CN101952777A - Method for producing cured resist using negative photosensitive resin laminate, negative photosensitive resin laminate, and use of negative photosensitive resin laminate - Google Patents

Abstract

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

Description

The using method of manufacture method, negative-type photosensitive resin laminate and the negative-type photosensitive resin laminate of the resist solidfied material of use negative-type photosensitive resin laminate

Technical field

The present invention relates to the manufacture method of resist solidfied material, it comprises the operation of using the negative-type photosensitive resin laminate with negative-type photosensitive resin bed and the operation that this negative-type photosensitive resin bed is exposed.And then in detail, the present invention relates to use negative-type photosensitive resin laminate in the manufacturing be suitable for P.e.c. (circuit) plate, lead frame, semiconductor packages etc. to make the method for resist solidfied material with negative-type photosensitive resin bed.The invention still further relates to the negative-type photosensitive resin laminate with negative-type photosensitive resin bed that i ray monochromatic exposure uses and the using method of negative-type photosensitive resin laminate.And then in detail, the present invention relates to be suitable for the negative-type photosensitive resin laminate of the negative-type photosensitive resin bed that the i ray monochromatic exposure with alkali-developable of the manufacturing of P.e.c. (circuit) plate, lead frame, semiconductor packages etc. uses and the using method of negative-type photosensitive resin laminate.

Background technology

In the past, printed circuit board (PCB) was by the photoetching process manufacturing.Photoetching process is meant, utilizes the light reaction of photosensitive polymer combination to carry out the method that pattern forms.Under the situation of the photosensitive polymer combination that uses minus, this photosensitive polymer combination is applied on the substrate, form after the photo-sensitive resin, carry out pattern exposure immediately, make the exposure portion polymerizing curable of this photosensitive polymer combination, remove unexposed portion with developer solution, on substrate, form corrosion-resisting pattern, and impose etching or plating processing, behind the formation conductive pattern, remove by this corrosion-resisting pattern is peeled off from this substrate, thereby can on substrate, form conductive pattern.

In the above-mentioned minus photoetching process, can use following arbitrary method: when being applied to negative light-sensitive resin combination on the substrate, with the solution coat of negative light-sensitive resin combination to substrate and make its dry method; Perhaps, lamination is successively had the layer that supporter and negative light-sensitive resin combination form (below be also referred to as " negative-type photosensitive resin bed ".) and the dry film resist layer that forms of protective seam as required, be laminated to the method on the substrate.In the manufacturing of printed circuit board (PCB), adopt the method that the dry film resist layer is laminated to the latter on the substrate mostly.

Carry out following explanation for the method for using dry film photoresist to make printed circuit board (PCB).At first, have at the dry film resist layer under the situation of protective seam, for example polyethylene film, peel off protective seam by the negative-type photosensitive resin bed.Then, use laminating machine order lamination negative-type photosensitive resin bed and supporter according to substrate, negative-type photosensitive resin bed, supporter on substrate, for example copper clad laminate.Then, across the photomask with wiring pattern, the ultraviolet rays such as i ray (under the wavelength 365nm) that utilize ultrahigh pressure mercury lamp to send expose to this negative-type photosensitive resin bed, thereby make the exposed portion polymerizing curable.Then, peeling off the supporter that is formed by polyethylene terephthalate etc. peels off.Then, remove or disperse to remove the unexposed portion of negative-type photosensitive resin bed, on substrate, form corrosion-resisting pattern by having developing solution dissolution such as weakly alkaline aqueous solution.Then, formed corrosion-resisting pattern as the protection mask, is carried out known etch processes or pattern plating and handles.At last, from this corrosion-resisting pattern of strippable substrate, make substrate, be printed circuit board (PCB) with conductive pattern.

In recent years, follow the miniaturization and of e-machines such as portable phone, notebook computer, the requirement of the miniaturization at interval of the wiring in the printed circuit board (PCB) is increased day by day.In order to tackle the requirement of such miniaturization, even the few monochromatic expectation of i ray of look receipts difference also uprises in to the exposure method of dry film resist layer to utilizing.In addition, in requiring high-resolution purposes, the influence of lubricant that is contained in the supporter etc. exposes after in advance supporter being peeled off sometimes.Yet, in the exposure method that uses present dry film photoresist, as shown in Figure 2, the resist layer chap at resist layer top and the resist layer at the bottom of the resist layer can take place attenuate, aspect the resist layer resizing problem is being arranged.In addition, shown in Figure 4 as described later under the situation of peeling off the supporter post-exposure in advance, the resist cross sectional shape is " a coiling tubular ", in addition, because the residual foot of resist is big, thereby has problems aspect the resist layer resizing.

The method of using dry film photoresist to make printed circuit board (PCB) has following steps: the ultraviolet rays such as i ray (under the wavelength 365nm) of using ultrahigh pressure mercury lamp to send, across photomask with wiring pattern, the negative-type photosensitive resin bed is exposed, thereby make the step of exposed portion polymerizing curable; By having the step that developer solutions such as weakly alkaline aqueous solution are removed the unexposed portion dissolving of negative-type photosensitive resin bed or disperse to remove; And other steps.The resist layer top broaden and the attenuating of resist layer bottom, the resist layer cross sectional shape becomes the coiling tubular and the residual foot of resist layer becomes big generation reason and produces not clear and definite as yet in which step.

Put down in writing in the patent documentation 1 at the dry film resist layer of having stipulated the absorbance under the wavelength 365nm.Yet, in patent documentation 1, do not have the record of relevant i ray monochromatic exposure.In addition, not record in patent documentation 1 about exposing after in advance supporter being peeled off.

Patent documentation 1: TOHKEMY 2006-145565 communique

Summary of the invention

Invent problem to be solved

Problem of the present invention is, the using method of manufacture method, negative-type photosensitive resin laminate and negative-type photosensitive resin laminate of the resist solidfied material of the corrosion-resisting pattern that brings develop back adhesion and excellent in resolution and excellent resist layer shape is provided.

The method that is used to deal with problems

The inventor has carried out deeply research repeatedly in order to address the above problem, found that, now, surprisingly, to having supporter (A), negative-type photosensitive resin bed (B), and the negative-type photosensitive resin laminate of substrate (C) is when exposing, by changing the transmittance of this negative-type photosensitive resin bed (B), specifically, by using the transmittance under the wavelength 365nm is the negative-type photosensitive resin bed (B) below 50% more than 25%, the resist that has the negative-type photosensitive resin bed manufacturing of present transmittance with use is compared, the adhesion of the corrosion-resisting pattern after the development and resolution and resist layer shape are improved rapidly, thereby finish the present invention.In addition, when the layered product with negative-type photosensitive resin bed is carried out i ray monochromatic exposure, find to count 100～600 by containing (a) carboxyl-content with acid equivalent if use, and, weight-average molecular weight is 5000～500000 binder resin: 20～90 quality %, (b) unsaturated compound of photopolymerization: 3～70 quality %, and (c) Photoepolymerizationinitiater initiater: the photosensitive polymer combination of 0.1～20 quality % is formed, and, transmittance under the wavelength 365nm is the negative-type photosensitive resin bed below 50% more than 25%, then compare with the situation that use has a negative-type photosensitive resin bed of above-mentioned extraneous transmittance, the adhesion of the corrosion-resisting pattern after development and resolution and resist layer vpg connection improve rapidly, thereby finish the present invention.Specifically, above-mentioned problem solves by the scheme of following [1]～[28].

[1] a kind of manufacture method of resist solidfied material, it comprises following operation:

Layered product forms operation: form the negative-type photosensitive resin laminate that is formed by supporter (A), negative-type photosensitive resin bed (B) and substrate (C) lamination at least;

Exposure process: use the light of projected light mask picture and, aforementioned negative-type photosensitive resin bed (B) is exposed across lens;

Developing procedure: remove the unexposed portion of aforementioned negative-type photosensitive resin bed (B) by development, form the resist solidfied material of forming by the cured portion of aforementioned negative-type photosensitive resin bed (B);

The transmittance of aforementioned negative-type photosensitive resin bed (B) under wavelength 365nm is more than 25% below 50%.

[2] according to the manufacture method of above-mentioned [1] described resist solidfied material, wherein, this light is i ray monochromatic light.

[3] according to the manufacture method of above-mentioned [1] or [2] described resist solidfied material, between this layered product formation operation and this exposure process, also comprise the supporter stripping process that this supporter (A) is peeled off from this negative-type photosensitive resin bed (B).

[4] according to the manufacture method of each described resist solidfied material of above-mentioned [1]～[3], the transmittance of this negative-type photosensitive resin bed (B) under wavelength 365nm is more than 35% below 45%.

[5] according to the manufacture method of each described resist solidfied material of above-mentioned [1]～[4], this negative-type photosensitive resin bed (B) is formed by negative light-sensitive resin combination, and this negative light-sensitive resin combination contains: (a) carboxyl-content counts 100～600 and unsaturated compound 3～70 quality % of binder resin 20～90 quality %s of weight-average molecular weight between 5000～500000, (b) photopolymerization and (c) Photoepolymerizationinitiater initiater 0.1～20 quality % with acid equivalent.

[6],, contain at least a kind of compound that is selected from the group of forming by benzophenone and benzophenone derivates as this (c) Photoepolymerizationinitiater initiater according to above-mentioned [5] described manufacture method.

[7], as this (c) Photoepolymerizationinitiater initiater, contain 2,4,5-triarylimidazoles dipolymer according to above-mentioned [5] or [6] described manufacture method.

[8] according to each described manufacture method of above-mentioned [5]～[7], as this (c) Photoepolymerizationinitiater initiater, contain at least a kind of compound and 2,4 that is selected from the group of forming by benzophenone and benzophenone derivates, 5-triarylimidazoles dipolymer the two.

[9] according to the manufacture method of each described resist solidfied material of above-mentioned [5]～[8], the unsaturated compound of this (b) photopolymerization is selected from the group of being made up of the compound of the compound of following general formula (I) expression and following general formula (II) expression:

[Chemical formula 1]

In the formula, R ₈And R ₉Be H or CH independently ₃, and, n ₂, n ₃And n ₄Be 3～20 integer independently of one another;

[Chemical formula 2]

In the formula, R ₁₀And R ₁₁Be H or CH independently ₃, A is C ₂H ₄, B is C ₃H ₆, n ₅+ n ₆Be 2～30 integer, n ₇+ n ₈Be 0～30 integer, n ₅And n ₆Be 1～29 integer independently, n ₇And n ₈Be 0～29 integer independently, repetitive-(A-O)-and-(B-O)-the optional random or block of arrangement, under the situation that is block, any can be the bisphenol group side.

[10] a kind of manufacture method of printed circuit board (PCB), it comprises following operation: the aforesaid base plate (C) that will have corrosion-resisting pattern carries out the operation of etching or plating, and wherein said corrosion-resisting pattern is formed by the resist solidfied material that makes by each described manufacture method in above-mentioned [1]～[9]; The operation that aforementioned resist solidfied material is removed from aforesaid base plate (C).

[11] a kind of negative-type photosensitive resin laminate, it is to be used for by i ray monochromatic light that uses projected light mask picture and the negative-type photosensitive resin laminate that the negative-type photosensitive resin bed is exposed and forms the resist solidfied material across lens,

It has the negative-type photosensitive resin bed (B) that supporter (A) and i ray monochromatic exposure are used at least,

The negative light-sensitive resin combination that this negative-type photosensitive resin bed (B) is used by i ray monochromatic exposure forms, the negative light-sensitive resin combination that described i ray monochromatic exposure is used contains: (a) carboxyl-content counts 100～600 and unsaturated compound 3～70 quality % of binder resin 20～90 quality %s of weight-average molecular weight between 5000～500000, (b) photopolymerization and (c) Photoepolymerizationinitiater initiater 0.1～20 quality % with acid equivalent, and

The transmittance of this negative-type photosensitive resin bed (B) under wavelength 365nm is more than 25% below 50%.

[12] according to above-mentioned [11] described negative-type photosensitive resin laminate, the transmittance of this negative-type photosensitive resin bed (B) under wavelength 365nm is more than 35% below 45%.

[13] according to above-mentioned [11] or [12] described negative-type photosensitive resin laminate, the glass transition temperature that is somebody's turn to do (a) binder resin is more than 100 ℃.

[14] according to each described negative-type photosensitive resin laminate of above-mentioned [11]～[13], the weight-average molecular weight of being somebody's turn to do (a) binder resin is between 10000～40000.

[15] according to each described negative-type photosensitive resin laminate of above-mentioned [11]～[14],, contain at least a kind of compound that is selected from the group of forming by benzophenone and benzophenone derivates as this (c) Photoepolymerizationinitiater initiater.

[16] according to each described negative-type photosensitive resin laminate of above-mentioned [11]～[15], as this (c) Photoepolymerizationinitiater initiater, contain 2,4,5-triarylimidazoles dipolymer.

[17] according to each described negative-type photosensitive resin laminate of above-mentioned [11]～[16], as this (c) Photoepolymerizationinitiater initiater, contain at least a kind of compound and 2,4 that is selected from the group of forming by benzophenone and benzophenone derivates, 5-triarylimidazoles dipolymer the two.

[18] according to each described negative-type photosensitive resin laminate of above-mentioned [11]～[17], the unsaturated compound of this (b) photopolymerization is selected from the group of being made up of the compound of the compound of following general formula (I) expression and following general formula (II) expression:

[chemical formula 3]

In the formula, R ₈And R ₉Be H or CH independently ₃, and n ₂, n ₃And n ₄Be 3～20 integer independently of one another;

[chemical formula 4]

In the formula, R ₁₀And R ₁₁Be H or CH independently ₃, A is C ₂H ₄, B is C ₃H ₆, n ₅+ n ₆Be 2～30 integer, n ₇+ n ₈Be 0～30 integer, n ₅And n ₆Be 1～29 integer independently, n ₇And n ₈Be 0～29 integer independently, repetitive-(A-O)-and-(B-O)-the optional random or block of arrangement, under the situation that is block, any can be the bisphenol group side.

[19] according to each described negative-type photosensitive resin laminate of above-mentioned [11]～[18], on aforementioned negative-type photosensitive resin bed (B), also has protective seam.

[20] a kind of using method of negative-type photosensitive resin laminate, it exposes when forming the resist solidfied material to the negative-type photosensitive resin bed at the i ray monochromatic light by using projected light mask picture and across lens, use negative-type photosensitive resin laminate as described below: described layered product has the negative-type photosensitive resin bed (B) that supporter (A) and i ray monochromatic exposure are used at least, wherein, the negative light-sensitive resin combination that aforementioned negative-type photosensitive resin bed (B) is used by i ray monochromatic exposure forms, the negative light-sensitive resin combination that described i ray monochromatic exposure is used contains (a) carboxyl-content counts 100～600 with acid equivalent, and binder resin 20～90 quality %s of weight-average molecular weight between 5000～500000, (b) unsaturated compound 3～70 quality % of photopolymerization, and (c) Photoepolymerizationinitiater initiater 0.1～20 quality %, and the transmittance of aforementioned negative-type photosensitive resin bed (B) under wavelength 365nm is more than 25% below 50%.

[21] according to above-mentioned [20] described using method, the transmittance of this negative-type photosensitive resin bed (B) under wavelength 365nm is more than 35% below 45%.

[22] according to above-mentioned [20] or [21] described using method, the glass transition temperature that is somebody's turn to do (a) binder resin is more than 100 ℃.

[23] according to each described using method of above-mentioned [20]～[22], the weight-average molecular weight of being somebody's turn to do (a) binder resin is between 10000～40000.

[24],, contain at least a kind of compound that is selected from the group of forming by benzophenone and benzophenone derivates as this (c) Photoepolymerizationinitiater initiater according to each described using method of above-mentioned [20]～[23].

[25], as this (c) Photoepolymerizationinitiater initiater, contain 2,4,5-triarylimidazoles dipolymer according to each described using method of above-mentioned [20]～[24].

[26] according to each described using method of above-mentioned [20]～[25], as this (c) Photoepolymerizationinitiater initiater, contain at least a kind of compound and 2,4 that is selected from the group of forming by benzophenone and benzophenone derivates, 5-triarylimidazoles dipolymer the two.

[27] according to each described using method of above-mentioned [20]～[26], the unsaturated compound of this (b) photopolymerization is selected from the group of being made up of the compound of the compound of following general formula (I) expression and following general formula (II) expression:

[chemical formula 5]

In the formula, R ₈And R ₉Be H or CH independently ₃, and n ₂, n ₃And n ₄Be 3～20 integer independently of one another;

[chemical formula 6]

In the formula, R ₁₀And R ₁₁Be H or CH independently ₃, A is C ₂H ₄, B is C ₃H ₆, n ₅+ n ₆Be 2～30 integer, n ₇+ n ₈Be 0～30 integer, n ₅And n ₆Be 1～29 integer independently, n ₇And n ₈Be 0～29 integer independently, repetitive-(A-O)-and-(B-O)-the optional random or block of arrangement, under the situation that is block, any can be the bisphenol group side.

[28], on this negative-type photosensitive resin bed (B), also has protective seam according to each described using method of above-mentioned [20]～[27].

The invention effect

According to the present invention, the adhesion after can obtaining to develop and the corrosion-resisting pattern of excellent in resolution and excellent resist layer shape.

Description of drawings

Fig. 1 is the electron micrograph of the resist layer shape of embodiment 2A.

Fig. 2 is the electron micrograph of the resist layer shape of comparative example 1A.

Fig. 3 is the electron micrograph of the resist layer shape of embodiment 2B.

Fig. 4 is the electron micrograph of the resist layer shape of comparative example 1B.

Embodiment

One aspect of the present invention provides a kind of manufacture method of resist solidfied material, and it comprises following operation:

Layered product forms operation: form the negative-type photosensitive resin laminate that is formed by supporter (A), negative-type photosensitive resin bed (B) and substrate (C) lamination at least;

Exposure process: use the light of projected light mask picture and, this negative-type photosensitive resin bed (B) is exposed across lens;

Developing procedure: remove the unexposed portion of this negative-type photosensitive resin bed (B) by development, form the resist solidfied material of forming by the cured portion of this negative-type photosensitive resin bed (B);

The transmittance of aforementioned negative-type photosensitive resin bed (B) under wavelength 365nm is more than 25% below 50%.

Another aspect of the present invention, a kind of negative-type photosensitive resin laminate is provided, it is used for by the i ray monochromatic light that uses projected light mask picture and across lens the negative-type photosensitive resin bed being exposed and forms the resist solidfied material, described layered product has the negative-type photosensitive resin bed (B) that supporter (A) and i ray monochromatic exposure are used at least, wherein, the negative light-sensitive resin combination that this negative-type photosensitive resin bed (B) is used by i ray monochromatic exposure forms, the negative light-sensitive resin combination that described i ray monochromatic exposure is used contains (a) carboxyl-content counts 100～600 with acid equivalent, and binder resin 20～90 quality %s of weight-average molecular weight between 5000～500000, (b) unsaturated compound 3～70 quality % of photopolymerization, and (c) Photoepolymerizationinitiater initiater 0.1～20 quality %, and the transmittance of this negative-type photosensitive resin bed (B) under wavelength 365nm is more than 25% below 50%.

Other aspects of the present invention, a kind of using method of negative-type photosensitive resin laminate is provided, it exposes when forming the resist solidfied material to the negative-type photosensitive resin bed at the i ray monochromatic light by using projected light mask picture and across lens, use negative-type photosensitive resin laminate as described below: described layered product has the negative-type photosensitive resin bed (B) that supporter (A) and i ray monochromatic exposure are used at least, wherein, the negative light-sensitive resin combination that aforementioned negative-type photosensitive resin bed (B) is used by i ray monochromatic exposure forms, the negative light-sensitive resin combination that described i ray monochromatic exposure is used contains (a) carboxyl-content counts 100～600 with acid equivalent, and binder resin 20～90 quality %s of weight-average molecular weight between 5000～500000, (b) unsaturated compound 3～70 quality % of photopolymerization, and (c) Photoepolymerizationinitiater initiater 0.1～20 quality %, and the transmittance of aforementioned negative-type photosensitive resin bed (B) under wavelength 365nm is more than 25% below 50%.

In this instructions, term " negative-type photosensitive resin bed (B) " is meant and is exposed to active ray, develops then, obtains the resin bed of the pattern of minus thus.In addition, " the negative-type photosensitive resin bed (B) that i ray monochromatic exposure is used " be meant, in the above-mentioned negative-type photosensitive resin bed (B), and by monochromatic exposure of i ray (under the wavelength 365nm) and exploring after this, thus the corrosion-resisting pattern that can obtain to expect.Transmittance under the wavelength 365nm of negative-type photosensitive resin bed of the present invention (B) is more than 25% below 50%.When the transmittance under the wavelength 365nm is above-mentioned scope, compare, can obtain the corrosion-resisting pattern of adhesion and excellent in resolution, and it is good that the resist layer resizing becomes with the situation of above-mentioned extraneous transmittance.In addition, among the present invention, an aspect of the using method of negative-type photosensitive resin laminate and negative-type photosensitive resin laminate is provided, by the transmittance under the wavelength 365nm is above-mentioned scope, use makes photomask as the i ray monochromatic light of projection and across lens, the negative-type photosensitive resin bed is exposed, thereby form the resist solidfied material, compare with the situation of above-mentioned extraneous transmittance this moment, can obtain the corrosion-resisting pattern of adhesion and excellent in resolution, and the resist layer resizing becomes good.Use makes the light of photomask as projection, across lens the negative-type photosensitive resin bed is exposed, thereby form under the situation of resist solidfied material, the resist layer cross sectional shape is the shape of falling from power, can produce the chap at resist layer top and attenuating of resist layer bottom, existing problems aspect the resist layer resizing.In addition, in the mode of after peeling off supporter in advance, exposing, use makes the light of above-mentioned photomask as projection, across lens the negative-type photosensitive resin bed is exposed, thereby form under the situation of resist solidfied material, the resist layer cross sectional shape is the coiling tubular, in addition, the residual foot of resist is big, existing problems aspect the resist layer resizing.On the other hand, surpass under 50% the situation, exist negative-type photosensitive resin bed (B) can not absorb the light of exposure, the problem that the exposure light sensitivity is reduced effectively at above-mentioned transmittance.When using i ray monochromatic light, these problems Billy produces more significantly.Therefore, from addressing these problems, and the viewpoint that forms excellent resist layer shape sets out, and the transmittance under the wavelength 365nm of negative-type photosensitive resin bed (B) is more than 25% below 50%.From the viewpoint of the adhesion of corrosion-resisting pattern, resolution and exposure light sensitivity, the transmittance under the wavelength 365nm of negative-type photosensitive resin bed of the present invention (B) is more preferably more than 30% below 45%, more preferably more than 35% below 45%.

As the method for regulating the transmittance of negative-type photosensitive resin bed (B) under wavelength 365nm, can list the method for in the negative light-sensitive resin combination that is used to form negative-type photosensitive resin bed (B), adding ultraviolet light absorber; Regulate the method for the amount of Photoepolymerizationinitiater initiater.As ultraviolet light absorber, can list benzotriazole system, benzophenone series, salicylate system, cyanoacrylate system, nickel system, triazine system etc.As benzotriazole is ultraviolet light absorber, can 2-(2-hydroxyl-5-tert-butyl-phenyl)-2H-benzotriazole, benzenpropanoic acid 3-(2H-benzotriazole-2-yl)-5-(1, the 1-dimethyl ethyl)-4-hydroxyl C be shown example _7-9Side chain and straight chained alkyl ester, 2-(2H-benzotriazole-2-yl)-4, two (1-methyl isophthalic acid-phenylethyl) phenol of 6-.

From can expecting further to improve the adhesion of corrosion-resisting pattern and the viewpoint of resolution, be preferably selected from least a kind of compound in the group that benzophenone described later and benzophenone derivates form especially as Photoepolymerizationinitiater initiater.

As the method for measuring the transmittance of negative-type photosensitive resin bed of the present invention (B) under wavelength 365nm, following method is arranged: on supporter, form negative-type photosensitive resin bed (B), supporter is put into reference to the light side, deduct the supporter part, by spectrophotometer (Hitachi High-Technologies Corporation makes U-3310), be set at slit (slit) 4nm, sweep velocity 600nm/ minute, measure.

Negative-type photosensitive resin bed of the present invention (B) can count 100～600 with acid equivalent by containing (a) carboxyl-content, and, binder resin 20～90 quality %s of weight-average molecular weight between 5000～500000, unsaturated compound 3～70 quality % and (c) the negative light-sensitive resin combination formation of Photoepolymerizationinitiater initiater 0.1～20 quality % of (b) photopolymerization.

In order to give the negative-type photosensitive resin bed, need the carboxyl in the binder resin with development, fissility to alkaline aqueous solution.From the viewpoint of development patience, resolution and adhesion, the amount of the carboxyl in the binder resin is preferably counted more than 100 with acid equivalent, and the viewpoint from development and fissility is preferably below 600.More preferably can be 250～400 in acid equivalent.Among the present invention, aspect the using method that negative-type photosensitive resin laminate and negative-type photosensitive resin laminate are provided, above-mentioned acid equivalent is 100～600, is preferably 300～400.Acid equivalent is meant to have the quality (gram equivalent) of the polymkeric substance (being binder resin) of the carboxyl of 1 equivalent in the resin glue.

The mensuration of acid equivalent is following carries out: use flat natural pond industry (strain) system flat natural pond automatic titration device (COM-555), use the NaOH of 0.1mol/L to utilize potential difference titration to carry out.

The weight-average molecular weight of (a) of the present invention binder resin can be between 5000～500000.(a) weight-average molecular weight of binder resin is preferably below 500000 from the viewpoint of development, and the viewpoint from lid pore membrane intensity and the reduction of excessive glue is preferably more than 5000.In order further to improve effect of the present invention, the weight-average molecular weight of preferred (a) binder resin is between 20000～300000.In addition, among the present invention, aspect the using method that negative-type photosensitive resin laminate and negative-type photosensitive resin laminate are provided, above-mentioned weight-average molecular weight is between 5000～500000, the viewpoint of the resolution when using projection exposure machine to improve i ray monochromatic exposure from improving, this weight-average molecular weight is preferably between 10000～40000.

Weight-average molecular weight is tried to achieve by Japanese beam split (strain) system gel permeation chromatography (GPC) [pump: Gulliver, PU-1580 type, post: clear and electrician's (strain) makes 4 series connection of Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5), mobile phase solvent: the typical curve of tetrahydrofuran, polystyrene standard sample (use utilizes clear and electrician's (strain) system Shodex STANDARD SM-105 Polystyrene)].

From the viewpoint of adhesion, (a) glass transition temperature of binder resin is preferably more than 100 ℃.(a) glass transition temperature of binder resin is more preferably more than 100 ℃ below 120 ℃.

The glass transition temperature of (a) binder resin among the present invention is calculated by the formula of following FOX:

[mathematical expression 1]

$\frac{1}{\mathrm{Tg}}=\frac{W_1}{{\mathrm{Tg}}_1}+\frac{W_2}{{\mathrm{Tg}}_2}+\frac{W_3}{{\mathrm{Tg}}_3}+...+\frac{W_n}{{\mathrm{Tg}}_n}$

(here, Tg represents the Tg of multipolymer.Tg ₁, Tg ₂, Tg ₃..., Tg _nThe Tg (K) that represents each homopolymer.W ₁, W ₂, W ₃..., W _nThe quality % that represents each monomer.)。

Used (a) binder resin of the present invention can be by obtaining the monomer copolymerization more than a kind or a kind separately in following 2 kinds of monomers.The-monomer is carboxylic acid or the acid anhydrides that has 1 polymerism unsaturated group in the molecule.For example, can list (methyl) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester etc.

Second monomer is to have 1 polymerism unsaturated group in nonacid, the molecule, for the various characteristics such as flexible of the patience in the development, etching and the plating operation that keep negative-type photosensitive resin bed (B), cured film, selects.As such material, for example can list (methyl) alkyl acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) vinyl cyanide etc.In addition, from improving the viewpoint of resolution, the preferred vinyl compound (for example, styrene, (methyl) benzyl acrylate) that uses with phenyl.

(a) of the present invention binder resin can carry out following synthetic: an amount of radical polymerization initiators such as benzoyl peroxide, azobis isobutyronitrile that add in the solution that the potpourri with above-mentioned monomer forms with acetone, MEK, the dilution of isopropyl alcohol equal solvent, thus synthetic by heating, stirring.Also there is the limit that the part of potpourri is added drop-wise to the situation that synthesize on the limit in the reactant liquor.Also respond after the end, add solvent again, be adjusted to the situation of desired concentration.As synthetic method, except solution polymerization, can also use bulk polymerization, suspension polymerization, emulsion polymerization etc.

The content of (a) binder resin overall with respect to negative light-sensitive resin combination is preferably the scope of 20～90 quality %, the more preferably scope of 30～70 quality %.From having the characteristic of resist layer, for example cover the viewpoint that has sufficient patience hole, etching and the various plating operation by exposure, the corrosion-resisting pattern that forms that develops, (a) content of binder resin is preferably the scope of 20～90 quality %.In addition, among the present invention, the aspect of the using method of negative-type photosensitive resin laminate and negative-type photosensitive resin laminate is provided, (a) the binder resin content overall with respect to negative light-sensitive resin combination be 20～90 quality % scope, be preferably the scope of 30～70 quality %.

Among the present invention, (b) unsaturated compound of photopolymerization is preferably the unsaturated compound of at least a kind of photopolymerization in the group that the compound of the compound that is selected from following general formula (I) expression and following general formula (II) expression forms.

The compound of general formula (I) expression:

[chemical formula 7]

In the formula, R ₈And R ₉Be H or CH independently ₃, and, n ₂, n ₃, and n ₄Be 3～20 integer independently of one another.}。

In the compound of above-mentioned general formula (I) expression, n ₂, n ₃And n ₄Boiling point than 3 hours these compounds reduces, and the foul smell grow of resist layer is difficult to use.n ₂, n ₃, and n ₄Surpass at 20 o'clock, the concentration step-down at the photolytic activity position of per unit weight, thereby the tendency of the light sensitivity step-down of existence practicality.

As the object lesson of the compound of above-mentioned general formula (I) expression, for example, can list at the two ends of the polypropylene glycol of the average 12 moles epoxypropane of addition the dimethylacrylate of the glycol of the average 3 moles oxirane of addition respectively.

The compound of general formula (II) expression:

[chemical formula 8]

In the formula, R ₁₀And R ₁₁Be H or CH independently ₃, A is C ₂H ₄, B is C ₃H ₆, n ₅+ n ₆Be 2～30 integer, n ₇+ n ₈Be 0～30 integer, n ₅And n ₆Be 1～29 integer independently, n ₇And n ₈Be 0～29 integer independently ,-(A-O)-and-(B-O)-the arrangement of repetitive can be random, also can be block, under the situation that is block, any can be a bis-phenol base side.}

In the compound of above-mentioned general formula (II) expression, n ₅+ n ₆And n ₇+ n ₈Surpass at 30 o'clock, the relative step-down of two key concentration in the negative-type photosensitive resin bed (B), so have the tendency of light sensitivity step-down.n ₅+ n ₆Be preferably 4～14, and n ₇+ n ₈Be preferably 0～14.

As the object lesson of the compound of above-mentioned general formula (II) expression, can list at the two ends of bisphenol-A the dimethylacrylate of the poly-alkane glycol that average 2 moles epoxypropane of addition respectively and average 6 moles oxirane forms, the dimethylacrylate (Xin Zhong village chemical industry (strain) system NK ESTER BPE-500) of the polyglycol that forms of the average 5 moles oxirane of addition respectively at the two ends of bisphenol-A.

As the unsaturated compound of (b) photopolymerization, except the unsaturated compound of the photopolymerization of the compound of above-mentioned general formula (I) expression and general formula (II) expression, can also use the compound of following formula (III) or formula (IV) expression.

The compound of formula (III) expression:

[chemical formula 9]

In the formula, R ₁₂Be alkyl, naphthenic base or the aryl of carbon number 4～12, R ₁₃And R ₁₄Be H or CH independently ₃, m ₁, m ₂, m ₃And m ₄Be 0～15 integer independently of one another ,-(OC ₃H ₆) _M1-(OC ₂H ₄) _M3-and-(OC ₃H ₆) _M2-(OC ₂H ₄) _M4-the optional random or block of arrangement of repetitive, and under the situation that is block, any can be the acryloyl group side.}

In the compound of above-mentioned general formula (III) expression, from the viewpoint of light sensitivity, m ₁, m ₂, m ₃And m ₄Be below 15.

Object lesson as the compound of above-mentioned general formula (III) expression, for example can list, hexamethylene diisocyanate, toluene diisocyanate, 2,2, has the urethane compound of the acrylate-based compound of hydroxyl and (methyl) (for example, 2-hydroxypropyl acrylate, oligomeric propylene glycol monomethyl acrylate, low polyethylene glycol monomethacrylate, oligomerisation of ethylene propylene glycol monomethyl acrylate etc.) etc. in diisocyanate cpd such as 4-trimethyl hexamethylene diisocyanate and a part.Specifically, can list the reactant of reactant, hexamethylene diisocyanate and the oligomerisation of ethylene propylene glycol monomethyl acrylate (Japanese grease (strain) is made, Premmer70PEP-350B) of reactant, hexamethylene diisocyanate and the low polyethylene glycol monomethacrylate (Japanese grease (strain) system, PremmerPE-200) of hexamethylene diisocyanate and oligomeric propylene glycol monomethyl acrylate (Japanese grease (strain) system, PremmerPP1000).

The compound of formula (IV) expression:

[Chemical formula 1 0]

In the formula, R ₁₅Be H or CH ₃, R ₁₆Be the alkyl of carbon number 1～14, A ' is C ₂H ₄, B ' is C ₃H ₆, m ₃Be 1～12 integer, m ₄Be 0～12 integer, m ₅Be 0～3 integer ,-(A '-O)-and-(B '-O)-the optional random or block of arrangement of repetitive, and under the situation that is block, any can be the phenyl side.}

In the compound of above-mentioned general formula (IV) expression, from the viewpoint of light sensitivity, m ₃And m ₄Be below 14, to be preferably below 12.

Object lesson as the compound of general formula (IV) expression, for example can list, the acrylate that the polyglycol that the average 7 moles oxirane of polypropylene glycol that the epoxypropane that addition is average 2 moles forms and addition forms adds to the compound that the ninth of the ten Heavenly Stems, phenol formed is 4-n-nonyl phenoxy group seven ethylene glycol bisthioglycolate propylene glycol acrylate.Can also list the acrylate that polyglycol that the oxirane that addition is average 8 moles forms adds to the compound that the ninth of the ten Heavenly Stems, phenol formed is 4-n-nonyl phenoxy group eight EDIAs (East Asia synthetic (strain) system, M-114).

As the unsaturated compound of (b) photopolymerization, except the compound of above-mentioned formula (I) to (IV) expression, can also be used in combination the unsaturated compound of following photopolymerization simultaneously.For example, can list 1,6-hexanediol two (methyl) acrylate, 1,4-cyclohexanediol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polyglycol two (methyl) acrylate, 2-two (p-hydroxybenzene) propane two (methyl) acrylate, glycerine three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, polyoxyethyl propyl trimethylolpropane tris (methyl) acrylate, polyoxy ethyl trimethylolpropane triacrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, trihydroxymethylpropanyltri diglycidyl ether three (methyl) acrylate, bisphenol A diglycidyl ether two (methyl) acrylate, with beta-hydroxy propyl group-β '-(acryloxy) propyl group phthalic ester.

The content of the unsaturated compound of (b) photopolymerization overall with respect to negative light-sensitive resin combination is preferably the scope of 3～70 quality %.From the viewpoint of light sensitivity, be preferably more than the 3 quality %, the viewpoint that the photo-sensitive resin when preventing to preserve oozes out is preferably below the 70 quality %.In addition, among the present invention, aspect the using method that negative-type photosensitive resin laminate and negative-type photosensitive resin laminate are provided, above-mentioned content is the scope of 3～70 quality %.Above-mentioned content is 10～60 quality %, 15～55 quality % more preferably more preferably.

Contain under the situation of unsaturated compound of at least a kind of photopolymerization in the group that the compound of the compound that is selected from general formula (I) expression and general formula (II) expression forms at negative light-sensitive resin combination, the content of this unsaturated compound overall with respect to negative light-sensitive resin combination is preferably the scope of 3～60 quality %, the more preferably scope of 3～45 quality %.From the viewpoint of adhesion, be preferably more than the 3 quality %, the viewpoint from the glue that overflows is preferably below the 60 quality %.

Contain at negative light-sensitive resin combination under the situation of the compound of general formula (III) expression or the compound that general formula (IV) is represented, the content of each unsaturated compound overall with respect to negative light-sensitive resin combination is preferably in the scope of 3～60 quality %, further preferably in the scope of 3～45 quality %.From the viewpoint of adhesion, be preferably more than the 3 quality %, the viewpoint from the glue that overflows is preferably below the 60 quality %.

From high-resolution viewpoint, negative light-sensitive resin combination preferably comprises 2,4,5-triarylimidazoles dipolymer as (c) Photoepolymerizationinitiater initiater.As this triarylimidazoles dipolymer, be preferably selected from especially in the group that the compound of the compound of following general formula (V) expression and following general formula (VI) expression forms at least a kind 2,4,5-triarylimidazoles dipolymer.

The compound of general formula (V) expression:

[Chemical formula 1 1]

{ in the formula, X, Y and Z represent any in hydrogen, alkyl, the alkoxy or halogen group independently of one another, and p, q and r are 1～5 integer independently of one another.}

The compound of general formula (VI) expression:

[Chemical formula 1 2]

{ in the formula, X, Y and Z represent any in hydrogen, alkyl, the alkoxy or halogen group independently of one another, and p, q and r are 1～5 integer independently of one another.}

As 2,4,5-triarylimidazoles dipolymer, for example can list 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer, 2-(Chloro-O-Phenyl)-4,5-couple-(m-methoxyphenyl) imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer etc., preferred especially 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer.

In addition, from can expecting further to improve the adhesion of corrosion-resisting pattern and the viewpoint of resolution, preferred negative light-sensitive resin combination contains at least a kind of compound being selected from the group that benzophenone and benzophenone derivates form as (c) Photoepolymerizationinitiater initiater.

And then, as (c) Photoepolymerizationinitiater initiater, can be used in combination above-mentioned general formula (V) or (VI) expression 2,4,5-triarylimidazoles dipolymer and be selected from least a kind of compound in the group that benzophenone and benzophenone derivates form.

Viewpoint from the exposure light sensitivity as benzophenone derivates, is preferably the p-aminophenyl ketone especially.As the p-aminophenyl ketone, for example can list, to aminobenzophenone, to the amino benzophenone of fourth, to the dimethylamino acetophenone, to dimethylamino benzophenone, p, p '-two (ethylamino) benzophenone, p, p '-two (dimethylamino) benzophenone [Michler's keton], p, p '-two (lignocaine) benzophenone, p, p '-two (dibutylamino) benzophenone.

In addition, as (c) Photoepolymerizationinitiater initiater, can be used in combination above-claimed cpd other Photoepolymerizationinitiater initiaters in addition.Here, other Photoepolymerizationinitiater initiaters can be the known compounds that makes its initiated polymerization by various active rays, for example ultraviolet isoreactivityization.

As other Photoepolymerizationinitiater initiaters, for example can list acridine compound, benzil dimethyl ketal, benzil diethyl ketal, pyrazoline compounds such as benzoin ethers such as aromatic series ketones such as quinones, benzophenone such as 2-EAQ, 2-tert-butyl group anthraquinone, benzoin, benzoin methyl ether, benzoin ethylether, 9-phenylacridine.In addition, for example can list thioxanthones, 2, the combination of tertiary amine compounds such as the thioxanthene ketone of 4-diethyl thioxanthone, 2-clopenthixal ketone etc. and dimethylamino benzoic acid alkyl ester compound.

As other Photoepolymerizationinitiater initiaters, can list 1-phenyl-1,2-propanedione-2-O-benzoyl oxime, 1-phenyl-1, oxime ester classes such as 2-propanedione-2-(O-ethoxy carbonyl) oxime.In addition, can use N-aryl-alpha-amino acid compound, preferred especially N-phenylglycine.

Content with respect to the overall Photoepolymerizationinitiater initiater of negative light-sensitive resin combination (c) is preferably 0.1 quality %～20 quality %.Viewpoint from the exposure light sensitivity more than the preferred 0.1 quality %, from the viewpoint of resolution, is preferably below the 20 quality %.In addition, among the present invention, aspect the using method that negative-type photosensitive resin laminate and negative-type photosensitive resin laminate are provided, above-mentioned content is 0.1 quality %～20 quality %.

Containing 2,4 as (c) Photoepolymerizationinitiater initiater, under the situation of 5-triarylimidazoles dipolymer, its with respect to the overall content of negative light-sensitive resin combination preferably in the scope of 0.1～10 quality %, further preferably in the scope of 0.5～4.5 quality %.From the viewpoint of light sensitivity, be preferably more than the 0.1 quality %, be preferably below the 10 quality % from the viewpoint of resolution.

Under the situation of at least a kind of compound in contain the group that is selected from benzophenone and benzophenone derivates composition as (c) Photoepolymerizationinitiater initiater, it is more than 25% below 50% that this compound is defined as transmittance under the wavelength 365nm with respect to the overall content of negative light-sensitive resin combination according to the thickness of negative-type photosensitive resin bed (B), preferred probably in the scope of 0.01～1.0 quality %, further preferred scope at 0.05～0.15 quality %.

Negative light-sensitive resin combination also can contain coloring materials such as dyestuff, pigment.As coloring material, for example can list magenta, phthalocyanine green, auramine alkali, the green S of alkoxide, paramagenta (paramagenta), crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (hodogaya chemical (strain) system ア イ ゼ Application (registered trademark) MALACHITE GREEN), alkali blue 20, diamond green (hodogaya chemical (strain) system ア イ ゼ Application (registered trademark) DIAMOND GREEN GH) etc.

The content of the coloring material overall with respect to negative light-sensitive resin combination is preferably the scope of 0.005～10 quality %, the more preferably scope of 0.01～1 quality %.From the viewpoint of resist layer visuality, above-mentioned content is preferably more than the 0.005 quality %, from the viewpoint of light sensitivity, is preferably below the 10 quality %.

The color development based dye that can contain color development in the negative light-sensitive resin combination by rayed.As the color development based dye, for example can list leuco dye and fluoran dyes.As leuco dye, for example can list three-(4-dimethylamino-2-aminomethyl phenyl) methane-[recessive crystal violet], three (4-dimethylamino-2-aminomethyl phenyl) methane-[concealed malachite greens] etc.

Leuco dye preferably is used in combination with halogenated compound.As halogenated compound, can list amyl bromide, isoamyl bromine, bromination isobutylene, ethylene bromide, diphenyl methyl bromine, benzal bromide, methylene bromide, trisbromomethyl phenyl sulfone, carbon tetrabromide, three (2, the 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-three chloro-2, two (p-chlorphenyl) ethane of 2-, carbon trichloride, halo triaizine compounds etc.

As the halo triaizine compounds, can list 2,4,6-three (trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4, two (the trichloromethyl)-s-triazine of 6-.

Particularly, the combination of the combination of trisbromomethyl phenyl sulfone and leuco dye, triaizine compounds and leuco dye is useful.

The content of the leuco dye overall with respect to negative light-sensitive resin combination is preferably in the scope of 0.005～10 quality %, further preferably in the scope of 0.01～1 quality %.From the viewpoint of coloring, above-mentioned content is preferably more than the 0.005 quality %, and viewpoint and the viewpoint of keeping storage stability from exposure portion and unexposed portion contrast are preferably below the 10 quality %.

The content of the halogenated compound overall with respect to negative light-sensitive resin combination is preferably in the scope of 0.005～10 quality %, further preferably in the scope of 0.01～1 quality %.From the viewpoint of coloring, above-mentioned content is preferably more than the 0.005 quality %, and viewpoint and the viewpoint of keeping storage stability from exposure portion and unexposed portion contrast are preferably below the 10 quality %.

For thermal stability and/or the storage stability that improves negative light-sensitive resin combination, preferably in negative light-sensitive resin combination, contain radical polymerization inhibitor.As such radical polymerization inhibitor, for example can list, p-metoxyphenol, quinhydrones, pyrogallol, naphthylamine, tert-butyl catechol, stannous chloride, 2,6-two-Butylated Hydroxytoluene, 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), diphenyl nitra-amine etc. are as concrete preferred example, can list pentaerythrite four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] etc.

The content of the radical polymerization inhibitor overall with respect to negative light-sensitive resin combination is preferably in the scope of 0.01～3 quality %, further preferably in the scope of 0.02～0.2 quality %.From the viewpoint of resolution, above-mentioned content is preferably more than the 0.01 quality %, from the viewpoint of light sensitivity, is preferably below the 3 quality %.

In addition, can also in negative light-sensitive resin combination of the present invention, contain plastifier as required.As plastifier, for example can list terephthalate classes such as diethyl terephthalate, para toluene sulfonamide, polypropylene glycol, polyalkylene glycol monoalkyl ether etc.

The content of the plastifier overall with respect to negative light-sensitive resin combination is preferably in the scope of 5～50 quality %, further preferably in the scope of 5～30 quality %.From the resist solidfied material being given the viewpoint of flexibility, above-mentioned content is preferably more than the 5 quality %, from suppressing to solidify the viewpoint of not enough and cold flow, is preferably below the 50 quality %.

As the substrate among the present invention (C), can list that the applying Copper Foil forms copper clad laminate on the glass epoxy resin substrate; The sheet metal of copper, aldary, iron-based alloy etc.; Has the film like base material of glass rib, Silicon Wafer and conductor layer etc.

Film like base material with conductor layer is the base material that has the conductor layer of copper, gold, silver, aluminium etc. on the insulating resin layer of film like, for example can list, the flexible substrate that the applying Copper Foil forms on the insulating resin layer of Kapton, mylar, BT resin (bismaleimides/cyanate resin) etc., TAB (Tape AutomatedBonding, the automatic combination of winding) band.

As go up the method that forms above-mentioned negative-type photosensitive resin bed (B) at substrate (C), can list following method: go up at supporter (A) (for example support film) in advance and form negative-type photosensitive resin bed (B), then, negative-type photosensitive resin bed (B) heating is crimped on the substrate (C) (for example use in printed circuit board substrate of metal), so that for example with the surface laminated substrate (C) of the opposite side of supporter (A) of negative-type photosensitive resin bed (B), promptly substrate (C) clips negative-type photosensitive resin bed (B) and is relative with supporter (A).

As the method that go up to form negative-type photosensitive resin bed (B) at supporter (A), can list above-mentioned negative light-sensitive resin combination is applied to method on the supporter (A).As used here supporter (A), the supporter of the active light of preferred transmission.Supporter as the active light of transmission can list pet film, polyvinyl alcohol film, polychlorostyrene vinyl film, ethlyene dichloride copolymer film, Vingon film, vinylidene chloride copolymer films, polymethyl methacrylate copolymer film, plasticon, polyacrylonitrile film, styrol copolymer film, polyamide film, cellulose derivative film etc.These films can stretch as required.

The mist degree of supporter (A) is preferably below 5.0.The thin thickness of supporter (A) be favourable aspect image formation property and the economy, but in order to keep intensity, thickness is 10～30 μ m usually.

With the surface of supporter (A) the side opposition side of negative-type photosensitive resin bed (B) lamination protective seam (liner) as required.The adhesion of protective seam and negative-type photosensitive resin bed (B) is sufficiently littler with the adhesion of negative-type photosensitive resin bed (B) than supporter (A), thereby can easily peel off protective seam, and this is the key property of protective seam.As such protective seam, for example can list polyethylene film, polypropylene film etc.

Have at the negative-type photosensitive resin laminate under the situation of protective seam; go up formation negative-type photosensitive resin bed (B) at substrate (C) and be pre-formed protective seam on the surface of this negative-type photosensitive resin bed (B) before; after peeling off this protective seam, negative-type photosensitive resin bed (B) heating is crimped onto on substrate (C) surface and carries out lamination.The heating-up temperature of this moment is generally 40～160 ℃.

The thickness of negative-type photosensitive resin bed (B) is generally 5～100 μ m, is preferably 5～50 μ m according to purposes and difference is being used for making printed circuit board (PCB) (printed circuit board (PCB)).The scope of thickness 5～25 μ m, so then resolution height, resist layer resizing property improvement effect excellence are more preferably.

The negative-type photosensitive resin laminate exposes by i ray monochromatic light, ultraviolet light isoreactivity light, preferred i ray monochromatic light.In this exposure process, the exposure portion of negative-type photosensitive resin bed (B) solidifies.As the light source that is used for exposure process, can list high-pressure sodium lamp, ultrahigh pressure mercury lamp, ultraviolet fluorescent lamp, carbon arc lamp, xenon lamp, laser etc.These light sources can directly use, and also can use bandpass filter etc. to make it form i ray monochrome.When exposure wavelength being made as i ray monochrome, having improved resolution, thereby preferably used i ray monochromatic light.Preferably form between operation and the exposure process, supporter (A) after negative-type photosensitive resin bed (B) is peeled off, is exposed residual negative-type photosensitive resin bed (B) in exposure process at layered product.In this case, so the shape that the resist layer cross sectional shape becomes rectangle, promptly almost do not have chap of resist layer top and resist layer bottom to attenuate is preferred especially.

Usually, as the Exposure mode that is used to expose, can list projection type Exposure mode (projection exposure mode), adhere to Exposure mode, directly describe mode etc., in the present invention, the projection type Exposure mode that photomask is exposed to the negative-type photosensitive resin bed across lens as the light of projection.In addition, in the typical form of the present invention, the light that is sent by light source passes through according to the order of photomask and lens, arrives the negative-type photosensitive resin bed, the light that sends by light source can also scioptics after, pass through photomask again.Among the present invention, by using the projection type Exposure mode, and to make transmittance under the wavelength 365nm be more than 25% below 50%, thereby the resist layer resizing is able to remarkable improvement.In addition, in the projection type Exposure mode, the transmittance that makes the negative-type photosensitive resin bed (B) under the wavelength 365nm is more than 25% below 50%, and peel off in advance in the mode of exposing behind the supporter (A), can access such advantage: the resist layer shape becomes rectangle, does not promptly almost have the resist layer top to broaden and shape that resist layer bottom attenuates.

Then, on negative-type photosensitive resin bed (B), exist under the situation of supporter (A), after removing supporter (A) as required, develop and remove the unexposed portion of negative-type photosensitive resin bed (B), thereby form the resist solidfied material of forming by the cured portion of negative-type photosensitive resin bed (B).As developing method, can list the method for for example using alkaline aqueous solution to remove the unexposed portion of negative-type photosensitive resin bed (B).As alkaline aqueous solution, can use aqueous solution such as sodium carbonate, sal tartari.These alkaline aqueous solutions can be selected according to the characteristic of negative-type photosensitive resin bed (B), but use the aqueous sodium carbonate of 0.5～3 quality % usually.As mentioned above, obtain resist solidfied material of the present invention.

The manufacture method of＜printed circuit board (PCB) 〉

Below further specify the manufacture method of the printed circuit board (PCB) that uses above-mentioned negative-type photosensitive resin laminate.The invention provides a kind of manufacture method of printed circuit board (PCB), it comprises following operation: the operation that the substrate with the formed corrosion-resisting pattern of resist solidfied material (C) that obtains by above-mentioned manufacture method is carried out the operation of etching or plating, removes the resist solidfied material from substrate (C).In the manufacture method of printed circuit board (PCB) of the present invention, the special sheet metal that uses is as substrate (C), by known etching method or the arbitrary method of plating method, on the metal covering that exposes by the developing procedure in the manufacture method of aforesaid resist solidfied material, form the picture pattern of metal.Then, by the aqueous solution of the alkalescence stronger, peel off and remove the corrosion-resisting pattern that has solidified than the alkaline aqueous solution that in development, uses usually.The alkaline aqueous solution of peeling off usefulness is not particularly limited, and uses the NaOH of 1～5 quality %, the aqueous solution of potassium hydroxide usually.

The application of the invention forms picture pattern, thereby can also form the rib of semiconductor-sealing-purpose substrate, lead frame, plasma display etc. except forming above-mentioned printed circuit board (PCB) (printed circuit board (PCB)).The cross section of the line against corrosion that obtains by the present invention demonstrates the good shape near rectangle (rectangle) as shown in Figure 1.Promptly, such problem attenuates bottom the resist layer top chap of the remarkable reduction of meeting meeting generation in the manufacture method of prior art as shown in Figure 2 and the resist layer, in addition, can significantly reduce as shown in Figure 4 peel off from the negative-type photosensitive resin bed in advance that the resist layer cross sectional shape becomes under the situation of exposing behind the supporter " coiling tubular ", the residual foot of resist becomes big such problem.Therefore, the present invention can be particularly suitable for conductor package substrate manufacturing usefulness.

Using the present invention to make under the situation of lead frame, the sheet metal that uses copper, aldary, iron-based alloy etc. is as aforesaid substrate (C), behind the exposure process and developing procedure in the manufacture method of aforesaid resist solidfied material, the real estate that exposes is carried out etching.At last, carry out peeling off of resist solidfied material, obtain desired lead frame.In addition, using the present invention to make under the situation of rib of plasma display, use the glass rib as substrate (C), behind the exposure process and developing procedure in the manufacture method of aforesaid resist solidfied material, by blasting craft the real estate that exposes is processed, peel off corrosion-resisting pattern, can obtain to have the substrate of relief pattern.

Embodiment

Below, specify embodiments of the present invention by embodiment, but the present invention is not limited to embodiment.

＜negative light-sensitive resin combination 〉

Following table 1 and 2 illustrates the composition of the negative light-sensitive resin combination that uses in embodiment and the comparative example.

In the table, with suspension points (composition of the negative light-sensitive resin combination of the expression of P-1～C-1) is at following＜symbol description〉in explanation.In the table, the value of P-1 and P-2 is the solid constituent amount.

＜symbol description 〉

P-1: the methyl ethyl ketone solution of 3 membered copolymers of methacrylic acid 30 quality %, styrene 20 quality %, benzyl methacrylate 50 quality % (102 ℃ of solid component concentration 40 quality %, weight-average molecular weight 55000, acid equivalent 287, glass transition temperature)

P-2: the methyl ethyl ketone solution of 2 membered copolymers of benzyl methacrylate 80 quality %, methacrylic acid 20 quality % (78 ℃ of solid component concentration 50 quality %, weight-average molecular weight 25000, acid equivalent 430, glass transition temperature)

M-1: the two ends of the polypropylene glycol that forms at the average 12 moles epoxypropane of addition are the dimethylacrylate of the poly-alkane glycol that forms of the average 3 moles oxirane of addition respectively

M-2: 7: 3 (mol ratio) potpourris of pentaerythritol triacrylate and tetramethylol methane tetraacrylate

M-3: the dimethylacrylate (Xin Zhong village chemical industry (strain) system NKESTER BPE-500) of the polyglycol that forms of the average 5 moles oxirane of addition respectively at the two ends of bisphenol-A

M-4: TEG dimethylacrylate

M-5: trimethylolpropane triacrylate

A-1:2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer

A-2:4,4 '-two (lignocaine) benzophenone

B-1: diamond green (hodogaya chemical (strain) system ア イ ゼ Application (registered trademark) DIAMOND GREEN GH)

B-2: recessive crystal violet

C-1: pentaerythrite four [3-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester]

The formation method of＜negative-type photosensitive resin bed (B) 〉

Then, describe going up the method that forms negative-type photosensitive resin bed (B) at supporter (A).

In embodiment and the comparative example, with MEK as solvent, the composition shown in the mixture table 1 and 2, uniform dissolution so that nonvolatile component concentration is 50 quality %, and modulation is with the solution of negative light-sensitive resin combination.The solution of the negative light-sensitive resin combination that obtains is coated with machine with rod is uniformly coated on the pet film as the thickness 20 μ m of supporter (A), in 95 ℃ exsiccator, make its dry 3 minutes.The thickness of the negative-type photosensitive resin bed (B) that obtains after the drying is 25 μ m.

The following mensuration of the transmittance of negative-type photosensitive resin bed (B) under wavelength 365nm that is forming on the above-mentioned polyethylene terephthalate: use HitachiHigh-Technologies Corporation system U-3310 shape spectrophotometer, above-mentioned pet film is put into reference to side measured.In addition, Ci Shi slit is set at 4nm, sweep velocity is set at 600nm/ minute.

Then, obtain at negative-type photosensitive resin bed (B) laminated film that polyethylene film as the thickness 25 μ m of protective seam forms of go up fitting.35 μ m rolled copper foil laminations are formed and hydro-peening grind surface as the copper clad laminate of substrate (C), when peeling off the polyethylene film of this laminated film negative-type photosensitive resin bed (B) is pressed onto on the substrate (C) 105 ℃ of lower floors by the hot-roll lamination machine, obtains the negative-type photosensitive resin laminate.

The making of＜resist solidfied material 〉

By mask film, use projection exposure machine (using (strain) ウ シ オ motor system UX2003SM-MS04, i ray bandpass filter) with 180mJ/cm ²To the above-mentioned negative-type photosensitive resin laminate irradiation i ray monochromatic light that obtains, negative-type photosensitive resin bed (B) is exposed with i ray monochromatic light.Then, spray about 40 seconds of 1 quality % aqueous sodium carbonate of 30 ℃, the unexposed portion dissolving is removed, thereby develop.Then, the cured portion (exposure portion) of residual negative-type photosensitive resin bed (B) is sprayed about 20 seconds with ion exchange water wash, obtain resist solidfied material of the present invention.In addition, for embodiment shown in the table 1 and comparative example, before spraying above-mentioned aqueous sodium carbonate, peel off pet film respectively, and, before above-mentioned exposure, peel off pet film respectively for embodiment shown in the table 2 and comparative example.

The following mensuration of exposure light sensitivity: use by transparent to be divided into 21 sections 27 sections stage metraster of Asahi Chemical Industry's system that carry out the lightness variation, measure to black.

Use following metewand, the evaluation of the resist solidfied material that enforcement obtains.

(1) in the above-mentioned exposure of resolution, uses line and the mask film exposure that is spaced apart 1: 1, develop.The minimum feature of cured pattern that can resulting separation is as resolution.

(2) in the above-mentioned exposure of tack, use line and the mask film exposure that is spaced apart L μ m: 200 μ m (L μ m represents line width), develop.The minimum wire spoke that can adhere to the cured pattern that obtains is as tack.

(3) in the above-mentioned exposure of resist layer shape, use the mask film of line width 12 μ m.Use electron microscope (the system Sm-500 of (strain) ト プ コ Application society), confirm the resist layer shape with accelerating potential 15kV, 1000 times of multiplying powers, pitch angle 60 degree.If the difference less than 1 μ m of the cured pattern wire spoke of resist layer top and resist layer bottom then be ◎, as if the above less than 2 μ m of 1 μ m, then be zero and as if more than the 2 μ m, then be *.

＜embodiment 1A～8A, comparative example 1A～4A, embodiment 1B～7B, comparative example 1B～4B 〉

The composition and the evaluation result of negative light-sensitive resin combination are shown in table 1 and 2.

Confirm: the transmittance under wavelength 365nm is the embodiment 1A～8A and the embodiment 1B～7B of scope of the present invention, compare transmittance at extraneous comparative example 1A～4A of the present invention and comparative example 1B～4B, in the metewand that comprises resolution, adhesion and resist layer shape, comprehensive excellence.

The electron micrograph of the resist layer shape of the resist solidfied material that obtains among embodiment 2A and the comparative example 1A is shown in Fig. 1 and Fig. 2 respectively.Among the embodiment 2A, the resist layer shape, is observed remarkable chap in resist layer top and resist layer bottom and is significantly attenuated with respect to this near rectangle in comparative example 1A.The electron micrograph of the resist layer shape of the resist solidfied material that obtains among embodiment 2B and the comparative example 1B is shown in Fig. 3 and Fig. 4 respectively.Among the embodiment 2B, the resist layer shape, is observed the resist layer bottom and is attenuated with respect to this near rectangle among the comparative example 1B, in addition, observes the residual foot of resist and becomes big (the resist layer cross sectional shape is " coiling tubular ").

Utilizability on the industry

The present invention can be widely used in the manufacturing of printed circuit board (PCB) (printed circuit board (PCB)), the manufacturing of IC chip carrying usefulness lead frame, the manufacturing of semiconductor packages etc.

Claims (28)

1. the manufacture method of a resist solidfied material, it comprises following operation:

Layered product forms operation: form the negative-type photosensitive resin laminate that is formed by supporter (A), negative-type photosensitive resin bed (B) and substrate (C) lamination at least;

Exposure process: use the light of projected light mask picture, and aforementioned negative-type photosensitive resin bed (B) is exposed across lens;

Developing procedure: remove the unexposed portion of aforementioned negative-type photosensitive resin bed (B) by development, form the resist solidfied material of forming by the cured portion of aforementioned negative-type photosensitive resin bed (B);

The transmittance of aforementioned negative-type photosensitive resin bed (B) under wavelength 365nm is more than 25% below 50%.

2. the manufacture method of resist solidfied material according to claim 1, wherein, aforementioned lights is an i ray monochromatic light.

3. the manufacture method of resist solidfied material according to claim 1 also comprises the supporter stripping process that aforementioned supporter (A) is peeled off from aforementioned negative-type photosensitive resin bed (B) between aforementioned laminates formation operation and aforementioned exposure process.

4. the manufacture method of resist solidfied material according to claim 1, the transmittance of aforementioned negative-type photosensitive resin bed (B) under wavelength 365nm are more than 35% below 45%.

5. the manufacture method of resist solidfied material according to claim 1, aforementioned negative-type photosensitive resin bed (B) is formed by negative light-sensitive resin combination, and this negative light-sensitive resin combination contains: (a) carboxyl-content counts 100～600 and unsaturated compound 3～70 quality % of binder resin 20～90 quality %s of weight-average molecular weight between 5000～500000, (b) photopolymerization and (c) Photoepolymerizationinitiater initiater 0.1～20 quality % with acid equivalent.

6. manufacture method according to claim 5 as aforementioned (c) Photoepolymerizationinitiater initiater, contains at least a kind of compound that is selected from the group of being made up of benzophenone and benzophenone derivates.

7. manufacture method according to claim 5 as aforementioned (c) Photoepolymerizationinitiater initiater, contains 2,4,5-triarylimidazoles dipolymer.

8. manufacture method according to claim 5 as aforementioned (c) Photoepolymerizationinitiater initiater, contains at least a kind of compound and 2,4 that is selected from the group of being made up of benzophenone and benzophenone derivates, 5-triarylimidazoles dipolymer the two.

9. the manufacture method of resist solidfied material according to claim 5, the unsaturated compound of aforementioned (b) photopolymerization are selected from the group of being made up of the compound of the compound of following general formula (I) expression and following general formula (II) expression:

[Chemical formula 1]

In the formula, R ₈And R ₉Be H or CH independently ₃, and, n ₂, n ₃And n ₄Be 3～20 integer independently of one another;

[Chemical formula 2]

In the formula, R ₁₀And R ₁₁Be H or CH independently ₃, A is C ₂H ₄, B is C ₃H ₆, n ₅+ n ₆Be 2～30 integer, n ₇+ n ₈Be 0～30 integer, n ₅And n ₆Be 1～29 integer independently, n ₇And n ₈Be 0～29 integer independently, repetitive-(A-O)-and-(B-O)-the optional random or block of arrangement, under the situation that is block, any can be the bisphenol group side.

10. the manufacture method of a printed circuit board (PCB), it comprises following operation: the aforesaid base plate (C) that will have corrosion-resisting pattern carries out the operation of etching or plating, and wherein said corrosion-resisting pattern is formed by the resist solidfied material that makes by each described manufacture method in the claim 1～9;

The operation that aforementioned resist solidfied material is removed from aforesaid base plate (C).

11. a negative-type photosensitive resin laminate, it is to be used for by i ray monochromatic light that uses projected light mask picture and the negative-type photosensitive resin laminate that the negative-type photosensitive resin bed is exposed and forms the resist solidfied material across lens,

It has the negative-type photosensitive resin bed (B) that supporter (A) and i ray monochromatic exposure are used at least,

The negative light-sensitive resin combination that aforementioned negative-type photosensitive resin bed (B) is used by i ray monochromatic exposure forms, the negative light-sensitive resin combination that described i ray monochromatic exposure is used contains: (a) carboxyl-content counts 100～600 and unsaturated compound 3～70 quality % of binder resin 20～90 quality %s of weight-average molecular weight between 5000～500000, (b) photopolymerization and (c) Photoepolymerizationinitiater initiater 0.1～20 quality % with acid equivalent, and

The transmittance of aforementioned negative-type photosensitive resin bed (B) under wavelength 365nm is more than 25% below 50%.

12. negative-type photosensitive resin laminate according to claim 11, the transmittance of aforementioned negative-type photosensitive resin bed (B) under wavelength 365nm are more than 35% below 45%.

13. negative-type photosensitive resin laminate according to claim 11, the glass transition temperature of aforementioned (a) binder resin is more than 100 ℃.

14. negative-type photosensitive resin laminate according to claim 11, the weight-average molecular weight of aforementioned (a) binder resin is between 10000～40000.

15. negative-type photosensitive resin laminate according to claim 11 as aforementioned (c) Photoepolymerizationinitiater initiater, contains at least a kind of compound that is selected from the group of being made up of benzophenone and benzophenone derivates.

16. negative-type photosensitive resin laminate according to claim 11 as aforementioned (c) Photoepolymerizationinitiater initiater, contains 2,4,5-triarylimidazoles dipolymer.

17. negative-type photosensitive resin laminate according to claim 11, as aforementioned (c) Photoepolymerizationinitiater initiater, contain at least a kind of compound and 2,4 that is selected from the group of forming by benzophenone and benzophenone derivates, 5-triarylimidazoles dipolymer the two.

18. negative-type photosensitive resin laminate according to claim 11, the unsaturated compound of aforementioned (b) photopolymerization are selected from the group of being made up of the compound of the compound of following general formula (I) expression and following general formula (II) expression:

[chemical formula 3]

In the formula, R ₈And R ₉Be H or CH independently ₃, and n ₂, n ₃And n ₄Be 3～20 integer independently of one another;

[chemical formula 4]

In the formula, R ₁₀And R ₁₁Be H or CH independently ₃, A is C ₂H ₄, B is C ₃H ₆, n ₅+ n ₆Be 2～30 integer, n ₇+ n ₈Be 0～30 integer, n ₅And n ₆Be 1～29 integer independently, n ₇And n ₈Be 0～29 integer independently, repetitive-(A-O)-and-(B-O)-the optional random or block of arrangement, under the situation that is block, any can be the bisphenol group side.

19. negative-type photosensitive resin laminate according to claim 11 also has protective seam on aforementioned negative-type photosensitive resin bed (B).

20. the using method of a negative-type photosensitive resin laminate, it exposes when forming the resist solidfied material to the negative-type photosensitive resin bed at the i ray monochromatic light by using projected light mask picture and across lens, use negative-type photosensitive resin laminate as described below: described layered product has the negative-type photosensitive resin bed (B) that supporter (A) and i ray monochromatic exposure are used at least

Wherein, the negative light-sensitive resin combination that aforementioned negative-type photosensitive resin bed (B) is used by i ray monochromatic exposure forms, the negative light-sensitive resin combination that described i ray monochromatic exposure is used contains (a) carboxyl-content counts 100～600 and unsaturated compound 3～70 quality % of binder resin 20～90 quality %s of weight-average molecular weight between 5000～500000, (b) photopolymerization and (c) Photoepolymerizationinitiater initiater 0.1～20 quality % with acid equivalent

And the transmittance of aforementioned negative-type photosensitive resin bed (B) under wavelength 365nm is more than 25% below 50%.

21. using method according to claim 20, the transmittance of aforementioned negative-type photosensitive resin bed (B) under wavelength 365nm are more than 35% below 45%.

22. using method according to claim 20, the glass transition temperature of aforementioned (a) binder resin is more than 100 ℃.

23. using method according to claim 20, the weight-average molecular weight of aforementioned (a) binder resin is between 10000～40000.

24. using method according to claim 20 as aforementioned (c) Photoepolymerizationinitiater initiater, contains at least a kind of compound in the group that is selected from benzophenone and benzophenone derivates composition.

25. using method according to claim 20 as aforementioned (c) Photoepolymerizationinitiater initiater, contains 2,4,5-triarylimidazoles dipolymer.

26. using method according to claim 20 as aforementioned (c) Photoepolymerizationinitiater initiater, contains at least a kind of compound and 2,4 that is selected from the group of being made up of benzophenone and benzophenone derivates, 5-triarylimidazoles dipolymer the two.

27. using method according to claim 20, the unsaturated compound of aforementioned (b) photopolymerization are selected from the group of being made up of the compound of the compound of following general formula (I) expression and following general formula (II) expression:

[chemical formula 5]

In the formula, R ₈And R ₉Be H or CH independently ₃, and n ₂, n ₃And n ₄Be 3～20 integer independently of one another;

[chemical formula 6]

In the formula, R ₁₀And R ₁₁Be H or CH independently ₃, A is C ₂H ₄, B is C ₃H ₆, n ₅+ n ₆Be 2～30 integer, n ₇+ n ₈Be 0～30 integer, n ₅And n ₆Be 1～29 integer independently, n ₇And n ₈Be 0～29 integer independently, repetitive-(A-O)-and-(B-O)-the optional 0 random or block of arrangement, under the situation that is block, any can be the bisphenol group side.

28. using method according to claim 20 also has protective seam on aforementioned negative-type photosensitive resin bed (B).

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