KR20150042775A - Photosensitive resin composition for permanent mask resist, photosensitive element, method for forming resist pattern, and method for producing printed wiring board - Google Patents
Photosensitive resin composition for permanent mask resist, photosensitive element, method for forming resist pattern, and method for producing printed wiring board Download PDFInfo
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- KR20150042775A KR20150042775A KR20157001461A KR20157001461A KR20150042775A KR 20150042775 A KR20150042775 A KR 20150042775A KR 20157001461 A KR20157001461 A KR 20157001461A KR 20157001461 A KR20157001461 A KR 20157001461A KR 20150042775 A KR20150042775 A KR 20150042775A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
- H05K3/0076—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the composition of the mask
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- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention relates to an epoxy resin composition comprising (A) an epoxy resin containing an acid-modified vinyl group, (B) a photopolymerization initiator, and (C) a nitrosyl compound, wherein the (C) nitrosyl compound contains a compound having a specific structure To provide a photosensitive resin composition for a mask resistor.
Description
The present invention relates to a photosensitive resin composition for a permanent mask resistor, a photosensitive element, a method of forming a resistor pattern, and a method of manufacturing a printed wiring board.
Conventionally, permanent mask resistors in the production of printed wiring boards have been manufactured by a method of screen printing a resist or ultraviolet curing type register ink. 2. Description of the Related Art In recent years, with the high integration of electronic devices, it has become necessary to make wiring patterns and insulating patterns of a printed wiring board finer (high definition). However, in the conventional method of forming a register by screen printing, blurring, sagging, or the like occurs during printing, so it is difficult to form a fixed register image. Thus, a resist image forming method by photolithography has been developed in order to form a fixed three-dimensional register image.
Specifically, the resist-image forming method by photolithography is a method in which a photosensitive resist of a dry film type is thermo-pressed on a substrate or a liquid photosensitive resistor is coated on a substrate with a curtain or a spray, Is irradiated through a negative mask and then developed to form a resist image.
As a method of forming a register pattern, a so-called direct-write exposure method in which a register pattern is directly drawn without using a mask pattern has attracted attention. According to this direct imaging exposure method, it is considered that it is possible to form a resist pattern with high resolution and a high resolution, and to improve the positional precision capable of coping with distortion of various substrates. In addition, in recent years, a direct-write exposure apparatus having a wide wavelength range of 350 to 450 nm in exposure wavelength has become practically usable.
Several photosensitive resin compositions intended to form a resist pattern by a direct imaging exposure method using a laser beam having an exposure wavelength of 405 nm as an active light source have been proposed so far (see, for example,
In addition, several photosensitive resin compositions using a nitroxyl compound have been proposed (for example, see
However, in the photosensitive resin composition described in
The present invention relates to a photosensitive resin composition for a permanent mask resistor which can induce a large amount of exposure to an exposure amount and can form a resist pattern with high reproducibility between samples and within the same substrate, a photosensitive element using the resist composition, a method of forming a resistor pattern, And a method thereof.
The present invention relates to a resin composition comprising (A) an epoxy resin containing an acid-modified vinyl group, (B) a photopolymerization initiator, and (C) a nitrosyl compound, wherein the (C) nitrosyl compound is represented by the following general formula The present invention provides a photosensitive resin composition for a permanent mask resistor.
Wherein R 1 represents a hydroxy group, an alkyl group having 1 to 5 carbon atoms, an acetamide group, an amino group, a chloroacetamide group, a cyano group, a benzoyloxy group or a group represented by the following general formula (2)
[In the formula (2), n1 represents an integer of 1 to 12]
According to such a photosensitive resin composition, it is possible to broaden the exposure dose and to form a resist pattern with good reproducibility between samples and in the same substrate, and particularly in a via-shape with good reproducibility. It is also possible to form a resist pattern using exposure light within a wavelength range of 350 nm to 450 nm and to form a resist pattern by a direct imaging exposure method with sufficient sensitivity and resolution.
Further, according to the photosensitive resin composition of the present invention having the above-described constitution, it is possible to form a high-performance cured film excellent in heat resistance, heat and humidity resistance, adhesiveness, mechanical properties and electrical characteristics and to produce printed wiring boards, high density multilayer boards and semiconductor packages Can be used suitably.
The photosensitive resin composition of the present invention can form resist patterns using exposure light within a wavelength range of 350 nm to 450 nm while maintaining characteristics such as developability, adhesion, heat resistance and solvent resistance as solder resists It becomes possible to perform the exposure with excellent sensitivity and resolution, and it becomes possible to improve the exposure amount, in particular.
The content of the acid-modified vinyl group-containing epoxy resin (A) is preferably 25% by mass or more based on the whole solid content of the photosensitive resin composition.
The acid-modified vinyl group-containing epoxy resin (A) is obtained by reacting a novolak type epoxy resin represented by the following general formula (3), a bisphenol type epoxy resin represented by the following general formula (4) Is preferably a resin obtained by reacting at least one epoxy resin (a) selected from the group consisting of a salicylaldehyde-type epoxy resin represented by the formula (1) and a vinyl group-containing monocarboxylic acid (b).
(3), R 6 represents a hydrogen atom or a methyl group, Y 1 represents a hydrogen atom or a glycidyl group (provided that the hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70) , and n 2 represents an integer of 1 or more. And R < 6 > and Y < 1 > which may be present in plural may be the same or different.
(4), R 7 represents a hydrogen atom or a methyl group, Y 2 represents a hydrogen atom or a glycidyl group (provided that the hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70) , and n 3 represents an integer of 1 or more. In addition, plural R < 7 > And Y < 2 > may be the same or different.]
[Wherein Y 3 represents a hydrogen atom or a glycidyl group (provided that the hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), and n 4 represents an integer of 1 or more. The plural Y 3 s may be the same or different.]
The present invention also provides a photosensitive element comprising, on a support, a photosensitive layer composed of the photosensitive resin composition for the permanent mask resist.
The present invention also provides a process for producing a permanent-type mask resistor, comprising the steps of: laminating a photosensitive layer made of the photosensitive resin composition for the permanent mask resist or a photosensitive layer of the photosensitive element on a substrate; and irradiating the photosensitive layer with an actinic ray in a picture- There is provided a method of forming a resist pattern including an exposure step of photo-curing an exposed part and a developing step of removing an area other than the exposed part.
The present invention also provides a method for producing a printed wiring board in which a permanent mask is formed on a substrate by the method for forming a resist pattern according to the present invention.
According to the method for forming a resist pattern and the method for producing a printed wiring board of the present invention, since the photosensitive resin composition of the present invention is used, the resist pattern having a wavelength of 350 nm to 450 nm It is possible to form the resist pattern using the exposure light in the range with sufficient sensitivity and resolution. In addition, it is possible to efficiently form a cured film such as a permanent mask (solder resist) capable of forming a resist pattern with high reproducibility such as a via shape and the like between samples and within the same substrate with a large induction to an exposure amount.
The present invention relates to a photosensitive resin composition for a permanent mask resistor which can induce a large amount of exposure to an exposure amount and can form a resist pattern with high reproducibility between samples and within the same substrate, a photosensitive element using the resist composition, a method of forming a resistor pattern, Method can be provided.
1 (a) is a schematic sectional view showing a core substrate on which a buildup layer is formed, (b) is a schematic cross-sectional view showing a process of forming a photosensitive layer, (c) is a schematic cross- (d) is a schematic sectional view showing a step of forming a resist pattern, and (e) is a schematic cross-sectional view showing a step of forming a permanent mask resistor.
[Fig. 2] Fig. 2 (a) is a schematic cross sectional view showing an electroless gold plating process, and Fig. 2 (b) is a schematic cross sectional view showing an electrolytic gold plating process.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as occasion demands. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and a duplicate description will be omitted. In the present invention, (meth) acrylic acid means acrylic acid or methacrylic acid, and the same applies to other similar expressions such as (meth) acrylate.
The photosensitive resin composition of the present invention is a photosensitive resin composition comprising (A) an acid-modified vinyl group-containing epoxy resin (hereinafter occasionally referred to as "component (A)") and (B) a photopolymerization initiator ) Component "), and (C) a nitrosyl compound (hereinafter, sometimes referred to as" component (C) "). Hereinafter, each component will be described in detail.
The component (A) is an epoxy resin containing an acid-modified vinyl group. For example, a resin obtained by modifying an epoxy resin with a vinyl group-containing monocarboxylic acid can be used. Examples of the component (A) include a novolak type epoxy resin represented by the following formula (3), a bisphenol A type epoxy resin or a bisphenol F type epoxy resin represented by the following formula (4) Is preferably a resin obtained by reacting at least one epoxy resin (a) selected from the group consisting of a salicylaldehyde-type epoxy resin and a vinyl group-containing monocarboxylic acid (b).
(3), R 6 represents a hydrogen atom or a methyl group, Y 1 represents a hydrogen atom or a glycidyl group (provided that the hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70) , and n 2 represents an integer of 1 or more. And R < 6 > and Y < 1 > which may be present in plural may be the same or different.
(4), R 7 represents a hydrogen atom or a methyl group, Y 2 represents a hydrogen atom or a glycidyl group (provided that the hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70) , and n 3 represents an integer of 1 or more. In addition, plural R < 7 > And Y < 2 > may be the same or different.]
[Wherein Y 3 represents a hydrogen atom or a glycidyl group (provided that the hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), and n 4 represents an integer of 1 or more. The plural Y 3 s may be the same or different.]
(A ') in addition to the reaction product of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) (hereinafter referred to as "reaction product (A' Addition reaction products obtained by adding a saturated or unsaturated group-containing polybasic acid anhydride (c) may also be used. Here, in the synthesis of the addition reaction product, a hydroxyl group is formed by the addition reaction of the epoxy group of the epoxy resin (a) with the carboxyl group of the vinyl group-containing monocarboxylic acid (b) in the first reaction, It is presumed that the acid anhydride group of the resulting hydroxyl group (including the hydroxyl group originally present in the epoxy resin (a)) and the polybasic acid anhydride (c) containing a saturated or unsaturated group is half-esterified.
Examples of the novolak-type epoxy resin represented by the above-mentioned general formula (3) include phenol novolac-type epoxy resin and cresol novolak-type epoxy resin. These novolak-type epoxy resins can be obtained, for example, by reacting phenol novolak resin or cresol novolac resin with epichlorohydrin by known methods, respectively.
The bisphenol A epoxy resin or the bisphenol F epoxy resin in which Y 2 is a glycidyl group in the compound represented by the general formula (4) can be obtained, for example, from bisphenol A represented by the following general formula (6) Type epoxy resin or bisphenol F type epoxy resin with epichlorohydrin.
[In the formula (6), R 7 represents a hydrogen atom or a methyl group, and n 3 represents an integer of 1 or more. The plural R 7 s present may be the same or different.]
In order to accelerate the reaction between the hydroxyl group and epichlorohydrin, it is preferable to carry out the reaction in a polar organic solvent such as dimethylformamide, dimethylacetamide or dimethylsulfoxide in the presence of an alkali metal hydroxide at a reaction temperature of 50 to 120 ° C Do. When the reaction temperature is 50 ° C or higher, the reaction can be performed quickly. When the reaction temperature is 120 ° C or lower, side reactions can be suppressed.
Specific examples of the salicylaldehyde-type epoxy resin represented by the above general formula (5) include FAE-2500, EPPN-501H and EPPN-502H (manufactured by Nippon Kayaku Co., Ltd.).
Examples of the vinyl group-containing monocarboxylic acid (b) include acrylic acid, a dimer of acrylic acid, methacrylic acid,? -Perfuryl acrylic acid,? -Styryl acrylic acid, cinnamic acid, crotonic acid, . In addition, a half ester compound, which is a reaction product of a hydroxyl group-containing acrylate and a saturated or unsaturated dibasic acid anhydride, and a reaction between a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester and a saturated or unsaturated dibasic acid anhydride And a half ester compound which is a product. These vinyl group-containing monocarboxylic acids (b) may be used singly or in combination of two or more kinds.
Examples of the hydroxyl group-containing acrylate used in the synthesis of the half ester compound which is an example of the vinyl group-containing monocarboxylic acid (b) include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) (Meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate can be given. . Examples of the vinyl group-containing monoglycidyl esters include glycidyl acrylate and glycidyl methacrylate.
Examples of the saturated or unsaturated dibasic acid anhydride used in the synthesis of the half ester compound include unsaturated dicarboxylic acids such as succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, Phthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride and itaconic anhydride.
The ratio of the vinyl group-containing monocarboxylic acid (b) to the epoxy group-containing monocarboxylic acid (b) in the reaction of the epoxy resin (a) with the vinyl group-containing monocarboxylic acid (b) , More preferably 0.8 to 1.0 equivalents, and particularly preferably 0.9 to 1.0 equivalents.
The epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) are preferably dissolved in an organic solvent and reacted. Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, Glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate; Aliphatic hydrocarbons such as toluene, xylene, decane and decane, and petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated naphtha and solvent naphtha.
In addition, it is preferable to use a catalyst to promote the reaction. Examples of the catalyst to be used include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium iodide and triphenylphosphine. The amount of the catalyst to be used is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b).
Further, for the purpose of preventing polymerization during the reaction, it is preferable to use a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol and pyrogallol. The amount of the polymerization inhibitor to be used is preferably 0.01 to 1 part by mass based on 100 parts by mass of the total amount of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). The reaction temperature is preferably 60 to 150 占 폚, more preferably 80 to 120 占 폚.
If necessary, the vinyl group-containing monocarboxylic acid (b) and a phenol compound such as p-hydroxyphenethyl alcohol, anhydrous trimellitic acid, anhydrous pyromellitic acid, benzophenone tetracarboxylic acid anhydride, And polybasic acid anhydrides such as tetracarboxylic anhydride can be used in combination.
As the epoxy resin containing an acid-modified vinyl group (A), the above-mentioned reaction product (A ') is preferably used in view of the fact that a derivative of the epoxy resin having an acid-modified vinyl group has a broad induction with respect to the exposure dose and forms a resist pattern with good reproducibility such as via- ) With a polybasic acid anhydride (c) containing a saturated or unsaturated group is preferably used.
Examples of the saturated or unsaturated group-containing polybasic acid anhydride (c) include the compounds exemplified as the saturated or unsaturated dibasic acid anhydrides used in the synthesis of the above-mentioned half ester compounds.
In the reaction of the reaction product (A ') with the saturated or unsaturated group-containing polybasic acid anhydride (c), the saturated or unsaturated group-containing polybasic acid anhydride (c) is added in an amount of 0.1 to 1.0 equivalent By reacting, the acid value of the acid-modified vinyl group-containing epoxy resin (A) can be adjusted.
As the component (A), a polyurethane compound obtained by reacting an epoxy acrylate compound having two or more hydroxyl groups and a vinyl group with a diisocyanate compound and a diol compound having a carboxyl group may be used. Such polyurethane compounds are commercially available, for example, as UXE-3011, UXE-3012 and UXE-3024 (manufactured by Nippon Kayaku Co., Ltd.).
The acid value of the acid-modified vinyl group-containing epoxy resin (A) is preferably 30 to 150 mgKOH / g, more preferably 50 to 120 mgKOH / g, and still more preferably 60 to 100 mgKOH / g. When the acid value is 30 mgKOH / g or more, the solubility of the photosensitive resin composition in the diluted alkali solution tends to be improved. When the acid value is 150 mgKOH / g or less, the electrical characteristics of the resulting cured film tend to be improved. The acid value of the component (A) can be measured in the following manner. That is, first, 1 g of a resin to be measured for an acid value is precisely weighed, then 30 g of acetone is added to this resin, and this is uniformly dissolved. When volatile components such as a synthetic solvent and a diluting solvent are contained in the resin, the volatile components are removed by heating at a temperature higher than the boiling point by about 10 캜 for 1 to 4 hours in advance. Then, an appropriate amount of phenolphthalein, which is an indicator, is added to the solution, and titration is carried out using 0.1 N aqueous potassium hydroxide (KOH) solution. The acid number is obtained by calculating the number of mg of KOH necessary for neutralizing the acetone solution of the resin to be measured. When a solution obtained by mixing a resin with a synthetic solvent, a diluting solvent, or the like is to be measured, the acid value is calculated by the following formula.
Acid value = 0.1 x Vf x 56.1 / (Wp x I / 100)
(% By mass) in the solution containing the measured resin, Vf represents the appropriate amount (ml) of KOH, Wp represents the weight (g) of the solution containing the measured resin, .
The reaction temperature of the reaction product (A ') with the saturated or unsaturated group-containing polybasic acid anhydride (c) is preferably 60 to 120 ° C.
If necessary, a part of the epoxy resin (a), for example, hydrogenated bisphenol A type epoxy resin may be used in combination. In addition to the acid-modified vinyl group-containing epoxy resin (A), the hydroxyethyl (meth) acrylate-modified product of the styrene-maleic anhydride copolymer or the hydroxyethyl (meth) acrylate of the styrene- Modified styrene-maleic acid-based resin may be used in combination.
The content of the component (A) in the photosensitive resin composition is preferably 25 to 70 mass%, more preferably 30 to 70 mass%, and more preferably 35 to 65 mass%, based on the whole solid content of the photosensitive resin composition %. When the content is within the above range, a coating film excellent in heat resistance, electrical properties and chemical resistance tends to be obtained.
Examples of the component (B) include benzoin compounds such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; Benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis (diethylamino) benzophenone, Michler's ketone, 4-benzoyl- Benzophenone compounds; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1- hydroxycyclohexyl phenyl ketone, 2-dimethyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, Acetophenone compounds such as diethoxyacetophenone and N, N-dimethylaminoacetophenone; acetophenone compounds such as 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, Quinone, and 2-aminoanthraquinone; anthraquinone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc. (O-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4 , And 5-di (m-methoxyphenyl) imidazole dimer. Acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9'-acridinyl) heptane, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and a phosphine oxide compound such as 1,2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)], Oxane compounds such as 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O- acetyloxime), etc .; anthracene compounds such as dibutoxyanthracene These may be used singly or in combination of two or more kinds. Among them, it is preferable to contain a thioxanthone compound or an anthracene compound.
The content of the component (B) in the photosensitive resin composition is preferably 0.5 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and more preferably 0.5 to 15 parts by mass, based on 100 parts by mass of the total amount of the component (A) Particularly desirable. When the content is more than 0.5 part by mass, the photosensitivity tends to be improved, and when it is less than 30 parts by mass, the heat resistance of the cured film tends to be improved.
The nitrosyl compound as the component (C) is a compound having a nitrile group represented by the following structural formula.
The component (C) includes a compound represented by the following general formula (1).
Wherein R 1 represents a hydroxy group, an alkyl group having 1 to 5 carbon atoms, an acetamide group, an amino group, a chloroacetamide group, a cyano group, a benzoyloxy group or a group represented by the following general formula (2)
[In the formula (2), n1 represents an integer of 1 to 12]
In the compound of the formula (1), as the R 1 , a hydroxy group, an acetamide group or a benzoyloxy group is preferable.
Examples of the compound represented by the formula (1) include 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 4-hydroxy- Tetramethylpiperidine-1-oxylbenzoate free radical, 4-acetamide-2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 4-amino-2,2,6 , 6-tetramethylpiperidine-1-oxyl free radical, 4- (2-chloroacetamide) -2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 4- 2,2,6,6-tetramethylpiperidine-1-oxyl free radical and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical.
As other component (C), for example, 2,2,6,6-tetramethylpiperidine-1-oxyl free radical can be mentioned. These compounds can be used in combination with the compound represented by the general formula (1), but since they are highly volatile, it is difficult to use them alone.
In the photosensitive resin composition, the content of the component (C) is preferably 0.005 to 10 parts by mass, more preferably 0.01 to 8 parts by mass, and more preferably 0.01 to 5 parts by mass based on 100 parts by mass of the total amount of the component (A) It is more desirable to be negative. When the content is 0.005 parts by mass or more, the effect can be more surely obtained, and when it is 10 parts by mass or less, the sensitivity tends to be improved.
The photosensitive resin composition preferably contains (D) an epoxy resin (hereinafter, sometimes referred to as " component (D) ") from the viewpoint of further improving the solvent resistance. Examples of the epoxy resin (D) include bisphenol F epoxy resins such as bisphenol A diglycidyl ether and bisphenol F diglycidyl ether; and bisphenol S diglycidyl ether. Bisphenol A type epoxy resins such as biphenyl type epoxy resins such as biphenyl type epoxy resin, biphenyl type epoxy resin, biphenyl type epoxy resin, biphenyl type epoxy resin and biphenyl type diglycidyl ether, Dibasic acid-modified diglycidyl ether type epoxy resin, biphenyl aralkyl type epoxy resin, and tris (2,3-epoxypropyl) isocyanurate. These may be used alone or in combination of two or more. The component (D) is different from the component (A).
As these compounds, commercially available compounds can be used. Examples of the bisphenol A diglycidyl ether include Epikote 828, Epikote 1001 and Epikote 1002 (both of which are manufactured by Japan Epoxy Resins Co., Ltd.). Examples of the bisphenol F diglycidyl ether include Epikote 807 (manufactured by Japan Epoxy Resin Co., Ltd.) and YSLV-80 (manufactured by Shinnitsu Tetsu Chemical Co., Ltd.). As the bisphenol S diglycidyl ether, EBPS- Kusaya Co., Ltd.) and Epicor EXA-1514 (manufactured by Dainippon Ink and Chemicals, Inc.).
Examples of the nonphenol diglycidyl ether include YL6121 (manufactured by Japan Epoxy Resins Co., Ltd.), and examples of nonylated glycidyl ether include YX4000H (manufactured by Japan Epoxy Resins Co., Ltd.). Examples of the hydrogenated bisphenol A glycidyl ether include ST-2004 and ST-2007 (both manufactured by Totogase Corporation).
As the phenol biphenyl aralkyl type epoxy resin, NC-3000H (manufactured by Nippon Kayaku) can be mentioned. These may be used alone or in combination of two or more.
Above all, it is preferable that bisphenol F type epoxy resin, phenol biphenyl aralkyl type epoxy resin or bisphenol novolak type epoxy resin is contained in terms of crack resistance. Examples of the bisphenol F type epoxy resin include YSLV-80 (manufactured by Shinnitetsu Chemical Co., Ltd.). Examples of the phenol biphenyl aralkyl type epoxy resin include NC-3000H (manufactured by Nippon Kayaku Co., Ltd.) and the like. As the bisphenol novolak type epoxy resin, available are EXA-7372 (bisphenol F type novolak type epoxy resin, manufactured by DIC) and 157S70 (bisphenol A type novolak type polyfunctional epoxy resin, available from Mitsubishi Chemical Corporation) Do. These may be used alone or in combination of two or more.
When the component (D) is used, the content thereof is preferably from 1 part by mass to 50 parts by mass, more preferably from 5 parts by mass to 50 parts by mass, more preferably from 10 parts by mass to 50 parts by mass, More preferably 50 parts by mass, and particularly preferably 20 parts by mass to 40 parts by mass.
It is preferable that the photosensitive resin composition further contains a diluent. As the diluent, for example, an organic solvent and / or a photopolymerizable monomer may be used. Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; Esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate; Aliphatic hydrocarbons such as octane and decane, and petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated naphtha and solvent naphtha.
Examples of the photopolymerizable monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; Mono or di (meth) acrylates of glycols such as ethylene glycol, methoxy tetraethylene glycol, and polyethylene glycol; (Meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; Aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate; Polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and trishydroxyethylisocyanurate, or an ethylene oxide or propylene oxide adduct thereof with (meth) acrylic acid and (Meth) acrylates; (Meth) acrylates of an ethylene oxide or propylene oxide adduct of phenols such as phenoxyethyl (meth) acrylate and polyethoxydi (meth) acrylate of bisphenol A; (Meth) acrylates and melamine (meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate.
These diluents may be used singly or in combination of two or more. The content of the organic solvent can be appropriately adjusted for the purpose of adjusting the viscosity of the photosensitive resin composition.
When a diluent is used, the content thereof is preferably 0.5 to 40 parts by mass, more preferably 1 to 30 parts by mass, based on 100 parts by mass of the total amount of the component (A). When the content is 0.5 parts by mass or more, the photosensitivity is improved and the exposure portion tends to be prevented from being eluted during development. When the content is 40 parts by mass or less, the heat resistance of the cured film tends to be improved.
From the viewpoint of further improving the heat resistance, the photosensitive resin composition according to the present embodiment can contain a curing agent.
As the curing agent, a compound which itself cures by heat, ultraviolet rays or the like, or a compound which reacts with a carboxyl group or a hydroxyl group in the component (A), which is a photo-curable resin component in the photosensitive resin composition, with heat or ultraviolet rays to cure. By using the curing agent, heat resistance, adhesion, chemical resistance, etc. of the finally obtained cured film can be improved.
As the curing agent, for example, an epoxy compound, a melamine compound, a urea compound, an oxazoline compound and a block type isocyanate compound can be mentioned as a thermosetting compound. Examples of the epoxy compound include a bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol A epoxy resin, a brominated bisphenol A epoxy resin, a novolak epoxy resin, a bisphenol S epoxy resin, a biphenyl epoxy resin A heterocyclic epoxy resin such as resin, triglycidyl isocyanurate and the like, and a beacilene type epoxy resin. Examples of the melamine compound include triaminotriazine, hexamethoxy melamine and hexabutoxylated melamine. Examples of the urea compound include dimethiol and the like. These curing agents may be used singly or in combination of two or more.
When a curing agent is used in the photosensitive resin composition, its content is preferably 1 to 60 parts by mass, more preferably 5 to 50 parts by mass based on 100 parts by mass of the total amount of the component (A). When the content is 1 part by mass or more, the heat resistance of the final cured coating film tends to be improved, and when it is 60 parts by mass or less, developability tends to be improved.
The photosensitive resin composition according to the present embodiment preferably contains an epoxy resin curing agent for the purpose of further improving properties of the cured film such as heat resistance, adhesiveness, and chemical resistance.
Specific examples of such an epoxy resin curing agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2 Imidazole derivatives such as phenyl-4-methyl-5-hydroxymethylimidazole; Guanamine such as acetoguanamine and benzoguanamine; Polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine and polybasic hydrazide; Organic acid salts and / or epoxy adducts thereof; Amine complexes of boron trifluoride; Triazine derived products such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine and 2,4-diamino-6-xylyl-S-triazine; But are not limited to, trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6- Tertiary amines such as methyl guanidine and m-aminophenol; Polyphenols such as polyvinyl phenol, polyvinyl phenol bromide, phenol novolac, and alkylphenol novolak; Organic phosphines such as tributylphosphine, triphenylphosphine, and tris-2-cyanoethylphosphine; Phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, and hexadecyl tributylphosphonium chloride; Quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; The above polybasic acid anhydrides; Diphenyl iodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, and 2,4,6-triphenylthiophenyl lithium hexafluorophosphate.
These epoxy resin curing agents are used singly or in combination of two or more. When an epoxy resin curing agent is used, the content thereof is preferably 1 to 60 parts by mass, and more preferably 5 to 50 parts by mass, based on 100 parts by mass of the total amount of the component (A).
The photosensitive resin composition according to the present embodiment may further contain at least one selected from the group consisting of barium sulfate, barium titanate, silica, talc, calcined kaolin, magnesium carbonate, aluminum oxide , Aluminum hydroxide, mica, and the like. These may be used singly or in combination of two or more. Among them, silica or barium sulfate is preferable from the viewpoint of improving printability and hardness of the cured film. When the inorganic filler is used, the content thereof is preferably 1 to 200 parts by mass, more preferably 5 to 150 parts by mass, and more preferably 10 to 120 parts by mass, based on 100 parts by mass of the total amount of the component (A) Is more preferable.
If necessary, known coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black and naphthalene black may be added to the photosensitive resin composition. Polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol and pyrogarol; Thickeners such as benton, montmorillonite and the like; Defoaming agents based on silicone, fluorine and vinyl resins; Silane coupling agents and the like can be used. Further, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphate compounds of phosphorus compounds, aromatic condensed phosphoric acid esters and halogenated condensed phosphoric acid esters, adhesion promoters, leveling agents, antioxidants and pigments can be used have.
The photosensitive resin composition can be obtained by homogeneously kneading or mixing the above-mentioned respective ingredients with a roll mill, a bead mill or the like.
The photosensitive resin composition is excellent in image formability, heat resistance, adhesiveness, mechanical properties, heat resistance, heat resistance, chemical resistance, heat resistance and the like in the field of electronic materials such as solder resists for printed wiring boards, interlayer insulating films for high density multilayer boards, It is useful as a permanent mask resistor having excellent chemical resistance, electric characteristics and the like.
Next, the photosensitive element using the above-described photosensitive resin composition will be described. The photosensitive element according to this embodiment comprises a support and a photosensitive layer provided on the support. The photosensitive layer is a layer made of the above-described photosensitive resin composition. The surface of the photosensitive element opposite to the support on the photosensitive layer may be coated with a protective film.
The photosensitive layer is preferably formed by dissolving the photosensitive resin composition according to the present embodiment in a solvent or a mixed solvent to prepare a solution having a solid content of about 30 to 70% by mass, and then coating the solution on a support.
The thickness of the photosensitive layer varies depending on the use, but is preferably 10 to 100 占 퐉, more preferably 20 to 60 占 퐉 in thickness after drying after removal of the solvent by heating and / or hot air jetting.
As the support provided in the photosensitive element, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be mentioned.
The thickness of the support is preferably 5 to 100 mu m, more preferably 10 to 30 mu m.
The photosensitive element composed of three layers of the photosensitive element or the support and the photosensitive layer and the protective film composed of two layers of the support and the photosensitive layer as described above may be stored as it is or may be stored as it is, It may be rolled up and stored.
A resist pattern forming method according to an embodiment of the present invention includes a lamination step of laminating a photosensitive layer made of the above-described photosensitive resin composition on a substrate, a step of irradiating the photosensitive layer with an actinic ray in an image- And a developing step of removing an area other than the exposure part.
The lamination of the photosensitive layer on the substrate (copper clad laminate or the like) can be performed by laminating the photosensitive resin composition on a substrate with a film thickness of 10 to 200 mu m by a screen printing method, a spray method, a roll coating method, a curtain coating method, And drying the coated film at 60 to 110 占 폚.
Further, the above-described photosensitive element may be used to laminate the photosensitive layer on the substrate. In this case, when the photosensitive element is provided with a protective film, the protective film is removed, and then the photosensitive layer is heated to about 70 ° C to about 130 ° C so that the substrate is exposed to a pressure of about 0.1 MPa to 1 MPa (1 kgf / cm 2 to 10 kgf / 2 ), and the like. Such a lamination step may be carried out under reduced pressure. The surface of the substrate on which the photosensitive layer is laminated is usually a metal surface, but is not particularly limited.
In this manner, the photosensitive layer laminated on the substrate is irradiated with actinic ray in the image plane to cure the exposed portion. Examples of the method of irradiating the active ray in the image plane include a method using a negative mask pattern, a direct imaging exposure method, and the like. At this time, when the photosensitive layer is laminated using the photosensitive element, a support is present on the photosensitive layer. However, when the support is transparent to the active ray, the active ray can be irradiated through the support. When the support exhibits light shielding property against the actinic ray, the support layer is removed and then the active layer is irradiated with the photosensitive layer.
As the light source of the active light beam, a conventionally known light source can be used. For example, it is effective to radiate an active ray such as a carbon arc or a mercury vapor arc, a high-pressure mercury lamp, an ultrahigh pressure mercury lamp, a gas laser such as an ultraviolet ray such as a xenon lamp or a argon laser, or a solid laser such as a YAG laser .
After formation of the exposed portion, a resist pattern is formed by removing the region other than the exposed portion (the unexposed portion of the photosensitive layer) by development. As a method of removing the unexposed portion, for example, in the case where a support is present on the photosensitive layer, the support is removed by an autofilter or the like, and a wet phenomenon by a developer such as an alkaline aqueous solution, an aqueous developer or an organic solvent, To remove the unexposed portion and to develop. As the alkaline aqueous solution used for the wet development, for example, a lean solution of 0.1 mass% to 5 mass% sodium carbonate, a lean solution of 0.1 to 5 mass% potassium carbonate, a lean solution of 0.1 mass% to 5 mass% sodium hydroxide, . The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted in accordance with developability of the photosensitive layer. The alkaline aqueous solution may be mixed with a surfactant, defoaming agent, organic solvent or the like. Examples of the developing method include a dip method, a spray method, brushing, and slapping.
Next, after the development, the exposed portion is sufficiently cured by post exposure (ultraviolet ray exposure) and / or post heating to obtain a cured film. The post exposure is preferably carried out at an exposure amount of 1 to 5 J / cm 2 . The post-heating is preferably carried out at 100 to 200 DEG C for 30 minutes to 12 hours.
In the method for manufacturing a printed wiring board according to the embodiment of the present invention, the substrate for circuit formation on which the resistor pattern is formed is etched or plated by the resist pattern forming method. Here, the resist pattern made of the photosensitive resin composition effectively functions as a permanent mask resistor having excellent phase morphology, heat resistance, adhesion, mechanical properties, chemical resistance, electrical characteristics and the like.
[Build-up substrate]
The photosensitive resin composition according to this embodiment can be suitably used for forming a permanent mask resistor of a printed wiring board for a build-up substrate. That is, according to this embodiment, it is possible to provide a build-up substrate having a permanent mask resistor made of a cured product of the above-mentioned photosensitive resin composition. Fig. 1 and Fig. 2 show an example in which a permanent mask resistor is formed on a build-up board printed wiring board.
Fig. 1 (a) is a schematic cross-sectional view showing a core substrate on which a buildup layer has been formed.
Example
Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.
[Synthesis of Resin A]
1052 parts by mass of a bisphenol F type epoxy resin (trade name: 806, manufactured by Japan Epoxy Resins Co., Ltd., epoxy equivalent: 180) as a component (a), 144 parts by mass of acrylic acid , 1 part by mass of methylhydroquinone, 850 parts by mass of carbitol acetate and 100 parts by mass of solvent naphtha were charged and the mixture was dissolved by heating at 70 占 폚. Next, the obtained solution was cooled to 50 占 폚, 2 parts by mass of triphenylphosphine and 75 parts by mass of solvent naphtha were added thereto, and the mixture was heated to 100 占 폚 and reacted until the solid acid value became 1 mgKOH / g or less. Next, the obtained solution was cooled to 50 占 폚, and 745 parts by mass of tetrahydrophthalic anhydride, 75 parts by mass of carbitol acetate and 75 parts by mass of solvent naphtha as a component (C) were added thereto and reacted at 80 占 폚 for 3 hours. Thus, an unsaturated group-containing polycarboxylic acid resin (Resin A) serving as the component (A) having a solid content of 80 mgKOH / g and a solid content of 62 mass% was obtained.
(Examples 1 to 12 and Comparative Examples 1 to 5)
Carbitol acetate was added so as to have a solid content concentration of 70% by mass, to obtain a photosensitive resin composition, after the composition was compounded according to the composition (unit: parts by mass) shown in Table 1 below. The blending amounts of the respective components in Table 1 indicate the blending amount of the solid content.
Details of each component in Table 1 are as follows.
(A) Component
EXP-2810: Cresol novolak type acid-modified epoxy acrylate (weight average molecular weight 7,000, acid value 65 mgKOH / g, manufactured by DIC)
ZAR-1753: Bisphenol A type acid-modified epoxy acrylate (weight average molecular weight 10,000, acid value 70 mgKOH / g, manufactured by Nippon Kayaku)
UXE-3024: urethane-modified bisphenol A type acid-modified epoxy acrylate (weight average molecular weight 10,000, acid value 67 mgKOH / g, manufactured by Nippon Kayaku Co., Ltd.)
Component (B)
I-907: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (Irgacure 907, manufactured by Ciba Specialty Chemicals)
I-651: 2,2-dimethoxy-1,2-diphenylethan-1-one (2,2-dimethoxy-
(IRGACURE-OXE-02, produced by BASF, Inc.), 1- [9-ethyl-6- Priests),
N-1919: oxime ester-based photopolymerization initiator (ADEKA OPTOMER N-1919, manufactured by ADEKA)
TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (LUCIRIN-TPO, manufactured by BASF),
I-819: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE-819, manufactured by BASF)
DETX: 2,4-diethylthioxanthone (KAYACURE-DETX-S, manufactured by Nippon Kayaku Co., Ltd.)
DBA: 9,10-dibutoxyanthracene (made by Kawasaki Kasei Co., Ltd., trade name).
(C) Component
4-hydroxy-TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.)
4-benzoyloxy-TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxylbenzoate free radical (manufactured by Tokyo Chemical Industry Co., Ltd.)
4-acetamide TEMPO: 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (made by Tokyo Chemical Industry Co., Ltd.).
(D) Component
NC-3000H: biphenyl aralkyl type epoxy resin (trade name, manufactured by Nippon Kayaku Co., Ltd.)
YSLV-80: Bisphenol F type epoxy resin (trade name, available from Shin-NTT Chemical Co., Ltd.).
Other ingredients
DPHA: dipentaerythritol hexaacrylate (Kayalad DPHA, manufactured by Nippon Kayaku),
C11-A: imidazole compound (manufactured by Shikoku Chemicals Co., Ltd.),
ESLV-120TE: 1,3,5-triglycidyl isocyanate (manufactured by Shinnitetsu Chemical Co., Ltd.)
TBC: 4-t-butyl catechol (manufactured by DIC),
Phthalocyanine green (manufactured by Sanyo Chemical Industries, Ltd.),
? -glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.),
Barium sulfate: B-30 (manufactured by Sakai Chemical Industry Co., Ltd.)
Silica: SC-2050 (manufactured by Admatex),
Melamine: (manufactured by Nissan Chemical Industries, Ltd.),
PB3600: epoxidized polybutadiene (manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.),
Pigment: phthalocyanine blue (available from Toyo Ink Co.).
(Preparation of evaluation substrate A)
The photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were coated on a copper clad laminate (copper clad laminate) with a thickness of 20 탆 by a spin coater and dried at 75 占 폚 Lt; / RTI > A polyethylene terephthalate film having a thickness of 16 mu m was laminated on the coated surface at 80 DEG C to obtain an evaluation substrate. Using the obtained test plate, evaluation of each characteristic was carried out by the following method. The results are summarized in Table 2.
(Preparation B of Evaluated Substrate)
The photosensitive resin compositions of Examples 4 to 12 and Comparative Examples 3 to 5 were uniformly coated on a polyethylene terephthalate film (G2-16, trade name, available from Dainippon Ink and Chemicals, Inc.) having a thickness of 16 mu m as a support to form a photosensitive layer, And dried at 100 DEG C for about 10 minutes using a hot air convection dryer. The thickness of the photosensitive layer after drying was 25 占 퐉.
Subsequently, a polyethylene film (NF-15, trade name, manufactured by TAMARO POLYESTER CO., LTD.) Was adhered as a protective film on the surface opposite to the side of the photosensitive layer in contact with the support to obtain a photosensitive element. Next, the copper surface of a substrate for a printed wiring board (E-679, Hitachi Chemical Co., Ltd.) having a copper foil with a thickness of 12 탆 laminated on a glass epoxy substrate was polished with an abrasive grain brush, washed with water and dried . Using a press type vacuum laminator (MVLP-500, manufactured by Meiji Seisakusho Co., Ltd.), a hot plate temperature of 70 ° C, a vacuum suction time of 20 seconds, a laminate press time of 30 seconds, a pressure of 4 kPa Hereinafter, the protective film of the photosensitive element was peeled off and laminated under the condition of a compression pressure of 0.4 MPa to obtain an evaluation substrate. Using the obtained test plate, evaluation of each characteristic was carried out by the following method. The results are summarized in Table 2.
(Developability)
An exposure dose of 200 mJ / cm 2 was irradiated using a parallel light exposure apparatus (trade name: EXM-1201, manufactured by Oak Seic Co.) with a mask having a via mask opening size of 100 m in the photosensitive layer of the evaluation substrate, Spraying was performed with an aqueous sodium carbonate solution at a pressure of 0.176 MPa (1.8 kgf / cm 2 ) for 60 seconds. Thereafter, the evaluation substrate was visually observed to confirm the presence or absence of a residue, and evaluation was carried out according to the following criteria.
A: No development residue.
B: Phenomenon residue.
(Resolution)
A phototool having a wiring pattern with a line width / space width of 6/6 to 47/47 (units: 占 퐉) was used as a negative resolution evaluation layer in the photosensitive layer of the evaluation substrate, and a parallel light exposure machine (trade name: EXM-1201 , Manufactured by Oak Seisakusho Co., Ltd.), and the total exposure dose was 200 mJ / cm 2 . Here, the smallest value (unit: 占 퐉) of the line width / space width formed without removing the unexposed portion by the developing process after exposure and without causing the line to meander or deficiency is referred to as resolution did. Evaluation of resolution is better as the numerical value is smaller.
(Exposure dose induction)
A pattern with a via width / space width = 50/50 (unit: 占 퐉) was formed on the photosensitive layer of the evaluation substrate by using a parallel light exposure machine (trade name: EXM-1201, manufactured by Oak Seisyu Corporation) at an integrated exposure dose of 200 mJ / cm 2 to 600 mJ / cm < 2 >. Thereafter, spraying was performed with a 1% aqueous solution of sodium carbonate for 60 seconds at a pressure of 0.176 MPa (1.8 kgf / cm 2 ). The amount of exposure until the vias of 50 mu m completely buried was observed and evaluated according to the following criteria.
A: 50 占 퐉 vias are not buried between 200 and 600 mJ / cm 2 .
B: Vias of 50 탆 are not buried between 200 and 400 mJ / cm 2 , but buried when exceeding 400 mJ / cm 2 .
C: When the vias of 50 탆 exceed 300 mJ / cm 2 , they are buried.
(Via shape reproducibility (1) Center-to-end of the same pattern)
A pattern of via width / space width = 100/100 (unit: 占 퐉) was irradiated to the photosensitive layer of the evaluation substrate at a total exposure dose of 200 mJ / cm 2 using a direct exposure apparatus LI-9700 (manufactured by Dainippon Screen) . Thereafter, spraying was performed with a 1% aqueous solution of sodium carbonate for 60 seconds at a pressure of 0.176 MPa (1.8 kgf / cm 2 ). Via shapes at the center and the end in the same substrate were compared.
A: A good via shape is formed at both the center and the end.
B: Via shape at center or end is not good.
(Via shape reproducibility (2) Space width 100 vs. 10 (unit: 占 퐉))
The layer of the evaluation substrate, using the exposure system jikmyo LI-9700 (Dai Nippon Screen Corporation), and the via width 100㎛, investigated the pattern space width of 100㎛ or 10㎛, as integrated exposure dose 200mJ / cm 2 . Thereafter, spraying was performed with a 1% aqueous solution of sodium carbonate for 60 seconds at a pressure of 0.176 MPa (1.8 kgf / cm 2 ). A via width of 100 mu m, a space width of 100 mu m and a width of 10 mu m and a via width of 100 mu m.
A: Both of the space widths of 100 탆 and 10 탆 have a good via shape.
B: Via shape with a space width of 100 占 퐉 or 10 占 퐉 is not good.
(Solvent resistance)
After the test plate was immersed in isopropyl alcohol at room temperature for 30 minutes, it was visually confirmed whether there was any abnormality in the appearance of the cured film. Thereafter, a peeling test was performed in which the cellophane tape was attached to the cured film and pulled up, and it was confirmed whether the cured film peeled off from the copper clad laminate. From the results, evaluation of solvent resistance was carried out according to the following criteria.
A: No abnormality in appearance of the cured film, and no peeling in the peeling test.
B: The appearance of the cured film is abnormal or peeled off in the peeling test.
(Solder heat resistance)
The rosin-based flux was applied to the surface of the cured film of the test plate, and then immersed in a solder bath of 260 ° C for 10 seconds. After repeating this cycle for one cycle for 6 cycles, the outer appearance of the cured film was visually observed, and the heat resistance was evaluated according to the following criteria.
A: No abnormality (peeling, swelling) in appearance of the cured film, and no dipping of solder.
B: The appearance of the cured film is abnormal (peeling, swelling), or there is diving of solder.
(Adhesion)
The test plate was subjected to a peel test according to the method according to JIS K5400. That is, 100 substrate eyes of 1 mm were formed on the cured film of the test plate, a cellophane tape was attached to the substrate eye, and then the substrate was pulled off. The peeling state of the substrate eye after pulling off was observed, and the adhesion was evaluated according to the following criteria.
A: More than 90/100 of the board eyes do not peel off.
B: Less than 50/100 and less than 90/100 of the substrate eyes.
C: Less than 50/100 of the substrate eyes do not peel off.
One … A core substrate on which a buildup layer is formed, 2 ... Copper wiring, 3 ... Photosensitive layer, 4 ... Mask for exposure, 5 ... Permanent mask register, 6 ... Electroless Ni-plated layer, 7 ... Electrolytic gold plating layer.
Claims (6)
(B) a photopolymerization initiator,
(C) a nitrosyl compound, wherein the (C) nitrosyl compound comprises a compound represented by the following general formula (1).
Wherein R 1 represents a hydroxy group, an alkyl group having 1 to 5 carbon atoms, an acetamide group, an amino group, a chloroacetamide group, a cyano group, a benzoyloxy group or a group represented by the following general formula (2)
[In the formula (2), n1 represents an integer of 1 to 12]
Wherein the content of the acid-modified vinyl group-containing epoxy resin (A) is 25% by mass or more based on the whole solid content of the photosensitive resin composition.
(A) an acid-modified vinyl group-containing epoxy resin,
(3), a bisphenol-type epoxy resin represented by the following general formula (4), and a salicylaldehyde-type epoxy resin represented by the following general formula (5) (A) at least one selected from among epoxy resins,
The vinyl group-containing monocarboxylic acid (b)
Wherein the photosensitive resin composition is a resin obtained by reacting a photosensitive resin composition with a photosensitive resin composition.
(3), R 6 represents a hydrogen atom or a methyl group, Y 1 represents a hydrogen atom or a glycidyl group (provided that the hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70) , and n 2 represents an integer of 1 or more. And R < 6 > and Y < 1 > which may be present in plural may be the same or different.
(4), R 7 represents a hydrogen atom or a methyl group, Y 2 represents a hydrogen atom or a glycidyl group (provided that the hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70) , and n 3 represents an integer of 1 or more. In addition, plural R < 7 > And Y < 2 > may be the same or different.]
[Wherein Y 3 represents a hydrogen atom or a glycidyl group (provided that the hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), and n 4 represents an integer of 1 or more. The plural Y 3 s may be the same or different.]
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012174063 | 2012-08-06 | ||
| JPJP-P-2012-174063 | 2012-08-06 | ||
| PCT/JP2013/071060 WO2014024804A1 (en) | 2012-08-06 | 2013-08-02 | Photosensitive resin composition for permanent mask resist, photosensitive element, method for forming resist pattern, and method for producing printed wiring board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20150042775A true KR20150042775A (en) | 2015-04-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR20157001461A KR20150042775A (en) | 2012-08-06 | 2013-08-02 | Photosensitive resin composition for permanent mask resist, photosensitive element, method for forming resist pattern, and method for producing printed wiring board |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPWO2014024804A1 (en) |
| KR (1) | KR20150042775A (en) |
| CN (1) | CN104520768A (en) |
| TW (1) | TWI589993B (en) |
| WO (1) | WO2014024804A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210038555A (en) * | 2018-08-01 | 2021-04-07 | 가부시키가이샤 아리사와 세이사쿠쇼 | Resin composition for resist and its use |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6785551B2 (en) * | 2015-04-03 | 2020-11-18 | 三菱製紙株式会社 | Etching method |
| JP2017003966A (en) * | 2015-06-12 | 2017-01-05 | Jsr株式会社 | Photosensitive composition and method for manufacturing plated molded article |
| JP6846102B2 (en) * | 2015-07-14 | 2021-03-24 | ローム・アンド・ハース電子材料株式会社 | Photosensitive resin composition |
| JP7007792B2 (en) * | 2015-09-30 | 2022-01-25 | 太陽インキ製造株式会社 | Curable resin composition, dry film, cured product and printed wiring board |
| JP7018168B2 (en) * | 2015-12-22 | 2022-02-10 | 昭和電工マテリアルズ株式会社 | A photosensitive resin composition, a dry film using the photosensitive resin composition, a printed wiring board, and a method for manufacturing the printed wiring board. |
| JP2018174250A (en) * | 2017-03-31 | 2018-11-08 | 住友ベークライト株式会社 | Thermosetting resin composition, resin film with carrier, prepreg, printed wiring board and semiconductor device |
| JP7228121B2 (en) * | 2018-04-25 | 2023-02-24 | エア・ウォーター・パフォーマンスケミカル株式会社 | Photopolymerization sensitizer composition |
| JP2020076945A (en) * | 2018-09-21 | 2020-05-21 | 旭化成株式会社 | Photosensitive resin composition |
| CN109541889B (en) | 2018-12-19 | 2020-06-26 | 江苏艾森半导体材料股份有限公司 | Negative photoresist for semiconductor packaging process |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5912106A (en) * | 1996-09-10 | 1999-06-15 | Ciba Specialty Chemicals Corporation | Method for improving photoimage quality |
| JP3247091B2 (en) * | 1997-11-28 | 2002-01-15 | 日立化成工業株式会社 | Photocurable resin composition and photosensitive element using the same |
| US6583198B2 (en) * | 1997-11-28 | 2003-06-24 | Hitachi Chemical Company, Ltd. | Photo curable resin composition and photosensitive element |
| JP3879316B2 (en) * | 1999-05-10 | 2007-02-14 | ダイヤニトリックス株式会社 | Active energy ray-curable resin composition |
| JP2002338639A (en) * | 2001-05-17 | 2002-11-27 | Nippon Shokubai Co Ltd | Free-radically curable resin composition and curing method |
| EP1783548B1 (en) * | 2005-11-08 | 2017-03-08 | Rohm and Haas Electronic Materials LLC | Method of forming a patterned layer on a substrate |
| CN101833241B (en) * | 2009-03-09 | 2012-07-04 | 村上精密制版（昆山）有限公司 | Photosensitive resin composition |
| JP2013057755A (en) * | 2011-09-07 | 2013-03-28 | Fujifilm Corp | Photosensitive resin composition, photosensitive film, photosensitive laminate, method for forming permanent pattern, and printed board |
-
2013
- 2013-08-02 KR KR20157001461A patent/KR20150042775A/en not_active Application Discontinuation
- 2013-08-02 CN CN201380041388.3A patent/CN104520768A/en active Pending
- 2013-08-02 WO PCT/JP2013/071060 patent/WO2014024804A1/en active Application Filing
- 2013-08-02 JP JP2014529476A patent/JPWO2014024804A1/en active Pending
- 2013-08-05 TW TW102127969A patent/TWI589993B/en active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210038555A (en) * | 2018-08-01 | 2021-04-07 | 가부시키가이샤 아리사와 세이사쿠쇼 | Resin composition for resist and its use |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104520768A (en) | 2015-04-15 |
| WO2014024804A1 (en) | 2014-02-13 |
| TW201418882A (en) | 2014-05-16 |
| TWI589993B (en) | 2017-07-01 |
| JPWO2014024804A1 (en) | 2016-07-25 |
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