TW200947116A - Method for producing cured resist using negative photosensitive resin laminate, negative photosensitive resin laminate, and use of negative photosensitive resin laminate - Google Patents

Abstract

Disclosed is a method for producing a cured resist which enables formation of a resist pattern having excellent adhesion and resolution after development, while having an excellent resist shape. Also disclosed are a negative photosensitive resin laminate, and use of a negative photosensitive resin laminate. Specifically disclosed is a method for producing a cured resist, which comprises a laminate-forming step wherein a negative photosensitive resin laminate, in which at least a supporting body (A), a negative photosensitive layer (B) and a substrate (C) are laminated, is formed, an exposure step wherein the negative photosensitive layer (B) is exposed through a lens using light projecting the image of a photomask, and a development step wherein a cured resist composed of the cured portion of the negative photosensitive layer (B) is formed by developing and removing the unexposed portion of the negative photosensitive layer (B). The negative photosensitive layer (B) has a light transmittance of not less than 25% but not more than 50% at a wavelength of 365 nm.

Description

[Technical Field] The present invention relates to a method for producing a resist cured product comprising the steps of using a negative photosensitive resin laminate having a negative photosensitive resin layer and The step of exposing the negative photosensitive resin layer. More specifically, the present invention relates to a negative photosensitive resin laminate having a negative photosensitive resin layer suitable for producing a printed circuit (wiring) board, a lead frame, a semiconductor package, etc., to produce a resist cured product. Methods. Further, the present invention relates to a negative photosensitive resin laminated body having a negative photosensitive resin layer for i-line single-color exposure and a method of using a negative photosensitive resin laminated body. More specifically, the present invention relates to a negative type of a negative photosensitive resin layer for i-line monochromatic exposure capable of performing alkaline development, which is suitable for manufacturing a printed circuit (wiring) board, a lead frame, a semiconductor package, or the like. A method of using a photosensitive resin laminate and a negative photosensitive resin laminate. [Prior Art] Previously, printed wiring boards were manufactured by photolithography. The photolithography method is a method of forming a pattern by photoreaction of a photosensitive resin composition. When a negative photosensitive resin composition is used, the photosensitive resin composition can be applied onto a substrate to form a photosensitive resin layer, and then the pattern is exposed, and the exposed portion of the photosensitive resin composition is cured by polymerization. And removing the unexposed portion by the developer to form a resist pattern on the substrate, performing etching or plating treatment to form a conductor pattern, and then removing the resist pattern from the substrate to form a conductor pattern on the substrate . In the negative photolithography method, when the negative photosensitive resin composition is applied to a substrate by 136693.doc 200947116, a solution of the negative photosensitive resin composition can be applied to the substrate and dried. A method of laminating a support layer, a layer containing a negative photosensitive resin composition (hereinafter also referred to as a "negative photosensitive resin layer"), and a dry film resist layer of an optional protective layer. Any of the methods on the substrate. When manufacturing a printed wiring board, a method of laminating a dry film resist on a substrate is often used. Hereinafter, a method of manufacturing a printed wiring board using a dry film anti-surname agent will be described. First, when the dry film resist has a protective layer such as a polyethylene film, the protective layer is first peeled off from the negative photosensitive resin layer. Then, a negative photosensitive resin layer and a support are laminated on a substrate, for example, a copper foil laminate, in the order of a substrate, a negative photosensitive resin layer, and a support, using a laminator. Then, the negative photosensitive resin layer is exposed through an ultraviolet ray such as an i-line (having a wavelength of 365 nm) emitted from an ultrahigh pressure mercury lamp via a photomask having a wiring pattern, whereby the exposed portion is polymerized and cured. Then, a support containing polyethylene terephthalate or the like is peeled off. Then, the unexposed portion of the negative photosensitive resin layer is dissolved or removed by a developing solution such as a weakly alkaline aqueous solution to form a resist pattern on the substrate. Then, a known etching process or pattern plating process is performed using the formed resist pattern as a protective mask. Finally, the anti-surname pattern is peeled off from the substrate to produce a substrate having a conductor pattern, that is, a printed wiring board. In recent years, with the miniaturization and weight reduction of electronic devices such as mobile phones and notebook computers, the wiring interval of printed wiring boards has become more and more demanding. In order to cope with this miniaturization requirement, in the exposure method for dry film resists 136693.doc 200947116, the expectation of using i-line monochromatic light having a small color difference is increasing. Further, in the application requiring high resolution, in order to avoid the squeaking of the lubricant or the like contained in the support, the support may be peeled off before exposure. However, in the exposure method using the dry film anti-surplus agent, as shown in Fig. 2, the anti-sufficiency agent at the top of the anti-surience agent and the anti-surname agent at the bottom of the anti-money agent are formed. There is a problem with dimensional reproducibility. In addition, when the support is peeled off and the exposure is performed in advance, as shown in FIG. 4 which will be described later, the cross-sectional shape of the resist becomes "a bobbin shape", and the anti-surname agent has a large residual amount. There is a problem with the dimensional reproducibility of the resist. A method of manufacturing a printed wiring board using a dry film anti-surname agent includes exposing a negative photosensitive resin layer to a negative photosensitive resin layer via a photomask having a wiring pattern by using an ultraviolet ray such as an i-line (having a wavelength of 365 nm) emitted from an ultrahigh pressure mercury lamp. The step of curing the exposed portion by polymerization; the step of dissolving or dispersing the unexposed portion of the negative photosensitive resin layer by a developing solution such as a weakly alkaline aqueous solution; and other steps. It is not clear in which step the cause of the coarseness of the top of the resist and the narrowness of the bottom of the resist, the cross-sectional shape of the rain resist being formed into a bobbin shape, and the residual of the resist are large. Patent Document 1 describes the dry film resist which defines the absorbance at a wavelength of 365 nm. However, Patent Document 1 does not describe the i-line single-color exposure. Further, Patent Document 1 does not describe the exposure after the support is peeled off in advance. [Patent Document 1] JP-A-2006-145565 SUMMARY OF INVENTION [Problems to be Solved by the Invention] 136693.doc 200947116 An object of the present invention is to provide an anti-adhesive and anti-dissolution property after development. A method for producing a resist cured product having an excellent resist pattern, a negative photosensitive resin laminate, and a method of using a negative photosensitive resin laminate. [Means for Solving the Problem] The present inventors have made intensive studies to solve the above problems, and as a result, it has been surprisingly found that the pair has a support (A), a negative photosensitive resin layer (B), and a substrate (C). When the negative photosensitive resin laminate is exposed, the light transmittance of the negative photosensitive resin layer (B) is changed, specifically, the light transmittance at a wavelength of 365 nm is 25% or more. 50% or less of the negative photosensitive resin layer (B), compared with a resist produced by using a negative photosensitive resin layer having a previous light transmittance, the adhesion and solution of the resist pattern after development The image and the shape of the resist are remarkably improved to complete the present invention. Moreover, the present inventors have found that when i-line single-color exposure is performed on a laminate having a negative photosensitive resin layer, the inclusion includes: (a) the carboxyl group content is io 〇〇 〇〇 6 以 in terms of acid equivalent The weight average molecular weight is 5,000 to 5 Å, the binder for the binder is 2 〇 to 9 〇 mass%, (8) the photopolymerizable unsaturated compound 3 to 7 〇 mass%, and (c) the photopolymerization initiation When the photosensitive resin composition of 0.1 to 20% by mass of the coating agent has a light transmittance of 25% or more and 5% by weight or less at a wavelength of 365, the light transmittance of the negative photosensitive resin layer having the above range is used. In the case of the negative photosensitive resin layer, the adhesion, the resolution, and the resist shape of the resist pattern after development are remarkably improved, thereby completing the present invention. Specifically, the above problems are solved by the following inventions [丨] to [28]. 136693.doc 200947116 π] A method for producing a resist cured product, comprising: a layer forming step of forming a layer formed by at least a support (8), a negative photosensitive tree layer (B) and a substrate (c) a negative photosensitive resin laminate; an exposure step of exposing the negative photosensitive resin layer (B) through a lens using light projected from the image of the mask; and a developing step of removing by development The unexposed portion of the negative photosensitive resin layer (8) forms an cured product of an anti-surname agent containing the cured portion of the negative photosensitive resin layer (B); and the negative photosensitive resin layer (B) is The light transmittance at a wavelength of 365 nm is 25% or more and 50% or less. [2] The method for producing a cured resist of the above [1], wherein the light is i-line monochromatic light. [3] The method for producing a cured resist of the above [1] or [2], wherein the layer forming step and the exposing step are further included from the negative photosensitive resin layer (B) The support peeling step of the support (A) is peeled off. [4] The method for producing a cured resist of any one of the above [1] to [3] wherein the negative photosensitive resin layer (B) has a light transmittance of 35% or more at a wavelength of 365 nm. , 45% or less. [5] The method for producing a cured resist of any one of the above [1] to [4] wherein the negative photosensitive resin layer (B) comprises: a negative photosensitive resin composition, the negative type The photosensitive resin composition contains (a) a resin having a reciprocal content of from 100 to 600 in terms of an acid equivalent, and a weight average molecular weight of from 5,000 to 500,000, 136,693.doc 200947116, a resin for a dispensing agent, 20 to 90% by mass, (b) 3 to 70% by mass of the photopolymerizable unsaturated compound, and (c) photopolymerization initiator 〇1 to 2 〇 mass 〇/〇. [6] The method for producing a cured cured material according to the above [5], which comprises at least one compound selected from the group consisting of a bismuth and a benzophenone derivative as the (c) photopolymerization Starting agent. [7] The method for producing a cured resist of the above [5] or [6], which comprises a 2,4,5·triarylimidazole dimer as the (photopolymerization initiator). The production method according to any one of the above [5] to [7] wherein at least one compound selected from the group consisting of benzophenone and a benzophenone derivative is used, and 2'4,5- The method of producing a cured film of a resist according to any one of the above [5] to [8], wherein the b) The unsaturated compound which can be photopolymerized is selected from the group consisting of a compound represented by the following formula (I) and a compound represented by the following formula: [Chemical Formula 1] 〇

Hzc C=CHz (1) Ο {wherein R8 and R9 are independently Η or CH3, and η2, η3, and ru are each independently an integer of 3 to 20}; ''' 136693.doc -10- 200947116 [Chemical 2 ]

0 Α-0》ιι·1 an «ΟΗ2 11

In the formula, ' Ri〇 and R】i are independently H or CH3 'A is C2H4, B is c3Hg, ri5+n6 is an integer of .2~30, Π7+η8 is an integer from 0 to 30, and 115 and n6 are independent An integer from 1 to 29, n? and h are independently integers from 〇 to 29, and the arrangement of repeating units · (Α_〇)_ and -(Β-0)- may be random or block, as a block In the case of both, it can be located on the bisphenol side}. [10] A method of manufacturing a printed wiring board, comprising the steps of: etching or plating a substrate (C) having any one of [1] to [9] as described above; a resist pattern formed by the resist cured product obtained by the manufacturing method; and a step of removing the resist cured material from the substrate (C). Π1] A negative photosensitive resin laminate for forming a resist cured product by exposing a negative photosensitive resin layer through a lens using i-line monochromatic light that projects an image of a photomask Further, it has at least a support (A) and a negative photosensitive resin layer (B) for i-line single-color exposure, and the negative photosensitive resin layer (B) includes a negative type for monochromatic exposure. The photosensitive resin composition, (4) type photosensitive resin composition contains (4) Wei Ke 136693.doc 200947116 Resin 2 resin having an acidity of 100 to 600 in terms of I and a weight average molecular weight of 5,000 to 500,000 〇~9〇 quality. /. (b) 3 to 70% by mass of the photopolymerizable unsaturated compound, and (c) 0.1 to 20% by mass of the photopolymerization initiator, and the negative photosensitive resin layer (B) at a wavelength of 365 nm The light transmittance is 25% or more and 50% or less. [12] The negative photosensitive resin laminate according to the above [11], wherein the negative photosensitive resin layer (B) has a light transmittance of 35% or more and 45% or less at a wavelength of 3 65 nm. [13] The negative photosensitive resin laminate according to [11] or [12] above, wherein the (a) binder resin has a glass transition temperature of 1 〇〇〇c or more. [14] The negative photosensitive resin laminate according to any one of the above [11] to [13] wherein the resin for the binder (a) has a weight average molecular weight of from 10,000 to 40,000. [15] The negative photosensitive resin laminate of any one of [11] to [14] which contains at least one compound selected from the group consisting of a benzophenone and a benzophenone derivative. The photo-polymerization initiator [16] The negative-type photosensitive resin laminate according to any one of the above-mentioned [丨丨彳 to !^ 5], which contains a 2,4,5-triarylimidazole dimer The negative photosensitive resin laminate according to any one of the above [11] to [16], which is selected from the group consisting of benzophenone and benzophenone. At least one of the compound group and the 2,4,5·triarylimidazole dimer are used as the (C) photopolymerization initiator. 136693.doc -12- 200947116 [18] as described above The negative photosensitive resin laminate of any one of [17], wherein the (a) photopolymerizable unsaturated compound is selected from the group consisting of the compound represented by the following formula (I) and A group consisting of a compound represented by the formula (11): [Chemical 3] h2c 〇-(C2H4〇)n2-(C3He〇)n3-(C2H4〇)n4-CC=CH2 ([) Ο

In the formula, Rs and R_9 are independently Η or CH3, and η2, Π3, and η4 are each independently an integer of 3 to 20}; [Chemical 4]

(ID 0-(Α-Ο)ηβ-<Β*Ο)ι», 11Γ {wherein R丨0 and R" are independent Η or CH3, Α is C2H4, Β is c3H, h+n6 is 2 An integer of ~3〇, h+h is an integer of 〇~3〇, ns and % are independent integers of 1~29, n? and ns are independent integers of 〇~29, and will be reserved _ ^ The arrangement of (Δ_〇)_ and -(B-0)- may be random or block, and in the case of a block, it may be located on the bisphenol side}. [19] The negative-type sensible resin laminate of any one of the above [11] to [18] which further has a protective layer 136693.doc on the negative photosensitive resin layer (B). -13-200947116 [20] A method of using a negative photosensitive resin laminate, which exposes a negative photosensitive resin layer through a lens by using i-line monochromatic light that projects an image of a photomask In the case of forming a cured resist, a negative-type photosensitive resin laminate is used, and the negative photosensitive resin laminate system has at least a support (A) and a negative photosensitive resin layer for i-line monochromatic exposure (B). And the negative photosensitive resin layer (B) contains: (a) a carboxyl group content of 100 to 600 in terms of acid equivalent, and a weight average molecular weight of 5, 〇〇〇~5 〇〇, 〇〇〇 20 to 90% by mass of the binder resin, (b) 3 to 70% by mass of the photopolymerizable unsaturated compound, and (c) photopolymerization initiator 〇·丨~2〇% by mass} Negative photosensitive resin composition for color exposure, and the negative photosensitive resin layer (B) transmits light at a wavelength of 365 nm More than 25%, 50% or less. [21] The method of using the negative photosensitive resin laminate according to the above [20], wherein the negative photosensitive resin layer (B) has a light transmittance of 35% or more and 45% or less at a wavelength of 365 nm. . [22] The method of using the negative photosensitive resin laminate of the above [20] or [21], wherein the glass transition temperature of the (a) binder resin is! Hey. More than one. [23] The method of using the negative photosensitive resin laminate according to any one of the above [20] to [22] wherein the (a) binder resin has a weight average molecular weight of 10,000 to 4 Å, 〇〇〇 between. [24] The method of using a negative photosensitive resin laminate according to any one of the above [2] to [23], wherein at least one selected from the group consisting of a benzophenone and a benzophenone derivative is contained A method of using a negative photosensitive resin laminate according to any one of the above [20] to [24], wherein the compound is used as a method of using a compound of the above-mentioned [20] to [24], wherein The use of the 2,4,5-triarylimidazole dimer as the (c) photopolymerization initiator. [26] Use of the negative photosensitive resin laminate according to any one of the above [20] to [25] a method comprising, as the (c) photopolymerization, at least one compound selected from the group consisting of a benzophenone and a benzophenone derivative, and a 2,4,5-triarylimidazole dimer [27] The method of using the negative photosensitive resin laminate according to any one of the above [20] to [26] wherein the (a) photopolymerizable unsaturated compound is selected from the group consisting of A group consisting of a compound represented by the formula (I) and a compound represented by the following formula (II): [Chemical 5]

(C2H4〇)n2-(C3H80)n3-(C2H40)n4-C

In the formula, R8 and R9 are independently Η or CH3, and n2, n3 and n4 are each independently an integer of 〜3~20}; [Chem. 6]

It C—CH3 136693.doc -15- 200947116 {wherein R 丨〇 and Rn are independently Η or CH3 ' A is C2H4, B is C3H6, ns+iu is an integer from 2 to 30, and new is 〇~30 Integer, ~ and ... are independent integers from 1 to 29 'η? and ns are independent integers from 〇 to 29, and the arrangement of repeating units _(Α〇)_ and -(Β-Ο)- can be random or embedded. In the case of the block, it can be located on the bisphenol side. [28] The method of using the negative photosensitive resin laminate according to any one of the above [20] to [27] wherein the negative photosensitive resin layer further has a protective layer. [Effect of the Invention] According to the present invention, a resist pattern excellent in adhesion and resolution after development and an excellent resist shape can be obtained. [Embodiment] In one aspect of the invention, there is provided a method for producing a cured product of a sizing agent, comprising: a layer forming step of forming at least a support (Α), a negative photosensitive resin layer (Β a negative photosensitive resin laminated layer formed by laminating the substrate (c), a film, and an exposure step, which uses light projected from the image of the photomask to pass the negative photosensitive resin layer through the lens (进行) performing exposure; and a developing step of removing the unexposed portion of the negative photosensitive resin layer (7) by development to form an hardened agent hardened portion including the hardened portion of the negative photosensitive resin layer (8) Further, the negative photosensitive resin layer has a light transmittance of 25% or more and 50% or less at a wavelength of 365 ηηητ. 136693.doc 200947116 In another aspect of the present invention, a negative photosensitive resin laminate is provided for use in negative-type photosensitive light through a lens by using i-line monochromatic light for projecting an image of a photomask The resin layer is exposed to form a cured product of an anti-money agent, and has at least a support (8) and a negative-type photosensitive resin layer (B) for monochromatic exposure, wherein the negative-type photosensitive resin layer includes A negative photosensitive resin composition for one-line single-color exposure, wherein the negative photosensitive resin composition contains (a) a carboxyl group content of from 100 to 600 in terms of acid equivalent, and a weight average molecular weight of 5,000 to 50 Å. The binder for the adhesive between the crucibles is 2 to 9 mass%, the photopolymerizable unsaturated compound is 3 to 7 mass%, and (c) the photopolymerization initiator is 0.1 to 20 mass%. The light transmittance of the negative photosensitive resin layer (B) at a wavelength of 365 ηιητ is 25% or more and 50% or less. In another aspect of the present month, a method of using a negative photosensitive resin stratified layer is provided, which uses a monochromatic light that projects an image of a reticle to be negatively sensitized via a lens. When the resin layer is exposed to form a cured agent, a negative photosensitive resin laminate is used, and the negative photosensitive resin layer system has at least a support (Α) and a negative photosensitive for i-line monochrome exposure. The resin layer (B) and the negative photosensitive resin layer (8) are a negative photosensitive resin composition for monochromatic exposure, and the negative photosensitive resin composition contains (a) a carboxyl group content. The acid equivalent is from 100 to 600, and the weight average molecular weight is from 5 to 90% by mass of the resin for binders, and (8) the photopolymerizable unsaturated compound is 136693.doc 200947116 3 to 70% by mass, and (c) photopolymerization initiator 〇·ΐ~2〇% by mass, and the light transmittance of the negative photosensitive resin layer (B) at a wavelength of 365 nm is 25% or more, 50 %the following. In the present specification, the term "negative photosensitive resin layer (B)" means a resin layer obtained by exposing with active light and then developing to obtain a negative pattern. Further, the term "negative photosensitive resin layer (B) for i-line monochromatic exposure" means that the negative photosensitive resin layer (B) can be monochromatic (by a wavelength of 365 nm) in a single color. The exposure and subsequent resolution are used to obtain the desired resist pattern. The negative photosensitive resin layer (B) of the present invention has a light transmittance of 25% or more and 50% or less at a wavelength nm. When the light transmittance at a wavelength of 365 nm is in the above range, a resist pattern excellent in adhesion and resolution can be obtained as compared with a case where the light transmittance is outside the above range, and the resist reproducibility is reproducible. good. Further, in the aspect of the method of using the negative photosensitive resin laminate and the negative photosensitive resin laminate according to the present invention, by making the light transmittance at a wavelength of 365 nm into the above range, When a resist-cured material is formed by exposing a negative-type photosensitive resin layer to a negative photosensitive resin layer by a lens by projecting the monochromatic light of the image of the reticle, compared with the case of light transmittance other than the above range A resist pattern excellent in adhesion and resolution is obtained, and resist reproducibility is good. When a resist cured product is formed by exposing the negative photosensitive resin layer to light through a lens, the resist cross-sectional shape becomes an inverted trapezoid, and a resist top is generated. The coarseness and the resistance of the (four) bottom are narrow and have anti-(four) size reproducibility problems. Further, in a state in which the support is peeled off in advance and then exposed, the light is projected by immersing the light of the image of the mask described above with 136693.doc 200947116, and the negative photosensitive resin layer is exposed through the lens to form an anti-(four) hardening. As a result of the material, the cross-sectional shape of the anti-(four) crucible is a bobbin shape, and the resist residue is large, so there is a problem of resist size reproducibility. On the other hand, in the case where the above light transmittance exceeds 50%, the negative photosensitive resin layer (B) cannot effectively absorb the exposed light, so that there is a problem that the exposure sensitivity is lowered. In the use of 丨 line monochromatic light ¥ These issues are more significant. Therefore, from the viewpoint of solving such problems and producing a superior resist shape, the light transmittance of the negative photosensitive resin layer (B) at a wavelength of 365 nm is 25% or more and 5% or less. The light transmittance of the negative photosensitive resin layer (B) of the present invention at a wavelength of 365 is more preferably 30% or more, from the viewpoint of the adhesion of the anti-money agent pattern, the resolution, and the exposure sensitivity. % or less, and more preferably 35% or more and 45% or less. As a method of adjusting the light transmittance of the negative photosensitive resin layer (B) at a wavelength of 365 η ηητ, a method for forming a negative photosensitive resin is exemplified. A method of adding a UV absorber to a negative photosensitive resin composition of a layer or a method of adjusting the amount of a photopolymerization initiator. Examples of the ultraviolet absorber include benzotriazole and diphenyl. An anthracene-based, a salicylate-based, a cyanoacrylate-based, a nickel-based, a three-tillage system, etc. As a benzotriazole-based ultraviolet absorber, 2_(2-hydroxy-5_t-butylbenzene) is exemplified Base)_2η·benzotriazole, phenylpropionic acid 3-(2Η-benzotriazol-2-yl)-5-(1,1_二Methyl ethyl)-4-hydroxy C7.9 side chain and linear alkyl ester, 2_(211_benzotriazol-2-yl)-4,6-bis(1-methyl-indole_phenyl Ethyl phenol. As a photopolymerization initiator, it is particularly preferable to select a smear of 136693.doc -19· 200947116 for the adhesion pattern and the resolution. At least a compound of the group consisting of a benzophenone and a benzophenone derivative. As a method of measuring the light transmittance of the negative photosensitive resin layer (B) of the present invention at a wavelength of 365 nm, there are the following methods. : A negative photosensitive resin layer (B) is formed on the support. 'The support is placed on the reference light side and the support portion is removed. The U 331 manufactured by Hitachi High-Tech (Mitachi) is used by a spectrophotometer. 〇), the slit ((丨) is set to 4 nm, and the scanning speed is set to nm/jjjin. ❹ The negative photosensitive resin layer (B) of the present invention may contain (a) a carboxyl group content in terms of acid equivalent. 20~600, and the resin with a weight average molecular weight of 5〇〇〇~5〇〇〇〇〇 is 20~90 The mass %, (b) can be formed by photopolymerization of a negative photosensitive resin composition of 3 to 70% by mass of a saturated compound, and (c) a photopolymerization initiator of 2% by mass. The carboxyl group in the resin is required for imparting developability or releasability to the alkaline aqueous solution to the negative photosensitive resin layer. The amount of the carboxyl group of the resin for the binder 2 is resistant to developability, resolution, and adhesion. In view of the viewpoint, it is preferable that the acid equivalent is 1 Å or more, and from the viewpoint of developability and peelability, t ' is preferably 600. More preferably, it is 250 to 400 in terms of acid equivalent. In the aspect of the method of using the negative photosensitive resin laminate and the negative photosensitive resin laminate according to the present invention, the acid equivalent is from 100 to 600, preferably from 3 to 4 Torr. The acid equivalent means a mass (gram equivalent) of a polymer having a m equivalent of 1 (i.e., a resin for a binder). 136693.doc •20· 200947116 The acid equivalent is measured by the potentiometric titration method using the Sugao automatic titrator (COM-5 5 5) manufactured by Hiranuma Sangyo Co., Ltd. using sodium hydroxide of 〇·! mol/L. The (a) binder resin of the present invention may have a weight average molecular weight of from 5,000 to 500,000. From the viewpoint of developability, the weight average molecular weight of the resin for the adhesive is preferably 500,000 or less, which is preferable from the viewpoint of the strength of the tenting film and the reduction of the edge fuse. It is 5,000 or more. In order to further enhance the effect of the present invention, (a) the weight average molecular weight of the resin for the adhesive is preferably between 20,000 and 300,000. Further, in the aspect of the method of using the negative photosensitive resin laminate and the negative photosensitive resin laminate according to the present invention, the weight average molecular weight is between 5,000 and 500,000, and the i-line is improved by using a projection exposure machine. From the viewpoint of the resolution at the time of monochrome exposure, the weight average molecular weight is preferably between 1 Torr and 40 40,000. The weight average molecular weight can be obtained by using Gel Permeation Chromatography (GPC) manufactured by JASCO Corporation [pump: Gulliver, PU-1580; column: Shodex (manufactured by 4 Showa Denko Co., Ltd.) Registered trademark) (KF-807, KF-806M, KF·806M, KF-802.5) in series; moving bed solvent: tetrahydrofuran; using polystyrene standard sample (Shodex STANDARD SM-105 Polystyrene manufactured by Showa Denko Co., Ltd.) The calibration curve is obtained. (a) The glass transition temperature of the resin for a binder is preferably from 10 C or more in terms of adhesion. (a) The glass transition temperature of the resin for a binder is preferably 10 ° C or more and 120 ° C or less. 136693.doc • 21 - 200947116 In the present invention, (a) the glass transition temperature of the resin for a binder can be calculated by the following FOX formula: [Number 1] 丄=!+W-.+l

Tg Tgl Tg2 Tg3 Tga (where Tg represents the Tg of the copolymer. Tg), Tg2, Tg3, ..., Tgn represents the Tg(K) of each homopolymer. Wl, W2, W3, and Wn represent the mass of each monomer. %). The (4) binder resin used in the present invention can be obtained by copolymerizing one or more monomers selected from the following two kinds of monoterpenes. The first monomer is a tickic acid or acid needle having one polymerizable unsaturated group in the molecule. For example, '(Alkyl) aglycolic acid, transbutyric acid, cinnamic acid, butyric acid methylene butyric acid, cis-succinic acid liver, cis-succinic acid half-vinegar, and the like can be exemplified. The second single system is selected in such a manner that it is non-acidic and has one polymerizable unsaturated group in the molecule, and can maintain the developability of the negative photosensitive resin layer (8), and the resistance to the etching and plating steps. Various characteristics such as ambiguity. Examples of such a monomer include (meth)acrylic acid methyl vinegar, (meth)acrylic acid ethyl vinegar, (meth)acrylic acid butyl vinegar, and (methyl)propionic acid 2 ethhexyl vinegar. (meth)acrylic acid ketone vinegar; (meth)acrylic acid 2_ mercaptoethyl ester, 2-hydroxypropyl (meth)acrylate, (meth)acrylonitrile, and the like. Further, from the viewpoint of the resolution of the south, it is preferred to use a berry compound having a phenyl group (e.g., styrene or benzyl (meth) acrylate). The resin for (a) binder of the present invention can be synthesized by diluting a mixture of the above monomers with a solvent such as propionium, methylidene or isopropanol by I36693.doc -22-200947116 An appropriate amount of a radical polymerization initiator such as benzamidine peroxide or azoisobutyronitrile is added to the obtained solution, and heating and mixing are carried out. In some cases, a part of the mixture may be added dropwise to the reaction liquid to synthesize the (a) binder resin of the present invention. After the completion of the reaction, a solvent may be further added to adjust to a desired concentration. As the synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, or the like can also be employed. (a) The content of the binder resin is preferably in the range of 20 to 90% by mass, more preferably in the range of 3 to 7 % by mass, based on the weight of the negative photosensitive resin composition. (a) The content of the resin for the adhesive, the resist pattern formed by exposure and development has sufficient characteristics as a resist, for example, sufficient resistance to capping, surname, and various plating steps. In particular, it is preferably in the range of 20 to 90% by mass. In the aspect of the method of using the negative photosensitive resin laminate and the negative photosensitive resin laminate according to the present invention, (a) the binder resin is contained in the entire negative photosensitive resin composition. It is in the range of 20 to 90% by mass, preferably in the range of % to 7% by mass. ° In the present invention, (b) the photopolymerizable unsaturated compound is preferably selected from the following formula ( At least one of the compound represented by I) and the compound represented by the following formula (Π) can be photopolymerized - an unsaturated compound: General formula (I): [Chemical 7] H2C = i -C0-(CzH40)n2~(C3He0)n3-(C2H40)n4-C-0*CH2 (I)

〇 II 136693.doc -23- 200947116 {wherein, R8 and R9 are independently Η or CH3, and n2, n3 and n4 are each independently an integer of 3 to 20}. In the compound represented by the above formula (1), when η2, ns, and & are less than 3', the boiling point of the compound is lowered, and the odor of the resist becomes strong and difficult to use. When ~h and η* exceed 2 Å, the concentration of the light-active portion per unit weight decreases, and the practical sensitivity tends to decrease. Specific examples of the compound represented by the above formula (1) include, for example, a diol in which an average of 3 moles of ethylene oxide is added to both ends of a polypropylene glycol having an average of 12 moles of propylene oxide. Dimercapto acrylate. General formula (II): [Chemical 8]

(ID Ο -(Α-0)ηβ-(Β^)ίΐ,-| aCHj {wherein 'Rl. and R" is independent Η or CH3' M is Mr β is (4), ― is the integer of (4)' (4) The integer '一蜀立为 (4) integer 'gn8 is an integer of Q~29's repeating unit (10)) _ :-(4)- The arrangement can be random or block, in the case of block, Can be located on the bisphenol side}. = more than 3 化合物 in the compound represented by the above formula (Π), and the double bond concentration in the shell-type photosensitive resin layer (8) is relatively lower than 136693.doc -24·200947116, so the sensitivity tends to decrease. Preferably, n5+n6 is 4 to 14, and H7 + I18 is preferably 0 to 14. Specific examples of the compound represented by the above formula (II) include the addition of an average of 2 moles of propylene oxide and an average of 6 moles of ethylene oxide to both ends of bisphenol A. a dimethacrylate of alkanediol, or a polyethylene glycol dimethacrylate having an average of 5 moles of ethylene oxide added to both ends of bisphenol A (Xinzhongcun Chemical Industry Co., Ltd.) Manufactured NK ester BPE-500). (b) The photopolymerizable unsaturated compound may be used in addition to the compound represented by the formula (I) and the photopolymerizable unsaturated compound represented by the formula (II). A compound represented by formula (III) or formula (IV): Formula (III): [Chemical 9] f?13 NHCO-(〇C3H6)m1-(〇c2H4)m3-〇C〇-C=CH2 |ΐ2 ( ΠΙ) NHC〇-(〇C3H6)m?-(〇c2H4)m4-〇C〇-C=CH2 R14 where R12 is an alkyl group having 4 to 12 carbon atoms, a cycloalkyl group or an aryl group, R13 and R14 is independently Η or CH3, rr^, m2, m3 and m4 are each independently an integer from 0 to 15, and the repeating unit -(〇C3H6)ml-(OC2H4)m3- and -(OC3H6)m2-(OC2H4)m4- The arrangement may be random or block, and in the case of a block, it may be located on the propylene sulfhydryl side}. 136693.doc -25- 200947116 For the compound represented by the above formula (m), 'm 1 , m 2 , m 3 and m 4 are 15 or less from the viewpoint of sensitivity. Specific examples of the compound represented by the above formula (m) include hexamethylene diisocyanate, toluene diisocyanate, and 2,2,4-trimethyl-iso-succinic acid. An isocyanic acid compound and a compound having a mesogenic and (meth)acryl group in one molecule (for example, acrylic acid 2, propyl propylene glycol, propylene glycol monomethacrylate, oligoethylene glycol monomethyl methacrylate) A urethane compound or the like of a acrylate, oligoethylene glycol propylene glycol monodecyl acrylate or the like. Specific examples thereof include a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethyl acrylate (Blemmer PP1000, manufactured by Nippon Oil & Fat Co., Ltd.), hexamethylene diisocyanate and oligomerization. Reaction of ethylene glycol monodecyl acetoacetate (manufactured by Nippon Oil & Fat Co., Ltd., Blenlrner PE_200), hexamethylene diisocyanate and polyethylene glycol propylene glycol monodecyl acrylate vinegar The reactant of Blemnler 70pep_350B) manufactured by the company. Formula (IV): [Chem. 10]

HjC—C-C-O—(A* -0)rnj—(Β·

(IV) {wherein R15 is Η or CH3, R16 is a burning group of carbon number 1~14, a' is GH4 'B' is C^H6 'claw 3 is an integer of 1~12, called divination] The integer, called the integer of 0~3, the repeating unit-(A'-O)- and -(B,_〇)_ can be arranged as random or block, and in the case of a block, Can be located on the phenyl side}. 136693.doc •26·200947116 = Among the compounds represented by the above formula (IV), S, m3 and 14 are preferably from 12 or less, and preferably 12 or less, from the viewpoint of sensitivity. Specific examples of the compound represented by the formula (IV) include, for example, a polypropylene glycol having an average of 2 moles of propylene oxide and an epoxy epoxide having an addition of 7 moles. Polyethylene glycol is added to the acrylic acid vinegar of the compound obtained, that is, 4-n-nonylphenoxy heptaethylene glycol dipropylene glycol propyl ester. Further, an acrylate which is obtained by adding a polyethylene glycol having an average of 8 moles of ethylene oxide to the indophenol, that is, 4-n-decylphenoxy octaethylene glycol acrylic acid, may be mentioned. Ester (manufactured by Toagosei Co., Ltd., M-114). (b) The unsaturated compound which can be photopolymerized, in addition to the compound represented by the above formula (1) to (IV), may be used together with the following photopolymerizable unsaturated compound i, for example, 丨, 6 - hexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2_二(对◎Phenylphenyl)propane di(meth)acrylate, glycerol tris(meth)acrylic acid vinegar, tri-f-propane tris(decyl)acrylate, polyoxypropyl tris Methylpropane tri(methyl) acrylate, polyoxyethyl trimethylolpropane triacrylate, pentaerythritol tris(decyl) acrylate, pentaerythritol tetrakis(meth)acrylate vinegar, dipentaerythritol (Meth) acrylate, tri-propyl mercapto-triglycidyl ether tri(meth) acrylate, bisphenol A diglycidyl ether di(meth) acrylate, and β-hydroxypropyl phthalate _β, _(propylene methoxy) propyl ester. (b) The content of the unsaturated compound which can be photopolymerized is relatively in the range of 3 to 7 % by mass based on the total amount of the photosensitive resin composition of the photoreceptor composition 136693.doc -27-200947116. In view of the sensitivity, the content is preferably 3% by mass or more, and from the viewpoint of preventing bleeding of the photosensitive resin layer during storage, it is preferably 70% by mass or less. In the aspect of the method of using the negative photosensitive resin laminate and the negative photosensitive resin laminate according to the present invention, the content is in the range of 3 to 7 % by mass. The above content is more preferably from 1 to 6 % by mass, still more preferably from 15 to 55% by mass. The negative photosensitive resin composition contains at least one photopolymerizable unsaturated compound selected from the group consisting of the compound represented by the formula (1) and the compound represented by the formula (Π). In the case of the negative photosensitive resin composition, the content of the unsaturated compound is preferably in the range of from 3 to 60% by mass, more preferably in the range of from 3 to 45% by mass. From the viewpoint of the adhesion, it is preferably 3% by mass or more, and from the viewpoint of melting the edge, it is preferably 60% by mass or less. When the negative photosensitive resin composition contains a compound represented by the formula or a compound represented by the formula (IV), the content of each unsaturated compound is preferably higher than that of the negative photosensitive resin composition as a whole. It is a range of 3 to 6 〇 mass% 'better is a range of 3 to 45 mass%. From the viewpoint of the adhesion, it is preferable that it is 3% by mass or more. From the viewpoint of melting the edge, it is preferably 60% by mass or less. From the viewpoint of high resolution, the negative photosensitive resin composition preferably contains a 2,4,5-triarylimidazole dimer as (c) a photopolymerization initiator. The triimidazole dimer is particularly preferably selected from the group consisting of a compound represented by the following formula (卩) and a compound represented by the following formula (VI): group 136693.doc -28- 200947116 At least one 2,4,5-triarylimidazole dimer in the formula: (V):

(V) is the one--, and p, q, and r are each an integer of ^;; General formula (VI): 〇 [Chemical 12]

Any of them - and p, respectively, are independent of the integer of 5}. It is 2,4,5-diaryl rice. Sitting on the polymer, for example, κ o-chlorobenzene:) bis 4,5-diphenylimidazolium dimer, 2-(o-chlorophenyl)-4,5-bis(metamethoxyoxy)methine dimerization 32, 2 · (p-methoxybenzene phantom diphenyl (tetra) two 136693.doc -29. 200947116 polymer etc. ' Particularly good is 2- (o-phenyl)-4,5-diphenylimidazole Further, the 'negative photosensitive resin composition contains a photopolymerization initiator selected from the group consisting of dibenzophenone and benzophenone, from the viewpoint of further improving the adhesion and resolution of the resist pattern. At least one compound selected from the group consisting of derivatives is also preferred. Further, it may be used in combination with the 24,5-triarylimidazole dimer represented by the above formula (V) or (VI), and selected from the group consisting of At least one compound selected from the group consisting of benzophenone and a benzophenone derivative is used as a photopolymerization initiator. As the benzophenone derivative, an amino phenyl ketone is particularly preferable from the viewpoint of exposure sensitivity. As the p-aminophenyl ketone, for example, p-aminobenzophenone, p-butylaminodibenzophenone, p-dimethylaminoacetophenone, p-monomethylaminobenzophenone may be mentioned. , p, p, · bis(ethylamino)benzophenone P'p-bis(monomethylamino)dipodone [micilene], ρ,ρΙ-bis(diethylamine) Benzo) benzophenone, p, p, bis (dibutylamino) benzophenone. Further, as the photopolymerization initiator, (4) a photopolymerization initiator other than the above compounds may be used in combination. Here, as another photopolymerization initiator, a known compound which can be activated by various active light rays such as ultraviolet rays to start polymerization can be used. Examples of the other photopolymerization initiators include aromatic lysines such as 2_ethyl hydrazine and 2 butyl butyl dioxin, benzoin and fragrant methyl ether, and benzoin. Class, 9_phenyl. Hey. Wait. Bite compound, benzoin dimethyl ketal, benzoin diethyl ketal, ° ° ° compound. Further, for example, an oxygen such as a star, a 2,4-diethyloxanol, a 2-gas sulfur such as a star, a sulfur-oxygen such as a star and a diterpenoid 136693.doc -30 - 200947116-amine can also be listed. A combination of a tertiary amine compound such as an alkyl benzoate compound. As other photopolymerization initiators, 1-phenyl-indole, 2-propanedione-2-(0-benzylidene) fluorene, phenylphenyl], 2-propanedione-2-(肟_Ethyl carbonyl) hydrazine and other oxime esters. Further, an aryl_α-amino acid compound can also be used, and particularly preferably Ν-phenylglycine.

The content of the photopolymerization initiator (c) is preferably from 0.1% by mass to 20% by mass based on the whole of the negative photosensitive resin composition. From the viewpoint of exposure sensitivity, the content is preferably (1) 丨 mass. From the viewpoint of the resolution, it is preferably 20% by mass or more. Further, in the aspect of the method of using the negative photosensitive resin laminate and the negative photosensitive resin laminate provided by the present invention, the content is (1) 丨 mass% to 2 〇 mass%. In the case where the 2,4,5-triarylmethicone dimer is used as the (4) photopolymerization initiator, the content of the 2,4,5-triaryldiene dimer is relative to the negative photosensitive resin combination. The whole material is preferably in the range of 〇~1Qf% by weight, more preferably in the range of 0.5-4.5% by mass. From the viewpoint of sensitivity, f is preferably (% by mass or more, and from the viewpoint of resolution, preferably 1% by mass or less. Containing a derivative selected from the group consisting of benzophenone and benzophenone) When at least one compound of the group is used as the (4) photopolymerization initiator, the content of the compound is adjusted relative to the negative photosensitive resin composition so that the light transmittance of the wavelength 365 is 25%. The above or less than 5% by weight is determined depending on the thickness of the resin layer (β), and is usually preferably in the range of 0.01 to 1.0% by volume. More preferably - in 〇·〇5~0 15% by mass 136693.doc -31 - 200947116 The negative photosensitive resin composition may contain a coloring matter such as a dye or a pigment. Examples of the coloring matter include magenta, phthalocyanine green, gold amine test, and Calgotoxide Green S. , parama (jienta, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, Malachite Green (AIZEN (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), Basic Blue 20, Diamond Green (Budong Valley) AIZEN (made by the Chemical Co., Ltd.) The content of the coloring matter is preferably in the range of 0.005 to 10% by mass, more preferably in the range of ομμ mass%, based on the entire negative photosensitive resin composition. The content of the above-mentioned content is preferably 0.005% by mass or more, and is preferably 5% by mass or less from the viewpoint of sensitivity. The negative photosensitive resin composition may be contained by light irradiation. A chromogenic dye is used as the chromogenic dye, for example, a leuco dye and a fluorane dye. Examples of the leuco dye include tris(4-diamine). Phenyl-2-mercaptophenyl)decane_[leuco crystal violet], tris(4-dimethylamino-2-methylphenyl)decane, [hidden malachite green], etc. Preferably, it is used in combination with a functional compound. As the compound, bromopentane, bromoisopentane, i, 2, dibromo-2-methylpropane, 1,2-dibromoethane, and Benzyl bromide, dibromotoluene, methane, tribromomethylphenyl sulfone, carbon tetrabromide, tris(2,3-dibromopropyl) phosphate , trimethylacetamide, iodopentane, iodine isobutane, 1,1, ^ three gas 2, 2 • bis (p-phenyl) ethane, hexa-ethane, functionalized three-till compounds. As a three-till compound for toothing, it can be exemplified by 2,4,6-tris(trichloroindenyl)_all 136693.doc -32· 200947116 tris H(4-methoxyphenyl)·4,6_double ( The trichloromethyl group is three tons. Particularly useful is the combination of Sanmomethylphenyl and leuco dyes, or the combination of the compound of the San17 well and the leuco dye. The content of the leuco dye is preferably in the range of 0 to _% by weight relative to the entire negative photosensitive resin composition, and more (4) ❹

The crime is inside. In view of the coloring property, the content is preferably 5% by mass or more, and from the viewpoint of the contrast between the exposed portion and the unexposed portion, and from the viewpoint of maintaining storage stability, it is preferably _% by weight or less. The third of the functionalized resin is preferably in the range of 0.005 to 10% by mass, more preferably in the range of % by mass, based on the entire negative photosensitive resin composition. In view of the coloring property, the content is preferably 0.005% by mass or more, and is preferably 10% by mass or less from the viewpoint of the contrast between the exposed portion and the unexposed portion and the storage stability. In order to improve the thermal stability and/or storage stability of the negative photosensitive resin composition, it is also preferred to include a radical polymerization inhibitor in the negative photosensitive resin composition. Examples of such a radical polymerization inhibitor include p-methoxybenzene, hydroquinone, o-trisphenol, naphthylamine, tert-butyl catechol, vaporized copper, 2,6- Di-t-butyl-p-cresol, 2,2,-indenylene bis(4-ethyl-6-tert-butylphenol), 2,2,-arylene di(4-methyl third As a specific preferred example, tetrakis[3-(3,5-di-t-butyl-4-pyridyl)propionic acid is exemplified as the butyl benzoate. Pentaerythritol vinegar and the like. The content of the radical polymerization inhibitor is preferably in the range of 1 to 3 mass%, more preferably 0.02 to 0.2 mass%, based on the total mass of the negative photosensitive resin composition. In view of the resolution, the above-mentioned content of 136693.doc -33 - 200947116 is preferably 0.01% by mass or more, and from the viewpoint of sensitivity, it is preferably 3% by mass or less. Further, the negative photosensitive resin composition of the present invention may optionally contain a plasticizer. Examples of the plasticizer include phthalic acid esters such as diethyl phthalate, p-toluenesulfonamide, polypropylene glycol, and polyethylene glycol monoalkyl ether. The content of the plasticizer is preferably in the range of 5 to 50% by mass, more preferably 5 to 3% by mass based on the whole of the negative photosensitive resin composition. In view of imparting flexibility to the cured material of the resist, the content is preferably 5% by mass or more, and from the viewpoint of suppressing insufficient hardening and cold flow, it is preferably 50% by mass or less. The substrate (c) in the present invention includes a copper foil laminated plate obtained by laminating a copper foil on a glass epoxy substrate, a metal plate such as copper, a copper alloy or an iron-based alloy, and a glass rib. A wafer, a film substrate having a conductor layer, and the like. The film-form substrate having a conductor layer has a conductor layer such as copper, gold, silver or aluminum on the film-shaped insulating resin layer, and examples thereof include a polyimide film, a polyester film, and a BT resin (double horse). Flexible substrate coated with copper foil or tape-type automatic bonding on the insulating resin layer such as yttrium imine-three-till resin (Tape)

Automated Bonding, TAB) tape. As a method of forming the negative photosensitive resin layer (B) on the substrate (c), a method of forming the negative photosensitive resin layer (B) on the support (A) (for example, a support film) is exemplified. Then, for example, a surface of the substrate (c) is laminated on the surface opposite to the side of the support (A) of the negative photosensitive resin layer (B), 136693.doc - 34 - 200947116, that is, to make the substrate (c) The negative photosensitive resin layer (B) is sandwiched between the support and the support (A). The negative photosensitive resin layer (B) is heat-pressure-bonded to the substrate (C) (for example, a metal printed circuit board) On the substrate). The method of forming the negative photosensitive resin layer (B) on the support (A) is a method of applying the negative photosensitive resin composition to the support (A). The support (A) used herein is preferably one which is transparent to active light. Examples of the permeable transparent light support include a polyethylene terephthalate film, a polyethylene glycol film, a polyethylene gas film, a gas ethylene copolymer film, a polyvinylidene chloride film, and a polyethylene gas copolymerization. A film, a polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, a cellulose derivative, or the like. These films may be used as extenders as needed. The haze of the support (A) is preferably 5. 〇 or less. The thickness of the support (A) is relatively thin in terms of image formation and economy, but in order to maintain the strength, the thickness is usually 10 to 30 μm, which is necessary for the negative photosensitive resin layer (Β). A protective layer (pad) is laminated on the surface opposite to the side of the support (Α) side. The adhesion between the protective layer and the negative photosensitive resin layer is higher than that of the support (Α) and the negative photosensitive resin layer (Β). The bonding force is sufficiently small, so the protective layer can be easily peeled off. The protective layer is important (for example, a polyethylene film, a polypropylene film, etc.). When the negative photosensitive resin laminate has a protective layer, it is a negative type. Before the photosensitive resin layer (Β) is formed on the substrate (c), a protective layer is formed on the surface of the negative photosensitive resin layer (B) in advance, and the protective layer is peeled off by 136693.doc • 35-200947116, by The negative photosensitive resin layer (B) is laminated on the surface of the substrate (c) by heating and pressing. The heating temperature at this time is usually 4 〇 16 〇 〇. The thickness of the negative photosensitive resin layer (B) is different. It is not the same in use. It is usually 5~1〇〇, preferably 5~50 μηι when used to make printed circuit boards (printed wiring boards). The resolution is higher and the resist size reproducibility is more remarkable. On the other hand, the film thickness is preferably in the range of 5 to 25 μm. The resin laminate may be exposed by i-line monochromatic light by i-line monochromatic light, active light such as ultraviolet light, etc. In the exposure step, the exposure portion of the negative photosensitive resin layer (B) is exposed. Hardening. As the light source used in the exposure step, high pressure mercury lamp, ultra high pressure mercury lamp, ultraviolet fluorescent lamp, carbon arc lamp, xenon lamp, laser, etc. can be used. These light sources can be used directly, and a band pass filter can also be used. If the exposure wavelength is formed as an i-line monochromatic, the resolution is improved, so it is preferable to use a sinusoidal monochromatic light. Between the laminate forming step and the exposure step, the self-negative photosensitive resin The support (A) is peeled off on the layer (B). Then, it is also preferable to expose the remaining negative photosensitive resin layer (B) in the exposure step. In this case, the resist cross-sectional shape is formed into a rectangular shape, that is, It is particularly preferable because it is formed to have almost no thickness of the top of the resist and a narrow shape of the bottom of the resist. Generally, as an exposure method used for exposure, a projection exposure method (projection exposure method) can be cited. In the present invention, a projection type exposure method is employed in which a light-projecting light is used to expose a negative photosensitive resin layer via a lens. Further, in the typical state of the present invention In the present invention, the light from the light source passes through the reticle and the lens to reach the negative photosensitive resin layer, but the light from the light source is also 136693.doc-36-200947116, which can pass through the lens and then pass through the reticle. The projection type exposure method is used, and the light transmittance at a wavelength of 365 nm is 25% or more and 50% or less, whereby the resist size reproducibility is remarkably improved. Further, in the projection type exposure method, the wavelength is 365 nm. The light transmittance of the negative photosensitive resin layer (B) is 25% or more and 50% or less, and the support (A) is peeled off before exposure, and the following advantages are obtained: the resist shape is formed as The rectangle 'is formed almost without the coarseness of the top of the resist and the narrow shape of the bottom of the resist.继 In the case where the support (A) is present on the negative photosensitive resin layer (B), the support (A) is removed as needed, and then the unexposed portion of the negative photosensitive resin layer (B) is developed and removed. Thereby, a resist cured product containing the cured portion of the negative photosensitive resin layer (B) is formed. As the developing method, for example, a method of removing the unexposed portion of the negative photosensitive resin layer (B) using an aqueous alkaline solution can be mentioned. As the alkaline aqueous solution, water/preparation liquid such as sodium carbonate or potassium carbonate can be used. These alkaline aqueous solutions can be selected according to the e characteristics of the negative photosensitive resin layer (B), and usually a sodium carbonate aqueous solution of ο" to 3% by mass is used. Thus, the anti-surname hardening of the present invention can be obtained. <Manufacturing Method of Printed Wiring Board> * The method of manufacturing the printed wiring board using the negative photosensitive resin laminate is described below. The present invention provides a method of manufacturing a printed wiring board, comprising the steps of: etching or plating a substrate (c) having a resist pattern formed by a resist cured product obtained by the above-described manufacturing method; The resist hardened material is removed on the substrate (c). In the method of manufacturing a printed wiring board according to the present invention, t is a metal plate to be used for the development step in the manufacturing method of the above-described anti-moisture hardened material by using a metal plate 136693.doc • 37· 200947116 as a substrate (c) On the exposed metal surface, an image pattern of the metal is formed by any of the known methods (methods) or electro-mineral methods. Then, the hardened resist pattern is peeled off by using an aqueous solution which is more alkaline than the alkaline aqueous solution which is usually used for development. The alkaline aqueous solution for peeling is not particularly limited, and an aqueous solution of sodium hydroxide or potassium hydroxide of 1 to 5% by mass is usually used. By forming the image pattern by using the present invention, in addition to the above-mentioned printed wiring board (printed circuit board), a semiconductor package substrate, a lead frame, a rib of a plasma display, or the like can be formed. As shown in Fig. i, the cross section of the resist line obtained by the present invention is shown to be close to a rectangular (rectangular) good shape. That is, the problem of the coarseness of the top of the resist and the narrowness of the bottom of the resist which are produced in the prior art manufacturing method as shown in FIG. 2 is remarkably reduced, and the pre-self-negative photosensitive resin layer as shown in FIG. When the support is peeled off and the exposure is performed, the cross-sectional shape of the resist is formed into a "spool shape", and the problem that the anti-surname agent is large is remarkably reduced. Therefore, the present invention can be particularly well applied to the manufacture of semiconductor package substrates. In the case of manufacturing the lead frame by using the present invention, a metal plate such as copper, a copper alloy or an iron-based alloy is used as the substrate (C), after the exposure step and the development step in the method for producing the anti-surname agent. The exposed substrate surface is etched. Finally, the resist hardened material is peeled off to obtain a desired lead frame. Further, in the case of using the present invention to manufacture a barrier wall of a plasma display panel, a glass rib can be used as the substrate (C), and an exposure step and a development step in the above-described method for producing a cured resist are 136693.doc -38- 200947116 After the surface is processed, the resist is removed, and the substrate pattern of the exposed substrate w convex pattern is obtained by the mouth sand method. [Embodiment] Hereinafter, the present invention will be more specifically described by way of examples. Embodiments, but the present invention is not limited to the embodiments. <Negative photosensitive resin composition> The compositions of the negative photosensitive resin compositions used in the examples and the comparative examples are shown in Tables 1 and 2 below. ❹ ❹ •39· 136693.doc 7 94 o 20 6 ΓΟ •ζ ο ο . /061 ς luw-1uni-1 03 ·0 •ζ ο ο o/olz •ς VZI4^- 03 0Ζ

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C/08Z y09€. /01 inch Zhu® FiF^^wKsuse •w ετιΞ 10- 〇9 ·inch iol — 6 ◎ — one inch 丨to- i6 ◎ OOPS99- • 41 200947116 In the table, the negative represented by the abbreviation (Ρ-l~Cl) The components of the photosensitive resin composition will be described in the following <Symbol Description>. In the table, 卩-丨 and! The value of 》·〗 is the amount of solid component. &lt;Symbol Description&gt; Ρ-l: a mercaptoethyl ketone solution of a terpolymer of 30% by mass of mercaptoacrylic acid, 20% by mass of styrene, and 50% by mass of benzyl methacrylate (solid content concentration of 40 mass%) %, weight average molecular weight is 55, 〇〇〇, acid equivalent is 287, glass transition temperature is l 〇 2 ° C) P-2: dimethyl methacrylate 80% by mass, methacrylic acid 20% by mass of binary copolymerization Methyl ethyl ketone solution (solid content concentration of 5% by mass, weight average molecular weight of 25,000 'acid equivalent of 430, glass transition temperature of 78 ° C) Μ-1: an average of 12 moles in addition The two ends of the polypropylene glycol of propylene oxide are respectively added to the average of 3 moles of ethylene oxide polyalkylene glycol dimethacrylate oxime-2: pentaerythritol triacrylate and pentaerythritol tetraacrylate 7: 3 (Morbi) mixture Μ-3. Adding an average of 5 moles of epoxy-glycolized polyethylene glycol dimercapto acrylate to both ends of bisphenol oxime (Xinzhongcun Chemical Industry Co., Ltd.) Manufactured NK ESTER BPE-500) M-4 : Tetraethylene Glycol Dimethacrylate M-5 : Trishydroxyl Propane triacrylate A-1 : 2-(o-phenyl)_4,5-diphenylimidazole dimer A-2 : 4,4^ bis(diethylamino) dimercapto ketone 136693.doc -42- 200947116 Bl : Diamond Green (aizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.) B-2: leuco crystal violet C-1: pentaerythritol tetra [3-(3,5-di- Third butyl_4_hydroxyphenyl)propionate] &lt;Formation method of negative photosensitive resin layer (B)&gt; Hereinafter, the negative photosensitive resin layer (B) is formed on a support (A) The method above is explained. In the examples and the comparative examples, the components shown in Tables i and 2 were mixed and uniformly dissolved by using mercaptoethyl ketone as a solvent so that the concentration of the nonvolatile component was 50% by mass to prepare a negative photosensitive resin. A solution of the composition. The solution of the obtained negative photosensitive resin composition was uniformly applied onto a polyethylene terephthalate Sb film having a thickness of 2 μm as a support (A) by using a bar coater at 95 C. Dry in a desiccator for 3 minutes. The thickness of the negative photosensitive resin layer (B) obtained after drying was 25 μm. The light transmittance of the negative photosensitive resin layer (Β) formed on the above polyethylene terephthalate at a wavelength of 365 nm is U-33 10 type spectroscopic manufactured by Hitachi High-Technologies Corporation. The photometer was measured by placing the above polyethylene terephthalate film on the reference side. Further, at this time, the slit was set to 4 nm ′ and the scanning speed was set to 600 nm/min. On the negative photosensitive resin layer (B), a polyethylene film having a thickness of 25 μm was bonded to the protective layer to obtain a laminated film. The surface of the copper foil laminate as the substrate (C) having 35 rolled copper foil laminated thereon was subjected to sandblasting, and the polyethylene film of the laminated film was peeled off, and the film was attached by a heat roller. 136693.doc -43- 200947116 The negative photosensitive resin layer (B) was laminated on a substrate at 105 ° C to obtain a negative photosensitive resin laminate. &lt;Preparation of Resist Hardened Material&gt; The above-mentioned photomask film was used at 180 mJ/cm 2 by a projection exposure machine (UX2003 SM-MS04 manufactured by USHI Electric Co., Ltd., using an i-line band pass filter). The negative photosensitive resin laminate obtained was irradiated with i-line monochromatic light ', and the negative photosensitive resin layer (B) was exposed with 1-line monochromatic light. Then, a 1% by mass aqueous sodium carbonate solution at 30 ° C was sprayed for about 4 sec seconds to dissolve and remove the unexposed portion, thereby performing development. Then, the hardened portion (exposure portion) of the remaining negative photosensitive resin layer (B) was sprayed with water for about 20 seconds using ion-exchanged water to obtain a cured resist of the present invention. Further, in the examples and comparative examples shown in Table 1, the polyethylene terephthalate (diacetate film) was peeled off before the above-mentioned sodium carbonate aqueous solution was sprayed, and in the examples and comparative examples shown in Table 2, The polyethylene terephthalate film was peeled off before the above exposure. The exposure sensitivity was measured using a 27-step stage tablet manufactured by Asahi Kasei, whose brightness was changed from transparent to black in 21 stages. The obtained resist cured product was evaluated using the following "valence basis." (1) Resolution: In the above exposure, a light-shielding film having a line and a gap of i: was used for exposure and development. The minimum line width that can be separated is taken as the resolution. (7) Adhesiveness: In the above exposure, the mask material with line and gap is μ_μΐη indicates line width) and the % of the mask is exposed. The minimum line width of the obtained hardened pattern can be closely connected. 136693.doc •44- 200947116 (3) Resist shape: In the above exposure, a photomask film with a line width of 12 μηι was used. An electron microscope (Sm-500 manufactured by TOPCON Co., Ltd.) was used. The shape of the anti-surname agent is confirmed at an acceleration voltage of 15 kV, a magnification of 1,000 times, and a tilt angle of 60 degrees. If the difference between the line width of the hardened pattern between the top of the anti-surname agent and the anti-surname agent is less than 1 μm, it is marked as ◎. If it is 1 μπι or more and less than 2 μηι, it is denoted by 〇, and if it is 2 μηι or more, it is denoted by X. <Example 1Α~8Α, Comparative Example 1Α~4Α, Example 1Β~7Β, Comparative Example 1Β~4Β&gt Negative photosensitive tree The composition of the composition and the evaluation results are shown in Tables 1 and 2. It can be confirmed that the light transmittance at a wavelength of 365 nm is within the range of the present invention, and the light transmittance is through the examples 1A to 8A and the examples 1B to 7B. The ratios of the comparative examples 1A to 4A and the comparative examples 1B to 4B which are outside the range of the present invention are superior in terms of the evaluation criteria including the resolution, the adhesion, and the shape of the anti-button agent. Example 2 A and Comparative Example 1A Electron micrographs of the resist shape of the obtained resist cured product are shown in Fig. 1 and Fig. 2. The resist shape in Example 2A is close to a rectangle, whereas the comparative example 观察A is observed. The apparent enlargement of the top of the resist and the apparent narrowness of the bottom of the resist. Electron micrographs of the resist opening of the cured resist obtained in Example 2B and Comparative Example 1B are shown in Fig. 3 and In Fig. 4, the resist shape in Example 2B is close to a rectangular shape, whereas the bottom of the resist is observed to be narrow in the comparative example (7), and the resist residue is observed to be large (the resist profile shape is "Spool"). [Industrial Applicability] 136693.doc -45· 200947116 The present invention can be widely applied to the manufacture of printed wiring boards (printed circuit boards), integrated circuits (1C), lead frames for wafer mounting, and semiconductor packages. Wait. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an electron micrograph of the shape of a resist of Example 2A. Fig. 2 is an electron micrograph of the shape of the resist of Comparative Example 1A. Figure 3 is an electron micrograph of the resist shape of Example 2B. Fig. 4 is an electron micrograph of the shape of the resist of Comparative Example 1B. 136693.doc 46·

Claims (1)

200947116 X. Patent application scope: 1. A method for manufacturing an anti-contact agent hardened material, comprising: a layer forming step, which is formed by at least a support (A), a negative-type photosensitive steep tree layer (B) a negative photosensitive resin laminate laminated with a substrate (C); an exposure step 'Using light for projecting an image of the mask' to expose the negative photosensitive resin layer (B) via a lens; and developing a step of forming a resist cured product including the cured portion of the negative photosensitive resin layer (B) by developing the unexposed portion of the negative photosensitive resin layer (B); and the negative type The light transmittance of the photosensitive resin layer (B) at a wavelength of 365 nm is 25% or more and 50% or less. 2. The method of producing a resist cured product according to claim 1, wherein the light is an i-line early color light. 3. The method for producing an anti-reagent hardened material according to claim 1, wherein the support is formed by peeling the support from the negative photosensitive resin layer (B) between the laminate forming step and the exposing step. The support stripping step. 4. The method for producing a cured resist of the present invention, wherein the negative photosensitive resin layer (B) has a light transmittance of 35% or more and 45% or less at a wavelength of 365 nm. 5. The method for producing a cured resist of claim 1, wherein the negative photosensitive resin layer (B) comprises a negative photosensitive resin composition, and the negative photosensitive resin composition contains (a) The content of the slow base is 136,693.doc 200947116 100 to 600 in terms of acid equivalent, and the weight average molecular weight is 5, 〇〇〇 5 〇〇, and the binder between the ruthenium is 20 to 90 by mass of the resin. /〇, (b) 3 to 70% by mass of the photopolymerizable unsaturated compound, and (c) photopolymerization initiator 〇1 to 20 mass 〇/0. 6. The method for producing a cured resist of claim 5, which comprises at least the above-mentioned compound selected from the group consisting of benzophenone and dibenzophenone derivatives as (c) photopolymerization initiator . 7. The method for producing a cured resist of claim 5, which comprises a 24 5 -diarylimidazole dimer as the above (c) photopolymerization initiator. 8. The method for producing a cured resist of claim 5, which comprises at least a compound selected from the group consisting of benzophenone and a benzophenone derivative, and 2,4,5·triaryl Both of the imidazole dimers are used as the above (c) photopolymerization initiator. 9. The method for producing a cured resist of claim 5, wherein the photopolymerizable unsaturated compound is selected from the group consisting of a compound represented by the following formula (1) and represented by the following formula („); a group consisting of: [Chemical 1] h2c ^_^〇'^〇2Η4〇^η2~(〇3Ηβ〇)η3-{〇2Η4〇)η4-〇—C=CH; (1) Ο {中中' RAR9 is independently Η or CH3, and n2 and n3An4 are each independently an integer of 3 to 20}; [Chemical 2] 136693.doc (II) 200947116 -iA-〇)n5-CB-〇)n7-C^«&lt;;Ha H,C-C-CH, -i Α-0^ηβ-( B-0)n, -c-^ {wherein, Rio and R&quot; are independently H or CH3, A is C2H4, B is C3H6, and ns+n6 is an integer from 2 to 30. ' For 〇~3〇 integer, ~ and !!6 is an integer of 1~29, phantom and!! 8 is an integer of 〇~29, repeating unit _(A_ 〇)-and-(B-0) - The arrangement may be random or block, and in the case of a block, both may be on the bisphenol side}. Οοι . ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι An anti-surname agent pattern formed by a hardened agent obtained by a manufacturing method; and a step of removing the above-mentioned resist cured material from the substrate (C). A negative photosensitive resin laminate for forming a resist cured product by exposing a negative photosensitive resin layer through a lens using i-line monochromatic light that projects an image of a photomask, and The negative photosensitive resin layer (B) having at least a support (A) and i-line monochromatic exposure, and the negative photosensitive resin layer (B) comprising: (4) a carboxyl group content, and an acid amount of 1 〇〇~600, and the weight average molecular weight is between 5 〇〇〇 5 〇 0'000 of the binder resin 20 to 90% by mass, (b) the light 136693.doc 200947116 polymerized unsaturated compound 3~ 70% by mass, and (c) a photopolymerization initiator 0·1 to 20% by mass of a negative photosensitive resin composition for i-line single-color exposure, and the negative photosensitive resin layer (B) at a wavelength of 365 The light transmittance at nm is 25% or more and 50% or less. 12. If the request is 丄! In the negative photosensitive resin laminate, the light transmittance of the negative photosensitive resin layer (B) at a wavelength of 365 nm is 35% or more and 45% or less. The negative photosensitive resin laminate according to claim 11, wherein the (a) binder resin has a glass transition temperature of 1 Torr. (1) The negative photosensitive resin laminate according to claim 11, wherein the weight average molecular weight of the (a) binder resin is between 1 〇 and 40 40,000. The negative photosensitive resin laminate comprising at least one compound selected from the group consisting of benzophenone and benzophenone derivatives as the photopolymerization initiator (C). A negative photosensitive resin laminate comprising a 2,4,5-triarylimidazole dimer as the above (C) photopolymerization initiator. 17. The negative photosensitive resin laminate according to claim 11, Containing at least one selected from the group consisting of benzophenone I and a benzophenone derivative, and 2,4,5-triarylimidazole dimer as the above (c) photopolymerization 18. The negative photosensitive resin laminate according to claim 11, wherein the photopolymerizable unsaturated compound is selected from the group consisting of a compound represented by the following formula (丨) and the following formula (II) ) The composition of the compound represented by 136693.doc (I) 200947116 «έ : [Chemical 3] H2C ===6-00 ·~(^2Η4〇)η2~(〇3ΗΒ0)η3-(〇2Η4〇)Π4—〇一6=CH2 0 A {wherein, Rs and R·9 are independently Η or CH3, and η2, 113 and ru Independently an integer of 3 to 20}; [Chemical 4] ❹ ❿ R, -&lt;Α-Ο}η$-0Β-Ο)«7-4·^«Κ;Η8 (Π) )-ί Α-0)ηβ-ι( Β·〇)ϊ»ι-^-^ aCK4 In the formula, R丨〇 and R&quot; are independently Η or CH3, Α is C2H4, Β is c3H6, h+ii6 is an integer from 2 to 30, and ~+~ is 整数~3〇 integer, ~ and ~ independent An integer of 1 to 29, ... and ... is an integer of 〇~29, and the repeating unit _(A_ 〇)- and the arrangement may be random or block, and in the case of a block, may be located in bisphenol Base side}. 19. The negative photosensitive resin laminate according to claim 5, further comprising a protective layer on said negative photosensitive resin layer (B). 2. A method of using a negative photosensitive resin laminate, which exposes a negative photosensitive resin layer via a lens by using i-line monochromatic light that projects an image of a photomask (4) In the case of the negative photosensitive resin layer (b), the negative photosensitive resin layer system has at least a support (A) and a negative photosensitive resin layer (b) for i-line single-color exposure. The negative photosensitive resin layer (B) contains a negative photosensitive resin composition for i-line single-color exposure, and the negative photosensitive resin composition contains (a) a carboxyl group content of 1 in terms of acid equivalent. 20 to 90% by mass of the binder resin having a weight average molecular weight of 5,000 to 500,000, (b) 3 to 70% by mass of the photopolymerizable unsaturated compound, and (photopolymerization) The starting agent is 0.1 to 20% by mass' and the light transmittance of the negative photosensitive resin layer (B) at a wavelength of 365 nm is 25% or more and 50% or less. 21. 22. 23. 24. 25. 26. A method of using a negative photosensitive resin laminate according to claim 20, wherein the above The photosensitive resin layer (B) has a light transmittance of 35% or more and 45% or less at a wavelength of 365 nm. The method of using the negative photosensitive resin laminate of claim 20, wherein the (a) adhesive is used. The glass transition temperature of the resin is i00 °c or more. The method of using the negative photosensitive resin laminate of claim 20, wherein the weight average molecular weight of the (a) binder resin is 〇〇〇〇~4〇, The method for using a negative photosensitive resin laminate according to claim 20, which comprises at least one compound selected from the group consisting of a benzophenone and a benzophenone derivative as the above ( c) Photopolymerization initiator. A method of using a negative photosensitive resin laminate according to claim 20, which comprises a 2,4,5-triarylimidazole dimer as the above (c) photopolymerization initiator. A method of using a negative photosensitive resin laminate of claim 20, wherein 136693.doc 200947116 contains at least one compound selected from the group consisting of dibenzophenone and a benzophenone derivative, and 2, 4, 5 - Triaryl taste ° sit dimer, as (c) a photopolymerization initiator. The method of using the negative photosensitive resin laminate according to claim 20, wherein the (a) photopolymerizable unsaturated compound is selected from the group consisting of the following formula (I) a group consisting of a compound represented by the following formula (II): [Chemical 5] ❹ H2c ==i-CO-(C2H4〇}n2-(C3HeO)n3-{C2H4〇) n4-C—C=CH2 (I) Ά II ο ο {wherein, the ruler 8 and R9 are independently Η or CH3, and η2, η3 and η4 are each independently an integer of 3 to 20}; [Chem. 6] (II) where R10 and Rii are independently Η or CH3, Α is C2H4, Β is C3H6, 115+116 is an integer from 2 to 30, n7+n8 is an integer from 0 to 30, and n5 and n6 are independently 1 An integer of ～29, n7 and n8 are independently an integer of 0 to 29, and the arrangement of the repeating unit -(A-0)- and -(B-0)- may be random or block, and is 136693 as a block. .doc 200947116 In both cases, it can be located on the bisphenol side}. The method of using a negative photosensitive resin laminate according to claim 20, further comprising a protective layer on the negative photosensitive resin layer (B). 136693.doc 200947116 VII. Designated representative map: (1) The representative representative of the case is: (2). (2) A brief description of the symbol of the representative figure: (No component symbol description) 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: h2c 4ι〇0-(C2H40)n2 - (C3He0&gt;n3 -{C2H40>n4-$-C=CH: Ο (1) 136693.doc