KR101175079B1 - Method for producing cured resist using negative photosensitive resin laminate, negative photosensitive resin laminate, and use of negative photosensitive resin laminate - Google Patents

Abstract

Provided are a method for producing a cured resist, a negative photosensitive resin laminate, and a negative photosensitive resin laminate, which provide a resist pattern having excellent adhesion and resolution and good resist shape after development. The manufacturing method of the resist hardened | cured material which concerns on this invention is a laminated body formation process of forming the negative photosensitive resin laminated body by which the support body (A), negative photosensitive resin layer (B), and the board | substrate (C) are laminated | stacked at least, The negative photosensitive property by developing and exposing the negative photosensitive resin layer (B) through the lens using the light which projected the image of the mask, and developing the unexposed part of the negative photosensitive resin layer (B). The manufacturing method of forming the resist hardened | cured material which consists of hardened parts of a resin layer (B), The light-transmittance in wavelength 365nm of this negative photosensitive resin layer (B) is 25%-50% or less The manufacturing method of the hardened | cured material to be.

Description

METHOD FOR PRODUCING CURED RESIST USING NEGATIVE PHOTOSENSITIVE RESIN LAMINATE, NEGATIVE PHOTOSENSITIVE RESIN LAMINATE, AND USE USE OF NEGATIVE PHOTOSENSITIVE RESIN LAMINATE}

The present invention relates to a method for producing a cured resist comprising using a negative photosensitive resin laminate having a negative photosensitive resin layer and exposing the negative photosensitive resin layer. More specifically, the present invention relates to a method for producing a cured resist using a negative photosensitive resin laminate having a negative photosensitive resin layer suitable for manufacturing printed circuit (wiring) plates, lead frames, semiconductor packages and the like. will be. This invention also relates to the negative photosensitive resin laminated body which has a negative photosensitive resin layer for i line | wire monochromatic exposure, and the method of using a negative photosensitive resin laminated body. More specifically, the present invention provides a negative photosensitive resin laminate and a negative type having a negative photosensitive resin layer for i developable single-line monochrome exposure, which is suitable for manufacturing printed circuit (wiring) plates, lead frames, semiconductor packages and the like. It relates to a method of using the photosensitive resin laminate.

The conventional printed wiring board was manufactured by the photolithography method. The photolithography method is a method of forming a pattern using the photoreaction of the photosensitive resin composition. When using a negative photosensitive resin composition, after apply | coating this photosensitive resin composition on a board | substrate to form a photosensitive resin layer, pattern exposure is carried out, the exposure part of this photosensitive resin composition is polymerized and hardened, the unexposed part is removed with a developing solution, After the resist pattern is formed and the conductor pattern is formed by etching or plating, the conductor pattern can be formed on the substrate by peeling off the resist pattern from the substrate.

In the said negative photolithography method, when apply | coating a negative photosensitive resin composition on a board | substrate, the method of apply | coating a negative photosensitive resin composition solution to a board | substrate and drying, or the layer which consists of a support body and a negative photosensitive resin composition (following) And also called "negative photosensitive resin layer." And if the method of laminating | stacking the dry film resist which laminated | stacked the protective layer sequentially on the board | substrate is used in some cases. In the manufacture of a printed wiring board, the latter method of laminating a dry film resist on a substrate is often used.

The method of manufacturing a printed wiring board using a dry film resist is demonstrated below. First, when a dry film resist has a protective layer, for example, a polyethylene film, a protective layer is peeled from a negative photosensitive resin layer. Subsequently, a negative photosensitive resin layer and a support body are laminated | stacked on a board | substrate, for example, a copper clad laminated board, in order of a board | substrate, a negative photosensitive resin layer, and a support body using a laminator. Subsequently, an exposure part is polymerized and hardened | cured by exposing the negative photosensitive resin layer with ultraviolet rays, such as i line | wire (wavelength 365nm) from which ultra-high pressure mercury lamp emits through the photomask which has a wiring pattern. Next, the support body which consists of polyethylene terephthalate etc. is peeled off. Subsequently, the unexposed part of the negative photosensitive resin layer is dissolved or removed by developing solution such as an aqueous solution having weak alkali property to form a resist pattern on the substrate. Next, a well-known etching process or pattern plating process is performed using the formed resist pattern as a protective mask. Finally, the resist pattern is peeled off from the substrate to produce a substrate having a conductor pattern, that is, a printed wiring board.

Recently, with the miniaturization and weight reduction of electronic devices such as mobile phones and laptops, the demand for miniaturization of wiring intervals in printed wiring boards is increasing. In order to meet such a miniaturization requirement, the expectation for using i-line monochromatic light with little chromatic aberration also increases in the exposure method to a dry film resist. Moreover, in the use which requires high resolution, in order to avoid the influence of the lubricating agent etc. which are contained in a support body, it may expose after peeling a support body beforehand. However, in the exposure method using the conventional dry film resist, as shown in FIG. 2, a resist is thick in a resist top and a resist is thin in a resist bottom, and there exists a problem in resist dimensional reproducibility. Moreover, when exposing after peeling a support body previously, as shown in FIG. 4 mentioned later, since the resist cross section shape became a "bobbin shape", and the resist foot was large, there existed a problem in resist dimensional reproducibility.

The method of manufacturing a printed wiring board using a dry film resist is exposed by exposing a negative photosensitive resin layer through a photomask having a wiring pattern, using ultraviolet rays such as i-line (wavelength 365 nm) emitted by an ultra-high pressure mercury lamp. Polymerizing and curing the part, dissolving or dispersing the unexposed part of the negative photosensitive resin layer with a developing solution such as an aqueous solution having weak alkali properties, and other steps. It is not known at what stage the cause of thickening in the resist top and thinning in the resist bottom, the cross-sectional shape of the resist becoming the bobbin shape, and the increase in the resist foot are generated.

Patent document 1 has description regarding the dry film resist which prescribed | regulated the absorbance in wavelength 365nm. However, there is no description regarding i line | wire monochromatic exposure in patent document 1. Moreover, in patent document 1, there is no description regarding exposing after peeling a support body beforehand.

Japanese Laid-Open Patent Publication 2006-145565

An object of the present invention is to provide a method of producing a cured resist, a negative photosensitive resin laminate, and a method of using a negative photosensitive resin laminate, which bring about a resist pattern having excellent adhesion and resolution and an excellent resist shape after development. will be.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, this time surprisingly, when exposing the negative photosensitive resin laminated body which has a support body (A), a negative photosensitive resin layer (B), and a board | substrate (C), By changing the light transmittance of the negative photosensitive resin layer (B), specifically, by using a negative photosensitive resin layer (B) having a light transmittance at a wavelength of 365 nm of 25% or more and 50% or less, the resist pattern after development It has been found that the present invention has been completed by discovering that the adhesion and resolution and the resist shape are dramatically improved as compared with a resist prepared using a negative photosensitive resin layer having a conventional light transmittance. Moreover, when carrying out i line | wire monochromatic exposure of the laminated body which has a negative photosensitive resin layer, (a) Resin for binders whose carboxyl content is 100-600 in acid equivalent and a weight average molecular weight is 5,000-500,000: 20-90 mass% and (b) a photopolymerizable unsaturated compound: 3 to 70 mass%, and (c) a photopolymerization initiator: 0.1 to 20 mass%, wherein the light transmittance at a wavelength of 365 nm is 25% or more and 50 By using a negative photosensitive resin layer of% or less, it has been found that the adhesion, resolution and resist shape of a resist pattern after development are dramatically improved as compared with the case of using a negative photosensitive resin layer having a light transmittance outside the above range. The present invention has been reached. Specifically, the said subject is solved by the invention of the following [1]-[28].

[1] a laminate-forming step of forming a negative photosensitive resin laminate in which at least the support (A), the negative photosensitive resin layer (B), and the substrate (C) are laminated;

An exposure step of exposing the negative photosensitive resin layer (B) through a lens using light projected from the image of the photomask,

The development process of forming the resist hardened | cured material which consists of hardened | cured parts of the negative photosensitive resin layer (B) by image development removal of the negative photosensitive resin layer (B),

The light transmittance in wavelength 365nm of this negative photosensitive resin layer (B) is 25% or more and 50% or less, The manufacturing method of the resist hardened | cured material.

[2] The method for producing a cured resist according to the above [1], wherein the light is i-ray monochromatic light.

[3] The above [1] or [2], further comprising a support peeling step of peeling the support A from the negative photosensitive resin layer (B) between the laminate forming step and the exposure step. The manufacturing method of the resist hardened | cured material of description.

[4] The method for producing a cured resist according to any one of the above [1] to [3], wherein the negative photosensitive resin layer (B) has a light transmittance at a wavelength of 365 nm of 35% or more and 45% or less.

[5] The negative photosensitive resin layer (B) is (a) 20 to 90 mass% of a resin for a binder having a carboxyl group content of 100 to 600 in acid equivalent and a weight average molecular weight of 5,000 to 500,000, and (b) photopolymerization. The manufacturing method of the resist hardened | cured material in any one of said [1]-[4] which consists of a negative photosensitive resin composition containing 3 to 70 mass% of the unsaturated compound which can be used, and 0.1-20 mass% of (c) photoinitiators.

[6] The production method according to the above [5], wherein the (c) photopolymerization initiator contains at least one compound selected from the group consisting of benzophenone and benzophenone derivatives.

[7] The production method according to the above [5] or [6], which contains 2,4,5-triarylimidazole dimer as the photopolymerization initiator (c).

[8] The above-mentioned (c) containing at least one compound selected from the group consisting of benzophenone and benzophenone derivatives as photopolymerization initiators, and both 2,4,5-triarylimidazole dimers. 5] to the manufacturing method in any one of [7].

[9] The unsaturated polymer (b) capable of photopolymerizing the following general formula (I):

[Formula 1]

{Wherein, R ₈ and R ₉ are independently H or CH _3, and, and n _2, n ₃ and n ₄ are each independently an integer from 3 to 20} the compound, and the following general formula (Ⅱ) represented by :

[Formula 2]

{Wherein R ₁₀ and R ₁₁ are independently H or CH ₃ , A is C ₂ H ₄ , B is C ₃ H ₆ , n ₅ + n ₆ is an integer from 2 to 30, n ₇ + n ₈ is an integer from 0 to 30, n ₅ and n ₆ are independently an integer from 1 to 29, n ₇ and n ₈ are an integer from 0 to 29 independently,-(AO)-and-(BO) The array of repeating units of-may be random or may be a block, and in the case of a block, either may be a bisphenol group side.} The resist according to any one of the above [5] to [8], which is selected from the group consisting of compounds. Method for producing a cured product.

[10] a step of etching or plating the substrate (C) having a resist pattern formed by the cured resist obtained by the production method described in any one of [1] to [9] above;

The manufacturing method of the printed wiring board containing the process of removing the resist hardened | cured material from this board | substrate (C).

[11] A negative photosensitive resin laminate used for forming a cured resist by exposing a negative photosensitive resin layer through a lens using i-line monochromatic light projecting an image of a photomask,

At least it has a support body (A) and the negative photosensitive resin layer (B) for i line | wire monochromatic exposure,

The negative photosensitive resin layer (B) is (a) 20 to 90% by mass of a resin for a binder having a carboxyl group content of 100 to 600 in an acid equivalent and a weight average molecular weight of 5,000 to 500,000, and (b) an unsaturated compound capable of photopolymerization. It consists of the negative photosensitive resin composition for i line | wire monochromatic exposure containing 3-70 mass% and (c) 0.1-20 mass% of photoinitiators, and

The negative photosensitive resin laminated body whose light transmittance in wavelength 365nm of this negative photosensitive resin layer (B) 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 at a wavelength of 365 nm of 35% or more and 45% or less.

[13] The negative photosensitive resin laminate according to [11] or [12], wherein the glass transition temperature of the resin for binder (a) is 100 ° C or higher.

[14] The negative photosensitive resin laminate according to any one of the above [11] to [13], wherein the weight average molecular weight of the resin for the (a) binder is between 10,000 and 40,000.

[15] The negative photosensitive resin laminate according to any one of [11] to [14], which contains at least one compound selected from the group consisting of benzophenone and benzophenone derivatives as the (c) photopolymerization initiator. .

[16] The negative photosensitive resin laminate according to any one of [11] to [15], containing 2,4,5-triarylimidazole dimer as the photopolymerization initiator (c).

[17] The above-mentioned (c) containing at least one compound selected from the group consisting of benzophenone and benzophenone derivatives as photopolymerization initiators, and both 2,4,5-triarylimidazole dimers. 11]-The negative photosensitive resin laminated body in any one of [16].

[18] The (b) photopolymerizable unsaturated compound is represented by the following general formula (I).

(3)

{Wherein, R ₈ and R ₉ are independently H or CH _3, and, and n _2, n ₃ and n ₄ are each independently an integer from 3 to 20} the compound, and the following general formula (Ⅱ) represented by :

[Formula 4]

{Wherein R ₁₀ and R ₁₁ are independently H or CH ₃ , A is C ₂ H ₄ , B is C ₃ H ₆ , n ₅ + n ₆ is an integer from 2 to 30, n ₇ + n ₈ is an integer from 0 to 30, n ₅ and n ₆ are independently an integer from 1 to 29, n ₇ and n ₈ are an integer from 0 to 29 independently,-(AO)-and-(BO) The arrangement of the repeating unit of-may be random or may be a block, and in the case of a block, the negative type according to any one of the above [11] to [17], which is selected from the group consisting of compounds represented by the above formula. Photosensitive resin laminated body.

[19] The negative photosensitive resin laminate according to any one of the above [11] to [18], which further has a protective layer on the negative photosensitive resin layer (B).

[20] A negative photosensitive resin layer for at least the support (A) and i-line monochrome exposure when forming a cured resist by exposing a negative photosensitive resin layer through a lens using i-line monochromatic light projecting an image of a photomask. As a negative photosensitive resin laminated body which has (B), the negative photosensitive resin layer (B) has (a) carboxyl group content of an acid equivalent in 100-600, and a weight average molecular weight between 5,000-500,000 resin for binders. It consists of the negative photosensitive resin composition for i line | wire monochromatic exposure containing 20-90 mass%, (b) 3-70 mass% of unsaturated compounds which can photopolymerize, and (c) 0.1-20 mass% of photoinitiators, and its negative type Negative photosensitive using the negative photosensitive resin laminated body whose light transmittance in wavelength 365nm of the photosensitive resin layer (B) is 25% or more and 50% or less. Usage of the resin laminate.

[21] The use method according to the above [20], wherein a light transmittance at a wavelength of 365 nm of the negative photosensitive resin layer (B) is 35% or more and 45% or less.

[22] The use method according to the above [20] or [21], wherein the glass transition temperature of the resin for the binder (a) is 100 ° C or higher.

[23] The use method according to any one of the above [20] to [22], wherein the weight average molecular weight of the resin for the (a) binder is between 10,000 and 40,000.

[24] The use method according to any one of [20] to [23], which contains at least one compound selected from the group consisting of benzophenone and a benzophenone derivative as the (c) photopolymerization initiator.

[25] The use method according to any one of [20] to [24], containing 2,4,5-triarylimidazole dimer as the photopolymerization initiator (c).

[26] The above-mentioned (c) containing at least one compound selected from the group consisting of benzophenone and benzophenone derivatives as photopolymerization initiators, and both 2,4,5-triarylimidazole dimers. 20]-the method of any one of [25].

[27] The (b) photopolymerizable unsaturated compound is represented by the general formula (I)

[Chemical Formula 5]

{Wherein, R ₈ and R ₉ are independently H or CH _3, and, and n _2, n ₃ and n ₄ are each independently an integer from 3 to 20} the compound, and the following general formula (Ⅱ) represented by :

[Formula 6]

{Wherein R ₁₀ and R ₁₁ are independently H or CH ₃ , A is C ₂ H ₄ , B is C ₃ H ₆ , n ₅ + n ₆ is an integer from 2 to 30, n ₇ + n ₈ is an integer from 0 to 30, n ₅ and n ₆ are independently an integer from 1 to 29, n ₇ and n ₈ are an integer from 0 to 29 independently,-(AO)-and-(BO) The arrangement of the repeating unit of-may be random or may be a block, and in the case of a block, any one may be a bisphenol group side.} The use according to any one of the above [20] to [26], which is selected from the group consisting of compounds. Way.

[28] The use method according to any one of [20] to [27], further comprising a protective layer on the negative photosensitive resin layer (B).

According to this invention, the resist pattern excellent in the adhesiveness and resolution after image development, and the outstanding resist shape can be obtained.

1 is an electron micrograph of the resist shape of Example 2A.
2 is an electron micrograph of a resist shape of Comparative Example 1A.
3 is an electron micrograph of a resist shape of Example 2B.
4 is an electron micrograph of a resist shape of Comparative Example 1B.

In one aspect of the present invention, a laminate-forming step of forming a negative photosensitive resin laminate in which at least a support (A), a negative photosensitive resin layer (B), and a substrate (C) are laminated,

An exposure step of exposing the negative photosensitive resin layer (B) through a lens using light projected from the image of the photomask,

The development process of forming the resist hardened | cured material which consists of hardened | cured parts of the negative photosensitive resin layer (B) by image development removal of the negative photosensitive resin layer (B),

The manufacturing method of the resist hardened | cured material whose light transmittance in wavelength 365nm of this negative photosensitive resin layer (B) is 25% or more and 50% or less is provided.

In another aspect of the present invention, there is provided a negative photosensitive resin laminate, which is used to form a cured resist by exposing a negative photosensitive resin layer through a lens using i-line monochromatic light projecting an image of a photomask,

At least it has a support body (A) and the negative photosensitive resin layer (B) for i line | wire monochromatic exposure,

The negative photosensitive resin layer (B) is (a) 20 to 90% by mass of a resin for a binder having a carboxyl group content of 100 to 600 in an acid equivalent and a weight average molecular weight of 5,000 to 500,000, and (b) an unsaturated compound capable of photopolymerization. It consists of the negative photosensitive resin composition for i line | wire monochromatic exposure containing 3-70 mass% and (c) 0.1-20 mass% of photoinitiators, and

The negative photosensitive resin laminated body whose light transmittance in wavelength 365nm of this negative photosensitive resin layer (B) is 25% or more and 50% or less is provided.

In another aspect of the present invention, at least for the support (A) and the i-line monochromatic exposure, when the cured resist is formed by exposing the negative photosensitive resin layer through the lens using the i-line monochromatic light projecting the image of the photomask. As a negative photosensitive resin laminated body which has a negative photosensitive resin layer (B), the negative photosensitive resin layer (B) has (a) carboxyl group content of 100-600 as acid equivalent, and weight average molecular weights 5,000-500,000 It consists of the negative photosensitive resin composition for i line | wire monochromatic exposure containing 20-90 mass% of resin for binders, (b) 3-70 mass% of unsaturated compounds which can photopolymerize, and (c) 0.1-20 mass% of photoinitiators, Moreover, the negative photosensitive resin laminated body whose light transmittance in wavelength 365nm of this negative photosensitive resin layer (B) is 25% or more and 50% or less The use method of the negative photosensitive resin laminated body which is used is provided.

In this specification, the term "negative photosensitive resin layer (B)" means the resin layer from which a negative pattern is obtained by exposing to actinic light and developing after that. Moreover, "negative photosensitive resin layer (B) for i line | wire monochromatic exposure" means the resist pattern desired by exposure in i line | wire (wavelength 365nm) monochromatic color and subsequent resolution among the said negative photosensitive resin layer (B). Say what you can get. The light transmittance in wavelength 365nm of the negative photosensitive resin layer (B) which concerns on this invention is 25% or more and 50% or less. When the light transmittance at a wavelength of 365 nm is in the above-described range, a resist pattern excellent in adhesion and resolution is obtained as compared with the case of the light transmittance outside the above-described range, and the resist dimensional reproducibility is improved. Moreover, in the aspect which provides the usage method of the negative photosensitive resin laminated body and negative photosensitive resin laminated body in this invention, the image of a photomask is projected because the light transmittance in wavelength 365nm is the range mentioned above. In the case of forming a cured resist by exposing a negative photosensitive resin layer through a lens using the i-line monochromatic light, a resist pattern excellent in adhesion and resolution is obtained as compared with the case of light transmittance outside the above-mentioned range. Moreover, resist dimension reproducibility becomes favorable. In the case of forming a cured resist by exposing a negative photosensitive resin layer through a lens using light projected from an image of a photomask, the cross-sectional shape of the resist becomes an inverted trapezoidal shape, which is thick at the resist top and thin at the resist bottom, resulting in resist dimensional reproducibility There is a problem. Moreover, in the aspect which performs exposure after peeling a support body previously, when forming a resist hardened | cured material by exposing the negative photosensitive resin layer through the lens using the light which projected the image of the said photomask, the resist cross-sectional shape will be There is a problem in resist dimensional reproducibility because it becomes a bobbin shape and the resist foot is large. On the other hand, when the said light transmittance exceeds 50%, since the negative photosensitive resin layer (B) cannot absorb the exposure light efficiently, there exists a problem that exposure sensitivity falls. These problems occur more remarkably when i-line monochromatic light is used. Then, the light transmittance at wavelength 365nm of a negative photosensitive resin layer (B) is 25% or more and 50% or less from a viewpoint of solving these problems and making it the outstanding resist shape. From the viewpoint of the adhesion and resolution of the resist pattern and the exposure sensitivity, the light transmittance at a wavelength of 365 nm of the negative photosensitive resin layer (B) of the present invention is more preferably 30% or more and 45% or less, and is 35% or more and 45% or less. The following is more preferable.

As a method of adjusting the light transmittance in wavelength 365nm of a negative photosensitive resin layer (B), The method of adding a ultraviolet absorber to the negative photosensitive resin composition used for forming a negative photosensitive resin layer (B), The method of adjusting the quantity of a photoinitiator is mentioned. Examples of the ultraviolet absorber include benzotriazole type, benzophenone type, salicylate type, cyanoacrylate type, nickel type, triazine type and the like. As a benzotriazole type ultraviolet absorber, 2- (2-hydroxy-5-t-butylphenyl) -2H- benzotriazole and benzene propanoic acid 3- (2H- benzotriazol-2-yl) -5- ( 1,1-dimethylethyl) -4-hydroxy C _7-9 side chain and straight chain alkyl ester, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1- Phenylethyl) phenol can be illustrated.

It is particularly preferable to select at least one compound selected from the group consisting of benzophenone and benzophenone derivatives described below as the photopolymerization initiator, in that a better improvement in adhesion and resolution of the resist pattern can be expected.

As a method of measuring the light transmittance at wavelength 365nm of the negative photosensitive resin layer (B) which concerns on this invention, a negative photosensitive resin layer (B) is formed on a support body, a support body is put in a reference light side, There is a method of canceling a portion and setting the slit to 4 nm and a scanning speed of 600 nm / minute with a spectrophotometer (manufactured by Hitachi Hi-Technologies, U-3310) and measuring it.

The negative photosensitive resin layer (B) which concerns on this invention is (a) 20-90 mass% of resin for binders whose content of carboxyl groups is 100-600 in acid equivalent, and a weight average molecular weight is 5,000-500,000, (b) photopolymerization It can be formed with the negative photosensitive resin composition containing 3-70 mass% of unsaturated compounds which can be formed, and 0.1-20 mass% of (c) photoinitiators.

The carboxyl group in resin for binders is necessary in order to provide developability and peelability with respect to aqueous alkali solution to a negative photosensitive resin layer. The amount of the carboxyl group in the binder resin is preferably 100 or more in terms of acid equivalent from the viewpoint of development resistance, resolution and adhesion, and preferably 600 or less in view of developability and peelability. More preferably, the acid equivalent may be 250 to 400. In view of providing a method of using the negative photosensitive resin laminate and the negative photosensitive resin laminate in the present invention, the acid equivalent is from 100 to 600, preferably from 300 to 400. An acid equivalent means the mass (gram equivalent) of the polymer (namely, binder resin) which has 1 equivalent of carboxyl groups.

The acid equivalent is measured by potentiometric titration using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Industries, Ltd., using 0.1 mol / L sodium hydroxide.

The weight average molecular weight of the resin for binders (a) which concerns on this invention can be between 5,000-500,000. (a) The weight average molecular weight of the resin for binder is preferably 500,000 or less from the viewpoint of developability, and 5,000 or more is preferable from the viewpoint of tenting film strength and edge fuse reduction. In order to heighten the effect of this invention further, it is preferable that the weight average molecular weights of (a) resin for binders are between 20,000-300,000. Moreover, from the aspect which provides the usage method of the negative photosensitive resin laminated body and negative photosensitive resin laminated body in this invention, the said weight average molecular weight is 5,000-500,000, and it was i-line monochrome exposure using the projection exposure machine. The weight average molecular weight is preferably between 10,000 and 40,000 in that the resolution at the time is improved.

The weight average molecular weight is a gel permeation chromatography (GPC) manufactured by Nippon Spectroscopy Co., Ltd. [pump: Gulliver, PU-1580 type, column: Showa Denko Co., Ltd., Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) 4 in-line, moving bed solvent: tetrahydrofuran, by using a calibration curve by polystyrene standard sample (Showa Denko Co., Shodex STANDARD SM-105 Polystyrene) Is saved.

(a) It is preferable from a viewpoint of adhesiveness that the glass transition temperature of resin for binders is 100 degreeC or more. (a) It is further more preferable that the glass transition temperature of resin for binders is 100 degreeC or more and 120 degrees C or less.

The glass transition temperature of the resin for binders (a) in this invention is a formula of the following FOX:

Where Tg represents the Tg of the copolymer. Tg ₁ , Tg ₂ , Tg ₃ , ..., Tg _n represent the Tg (K) of each homopolymer. W ₁ , W ₂ , W ₃ , ..., W _n represents the mass% of each monomer.

Resin for (a) binders used for this invention can be obtained by copolymerizing 1 type or more of monomers among the following 2 types of monomers, respectively. The first monomer is a carboxylic acid or an acid anhydride having one polymerizable unsaturated group in the molecule. For example, (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid semiester, etc. are mentioned.

The second monomer is non-acidic and has one polymerizable unsaturated group in the molecule so as to maintain various properties such as developability of the negative photosensitive resin layer (B), resistance in etching and plating processes, flexibility of the cured film, and the like. Is selected. As such a thing, alkyl (meth) acrylate, 2-hydride, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, for example. Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylonitrile and the like. Moreover, since the resolution can be improved, it is preferable to use the vinyl compound (for example, styrene and benzyl (meth) acrylate) which has a phenyl group.

The resin for binders (a) which concerns on this invention adds the appropriate amount of radical polymerization initiators, such as benzoyl peroxide and azoisobutyronitrile, to the solution which diluted the mixture of the said monomers with solvents, such as acetone, methyl ethyl ketone, isopropanol, It can synthesize | combine by heating and stirring. In some cases, the mixture may be added dropwise to the reaction solution. After completion | finish of reaction, a solvent may be further added and it may adjust to desired density | concentration. As a synthesis | combining means, you may use block polymerization, suspension polymerization, emulsion polymerization, etc. other than solution polymerization.

The content of the resin for the binder (a) to the entire negative photosensitive resin composition is preferably in the range of 20 to 90 mass%, more preferably in the range of 30 to 70 mass%. (a) The content of the binder resin is preferably in the range of 20 to 90% by mass in view of the resist pattern formed by exposure and development having sufficient resistance as a resist, for example, in tenting, etching and various plating processes. Do. Moreover, from the point which provides the usage method of the negative photosensitive resin laminated body and negative photosensitive resin laminated body in this invention, content of the whole negative photosensitive resin composition of (a) binder resin is 20-90 mass. It is the range of%, Preferably it is the range of 30-70 mass%.

In the present invention, (b) the photopolymerizable unsaturated compound is preferably at least one photopolymerizable unsaturated selected from the group consisting of a compound represented by the following general formula (I) and a compound represented by the following general formula (II). Compound.

General formula (Ⅰ):

[Formula 7]

{In formula, R <_8> and R <_9> is independently H or CH <_3> , and n <_2> , n <_3> and n <_4> are the integers of 3-20 each independently.} A compound represented by these.

In the compound represented by the general formula (I), when n ₂ , n _3, and n ₄ are smaller than 3, the boiling point of the compound decreases, and the odor of the resist becomes strong, making it difficult to use. n ₂ , n ₃ and n ₄ When exceeds 20, since the density | concentration of the photoactive site per unit weight becomes low, there exists a tendency for practical sensitivity to become low.

As a specific example of the compound represented by the said general formula (I), the dimethacrylate of the glycol which added an average of 3 mol ethylene oxide to the both ends of the polypropylene glycol to which the average 12 mol of propylene oxide was added, for example, Can be mentioned.

General formula (II):

[Formula 8]

{Wherein R ₁₀ and R ₁₁ are independently H or CH ₃ , A is C ₂ H ₄ , B is C ₃ H ₆ , n ₅ + n ₆ is an integer from 2 to 30, n ₇ + n ₈ is an integer from 0 to 30, n ₅ and n ₆ are independently an integer from 1 to 29, n ₇ and n ₈ are an integer from 0 to 29 independently,-(AO)-and-(BO) The arrangement of the repeating unit of-may be random or may be a block, and in the case of a block, either may be the bisphenol group side.}.

In the compound represented by the above general formula (II), when n ₅ + n ₆ and n ₇ + n ₈ exceed 30, since the double bond concentration in the negative photosensitive resin layer (B) is relatively low, the sensitivity is low. Tend to lose. n ₅ + n ₆ is a 4 to 14 are preferred, and n ₇ + n ₈ is preferably from 0 to 14.

As a specific example of the compound represented by the said General formula (II), the dimethacrylate of the polyalkylene glycol which added an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide to both ends of bisphenol A, and bisphenol A, respectively The dimethacrylate (The Shin-Nakamura Chemical Industry Co., Ltd. product, NK ester BPE-500) of polyethyleneglycol which added 5 mol of ethylene oxide on the both ends of each is mentioned.

(b) As a unsaturated compound which can be photopolymerized, the compound represented by following formula (III) or formula (IV) is used besides the compound represented by said general formula (I) and the photopolymerizable unsaturated compound represented by general formula (II). Can be.

Formula (III):

[Chemical Formula 9]

{Wherein, R ₁₂ are, each carbon number is 4-12 alkyl group, a cycloalkyl group or an aryl group, R ₁₃ and R ₁₄ are independently H or _{CH 3, m 1, m 2} , m 3 and m ₄ are independently is an integer of _{0 ~ 15, - (OC 3} H 6) m1 - (OC 2 H 4) m3 - , and _{- (OC 3 H 6) m2} - (OC 2 H 4) m4 - arrangement of the repeating unit is may be random in Or a block, and in the case of a block, either may be the acryloyl group side.}.

In the compound represented by the general formula (III), m ₁ , m ₂ , m ₃ and m ₄ are 15 or less from the viewpoint of sensitivity.

As a specific example of the compound represented by the said General formula (III), For example, diisocyanate compounds, such as hexamethylene diisocyanate, tolylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, and a hydroxide in 1 molecule With a compound having a real group and a (meth) acryl group (for example, 2-hydroxypropyl acrylate, oligopropylene glycol monomethacrylate, oligoethylene glycol monomethacrylate, oligoethylene propylene glycol monomethacrylate, etc.) Urethane compounds etc. are mentioned. Specifically, a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (manufactured by Nippon Oils and Fats, Inc., Brenma PP1000), and hexamethylene diisocyanate and oligoethylene glycol monomethacrylate (Nippon Oil and Fats Co., Ltd.) And reactants of hexamethylene diisocyanate and oligoethylene propylene glycol monomethacrylate (manufactured by Nippon Oils & Fats, Inc., Brenma 70PEP-350B).

Formula (IV):

[Formula 10]

{Wherein, R ₁₅ is H or CH _3, R ₁₆ is an alkyl group of carbon number 1 ~ 14, A 'is C ₂ H _4, B' are C ₃ H _6, m ₃ is an integer of 1-12 M ₄ is an integer from 0 to 12, m ₅ is an integer from 0 to 3, and the arrangement of the repeating units of-(A'-O)-and-(B'-O)-may be random or block. And in the case of a block, either side may be a phenyl group.}.

In the compound represented by the general formula (IV), m ₃ and m ₄ are 14 or less, preferably 12 or less from the viewpoint of sensitivity.

As a specific example of the compound represented by general formula (IV), For example, the acryl of the compound which added the polypropylene glycol which added an average of 2 mol of propylene oxide, and the polyethylene glycol which added an average of 7 mol of ethylene oxide to nonylphenol. 4-normal nonyl phenoxy hepta ethylene glycol dipropylene glycol acrylate which is a rate is mentioned. The 4-normal nonyl phenoxy octaethylene glycol acrylate (The Toa Synthetic Co., Ltd. product, M-114) which is an acrylate of the compound which added the polyethyleneglycol which added an average of 8 mol ethylene oxide to nonylphenol is also mentioned.

(b) As a photopolymerizable unsaturated compound, in addition to the compound represented by said formula (I)-(IV), the following photopolymerizable unsaturated compound can also be used together. For example, 1, 6- hexanediol di (meth) acrylate, 1, 4- cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propanedi (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, poly Oxyethyltrimethylol propane triacrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri glycidyl ether tree ( Meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, and β-hydroxypropyl-β '-(acryloyloxy) propylphthalate.

It is preferable that content of (b) photopolymerizable unsaturated compound with respect to the whole negative photosensitive resin composition is 3 to 70 mass%. 3 mass% or more is preferable from a viewpoint of a sensitivity, and 70 mass% or less is preferable from a viewpoint of preventing the photosensitive resin layer at the time of preservation from protruding. Moreover, in the aspect which provides the usage method of the negative photosensitive resin laminated body and negative photosensitive resin laminated body in this invention, the said content is the range of 3-70 mass%. More preferably, the said content is 10-60 mass%, More preferably, it is 15-55 mass%.

When the negative photosensitive resin composition contains at least one photopolymerizable unsaturated compound selected from the group consisting of a compound represented by the general formula (I) and a compound represented by the general formula (II), the entire negative type photosensitive resin composition It is preferable that it is the range of 3-60 mass%, and, as for content of the said unsaturated compound, it is more preferable that it is the range which is 3-45 mass%. 3 mass% or more is preferable from a viewpoint of adhesiveness, and 60 mass% or less is preferable from an viewpoint of an edge fuse.

When the negative photosensitive resin composition contains the compound represented by general formula (III) or the compound represented by general formula (IV), content of each unsaturated compound with respect to the whole negative photosensitive resin composition is 3-60 mass% of range. It is preferable to exist in it, and it is more preferable to exist in the range of 3-45 mass%. 3 mass% or more is preferable from a viewpoint of adhesiveness, and 60 mass% or less is preferable from an viewpoint of an edge fuse.

From the viewpoint of high resolution, the negative photosensitive resin composition preferably contains 2,4,5-triarylimidazole dimer as (c) a photopolymerization initiator. As the triarylimidazole dimer, at least one 2,4,5-triaryl selected from the group consisting of a compound represented by the following general formula (V) and a compound represented by the following general formula (VI) is Midazole dimers are particularly preferred.

General formula (Ⅴ):

[Formula 11]

{In formula, X, Y, and Z respectively independently represent either hydrogen, an alkyl group, an alkoxy group, or a halogen group, and p, q, and r are each independently the integer of 1-5.} The compound represented by these.

General formula (Ⅵ):

[Chemical Formula 12]

(In formula, X, Y, and Z respectively independently represent either hydrogen, an alkyl group, an alkoxy group, or a halogen group, and p, q, and r are each independently the integer of 1-5.) The compound represented by these.

As 2,4,5-triarylimidazole dimer, for example, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-bis- (m-methoxyphenyl) imidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, and the like, and the like, in particular 2- (o-chloro Phenyl) -4,5-diphenylimidazole dimer is preferred.

Moreover, when a negative photosensitive resin composition contains (c) at least 1 sort (s) of compound chosen from the group which consists of a benzophenone and a benzophenone derivative as a photoinitiator, the improvement of the adhesiveness and resolution of a resist pattern can be expected further. It is preferable in that it exists.

(C) at least 1 selected from the group consisting of 2,4,5-triarylimidazole dimers represented by the general formula (V) or (VI), and a benzophenone and a benzophenone derivative as the photopolymerization initiator. You may use a compound of a species together.

As a benzophenone derivative, p-aminophenyl ketone is especially preferable from a viewpoint of exposure sensitivity. As p-aminophenyl ketone, p-amino benzophenone, p-butylamino phenone, p-dimethylamino acetophenone, p-dimethylamino benzophenone, p, p'-bis (ethylamino) benzophenone, p, p'-bis (dimethylamino) benzophenone [Mihilerketone], p, p'-bis (diethylamino) benzophenone, and p, p'-bis (dibutylamino) benzophenone are mentioned.

Moreover, (c) use of photoinitiators other than the above-mentioned compound as a photoinitiator is also possible. Here, the other photopolymerization initiator may be a known compound which is activated by various actinic rays, for example, ultraviolet rays, to initiate the polymerization.

As another photoinitiator, For example, quinones, such as 2-ethyl anthraquinone and 2-tert- butyl anthraquinone, aromatic ketones, such as benzophenone, benzoin, such as benzoin, benzoin methyl ether, and benzoin ethyl ether, for example. Acridine compounds, such as ethers and 9-phenyl acridine, benzyl dimethyl ketal, benzyl diethyl ketal, a pyrazoline compound, are mentioned. Moreover, the combination of thioxanthones, such as thioxanthone, 2, 4- diethyl thioxanthone, and 2-chloro thioxanthone, and tertiary amine compounds, such as a dimethylamino benzoic acid alkyl ester compound, is also mentioned, for example. .

-아미노산 화합물을 사용할 수도 있으며, 특히 N-페닐글리신이 바람직하다. As other photoinitiators, oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime Can be mentioned. In addition, N-aryl-

Amino acid compounds can also be used, with N-phenylglycine being particularly preferred.

It is preferable that content of the photoinitiator (c) with respect to the whole negative photosensitive resin composition is 0.1 mass%-20 mass%. 0.1 mass% or more is preferable from a viewpoint of exposure sensitivity, and 20 mass% or less is preferable from a viewpoint of a resolution. Moreover, in the aspect which provides the usage method of the negative photosensitive resin laminated body and negative photosensitive resin laminated body in this invention, the said content is 0.1 mass%-20 mass%.

(c) When a 2,4,5-triaryl imidazole dimer is included as a photoinitiator, it is preferable that content with respect to the whole negative photosensitive resin composition exists in the range of 0.1-10 mass%, and is 0.5-10. It is more preferable to exist in the range of 4.5 mass%. 0.1 mass% or more is preferable from a viewpoint of a sensitivity, and 10 mass% or less is preferable from a viewpoint of a resolution.

(c) When it contains at least 1 sort (s) of compound chosen from the group which consists of a benzophenone and a benzophenone derivative as a photoinitiator, content of the said compound with respect to the whole negative photosensitive resin composition has the light transmittance in wavelength 365nm. Although it depends on the thickness of the negative photosensitive resin layer (B) so that it may be 25% or more and 50% or less, it is preferable to exist in the range of 0.01-1.0 mass% generally, and it is more preferable to exist in the range which is 0.05-0.15 mass%.

The negative photosensitive resin composition may contain coloring substances, such as dye and a pigment. As a coloring substance, For example, fuchsine, phthalocyanine green, auramin base, carcock seed green S, paramagenta, crystal violet, methyl orange, nile blue 2B, victoria blue, malachite green (Hodogaya Chemical Co., Ltd.) Production, Eisen (registered trademark) MALACHITE GREEN), basic blue 20, diamond green (made by Hodogaya Chemical Co., Ltd., Eisen (registered trademark) DIAMOND GREEN GH), etc. are mentioned.

It is preferable that it is the range of 0.005-10 mass%, and, as for content of the coloring substance with respect to the whole negative photosensitive resin composition, it is more preferable that it is the range which is 0.01-1 mass%. 0.005 mass% or more is preferable from a viewpoint of resist visibility, and, as for the said content, 10 mass% or less is preferable from a viewpoint of a sensitivity.

The negative photosensitive resin composition can also be made to contain the color-based dye developed by light irradiation. As chromophoric dye, a leuco dye and a fluorane dye are mentioned, for example. Examples of the leuco dye include tris- (4-dimethylamino-2-methylphenyl) methane- [leuco crystal violet], tris (4-dimethylamino-2-methylphenyl) methane- [leuco malachite green], and the like. have.

It is preferable to use leuco dye in combination with a halogenated compound. As a halogenated compound, amyl bromide, isoamyl bromide, isobutyl bromide, ethylene bromide, diphenyl methyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, and tris (2,3-dibromo Propyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, halogenated triazine compounds and the like. have.

Halogenated triazine compounds include 2,4,6-tris (trichloromethyl) -s-triazine and 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine. Can be mentioned.

In particular, the combination of tribromomethylphenyl sulfone and a leuco dye, and the combination of a triazine compound and a leuco dye are useful.

It is preferable that content of the leuco dye with respect to the whole negative photosensitive resin composition exists in the range of 0.005-10 mass%, and it is more preferable to exist in the range which is 0.01-1 mass%. 0.005 mass% or more is preferable from a viewpoint of colorability, and, as for the said content, 10 mass% or less is preferable from a viewpoint of the contrast of an exposure part and an unexposed part, and maintenance of storage stability.

It is preferable that content of the halogenated compound with respect to the whole negative photosensitive resin composition exists in the range of 0.005-10 mass%, and it is more preferable to exist in the range which is 0.01-1 mass%. 0.005 mass% or more is preferable from a viewpoint of colorability, and, as for the said content, 10 mass% or less is preferable from a viewpoint of the contrast of an exposure part and an unexposed part, and maintenance of storage stability.

In order to improve the thermal stability and / or storage stability of a negative photosensitive resin composition, it is also preferable to contain a radical polymerization inhibitor in a negative photosensitive resin composition. Such radical polymerization inhibitors include, for example, p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p- Cresol, 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), diphenylnitrosoamine, etc. are mentioned. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate].

It is preferable that content of the radical polymerization inhibitor with respect to the whole negative photosensitive resin composition exists in the range of 0.01-3 mass%, and it is more preferable to exist in the range which is 0.02-0.2 mass%. 0.01 mass% or more is preferable from a viewpoint of the resolution, and, as for the said content, 3 mass% or less is preferable from a viewpoint of a sensitivity.

Moreover, the negative photosensitive resin composition of this invention can also be made to contain a plasticizer as needed. As a plasticizer, phthalic acid esters, such as diethyl phthalate, p-toluene sulfonamide, polypropylene glycol, polyethyleneglycol monoalkyl ether, etc. are mentioned, for example.

It is preferable to exist in the range of 5-50 mass%, and, as for content of the plasticizer with respect to the whole negative photosensitive resin composition, it is more preferable to exist in the range which is 5-30 mass%. 5 mass% or more is preferable from a viewpoint of providing flexibility to a resist hardened | cured material, and 50 mass% or less is preferable from a viewpoint of suppressing lack of hardening and a cold flow.

As a board | substrate (C) in this invention, the film-like base material which has the copper clad laminated board which coated copper foil on the glass epoxy board | substrate, metal plates, such as copper, a copper alloy, and an iron type alloy, a glass rib, a silicon wafer, and a conductor layer, etc. are mentioned. have.

The film base material which has a conductor layer has conductor layers, such as copper, gold, silver, and aluminum, in a film-shaped insulated resin layer, For example, a polyimide film, a polyester film, BT resin (bismaleimide tree Flexible base materials which coated copper foil on insulating resin layers, such as azine resin, and TAB (Tape Automated Bonding) tape are mentioned.

As a method of forming the said negative photosensitive resin layer (B) on the board | substrate C, the negative photosensitive resin layer (B) is formed in advance on the support body A (for example, a support film), and then For example, the substrate C is laminated on the surface opposite to the support A of the negative photosensitive resin layer B, that is, the substrate C is provided with the negative photosensitive resin layer B interposed therebetween. The negative pressure photosensitive resin layer (B) is heat-compression-bonded on the board | substrate C (for example, the board | substrate for metal printed circuit boards) so that it may face to.

As a method of forming a negative photosensitive resin layer (B) on a support body (A), the method of apply | coating said negative photosensitive resin composition on a support body (A) is mentioned. As a support body (A) used here, the transparent thing which permeate | transmits an actinic light is preferable. As a support which permeate actinic light, a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film , Polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film and the like. These films may be stretched as needed.

It is preferable that the haze of the support body (A) is 5.0 or less. Although the thickness of the support body (A) is advantageous in terms of image formation and economical efficiency, the thickness is generally 10 to 30 µm in order to maintain the strength.

The protective layer (liner) is laminated | stacked on the surface on the opposite side to the support body (A) side of a negative photosensitive resin layer (B) as needed. Since the adhesion between the protective layer and the negative photosensitive resin layer (B) is sufficiently smaller than the adhesion between the support (A) and the negative photosensitive resin layer (B), it is an important characteristic as the protective layer that the protective layer can be easily peeled off. . As such a protective layer, a polyethylene film, a polypropylene film, etc. are mentioned, for example.

In the case where the negative photosensitive resin laminate has a protective layer, a protective layer is previously formed on the surface of the negative photosensitive resin layer (B) prior to the formation of the negative photosensitive resin layer (B) on the substrate (C). After peeling off this protective layer, the negative photosensitive resin layer (B) is heat-compressed and laminated | stacked on the board | substrate (C) surface. The heating temperature at this time is generally 40-160 degreeC.

Although the thickness of a negative photosensitive resin layer (B) differs in a use, in manufacture for a printed circuit board (printed wiring board), it is 5-100 micrometers normally, Preferably it is 5-50 micrometers. The range of the film thickness of 5-25 micrometers is more preferable at the point that resolution is high and the effect of improving the resist dimensional reproducibility is dramatic.

A negative photosensitive resin laminated body is exposed by actinic light, such as i line | wire monochromatic light and an ultraviolet light, Preferably, it exposes by i line | wire monochromatic light. In this exposure process, the exposed portion of the negative photosensitive resin layer (B) is cured. As a light source used for an exposure process, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, a xenon lamp, a laser etc. are mentioned. These light sources may be used as they are or may be i line monochrome using a band pass filter or the like. Since the resolution is improved when the exposure wavelength is i-line monochromatic, it is preferable to use i-line monochromatic light. It is also preferable to peel a support body A from the negative photosensitive resin layer (B) between a laminated body formation process and an exposure process, and to expose the remaining negative photosensitive resin layer (B) by an exposure process. In this case, the cross-sectional shape of the resist is particularly preferable because it becomes rectangular, that is, a shape that is thick at the resist top and hardly thin at the resist bottom.

Generally, as an exposure method used for exposure, a projection type exposure method (projection exposure method), a close exposure method, a direct drawing method, etc. are mentioned, In this invention, using the light which projected the image of the photomask, The projection type exposure method which exposes a negative photosensitive resin layer through a lens is used. In a typical embodiment of the present invention, the light from the light source passes through the photomask and the lens in this order to reach the negative photosensitive resin layer. The light from the light source may pass through the photomask after passing through the lens. In the present invention, the resist dimensional reproducibility is remarkably improved by using the projection type exposure method and by setting the light transmittance at a wavelength of 365 nm to 25% or more and 50% or less. Moreover, in the projection type exposure system, in the aspect which exposes the light transmittance of the negative photosensitive resin layer (B) in wavelength 365nm to 25% or more and 50% or less, and after exfoliating support body A beforehand, An advantage is obtained that the resist shape becomes rectangular, i.e., a shape that is thick at the resist top and hardly thin at the resist bottom.

Next, when the support body (A) exists on the negative photosensitive resin layer (B), after removing a support body (A) as needed, it is negative by developing and removing the unexposed part of the negative photosensitive resin layer (B). The resist hardened | cured material which consists of a hardening part of a type photosensitive resin layer (B) is formed. As a developing method, the method of removing the unexposed part of negative photosensitive resin layer (B) using alkaline aqueous solution, for example is mentioned. As aqueous alkali solution, aqueous solution, such as sodium carbonate and potassium carbonate, can be used. Although these aqueous alkali solution is selected according to the characteristic of a negative photosensitive resin layer (B), 0.5-3 mass% sodium carbonate aqueous solution is generally used. As described above, the cured resist of the present invention can be obtained.

<Method of manufacturing a printed wiring board>

The manufacturing method of the printed wiring board using said negative photosensitive resin laminated body is further demonstrated below. The invention includes a step of etching or plating a substrate (C) having a resist pattern formed by the resist cured product obtained by the above-described manufacturing method, and a step of removing the resist cured product from the substrate (C). The manufacturing method of a wiring board is provided. In the manufacturing method of the printed wiring board which concerns on this invention, a metal plate is used especially as a board | substrate (C), and any of the etching methods or plating methods which are already known by the metal surface exposed by the image development process in the manufacturing method of the resist hardened | cured material mentioned above are known. A metal image pattern is formed by the method. Thereafter, the cured resist pattern is peeled off by an alkaline aqueous solution which is stronger than the aqueous alkali solution generally used in development. Although aqueous alkali solution for peeling does not have a restriction | limiting in particular, The aqueous solution of 1-5 mass% sodium hydroxide and potassium hydroxide is generally used.

By forming an image pattern using the present invention, in addition to the above printed wiring board (printed circuit board), a semiconductor package substrate, a lead frame, a rib of a plasma display, and the like can be formed. The cross section of the resist line obtained by this invention shows a favorable shape near a rectangle (rectangle), as shown in FIG. That is, the problem that the thickness of the resist top resulting from the manufacturing method of the prior art as shown in FIG. 2 and the thinness at the resist bottom is remarkably reduced, and after peeling the support from the negative photosensitive resin layer as shown in FIG. 4 in advance. In the case of exposure, the problem that the resist cross-sectional shape becomes a "bobbin shape" and the resist foot becomes large is significantly reduced. Therefore, the present invention can be particularly preferably applied to semiconductor package substrate manufacture.

When manufacturing a lead frame using this invention, it exposes after the exposure process and image development process in the manufacturing method of the resist hardened | cured material mentioned above using metal plates, such as copper, a copper alloy, an iron type alloy, as said board | substrate (C). The substrate surface is etched. Finally, the cured resist is peeled off to obtain a desired lead frame. Moreover, when manufacturing the rib of a plasma display panel using this invention, after exposing process and image development process in the manufacturing method of the resist hardened | cured material mentioned above using glass rib as a board | substrate (C), the exposed substrate surface is sanded. It is processed by the blasting method, the resist pattern is peeled off, and a substrate having an uneven pattern can be obtained.

Example

Hereinafter, although an Example demonstrates embodiment of this invention concretely, this invention is not limited to an Example.

<Negative photosensitive resin composition>

The composition of the negative photosensitive resin composition used by the Example and the comparative example is shown to the following Tables 1 and 2.

In the table, the component of the negative photosensitive resin composition shown by symbol (P-1-C-1) is demonstrated in the following <symbol description>. In the table, the values of P-1 and P-2 are amounts of solids.

<Symbol explanation>

P-1: Methyl ethyl ketone solution of the ternary copolymer of 30 mass% of methacrylic acid, 20 mass% of styrene, and 50 mass% of benzyl methacrylate (solid content concentration 40 mass%, weight average molecular weight 55,000, acid equivalent 287, glass Transition temperature 102 ℃)

P-2: Methyl ethyl ketone solution of the binary copolymer of 80 mass% of benzyl methacrylate and 20 mass% of methacrylic acid (solid content concentration 50 mass%, weight average molecular weight 25,000, acid equivalent 430, glass transition temperature 78 degreeC)

M-1: Dimethacrylate of polyalkylene glycol to which an average of 3 mol of ethylene oxide was added to both ends of polypropylene glycol to which an average of 12 mol of propylene oxide was added.

M-2: 7: 3 (molar ratio) mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate

M-3: Dimethacrylate of polyethyleneglycol which added an average of 5 mol of ethylene oxide to both ends of bisphenol A (manufactured by Shin-Nakamura Chemical Industries, Ltd., NK SL BPE-500)

M-4: tetraethylene glycol dimethacrylate

M-5: trimethylolpropane triacrylate

A-1: 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer

A-2: 4,4'-bis (diethylamino) benzophenone

B-1: Diamond Green (Hodogaya Chemical Co., Ltd., Eisen (registered trademark) DIAMOND GREEN GH)

B-2: Leuco Crystal Violet

C-1: pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]

<Formation method of negative photosensitive resin layer (B)>

Next, the method of forming a negative photosensitive resin layer (B) on a support body (A) is demonstrated.

In the Example and the comparative example, the component shown in Table 1 and 2 was mixed and melt | dissolved uniformly so that methyl ethyl ketone might be used as a solvent so that a non-volatile component concentration might be 50 mass%, and the solution of the negative photosensitive resin composition was prepared. The solution of the obtained negative photosensitive resin composition was apply | coated uniformly to the 20-micrometer-thick polyethylene terephthalate film as a support body (A) using a bar coater, and it dried for 3 minutes in 95 degreeC dryer. The thickness of the negative photosensitive resin layer (B) obtained after drying was 25 micrometers.

As for the light transmittance in wavelength 365nm of the negative photosensitive resin layer (B) formed on the said polyethylene terephthalate, the said polyethylene terephthalate film was used for reference using the U-3310 type spectrophotometer by a Hitachi High-Technologies Corporation. Was measured. Moreover, the slit setting at this time was 4 nm, and the scanning speed setting was 600 nm / min.

Subsequently, a 25-micrometer-thick polyethylene film was stuck as a protective layer on the negative photosensitive resin layer (B), and the laminated | multilayer film was obtained. Jet scrub-polishing the surface of the copper clad laminated board as a board | substrate C which laminated | stacked 35 micrometers rolled copper foil, and peeling off the polyethylene film of this laminated | multilayer film, 105 degreeC of a negative photosensitive resin layer (B) with a hot roll laminator. It laminated on the board | substrate (C) at the time, and obtained the negative photosensitive resin laminated body.

<Production of Cured Resistant>

The mask film was made to pass through the negative photosensitive resin laminated body obtained above, and i line monochromatic light was irradiated at 180 mJ / cm <2> by the projection exposure machine (The Ushio Electric Co., Ltd. make, UX2003 SM-MS04, i line band pass filter). The negative photosensitive resin layer (B) was exposed to i-line monochromatic light. Next, it developed by spraying 30 degreeC 1 mass% sodium carbonate aqueous solution for about 40 second, and removing an unexposed part. Then, the hardened part (exposure part) of the residual negative photosensitive resin layer (B) was spray-washed for about 20 second using ion-exchange water, and the resist hardened | cured material which concerns on this invention was obtained. In addition, about the Example and comparative example shown in Table 1, the polyethylene terephthalate film was peeled off before spraying of the said sodium carbonate aqueous solution, and about the Example and comparative example shown in Table 2, respectively, before the said exposure.

The exposure sensitivity was measured using a 27-stage tablet manufactured by Asahi Kasei, whose brightness was changed from transparent to black in 21 steps.

The obtained resist hardened | cured material was evaluated using the following evaluation criteria.

(1) Resolution In the said exposure, it exposed and developed using the mask film whose line and space are 1: 1. The minimum line width which the obtained hardening pattern can isolate | separate was made into the resolution.

(2) Adhesiveness In the said exposure, it exposed and developed using the mask film whose line and space are L micrometer: 200 micrometers (L micrometer shows a line width). The minimum line width which the obtained hardening pattern can adhere to was made into adhesiveness.

(3) Resist shape In the above exposure, a mask film having a line width of 12 µm was used. The resist shape was confirmed at 15 kPa of acceleration voltages, 1,000 times magnification, and 60 degree of tilt angles using the electron microscope (Tomcon Co., Ltd. product Sm-500). When the difference in the cured pattern line width between the resist top and the resist bottom was less than 1 µm,?

<Examples 1A-8A, Comparative Examples 1A-4A, Examples 1B-7B, Comparative Examples 1B-4B>

The components and the evaluation results of the negative photosensitive resin composition are shown in Tables 1 and 2. In Examples 1A to 8A and Examples 1B to 7B in which the light transmittance at a wavelength of 365 nm falls within the range of the present invention, the light transmittance is more than in Comparative Examples 1A to 4A and Comparative Examples 1B to 4B, which are outside the range of the present invention. It was confirmed that they were comprehensively excellent in evaluation criteria including resolution, adhesion and resist shape.

The electron microscope photograph of the resist shape of the resist hardened | cured material obtained in Example 2A and Comparative Example 1A is shown to FIG. 1 and FIG. 2, respectively. In Example 2A, while the resist shape was close to a rectangle, it was observed that in Comparative Example 1A, it was remarkably thick at the resist top and remarkably thin at the resist bottom. Electron micrographs of the resist shape of the cured resist of Example 2B and Comparative Example 1B are shown in FIGS. 3 and 4, respectively. In Example 2B, while the resist shape was close to a rectangle, in Comparative Example 1B, a thin resist bottom was observed, and a large resist foot was observed (resist cross-sectional shape was "bobbin shape").

Industrial Applicability The present invention can be widely used for the manufacture of printed wiring boards (printed circuit boards), the manufacture of lead frames for mounting IC chips, the manufacture of semiconductor packages, and the like.

Claims (28)

A laminate formation step of forming a negative photosensitive resin laminate in which at least a support (A), a negative photosensitive resin layer (B), and a substrate (C) are laminated;
An exposure step of exposing the negative photosensitive resin layer (B) through a lens using light projected from an image of a photomask,
A developing step of forming a cured resist of the hardened portion of the negative photosensitive resin layer (B) by developing and removing the unexposed portion of the negative photosensitive resin layer (B),
The manufacturing method of the resist hardened | cured material whose light transmittance in wavelength 365nm of the said negative photosensitive resin layer (B) is 25%-36%. The method of claim 1,
A method for producing a cured resist, wherein the light is i-ray monochromatic light. The method of claim 1,
The manufacturing method of the cured resist further including the support body peeling process which peels the said support body (A) from the said negative photosensitive resin layer (B) between the said laminated body formation process and the said exposure process. The method of claim 1,
The manufacturing method of the resist hardened | cured material whose light transmittance in wavelength 365nm of the said negative photosensitive resin layer (B) is 35%-36%. The method of claim 1,
The said negative photosensitive resin layer (B) is 20-90 mass% of binder resins (b) photopolymerizable unsaturated compound whose (a) carboxyl group content is 100-600 in acid equivalent, and a weight average molecular weight is 5,000-500,000, (b) The manufacturing method of the resist hardened | cured material which consists of negative photosensitive resin composition containing 3-70 mass% and (c) 0.1-20 mass% of photoinitiators. The method of claim 5, wherein
The manufacturing method containing at least 1 sort (s) of compound chosen from the group which consists of benzophenone and a benzophenone derivative as said (c) photoinitiator. The method of claim 5, wherein
The manufacturing method containing 2,4,5-triaryl imidazole dimer as said (c) photoinitiator. The method of claim 5, wherein
The manufacturing method containing both at least 1 sort (s) of compound chosen from the group which consists of a benzophenone and a benzophenone derivative as said photoinitiator, and a 2,4,5-triarylimidazole dimer. The method of claim 5, wherein
Said (b) photopolymerizable unsaturated compound is a following general formula (I):
[Formula 1]

{Wherein, R ₈ and R ₉ are independently H or CH _3, and, and n _2, n ₃ and n ₄ are each independently an integer from 3 to 20} the compound, and the following general formula (Ⅱ) represented by :
(2)

{Wherein R ₁₀ and R ₁₁ are independently H or CH ₃ , A is C ₂ H ₄ , B is C ₃ H ₆ , n ₅ + n ₆ is an integer from 2 to 30, n ₇ + n ₈ is an integer from 0 to 30, n ₅ and n ₆ are independently an integer from 1 to 29, n ₇ and n ₈ are an integer from 0 to 29 independently,-(AO)-and-(BO) The arrangement of the repeating unit of-may be random or may be a block, and in the case of a block, either may be the bisphenol group side. The process of etching or plating the said board | substrate (C) which has a resist pattern which the resist hardened | cured material obtained by the manufacturing method in any one of Claims 1-9 forms, and
The manufacturing method of the printed wiring board containing the process of removing the said hardened | cured material from the said board | substrate (C). A negative photosensitive resin laminate used to form a cured resist by exposing a negative photosensitive resin layer through a lens using i-line monochromatic light projecting an image of a photomask,
At least it has a support body (A) and the negative photosensitive resin layer (B) for i line | wire monochromatic exposure,
The said negative photosensitive resin layer (B) is 20-90 mass% of binder resins (b) photopolymerizable unsaturated compound whose (a) carboxyl group content is 100-600 in acid equivalent, and a weight average molecular weight is 5,000-500,000, (b) It consists of the negative photosensitive resin composition for i line | wire monochromatic exposure containing 3-70 mass% and (c) 0.1-20 mass% of photoinitiators, and
The negative photosensitive resin laminated body whose light transmittance in wavelength 365nm of the said negative photosensitive resin layer (B) is 25%-36%. The method of claim 11,
The negative photosensitive resin laminated body whose light transmittance in wavelength 365nm of the said negative photosensitive resin layer (B) is 35%-36%. The method of claim 11,
The negative photosensitive resin laminated body whose glass transition temperature of the said resin for binders (a) is 100 degreeC or more. The method of claim 11,
The negative photosensitive resin laminated body whose weight average molecular weights of said resin for binders (a) are between 10,000-40,000. The method of claim 11,
The negative photosensitive resin laminated body containing at least 1 sort (s) of compound chosen from the group which consists of a benzophenone and a benzophenone derivative as said (c) photoinitiator. The method of claim 11,
The negative photosensitive resin laminated body containing 2,4,5-triaryl imidazole dimer as said (c) photoinitiator. The method of claim 11,
The negative photosensitive resin laminated body containing both (c) at least 1 sort (s) of compound chosen from the group which consists of a benzophenone and a benzophenone derivative as a photoinitiator, and a 2,4,5-triaryl imidazole dimer. . The method of claim 11,
Said (b) photopolymerizable unsaturated compound is the following general formula (I)
(3)

{Wherein, R ₈ and R ₉ are independently H or CH _3, and, and n _2, n ₃ and n ₄ are each independently an integer from 3 to 20} the compound, and the following general formula (Ⅱ) represented by :
[Chemical Formula 4]

{Wherein R ₁₀ and R ₁₁ are independently H or CH ₃ , A is C ₂ H ₄ , B is C ₃ H ₆ , n ₅ + n ₆ is an integer from 2 to 30, n ₇ + n ₈ is an integer from 0 to 30, n ₅ and n ₆ are independently an integer from 1 to 29, n ₇ and n ₈ are an integer from 0 to 29 independently,-(AO)-and-(BO) The arrangement of the repeating unit of-may be random or may be a block, and in the case of a block, a negative photosensitive resin laminate selected from the group consisting of the compounds represented by the above formula}. The method of claim 11,
The negative photosensitive resin laminated body which has a protective layer further on the said negative photosensitive resin layer (B). When forming a cured resist by exposing a negative photosensitive resin layer through a lens using i-line monochromatic light projecting an image of a photomask, at least the support A and the negative photosensitive resin layer for i-line monochrome exposure (B) As a negative photosensitive resin laminated body which has the above-mentioned, The said negative photosensitive resin layer (B) is a resin for binders 20-90 whose (a) carboxyl group content is 100-600 in acid equivalent, and a weight average molecular weight is 5,000-500,000. It consists of the negative photosensitive resin composition for i line | wire monochromatic exposure containing mass%, (b) 3-70 mass% of unsaturated compounds which can photopolymerize, and (c) 0.1-20 mass% of photoinitiators, and the said negative photosensitive resin layer Negative photosensitive resin using the negative photosensitive resin laminated body whose light transmittance in (B) wavelength 365nm is 25%-36%. How to use cheungche. 21. The method of claim 20,
The usage method whose light transmittance in wavelength 365nm of the said negative photosensitive resin layer (B) is 35%-36%. 21. The method of claim 20,
The glass transition temperature of the said resin for binders (a) is 100 degreeC or more. 21. The method of claim 20,
The use method whose weight average molecular weights of said resin for binders (a) are 10,000-40,000. 21. The method of claim 20,
Use method containing the at least 1 sort (s) of compound chosen from the group which consists of benzophenone and a benzophenone derivative as said (c) photoinitiator. 21. The method of claim 20,
Use method containing 2,4,5-triarylimidazole dimer as said (c) photoinitiator. 21. The method of claim 20,
The use method containing both at least 1 sort (s) of compound chosen from the group which consists of a benzophenone and a benzophenone derivative as said photoinitiator, and a 2,4,5-triarylimidazole dimer. 21. The method of claim 20,
Said (b) photopolymerizable unsaturated compound is the following general formula (I)
[Chemical Formula 5]

{Wherein, R ₈ and R ₉ are independently H or CH _3, and, and n _2, n ₃ and n ₄ are each independently an integer from 3 to 20} the compound, and the following general formula (Ⅱ) represented by :
[Formula 6]

{Wherein R ₁₀ and R ₁₁ are independently H or CH ₃ , A is C ₂ H ₄ , B is C ₃ H ₆ , n ₅ + n ₆ is an integer from 2 to 30, n ₇ + n ₈ is an integer from 0 to 30, n ₅ and n ₆ are independently an integer from 1 to 29, n ₇ and n ₈ are an integer from 0 to 29 independently,-(AO)-and-(BO) The array of repeating units of-may be random or may be a block, and in the case of a block, either may be the bisphenol group side. 21. The method of claim 20,
The usage method which has a protective layer further on the said negative photosensitive resin layer (B).

Images