularly preferred compounds include compounds having a —N (CH 2 OR) 2 group in the molecule (wherein R represents an alkyl group or a hydrogen atom). In particular, formalin is allowed to act on urea or melamine. Or an alkyl-modified product thereof.

<(CN-3) acid generator>
The (CN-3) acid generator in the chemically amplified negative photosensitive resin composition of the present invention is a compound that generates an acid when the photosensitive composition is irradiated with actinic rays, for example, Halogen-containing alkanes, halogen-containing compounds such as halomethylated s-triazine derivatives, onium salts, and sulfone compounds are preferred, and halomethylated s-triazine derivatives, onium salts, and sulfone compounds are more preferred. Particularly preferred are sulfone compounds that generate sulfonic acids. At this time, these acid generators themselves may generate an acid by absorbing the irradiated actinic light, or the photoacid generator itself does not absorb the irradiated actinic light, and the above-mentioned ( D) The sensitizing dye may generate an acid by receiving photoexcitation energy obtained by absorbing the energy of the actinic ray.

Here, specific examples of the halogen-substituted alkane in the halogen-containing compounds include dichloromethane, trichloromethane, 1,2-dichloroethane, 1,2-dibromoethane, and the like. Among the halogen-containing compounds, as the halomethylated s-triazine derivative, specifically, for example, 2,4,6-tris (trichloromethyl) -s-
Triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-
Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [1- (p
-Methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(P-methoxy-m-hydroxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, etc. Can be mentioned.

  Examples of the onium salts include ammonium salts such as tetraethylammonium bromide, iodonium salts such as diphenyliodonium tetrafluoroborate and dicyclohexyliodonium tetrafluoroborate, sulfonium salts such as triphenylsulfonium tetrafluoroborate and tricyclohexylsulfonium tetrafluoroborate. Is mentioned.

Examples of the sulfone compounds include bis (sulfonyl) methane compounds, carbonyl (sulfonyl) methane compounds, bis (sulfonyl) diazomethane compounds, carbonyl (sulfonyl) diazomethane compounds, sulfonic acid imidyl ester compounds, and the like. And fluorinated sulfonic acid imidyl ester compounds are particularly preferred. Specific examples of particularly preferred fluorinated sulfonic acid imidyl ester compounds include maleimidyl trifluoromethanesulfonate, trifluoromethanesulfonic acid 1,2
-Phthalimidyl, 2,3-naphthalimidyl trifluoromethanesulfonate, 1,8-naphthalimidyl trifluoromethanesulfonate, 1,8-naphthalimidyl nonafluorobutanesulfonate, and the like.

<Composition of chemically amplified negative photosensitive resin composition>
In the chemically amplified negative photosensitive resin composition of the present invention, (CN-1) alkali-soluble resin 100
(CN-2) The crosslinking agent that acts on the alkali-soluble resin under acidic conditions is usually 1 to 80 parts by weight.
Parts by weight, preferably 5-60 parts by weight, (CN-3) acid generator is usually 0.001-30 parts by weight, preferably 0.005-20 parts by weight, and (D) sensitizing dye is usually 0.01-30 parts by weight, preferably Is used in an amount of 0.05 to 20 parts by weight. The ratio of the crosslinking agent of the (CN-2) component to the (CN-3) acid generator is usually 0.05 to 30,000 parts by weight, preferably 0.5 to 10,000 parts by weight. The ratio of the sensitizing dye of component (D) to the (CN-3) acid generator is usually 0.001 to 30,000 parts by weight, preferably 0.05 to 4,000 parts by weight. When the amount of the crosslinking agent of the (CN-2) component is less than the above range, a sufficient crosslinking effect cannot be obtained, and the resulting image pattern tends to be poor. There exists a tendency for the application | coating characteristic of a photosensitive composition to fall. (D) If the amount of the sensitizing dye is less than this range, the sensitivity tends to be low, and if the amount of the sensitizing dye is more than this range, the transparency of the resist film is decreased due to the sensitizing dye. As a result, the resist pattern has an inverted trapezoidal shape and tends to cause a decrease in resolution.

<Other ingredients>
The chemically amplified negative photosensitive resin composition of the present invention includes the above (CN-1), (CN-2), (CN-3) and (D
) In addition to components, colorants such as dyes and pigments, exposure visible paints, plasticizers, surfactants, adhesion improvers, heat resistance or chemical resistance imparting agents may be contained. The content ratio of these components may be in a range that does not impair the performance of the photosensitive resin composition, but is usually 20% by weight or less, preferably 15% by weight or less, and more preferably based on the entire composition. 10% by weight or less.

<< Chemically Amplified Positive Photosensitive Resin Composition >>
Among the photosensitive resin compositions of the present invention, the chemically amplified positive type may include (CP-1) an acid-decomposable group-containing polymer and (CP-2) a composition containing an acid generator. I can do it.

<(CP-1) acid-decomposable group-containing polymer>
The (CP-1) acid-decomposable group-containing polymer in the chemically amplified positive photosensitive resin composition of the present invention includes acid generation as an active compound when the photosensitive resin composition is irradiated with actinic rays. The polymer is not particularly limited as long as it is a polymer containing an acid-decomposable group that decomposes with an acid generated by the agent and imparts alkali solubility to the polymer itself. Specific examples of the acid-decomposable group include alkoxy groups having 1 to 15 carbon atoms such as methoxy group, i-propoxy group, and t-butoxy group, methoxymethoxy group, 1-methoxyethoxy group, and 1-ethoxyethoxy group. An alkoxyalkoxy group having 2 to 15 carbon atoms such as a 1-cyclohexyloxyethoxy group, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an i-propoxycarbonyloxy group,
C2-C15 alkoxycarbonyloxyalkoxy such as t-butoxycarbonyloxy group such as 2-15 alkoxycarbonyloxy group, ethoxycarbonyloxymethoxy group, i-propoxycarbonyloxymethoxy group, t-butoxycarbonyloxymethoxy group Group, etc., and an alkoxyalkoxy group, an alkoxycarbonyloxy group, an alkoxycarbonyloxyalkoxy group and the like are preferable.

  Examples of the polymer containing the acid-decomposable group include etherification or esterification of at least a part of the phenolic hydroxyl group of a phenolic hydroxyl group-containing resin such as a novolac resin, a resole resin, and a polyvinyl phenol resin. A resin having an acid-decomposable group introduced is preferred. Among them, in the present invention, a resin in which the acid-decomposable group is introduced into a novolak resin or a polyvinylphenol resin is preferable, and a resin in which the acid-decomposable group is introduced into a polyvinylphenol resin is particularly preferable.

In addition, as the polymer containing other acid-decomposable groups, for example, the acid-decomposable group is introduced by esterifying at least a part of the carboxyl groups of those exemplified as the polymer having the (N-1) carboxyl group described above. The preferred resins can also be mentioned as preferred.

<(CP-2) acid generator>
As the (CP-2) acid generator in the chemically amplified positive photosensitive resin composition of the present invention, the same acid generators listed as the above-mentioned (CN-3) component can be used, and sulfonic acid Are preferred, sulfonic acid imidyl ester compounds are more preferred, and fluorine-containing sulfonic acid imidyl ester compounds are particularly preferred.

<Composition of chemically amplified positive photosensitive resin composition>
In the chemically amplified positive photosensitive resin composition of the present invention, the (CP-2) acid generator is usually 0.001 to 30 parts by weight per 100 parts by weight of the (CP-1) acid-decomposable group-containing polymer. Preferably, 0.005 to 10 parts by weight, and (D) a sensitizing dye is used in an amount of 0.01 to 30 parts by weight, preferably 0.1 to 20 parts by weight. The ratio of (D) sensitizing dye to (CP-2) acid generator is usually 0.001 to 30,000 parts by weight, preferably 0.01 to 4,000 parts by weight. (D) If the amount of the sensitizing dye is less than this range, the sensitivity tends to be low.
When the amount of the sensitizer is larger than this range, the resist pattern becomes an inverted trapezoid due to a decrease in the transparency of the resist film due to the sensitizing dye, and the resolution tends to decrease.

<Other ingredients>
In addition to the components (CP-1), (CP-2), and (D), the chemically amplified positive photosensitive resin composition of the present invention includes colorants such as dyes and pigments, exposure visible image agents, plastics An agent, surfactant, adhesion improver, heat resistance or chemical resistance imparting agent may be contained. The content ratio of these components may be in a range that does not impair the performance of the photosensitive resin composition, but is usually 20% by weight or less, preferably 15% by weight or less, and more preferably based on the entire composition. 10% by weight or less.

<<< Image forming material >>>
In the present invention, the photosensitive resin composition is usually coated on a support as a coating solution in which the above components are dissolved or dispersed in an appropriate solvent, and then heated and dried. By forming the adjustment layer and / or the oxygen blocking layer, an image forming material having a layer made of the photosensitive composition on the support is obtained. The image forming material may be formed on both the front and back surfaces of the support.

  When the photosensitive resin composition of the present invention is used as a so-called dry film resist material, the coating solution is applied on a temporary support film and dried, and the surface of the photosensitive resin composition layer is covered with a coating film. A so-called dry film resist material is formed by covering with. The dry film resist material is used as an image forming material by removing the coating film and laminating the photosensitive resin composition layer on a support on which image formation is to be performed. As the temporary support film, for example, a conventionally known film such as a polyethylene terephthalate film, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is used. Moreover, you may give light transmittance adjustment capability by making a light-absorbing agent exist in a temporary support body film. As the covering film, a conventionally known film such as a polyethylene film, a polypropylene film, a polytetrafluoroethylene film, or the like is used. As a method for laminating the support, it can be laminated by heating, pressurizing, etc. using a laminator or the like as in the case of a normal dry film resist material.

<< Image forming material: support >>
As the support, an image formed using the photosensitive resin composition and the image forming method of the present invention is used to cover the image portion (that is, the surface of the support is not removed after development without removing the photosensitive resin composition layer). The non-image portion (that is, the portion where the photosensitive resin composition layer is removed after development and the surface of the support is exposed) is etched or plated, using the mask as a mask. A support used for the purpose of forming an image pattern on the substrate (in the present invention, simply referred to as “substrate to be processed”) is used.

  Specific examples of the substrate to be processed include metal plates such as copper, aluminum and gold, thermosetting resins such as epoxy resin, polyimide resin, phenol resin and melamine resin, saturated polyester resin, polycarbonate resin and acrylic resin. , Polyamide resins, polystyrene resins, polyvinyl chloride resins, thermoplastic resins such as fluororesins, paper, glass, alumina, silica and other inorganic materials, or glass cloth base epoxy resin, glass nonwoven base epoxy resin, paper Examples thereof include a support made of composite materials such as a base epoxy resin and a paper base phenol resin. As another specific example of the substrate to be processed, the metal, indium oxide, tin oxide is formed on the surface of the support that is insulative and has a thickness of about 0.02 to 10 mm. A conductive layer having a thickness of about 1 to 100 μm by heating, pressure laminating a metal foil such as metal oxide such as indium oxide doped tin oxide (ITO), or sputtering, vapor deposition, plating, etc. A metal-clad laminate having a metal layer, a wafer in which an electronic circuit element and / or an insulating layer are formed on a silicon wafer, and a metal layer such as copper, aluminum, or gold are used. Of these, glass, metal-clad laminate and wafer are preferably used.

<< Image forming material: solvent >>
The solvent is not particularly limited as long as it has sufficient solubility with respect to the components used and gives good coating properties, but for example, cellosolve solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, Propylene glycol solvents such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol dimethyl ether, ester solvents such as butyl acetate, amyl acetate, ethyl butyrate, ethyl-2-hydroxybutyrate, methyl 3-methoxypropionate Alcohol solvents such as normal propanol, isopropanol, normal butanol, isobutanol, sec-butanol, heptanol, hexanol, diacetone alcohol, methyl ethyl ketone, cyclohexane Ketone solvents non like, dimethylformamide, N- highly polar solvents such as methyl pyrrolidone, or a mixture of these solvents, more like those in which the addition of aromatic hydrocarbons. When the composition layer to be formed is thick, such as when the photosensitive resin composition of the present invention is used as a dry film resist material, a solvent having a low boiling point and high volatility such as isopropanol and methyl ethyl ketone is used. Is preferred. The proportion of the solvent used is usually in the range of about 1 to 40 times by weight with respect to the total amount of the photosensitive resin composition.

<< Image forming material: coating method >>
As the coating method, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, and curtain coating can be used. The coating amount varies depending on the application, but the dry film thickness is usually 0.3 to 30 μm.
In the case where the photosensitive resin composition of the present invention is used as a dry film resist material, the dry film thickness is preferably used for image formation and subsequent etching or the like. From the viewpoint of workability such as plating, it is usually preferably 10 μm or more, more preferably 15 μm or more, and from the viewpoint of sensitivity or the like, it is preferably 200 μm or less, and more preferably 100 μm or less.

<< Image forming material: drying method >>
Further, the drying method is not particularly limited, but the residual ratio of the solvent in the composition layer is usually 10% by weight by a conventionally known method such as a method of heating using a hot plate, a heating oven or a lamp. Hereinafter, it is preferably carried out so as to be 5% by weight or less. As a method of heating with a hot plate or a heating oven, usually at a temperature of 40 to 130 ° C., preferably 50 to 120 ° C., 5 seconds or more, preferably 20 seconds or more, and preferably within 60 minutes, more preferably 30 minutes. Should be done within. In this case, a method of combining a plurality of heating methods or changing the heating temperature stepwise may be used. In particular, when the dry film thickness is 10 μm or more, a method in which the solvent in the composition layer is effectively discharged out of the layer, such as changing the heating temperature stepwise, is preferably used. It is done.

<< Image forming material: oxygen blocking layer, light transmission adjusting layer >>
In addition, a light transmission adjusting layer may be formed on the photosensitive resin composition layer of the image forming material in order to adjust a wavelength region having spectral sensitivity. In the case where the photosensitive resin composition is a photopolymerization type, an oxygen blocking layer may be formed to prevent the polymerization inhibiting action due to oxygen of the composition.

  Here, what constitutes the light transmittance adjusting layer includes, for example, a plastic film or a polymer binder containing a light-absorbing dye in the visible region such as a coumarin dye. A protective layer having an oxygen blocking ability and a light transmittance adjusting ability is obtained by using polyvinyl alcohol or a derivative thereof or a polyvinyl pyrrolidone-based polymer as a polymer binder of the following to be used for an oxygen blocking layer described later. You can also.

The oxygen barrier layer is composed of water or a water-soluble polymer that is soluble in a mixed solvent of water and a water-miscible organic solvent such as alcohol or tetrahydrofuran, or a water-insoluble polymer such as polyethylene terephthalate. Specifically, for example, polyvinyl alcohol, its partially acetalized product, its cation-modified product with quaternary ammonium salt, etc., its anion-modified product with sodium sulfonate, etc., polypinylpyrrolidone, polyethylene Examples thereof include oxide, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like. Among them, polyvinyl alcohol and derivatives thereof are preferable from the viewpoint of oxygen barrier properties, etc., and polyvinyl pyrrolidone, vinyl pyrrolidone-vinyl acetate copolymer, etc. from the viewpoint of adhesion to the photosensitive resin composition layer, etc. The vinylpyrrolidone-based polymer is preferable. As the oxygen barrier layer in the present invention, a polyvinyl pyrrolidone polymer is preferably used in a mixture of 1 to 20 parts by weight, more preferably 3 to 15 parts by weight with respect to 100 parts by weight of polyvinyl alcohol or a derivative thereof. Is preferred. In addition, from the viewpoint of imparting preservability, it is preferable to contain an organic acid such as oxalic acid or an organic acid salt such as ethylenediaminetetraacetic acid, and nonionic, dodecylbenzenesulfonic acid such as polyoxyethylene alkylphenyl ether. It may contain an anionic agent such as sodium, a cationic agent such as alkyltrimethylammonium chloride, an antifoaming agent, a dye, a plasticizer, a pH adjuster, etc., and the total content thereof is 10 wt. % Or less is preferable.

When these light transmission control layers and oxygen barrier layers are plastic films, the solution of water or a mixed solvent of water and a water-miscible organic solvent is obtained by a method of heating and pressurizing with a laminator or the like. In this case, it is formed by the same application and drying method as the above-described photosensitive resin composition layer, and the application amount is preferably in the range of 1 to 10 g / m ² as a dry film thickness, More preferably, the range is 7 g / m ² .

<<< Image Forming Method >>>
Then, the photosensitive layer of the image forming material can be exposed by scanning with a laser light source and then developed with an alkali developer to reveal an image.

<< Image forming method: laser exposure >>
Here, as the laser exposure light source, a light source that generates laser light in the blue-ultraviolet region in the wavelength range of 390 to 430 nm is used. Although not particularly limited, specifically, laser light in the vicinity of 405 nm is oscillated. And an indium gallium nitride semiconductor laser. When using the image forming material of the present invention, in particular, as described above, in the vicinity of a wavelength of 405 nm, for example, a wavelength range of 400 to 420 nm.
Therefore, since the difference in sensitivity is small, the oscillation wavelength of the laser light source may have a distribution in this wavelength region.

Also, the scanning exposure method is not particularly limited, and examples thereof include a plane scanning exposure method, an outer drum scanning exposure method, an inner drum scanning exposure method, and the like. 10W, preferably 0.002-5W, beam spot diameter is usually 0.5-30μm
The laser exposure amount on the photosensitive layer is usually 1 to 50 mJ / cm2 or less, preferably 1.5 to 30 mJ / cm2 or less, more preferably 2 to 20 mJ / cm2 or less. Scan exposure. In addition, for example, when using a plane scanning exposure method, when the same surface is exposed simultaneously by a plurality of laser light sources, or image forming materials are formed on both front and back surfaces of the substrate to be processed, for example, to shorten the exposure time. The both sides may be exposed at the same time.

In particular, when the photosensitive resin composition is a chemically amplified negative type or a chemically amplified positive type, the crosslinking or decomposition by the acid generated by exposure is promoted, and the photosensitive resin composition of the exposed portion and the non-exposed portion is promoted. For the purpose of, for example, expanding the difference in solubility in an alkaline developer, heating at 50 to 150 ° C., preferably 70 to 130 ° C., usually 0.5 to 30 minutes, preferably 1 to 20 minutes may be performed. .

<< Image Forming Method: Development >>
The development after the laser scanning exposure is performed using an alkali developer, and examples of the alkali developer include sodium silicate, potassium silicate, ammonium silicate, sodium metasilicate, potassium metasilicate, sodium hydroxide, Consists of an aqueous solution of about 0.1 to 5% by weight of an inorganic alkali salt such as potassium hydroxide, sodium carbonate, sodium bicarbonate or potassium carbonate, or an organic amine compound such as monoethanolamine, diethanolamine, triethanolamine or tetramethylammonium hydroxide. A developer is used. In particular, as the alkali developer, inorganic alkali salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and the like are preferable, and a plurality of combinations thereof may be used.

The alkaline developer may contain a nonionic, anionic, cationic, or amphoteric surfactant from the viewpoint that the range of development conditions can be stably expanded. Among these surfactants, nonionic surfactants, anionic surfactants, or amphoteric surfactants are preferable. The surfactant is contained in the alkali developer at a concentration of preferably 0.0001 to 20% by weight, more preferably 0.0005 to 10% by weight, and particularly preferably 0.001 to 5% by weight.

In addition, the alkali developer further includes an antifoaming agent such as a silicone compound, a water-soluble organic solvent such as a polyhydric alcohol, a hard water softener such as an aminopolycarboxylate, a phenolic compound, Additives such as reducing agents such as amine compounds, chelating agents such as phosphonoalkanetricarboxylic acids and their salts, and pH adjusting agents such as inorganic acids, organic acids and their salts can be contained. These additives are preferably contained in the alkali developer at a concentration of 0.001 to 5% by weight, particularly preferably 0.005 to 3% by weight. The pH of the alkali developer is preferably 10 or more.

The developing method is usually a known developing method such as immersing the image-forming material after laser exposure in the developer or spraying the developer on the image-forming material. It is performed at a temperature of about 50 ° C., more preferably about 15 to 45 ° C., for a time of about 5 seconds to 10 minutes. At that time, when an oxygen blocking layer is provided, it may be removed with water or the like in advance or may be removed during development. In the case of a dry film resist material, development is performed after the temporary support film is peeled off.

<<< Processing after image formation >>>
Using the image formed on the substrate to be processed as described above, the image portion (that is, the portion where the photosensitive resin composition layer is not removed after development and the surface of the support is coated) is used as a non-image. An image pattern is formed on the surface of the support by etching or plating the portion (that is, the portion where the photosensitive resin composition layer is removed after development and the support surface is exposed) by a conventional method, and thereafter By removing the photosensitive resin composition layer remaining in the image portion by a conventionally known method such as dissolving in a strong alkaline aqueous solution, a substrate to be processed having an image pattern on the surface can be obtained. The substrate is used, for example, as a printed wiring board or a display circuit board.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

Examples 1 to 6 (photopolymerization type photosensitive resin composition)
(N-1) component carboxyl group-containing polymer, (N-2) component ethylenically unsaturated compound, (N-3) component photopolymerization initiator, (D) component sensitizing dye, and Other components were added to 100 parts by weight of methyl ethyl ketone and dissolved by stirring at 40 ° C. for 2 hours to prepare a coating solution. Polyethylene terephthalate film as a temporary support film (thickness 25 μm)
A polyethylene film (thickness: 22 μm) as a coating film is formed on the photosensitive composition layer by applying it on the top with an applicator to a dry film thickness of 20 μm and drying at 90 ° C. for 10 minutes. Were laminated to prepare a dry film resist material.
Next, with respect to the dry film resist material, the covering film is removed from a copper-clad laminate (Mitsubishi Gas Chemical Co., Ltd., CCL-EL-170) whose copper foil surface has been previously polished. With a roll laminator, roll temperature 100 ° C, roll pressure 0.3M
An image forming material was prepared by laminating at Pa and a laminating speed of 1.5 m / min.

<< Composition of photosensitive resin composition >>
<Polymer having (N-1) carboxyl group>
Methyl methacrylate (35% by weight) / 2-ethylhexyl acrylate (10% by weight) / n-butyl methacrylate (10% by weight) / 2-hydroxyethyl methacrylate (15% by weight) / styrene (10% by weight) / Copolymer of methacrylic acid (20% by weight) (Mw about 50,000, Mw / Mn about 2.0, acid value 137 mgKOH / g); 55 parts by weight <(N-2) ethylenically unsaturated compound>
2,2-bis [4- (methacryloxy / polyethoxy) phenyl] propane (containing about 10 equivalents of ethoxy group); 40 parts by weight <(N-3) photopolymerization initiator>
2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole; 4 parts by weight <(D) sensitizer>
Compounds listed in Table 1; Amounts listed in Table 1 <Other components>
Leuco Crystal Violet; 0.33 parts by weight Crystal Violet; 0.02 parts by weight

<< Evaluation method >>
The obtained image forming material was evaluated as follows.

<Measurement of the minimum exposure that can form an image>
A sample obtained by cutting the image forming material into a size of 50 × 60 mm is 350 using a diffraction spectroscopic irradiation device (“RM-23” manufactured by Narumi) and a xenon lamp (“UI-501C” manufactured by USHIO INC.) As a light source. The light divided in the wavelength region of ˜650 nm was exposed by irradiating for 10 seconds with the exposure wavelength linearly set in the horizontal axis direction and the exposure intensity changed logarithmically in the vertical axis direction. An aqueous solution containing 0.7% by weight of sodium is sprayed for 40 seconds at a spray pressure of 0.1 MPa and 25 ° C, and then washed with water, so that an image corresponding to the sensitivity of each exposure wavelength can be obtained. The exposure energy was calculated. Minimum exposure doses S [400nm], S [405nm], S [420nm], S [450nm], and S [450-650nm that can be imaged at the obtained wavelengths 400, 405, 420, 450, and 450-650nm From [mJ / cm ² ], S [400 nm] / S [420 nm], S [405 nm] / S [450 nm], and S [405 nm] / S [450-650 nm] were calculated and shown in Table 1. .

<Measurement of UV visible absorption spectrum>
When the photosensitive resin composition layer of the image forming material and the entire layer including the light transmission adjusting layer and / or the oxygen blocking layer are measured, a UV-visible absorption spectrum is measured by a conventionally known method. The absorbance ABS [400 nm] and ABS [420 nm] at wavelengths of 400 and 420 nm were measured, and the ratio ABS [400 nm] / ABS [420 nm] was calculated and shown in Table 1.

<Image formation evaluation>
The image forming material is a blue-violet semiconductor laser that oscillates at a wavelength of 405 nm (“NL” manufactured by Nichia Corporation).
HV500C ”, laser output 5 mW, beam spot diameter 8 μm), scanning exposure was performed while changing the beam scanning interval and scanning speed. After exposure, the polyethylene terephthalate film as a temporary support is removed, and a minimum development time (the unexposed part is completely dissolved and removed at a spray pressure of 0.1 MPa using a 0.7 wt% sodium carbonate aqueous solution at 25 ° C. as a developer. The negative image was revealed by spray development in 1.5 times the time. As a result, the minimum exposure amount capable of satisfactorily displaying a 20 μm thin line image was determined and shown as “laser sensitivity (mJ / cm ² )” in Table 1.

Comparative example (photopolymerizable photosensitive composition described in Example 1 of JP-A-2002-296764)
In Example 1 of JP 2002-296764 A, a photosensitive lithographic printing plate for blue-violet laser exposure was used in the same manner except that the drying conditions for forming the photosensitive composition layer and the protective layer were 70 ° C. for 2 minutes. It was created. For this photosensitive lithographic printing plate for blue-violet laser exposure, an aqueous solution containing 0.7% by weight sodium carbonate at 28 ° C. and 0.5% by weight anionic surfactant (PEX NBL manufactured by Kao Corporation) was used as a developer. The same evaluation as in Example 1 was performed except that immersion development was performed for 30 seconds as a development method. The results are shown in Table 1.

Example 7 (Chemically Amplified Negative Photosensitive Resin Composition)
Increase in the following (CN-1) component alkali-soluble resin, (CN-2) component crosslinking agent that acts on the alkali-soluble resin under acidic conditions, (CN-3) acid generator, and (D) component increase The dye was dissolved in 170 parts by weight of propylene glycol monomethyl ether acetate and 110 parts by weight of cyclohexanone to prepare a coating solution. This coating solution was applied onto a glass substrate using a spin coater so as to have a dry film thickness of 10 μm, and dried at 90 ° C. for 10 minutes to prepare an image forming material.
For the obtained image forming material, a 0.5 wt% potassium hydroxide aqueous solution at 20 ° C. was used as a developer, an immersion development method was performed for 80 seconds as a developing method, and a heat treatment at 100 ° C. for 10 minutes after exposure. The evaluation was performed in the same manner as in Example 1 except that the test was performed, and the results are shown in Table 1.

<< Photosensitive resin composition >>
<(CN-1) alkali-soluble resin>
Poly-p-hydroxystyrene (Mw about 5,000); 100 parts by weight <(CN-2) cross-linking agent acting on alkali-soluble resin under acidic conditions>
Hexamethoxymethylmelamine; 45 parts by weight <(CN-3) acid generator>
1,8-naphthalimidyl trifluoromethanesulfonate; 3 parts by weight 1,8-naphthalimidyl nonafluorobutanesulfonate; 3 parts by weight <(D) sensitizing dye>
Compound (I-2); 0.8 parts by weight

  From these Examples and Comparative Examples, it can be seen that the image forming material of the present invention has a small difference in sensitivity and can form a uniform image even when exposed to any light source having a wavelength of 400 nm to 420 nm.

Claims (8)

An image forming material having at least a blue-violet semiconductor laser photosensitive resin composition layer on a substrate to be processed, which satisfies the following (1):
(1) Minimum exposure amount S [400 nm] (mJ / cm ² ) capable of forming an image by exposure with a light source having a wavelength of 400 nm
) And the minimum exposure S (420nm) that can form an image by exposure with a light source with a wavelength of 420nm (
mJ / cm ²⁾ the ratio of the S [400nm] / S [420nm ] is 0.47 or more, is 1.53 or less The image forming material according to claim 1, wherein the following (2) or (3) is satisfied.
(2) Minimum exposure amount S [405nm] (mJ / cm) capable of forming an image by exposure with a light source with a wavelength of 405nm
² ) and the minimum exposure S (450nm) that allows image formation by exposure with a light source with a wavelength of 450nm
(mJ / cm ²⁾ the ratio of the S [405nm] / S [450nm ] is, is 0.2 or less and (3) the S [405nm] (mJ / cm 2) according to each wavelength of the light source wavelength 450~650nm By exposure
Ratio S [405nm] / S [450-6] with minimum exposure S (450-650nm) (mJ / cm ² ) capable of image formation
50nm] is 0.2 or less The image forming material according to claim 1 or 2, wherein the sensitivity to a blue-violet semiconductor laser having a wavelength of 405 nm is 30 mJ / cm ² or less. The image forming material according to claim 1, wherein the photosensitive resin composition layer contains the following (N-1), (N-2), and (N-3).
(N-1) Polymer having carboxyl group (N-2) Ethylenically unsaturated compound (N-3) Photopolymerization initiator The image forming material according to claim 1, wherein the photosensitive resin composition layer contains the following (CN-1), (CN-2), and (CN-3).
(CN-1) Alkali-soluble resin
(CN-2) Crosslinking agent that acts on alkali-soluble resins under acidic conditions
(CN-3) acid generator The image forming material according to claim 1, wherein the photosensitive resin composition layer contains (D) a sensitizing dye having a spectral sensitivity at a wavelength of 390 to 430 nm. The dry film resist material obtained by laminating the temporary support / photosensitive resin composition layer / coated film in this order is removed so that the coated film is removed and the photosensitive resin composition layer is laminated so as to be in contact with the substrate to be processed. The image forming material according to claim 1, which is obtained as described above. 8. An image forming method, wherein the image forming material according to claim 1 is exposed with a blue-violet semiconductor laser having a wavelength of 390 to 430 nm and then developed with an alkali developer.