TW200809415A - Photosensitive resin laminate - Google Patents

Abstract

This invention provides a photosensitive resin laminate that develops a high level of resolution and a high level of adhesion, can realize a steady side wall in a resist pattern, is free from concaves on the surface of the resist pattern, and is very small in skirt part after development. The photosensitive resin laminate has an additional advantage that there is no problem of the separation of a support film. The photosensitive resin laminate comprises a support film, and an intermediate layer having a thickness of not less than 0.1 μm and not more than 10 &mgrlm and a photosensitive resin layer provided in that order on the support film. The intermediate layer is characterized by comprising polyvinyl alcohol and a specific compound.

Description

200809415 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a photosensitive resin laminate and a use thereof. More specifically, the present invention relates to a printed wiring board having a conductor pattern, a flexible substrate, a lead frame substrate, a C〇F (Chip 〇n Fum) substrate, and a semiconductor package. Manufacture of a substrate, a transparent electrode for liquid crystal as a conductor pattern, a TFT for driving a liquid crystal (Thin Film Transistor), and a PDP (Plasma DispUy)

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The photosensitive resin laminate of the substrate for the electrode, the method for forming the photoresist pattern, and the method for producing the conductor pattern. [Prior Art] In an electronic device such as a personal computer or a mobile phone, for example, a printed wiring board can be used as a component or a semiconductor mounting substrate. As a photoresist for producing a printed wiring board, a photosensitive resin layer which is formed by laminating a photosensitive resin layer on a support film and a protective layer on the photosensitive resin layer as needed, so-called dry film photoresist . As the photosensitive resin layer used herein, an inspective development type using a weak test raw water/gluten solution as a developing solution is generally used. A general method of manufacturing a printed wiring board using dry film photoresist is briefly described. First, when there is a protective layer, the protective layer is peeled off. Thereafter, a photosensitive resin layer which is formed on the substrate for permanent circuit fabrication by a bonding machine, for example, a copper foil laminate or a flexible plate, is used as a body. The second time is through the wiring pattern 1 " The exposure method is based on the application. There is also no need to expose the mask without a mask, for example, by means of laser 120566.doc 200809415. Then, when the support film remains, it is peeled off by the developer to dissolve the unexposed portion of the photosensitive resin or removed, and a cured photoresist pattern is formed on the substrate (hereinafter referred to as 'abbreviation For the photoresist pattern). After the shape of the photoresist pattern, the process of forming the circuit can be roughly divided into two methods: the second method is the removal of the copper of the substrate without the photoresist pattern, and only the ruthless shirt/night is stronger. Method for removing the resist pattern portion by aqueous solution). The second method is a method of using a copper solder or a nickel plating treatment to remove the photoresist pattern portion and further etching the exposed copper surface of the substrate (coating method). For etching, a solution of copper chloride, iron sulphide, and copper ammonia complex can be used. In recent years, in order to meet the demand for miniaturization of the conductor pattern of the printed wiring board, the company has sought to obtain the light ρ and the high resolution and adhesion of the pattern (Patent Document). The crosslink density of the material is only present. However, if the crosslink density is increased, the following problems occur. The photoresist pattern after exposure will become hard and brittle, and the self-developing step to the etching or coating step will be '%. One of the resistance patterns is partially defective. Further, in particular, in the case where the photosensitive tree = layer has a thickness of 1 G (four or less), the film is exposed to the surface of the substrate by exposure to light, and the photosensitive resin layer which is not exposed to light is also exposed to light. Since the photosensitive portion affects the photoresist pattern, it will cause a new road. Moreover, when exposed, the light is reflected on the surface of the substrate, so that the bottom surface of the photoresist pattern t produces a development residue called halation. If the halo is produced, there is a problem that the curling on the copper circuit occurs in the step of the money according to the size thereof. 120566.doc 200809415 As a support film for dry film photoresist, a polyester film is generally used. The polyester film contains: a trace amount of I, such as a moisturizing. #The trace component will be generated when one of the tiny parts is exposed to light. As a result, warping or depression occurs on the side wall (side wall) of the resist pattern or the surface (surface) of the substrate of the photoresist pattern. In particular, when forming a fine wiring having a conductor pattern width of 1 〇 ^ ❿ or less, the influence cannot be ignored. /乍 In order to achieve other methods of high resolution, a method of providing an intermediate layer containing polyvinyl alcohol between a support film and a photosensitive resin layer is known. The support film may be peeled off before the exposure step, and exposure is performed from the intermediate layer, thereby eliminating the high resolution and the trace amount of the resist pattern pattern generated by the trace components contained in the support film. When the vinyl alcohol is formed into an intermediate layer, it is produced in the peeling property with the support film or the solubility in the test developer. The technique disclosed in Patent Document 2 discloses the provision of an intermediate layer containing polyvinyl alcohol and ethyl cellulose. . However, this technique is extremely difficult to control the peeling property between the support film and the intermediate layer, and the composition of the intermediate layer must be studied. Patent Document 3 discloses a technique in which a polyethylene resin is used in an intermediate layer, and a photosensitive resin layer contains a vinegar in which a (meth)acrylic acid is partially vinegared. Document 4 discloses that the intermediate layer will be a polyethylene glycol obtained by copolymerizing an olefin in a specific amount, a polyepoxylate having a polymerization degree of 4 or more, an acrylic acid containing a plurality of groups, and a dibasic acid. The technique of selecting the main components of the two materials from the group consisting of the copolymer of the diluted hydrocarbons, but these methods also fail to solve the problem of high resolution and (4), characterization, and halo of the photoresist pattern after development. 120566.doc 200809415 In the case of producing a printed wiring board having a fine conductor pattern, when a substrate for a (3) F which is required to have high resolution is produced by a film, the semiconductor sealing substrate can be formed to exhibit high resolution, and after development, The photosensitive resin composition and the photosensitive resin laminated body which are not swelled on the surface of the photoresist pattern shape, and which have a surface which does not have a recess, and which have a very small halo after development. [Patent Document 1] Japanese Patent Laid-Open No. 2 〇〇1·159817 Document 2] Japanese Patent Laid-Open Publication No. 63497942 [Patent Document 3] Japanese Patent Laid-Open No. 371,957 Publication Heart

[Patent Document 4] Japanese Patent Laid-Open No. Hei 6-24261 No. 1 [Invention] [The problem to be solved by the invention] The purpose of the present invention is to provide a photosensitive resin laminate which is high in resolution and high in density. Correction:, ^ The steep side of the photoresist pattern has no surface on the side of the photoresist pattern, the surface of the pattern is sag, 曰fe and the characteristics of the military light after development are small, i hold the film peeling aspect i ask 颞 /, sound body SUMMARY OF THE INVENTION The present invention provides a method of forming the prior art and a method of manufacturing a conductor pattern. [Means for Solving the Problem] The inventors of the present invention studied the solution of μ, +, and % by using the ρ π row, and found that the laminate layer supports the peeling property of the photosensitive resin and the fork of the film. No problem, after development, it shows the ancient. The side wall of the first resistance pattern has no bell, the heart and the picture macro make the surface have no depression, and the development of the halo pattern is extremely small, thus completing the present invention. That is, the present invention is a photosensitive resin laminate, a method, and a method for producing a conductor pattern as follows. Pattern forming 120566.doc 200809415 (1) A photosensitive resin laminate comprising a support film, an intermediate layer having a thickness of 〇·1 μηι or more and 1 〇 or less on the support film, and photosensitivity In the case of a resin layer, the intermediate layer contains at least one or more selected from the group consisting of polyvinyl alcohol and a group consisting of compounds represented by the following formula (I).

Ri-0-(CH2CH20)ni-R2 (I) (Heart and R2 are Η or CH3, and these may be the same or different, and ~ is an integer of 3 to 25.) (2) Photosensitive resin as (1) The laminate is formed by laminating a protective layer on the photosensitive resin layer. (3) The photosensitive resin laminate according to (1) or (2), wherein the photosensitive resin layer contains a photosensitive resin composition, and the photosensitive resin composition S has (a) a thiol-containing acid When the juice is 1〇〇~6〇〇, and the weight average molecular weight is 5000~50000, the binder resin is 20~9〇% by mass; (b) at least one photopolymerizable unsaturated compound: 3~70 (%) Photopolymerization initiator: 0.1 to 20% by mass. (4) The photosensitive resin laminate according to (3), wherein the (a) binder resin contains benzyl (meth)acrylate as a copolymerization component. (5) The photosensitive resin laminate according to (3) or (4), wherein the at least one photopolymerizable unsaturated compound (b) is a compound represented by the following formula (11) to (νυ) At least one selected from the group consisting of photopolymerizable unsaturated compounds. 120566.doc 200809415 [Chemical] CH, H2C = 〇-〇〇-(〇2Η4〇)η2^(ΟΗ2〇ΗΟ)η3 OCH2 (H) (wherein R4 and R5 are H or CH3, and the same may be the same or different, and h is independently an integer of 3 to 20.) [Chem. 2] 0 Re Ο*- (A-0) ri6- (B -0) ns^CC—CHe

H3C—C-CH3 (UI) 0 〇, (A-0) Π7—(B-0) n9-C — C=CH2 0

KJ (where R6 is H or CH3, these may or may not be I, J2, C2H4, B is CH2CH(CH3), n6 is an integer of 2~4〇, 整数40 integer, ~ and n7 respectively Independently from 1 to 39 integers, ~ and 9 are independent integers of 〇~4〇; _(Α_〇)· and _(B-〇)• Repeating units < 9 are random or block In the case of a block, in the order of -(A, arrangement 〇)-, any one can be on the diphenyl side.) and -(B-A is 120566.doc -10- 0200809415 [ 3] 0- (D -0) mi—(E.«〇) m3_g-c=CH2

H3C—C—CH3 (IV) (Ε-_—ΓCH2 o R9 (wherein Rs and R9 are H or CH3, these may be the same or different, d is C2H4, E is CH2CH(CH3), 1x ^ + 1112 is an integer from 2 to 40, m3+m4 is an integer from 0 to 40, and 叱 and 叱 are each an integer of 丨~39, and are called integers of 0~4〇, respectively; -(D-〇 ) and - (E-〇) - the arrangement of repeating units may be random 'may also be a block; in the case of a block, in the order of ♦0)- and _(E_0)_, any Can be on the cyclohexyl side.) [Chemical 4] ^11 CH' NHCO-(OCHCH2)m5.〇CO-C=:CH2?10 NHCO-(OCHCH2)m6OCO^C^CH2 CH, (V)

R 12 (wherein, Ri 〇 is a carbon number of 4 to 12 2 CH 3 , which may or may not be n and R 12 is H or σ, ... and are respectively independent of 1 to 15 of 120566.doc -11 - ( VI) 200809415 number.) [Chemical 5]

R 13 H2C=Ct〇-(A,-〇)m factory (Β,, 0)ηΐ8 0

(R14)m9

(wherein R13 is H or CH3, R14 is a burnt group having a carbon number of 4 to 14, and A is (4) is a yang, and the integer of the heart is called an integer of (4) '019 is an integer of 0 to 3; -(A,·0)· and _(Β·-〇)-The arrangement of the repeating units may be random or block; in the case of a block, the handle)· and _(Β,-0) - In terms of order, either can be on the stupid side). (6) A method for forming a resist pattern, which is characterized in that: the sequential package = laminated photosensitive resin laminate according to any one of items (1) to (5) on a metal plate or a metal coating The laminating step of the surface of the insulating sheet, the exposure step of peeling off the support film and then exposing, and the developing step of removing the unexposed portion by development. (7) A method of producing a conductor pattern, characterized in that the substrate on which the photoresist pattern is formed is etched or plated by the method of (6). [Effects of the Invention] According to the present invention, it is possible to provide a problem that the peeling property of the support film is no problem, and after development, it exhibits high resolution and high adhesion, the sidewall of the resist pattern is not warped, and the surface of the resist pattern has no depression. A photosensitive resin laminate having a very small halo after development, a method of forming a photoresist pattern using the laminate, and a method for producing a conductor pattern of 120566.doc 12 200809415. [Embodiment] Hereinafter, the present invention will be specifically described. In the photosensitive resin layering system of the present invention, a photosensitive resin laminate having a thickness of 0.1 μm or more and 10 μm or less and a photosensitive resin layer is sequentially laminated on the support film. The photosensitive tree layer laminate of the present invention is characterized in that the 35 intermediate layer contains at least one or more selected from the group consisting of polyvinyl alcohol and a compound represented by the following formula (1). Ri-〇-(CH2CH20)ni.R2 (1) (8) and R4H or CH3, these may be the same or different, and the integers of n...~25. The ratio of the addition weight of the polyvinyl alcohol to the intermediate layer and the lining ratio is preferably 5 〇 mass 里 / 〇 or more and 95 皙 % or less from the viewpoint of developability and cost. More preferably, it is 70% by mass or more, more preferably, J疋〇Bei% or more, and 90% by mass or less. v, / As the weight ratio of the compound of the formula (1) to the intermediate layer, from the viewpoint of supporting the peeling property of the film and the intermediate layer, 'thousands are 5 皙 〇 / 上, 50% by mass or less More preferably, it is 5 masses, denier/0 Μ, 3 〇 mass% or less, more preferably 5% by mass or more, and 丨5 mass y. the following. t Ethyl alcohol is usually produced by assaying poly(vinyl acetate). The average weight of polyvinyl alcohol used in Taiming

The number of knives is better from B 1,000 to 100,000. In terms of oxygen shielding and developability, the weight average molecular weight of the competition is 5, 〇〇〇 to 50,000. Also, Zhong Du ° ^ '9 颂 颂 而 120 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 566 More than Mole. In the present invention, the weight average molecular weight of the polyvinyl alcohol used in the photosensitive resin laminate is a GPC (gel permeation chromatography) (^: Gulliver) manufactured by 曰本分光(股) ^ PU- 1580 type 'column: Shodex (registered trademark) (hfIP-805, Cong p_8〇3) manufactured by Showa Denko (share) 2 in series, flowing layer solvent · hexa-isopropanol, using polystyrene The analytical curve of the standard sample was obtained as the weight; the molecular weight Ϊ (converted in terms of polystyrene). From the viewpoint of the odor, the compound represented by the above formula (1) is preferably at least 3 or more in terms of compatibility with the polyethyl propylene glycol and developability, and is preferably 25 or less. Ηι is more preferably 5 or more, 2 () or less, and more preferably 〇 or less. As a compound of the above formula (I), a polyethylene glycol having an average molecular weight of 200 (Japanese fats and oils limited: PEG manufactured by the company) and a polyethylene glycol having an average molecular weight of 3 (10) (Japan) PEG3〇〇 manufactured by Oils and Fats Co., Ltd.), polyethylene glycol with an average molecular weight of 4〇〇 (pEG4〇〇 manufactured by Nippon Oil & Fat Co., Ltd.), and polyethylene glycol with an average molecular weight of 600 (Japan Oil & Fats Co., Ltd.) PEG600), polyethylene glycol with an average molecular weight of 1〇〇〇 (PEG1000 manufactured by Nippon Oil & Fat Co., Ltd.), or polyethylene glycol monomethyl ether with an average molecular weight of 4〇〇 (Japan Oil & Fats Co., Ltd.) Manufactured υηί〇χ M_4〇〇), flat ^ ethanediol monomethyl hydrazine with a molecular weight of 550 (Uniox M-550 manufactured by Nippon Oil & Fat Co., Ltd.) 'Polyethylene glycol single with an average molecular weight of 1 〇〇〇 Methyl ether (Uni〇x M_1〇〇 manufactured by Sakamoto Oil Co., Ltd. (〇. 120566.doc -14· 200809415 Further, in the intermediate layer, in addition to the above, a well-known water-soluble polymer may be added. Gather Specific examples of the material include polyvinyl ether _ Malay & C anhydride water, glutamate salt, carboxyalkyl starch water-soluble salt, polypropylene decylamine, polyamine, polyacrylic acid water-soluble salt, gelatin, Polypropylene glycol and polyvinylpyrrolidine are the same. As a specific example of polyvinylpyrrolidone, the weight average molecular weight manufactured by Nippon Shokubai Co., Ltd. is (10)...(10), the weight average molecular weight is 100,000 K-30, and the weight average The molecular weight is 900,000 K-85, and the weight average molecular weight is 1 【 [9〇.

The layer thickness of the intermediate layer is preferably 10 μηι or less, more preferably 5 μηι or less, and still more preferably 3 Å or less in terms of resolution, adhesion, and developability. Further, from the viewpoint of oxygen shielding properties, it is 0·1 μm or more, preferably 〇·5 μηι or more, more preferably 丨μηη or more. In the present invention, in order to achieve high resolution, it is preferred to peel off the support enthalpy before exposure. In the case of peeling _ support film before exposure, the support film can be a transparent film for transmitting light for exposure, or it can be opaque. As a support film in the present invention, there is a thickness of 1 〇μηι or more and 1 〇〇 or less, which is represented by polyethylene scorpion, poly(tetra), polycarbon _, and polyethylene terephthalate. . It is generally preferred to use a polyethylene terephthalate having moderate flexibility and strength. It is difficult to cause wrinkles during lamination, and in order to prevent breakage of the support film, the film thickness is preferably 1 μm or more. The photosensitive resin laminate of the present invention is excellent in the releasability of the intermediate layer by the above-mentioned structure supporting film. That is, it is a photosensitive resin laminate in which the adhesion between the support film and the intermediate layer is lower than the adhesion between the intermediate layer and the photosensitive twin layer when the support is removed before the exposure step. 120566.doc -15- 200809415 Into, as the photosensitive Φ pe of the present invention „ ^ laminated body, which can be laminated on the support film in addition to the sequential layer _ interlayer and photosensitive layer. As a property of the protective layer, the interlayer adhesion between the photosensitive resin layer and the protective layer of the important n ^ s^ ^ 罟 is lower than that between the interlayer of the support film, and the interlayer adhesion between the Y layers. The protective layer can be easily peeled off at the time of lamination. As a protective layer, there is a thick; # A , Λ and _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Among them, it is better to use 哿, prepared

KJ uses a vinyl ruthenium or polypropylene film. The upper limit of the degree of itching and the twist of the photosensitive resin layer of the present invention is preferably 100 μη or less, more preferably 5 ο or less, and more preferably 疋3〇μηι or less. It is 10 μηι or less. The lower limit of the thickness of the film is preferably 5 μm or more, more preferably 1 μm or more. The photosensitive resin layer in the photosensitive resin laminate of the present invention preferably contains photosensitivity. A layer of a resin composition containing (a) a resin having a carboxyl group content of from 1 to 6 Å in terms of acid equivalent, and a weight average molecular weight of from 5,000 to 500,000: 2 〇 to 9 〇% by mass, (b) at least one kind of unsaturated compound which can be added to light 1 : 3 to 7 % by mass, (c) photopolymerization initiator · 0·1 to 20% by mass. Hereinafter, the present invention will be described in detail. The photosensitive resin composition used for the photosensitive resin laminate. (a) The amount of the Wei group contained in the binder resin is preferably from 100 to 600, more preferably from 250 to 450, in terms of acid equivalent. More preferably, it is 300 to 45 Å. The acid equivalent is a mass of a resin for a binder having 1 equivalent of a carboxyl group. 120566.doc -16- 200809415 A carboxyl group in a resin for a binder, which imparts a photosensitive resin The layer is necessary for the developability or releasability of the aqueous solution. From the viewpoint of development resistance, resolution, and adhesion, it is preferably 1 Å or more, and from the viewpoint of developability and peelability, it is preferably 6 Å or less. (a) Adhesion The weight average molecular weight of the resin for the agent is preferably 5,000 to 5 G0'_. The weight average molecular weight f of the resin for the adhesive is preferably 500,000 or less from the viewpoint of resolution, from the viewpoint of edge fusion. More preferably, it is 5,000 or more. In order to exert the effect of the present invention more preferably, the weight average molecular weight of the resin for the binder is preferably 5,000 to 200, _, more preferably 5, _1 to 1 () (), The degree of dispersion (also referred to as molecular weight distribution) can be expressed as the ratio of the weight average molecular weight to the number average molecular weight of the following formula: (dispersion) = (weight average molecular weight) / (number average molecular weight). Dispersion using 1 to 6 For the right and left, it is preferably 丨~4. In addition, the acid equivalent is measured by using the Pingyu automatic titrator (COM-555) manufactured by Hiranuma Industry Co., Ltd., using a sodium hydroxide solution of mol. i mol/L. , by potentiometric titration. Molecular weight 'by day Gel permeation chromatography (GPC) manufactured by spectrophotometer (pump: Gulliver, column: Shodex (registered trademark) manufactured by Showa Denko (share) (KF 8〇7, KF_8〇6M, KF-806M, KF-802.5) 4 series of tantalum, flow layer solvent · tetrahydrofuran, using the polystyrene standard sample (Shodex STANDARD SM-1 05 manufactured by Showa Denko) Molecular weight and number average molecular weight (converted in terms of polystyrene) 120566.doc -17- 200809415 (a) A resin for a binder by polymerizing one or more of the following two monomers; obtain. The first single system molecule has a polymerizable unsaturated group of tickic acid or acid anhydride. For example, (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester can be mentioned. Among them, (meth)acrylic acid is particularly preferred. Here, (meth)acrylic acid means propylene foiec acid and methacrylic acid. The same is true below. The second monomer is non-acidic and has a polymerizable unsaturated in the molecule

And base compounds. This compound is selected to maintain the developability of the photosensitive resin layer, the resistance in the last name and the bonding step, and the flexibility of the cured film. As the compound, an alkyl (meth)acrylate such as methyl methacrylate, ethyl (meth) acrylate, butyl acrylate (meth) acrylate, or (meth) acrylate 2 can be used. Ethylhexyl ester, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylonitrile, benzyl (meth) acrylate, methoxy (meth) acrylate Benzyl ester, benzyl (meth) acrylate, furan methyl (meth) acrylate, tetrahydrofuran methyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, ( Methyl) cresyl methacrylate, naphthyl (meth) acrylate, vinyl compound having a phenyl group (for example, styrene). In particular, from the viewpoint of analytical properties and developer cohesiveness, (meth)acrylic acid is preferred. (4) The resin for the binder is preferably added in a solution obtained by diluting the first monomer and the second monomer with a solvent such as acetone, methyl ethyl ketone or isopropyl alcohol. The base polymerization initiator is, for example,: benzamidine or azoisobutyronitrile, and is further synthesized by superheating and stirring. There is also = 120566.doc 200809415 Adding the mixture to the reaction mixture, and the neighbors, while carrying out the situation. After the reaction is completed, the sputum is added to the acne and the solvent is added to adjust to the condition of the period. As a synthesis method, ^ Λ田台Μ 矛,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,吏 ( The range of the resin for the mixture is from 2 to 9% by mass, more preferably from 3 to 7% by mass based on the total mass of the photosensitive composition. The optical pattern has characteristics as a photoresist.

For example, from the viewpoints of sufficient resistance to boring, etching, various plating, and ν, it is preferably ❶ ❶ or more and 90% by mass or less. As (b) at least one which can be photopolymerized The saturated compound is preferably a state in which at least one photopolymerizable unsaturated compound is selected from the group consisting of compounds represented by the following formula (Π) (VI) from the viewpoint of high resolution. Used in a photosensitive resin composition. [Chem. 6] V: H2C = ι } ?h3 r5 C-fO-(C2H40)n2iCH2CH0)n3—(C2H4Q)nrC-0:CH2) 0

(ID (where Ri is H or CH3, these may be the same or different, ..., n4 and n5 are each an integer of 3 to 20 respectively.) 120566.doc 19 200809415 [化7] 0—(A— 0>叫-(B-0) - 0=03⁄4

H3C-C-CH3

(III) 0, (A-0) r»7-(B - 0) ti9-C-C=CH2 0 R7 (wherein R6 and R7 are H or CH3, and these may be the same or different, A is C2H4, B is CH2CH(CH3), n6 + n7 is an integer from 2 to 40, n8 + n9 is an integer from 0 to 40, 116 and 117 are each independently an integer from 1 to 39, and 118 and 119 are independently 0 to 40, respectively. The integers; -(A-Ο)- and -(B-Ο)- repeating units can be arranged randomly or as blocks; in the case of blocks, -(A-Ο)- and -( In the order of B-〇)-, either can be on the diphenyl side.) [Chemical 8] ? One (D-0) mi — (E-0) m3—CC=CH2

(IV) (wherein, R8 and R9 are Η or CH3, and these may be the same or different, D is 120566.doc -20- 200809415 coffee, __ Yang 3), and heart 2 is an integer of 2 to 4 () , _4 is an integer of 〇~4〇, called and called respectively independent:: then ® a reaches a, 々 叹 3 3 and m4 are each an integer of 0~40, respectively; and the arrangement of the tearing repeating unit can be random 'Also can be a block; in the case of a block, in the order of meals 0)_ and (E-Ο)-, either can be on the cyclohexyl side. ) [Chem. 9] CH,

R 11 NHC0-(0CHCH2)m5-0C0-C=CH2 ^10NHCO-(OCHCH2)rng-OCO-C:=rQ|-jl3CH, (V)

R 12 (wherein R1〇 is a divalent organic group having a carbon number of 4 to 12, and Rii&R ch3 may be the same or different, and m&m6 is independently an integer.) [10] M3 H2C = CC-〇-(A, -0)m7—(Bj ^〇)m8 0

(VI) (R14)ms (wherein Ru is H or CH3, Ru is a carbon number 4-14, A is C2H4, B' is CH2CH(CH3), and an integer of m74l~12 is called 〇 ～12之120566.doc •21 - 200809415 The integer 'm9 is an integer of (2); _(A, _〇)· and _(Β, _〇)_ the arrangement of repeating units can be random or can be a slay; In the case of a block, in the order of _(a_ and -(B,-〇)-, ## can be on the phenyl side.) + = compound represented by formula (II), From the viewpoint of point and odor, the car is better than 'n3, njn43 or more. From the viewpoint of sensitivity depending on the concentration of the photoactive portion per unit mass, n3Un^ is preferably 20 or less. Specific examples of the compound represented by the above formula (9) used are, for example, preferably: an average addition of two ends of a polypropylene glycol having a U-mole propylene propylene oxide, and an average addition of 3 moise earrings. Dimethyl methacrylate of diol formed by oxyethane. Among the compounds represented by the above formula _, (4) and ― must be 4 Å or less, and if it exceeds 40, it is not preferable from the viewpoint of sensitivity. of 30. The following is an example of the compound of the compound of the above formula (ιπ) used in the present invention, which has an average addition of 2 moles of propylene oxide and an average addition at both ends of the bismuth. It is made into a 6-mole epoxy-fired poly-glycol diol dimethacrylate vinegar, or an average addition of two moles of epoxy propylene acetate at both ends of the double sputum, and an average addition of 15 moles. The epoxy-baked polyglycol diol dimethacrylate _ in the ear, which is added to the two ends of the double-prepared A, respectively, with 5 moles of epoxy b-ethene-poly(H)-(di) acid (Xinzhongcun Chemical) NK ester BPE-500 manufactured by the industry (shares), and the average addition of the two ends of the bisphenol A to the 8% of the polyethylene glycol Methyl acrylate acid (NK ester BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.) In the compound represented by the above formula (iv), mi+m^ must be 120566.doc -22- 200809415 40 or less 'If it exceeds 4, it is not preferable from the viewpoint of sensitivity. It is preferably 30 or less. Specific examples of the compound represented by the above formula (IV) include: 2, 2·double {(4) -Acetylene Polyvinyloxy)cyclohexyl}propane or 2,2•bis{(4-mercaptopropenyloxypolyoxy)cyclohexyl}propane. This compound has a poly(ethylene) xy group. Preferably, it is derived from a monoethyloxy group, a diethyleneoxy group, a triethyleneoxy group, a tetraethyleneoxy group, a pentaethyleneoxy group, a hexyl group, a hexaethyleneoxy group, a heptaethyleneoxy group, Selected from the group consisting of human ethylene base, ninth ethylene oxide, decavinyloxy, undecyloxy, dodecyloxy, tridecethyltetradecyloxy, and pentadecyloxy Any group. Further, 2,2-bis{(4-propenyloxypolylactyl)cyclohexyl}propane or 2,2-bis{(4-methacryloxypolyoxy)-hexyl group can also be mentioned. } Propane. The polyalkenyloxy group (P〇iyalkyieneoxy) which the compound has may be exemplified by a mixture of a vinyloxy group and a propyleneoxy group and a state of the state of California, preferably an octaethyleneoxy group and a di(tetra)oxy group. a block structure adduct or a random structure adduct, and a block structure adduct of a tetravinyloxy group and a tetrapropenyloxy group or a random structure adduct, a fifteen alkenyloxy"-propyleneoxy group The segment structure adduct or the random structure addition compound 3 or the like is preferably 2,2_bis{(4·methacryloxypentapentaoxy)cyclohexyl}propane. The above formula (7) In the formula, in the formula, if m6 or more is exceeded, sufficient sensitivity cannot be obtained, and in the formula, & is a residue having a carbon number of 4 to 2, and is a residue of a diisocyanate. Specific examples of the compound represented by _, fly, can be listed as two 120566.doc -23- 200809415 isocyanate si compounds, for example, dihexyl diisocyanate, guanidine diisocyanate, or diiso 2,2,4-trimethylhexyl cyanate, a compound having a hydroxyl group and a (fluorenyl)propenyl group in one molecule, for example, acrylic acid 2_ A propyl phthalate ester, a phthalic acid propylene glycol methacrylate, an amine phthalate compound. Specifically, lysine dihexyl isocyanate and isopropyl monomethacrylate (made by Nippon Oil & Fats Co., Ltd., Blemmer The compound represented by the above formula (VI), if it is called or more than 12, cannot obtain sufficient sensitivity. If it exceeds 3, sufficient sensitivity cannot be obtained. Specific examples of the compound represented by the method include, for example, addition of polyethylene glycol having an average addition of 2 moles of propylene oxide to polyethylene glycol having an average addition of 7 moles of ethylene oxide. The acrylate of the compound on the indophenol, that is, 4-n-nonylphenoxy hexaethylene glycol acrylate. It is also possible to add a polyethylene oxide having an average of 8 moles of ethylene oxide. An acrylate of a compound formed on indophenol, that is, n-decylphenoxy octaethylene glycol acrylate (manufactured by East Asia Synthetic Co., Ltd.) as (b) at least one photopolymerizable unsaturated The compound does not belong to the above formula (III), (IV), (VI) And the compound of the group consisting of the compound represented by (νπ) has an unsaturated compound which can be photopolymerized as follows. For example, hydrazine, hexane hexane di(meth) acrylate, 1, 4-cyclohexanediol di(meth)acrylate, polypropylene glycol di(meth)acrylic acid, S, water, ethylene glycol di(meth)acrylic acid, 2-di(p-phenyl)propane Di(meth)acrylate, tris(meth)acrylate, trimethylolpropane di(meth)acrylate, polyoxypropyltrimethylolpropane tris(A 120566.doc -24- 200809415 Acrylate, polyoxyethyl trimethylolpropane triacrylate, pentaerythritol tetrakis (meth) acrylate, dipentaerythritol penta (meth) acrylate, dimethylolpropane triglycidyl ether (Meth) acrylate, bisphenol A diglycidyl ether di(meth) acrylate, phthalic acid hydroxy propyl ketone - β '- (methyl propionic acid oxy) propyl vinegar, phenoxy poly Ethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate. (2) Workers (1)) ~ (VI) Table +, children. Yang π group

At least one of the photopolymerizable unsaturated compounds has a ratio of from 3 to 7 % by mass based on the total of the photosensitive resin composition. When the resolution = ... is 3% by mass or more, is the viewpoint of the flexibility of the resist pattern? , for shoulders below %. More preferably, it is 3 to 3 % by mass or less.杓": The total amount of unsaturated compounds in the order of light, relative to the overall ratio of the photosensitive tree sap composition, ^ quality. From the point of view of Limin, it is better 3; From the viewpoint of the combination, it is preferably 70% by mass as a good: 疋1 ° '% by mass, more preferably 15 to 55% by mass. As (c) a photopolymerization initiator, the line may be activated. For the illuminating, for example, the compound of the ultraviolet polymer, the photopolymerizable unsaturated aryl imidazole dimer is represented by the 2,4,5_triform of the formula 34 (VH). From the point of view, it is better to implement 120566.doc -25· 200809415 (VII) ^,..., q^r/knife is independently an integer from 1 to 5.) As represented by the above formula (VII) In a one-molecular imidazole dimer, a covalent bond of two less than a few groups may be bonded, which may be a horse I, 1 -, 1, 4, 2, 2, -, 2, 4, - or 4 - bond荨' is preferably a compound of the above formula (VII) in which the 兮丘μ /, the mussel bond is 1,1'· bond. The 2,4,5-triaryl call is taken-in the main one, For example, there is 2-(o-chlorophenylhydrazine)

; I: 4,5·diphenyl-saliva dimer' 2-(o-chlorophenyl)-4,5-bis(metamethoxycarbenyl) meth. Sit dimer, 2_(p-methoxyphenyl)-4,5-diphenylmethane dimer dimer, particularly preferably 2_(o-chlorophenyl)_4,5-diphenyl, fluorene Polymer. As the (4) photopolymerization initiator used in the present invention, it is preferred to use the 2,4,5-triaryl miso dimer represented by the above formula (VII) in combination with p-aminobenzene. The system. Examples of the p-aminobenzenes include, for example, an aminodicarbyl hydrazine, a butyl butyl acetophenone, a p-dimethylaminoacetophenone, a p-dimethylaminodiphenyl ketone, and a P. , P'_bis(ethylamino)diphenyl ketone, p,p,.bis(monomethylamino)diphenyl-[Michler, s ketone], p,p, · bis(monoethylamino)diphenyl ketone, ^Guangshuang(dibutylamino)diphenyl 120566.doc -26- 200809415

+, the heart is a photopolymerization initiator other than the compound shown above, there is a collection:: ampoule: 2: "onion stuffed, 2_ third butyl onion, 1 scented ether, example 9 stupid: ^ U fragrant Anthracene ether, benzoin ethyl ether; acridine compound, for example: the same as the other; other have 'knot dimethyl lysine, benzyl hydrazine hydrazine also has a ton g of the same kind 'such as sevotonone' 2,4 _ Ethyl ketoxime, 2 - gas sputum g, blood Chu 2

/" \ V/ Women-based compounds such as dimercaptoamine-based compounds are combined. Further, the brewing type may, for example, be 1-phenyl-1,2-propanediyl, -2-o-benzylidene-based, or κ-phenyl #propylenedione 2-(o-ethoxymethyl). Further, it is also possible to use an aryl group-based acid compound. Among them, N-phenylglycine is particularly preferable. In the photosensitive resin composition of the photosensitive resin laminate of the present invention, the photopolymerization initiator is preferably contained in an amount of 〇·1 to 2% by mass based on the total amount of the photosensitive resin composition. From the viewpoint of obtaining sufficient sensitivity, a fineness of 0.1% by mass or more is preferably a quality of 2 Å from the viewpoint of preventing reflection of light on the surface of the substrate during exposure. /. the following. A basic dye can be used in the photosensitive resin composition. As an example of a basic dye, it is listed as a magenta, a cyanine green, an auramine base, a Chalcoxide Green S, a crystal violet, a thiol orange, a Nile blue 2B peacock, and a library (Baotu Valley Chemical Co., Ltd.) Manufactured Aizen (registered trademark) MALACHITE GREEN), Alkaline Blue 2〇, Diamond Green (Aizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.), Victoria Pure Supervisor (Aizen by Baotu Valley Chemical Co., Ltd.) (registered trademark) VICTORIA PURE BLUE). 120566.doc -27- 200809415 The photosensitive resin composition may further contain a color-developing dye which develops color by light irradiation. As a color-developing dye used, an example There is a combination of a leuco dye and a halide. As the leuco dye, for example, tris(4-dimethylamino-2-methylphenyl)methane [colorless crystal violet], tris(4-dimethyl) Amino-2-methylphenyl)methane [colorless malachite green].

As the _ compound, there may be mentioned: desertification, pentylene, evolution of isoprene &, d-di-methyl propane, di-di-ethane, desertified diphenylmethane, dioxanylbenzene/odorous methane, dibromo Methyl phenyl sulfone, carbon tetrabromide, tris(2,3-dibromopropyl «acid vinegar, trichloroacetamide, valproate, oxime, bismuth, bismuth-2,2-bis ( p-Chlorophenyl) Ethyl _, hexaqi, Ethylene, and saponified compound. As the 1,3-triazine compound, 2, 4, 6 • tris(trimethyl) s-triazine, 2-(4-Methoxyphenyl)_4,6-bis(trichloromethyls-triazine). Among such chromogenic dyes, useful is the combination of tribromomethylphenylsulfone with a leuco dye, or halogenation. The combination of a triazine compound and a leuco dye. 3 has a halide shape of a halide. The halide content in the photosensitive resin composition is preferably 0 · 〇 1 to 5 mass %. In the case of the photosensitive resin composition, it is preferable that the sputum of the sputum 乂 乂 乂 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 0/〇. You can see the aspect of sufficient coloration (color rendering) In ancient times, it is better that the 鲈 ^ ^ ° is preferably 0.01% by mass or more in terms of the difference between the exposed portion and the unexposed portion, and in terms of maintaining storage stability. It is 5% by mass or less. Further, in order to improve the storage stability of the present invention, it is preferred to use a polymerization inhibitor or a benzotriazole. Thermal stability and lightness of the photofinishing composition The resin composition contains a radical 120566.doc -28 - 200809415 as such a radical polymerization ageing, p-benzoic acid, o-benzene triterpenoid, amine, and, for example, p-methoxy steel, 2, 6-二第... ❹ 4 4 butyl catechin 酴, chlorination: butyl ... T phenol, 2, 2 '· methylene bis (" carbaryl base sulfhydryl aluminum salt, diphenyl nitrite Further, as benzoquinone = azole _, ..., 颉, for example, 1,2,3·benzotriazole, benzene: bis, yttrium, bis(indenylhexyl)aminomethylene Cut-tris(diethylhexyl)aminomethylene-1,2,3-methylphenyl bis(N-2-carbylethyl)aminomethylene], 2,3-ylbenzoquinone Saliva, for example, can be cited as: 幷二. Sit, 4-base benzoquinone III. Sit, N satirize N_2, hexylaminomethylene carboxy benzoquinone, triyl benzoquinone, tris(Ν'Ν--2-ethylhexyl)amine, ethyl carboxylic acid, free radical polymerization · And the total addition amount of benzoquinone trisal, the amount of comparison, and the amount of G.G5~1f. The amount of the photosensitive tree is preferably 001: The above, in addition, from the viewpoint of maintaining the light sensitivity, t is less than the mass%. And the radical polymerization inhibitor such as α Hai or the benzoxazoles can be used alone. Further, in the photosensitive resin composition, a moldable enamel may be contained as needed. As such a plasticizer, there are phthalates (for example, m - r ^ u to dimethyl methacrylate), o-toluene sulfonamide, p-toluene sulfonamide, citric acid three 120566.doc • 29- 200809415 vinegar, citric acid tri-u, ethyl citrate triethyl ethoxide, tri-n-propyl propylate, tri-n-butyl ethoxide, polypropylene glycol, polyethylene glycol, polyethylene glycol The base of the ether and polypropylene glycol shouted. The content in the case of containing (4) is preferably W mass in the photosensitive resin composition. /. More preferably, it is 5 to 30% by mass. From the viewpoint of suppressing the delay of the development time or imparting flexibility to the cured film, it is preferably 5% by mass or more, and the viewpoint of suppressing insufficient hardening or cold flow is also suppressed! It is preferably 5 〇 or less by mass%. Hereinafter, a method of producing a photosensitive resin laminate by sequentially laminating the support film 1, the intermediate layer 2, the photosensitive resin layer 3, and the protective layer 4 as needed will be described with reference to Figs. 1 and 2 . "Bai Xian' will be a polyvinyl alcohol, for example, KUraray Monaco PVA carrying resin, and a compound represented by the above formula (1): a compound of more than one type selected from the group 'with a solid content ratio of 5 ~%% 之% of the amount, slowly added to the warmth to 6 〇 ~ thief in the water, and give a drop (hour 'dissolve its average sentence, and obtain the above-mentioned intermediate layer of the composition of the water: liquid. Contains poly The viscosity of the aqueous solution of the composition of the interpenetrating layer of the ethoxylated alcohol is preferably adjusted to 10 to 500. Then, the aqueous solution is applied to the branch (4) using a bar coater or a coater, and is carried out. In the dry furnace, the support film 附带 with the intermediate layer 2 is obtained. Ben 8: External: Preparation of a photosensitive resin composition. The viscosity of the photosensitive resin group is d, which is preferably (25) at 25 lt. The solvent is added in the form of ~*mP. As the solvent to be used*, the network represented by E. EK), or an alcohol, for example, 120566.doc -30- 200809415 alcohol, ethanol, and isopropanol. Using a bar coater or a roll coater, the same coating method as the middle door A and the interlayer 2 is applied to the support film 1 of the intermediate layer 2, and the nua skin layer is coated on the T layer. The photosensitive resin layer 3 of the photosensitive resin composition is dried. Then, the photosensitive resin layered body can be produced by laminating the protective layer 4 on the photosensitive resin layer 3. a Next, an example of a method of producing a printed wiring board using the photosensitive resin laminate of the present invention will be described. The printed wiring board is manufactured through the following steps. (1) When the laminating step has a protective layer on the photosensitive resin laminate, the protective layer is peeled off, and a heat roller laminator is used on the substrate, for example, a copper deposited laminate or a slidable substrate. Its close steps. (2) Exposure step The support film is peeled off from the photosensitive resin laminate. The photomask film having the desired wiring pattern is adhered to the intermediate layer, and the exposure is performed using an active light source. (3) Developing step The step of forming a hardened photoresist pattern on the substrate by dissolving or dispersing the unexposed portion of the intermediate layer and the photosensitive resin layer is carried out by using a base. (4) a step of etching or coating a step of spraying an etching solution on the formed photoresist pattern, etching a steel surface not covered by the photoresist pattern, or performing copper on a steel surface not covered by the photoresist pattern, Solder, nickel and tin are representative steps of the coating process. This can be used to make conductor patterns from 120566.doc -31 - 200809415. (5) Peeling step The step of removing the photoresist pattern from the substrate using an alkaline stripping solution.

Examples of the active light source used in the above (2) exposure step include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, and a xenon lamp. Also, in order to obtain a finer photoresist pattern, it is more preferable to use a parallel light source. In the case of trying to reduce the influence of dust or foreign matter, there is also a case where exposure (close exposure) is performed in a state in which the photomask is suspended on the support film by several tens (four) or more and hundreds of times or less. Further, as the organic developer used in the above (3) development step, an aqueous solution of sodium carbonate or sodium carbonate may be mentioned. These alkaline aqueous solutions can be selected according to the characteristics of the photosensitive resin layer, and a sodium carbonate aqueous solution of 0.5% by mass or more and 3% by mass or less is usually used. The above (4) button engraving step can be carried out, for example, by an acidic (four), inspective residue, or a method of selecting a dry film resist suitable for use. The test stripping liquid used in the above (5) peeling step may be an aqueous solution which is more inspectable than the usual aqueous solution for development, and may, for example, be 1 berry. Above, 5% by mass or less of sodium hydroxide or an aqueous solution of sodium hydroxide. Further, when the barrier shape of the plating step is selected, the photoresist pattern is peeled off, and then the copper surface of the mountain under the photoresist pattern is etched. Hereinafter, an example of an embodiment of the present invention will be described in detail by way of embodiments. [Examples] 120566.doc • 32- 200809415 Hereinafter, the preparation of the samples for evaluation of the examples and the comparative examples, and the evaluation methods and evaluation results of the obtained samples were disclosed. [Examples 1 to 12] and [Comparative Examples 1 to 3] Preparation of Samples for Evaluation I The photosensitive resin layered systems of the examples and the comparative examples were produced as follows. Industrial Production <Production of Photosensitive Resin Laminate> First, the intermediate layer composition shown in Table 1 was slowly added to water heated to 85 ° C so that the solid content ratio became 1% by mass. The i J was uniformly dissolved while stirring, and a uniform aqueous solution of the composition of the intermediate layer was obtained. As the support film, a polyethylene terephthalate film having a thickness of 16 μm was used, and the aqueous solution was applied onto a support film using a bar coater. Then, it was dried in a drier at 3 ° C for 3 minutes to form a uniform intermediate layer on the support crucible. The thickness of the intermediate layer is 2 μηη. Using a bar coater, the photosensitive resin composition of the table was uniformly coated on an intermediate layer laminated on a supporting crucible in a 95 C drier for 3 minutes to form a uniform photosensitive resin layer. The thickness of the photosensitive resin layer was 3 μm. On the surface of the photosensitive resin layer, a polyethylene film having a thickness of 25 μm was bonded as a protective layer to obtain a photosensitive resin laminate. <Substrate> Analytical, parity, adhesion evaluation including independent cylindrical adhesion, halo evaluation of photoresist pattern, evaluation of the sidewall of the photoresist pattern, and surface of the photoresist pattern Per's use of Persian metal (stock) with 8 μηι copper foil laminated on an insulating resin, evaluated by Perflex. 120566.doc -33-200809415 <Lamination> The protective layer of the photosensitive resin laminate of the present invention is peeled off by a heating roll laminator (Al-70, manufactured by Asahi Kasei Engieering Co., Ltd.) Lamination was carried out at a roll temperature of 105 °C. The air pressure was set to 0.35 MPa, and the lamination speed was set to 1. 〇 m/min. <Exposure>

After the support film was peeled off, a photomask film necessary for the evaluation of the photosensitive resin layer was exposed to an exposure amount of SO mj/cm 2 on an intermediate layer by an ultrahigh pressure mercury lamp (HMW-SO1 manufactured by 〇rc). <Development> Spray 3 at a specific time (TC 〇.5 mass. /(^心(: 〇3 aqueous solution, dissolve and remove the unexposed portion of the photosensitive resin layer. At this time, the sensitization of the unexposed portion is completely dissolved) The minimum time required for the resin layer is set to the minimum development time. The development is performed at a time when the development time is twice the minimum development time to obtain a hardened photoresist pattern. 2. Evaluation method (1) Evaluation of peelability of the support film When the support film was peeled off by the exposure, the peeling property was evaluated as the following grade: ◦ (good): only the support film was peeled off. △ (may) · A part of the intermediate layer adhered to the support film and peeled off at the same time. x (not) Support The film is peeled off together with the intermediate layer (the middle door layer and the photosensitive resin layer are peeled off). (2) The analytical evaluation mask is used as a line graph in which the ratio of the width of the exposed portion to the unexposed portion is 1 ··1. .doc -34- 200809415 For the photomask film during exposure, the substrate which has been laminated for 5 minutes after lamination is exposed and developed in the above manner. The minimum mask width of the normally formed hardened photoresist pattern is set as the resolution. Value, will be analytical The value is 如下(excellent)·the resolution is 5 μχη or less 〇(good): the resolution value exceeds 5 μηη, and is 1〇μχη or less △(may): the resolution value exceeds 10 μηη, and 15 μιη or less χ (not available): the resolution value exceeds 15 μηι (3) The adhesion evaluation is performed using a line mask separately as an exposure part as a mask film during exposure, in the above manner, after lamination The substrate was exposed for 15 minutes and developed. The minimum mask width of the normally formed cured photoresist pattern was used as the value of the adhesion, and the adhesion was evaluated as follows. ◎ (Excellent) The value of the desired property was 5 The following values of 〇(good)·adhesiveness exceed 5 μιη and are 1〇μηη or less △(叮)· after:%• The value of sex exceeds 10 and is 1 5 is the following χ (not): Adhesive The value exceeds ^^ melon (4) The evaluation of the independent cylindrical adhesion is performed by using a cylindrical pattern mask which is an exposure portion as a photomask film at the time of exposure, and in the above manner, the substrate which has been subjected to lamination for 15 minutes is exposed and developed. The diameter of the cylindrical mask that will normally form a hardened photoresist pattern The small width is set to the value of the independent circular adhesion, and the evaluation is for the grade. ◎ (Excellent): The value of the independent cylindrical adhesion is 5 μπι or less (good) · The value of the independent cylindrical adhesion is more than 5 μιη And less than 1 pm △ (may): independent cylindrical adhesion value exceeds 10 μπι and is less than 15 μΐΏ 120566.doc -35- 200809415 X (not): independent cylindrical adhesion value exceeds 15 μπι (5 The halo evaluation of the photoresist pattern is performed by using a chrome glass mask as the photomask film at the time of exposure, and as described above, the exposure, and the shape of the hardened pattern of the known hardened pattern is evaluated as follows. grade. ◎ (k). The traces of the hardened photoresist are good and there is no halation. 〇 (good) · The trace of the foot of the hardened photoresist is good, and the halo is very small. △ (may) be able to confirm the dimming of the foot below 3 pm. A vignet of more than 3 can be confirmed at the foot of the X (not) hardened photoresist. (6) The evaluation of the lifting of the side wall of the photoresist pattern is performed by using a chrome glass reticle, and the screen body laminated on the substrate is exposed and exposed. . The side wall shape of the photoresist pattern of the 10 μηι line of the obtained hardened pattern was evaluated as the blank level. , 〇 (good) · The photoresist sidewall formed is almost no warping. △ (may): The formed photoresist sidewall has a slight lift. χ (not) · The formed photoresist sidewall has an upturn everywhere. (7) Evaluation of the surface state of the photoresist pattern Using a chrome glass mask, the film was laminated on the substrate and exposed to a laminate on the surface of the substrate, and the vestilator was used. The surface state was evaluated as follows: μη1 line 〇 (good): The formed photoresist surface has almost no depression. △ (may): there is a fine depression on the surface of the formed photoresist. 光 (not) formed photoresist surface There are depressions everywhere. 3 · Evaluation results 120566.doc 36 200809415 The evaluation results of the examples and comparative examples are shown in Table 12. The mass of the mixture is divided into methyl ethyl ketone. Table 1 Interlayer, Comparative Example 2 The film thickness of the intermediate layer is relatively thick, and the compound represented by the above formula (I) is absent. Among the P-1 to P- in Table 1, the intermediate layer of Comparative Example 1 is not in Comparative Example 1.

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Mft «^w^f every W thief 凾 ¥11 mining iH4t, ^va^w miscellaneous ® - -38- 200809415 < note description > Q-1 : polyvinyl alcohol ((K) Kuraray PVA_205) Q- 2: Polyethylene glycol (weight average molecular weight 4 〇〇) Q_3 : Polyoxyethylene ethyl monomethyl ether (Uni 〇 x m-550, 曰 油脂 油脂 , ,, weight average molecular weight 550) Q-4·Poly浠吼 烧 烧 1 (weight average molecular weight 4 〇, 〇〇〇) pl : benzyl methacrylate 80 mass 〇 / 〇, methacrylic acid 2 〇 mass% of the 2 - copolymer methyl ethyl ketone solution ( Solid content concentration 5% by mass, weight average molecular weight 25,000, acid equivalent: 430, dispersion 2.7) p-2 · methyl methacrylate 50% by mass, methacrylic acid 25% by mass, styrene 25 ϊ 2 % Methyl ethyl ketone solution of the copolymer (solid content concentration 35 mass%, weight average molecular weight 5 〇, 〇〇〇, acid equivalent 344, dispersion 3.1) M-1 : 12 m ring in average addition The two ends of the polypropylene glycol of oxypropane, and the average addition of 3 moles of ethylene oxide to the polyalkylene glycol dimethyl acrylate M-2: the average addition of the two ends of the double a Moore's Ring Acrylic and average addition of 6 moles of Ethylene Ethylene Glycol Dimethyl Acetate M-3: The average addition of both ends of the two ages is 2 moles of epoxy B Burned ίκ-ethyl dimethyl acrylate acid (new traitor

NK Ester ΒΡΕ-200) manufactured by T-mura Chemical Industry Co., Ltd. Μ-4: average ^9 addition of bisphenol a to polyethylene oxide dimethacrylate with 5 moles of ethylene oxide Ester

, NK ester ΒΡΕ-500 manufactured by T-mura Chemical Industry Co., Ltd. 120566.doc -39- 200809415 M-5 : 2,2-double {4-(methacryloxypentapentaethoxy)cyclohexyl Propane-propane M-6: urethane-polypropylene glycol dimethacrylate M- as a reactant of hexanediol diisocyanate and oligopropylene glycol monomethacrylate (made by Nippon Oil & Fats Co., Ltd., Blemmer PP1000) 7· > Methyl propylene didecyl acrylate acid M-8: > oxyethyl triterpene propyl propyl triacetate (NIUI manufactured by Shin-Nakamura Chemical Co., Ltd.) A_TMPT-3EO) • M-9: Nine-ethylene glycol diacrylate 〇G-ι : 4,4'-bis(diethylamino)diphenyl ketone G-2 : 2-(o-phenyl) -4,5-diphenylimidyl dimer J-1: Diamond Green (Aizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.) J-2 · Colorless crystal violet Ll· 1-(2 a 1:1 mixture of 1-n-butylaminomethyl)-5-weigphenyl benzotriazole and (2-di-n-butylaminomethyl)-6-carboxybenzotriazole: Ciba Specialty Chemicals IRGANOX 245) [Industrial Applicability] The photosensitive resin laminate of the present invention is used for producing a printed wiring board having a conductor pattern, a flexible substrate, a lead frame substrate, a C〇F substrate, and a semiconductor package. The substrate and the field of manufacturing a transparent plate having a liquid crystal transparent electrode as a conductor pattern, a liquid crystal TFT wiring, and a PDP (plasma display panel) electrode are suitable for etching photoresist or coating photoresist. [Brief Description of the Drawings] Fig. 1 is a schematic view of a photosensitive resin laminate of the present invention (the above item (1)). Fig. 2 is a schematic view of a photosensitive resin laminate of the present invention (the above item (2)). [Main component symbol description] 1 Support film 2 Intermediate layer 3 Photosensitive resin layer 4 Protective layer 120566.doc -41-

Claims (1)

200809415 X. Patent application scope: !· A photosensitive resin laminate, characterized in that it comprises a support film in order, and the thickness of the support film is 〇1 μηι or more and 1 pm# In the case of a photosensitive resin layer, the intermediate layer contains one or more compounds selected from the group consisting of polyethyl alcohol and a compound represented by the following formula (I): Ri-0-(CH2CH20) n1-R2 (1) (Heart and Han 2 are Η or CH3, and these may be the same or different, and ~ is an integer of 3 to 25). 2. The photosensitive resin laminate according to claim 1, which is obtained by laminating a protective layer on the photosensitive resin layer. 3. The photosensitive resin laminate according to claim 2, wherein the photosensitive resin layer comprises a photosensitive resin composition, and the photosensitive resin contains: (a) a carboxyl group content of 1 酸 in terms of acid equivalent Resin for 黏~6〇〇, and weight average molecular weight of 5000~500000: 2〇~9〇% by mass to 乂, species can be immersed in photo-hydrated unsaturated compound: 3~70% by mass · (c ) Photopolymerization initiator: 0.1 to 20% by mass. 4. The photosensitive resin laminate according to claim 3, wherein the resin for the binder contains benzyl (meth) acrylate as a copolymerization component. 5. The photosensitive resin laminate according to claim 3, wherein the above 1)) at least one photopolymerizable unsaturated compound is at least one photopolymerizable unsaturated compound selected from the group consisting of the compounds represented by the following general formulae (11) to (VI) 120566.doc 200809415 [化i] CHq 0 H2C =CC〇iC2H4〇)n2iCH2CHO)n3—(C2H4〇)nrC-C=CH2 (H) 0 (wherein R4 and Rs are H or CH3, which may be the same or different , 〇 and n5 respectively represent an integer from 3 to 20); [Chemical 2] 0 Re q—(A—〇) w (B-0> (III) H3C-C_CH3 (HA-0) η?—(B - 0) r»9-C—C=CH2 II » 0 R7 (wherein R6 and R? are H or CH3, and the same or different, A is C2H4 'B is CH2CH(CH3), n6+n7 is an integer from 2 to 40, and ~+119 is an integer from 0 to 40'... and n? are independent integers of 丨~39, respectively... and ^ are independently 0~40 An integer; - (A-〇l· and -(B-0)- repeating units can be arranged randomly or as blocks; in the case of blocks, _(α·〇)_ and -( In the order of Β-0)-, either can be on the side of the diphenyl group; 120566.doc 200809415 [Chemical 3] 〇-(D~0) mi—(Ε-0) m3—CC=CH2 (D - 0) m2 — (E—0) rru—c—C=CH? II ^ 0 Rg ί % I- (where, and R9 is H or CIH3, the temple can be the same or different, d is C2H4, E is CH2CH(CH3), mi+n^ is an integer of 2~40, called + 〇~40 The integers, 叱 and 叱 are each an integer of 丨~39, and are called integers of 0~40, respectively; -(〇-0)- and _(^〇)·The arrangement of repeating units can be random, also It may be a block; in the case of a block, in the order of -(EO)-, either of them may be on the cyclohexyl side; [Chemical 4] Yan 3 R11 NHCO-(OCHCH2)m5.〇 CO-C=CH2 ?1〇(V) NHCO-(OCHCH2)m6.〇CO-C==CH2 CH3 m (where ch3, '“ is a 2-valent organic group with carbon number 4~12' R" and RI2_ These may be the same or different, called and called respectively 120156.doc (VI) ^13 200809415 integer); [5] H2C ==c - C—0—(A′ -0)iri7—(B′ -0)m8 0 (wherein R13 is H or CH3 ' R14 is a carbon number 4-14, C2H4, B' For CH2CH(CH3), m7 is an integer from 1 to 12, which is an integer from 〇~12, m9 is an integer from 0 to 3; -(A,-〇)_ and ·(Β,_〇)-repeat unit The arrangement may be random or block; in the case of a block, any of _(Α,_ 〇) and -(Β'_0)- may be on the stupid side. A method for forming a resist pattern, which comprises sequentially laminating a photosensitive resin laminate according to any one of items 1 to 5 on a surface of a metal plate or a metal-clad insulating plate. The laminating step, an exposure step of peeling off the support film and performing exposure, and a developing step of removing the unexposed portion by development. A method of producing a conductor pattern, characterized in that the substrate on which the photoresist pattern is formed is etched or plated by the method of the method of J. 120566.doc