CN101952777B - 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 and uses the operation of 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 the negative-type photosensitive resin laminate with negative-type photosensitive resin bed in the manufacture be suitable for P.e.c. (circuit) plate, lead frame, semiconductor packages etc. to manufacture the method for resist solidfied material.The invention still further relates to and there is the negative-type photosensitive resin laminate of negative-type photosensitive resin bed and the using method of negative-type photosensitive resin laminate that i ray monochromatic exposure is used.And then in detail, the present invention relates to be suitable for the negative-type photosensitive resin laminate of negative-type photosensitive resin bed and the using method of negative-type photosensitive resin laminate that the i ray monochromatic exposure with alkali-developable of the manufacture of P.e.c. (circuit) plate, lead frame, semiconductor packages etc. is used.

Background technology

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

In above-mentioned minus photoetching process, can use following either method: when negative light-sensitive resin combination is applied on substrate, by the solution coat of negative light-sensitive resin combination to substrate and make its dry method; Or, lamination is successively had to layer that supporter and negative light-sensitive resin combination form (below 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 substrate.In the manufacture of printed circuit board (PCB), mostly adopt the method that dry film resist layer is laminated to the latter on substrate.

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

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

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

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

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 the negative-type photosensitive resin laminate of the resist solidfied material that brings the develop corrosion-resisting pattern of rear adhesion and excellent in resolution and the resist layer shape of excellence is provided.

For the method for dealing with problems

The inventor has carried out deeply research repeatedly in order to address the above problem, found that, now, surprisingly, to thering is supporter (A), negative-type photosensitive resin bed (B), and the negative-type photosensitive resin laminate of substrate (C) is when expose, by changing the transmittance of this negative-type photosensitive resin bed (B), specifically, by using the transmittance under wavelength 365nm, it is the more than 25% negative-type photosensitive resin bed (B) below 50%, the resist with use with the negative-type photosensitive resin bed manufacture of current transmittance is compared, the adhesion of the corrosion-resisting pattern after development and resolution and resist layer shape are improved rapidly, thereby complete the present invention.In addition, when thering is the layered product of negative-type photosensitive resin bed and carry out i ray monochromatic exposure, if find, use and with acid equivalent, count 100～600 by containing (a) carboxyl-content, 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 % forms, and, transmittance under wavelength 365nm is the more than 25% negative-type photosensitive resin bed below 50%, the situation that has a negative-type photosensitive resin bed of above-mentioned extraneous transmittance with use is compared, the adhesion of the corrosion-resisting pattern after development and resolution and resist layer vpg connection improve rapidly, thereby complete the present invention.Specifically, above-mentioned problem solves by the scheme of following [1]～[28].

[1] manufacture method for resist solidfied material, it comprises following operation:

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

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

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

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 the resist solidfied material above-mentioned [1] Suo Shu, wherein, this light is i ray monochromatic light.

[3], according to the manufacture method of the resist solidfied material above-mentioned [1] or [2] Suo Shu, at this layered product, form between operation and this exposure process and 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 the resist solidfied material described in any one 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 the resist solidfied material described in any one 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], according to the manufacture method above-mentioned [5] Suo Shu, as this (c) Photoepolymerizationinitiater initiater, contain at least a kind of compound in the group of selecting free benzophenone and benzophenone derivates composition.

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

[8] according to the manufacture method described in any one of above-mentioned [5]～[7], as this (c) Photoepolymerizationinitiater initiater, contain at least a kind of compound selecting in the group that free benzophenone and benzophenone derivates form and 2,4,5-triarylimidazoles dipolymer the two.

[9], according to the manufacture method of the resist solidfied material described in any one of above-mentioned [5]～[8], be somebody's turn to do the group of the unsaturated compound choosing compound that freely following general formula (I) represents and the compound composition that following general formula (II) represents of (b) photopolymerization:

[Chemical formula 1]

In 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 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, in the situation that being block, any can be bisphenol group side.

[10] a kind of manufacture method of printed circuit board (PCB), it comprises following operation: the aforesaid base plate (C) with corrosion-resisting pattern is carried out to the operation of etching or plating, the resist solidfied material that wherein said corrosion-resisting pattern is made by the manufacture method by described in any one in above-mentioned [1]～[9] forms; The operation that aforementioned resist solidfied material is removed from aforesaid base plate (C).

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

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

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

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

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

[15], according to the negative-type photosensitive resin laminate described in any one of above-mentioned [11]～[14], as this (c) Photoepolymerizationinitiater initiater, contain at least a kind of compound in the group of selecting free benzophenone and benzophenone derivates composition.

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

[17] according to the negative-type photosensitive resin laminate described in any one of above-mentioned [11]～[16], as this (c) Photoepolymerizationinitiater initiater, contain at least a kind of compound selecting in the group that free benzophenone and benzophenone derivates form and 2,4,5-triarylimidazoles dipolymer the two.

[18], according to the negative-type photosensitive resin laminate described in any one of above-mentioned [11]～[17], be somebody's turn to do the group of the unsaturated compound choosing compound that freely following general formula (I) represents and the compound composition that following general formula (II) represents of (b) photopolymerization:

[chemical formula 3]

In 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 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, in the situation that being block, any can be bisphenol group side.

[19] according to the negative-type photosensitive resin laminate described in any one of above-mentioned [11]～[18], on aforementioned negative-type photosensitive resin bed (B), also there is protective seam.

[20] a kind of using method of negative-type photosensitive resin laminate, it is by using the i ray monochromatic light of projected light mask picture and across lens, negative-type photosensitive resin bed being exposed while forming resist solidfied material, use negative-type photosensitive resin laminate as described below: described layered product at least has the negative-type photosensitive resin bed (B) that supporter (A) and i ray monochromatic exposure are used, 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 the using method above-mentioned [20] Suo Shu, the transmittance of this negative-type photosensitive resin bed (B) under wavelength 365nm is more than 35% below 45%.

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

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

[24], according to the using method described in any one of above-mentioned [20]～[23], as this (c) Photoepolymerizationinitiater initiater, contain at least a kind of compound in the group of selecting free benzophenone and benzophenone derivates composition.

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

[26] according to the using method described in any one of above-mentioned [20]～[25], as this (c) Photoepolymerizationinitiater initiater, contain at least a kind of compound selecting in the group that free benzophenone and benzophenone derivates form and 2,4,5-triarylimidazoles dipolymer the two.

[27], according to the using method described in any one of above-mentioned [20]～[26], be somebody's turn to do the group of the unsaturated compound choosing compound that freely following general formula (I) represents and the compound composition that following general formula (II) represents of (b) photopolymerization:

[chemical formula 5]

In 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 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, in the situation that being block, any can be bisphenol group side.

[28] according to the using method described in any one of above-mentioned [20]～[27], on this negative-type photosensitive resin bed (B), also there is protective seam.

Invention effect

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

Accompanying drawing explanation

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 at least being formed by supporter (A), negative-type photosensitive resin bed (B) and substrate (C) lamination;

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

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

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 for by using the i ray monochromatic light of projected light mask picture and across lens, negative-type photosensitive resin bed being exposed and forms resist solidfied material, described layered product at least has the negative-type photosensitive resin bed (B) that supporter (A) and i ray monochromatic exposure are used, 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 is by using the i ray monochromatic light of projected light mask picture and across lens, negative-type photosensitive resin bed being exposed while forming resist solidfied material, use negative-type photosensitive resin laminate as described below: described layered product at least has the negative-type photosensitive resin bed (B) that supporter (A) and i ray monochromatic exposure are used, 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) " refers to and is exposed to active ray, then develops, and obtains thus the resin bed of the pattern of minus.In addition, " the negative-type photosensitive resin bed (B) that i ray monochromatic exposure is used " refers to, in above-mentioned negative-type photosensitive resin bed (B), by the monochromatic exposure of i ray (under wavelength 365nm) and exploring after this, thereby can obtain the corrosion-resisting pattern of expectation.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 wavelength 365nm is above-mentioned scope, compare with the situation of above-mentioned extraneous transmittance, can obtain the corrosion-resisting pattern of adhesion and excellent in resolution, and it is good that resist layer resizing becomes.In addition, in 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 wavelength 365nm, it is above-mentioned scope, use makes photomask as the i ray monochromatic light of projection and across lens, negative-type photosensitive resin bed is exposed, thereby form resist solidfied material, now compare with the situation of above-mentioned extraneous transmittance, can obtain the corrosion-resisting pattern of adhesion and excellent in resolution, and resist layer resizing becomes good.Use makes photomask as the light of projection, across lens, negative-type photosensitive resin bed is exposed, thereby form in the situation of resist solidfied material, 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 resist layer resizing.In addition, in the mode of exposing after peeling off supporter in advance, use makes above-mentioned photomask as the light of projection, across lens, negative-type photosensitive resin bed is exposed, thereby form in the situation of resist solidfied material, resist layer cross sectional shape is coiling tubular, in addition, the residual foot of resist is large, existing problems aspect resist layer resizing.On the other hand, in the situation that above-mentioned transmittance surpasses 50%, exist negative-type photosensitive resin bed (B) can not effectively absorb the problem that the light of exposure, the light sensitivity that makes to expose reduce.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%.

Method as the transmittance that regulates negative-type photosensitive resin bed (B) under wavelength 365nm, can list the method for adding ultraviolet light absorber in the negative light-sensitive resin combination of negative-type photosensitive resin bed (B) to being used to form; 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, be ultraviolet light absorber, can exemplify 2-(2-hydroxyl-5-tert-butyl-phenyl)-2H-benzotriazole, benzenpropanoic acid 3-(2H-benzotriazole-2-yl)-5-(1,1-dimethyl ethyl)-4-hydroxyl C _7-9side chain and straight chained alkyl ester, 2-(2H-benzotriazole-2-yl)-4, two (1-methyl isophthalic acid-phenylethyl) phenol of 6-.

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

As the method for measuring the transmittance of negative-type photosensitive resin bed of the present invention (B) under wavelength 365nm, there is following method: on supporter, form negative-type photosensitive resin bed (B), supporter is put into reference to light side, deduct supporter part, by spectrophotometer (Hitachi High-Technologies Corporation U-3310 processed), be set as 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 negative-type photosensitive resin bed with to the developability of alkaline aqueous solution, fissility, need the carboxyl in binder resin.From the viewpoint of development patience, resolution and adhesion, the amount of the carboxyl in binder resin is preferably counted more than 100 with acid equivalent, and the viewpoint from developability and fissility, is preferably below 600.More preferably the acid equivalent of take can be 250～400.In the present invention, provide negative-type photosensitive resin laminate and negative-type photosensitive resin laminate using method aspect, above-mentioned acid equivalent is 100～600, is preferably 300～400.Acid equivalent refers in resin glue, to have the quality (gram equivalent) of the polymkeric substance (being binder resin) of the carboxyl of 1 equivalent.

Being determined as follows of acid equivalent carried out: use flat natural pond industry (strain) to make flat natural pond automatic titration device (COM-555), with the NaOH of 0.1mol/L, 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 developability, 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, preferably the weight-average molecular weight of (a) binder resin is between 20000～300000.In addition, in the present invention, providing aspect the using method of negative-type photosensitive resin laminate and negative-type photosensitive resin laminate, above-mentioned weight-average molecular weight is between 5000～500000, the viewpoint of the resolution while 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 light splitting (strain) gel permeation chromatography processed (GPC) [pump: Gulliver, PU-1580 type, post: clear and 4 series connection of electrician's (strain) Shodex processed (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) Shodex STANDARD processed 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 more preferably 100 ℃ above below 120 ℃.

The glass transition temperature of (a) binder resin in 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.)。

The present invention's (a) binder resin used can be by obtaining more than a kind or the a kind monomer copolymerization separately in following 2 kinds of monomers.The-monomer is carboxylic acid or the acid anhydrides in molecule with 1 polymerism unsaturated group.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, molecule, in order to keep the various characteristics such as flexible of patience in developability, etching and the plating operation of 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 putting forward high-resolution viewpoint, preferably use the vinyl compound (for example, styrene, (methyl) benzyl acrylate) with phenyl.

(a) of the present invention binder resin can synthesize as follows: will in the solution that for potpourri, acetone, MEK, the dilution of isopropyl alcohol equal solvent form of above-mentioned monomer, add in right amount the radical polymerization initiators such as benzoyl peroxide, azobis isobutyronitrile, thus synthetic by heating, stirring.Also there is limit that a part for potpourri is added drop-wise to limit in reactant liquor and carry out synthetic situation.Also respond after end, then add solvent, 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 %.For example, from being had the characteristic of resist layer, covered the viewpoint hole, etching and various plating operation with sufficient patience by exposure, the corrosion-resisting pattern forming that develops, (a) content of binder resin is preferably the scope of 20～90 quality %.In addition, in 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 %.

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

The compound that general formula (I) represents:

[chemical formula 7]

In 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 that above-mentioned general formula (I) represents, n ₂, n ₃and n ₄than the boiling point of 3 hours these compounds, reduce, 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 there is the tendency of practical light sensitivity step-down.

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

The compound that general formula (II) represents:

[chemical formula 8]

In 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, can be also block, in the situation that being block, any can be bis-phenol base side.}

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

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

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

The compound that formula (III) represents:

[chemical formula 9]

In formula, R ₁₂for 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 in the situation that being block, any can be acryloyl group side.}

In the compound that above-mentioned general formula (III) represents, from the viewpoint of light sensitivity, m ₁, m ₂, m ₃and m ₄be below 15.

The object lesson of the compound representing as above-mentioned general formula (III), for example can list, hexamethylene diisocyanate, toluene diisocyanate, 2,2, in the diisocyanate cpds such as 4-trimethyl hexamethylene diisocyanate and a part, there is the urethane compound of the acrylate-based compound of hydroxyl and (methyl) (for example, 2-hydroxypropyl acrylate, low polypropylene glycol monomethacrylate, low polyethylene glycol monomethacrylate, oligomerisation of ethylene propylene glycol monomethyl acrylate etc.) etc.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 low polypropylene glycol monomethacrylate (Japanese grease (strain) system, PremmerPP1000).

The compound that formula (IV) represents:

[Chemical formula 1 0]

In formula, R ₁₅for H or CH ₃, R ₁₆for 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 in the situation that being block, any can be phenyl side.}

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

The object lesson of the compound representing as general formula (IV), for example can list, the acrylate that the polyglycol that the oxirane that the polypropylene glycol that the epoxypropane of average 2 moles of addition is formed and addition are average 7 moles 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 the polyglycol that the oxirane of average 8 moles of addition is formed 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 that above-mentioned formula (I) to (IV) represents, 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-bis-(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, more than being preferably 3 quality %, the viewpoint that the photo-sensitive resin when preventing from preserving oozes out, is preferably below 70 quality %.In addition, in the present invention, provide negative-type photosensitive resin laminate and negative-type photosensitive resin laminate using method aspect, above-mentioned content is the scope of 3～70 quality %.Above-mentioned content is 10～60 quality %, 15～55 quality % more preferably more preferably.

In the situation that the unsaturated compound that negative light-sensitive resin combination contains at least a kind of photopolymerization in the group that is selected from the compound of general formula (I) expression and the compound composition that general formula (II) represents, 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, more than being preferably 3 quality %, the viewpoint from the glue that overflows, is preferably below 60 quality %.

In the situation that the compound that the compound that negative light-sensitive resin combination contains general formula (III) expression or general formula (IV) represent, 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, more than being preferably 3 quality %, the viewpoint from the glue that overflows, is preferably below 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 particularly preferably selected from the group that compound that compound that following general formula (V) represents and following general formula (VI) represent forms at least a kind 2,4,5-triarylimidazoles dipolymer.

The compound that general formula (V) represents:

[Chemical formula 1 1]

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

The compound that general formula (VI) represents:

[Chemical formula 1 2]

{ in formula, X, Y and Z represent any in hydrogen, alkyl, 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., 2-(Chloro-O-Phenyl)-4 particularly preferably, 5-diphenyl-imidazole dipolymer.

In addition, from expecting further to improve the adhesion of corrosion-resisting pattern and the viewpoint of resolution, preferably 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) represent 2,4,5-triarylimidazoles dipolymer and be selected from benzophenone and group that benzophenone derivates forms at least a kind of compound.

Viewpoint from exposure light sensitivity, as benzophenone derivates, is particularly preferably p-aminophenyl ketone.As p-aminophenyl ketone, for example can list, to aminobenzophenone, to the amino benzophenone of fourth, to dimethylamino acetophenone, to dimethylamino benzophenone, p, p '-bis-(ethylamino) benzophenone, p, p '-bis-(dimethylamino) benzophenone [Michler's keton], p, p '-bis-(lignocaine) benzophenone, p, p '-bis-(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 for example can be, by various active rays, ultraviolet isoreactivity makes the known compound of its initiated polymerization.

As other Photoepolymerizationinitiater initiaters, for example can list acridine compounds, benzil dimethyl ketal, benzil diethyl ketal, the pyrazoline compounds such as the benzoin ethers such as the aromatic series ketones such as quinones, the 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 the tertiary amine compounds such as the thioxanthene ketone of 4-diethyl thioxanthone, CTX 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, the oxime ester classes such as 2-propanedione-2-(O-ethoxy carbonyl) oxime.In addition, can use N-aryl-alpha-amino acid compound, particularly preferably N-phenylglycine.

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

In the situation that contains 2,4,5-triarylimidazoles dipolymer as (c) Photoepolymerizationinitiater initiater, 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, more than being preferably 0.1 quality %, from the viewpoint of resolution, be preferably below 10 quality %.

In the situation that contain at least a kind of compound in 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 Phase is defined as transmittance under wavelength 365nm for 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 %, the further preferred scope at 0.05～0.15 quality %.

Negative light-sensitive resin combination also can contain the 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) ア イ processed ゼ Application (registered trademark) MALACHITE GREEN), alkali blue 20, diamond green (hodogaya chemical (strain) ア イ processed 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, more than above-mentioned content is preferably 0.005 quality %, from the viewpoint of light sensitivity, be preferably below 10 quality %.

The color development based dye that can contain the color development by irradiation in negative light-sensitive resin combination.As 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 is preferably 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 (2,3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-tri-is chloro-2, two (p-chlorphenyl) ethane of 2-, carbon trichloride, halo triaizine compounds etc.

As halo triaizine compounds, can list 2,4,6-tri-(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, more than above-mentioned content is preferably 0.005 quality %, from by the viewpoint and the viewpoint that maintains storage stability of exposure portion and unexposed portion contrast, be preferably below 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, more than above-mentioned content is preferably 0.005 quality %, from by the viewpoint and the viewpoint that maintains storage stability of exposure portion and unexposed portion contrast, be preferably below 10 quality %.

In order to improve thermal stability and/or the storage stability of 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-bis--Butylated Hydroxytoluene, 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), diphenyl nitra-amine etc., as concrete preferred example, can list pentaerythrite four [3-(3,5-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, more than above-mentioned content is preferably 0.01 quality %, from the viewpoint of light sensitivity, be preferably below 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 the 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 resist solidfied material being given to the viewpoint of flexibility, more than above-mentioned content is preferably 5 quality %, from suppressing to solidify the viewpoint of not enough and cold flow, be preferably below 50 quality %.

As the substrate in the present invention (C), can list the Copper Foil of fitting and form copper clad laminate on glass epoxy resin substrate; The sheet metal of copper, aldary, iron-based alloy etc.; There is the film-form base material of Glass Rib, Silicon Wafer and conductor layer etc.

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

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

As in the upper method that forms negative-type photosensitive resin bed (B) of supporter (A), can list above-mentioned negative light-sensitive resin combination is applied to the method on supporter (A).As supporter used here (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), is being favourable aspect image formative and economy, but in order to maintain intensity, thickness is 10～30 μ m conventionally.

The lamination protective seam (liner) as required on the surface of the supporter with negative-type photosensitive resin bed (B) (A) side opposition side.The adhesion of protective seam and negative-type photosensitive resin bed (B) is sufficiently less 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.

In the situation that negative-type photosensitive resin laminate has protective seam; at the upper negative-type photosensitive resin bed (B) that forms of substrate (C), on the surface of this negative-type photosensitive resin bed (B), be pre-formed protective seam 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.Heating-up temperature is now generally 40～160 ℃.

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

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 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 be used, and also can use bandpass filter etc. to make it form i ray monochromatic.When exposure wavelength being made as to i ray monochrome, having improved resolution, thereby preferably used i ray monochromatic light.Preferably at layered product, form between operation and 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.In this case, the shape that resist layer cross sectional shape becomes rectangle, almost do not have the chap of resist layer top and resist layer bottom to attenuate, therefore particularly preferably.

Conventionally, as the Exposure mode for exposing, 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 as the light of projection across lens to negative-type photosensitive resin bed.In addition, in typical form of the present invention, the light being sent by light source passes through according to the order of photomask and lens, arrives negative-type photosensitive resin bed, after all right scioptics of the light being sent, then passes through photomask by light source.In the present invention, by using projection type Exposure mode, and to make transmittance under wavelength 365nm be more than 25% below 50%, thereby resist layer resizing is able to remarkable improvement.In addition, in projection type Exposure mode, the transmittance that makes the negative-type photosensitive resin bed (B) under wavelength 365nm is more than 25% below 50%, and peel off in advance in the mode of exposing after supporter (A), can access such advantage: resist layer shape becomes rectangle, almost do not have resist layer top to broaden and shape that resist layer bottom attenuates.

Then, the in the situation that of there is supporter (A) on negative-type photosensitive resin bed (B), remove as required after supporter (A), develop and to remove the unexposed portion of negative-type photosensitive resin bed (B), thereby form the resist solidfied material that the cured portion by negative-type photosensitive resin bed (B) forms.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 the 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 conventionally use the aqueous sodium carbonate of 0.5～3 quality %.As mentioned above, obtain resist solidfied material of the present invention.

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

Below further illustrate 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 substrate with the formed corrosion-resisting pattern of resist solidfied material (C) obtaining by above-mentioned manufacture method is carried out to the operation of etching or plating, the operation of removing 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 plating method either method, on the metal covering that the developing procedure in the manufacture method by aforesaid resist solidfied material exposes, form the picture pattern of metal.Then, by the stronger alkaline aqueous solution of alkaline aqueous solution than conventionally using in development, peel off and remove curing corrosion-resisting pattern.The alkaline aqueous solution of peeling off use is not particularly limited, and conventionally uses 1～5 NaOH of quality %, the aqueous solution of potassium hydroxide.

The application of the invention forms picture pattern, thereby can, except forming above-mentioned printed circuit board (PCB) (printed circuit board (PCB)), can also form the rib of base plate for encapsulating semiconductor, lead frame, plasma display etc.The cross section of the line against corrosion obtaining by the present invention as shown in Figure 1, demonstrates the good shape that approaches rectangle (rectangle).; 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 resist layer; in addition, resist layer cross sectional shape in the situation of exposing in advance as shown in Figure 4 be can significantly reduce from negative-type photosensitive resin bed is peeled off supporter and " coiling tubular ", the large such problem of the residual foot change of resist become.Therefore, the present invention can be particularly suitable for conductor package substrate manufacture use.

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

Embodiment

Below, by embodiment, illustrate embodiments of the present invention, 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 using in embodiment and comparative example.

In table, the composition of the negative light-sensitive resin combination representing with suspension points (P-1～C-1) illustrates in following < symbol description >.In table, the value of P-1 and P-2 is 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 dimethylacrylate of the two ends of the polypropylene glycol forming at the epoxypropane of average 12 moles of the addition poly-alkane glycol that the oxirane of average 3 moles of addition forms 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) NKESTER BPE-500 processed) of the polyglycol that the oxirane of average 5 moles of addition forms 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 '-bis-(lignocaine) benzophenone

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

B-2: Recessive Crystal Violet

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

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

Then, to describing in the upper method that forms negative-type photosensitive resin bed (B) of supporter (A).

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

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

Then, obtain the laminated film that forms as the polyethylene film of the thickness 25 μ m of protective seam in the upper laminating of negative-type photosensitive resin bed (B).35 μ m rolled copper foil laminations are formed and hydro-peening grind as the surface of 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 to substrate (C) by hot-roll lamination Ji105℃ lower floor upper, obtains negative-type photosensitive resin laminate.

The making > of < resist solidfied material

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

Exposure light sensitivity is measured as follows: use and to black, be divided into 21 sections of 27 sections of stage metraster of Asahi Chemical Industry's system that carry out lightness variation by transparent, measure.

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

(1) in the above-mentioned exposure of resolution, use 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.Can adhere to the minimum wire spoke of the cured pattern obtaining 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 ((strain) トプコン Sm-500 processed of society), with accelerating potential 15kV, 1000 times of multiplying powers, pitch angle 60 degree, confirm resist layer shape.If the difference less than 1 μ m of the cured pattern wire spoke of resist layer top and resist layer bottom,, if be the above less than 2 μ m of ◎ 1 μ m, if be more than zero and 2 μ m, be *.

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

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

Confirm: embodiment 1A～8A that the transmittance under wavelength 365nm is scope of the present invention and embodiment 1B～7B, 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 obtaining in embodiment 2A and comparative example 1A is shown in to Fig. 1 and Fig. 2.In embodiment 2A, resist layer shape approaches rectangle, with respect to this, observes the remarkable chap in resist layer top and resist layer bottom and significantly attenuate in comparative example 1A.The electron micrograph of the resist layer shape of the resist solidfied material obtaining in embodiment 2B and comparative example 1B is shown in to Fig. 3 and Fig. 4.In embodiment 2B, resist layer shape approaches rectangle, with respect to this, observes resist layer bottom and attenuate in comparative example 1B, in addition, observes the residual foot of resist and becomes large (resist layer cross sectional shape is " coiling tubular ").

Utilizability in industry

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

Claims (18)

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

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

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

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

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

Between aforementioned laminates formation operation and aforementioned exposure process, also comprise the supporter stripping process that the supporter (A) of the active light of aforementioned transmission is peeled off from aforementioned negative-type photosensitive resin bed (B), described supporter (A) is 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 or cellulose derivative film.

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

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

4. 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.

5. manufacture method according to claim 4, as aforementioned (c) Photoepolymerizationinitiater initiater, contains at least a kind of compound in the group of selecting free benzophenone and benzophenone derivates composition.

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

7. manufacture method according to claim 4, as aforementioned (c) Photoepolymerizationinitiater initiater, contain at least a kind of compound selecting in the group that free benzophenone and benzophenone derivates form and 2,4,5-triarylimidazoles dipolymer the two.

8. the manufacture method of resist solidfied material according to claim 4, the group that the unsaturated compound choosing compound that freely following general formula (I) represents of aforementioned (b) photopolymerization and the compound that following general formula (II) represents form:

[Chemical formula 1]

In 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 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, in the situation that being block, any can be bisphenol group side.

9. the manufacture method of a printed circuit board (PCB), it comprises following operation: the aforesaid base plate (C) with corrosion-resisting pattern is carried out to the operation of etching or plating, the resist solidfied material that wherein said corrosion-resisting pattern is made by the manufacture method by described in any one in claim 1～8 forms;

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

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

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%,

Aforementioned resist solidfied material is between operation and aforementioned exposure process, also to comprise that by forming in aforementioned laminates the manufacture method of the supporter stripping process that the supporter (A) of the active light of aforementioned transmission is peeled off from aforementioned negative-type photosensitive resin bed (B) makes.

11. using method according to claim 10, the transmittance of aforementioned negative-type photosensitive resin bed (B) under wavelength 365nm is more than 35% below 45%.

12. using method according to claim 10, the glass transition temperature of aforementioned (a) binder resin is more than 100 ℃.

13. using method according to claim 10, the weight-average molecular weight of aforementioned (a) binder resin is between 10000～40000.

14. using method according to claim 10, as aforementioned (c) Photoepolymerizationinitiater initiater, contain at least a kind of compound in the group that is selected from benzophenone and benzophenone derivates composition.

15. using method according to claim 10, as aforementioned (c) Photoepolymerizationinitiater initiater, contain 2,4,5-triarylimidazoles dipolymer.

16. using method according to claim 10, as aforementioned (c) Photoepolymerizationinitiater initiater, contain at least a kind of compound selecting in the group that free benzophenone and benzophenone derivates form and 2,4,5-triarylimidazoles dipolymer the two.

17. using method according to claim 10, the group that the unsaturated compound choosing compound that freely following general formula (I) represents of aforementioned (b) photopolymerization and the compound that following general formula (II) represents form:

[chemical formula 5]

In 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 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)-5 and-(B-O)-the optional 0 random or block of arrangement, in the situation that being block, any can be bisphenol group side.

18. using method according to claim 10 also have protective seam on aforementioned negative-type photosensitive resin bed (B).

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