TWI424266B - A method for producing a resist hardener using a negative photosensitive resin laminate, a method for using a negative photosensitive resin laminate, and a negative photosensitive resin laminate - Google Patents

Description

Method for producing resist cured product using negative photosensitive resin laminate, method for using negative photosensitive resin laminate, and method for using negative photosensitive resin laminate

The present invention relates to a method for producing a cured resist comprising a step of using a negative photosensitive resin laminate having a negative photosensitive resin layer and a 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. Moreover, 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.

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, followed by pattern exposure to cure and cure the exposed portion of the photosensitive resin composition. And removing the unexposed portion with a developing solution 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 onto a substrate, a method in which a solution of the negative photosensitive resin composition is applied onto a substrate and then dried is used, or A layer of a support, a layer containing a negative photosensitive resin composition (hereinafter also referred to as a "negative photosensitive resin layer"), and a dry film resist of an optional protective layer are laminated on the substrate. Any of the methods. 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 resist will be described. First, in the case where 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 to ultraviolet light such as an i-line (wavelength: 365 nm) emitted from an ultrahigh pressure mercury lamp through a mask having a wiring pattern, whereby the exposed portion is polymerized and cured. The support containing polyethylene terephthalate or the like is then peeled off. Next, 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 resist pattern was 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 of the dry film resist, 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 influence of the lubricant or the like contained in the support, the support may be peeled off before exposure. However, in the prior exposure method using a dry film resist, as shown in FIG. 2, the resist on the top of the resist is coarsened and the resist on the bottom of the resist is narrow, and the size of the resist is reproduced. There is a problem with sex. 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 "bobbin", and the resist residue is large, so that the resist is resisted. There is a problem with the dimensional reproducibility of the agent.

A method of manufacturing a printed wiring board using a dry film resist 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 and curing the exposed portion; 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 resist being formed into a bobbin shape, and the residual of the resist are large.

Patent Document 1 describes a dry film resist in which the absorbance at a wavelength of 365 nm is specified. However, Patent Document 1 does not describe the i-line monochrome exposure. Further, Patent Document 1 does not describe the exposure after the support is peeled off in advance.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-145565

An object of the present invention is to provide a resist pattern having excellent adhesion and resolvability after development, a method for producing a resist cured product having an excellent resist shape, a negative photosensitive resin laminate, and a negative type. A method of using a photosensitive resin laminate.

The present inventors have made intensive studies to solve the above problems, and as a result, it has been found that a negative photosensitive resin layer having a support (A), a negative photosensitive resin layer (B), and a substrate (C) has been found. When the body 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 and 50% or less. The resin layer (B) is obtained by using a resist produced by using a negative photosensitive resin layer having a previous light transmittance, and the adhesion, resolution, and resist shape of the resist pattern after development are obtained. Significant improvements have been made to complete the present invention. Further, the present inventors have found that when i-line single-color exposure is applied to a laminate having a negative photosensitive resin layer, the use thereof includes: (a) a carboxyl group content of from 100 to 600 in terms of acid equivalent, and a weight average molecular weight of Between 5,000 and 500,000, 20 to 90% by mass of the binder resin, (b) 3 to 70% by mass of the photopolymerizable unsaturated compound, and (c) the photopolymerization initiator 0.1 to 20% by mass of the photosensitive resin combination The negative photosensitive resin layer having a light transmittance of 25% or more and 50% or less at a wavelength of 365 nm is developed in comparison with the case of using a negative photosensitive resin layer having a light transmittance outside the above range. The adhesion of the subsequent resist pattern, the resolution, and the shape of the resist are remarkably improved, thereby completing the present invention. Specifically, the above problems are solved by the inventions of the following [1] to [28].

[1] A method for producing a cured resist, comprising: a laminate forming step of forming at least a support (A), a negative photosensitive resin 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 photomask; and a developing step of removing the negative by development a resist cured product including a cured portion of the negative photosensitive resin layer (B) in an unexposed portion of the photosensitive resin layer (B); and the negative photosensitive resin layer (B) at a wavelength The light transmittance at 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 carboxyl group content of from 100 to 600 in terms of acid equivalent, and a weight average molecular weight of from 5,000 to 500,000 in an amount of from 20 to 90% by mass of the binder resin, and (b) photopolymerization. 3 to 70% by mass of the unsaturated compound and (C) 0.1 to 20% by mass of the photopolymerization initiator.

[6] The method for producing a cured resist of the above [5], which comprises at least one compound selected from the group consisting of benzophenone and benzophenone derivatives as the (c) photopolymerization Starting agent.

[7] The method for producing a cured resist of the above [5] or [6], which comprises the 2,4,5-triarylimidazole dimer as the (c) photopolymerization initiator.

[8] 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 benzophenone derivatives, and 2, 4, Both of the 5-triaryl imidazole dimers are used as the (c) photopolymerization initiator.

[9] The method for producing a cured resist of any one of the above [5] to [8] wherein the (b) photopolymerizable unsaturated compound is selected from the group consisting of the following formula (I) a compound represented by the compound represented by the following formula (II):

[Chemical 1]

Wherein R ₈ and R _{9 are} independently H or CH ₃ , and n ₂ , n ₃ and n ₄ are each independently an integer of from 3 to 20};

[Chemical 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, and n ₇ + n ₈ is 0~ An integer of 30, n ₅ and n _{6 are} independently integers from 1 to 29, n ₇ and n _{8 are} independently integers from 0 to 29, and the arrangement of repeating units -(AO)- and -(BO)- may be random It is a block, and in the case of a block, 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 method of producing the article; and a step of removing the cured resist from the substrate (C).

[11] 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 for i-line monochrome exposure. The photosensitive resin composition containing (a) a resin having a carboxyl group content of from 100 to 600 in terms of acid equivalent weight and a weight average molecular weight of from 5,000 to 500,000 %, (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 365 nm.

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

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

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

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

The negative photosensitive resin laminate according to any one of the above [11], which contains at least one compound selected from the group consisting of benzophenone and benzophenone derivatives, As the (c) photopolymerization initiator, both of the 2,4,5-triarylimidazole dimer.

[18] The negative photosensitive resin laminate according to any one of [11] to [17] wherein the (b) photopolymerizable unsaturated compound is selected from the group consisting of the following formula (I) a compound consisting of a compound represented by the following formula (II):

[Chemical 3]

Wherein R ₈ and R _{9 are} independently H or CH ₃ , and n ₂ , n ₃ and n ₄ are each independently an integer of from 3 to 20};

[Chemical 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, and n ₇ + n ₈ is 0~ An integer of 30, n ₅ and n _{6 are} independently integers from 1 to 29, n ₇ and n _{8 are} independently integers from 0 to 29, and the arrangement of repeating units -(AO)- and -(BO)- may be random It is a block, and in the case of a block, it can be located on the bisphenol side}.

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

[20] A method of using a negative photosensitive resin laminate which forms a resist hardened by exposing a negative photosensitive resin layer through a lens using i-line monochromatic light that projects an image of a photomask In the case of the negative photosensitive resin layer, the negative photosensitive resin layer system has at least a support (A) and a negative photosensitive resin layer (B) for i-line monochromatic exposure, and the negative The photosensitive resin layer (B) contains (a) a resin having a carboxyl group content of from 100 to 600 in terms of acid equivalent weight and a weight average molecular weight of from 5,000 to 500,000, and a resin for binders of 20 to 90% by mass, (b) a negative photosensitive resin composition for i-line single-color exposure of photopolymerized unsaturated compound 3 to 70% by mass, and (c) photopolymerization initiator 0.1 to 20% by mass, and the negative photosensitive resin The light transmittance of the layer (B) at a wavelength of 365 nm is 25% or more and 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 according to [20] or [21] above, wherein the (a) binder resin has a glass transition temperature of 100 ° C or higher.

[23] The method of using the negative photosensitive resin laminate according to any one of [20] to [22] wherein the (a) binder resin has a weight average molecular weight of 10,000 to 40,000.

[24] The method of using a negative photosensitive resin laminate according to any one of the above [20] to [23] wherein at least one selected from the group consisting of benzophenone and benzophenone derivatives is contained. The compound is used as the (c) photopolymerization initiator.

[25] A method of using a negative photosensitive resin laminate according to any one of the above [20] to [24], wherein a 2,4,5-triarylimidazole dimer is contained as the (c) photopolymerization Starting agent.

The method of using a negative photosensitive resin laminate according to any one of the above [20] to [25] wherein at least one selected from the group consisting of benzophenone and benzophenone derivatives is contained. The compound and the 2,4,5-triarylimidazole dimer are used as the (c) photopolymerization initiator.

[27] The method of using the negative photosensitive resin laminate according to any one of the above [20] to [26] wherein the (b) photopolymerizable unsaturated compound is selected from the following formula (I) a compound represented by the compound represented by the following formula (II):

[Chemical 5]

Wherein R ₈ and R _{9 are} independently H or CH ₃ , and n ₂ , n ₃ and n ₄ are each independently an integer of from 3 to 20};

[Chemical 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, and n ₇ + n ₈ is 0~ An integer of 30, n ₅ and n _{6 are} independently integers from 1 to 29, n ₇ and n _{8 are} independently integers from 0 to 29, and the arrangement of repeating units -(AO)- and -(BO)- may be random It is a block, and in the case of a 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], further comprising a protective layer on the negative photosensitive resin layer (B).

According to the present invention, a resist pattern excellent in adhesion and resolution after development and an excellent resist shape can be obtained.

In one aspect of the invention, there is provided a method of producing a resist cured product, comprising: a laminate forming step of forming at least a support (A), a negative photosensitive resin layer (B), and a substrate ( C) a negative photosensitive resin laminated body formed by laminating; an exposure step of exposing the negative photosensitive resin layer (B) through a lens using light projected from the image of the photomask; and a developing step The unexposed portion of the negative photosensitive resin layer (B) is removed by development to form a cured resist containing the cured portion of the negative photosensitive resin layer (B); and the negative photosensitive resin The light transmittance of the layer (B) at a wavelength of 365 nm is 25% or more and 50% or less.

In another aspect of the invention, there is provided a negative photosensitive resin laminate which is used for exposing a negative photosensitive resin layer via a lens by using i-line monochromatic light which projects an image of a photomask Further, a resist-cured material is formed, and at least a support (A) and a negative-type photosensitive resin layer (B) for i-line monochromatic exposure are provided, and the negative-type photosensitive resin layer (B) contains: i A negative photosensitive resin composition for linear monochromatic exposure, wherein the negative photosensitive resin composition contains (a) a carboxyl group having an acid equivalent weight of from 100 to 600 and a weight average molecular weight of from 5,100 to 500,000. 20 to 90% by mass of the resin for the agent, (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) The light transmittance at a wavelength of 365 nm is 25% or more and 50% or less.

In still another aspect of the invention, there is provided a method of using a negative photosensitive resin laminate, which uses a pair of monochromatic light that projects an image of a photomask, and a negative photosensitive resin via a lens. When the layer is exposed to form a resist cured product, the negative photosensitive resin layered body having at least a support (A) and a negative photosensitive resin for i-line single-color exposure is used. In the layer (B), 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. The acid equivalent is from 100 to 600, and the weight average molecular weight is from 5,000 to 500,000, and the binder resin is from 20 to 90% by mass, (b) the photopolymerizable unsaturated compound is from 3 to 70% by mass, and (c) The photopolymerization initiator 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.

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. In addition, the negative photosensitive resin layer (B) for i-line monochrome exposure means that the negative photosensitive resin layer (B) can be monochromatic by i-line (wavelength: 365 nm). The desired resist pattern is obtained by exposure and subsequent resolution. 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 of 365 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 dimensional reproducibility is good. . Further, in the aspect of using the negative photosensitive resin laminate and the negative photosensitive resin laminate according to the present invention, by using the light transmittance at a wavelength of 365 nm in the above range, it is possible to use When the i-line monochromatic light projected by the image of the reticle is exposed to the negative photosensitive resin layer through the lens to form a resist cured product, it is obtained as compared with the case of light transmittance other than the above range. A resist pattern excellent in adhesion and resolution, and good resist reproducibility. 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 narrowness of the bottom of the resist have problems with resist size reproducibility. In the case where the support is previously peeled off and then exposed, the resist is cured by exposing the negative photosensitive resin layer through the lens by using the light projected by the image of the mask described above. The resist cross-sectional shape becomes a bobbin shape, and the resist residue is large, so there is a problem of resist size reproducibility. On the other hand, when the light transmittance is more than 50%, the negative photosensitive resin layer (B) cannot effectively absorb the exposed light, and thus there is a problem that the exposure sensitivity is lowered. These problems are more pronounced when using i-line monochromatic light. Therefore, from the viewpoint of solving such problems and producing an excellent resist shape, the light transmittance of the negative photosensitive resin layer (B) at a wavelength of 365 nm is 25% or more and 50% or less. The negative photosensitive resin layer (B) of the present invention has a light transmittance of 30% or more at a wavelength of 365 nm from the viewpoint of the adhesion of the resist 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 nm, ultraviolet absorption is added to the negative photosensitive resin composition for forming the negative photosensitive resin layer (B). The method of the agent, or the method of adjusting the amount of the photopolymerization initiator. Examples of the ultraviolet absorber include a benzotriazole system, a benzophenone system, a salicylate system, a cyanoacrylate system, a nickel system, and a trisole. Department and so on. As the benzotriazole-based ultraviolet absorber, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole and phenylpropionic acid 3-(2H-benzotriazole- 2-yl)-5-(1,1-dimethylethyl)-4-hydroxy C _7-9 side chain and linear alkyl ester, 2-(2H-benzotriazol-2-yl)- 4,6-bis(1-methyl-1-phenylethyl)phenol.

As a photopolymerization initiator, from the viewpoint of further improving the adhesion and resolution of the resist pattern, it is particularly preferable to select a composition selected from the group consisting of benzophenone and benzophenone derivatives. At least one compound in the population.

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 is a method of forming a negative photosensitive resin layer (B) on a support and placing the support. The measurement was carried out by using a spectrophotometer (U-3310 manufactured by Hitachi High-Technologies Co., Ltd.), and the slit was set to 4 nm and the scanning speed was set to 600 nm/min. .

The negative photosensitive resin layer (B) of the present invention may contain 20 to 90% by mass of a binder resin having a (a) carboxyl group content of from 100 to 600 in terms of acid equivalent weight and a weight average molecular weight of from 5,000 to 500,000 ( b) A negative photosensitive resin composition which is photo-polymerizable unsaturated compound 3 to 70% by mass and (c) photopolymerization initiator 0.1 to 20% by mass.

The carboxyl group in the resin for the binder is required to impart developability or releasability to the alkaline aqueous solution to the negative photosensitive resin layer. The amount of the carboxyl group in the resin for a binder is preferably 100 or more in terms of acid resistance, from the viewpoint of developability and releasability, from the viewpoint of developability, resolvability, and adhesion. It is preferably 600 or less. More preferably, it can reach 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 300 to 400. The acid equivalent refers to the mass (gram equivalent) of a polymer having 1 equivalent of a carboxyl group (i.e., a resin for a binder).

The acid equivalent was measured by a potentiometric titration method using a Pingyu automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd. using 0.1 mol/L of sodium hydroxide.

The (a) binder resin of the present invention may have a weight average molecular weight of 5,000 to 500,000. From the viewpoint of developability, (a) the weight average molecular weight of the resin for a binder is preferably 500,000 or less, which is preferable from the viewpoint of the strength of the tenting film and the reduction of 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 binder 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 resolution in monochrome exposure, the weight average molecular weight is preferably between 10,000 and 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 100 ° C or more from the viewpoint of adhesion. (a) The glass transition temperature of the resin for a binder is preferably 100 ° C or more and 120 ° C or less.

The glass transition temperature of the (a) resin for a binder in the present invention can be calculated by the following FOX formula:

[Number 1]

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

The (a) binder resin used in the present invention can be obtained by copolymerizing one or more monomers from the following two monomers. 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, methylene succinic acid, maleic anhydride, maleic acid half ester, etc. are mentioned.

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 (B), resistance to etching and plating steps, and cured film. Various characteristics such as flexibility. Examples of such a monomer include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate (methyl). Alkyl acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylonitrile, and the like. Further, from the viewpoint of improving the resolution, it is preferred to use a vinyl compound having a phenyl group (for example, styrene or benzyl (meth)acrylate).

The (a) binder resin of the present invention can be synthesized by diluting a mixture of the above monomers with a solvent such as acetone, methyl ethyl ketone or isopropanol, and adding an appropriate amount to the obtained solution. A radical polymerization initiator such as benzamidine peroxide or azoisobutyronitrile is heated and stirred. The (a) binder resin of the present invention may be synthesized while a part of the mixture is added dropwise to the reaction liquid. After the completion of the reaction, a solvent may be further added to adjust the concentration 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 30 to 70% by mass, based on the total amount 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, etching, and various plating steps. In other words, it is preferably in the range of 20 to 90% by mass. 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 content of the (a) binder resin relative to the negative photosensitive resin composition is The range of 20 to 90% by mass, preferably 30 to 70% by mass.

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

General formula (I):

[Chemistry 7]

In the formula, R ₈ and R _{9 are} independently H or CH ₃ , and n ₂ , n ₃ and n ₄ are each independently an integer of 3 to 20}.

In the compound represented by the above formula (I), when n ₂ , n ₃ and n _{4 are} less than 3, the boiling point of the compound is lowered, and the odor of the resist becomes strong and it is difficult to use. When n ₂ , n ₃ and n ₄ exceed 20, the concentration of the photoactive site per unit weight is lowered, so that the practical sensitivity tends to decrease.

Specific examples of the compound represented by the above formula (I) include, for example, addition of an average of 3 moles of ethylene oxide to both ends of a polypropylene glycol having an average of 12 moles of propylene oxide. Dimethacrylate of diol.

General formula (II):

[化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, and n ₇ + n ₈ is 0~ An integer of 30, n ₅ and n _{6 are} independently integers from 1 to 29, n ₇ and n _{8 are} independently integers from 0 to 29, and the arrangement of repeating units -(AO)- and -(BO)- may be random It is a block, and in the case of a block, it can be located on the bisphenol side}.

In the compound represented by the above formula (II), if n ₅ + n ₆ and n ₇ + n ₈ exceed 30, the concentration of the double bond in the negative photosensitive resin layer (B) is relatively lowered, so that the photosensitive layer is present. The tendency to decline. n ₅ + n _{6 is} preferably 4 to 14, and n ₇ + n _{8 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):

[Chemistry 9]

Wherein R ₁₂ is an alkyl group having 4 to 12 carbon atoms, a cycloalkyl group or an aryl group, R ₁₃ and R _{14 are} independently H or CH ₃ , and m ₁ , m ₂ , m ₃ and m ₄ are each independently 0. An integer of ~15, the repeating unit -(OC ₃ H ₆ ) _m1 -(OC ₂ H ₄ ) _m3 - and -(OC ₃ H ₆ ) _m2 -(OC ₂ H ₄ ) _m4 - may be randomly or Blocks, and in the case of blocks, can be located on the propylene sulfhydryl side}.

With respect to the compound represented by the above formula (III), 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 (III) include dihexyl diisocyanate, toluene diisocyanate, and 2,2,4-trimethyldiisocyanate. An isocyanate compound and a compound having a hydroxyl group and a (meth)acryl group in one molecule (for example, 2-hydroxypropyl acrylate, oligopropylene glycol monomethacrylate, oligoethylene glycol monomethacrylate, oligomeric ethylene) A urethane compound such as alcohol propylene glycol monomethacrylate or the like. Specific examples thereof include a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (manufactured by Nippon Oil & Fat Co., Ltd., Blemmer PP1000), hexamethylene diisocyanate and oligoethylene Reaction of alcohol monomethacrylate (manufactured by Nippon Oil & Fat Co., Ltd., Blemmer PE-200), hexamethylene diisocyanate and oligoethylene glycol propylene glycol monomethacrylate (manufactured by Nippon Oil & Fats Co., Ltd.) The reactant of Blemmer 70PEP-350B).

Formula (IV):

[化10]

Wherein R ₁₅ is H or CH ₃ , R ₁₆ is an alkyl group having 1 to 14 carbon atoms, A' is C ₂ H ₄ , B' is C ₃ H ₆ , and m ₃ is an integer of 1 to 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 -(A'-O)- and -(B'-O)- may be random or block, and In the case of a block, it can be located on the phenyl side}.

In the compound represented by the above formula (IV), m ₃ and m ₄ are 14 or less, 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 a polyethylene having an average of 7 moles of ethylene oxide. The acrylate of the compound obtained by adding a diol to indophenol, that is, 4-n-decylphenoxy heptaethylene glycol dipropylene glycol acrylate. An acrylate which is a compound 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 acrylate (Manufactured by East Asia Synthetic Co., Ltd., M-114).

As the (b) unsaturated polymer which can be photopolymerized, in addition to the compound represented by the above formulas (I) to (IV), the following unsaturated photopolymerizable compound can be used in combination. For example, 1,6-hexanediol di (meth)acrylate, 1,4-cyclohexanediol di (meth)acrylate, polypropylene glycol di (meth)acrylate, polyethylene glycol II (Meth) acrylate, 2-bis(p-hydroxyphenyl)propane di(meth) acrylate, glycerol tri(meth) acrylate, trimethylolpropane tri(meth) acrylate, poly Oxypropyl trimethylolpropane tri(meth)acrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol (Meth) acrylate, trimethylolpropane 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 relative to the negative type The entire photosensitive resin composition is preferably in the range of 3 to 70% by mass. 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. 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 content is in the range of 3 to 70% by mass. The above content is more preferably from 10 to 60% by mass, and even 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 a compound represented by the formula (I) and a compound represented by the formula (II). In the case of the negative photosensitive resin composition, the content of the unsaturated compound is preferably in the range of 3 to 60% by mass, more preferably in the range of 3 to 45% by mass. From the viewpoint of adhesion, it is preferably 3% by mass or more, and from the viewpoint of edge melting, it is preferably 60% by mass or less.

When the negative photosensitive resin composition contains the compound represented by the formula (III) or the compound represented by the formula (IV), the content of each unsaturated compound is relative to the entire negative photosensitive resin composition. It is preferably in the range of 3 to 60% by mass, more preferably in the range of 3 to 45% by mass. From the viewpoint of adhesion, it is preferably 3% by mass or more, and from the viewpoint of edge melting, 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 triaryl imidazole dimer is particularly preferably at least one selected from the group consisting of a compound represented by the following formula (V) and a compound represented by the following formula (VI). 4,5-triaryl imidazole dimer:

General formula (V):

[11]

Wherein X, Y and Z are each independently hydrogen, alkyl, alkoxy or halo, and p, q and r are each independently an integer from 1 to 5};

General formula (VI):

[化12]

In the formula, X, Y and Z are each independently hydrogen, an alkyl group, an alkoxy group or a halogen group, and p, q and r are each independently an integer of 1 to 5}.

Examples of the 2,4,5-triaryl imidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer and 2-(o-chlorophenyl)-4. 5-bis(m-methoxyphenyl)imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, etc., particularly preferably 2-(o-chlorobenzene) Base 4,5-diphenylimidazole dimer.

Further, from the viewpoint of further improving the adhesion and resolution of the resist pattern, the negative photosensitive resin composition contains, as (C) a photopolymerization initiator, selected from benzophenone and benzophenone. At least one of the compounds consisting of the derivatives is also preferred.

Further, it may be used in combination with a 2,4,5-triarylimidazole dimer represented by the above formula (V) or (VI), and a group selected from the group consisting of benzophenone and benzophenone derivatives. At least one of the compounds is used as (c) a photopolymerization initiator.

As the benzophenone derivative, an amino phenyl ketone is particularly preferable from the viewpoint of exposure sensitivity. Examples of the p-aminophenyl ketone include p-aminobenzophenone, p-butylaminobenzophenone, p-dimethylaminoacetophenone, and p-dimethylaminobenzophenone. , p,p'-bis(ethylamino)benzophenone, p,p'-bis(dimethylamino)benzophenone [micilenone], p,p'-double (two Ethylamino)benzophenone, p,p'-bis(dibutylamino)benzophenone.

Further, as the photopolymerization initiator, (c) 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, for example, ultraviolet rays, to start polymerization can be used.

Examples of the other photopolymerization initiator include an anthracene such as 2-ethylanthracene or 2-tert-butylindole, an aromatic ketone such as benzophenone, benzoin, benzoin methyl ether, and benzoin ethyl ether. Such as benzoin ethers, acridine compounds such as 9-phenyl acridine, benzoin dimethyl ketal, benzoin diethyl ketal, pyrazoline compounds. Further, for example, 9-oxygen sulfur can also be cited. 2,4-diethyl-9-oxosulfur 2-chloro-9-oxosulfur 9-oxosulfur A combination of a tertiary amine compound such as an alkyl dimethyl benzoate compound.

As other photopolymerization initiators, 1-phenyl-1,2-propanedione-2-(O-benzylidene) fluorene, 1-phenyl-1,2-propanedione- An oxime ester such as 2-(O-ethoxycarbonyl)anthracene. Further, an N-aryl-α-amino acid compound can also be used, and N-phenylglycine is particularly preferred.

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 the exposure sensitivity, the content thereof is preferably 0.1% by mass or more, and from the viewpoint of the resolution, it is preferably 20% by mass or less. Moreover, 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 0.1% by mass to 20% by mass.

When the 2,4,5-triarylimidazole dimer is used as the (c) photopolymerization initiator, the content of the 2,4,5-triarylimidazole dimer is compared with the negative photosensitive resin composition. The whole material is preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.5 to 4.5% by mass. From the viewpoint of sensitivity, it is preferably 0.1% by mass or more, and from the viewpoint of resolution, it is preferably 10% by mass or less.

In the case where at least one compound selected from the group consisting of benzophenone and benzophenone derivatives is used as the (c) photopolymerization initiator, the content of the compound is compared with the negative photosensitive resin composition. The whole material is determined so that the light transmittance at a wavelength of 365 nm is 25% or more and 50% or less, depending on the thickness of the negative photosensitive resin layer (B), and is usually preferably 0.01 to 1.0% by mass. Within the range, it is more preferably in the range of 0.05 to 0.15 mass%.

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, auramine base, Calkoxide Green S, Paramadienta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, and malachite green (manufactured by Hodogaya Chemical Co., Ltd.) AIZEN (registered trademark) MALACHITE GREEN), alkaline blue 20, diamond green (AIZEN (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.), and the like.

The content of the coloring matter is preferably in the range of 0.005 to 10% by mass, more preferably in the range of 0.01 to 1% by mass, based on the entire negative photosensitive resin composition. The content is preferably 0.005% by mass or more from the viewpoint of resist visibility, and is preferably 10% by mass or less from the viewpoint of sensitivity.

The negative photosensitive resin composition may also contain a chromogenic dye which is colored by light irradiation. Examples of the chromogenic dye include a leuco dye and a fluorane dye. As the leuco dye, for example, tris(4-dimethylamino-2-methylphenyl)methane-[leuco crystal violet], tris(4-dimethylamino-2-methylphenyl) can be mentioned. Methane - [hidden malachite green] and so on.

The leuco dye is preferably used in combination with a halogenated compound. Examples of the halogenated compound include bromopentane, bromoisopentane, 1,2-dibromo-2-methylpropane, 1,2-dibromoethane, diphenylbromomethane, dibrominated toluene, and dibromomethane. , tribromomethylphenylhydrazine, carbon tetrabromide, tris(2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, iodoisobutane, 1,1,1-three Chloro-2,2-bis(p-chlorophenyl)ethane, hexachloroethane, halogenated three Compounds, etc.

Halogenated three The compound may, for example, be 2,4,6-tris(trichloromethyl)-all three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-all three .

Particularly useful is a combination of tribromomethylphenylhydrazine and a leuco dye, or three A combination of a compound and a leuco dye.

The content of the leuco dye is preferably in the range of 0.005 to 10% by mass, more preferably in the range of 0.01 to 1% by mass, based on the whole of the negative photosensitive resin composition. In view of the coloring property, the content is preferably 0.005% 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 10% by mass or less.

The content of the halogenated compound is preferably in the range of 0.005 to 10% by mass, more preferably 0.01 to 1% by mass, based on the whole of the negative photosensitive resin composition. In view of the coloring property, the content is preferably 0.005% 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 10% by mass or less.

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-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butyl catechol, copper chloride, and 2,6-di. - tert-butyl-p-cresol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6 -T-butylphenol), N-nitrosodiphenylamine, etc., as a specific preferred example, tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid Pentaerythritol ester and the like.

The content of the radical polymerization inhibitor is preferably in the range of 0.01 to 3% by mass, more preferably 0.02 to 0.2% by mass based on the whole of the negative photosensitive resin composition. In view of the resolution, the content 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 in the range of 5 to 30% 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 is preferably 50% by mass or less from the viewpoint of suppressing insufficient hardening and cold flow.

The substrate (C) in the present invention may be a copper foil laminate 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, or 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).醯iimine-three A flexible substrate or a Tape Automated Bonding (TAB) tape coated with a copper foil on an insulating resin layer such as a resin.

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 substrate (C) is laminated on the surface of the negative photosensitive resin layer (B) opposite to the support (A), that is, the substrate (C) is sandwiched with a negative photosensitive resin. The layer (B) is placed on the substrate (C) (for example, a metal substrate for a printed circuit board) by heating and pressing the negative photosensitive resin layer (B) so as to face the support (A).

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 the active light. Examples of the permeable transparent light support include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, and vinylidene chloride copolymerization. A film, a polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, a cellulose derivative film, or the like. These films may be extended as needed.

The haze of the support (A) is preferably 5.0 or less. Regarding the thickness of the support (A), a thinner one is advantageous in terms of image formation property and economy, but in order to maintain strength, the thickness is usually 10 to 30 μm.

A protective layer (pad) is laminated on the surface of the negative photosensitive resin layer (B) opposite to the side of the support (A) as needed. 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), so that the protective layer can be easily peeled off. The important characteristics of the layer. 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, the surface of the negative photosensitive resin layer (B) is previously formed before the negative photosensitive resin layer (B) is formed on the substrate (C). After the protective layer is formed and the protective layer is peeled off, the negative photosensitive resin layer (B) is laminated on the surface of the substrate (C) by heat bonding. The heating temperature at this time is usually 40 to 160 °C.

The thickness of the negative photosensitive resin layer (B) is different for different applications, and is usually 5 to 100 μm, preferably 5 to 50 μm, for producing a printed circuit board (printed wiring board). The film thickness is preferably in the range of 5 to 25 μm in terms of high resolution and improved resist reproducibility.

The negative photosensitive resin laminate may be exposed by active light such as i-line monochromatic light or ultraviolet light, preferably by i-line monochromatic light. In the exposure step, the exposed portion of the negative photosensitive resin layer (B) is cured. Examples of the light source used in the exposure step include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, a xenon lamp, and a laser. These light sources can be used directly, or a line pass filter or the like can be used to form an i-line monochrome. If the exposure wavelength is formed as an i-line monochrome, the resolution is improved, so it is preferable to use i-line monochromatic light. The support (A) is peeled off from the negative photosensitive resin layer (B) between the laminate forming step and the exposure step, and then the remaining negative photosensitive resin layer (B) is preferably exposed in the exposure step. . In this case, the resist cross-sectional shape is formed into a rectangular shape, that is, it is formed to have almost no thickness of the top of the resist and a narrow shape of the bottom of the resist, which is particularly preferable.

In general, as an exposure method used for exposure, a projection exposure method, a projection exposure method, a direct drawing method, and the like can be cited. In the present invention, a projection type exposure method is used, which uses a light that projects an image of a photomask. The negative photosensitive resin layer is exposed through a lens. Furthermore, in a typical aspect of the invention, the light from the light source passes through the reticle and the lens and then reaches the negative photosensitive resin layer, but the light from the light source may first pass through the lens and then pass through the reticle. In the present invention, the projection type exposure method is employed, 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. In the projection type exposure method, the light transmittance of the negative photosensitive resin layer (B) at a wavelength of 365 nm is 25% or more and 50% or less, and the support (A) is peeled off before exposure. The advantage that the resist shape is formed into a rectangular shape, that is, is formed to have almost no coarseness of the top of the resist and a narrow shape of the bottom of the resist.

Then, when 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, an aqueous solution of sodium carbonate, potassium carbonate or the like can be used. These alkaline aqueous solutions can be selected according to the characteristics of the negative photosensitive resin layer (B), and a sodium carbonate aqueous solution of 0.5 to 3% by mass is usually used. Thus, the cured film of the present invention can be obtained.

<Method of Manufacturing Printed Wiring Board>

Hereinafter, a method of manufacturing the printed wiring board using the negative photosensitive resin laminate will be described. 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 for producing a printed wiring board according to the present invention, in particular, a metal plate is used as the substrate (C), and the metal surface exposed by the developing step in the method for producing a cured resist is used. An image pattern of metal is formed by any one of an etching method or an electroplating method. 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 1 to 5% by mass of sodium hydroxide or potassium hydroxide is usually used.

By forming the image pattern by using the present invention, in addition to the above-described printed wiring board (printed circuit board), a semiconductor package substrate, a lead frame, a barrier rib of a plasma display, or the like can be formed. As shown in Fig. 1, the cross section of the resist line obtained by the present invention is shown to be close to a good shape of a rectangle (rectangular 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 alleviated, and the pre-self-receptive 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 "coil shape", and the problem that the resist residue is large is remarkably reduced. Therefore, the present invention can be particularly preferably applied to the manufacture of a semiconductor package substrate.

When the lead frame is manufactured 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 cured resist. 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), after the exposure step and the development step in the method of manufacturing the resist cured product, by The exposed substrate surface is processed by a sandblasting method, and the resist pattern is peeled off to obtain a substrate having a concave-convex pattern.

[Examples]

Hereinafter, embodiments of the present invention will be specifically described by way of examples, but the present invention is not limited to the examples.

<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.

In the table, the components of the negative photosensitive resin composition represented by the abbreviation (P-1 to C-1) will be described in the following <Symbol Description>. In the table, the values of P-1 and P-2 are solid content.

<Symbol description>

P-1: a methyl ethyl ketone solution of a terpolymer of 30% by mass of methacrylic acid, 20% by mass of styrene, and 50% by mass of benzyl methacrylate (solid content concentration: 40% by mass, weight average molecular weight is 55,000, acid equivalent of 287, glass transition temperature of 102 ° C)

P-2: a methyl ethyl ketone solution of a binary copolymer of 80% by mass of benzyl methacrylate and 20% by mass of methacrylic acid (solid content concentration: 50% by mass, weight average molecular weight: 25,000, acid equivalent: 430) , glass transfer temperature is 78 ° C)

M-1: a dialkyl diol of a polyalkylene glycol having an average of 3 moles of ethylene oxide added to both ends of a polypropylene glycol having an average of 12 moles of propylene oxide.

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

M-3: a polyethylene glycol dimethacrylate of an average of 5 moles of ethylene oxide at both ends of bisphenol A (NR ESTER BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.) )

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 (AIZEN (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.)

B-2: leuco crystal violet

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

<Method of Forming Negative Photosensitive Resin Layer (B)>

Hereinafter, a method of forming the negative photosensitive resin layer (B) on the support (A) will be described.

In the examples and the comparative examples, the components shown in Tables 1 and 2 were mixed and uniformly dissolved by using methyl ethyl ketone as a solvent so that the concentration of the nonvolatile component was 50% by mass, thereby preparing 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 film having a thickness of 20 μm as a support (A) by a bar coater, and dried at 95 ° C. Dry in the unit for 3 minutes. The negative photosensitive resin layer (B) obtained after drying had a thickness of 25 μm.

The light transmittance of the negative photosensitive resin layer (B) formed on the above polyethylene terephthalate at a wavelength of 365 nm is obtained by using a U-3310 spectrophotometer manufactured by Hitachi High-Technologies Corporation. The ethylene terephthalate film was placed on the reference side for measurement. Further, the slit at this time was set to 4 nm, and the scanning speed was set to 600 nm/min.

Next, a polyethylene film having a thickness of 25 μm as a protective layer was bonded to the negative photosensitive resin layer (B) to obtain a laminated film. The surface of the copper foil laminate which is a substrate (C) laminated with a rolled copper foil of 35 μm was subjected to sandblasting, and the polyethylene film of the laminated film was peeled off, and the negative film was pressed at 105 ° C by a heat roll laminator. The photosensitive resin layer (B) was laminated on the substrate (C) to obtain a negative photosensitive resin laminate.

<Production of resist cured product>

The negative photosensitive resin laminate obtained above was irradiated at 180 mJ/cm ² by a projection film exposure machine (UX2003 SM-MS04 manufactured by USHIO Electric Co., Ltd. using an i-line band pass filter). The monochromatic light is lined to expose the negative photosensitive resin layer (B) with i-line monochromatic light. Then, a 1% by mass aqueous sodium carbonate solution at 30 ° C was sprayed for about 40 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 spray-washed with ion-exchanged water for about 20 seconds to obtain a cured resist of the present invention. Further, in the examples and comparative examples shown in Table 1, the polyethylene terephthalate 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 evaluation criteria.

(1) Resolution: In the above exposure, exposure and development were carried out using a photomask film having a line and a gap of 1:1. The minimum line width at which the obtained hardened pattern can be separated is taken as the resolution.

(2) Adhesiveness: In the above exposure, a mask film having a line and a gap of L μm: 200 μm (L μm indicates a line width) was used for exposure and development. The minimum line width at which the obtained hardened pattern can be adhered is used as the adhesion.

(3) Resist shape: In the above exposure, a photomask film having a line width of 12 μm was used. The shape of the resist was confirmed using an electron microscope (Sm-500 manufactured by TOPCON Co., Ltd.) at an acceleration voltage of 15 kV, a magnification of 1,000 times, and a tilt angle of 60 degrees. When the difference between the line width of the hardened pattern between the top of the resist and the bottom of the resist is less than 1 μm, it is denoted by ◎, and when it is 1 μm or more and less than 2 μm, it is denoted by ○, and when it is 2 μm or more, it is denoted by ×.

<Examples 1A to 8A, Comparative Examples 1A to 4A, Examples 1B to 7B, and Comparative Examples 1B to 4B>

The components and evaluation results of the negative photosensitive resin composition are shown in Tables 1 and 2. It can be confirmed that Examples 1A to 8A and Examples 1B to 7B in which the light transmittance at a wavelength of 365 nm is within the range of the present invention, and Comparative Examples 1A to 4A and Comparative Example 1B in which the light transmittance is outside the range of the present invention. Compared with 4B, it is excellent in comprehensiveness in terms of evaluation criteria including resolution, adhesion, and resist shape.

Electron micrographs of the resist shapes of the cured resists obtained in Example 2A and Comparative Example 1A are shown in Figs. 1 and 2, respectively. The resist shape in Example 2A was close to a rectangular shape, whereas the apparent coarseness of the top of the resist and the sharpness of the bottom of the resist were observed in Comparative Example 1A. Electron micrographs of the resist shapes of the cured resists obtained in Example 2B and Comparative Example 1B are shown in Figs. 3 and 4, respectively. In the second embodiment, the resist shape was close to a rectangular shape. On the other hand, in the comparative example 1B, the bottom of the resist was observed to be narrow, and the resist residue was observed to be large (the resist cross-sectional shape was "a bobbin shape"). ).

[Industrial availability]

The present invention can be widely used in the manufacture of printed wiring boards (printed circuit boards), integrated circuit (IC) wafer mounting lead frames, semiconductor packages, and the like.

Figure 1 is an electron micrograph of the shape of the 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.

(no component symbol description)

Claims (28)

A method for producing a resist cured product, comprising: a laminate forming step of forming a negative layer formed by at least a support (A), a negative photosensitive resin layer (B) and a substrate (C) a 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 the negative sensitivity by development a resist cured product including the cured portion of the negative photosensitive resin layer (B) is formed in the unexposed portion of the resin layer (B); and the negative photosensitive resin layer (B) is at a wavelength of 365 nm. The light transmittance is 25% or more and 50% or less. A method of producing a resist cured product according to claim 1, wherein the light is i-line monochromatic light. The method for producing a cured resist of claim 1, wherein the support (A) is peeled off from the negative photosensitive resin layer (B) between the laminated body forming step and the exposure step. Support stripping step. The method for producing a cured resist of claim 1, 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. The method for producing a cured resist of claim 1, wherein the negative photosensitive resin layer (B) comprises: a negative photosensitive resin composition containing (a) a carboxyl group content In terms of acid equivalent 100 to 600, and a weight average molecular weight of 5,000 to 500,000, 20 to 90% by mass of the binder resin, (b) 3 to 70% by mass of the photopolymerizable unsaturated compound, and (c) photopolymerization initiation The agent is 0.1 to 20% by mass. The method for producing a cured resist of claim 5, which comprises at least one compound selected from the group consisting of benzophenone and benzophenone derivatives as the above (c) photopolymerization initiator. A method for producing a cured resist of claim 5, which comprises a 2,4,5-triarylimidazole dimer as the above (c) photopolymerization initiator. The method for producing a cured resist of claim 5, which comprises at least one compound selected from the group consisting of benzophenone and benzophenone derivatives, and 2,4,5-triarylimidazole Both of the polymers are used as the above (c) photopolymerization initiator. The method for producing a cured resist of claim 5, wherein the (a) photopolymerizable unsaturated compound is selected from the group consisting of the compound represented by the following formula (I) and the following formula (II); a group consisting of the indicated compounds: Wherein R ₈ and R _{9 are} independently H or CH ₃ , and n ₂ , n ₃ and n ₄ are each independently an integer of from 3 to 20}; 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, and n ₇ + n ₈ is 0. n ₅ and n _{6 are} independently an integer from 1 to 29, n ₇ and n ₈ are each 0, and the arrangement of the repeating units -(AO)- and -(BO)- may be random or block, and is a block. In the case of both, it can be located on the bisphenol side}. A method of manufacturing a printed wiring board, comprising the steps of: etching or plating the substrate (C), the substrate (C) having the manufacturing method according to any one of claims 1 to 9 a resist pattern formed by the resist cured material; and a step of removing the resist cured material from the substrate (C). A negative-type photosensitive resin laminate for forming a resist cured product by exposing a negative-type 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: (a) a carboxyl group content in terms of acid equivalent 100~600, and the weight average molecular weight is 5,000~ 50 to 90% by mass of the binder resin between 500,000, (b) 3 to 70% by mass of the photopolymerizable unsaturated compound, and (c) 0.1 to 20% by mass of the photopolymerization initiator In the negative photosensitive resin composition for exposure, the light transmittance of the negative photosensitive resin layer (B) at a wavelength of 365 nm is 25% or more and 50% or less. The negative photosensitive resin laminate according to claim 11, 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. The negative photosensitive resin laminate according to claim 11, wherein the (a) binder resin has a glass transition temperature of 100 ° C or higher. The negative photosensitive resin laminate according to claim 11, wherein the (a) binder resin has a weight average molecular weight of 10,000 to 40,000. The negative photosensitive resin laminate according to claim 11, which contains at least one compound selected from the group consisting of benzophenone and a benzophenone derivative as the above (c) photopolymerization initiator. The negative photosensitive resin laminate according to claim 11, which contains the 2,4,5-triarylimidazole dimer as the above (c) photopolymerization initiator. The negative photosensitive resin laminate according to claim 11, which comprises at least one compound selected from the group consisting of benzophenone and benzophenone derivatives, and dimerized with 2,4,5-triarylimidazole Both of them are used as the above (c) photopolymerization initiator. The negative photosensitive resin laminate according to claim 11, wherein the (a) photopolymerizable unsaturated compound is selected from the group consisting of a compound represented by the following formula (I) and represented by the following formula (II) a group of compounds: Wherein R ₈ and R _{9 are} independently H or CH ₃ , and n ₂ , n ₃ and n ₄ are each independently an integer of from 3 to 20}; 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, and n ₇ + n ₈ is 0. n ₅ and n _{6 are} independently an integer from 1 to 29, n ₇ and n ₈ are each 0, and the arrangement of the repeating units -(AO)- and -(BO)- may be random or block, and is a block. In the case of both, it can be located on the bisphenol side}. The negative photosensitive resin laminate according to claim 11, further comprising a protective layer on the negative photosensitive resin layer (B). A method of using a negative photosensitive resin laminate in which a negative photosensitive tree is irradiated through a lens by using i-line monochromatic light that projects an image of a photomask When the fat layer is exposed to form a cured resist, the following negative photosensitive resin laminated body is used, and the negative photosensitive resin laminated system has at least a negative photosensitive property for the support (A) and i-line monochromatic exposure. In the resin layer (B), the negative photosensitive resin layer (B) includes a negative photosensitive resin composition for i-line single-color exposure, and the negative photosensitive resin composition contains (a) a carboxyl group content. 20 to 90% by mass of the resin for binders having a weight average molecular weight of 5,000 to 500,000, and (b) 3 to 70% by mass of the unsaturated compound capable of photopolymerization, and (c) The photopolymerization initiator 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. The method of using the negative photosensitive resin laminate according to claim 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. The method of using the negative photosensitive resin laminate of claim 20, wherein the (a) binder resin has a glass transition temperature of 100 ° C or higher. The method of using the negative photosensitive resin laminate of claim 20, wherein the (a) binder resin has a weight average molecular weight of between 10,000 and 40,000. 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 benzophenone and benzophenone derivatives 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 according to claim 20, which comprises at least one compound selected from the group consisting of benzophenone and benzophenone derivatives, and 2,4,5-triaryl Both of the imidazole dimers are used as the above (c) photopolymerization initiator. The method for using a negative photosensitive resin laminate according to claim 20, wherein the (a) photopolymerizable unsaturated compound is selected from the group consisting of the compound represented by the following formula (I) and the following formula (II) a group of compounds represented by: Wherein R ₈ and R _{9 are} independently H or CH ₃ , and n ₂ , n ₃ and n ₄ are each independently an integer of from 3 to 20}; 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, and n ₇ + n ₈ is 0. n ₅ and n _{6 are} independently an integer from 1 to 29, n ₇ and n ₈ are each 0, and the arrangement of the repeating units -(AO)- and -(BO)- may be random or block, and is a block. In the case of both, it can be located on the bisphenol side}. A method of using a negative photosensitive resin laminate according to claim 20, further comprising a protective layer on the negative photosensitive resin layer (B).