TWI353489B - Photosensitive resin laminate - Google Patents

Description

1353489 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 substrate for C〇F (Chip 〇n Fi丨m), and a semiconductor. Manufacture of a substrate for packaging, a transparent electrode for liquid crystal as a conductor pattern, a TFT for driving a liquid crystal (Thin Film Transistor), a PDP (Plasma...

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 pure resin layer of the above (4), it is generally used as an invisible developing type using a weak aqueous solution as a developing solution. , ', one, % double < general method First, in the case of a protective layer, the protective shore is peeled off. , θ Dan Jun, for the machine, on the substrate for permanent circuit fabrication, such as a steel strip laminate or a substrate, the laminate and the support film are subjected to the photosensitive exposure, and exposed through the wiring pattern mask film. The next day, the female eve, the female, the female, and the other. There is also a helmet that does not require a reticle, and the hood is exposed first, for example, by direct drawing by 120566.doc 1353489. Then, when the support film remains, = peeling 'dissolving the unexposed portion of the photosensitive resin by the developer, 'or dispersing and removing it, forming a cured photoresist pattern on the substrate (hereinafter referred to as 'abbreviation For the photoresist pattern).

After the photoresist pattern is formed, the process of forming the circuit can be roughly divided into two methods. The first method is a method of removing the photoresist pattern portion by using a stronger alkaline aqueous solution than the developer after etching the copper surface of the substrate which is not coated with the photoresist pattern (money method). The method is as follows: a method of removing the photoresist pattern portion after the copper solder is applied to the copper surface of the substrate, and then removing the resist pattern portion, and further exposing the substrate copper surface (mine film method). When the surname is engraved, a solution of copper chloride, triiron sulphide or copper ammonia complex can be used. In recent years, in order to meet the demand for miniaturization of the conductor pattern of the printed (four) wiring board, the industry has sought to achieve high-resolution adhesion of the photoresist pattern (Patent Document 1). The resolution is usually achieved by increasing the crosslinking density of the photosensitive resin composition, but if the crosslinking density is increased, there is the following problem: after exposure

The photoresist pattern becomes hard and brittle. In the transfer step from the self-developing step to the sculpt or the film-forming step, one of the photoresist patterns is partially defective. Further, in particular, the film having a film thickness of the photosensitive resin layer of H) or less has a case where light is reflected on the surface of the substrate during exposure, and (4) photosensitive resin layer which is not exposed is also photosensitive. This photosensitive portion affects the photoresist pattern and causes a short circuit. X, when exposed, "reflects on the surface of the substrate. Therefore, the bottom surface of the S-resist pattern produces a developmental residue called halo. If Twilight is produced, there is a problem that the warping occurs on the copper circuit in accordance with the size of the engraving step. I20566.doc 1353489 As a support film for dry film photoresist, a polyester film is generally used. The polyester film contains trace components such as lubricants. This trace component causes a phenomenon in which one of the extremely small portions is blocked by 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 the fine wiring having a conductor pattern width of 10 μm is formed, the influence cannot be ignored.

As another method for achieving 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 influence of the "micro-components on the shape of the resist pattern" contained in the support_however, if polyethylene is used alone The alcohol forms an intermediate layer, which is inferior to the release property of the support film or the solubility in the test developer. The invention is disclosed in the patent document 2, which is provided with the intermediate of polyethylene glycol and hydroxyethyl cellulose. The technique of the layer. However, this technique is extremely difficult to control the peelability between the support film and the spring, and the composition of the intermediate layer must be studied. Patent Document 3 discloses that ((10)yPr〇Pylene) An oxygen-containing propylene-based polyol disk (a phantom core ^ 'a photosensitive resin layer containing /, (meth) acrylic acid partially esterified is disclosed in 4, the middle layer will be two:. Alcohol, a polymerization degree of 4_ or more, a polyester resin, a polyester resin made of a hydrocarbon, and a binary hydrazine/ethane, a carboxyl group-containing acrylic acid, and a group of t as a main component are selected. To 0^ night surgery, but the degree and high density, In the case of a printed wiring board having a fine conductor pattern, a substrate for COF requiring high resolution is required for the production of a printed circuit board having a fine conductor pattern. In the case of producing a substrate for a semiconductor package, a photosensitive resin which exhibits high resolution, has no wrinkling on the sidewall of the resist pattern after development, has no surface depression, and exhibits minimal halation after development. [Patent Document 1] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Problem to be Solved by the Invention] An object of the present invention is to provide a photosensitive resin laminate which exhibits high resolution and high density. Properties, the side wall of the photoresist pattern has no warp, the surface of the photoresist pattern has no depression, and the characteristics of the halo after development are extremely small, and the support film has no problem in peelability, and The present invention provides a method for forming a photoresist pattern using the laminate and a method for producing a conductor pattern. [Technical means for solving the problem] The present inventors have studied to solve the above problems, and as a result, found that by using a specific The photosensitive resin laminate can provide a photosensitive resin laminate, which has no problem in peeling property of the support film, and exhibits high resolution and high adhesion after development, and the sidewall of the photoresist pattern has no warpage, and the resist pattern The surface of the film is not recessed, and the halo after development is extremely small, thereby completing the present invention. P is a photosensitive resin laminate, a photoresist pattern forming method, and a method for producing a conductor pattern as follows: 120566.doc 1353489 (1) A photosensitive resin laminate, characterized in that it comprises a support film on the support film, and the thickness of the support film is 0. 丨μηι or more, 1 〇 ^ claw to ^; the intermediate layer and the photosensitive resin layer In the above, the intermediate layer is composed of polyvinyl alcohol and a compound selected from the group consisting of compounds represented by the following formula (I).

Ri-〇-(CH2CH20)ni-R2 (I) (The heart and the ruler 2 are Η or eh, and these may be the same or different, and are the integers of 扒.) (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 contains (a) a carboxyl group content in terms of acid equivalent 100~6〇〇, and the weight average molecular weight is 5000~500000 adhesive resin: 2〇~9〇% by mass; (匕) at least one photopolymerizable unsaturated compound: 3~7〇 quality (hook (4) The photosensitive resin laminate according to (7), wherein the (4) binder resin contains (benzyl) benzyl acrylate as a copolymer component. (3) The photosensitive resin laminate of (4), wherein at least one of the photopolymerizable unsaturated compounds is at least selected from the group consisting of compounds represented by the following formulas (π) to (νι) An unsaturated compound capable of photopolymerization. 120566.doc 1353489 [Chemical 1] ?4 严r5 状^'#2_η2-ρ2^η3~_4α>η4_"^9 rm Ο » 2(11) (wherein R4 And R5 is Η or CH3, and these may be the same or different and n5 is independently an integer of 3 to 20.) n3, n4 [ 2]

0 Re 〇~(A-0) n6- (B-O) n8-C-C=CH2

H3C—C—CH3 0 (HI) 〇~ (A—0) (17—(B-0) n9~C—C=CH〇II 1 2 0 R7 (wherein R·6 and R7 are H or CH3 , these may be the same or different, A is C2H4, B is CH2CH (CH3), n6+n7*2 ~ 40 integer, ~ is an integer of 0~40, ~ and n? are independent of the integer of 39, respectively ~ and ~ are independently integers from 0 to 40; _ (eight_〇)_ and _(1〇)_ repeating units can be arranged randomly or as blocks; in the case of blocks, (B_ 〇)- In the order of 'any one can be on the diphenyl side.) I20566.doc -10- 丄功489 [化3] 〇Re 9— (D —0) mi — (E—0 〉阳—(} A C=CH2 person (10)

H3C-C-CH3

0-(D-0)m2—(E-0)m4—g~C=CH5 II 1 ^ 〇Rs (wherein R8 and R9 are H or CH3, and these may be the same or different 'D is C2H4, E is CH2CH(CH3), mdrr^ is an integer of 2~40, m3+ni4 is an integer of 〇~40, 1111 and 1112 are each an integer of 1~39, and 1113 and 1114 are each an integer of 0~40; -(D-Ο)- and ·(Ε_〇)_The arrangement of repeating units can be random 'can also be block; in the case of block, it is gas D-Ο)- and -(E-Ο) - Any order can be on the cyclohexyl side. )

[Chemical 4] CH'

R 11 NHC0-(0CHCH2)m5-0C0-C=CH2 (V) ?10 NHC0-(0CHCH2)m6-0C0-C=CH2 CH,

R 12 (wherein Rl〇 is the inverse of the stone 4~12, the 2nd organic group of the ancient MA η, R丨〗 and R12 is H or CH3'. These may be the same or better ^ - \ JI , Π15 and m0 are independent of the total of 120566.doc • 11 · ?13 [化5] tt 〇-(A, 0)m7L8.

(VI) In the second H, 'RU is the occupational yang, Rl4 is an alkyl group having a carbon number of 4 to 14, and A is B is CH2CH(CH3) ′ is an integer of ～12, which is called 〇~. The sigh of 'm9 is an integer of 〇~3. (a · „ column can be “number of entries, . (A·0)···-0)--repetition of the unit and: random” can also be block In the case of a block, in the order of _(a, _〇)_ -〇)-, either can be on the phenyl side). A method for forming a resist pattern is characterized in that the photosensitive resin laminate of any one of items (1) to (5) is laminated on a plate or a metal-clad insulating plate. The step of laminating the surface, the step of exposing the peeling support film to the exposure, and the developing step of removing the unexposed portion by development. (7) The method for producing a kind of conductor pattern is characterized in that it is by 0 (6) The method of etching/coating a substrate on which a photoresist pattern is formed. [Effects of the Invention] According to the present invention, it is possible to provide a support for the peeling property of the crucible without problems, and after development, exhibits high resolution and high adhesion, and the photoresist a photosensitive resin laminated body having no surface on the surface of the resist pattern, no recess on the surface of the resist pattern, and a small halo after development, and a method for forming a photoresist pattern using the laminated body, and a method for manufacturing a conductor pattern of I20566.doc 1353489 [Embodiment] The present invention will be specifically described below. The photosensitive resin layering system of the present invention sequentially laminates an intermediate layer having a layer thickness of 0.1 μm or more and 1 μm or less on the support film. The photosensitive resin laminate of the photosensitive resin layer of the present invention is characterized in that the intermediate layer is composed of a polyethylidene alcohol and a compound represented by the following formula (I) A compound selected from at least one of the group consisting of R|-〇-(CH2CH20)n]-R2 (I) (Ri and R2 are Η or CH3, and the same or different, ηι is 3~ In addition, the weight ratio of the polyethylene glycol to the intermediate layer is preferably from 50% by mass to 95% by mass in terms of developability and cost. More preferably, it is 70% by mass. More than or equal to, more preferably, it is 75 mass% or more, and 9 mass% or less. As a weight ratio of the compound of the formula (I) to the intermediate layer, from the viewpoint of supporting the peeling property of the film and the intermediate layer, It is preferably 5% by mass or more and 5% by mass or less, more preferably 5% by mass or more and 3% by mass or less, and more preferably 5% by mass or more and 15% by mass or less. Polyvinyl acetate is produced by inspecting the poly(vinyl alcohol) used in the present invention. The weight average molecular weight is preferably 1,000 to 1 Torr, and the weight average molecular weight is from 5,000 to 50,000 in terms of oxygen shielding property and developability. 120566.doc 1353489 It is preferable that the degree of specialization is 5 〇 mol% or more, more preferably 7 〇 mol% or more, more preferably 80 mol% or more. In the photosensitive resin laminate of the present invention The weight average molecular weight of the polyvinyl alcohol used is a gel permeation chromatography (GPC. gel permeation chromatography) manufactured by 曰本分光(股). (^ : GulHver ^ pu 1 predicate, column: Showa Denko (〇) manufactured by Sh〇dex (registered trademark) (HFIP-805, HFIP_803) 2 in series, flowing layer solvent: hexafluoropropanol, using polystyrene standard sample analysis curve), as the weight average molecular weight (in It is obtained by converting polystyrene. The compound represented by the above formula (1) is preferably 3 or more in terms of odor, and is preferably 25 or less in terms of compatibility with the polyethyl alcohol and developability. ...more preferably 5 or more, 2 inches or less, more preferably 7 or more, 15 to T. As a compound represented by the above formula (1), a monomer having a mean molecular weight of 200 (PEG 200 manufactured by Sakamoto Oil Co., Ltd.) and a polyethylene glycol having an average molecular weight of 3 Å (Japanese oil and fat shares) PEG3〇〇 manufactured by 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 (manufactured by Nippon Oil & Fats Co., Ltd.) PEG600), polyethylene glycol having a molecular weight of one side (PEG1000 manufactured by Nippon Oil & Fat Co., Ltd.), or polyethylene glycol monomethyl ether having an average molecular weight of 4〇〇 (Uniox M-400 manufactured by Nippon Oil & Fat Co., Ltd.) ), polyethylene glycol monomethyl ketone with an average molecular weight of 550 (Uniox M-550 manufactured by Nippon Oil & Fat Co., Ltd.), polyethylene glycol monomethyl ether having an average molecular weight of 1 ( (manufactured by Nippon Oil & Fats Co., Ltd.) Uni〇xM_1〇〇〇). I20566.doc 1353489 Further, in the intermediate layer, in addition to the above, a well-known water-soluble polymer may be added. Specific examples of the water-soluble polymer include a polyethylene salt, a maleic acid needle water-soluble salt, a certain base-based powder, a water-soluble salt, a polyacrylamide amine, a polyamine amine, and a polyacrylic acid water-soluble salt. Class, gelatin, polypropylene glycol, polyethylene. Bilo (four). As a specific example of the polyethylene sulphate, the weight average molecular weight of Japan Catalyst Co., Ltd. is 40, _ K_15, the weight average molecular weight is 丨 (10) (4), and the weight average molecule is 900,000 Κ -85 The weight average molecular weight is 〇〇〇〇〇〇·9〇 of 1〇〇〇〇〇〇. The thickness of the layer of the intermediate layer is preferably Π)_ or less, more preferably 5 (four) or less, more preferably 3 μπι or less in terms of resolution, adhesion, and developability. Further, from the viewpoint of oxygen shielding properties, it is preferably 1 叩 or more, more preferably 0.5 μηι or more, and still more preferably 丨 μηη or more. In the present invention, in order to achieve high resolution, it is preferred to peel off the support film before exposure. In the case where the support film is peeled off before the exposure, the support film may be a transparent film through which light for exposure is transmitted, or may be an opaque film. As the support film of the present invention, there is a human resin film represented by polyethylene, polypropylene, polycarbonate or polyethylene terephthalate having a thickness of 10 Å or more and 1 Å or less. Generally, it is preferred to use a polyparaphenylene-1-ethyl ester 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 or more. Since the photosensitive resin laminate of the present invention has the above-described structure because of the intermediate layer, the release film of the support film is excellent, that is, it is excellent in that it is attached to the interlayer of the support film and the intermediate layer when the support film is peeled off before the exposure step. Then, the adhesive layer is lower than the adhesive force of the photosensitive resin layer of the intermediate layer disk. 120566.doc -15- 1353489 Further, as the photosensitive resin laminate of the present invention, the laminated film is sequentially laminated on the support film. The intermediate layer and the photosensitive resin layer may further be laminated with a protective layer. As a property of the protective layer, it is important that the interlayer adhesion between the photosensitive resin layer and the protective layer is lower than the interlayer adhesion between the support film and the intermediate layer. Therefore, the protective layer can be easily peeled off during lamination. As a protective layer, the thickness is 10 to 1 〇〇μηη, which is represented by polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. The synthetic resin film is preferably a polyethylene film or a polypropylene film. The upper limit of the film thickness of the photosensitive resin layer of the present invention is preferably 1 〇〇 pm or less, more preferably 疋 50 μ π ι or less. more The lower limit of the film thickness is preferably 〇5 μπι or more, more preferably 1 μm or more. The photosensitive resin layer in the photosensitive resin laminate of the present invention is more preferably Preferably, it is a layer containing a photosensitive resin composition containing (a) an acid equivalent, a carboxyl group content of 1 〇〇 6 〇〇, and a weight average molecular weight of 5 〇〇〇 5 5 〇〇. Resin for binder: 2〇~9〇% by mass, 0) at least one photopolymerizable unsaturated compound: 3 to 7〇% by mass, (c) photopolymerization initiator: 0.1 to 20% by mass In the following, the photosensitive resin composition used for the photosensitive resin laminate of the present invention will be described in detail. (a) The amount of the carboxyl group contained in the resin for the binder is preferably from 100 to 600, more preferably in terms of acid equivalent. Preferably, it is 25 〇 to 45 〇, and more preferably 3 〇〇 to 45 〇. The so-called acid equivalent refers to the quality of the resin for the binder of the center and the right side of the carboxyl group. .doc 1353489 Adhesives are used in the tree, and the system is pure It is necessary for the developability or the releasability. The acid equivalent is preferably in terms of resistance to reproducibility, resolution, and adhesion, and is preferably from the viewpoint of developability and releasability. It is below 6 inches.

U) The weight average molecular weight of the resin for the binder is preferably 5'_~_,_. The weight average molecular weight of the binder resin is preferably 500 or more in terms of resolution, and is preferably 5,000 or more in terms of edge fusion. In order to better exert the effects of the present invention, the weight average molecular weight of the binder resin is preferably from 5'000 to 200,000, more preferably from 5, -1 to 1 Torr. The degree of dispersion (also known as the distribution in the knife) can be expressed as the ratio of the weight average molecular weight to the number average molecular weight of the following formula. (Dispersity) = (weight average molecular weight) / (number average molecular weight). The degree of dispersion is about 1 to 6, and preferably it is 4. In addition, the measurement of the acid equivalent was carried out by a potentiometric titration method using a Hignata automatic titrator (COM-555) manufactured by Hiranuma Industries Co., Ltd., using a sodium hydroxide aqueous solution of 〇·ι m〇i/L. The molecular weight ' is a gel permeation chromatography (GPC) manufactured by Japan Spectrophotometer (GPC) (^. Gulliver, PU-1580, column: Shodex (registered trademark) manufactured by Showa Denko (share) (KF_8〇7 , kF-8〇6M, KF-806M, KF-802_5) 4 in series, flowing layer solvent: tetrahydrofuran, analysis using polystyrene standard sample (Sh〇dex STANDARD SM-105 manufactured by Showa Denko) Curve)) The weight average molecular weight and the number average molecular weight (converted in terms of polyphenylene) were obtained. U0566.doc • 17-1353489 (a) A resin for a binder obtained by polymerizing one or more of the following two monomers. 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 acrylic acid and methacrylic acid. The same is true below. The second monomer is a non-acidic & is a compound having a polymerizable unsaturated group in the molecule. This compound is selected to maintain the visibility of the photosensitive resin layer, the resistance in the etching and plating steps, and the flexibility of the cured film. As the compound, an alkyl (meth)acrylate such as (mercapto) decyl acrylate, (mercapto) acrylate, (mercapto) acrylate, 2-ethyl (meth) acrylate can be used. Hexyl ester, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylonitrile, benzyl (meth)acrylate, methoxy (meth)acrylate , (meth)acrylic acid, brewing, methyl (meth) acrylate, methyl (meth) propyl benzoate, phenoxyethyl (meth) acrylate, (methyl) Phenyl acrylate, (mercapto)acrylic acid toluene S, (fluorenyl) propyl (10) naphthalene _, an ethylene compound having a phenyl group (for example, styrene). In particular, from the viewpoint of analytical properties and developer cohesiveness, (meth)acrylic acid benzyl vinegar is preferred. (4) The resin for the binder is preferably added in a solution obtained by diluting the mixture of the first monomer and the second monomer with a solvent such as acetone, methylethyl or isopropanol. The hydrazine polymerization hair styling agent, such as benzamidine peroxide, azoisobutyronitrile, and An hydrazine, is further stirred and heated to be synthesized. There is also a 120566.doc •18· while the mixture is added to the reaction solution. It is also possible to add a solvent after the anti-beam, and then add the solvent to adjust the desired condition: f. As a synthesis method, in addition to solution polymerization, = bulk polymerization, suspension polymerization, or emulsion polymerization. The square 'a ratio of the resin for the (a) point-to-point compound to the total of the composition of the sensible drink is more than 2 〇 to 9 〇 mass%, more preferably 3 〇 to 70 mass%. The resist pattern has characteristics as a photoresist, and is preferably at least % by mass and not more than 90% by mass from the viewpoint of having sufficient resistance to the cover hole, _, and various clocks and v steps. (b) at least one photopolymerizable unsaturated compound, from the viewpoint of high resolution, a preferred group is a group consisting of compounds represented by the following general formulae (II) to (VI) At least one of the photopolymerizable unsaturated compounds selected for use in the photosensitive resin composition is selected. [化6] ^ 〒H3 R5 0 H2C =〇-〇〇-(〇2Η40)η2-(ΟΗ2〇ΗΟ)η3—(〇2Η40)η4-(|-〇::ΟΗ2 (π) 0 (where, R^RS is Η or CH3, and these may be the same or different, and η3 ' η4 and η5 are each independently an integer of 3 to 20.) 120566.doc •19- 1353489 [Chem. 7] 0 Re 0 — (A—〇 ) ηβ-(Β-Ο)

(III)

(wherein R6 and R7 are H or CH3, and the same may be the same or different, A is C2H4, B is CH2CH(CH3), n6+n7 is an integer of 2 to 40, and 118+119 is an integer of 0 to 40. , 116 and n7 are each independently an integer from 1 to 39, and 118 and n9 are each independently an integer of 0 to 40; the arrangement of -(A-Ο)- and -(B-0)-repetition units can be random or In the case of a block; in the case of a block, in the order of -(A-Ο)- and -(B-〇)-, either can be on the diphenyl side.) [Chem. 8]

H3C—C_CH3 person (IV)

O-(DO) m2—(E-〇)m4—c—C=CH? II ' 0 Rg (wherein R8 and R9 are H or CH3, which may or may not be the same, D is 120566.doc • 20· 1353489 C2H4, E is CH2CH(CH3) 'Call + is called an integer of 2~4〇, called + is an integer of 〇~40, m丨 and 叫 are independent of 整数~39 integer, called and called respectively Independently an integer from 0 to 40; ·(〇_〇)_ and _(匕〇)_ The arrangement of repeating units can be random or block; in the case of blocks, _(D〇) and -(Ε·0)- in terms of order, either can be on the cyclohexyl side.) [Chem. 9]

Ch3

R 11 NHCO-(OCHCH2)m5-OCO-C=CH: RioNHCO-(OCHCH2)m6OCO-p=CH' ch3 (V)

R 12 (wherein R10 is a divalent organic group having a carbon number of 4 to 12, and R11 and R丨2 are H or CH3, and these may be the same or different, and are called independent integers of 15 respectively.)

[化10]

(R14)m9 (wherein Ri3 is Η or CH3' R14 is an alkyl group having 4 to 14 carbon atoms, A' is C2H4 'B' is CH2CH(CH3)' m7 is an integer of 1 to 12, and is called ❹~ 12 of I20566.doc • 21 · 1353489

It is better to say 'n3Un543 or more. From the viewpoint of the sensitivity per unit mass of light and the concentration of the tongue portion, &, ~ and ~ are preferably 2 G or less. Specific examples of the compound represented by the above formula („) used in the present invention include, for example, preferably both ends of a polypropylene glycol having an average addition of U-mole epoxy propylene. Dimethyl methacrylate of diol which is formed by adding an average of 3 moles of ethylene oxide. In the compound represented by the above formula _, the "heart" must be 4 Å or less - if it exceeds 40, the sensitivity is considered. It is not good. It is preferably less than 30.

An integer, called an integer of 〇~3; -(Αι·〇)_&_(Β,_〇) The arrangement of repeating units can be random or block; in the case of a block, (△ , _〇)_ and -(Β,·〇)-, in the order of any, can be on the phenyl side). The compound represented by the above formula (II) is a compound represented by the above formula (ιπ) used in the present invention from the viewpoint of boiling point and odor, and the average of the two parts of the formula (4) The addition has 2 moles of epoxy propylene and an average addition of 6 moles of epoxy-based polyalkylene glycol di-f-propyl acetoacetate, or the average addition at both ends of the two-year-old eight There are 2 moles of propylene oxide and a dialkyl acrylate of a polyalkylene glycol with an average addition of 15 moles of ethylene oxide. The average addition of bisphenol A to both ends is 5 moles. Ethylene glycol polyethylene glycol dimethyl acetoacetate (Nippon Nakamura Chemical Industry Co., Ltd. NK vinegar BPE-500)' and the average addition of bisphenol A at both ends have 2 Mo Polyethylene glycol dimethacrylate of ethylene oxide in the ear (NK ester BPE-200 manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). The compound t, mi+m^m3+m4 represented by the above formula (IV) must be I20566.doc -22 to 1353489 4 Å or less, and if it exceeds 40, it is not preferable from the viewpoint of sensitivity. Preferably, it is 30 or less. Specific examples of the compound represented by the above formula (IV) include 2,2-bis{(4-propenyloxypolyoxy)cyclohexylpropanepropane or 2,2_double{(4- Methyl propylene methoxy group / ethyl ethoxy) cyclohexyl} propyl & The compound has an ethoxylated ethoxy group (ethyiene〇xy), preferably from a mono-extended ethoxy group, a diethyleneoxy group, a triethyleneoxy group, a tetraethyleneoxy group, a pentethyleneoxy group, Hexaethylene, hexaethyleneoxy, oxime, hexaethyleneoxy, decyleneoxy, eleven ethyleneoxy, dodecaethyleneoxy, thirteenthyloxy, tetradecyl Dilute gas base; the choice of the group consisting of -products and fifteen Ethyloxy groups. Further, it can also be exemplified by 2,2_bis((4-acryloxypolyoxy)cyclohexyl}propyl or 2 2-雔/,/ΐ, and {(4-methacryloxylated) Alkenyloxy)cyclohexyl}propane. As the polyalkenyloxy group (P〇lyalkylen_y) of the compound, it can be exemplified by a mixture of ethyleneoxyl and propyleneoxy-(10)xy), preferably eight. a structural addendum or a random structure adduct of a dilute oxy group and a dipropoxy oxy group, and a block of tetraethyleneoxyl and tetrapropyloxy groups, #上土_ constituting w adduct or random Constructing adduct, fifteen

Blocks of ethyleneoxyl and propyleneoxy. A a slaved adduct or a randomly constructed adduct. Among these, the most preferred is 2,2-decyloxy)cyclohexyl}propane. ·Methylpropyl decyloxypentaethylene The compound represented by the above formula (V), the formula ^ 15 ' can not be sufficiently sensitive. Right 叱 or more than the formula "Rio is a carbon number 4 to 12 eve? The valence organic group is a residue of a diisocyanate. The number 12 is 2. Specific examples of the octagonal compound represented by the above formula (V) include two 120566.doc • 23-cut 3489^ cyanide vinegar compounds, for example, diisocyanine hexane vinegar, Isocyanate toluene vinegar, or diisocyanoguanidine 2,2,4•trif-hexane diacetate, and a compound having a trans group and a (meth)propenyl group in one molecule, for example, 2-hydroxypropyl acrylate, An amino-based f-ester compound of propylene glycol acrylate. Specifically, there is a reactant of hexamethylene diisocyanate and propylene propylene monomethacrylate (Blemmer-PPiooo, manufactured by Emu Oil Co., Ltd.). The compound represented by the above formula (vi), if called or called more than 12, is not

The method obtains sufficient sensitivity. If m9 exceeds 3, sufficient sensitivity cannot be obtained. Specific examples of the compound represented by the above formula (VI) include, for example, a polymerization of polypropylene glycol having an average addition of 2 moles of propylene oxide and an average addition of 7 moles of ethylene oxide. Addition of ethylene glycol to indophenol: The acrylic acid of the product is 4_n-decylphenoxy heptaethylene glycol acrylic acid. It is also possible to exemplify a lactic acid ester of a compound which is added to an average of 8 moles of ethylene oxide to a compound of 4, n-decylphenoxy octaethylene glycol. Acrylate (M-114, manufactured by Toagos Corporation) » As (b) at least one photopolymerizable unsaturated compound, does not belong to the above formula (III), (IV), (V), (VI) And a compound of the group formed by the compound represented by (νπ), which has an unsaturated compound which can be photopolymerized as shown below. For example, hydrazine, 6-hexanediol di(meth)acrylic acid 8 fluorene, 1,4-% hexanediol di(meth) acrylate, polypropylene glycol di(meth) propylene I s 曰, poly Ethylene glycol bis(indenyl) acrylate, 2-di(p-hydroxyphenyl)propane di(meth) acrylate, tris(meth) acrylate, tris(hydroxymethyl)propyl bis(indenyl) acrylate g, polyoxypropyl trimethylolpropane tris (a 120566.doc •24-1353489 base) acrylate, polyoxyethyl trimethylolpropane triacrylate, pentaerythritol tetra (T-) acrylate Dipentaerythritol penta(meth)acrylic acid s曰, dihydroxydecylpropane triglycidyl ether tri(meth)acrylate bisphenol A-glycidyl ether di(meth)acrylate, phthalic acid p-hydroxyl Propyl ester β, —(methylpropoxy)propyl ester, phenoxy polyethylene glycol (mercapto) acrylic acid, polypropylene glycol mono (meth) acrylate. At least one photopolymerizable unsaturated compound selected from the group consisting of the compounds represented by the above formulas (II) to (VI), and the ratio thereof to the total photosensitive resin composition is 3 to 7 % by mass. The scope. From the viewpoint of the degree of resolution, it is 3% by mass or more, and the viewpoint of the flexibility of the f-light-resistance pattern is 70% by mass or less. Better is 3 to 3 〇 quality. ,. the following. (b) The ratio of the overall photopolymerization of the photopolymerizable unsaturated compound to the total of the photosensitive resin composition is preferably 3% by mass or more from the viewpoint of sensitivity. Good is 7〇 quality: below. More preferably, it is 10 to 6 % by mass, more preferably 15 to 55% by mass.

As the (4) photopolymerization initiator, a compound which can be polymerized by a variety of active light rays can be used as a starting point. (8) A compound which can be polymerized by photopolymerization uses a compound group represented by the following formula (VII). ', spit dimer'? Especially high-resolution view of ',: two-state. Implementation of the wilderness

L2〇566.dOC •25· 1353489

[ηη]

And any of the halogen groups, p, q and r are each independently an integer of i 5 . The covalent bond of the two arylene groups in the <triaryl imidazole dimer represented by the above formula (VII) may be i, r·, 1 > 2, ... M, _, 2, 2 , _, 2, 4, _

Or a 4, 4 bond or the like, preferably a compound of the above formula (VH) wherein the covalent bond is 丨, 〖, - bond. Among the 2,4,5-triaryl imidazole dimers, for example, 2_(o-phenyl) 4,5-stupyl imidazole monomer, 2-(o-chlorophenylbis(metamethoxyphenyl)imidazole Dimer, 2-(p-nonyloxyphenyl)-4,5-diphenylimidazole dimer, particularly preferably 2-(ozone)- 4,5-diphenylimidazole dimer The (4) photopolymerization initiator used in the present invention is preferably a system in which a 2,4,5-triarylimidazole dimer represented by the above formula (VII) is used in combination with p-aminobenzophenone. Examples of the p-aminobenzophenone include p-aminodiphenyl ketone, p-butylaminoacetophenone, p-didecylaminoacetophenone, p-dimethylaminodiphenyl ketone, and ^. Bis(ethylamino)diphenyl ketone, ρ,ρ|bis(dimethylamino)diphenyl_ι[Michler, s ket〇ne], ρ ρ, _ double (monoethylamino)diphenyl ketone, ρ,ρι_bis(dibutylamino)diphenyl I20566.doc •26- 1353489 Also as a photopolymerization initiator other than the above-mentioned compounds, G-types such as 2-ethyl hydrazine, 2-tert-butyl hydrazine, benzoin ethers, such as Aroma, benzoin ether, benzoin ethyl ether; acridine compounds, such as 9-phenyl acridine; others, benzyl dimethyl ketal, benzyl diethyl ketal. Also 'also ketoxime, such as a combination of sultone, 2,4-diethyl sultone, 2-xanthone and a tertiary amine compound such as an alkyl dimethyl benzoate compound. Terpene esters, for example, have

1-phenyl-1,2-propanedione-2-o-benzylidene hydrazine, 1 phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) hydrazine. Further, an N-aryl_α-amino acid compound can also be used, and among these, Ν-phenylglycine is particularly preferable. The photosensitive resin composition in the photosensitive resin laminate of the present invention preferably contains 〇. ^20 mass 0 / 相对 with respect to the entire photosensitive resin composition.

(c) a photopolymerization initiator. From the viewpoint of obtaining sufficient sensitivity, it is preferably 0.1% by mass or more, and it is preferably 2% by mass or less from the viewpoint of preventing reflection of light on the surface of the substrate during exposure. A basic dye can be used in the photosensitive resin composition. Specific examples of the basic dye include magenta, phthalocyanine green, auramine base, Chalcoxide Green s, crystal violet, methyl orange, Nile blue 2B, and malachite green. ) Manufacture of the eight '(registered trademark) MALACHITE GREEN), alkaline blue 2 〇, diamond green (Aizen (voice book) trademark Diam〇nd (10) deleted gh), Victoria Pure Blue (Budong Valley) Chemical (share) system gossip (10) (registered trademark) VICTORIA PURE BLUE). 120566.doc ·27· 1353489 The photosensitive resin composition may further contain a color-developing dye which develops color by light irradiation. As the chromogenic dye to be used, for example, there is a combination of a leuco dye and an i-form. As the leuco dye, for example, tris(4-didecylamino-2-methylphenyl)methane [colorless crystal violet], tris(4-dimethylamino-2-methylphenyl)methane [ Colorless peacock green]. Examples of the halide include pentane bromide, isopentane bromide, oxime, 2-dixi-2-methylpropane, i, 2. Erdiyiyuan, desertified diphenyl pit, and two. Methylbenzene, dibromomethane, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, diethyleneacetamide, iodopentane, iodoisobutane, 1 1,1,3 gas-2,2-bis(p-chlorophenyl)ethane, hexachloroethane, a halogenated triazine compound. Examples of the halogenated triazine compound include 2,4,6 tris(trimethylmethyl)s-triazine and 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)· Triazine. Among such chromogenic dyes, tribromophenyl sulfone and a leuco dye are used, and a combination of δ or a oxadiazine compound and a leuco dye is used. In the case of a _-form, a photo-resin composition The content of the toothed material in the middle is preferably 〇·01 to 5 mass%. The content in the case of containing an anionic dye and a leuco dye is preferably 〇 〇 ι 〜 〇 〇 mass % in the photosensitive :: composition. In terms of the coloring of the filling knife (color rendering property), it is preferable that the mass % differs from the unexposed portion in terms of exposure, and the viewpoint of maintaining storage stability 11 is preferable. 10% by mass or less. Further, it is preferred that the photosensitive resin composition of the present invention contains a radical polymerization inhibitor or a benzotriazole. I20566.doc -28- 1353489 as such a free dragon; from the base polymerization inhibitor, for example, p-methoxyphenol, hydroquinone, ortho-triphenyl-copper, 2,6-two third-butyl ...the second butyl tea, chlorinated _ soil p-cresol, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylene double (4 US tertiary butyl phenol), nitroso-based amide amine salt, diphenyl nitrosamine. Further, examples of the benzoquinone=ground phase-azole include 1,2,3·benzotriazole, _milk-1,2,3·benzoquinone, and heterogeneous 7 «· ^ _ again ( N_2_ethylhexyl)aminomethylene-1,2,3-

This triterpene, bis(tetra)-ethylhexyl)aminomethylene·ΐ2,3·methylbenzoquinone trisal, bis(indolyl 2,ylethyl)aminomethylene benzoquinone triple spit. =, as a few base benzoquinones, for example, 4: a few groups ... ... - benzoquinone, 5 old deca 2,3-benzoquinone trisal, called NU-ethylhexyl) = (four) Tris, Ν·(Ν,Ν-ylethyl)aminomethylene sulfhydryl albendazole, n_€N r Ρ f, phenyl hydrazine tris, N-2-ethylhexylamine Base rebellion of free radical polymerization inhibits clumsy three. The total addition amount of the sitting class is preferably 〇. /. More preferably, it is one mass%. The photosensitive tree is added to the photosensitive tree, and the amount is preferably 0.001% by mass or more, and is preferably 5% by mass or less from the viewpoint of maintaining light sensitivity. These radical polymerization inhibitors or benzotriazole compounds may be used singly or in combination of two or more. Further, the photosensitive resin composition may contain a plasticizer as needed. As such a plasticizer, there are phthalates (for example, monoethyl terephthalate), o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate 120566.doc -29- 1353489 can, lemon Acid triethyl vinegar, acetonitrile citrate triethyl sulphate, ethyl succinyl tri-n-propyl citrate, acetyl citrate tri-n-butyl acrylate, polypropylene glycol, polyethylene glycol, polyethylene glycol burning riddle, Polypropylene glycol base bond. The content in the case of containing a plasticizer is preferably from 5 to 5% by mass, more preferably from 5 to 30% by mass, based on the photosensitive resin composition. 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 from the viewpoint of suppressing insufficient hardening or cold flow, it is preferably Μ mass ° / 〇 Hereinafter, a method of producing a photosensitive: lipid laminate according to the sequential build-up support film, the intermediate layer 2, the photosensitive resin layer 3, and the protective layer 4 as needed will be described with reference to FIG. 2 and FIG. First, a polyethylene glycol, for example, a PVA-205 resin manufactured by Ku-Y Co., Ltd., and a compound selected from the group consisting of compounds represented by the above formula (1) (1), θ is solid. The fractional ratio is 5 to 30 by 1%. The mixture is slowly added to water heated to 6 Torr to 9 Torr, and stirred for 1 hour, and uniformly dissolved to obtain a homogeneous aqueous solution of the composition of the above intermediate layer. The viscosity of the homogeneous aqueous solution of the group of polyvinyl alcohol-containing intermediate layer is preferably adjusted to 10 to 500 mp., ± b S, and then the aqueous solution is coated using a bar coater or a roll coater. The support film 1 is attached to the supporter 1 and dried to obtain the support film 1 with the intervening layer 2. In addition, the photosensitive resin composition was produced at the beginning of the week and the liquid was 5 weeks old. The viscosity of the blending agent of the photosensitive resin group σ is preferably such that ρ ' 25 C is added in a manner of 500 to 4000 mPa·sec. As the ethyl ketone (M is represented by (4), it is used: the agent 'has a methyl 4 alcohol, for example, a: 120566.doc 1353489 alcohol, ethanol, isopropanol β using a bar coater or a roll coater The photosensitive resin layer 3 containing the photosensitive resin composition is applied onto the intermediate layer of the support film i with the intermediate layer 2 in the same coating method as the intermediate layer 2, and dried. The photosensitive resin layer 3 is laminated on the photosensitive resin layer 3 to produce a photosensitive resin laminated body. An example of a method of producing a printed wiring board using the photosensitive resin laminated body of the present invention will be described.

The printed wiring board is manufactured through the following steps. (1) In the case where the laminating step has a protective layer on the photosensitive resin laminate, the peeling layer is peeled off on the substrate 'for example, a copper-layer; or the heat-roller can be used on the K-base substrate. Its close steps. (2) Exposure step The support 胄 is peeled off from the photosensitive resin laminate to make the wiring with the desired

The mask film of the pattern is adhered to the intermediate layer ±, and the exposure step is performed using an active light source. (•3) Developing step The step of forming a hardened photoresist on the substrate by dissolving or dispersing the intermediate layer and the unexposed portion of the photosensitive wax layer using an organic developer. (4) #刻步骤 or mineral film step spraying on the formed photoresist circle (4) the step of engraving the copper surface not covered by the photoresist pattern, or copper on the steel surface not covered by the photoresist (4) The steps of processing the mineral film represented by solder, recording and tin. This makes it possible to make a conductor pattern of 120566.doc. (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 dust mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet fluorescent lamp, and a carbon solitary xenon lamp. Also, in order to obtain a finer photoresist pattern, it is more preferable to use a parallel light source. In the case where the influence of dust or foreign matter is to be minimized, exposure (close exposure) is performed in a state where the reticle is suspended on the support film by several tens or more and several hundred (four) or less. Further, as the alkaline developing solution used in the above (3) developing step, an aqueous solution of sodium carbonate or sodium carbonate may be mentioned. The aqueous solution can be selected according to the characteristics of the resin layer, and an aqueous solution of sodium carbonate of 0.5% by mass or more and 3% by mass or less is usually used. The above (the engraving step can be carried out, for example, by an acid money engraving, an inspective method. These methods can be selected to suit the dry film resist produced. As the above (5) stripping step, the estimated τ 彳 history The alkaline stripping solution used is an aqueous solution which is more alkaline than the aqueous solution which is used for development, and is, for example, more than 1% by mass, 5% by mass ^&amp; The following sodium hydroxide or sodium hydroxide aqueous solution. In the 'Selective coating step 愔 It ^ time' also has a stripping photoresist pattern and the light-etched pattern under the Xia ψ + & ^ The case where the copper surface of the r nr path is shown. Hereinafter, an embodiment of the present invention will be described in detail by way of examples and examples. [Examples] 120566.doc -32 - 1353489 Hereinafter, the evaluation of the examples and comparative examples is disclosed. Sample preparation method and evaluation method and evaluation result of the obtained sample. [Examples 1 to 12] and [Comparative Examples 1 to 3] 1 Production of Samples for Evaluation Samples of Photosensitive Resins in Production Examples and Comparative Examples The system was produced in the following manner: $ &lt;Photosensitive resin Production of the layered body First, the intermediate layer composition shown in Table 1 was slowly added to the water heated to 85 &lt; t so that the solid content ratio became 10% by mass, and the mixture was stirred for about 1 hour to be uniformly dissolved. And obtaining a uniform aqueous solution of the composition of the intermediate layer. As a support film, a polyethylene terephthalate film having a thickness of 16 μm was used, and the aqueous solution was applied onto the support film using a bar coater. Then, at 100 The mixture was dried in a drier at ° C for 3 minutes to form an intermediate layer on the support film. The thickness of the intermediate layer was 2 μηι. The photosensitive resin composition of the watch was uniformly coated with a bar coater. On the intermediate layer laminated on the support crucible, it was dried in a dryer of 95 c for 3 minutes to form a uniform photosensitive resin layer. The thickness of the photosensitive resin layer was 3 μm. Then, on the photosensitive resin layer On the surface, a polyethylene film having a thickness of 25 was used as a protective layer to obtain a photosensitive resin laminate. <Substrate> Analytical evaluation, adhesion evaluation including independent cylindrical adhesion, and photoresist pattern Halo Evaluation of the surface of the side wall of the valence and resist pattern, and the surface state of the photoresist pattern, were evaluated using S'Perflex manufactured by Sumitomo Metal Co., Ltd. with 8 pm copper foil laminated on an insulating resin. 120566.doc • 33·1353489 &lt;Lamination&gt; The protective layer of the photosensitive resin laminate of the present invention is peeled off by a heating roll laminator (A-70 by Asahi Kasei Engieering Co., Ltd.) at a roll temperature of 1051 Lamination was carried out. The air pressure was set to 0.35 MPa, and the lamination speed was set to 1.0 m/min. &lt;Exposure&gt;

After the support film was peeled off, the photomask film necessary for the evaluation of the photosensitive resin layer was exposed to an exposure amount of 80 mJ/cm 2 by an ultrahigh pressure mercury lamp (HMW-801, manufactured by 〇rc) on the intermediate layer. &lt;Development&gt; A 0.5 mass% Na2C〇3 aqueous solution of 30 t was sprayed at a specific time to dissolve and remove the unexposed portion of the photosensitive resin layer. At this time, the minimum time required to completely dissolve the photosensitive resin layer of the unexposed portion is set as the minimum apparent time. A hardened photoresist pattern is obtained in the case of actual development, which is twice the time of the minimum development time. Ding .... 2. Evaluation method

(1) Evaluation of peelability of support 貘 When peeling off the support film before exposure, the peeling property was evaluated (good): only the support film was peeled off. "Level. △ (may). A part of the intermediate x (not available) adhered to the support film: the support film and the intermediate layer - the same peeling layer and peeled off. (The surface layer is toughened between the photosensitive resin layer (2 Analytical evaluation using a line mask of the ratio of the exposed portion to the unexposed portion of 1 · 1 for I20566.doc • 34 - 1353489 is the mask film for exposure, in the above manner, after 15 minutes after layering The substrate was exposed and developed. The minimum mask width of the normally formed cured photoresist pattern was taken as the value of the resolution. The analytical performance was evaluated as follows. ◎ (Excellent): The resolution value was 5 μηι or less 〇 ( Good): The resolution value exceeds 5 μπι and is 1〇μηι or less △ (may): the resolution value exceeds 10 μπι and is 15 μηι or less 不可 (not): the resolution value exceeds the jaw claw ( 3) Adhesion evaluation A line mask which is an exposure portion alone was used as a photomask film at the time of exposure, and the substrate which was passed after lamination for 5 minutes was exposed and developed in the above manner. The hardened photoresist was normally formed. The minimum mask width of the pattern as the adhesion The value 'is evaluated as the following level. ◎ (Excellent) · The value of the 耆 property is 5 or less 〇 (good): The value of the adhesion is more than 5 μηι and is 1 〇 μηη or less △ (可)·密密The value of the property exceeds 1〇|^1111 and is 15μπι or less 不可 (not available): the value of the adhesion is more than 15 μπι (4) Evaluation of the independent cylindrical adhesion Using the cylindrical pattern mask which is the exposure portion as the exposure time In the above manner, the substrate subjected to lamination for 15 minutes is exposed and developed in the above manner. The minimum width of the cylindrical mask diameter which normally forms the hardened resist pattern is equal to the value of the independent cylindrical adhesion. The evaluation is as follows: ◎ (excellent): the value of the independent cylindrical adhesion is 5 μηι or less (good) The value of the independent cylindrical adhesion is more than 5 μηι and is less than 1 〇 μηι △ (may). Independent cylindrical dense The value of the property exceeds 1〇μιη and is 15 or less 12056o.doc •35· 1353489 X (not): the value of the independent cylindrical adhesion exceeds 15 μηη (5) The halo evaluation of the photoresist pattern uses the glass reticle as the The photomask film at the time of exposure was exposed and developed as described above. Evaluation 1 billion μηι line shape pattern of hardened resulting into the following grades of ◎ (excellent): harden the photoresist trace foot well without halation.

〇 (good): The traces of the foot of the hardened photoresist are good and the fainting is minimal. △ (可可): The vignetting of 3 μηι or less can be confirmed at the foot of the hardened photoresist. Χ (not available): The foot of the hardened photoresist can be confirmed to exceed 3 ^ yang. (6) Evaluation of the lifting of the side wall of the resist pattern Using a chrome glass mask, the laminate laminated on the substrate was exposed and developed in the above manner. The side wall shape of the photoresist pattern of the 1 〇 pm line of the obtained hardened pattern was evaluated as the following grade. 〇 (good): The formed photoresist sidewall has almost no warping.

△ (may) · The sidewall of the photoresist formed has a slight lift. χ (not): The formed photoresist sidewall has an upturn everywhere. (7) Evaluation of the surface state of the resist pattern Using a glass reticle, the laminate laminated on the substrate was exposed and developed in the above manner by μ, μμ士_ drought. The state of the photoresist surface of the obtained hardened pattern was evaluated as the following grade. The surface of the photoresist formed by the line (good) has almost no depression. (°) There is a fine depression on the surface of the photoresist formed. χ (not available): There are depressions on the surface of the shaped silk. 3. Evaluation results I20566.doc • 36 - 1353489 The evaluation results of the examples and comparative examples are shown in Table 12. The mass of the mass fraction is divided into methyl ethyl ketone. In the intermediate layer of Table 1, the film of the intermediate layer of Comparative Example 2 was thick, and the compound represented by the above formula (I) was absent. . Among P-1 to P- in Table 1, Comparative Example 1 is absent. Intermediate layer of Comparative Example 3

120566.doc 37- 1353489

[一嵴] 120566.doc I &lt; Comparative Example 3 〇ο α\ fN *η 〇l〇Ό V) ο m ο ro (N 〇\r\ 〇O CN o 〇X 联·Μ体迨迨G letter蚪 里 to to n n n n n n n n n n n n 12 12 12 12 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ;〇om ir&gt; ο ro ο m &lt;N 〇vn oo (N 〇om 〇00 〇〇1〇(NX *〇 〇ο m ci fO &lt;N 〇«〇oo ( N 〇 〇 〇 〇 〇 〇〇 〇 〇 = = = = = CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN I 〇〇〇镩2 〇ο 〇sm V~io »r&gt;&lt;n V-) ο m ο m &lt;N 〇ir» oo &lt;N 〇om 〇V) ◎ VO 〇Ό 〇〇〇〇§ 〇Ο 〇Ν — •no «〇to &lt;n ο m ο m &lt;N 〇•r&gt; oo (N 〇o to 〇◎ ◎ in ◎ 〇〇〇镩°° fk Ρ 卜 ο Μ Ο ITi Ό O m ο r&lt;&gt; (N 〇ίΝ 〇&lt;N (N 〇o 〇 ◎ ◎ ◎ Tj- ◎ 〇〇〇〇ο 〇Ν (Ν Ο vn v〇o ο m fN 〇fS o (N 〇fN 〇or^» 〇 ◎ ◎ ◎ 〇〇〇 〇 v〇 § 〇ο g (Ν Ο »〇mom ο (N d (N o CN 〇(N 〇o CO 〇◎ ◎ ◎ 〇〇〇镩·η § 〇ο 〇\ &lt;Ν V) S o in ο ΓΟ Ο m (N 〇«η O o (N 〇om 〇◎ inch ◎ ◎ 〇〇〇和:军〇ο (Ν V~) w-&gt; Ό V&quot;J m «〇ο ΓΛ Ο mo w-&gt; oo 〇o 〇«Λ ◎ •η ◎ 00 〇〇〇〇Ρ» 卜ο Os (Ν «〇o »〇m ο ΓΟ Ο m (N ddo &lt;soo cn 〇*〇◎ \Tt ◎ m ◎ 〇〇〇镩&lt;N 〇ο σ\ CN WJ o »r&gt;«〇u-&gt; ο r*&gt; Ο ΓΛ (N 〇v&gt; oo (N oom 〇ΙΛ ◎ ◎ 00 〇〇〇〇鸯 - buckle 5 〇 ο § (Ν no no no no no no no no no CN 1 CN έ ri ύ •o Ό ή 00 ΟΝ ύ 6 (N 0 A &lt;N Jj &lt;NI Methyl Ethyl 1 1 1 Level 1 r^· Λ Level 1 Level I Composition of the intermediate layer (mass) φ ΦΊ 铋S Fry 1 Film thickness of the oxygen mask Composition of photosensitive resin layer (mass fraction) φ m 1 Film thickness of photosensitive resin layer 1 Evaluation of peeling property of supporting film 1 1 Analytical evaluation 1 1 Evaluation of adhesion 1 1 Evaluation of adhesion of independent cylinder 1 Μ Evaluation of the surface state of the sidewall of the 艉m 1 photoresist® I 1 photoresist pattern | •38- 1353489 &lt;Symbol description&gt; Q-1: Polyvinyl alcohol (PVA-205 manufactured by Kuraray) Q-2: Polyethylene glycol (weight average molecular weight 4 〇〇) Q-3 · Polyoxyethylene ethyl monomethyl bond (uni 〇x M-550, weight average molecular weight 550) Q_4 : polyvinylpyrrolidone (weight average molecular weight 4 〇, 〇〇〇)

P-1: a methyl ethyl ketone solution of a copolymer of 80% by mass of benzyl methacrylate and 2% by mass of methacrylic acid (solid content concentration: 5% by mass, weight average molecular weight: 25, 0 Å, Acid equivalent: 43 〇, dispersion 2 7) P-2. methyl ketone solution of methyl methacrylate 5 〇 mass%, thioglycol 25% by mass, styrene 25 nymol binary copolymer (solid content concentration 35 mass. / 〇 'weight average molecular weight 5M (10), 胄 equivalent 344, dispersion 3.1) M-1: average addition of 12 moles of propylene oxide to the two ends of the polypropylene glycol, and then the average addition There are 3 moles of epoxy-fired polyalkylene glycol dimethacrylate

M-2: The average addition of both ends of the double-sided A has 2 moles of propylene-acrylic acid and the average addition of 6 moles of epoxy diol diol methacrylate vinegar M-3 : Polyethylene glycol dimethyl acrylate vinegar with 2 moles of ethylene oxide is added to both ends of bisphenol A (New Zealand only group I ah Zhongcun Chemical Industry Co., Ltd. ) 制造 制造 ΒΡΕ 200 -200)

NK Μ-4 manufactured by the Village Chemical Industry Co., Ltd. with 5 moles of ethylene oxide: the average of the bisphenol oxime on both ends of the bisphenol oxime (new carbene BPE- 500) 120566.doc -39. 1353489 Μ·5 : 2,2-bis{4-(methacryloxypentapentaethoxy)cyclohexyl oxime propane: as hexanediol diisocyanate and oligopropylene glycol monoterpene Amino methacrylate polypropylene glycol dimethacrylate: trimethylolpropane dimethacrylate M_8: trioxyethyl trishydroxyl ester of the reaction product of acrylic acid (made by Nippon Oil & Fats Co., Ltd., Blemmer PP1000) Methylpropane triacrylate (NK ester A-TMPT-3EO manufactured by Shin-Nakamura Chemical Co., Ltd.) Μ·9: Nine-ethylene glycol diacrylate G-1 : 4,4'-bis(diethylamine) Diphenyl ketone G 2 : 2-(o-phenyl)-4,5-diphenylimidazole dimer•M : Diamond Green (Aizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd. ) : colorless crystal violet Ll : 1-(2-di-n-butylaminoindenyl)-5-carboxy aglycoltriazole and 1-(2-di-n-butylaminoindenyl)-6-carboxyphenylhydrazine 1:1 mixture of triazole L-2: 3,5- of pentaerythritol Di-tert-butyl-4-hydroxyphenylpropionic acid tetra-energy (IRGANOX245, manufactured by Ciba Specialty Chemicals Co., Ltd.) [Industrial Applicability] The photosensitive resin laminate of the present invention, which is produced by having a conductor pattern a printed wiring board, a flexible substrate, a lead frame substrate, a COF substrate, a semiconductor package substrate, and a transparent electrode for liquid crystal, a liquid crystal TFT wiring, and a PDP (plasma display panel) electrode. The field of substrates is suitable for etching photoresist or film photoresist. [Brief Description of the Drawings] 120566.doc • 40· 1353489 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

I20566.doc -41 -

Claims (1)

1353489 Patent application range: A photosensitive resin laminated body comprising a support film, an intermediate layer having a thickness of 〇1 μm or more and 1 〇 or less, and a photosensitive resin layer on the support film. The intermediate layer is composed of polyvinyl alcohol and one or more selected from the group consisting of compounds represented by the following formula (I): Ri-0-(CH2CH20)n, -R2 (J) The team and 1 are 11 or (: 113, these may be the same or different, 111 is an integer from 3 to 25). 2. The photosensitive resin laminate according to the claims, which is formed 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 tree has: (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; (b) at least one photopolymerizable unsaturated compound: 3~7〇% by mass; c) Photopolymerization initiator: 〇.1 to 2〇% by mass. 4. The photosensitive resin laminate according to claim 3, wherein the (4) binder resin contains benzyl (meth) acrylate as a copolymerization component. 5. The photosensitive resin laminate according to claim 3, wherein the (a) to + one photopolymerizable unsaturated compound is selected from the group consisting of the following formula (11) to the compound represented; Photopolymerizable unsaturated compound at least _ y 120566.doc 1353489 [Chemical 1] f4 俨3 R5 H2C =C-C0-(C2H4O)n2-(CH2CHO)n3—(C2H40)nrC - i:CH2 〇〇 0 n (wherein R·4 is H or CH3, and these may be the same or different, and n3, w and n5 respectively represent integers of 3 to 20); [Chemical 2] 0- (Α-0) Π7—(B-0) n9-C—C=CH2 0 R7 (III) (In the formula, Re and R? are H or CH, 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 of 〇~4〇, ... and ~ are each independently an integer from 1 to 39, and n8&amp;n9 are independent of 〇 An integer of ～40; -(A-Ο)- and -(B-Ο)-the arrangement of repeating units may be random or block; in the case of a block, _(A-〇)- and -(B-Ο)- in terms of order, either can be on the diphenyl side); 120566.doc 1353489 [Chemical 3] Λ o Rs Ο-(D-0) mi—(Ε-〇) ^ -()-0=^2 H3C-c-CH3 (IV) 〇-(D-0)m2(E-〇)ni4—cC=CH2 II « 0 «9 Yuci Temple can be the same or different (in the formula, R8 and r9 are H or C2h, E is postal (10)) 'called... is an integer of 2~4〇, called + is an integer of 〇~4〇,叫 and 叱 are independent of 整数~39 integers, called and called independent integers 〇~40; _(D_〇)_ and ·(Ε·〇) repeating units can be arranged randomly or inlaid a segment; in the case of a block _, in the order of (〇_〇)_ and -(Ε-Ο)-, either can be on the cyclohexyl side); [Chemical 4] CH3 ρ | 0 r&lt;n NHC0-(0CHCH2)m5-0C0-C=CH2 〒1〇(V) NHCO-(OCHCH2)m6-〇C〇.C=CH2 CH3 r12 (wherein R|〇 is carbon The number 2 to 12 of the valence organic group, Rh and R12 are H or CH3 ° Xuan, etc. may be the same or different, called and called respectively I 15566.doc ^131353489 integer); [5] h2c =0 -0-0-(^ -0)m7—(BJ -0)^ 0 (VI) (Ri4)ms (wherein Ru is H or CH3, Rl4 is an alkyl group having a carbon number of 4 to i4, a, an integer 'm9 is 0 to 3 m〇), and _(β··〇) is repeated The arrangement of the units can be random, and can also be used in the case of rabbits &amp;&amp;&amp;&amp;&amp;, force, and block, in the case of blocks, (Α, _ 6. 〇)- and - (Β,·〇 In the order of -, all can be on the phenyl side). A method for forming a photoresist (4), which comprises the steps of laminating a photosensitive resin laminate of the first to fifth items of 3 to 5 on a surface of a metal plate or a metal-coated insulating plate, and peeling off An exposure step of supporting the film and performing exposure, and a developing step of removing the unexposed portion by development. The 'manufacturing method of the conductor® case' is characterized in that it is formed by the method of the request 6 to form a substrate button or a forged film having a photoresist pattern. 120566.doc