CN103430100A - Photosensitive resin composition, photoresist film using same, resist pattern forming method, and conductor pattern forming method - Google Patents

Photosensitive resin composition, photoresist film using same, resist pattern forming method, and conductor pattern forming method Download PDF

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CN103430100A
CN103430100A CN2012800115818A CN201280011581A CN103430100A CN 103430100 A CN103430100 A CN 103430100A CN 2012800115818 A CN2012800115818 A CN 2012800115818A CN 201280011581 A CN201280011581 A CN 201280011581A CN 103430100 A CN103430100 A CN 103430100A
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methyl
photosensitive polymer
polymer combination
corrosion
layer
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CN103430100B (en
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丰田大贵
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Changxing Materials Industry Co.,Ltd.
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Nichigo Morton Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/085—Photosensitive compositions characterised by adhesion-promoting non-macromolecular additives
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/061—Etching masks
    • H05K3/064—Photoresists

Abstract

The present invention relates to a photosensitive resin composition comprising a binder polymer, a photopolymerizable monomer containing an amine group, a photopolymerization initiator, and a benzotriazole derivative containing a carboxyl group. The present invention also relates to a photoresist film containing a photosensitive resin composition layer comprising the photosensitive resin composition and a support layer. The photosensitive resin composition and photoresist film provide excellent resolution and adhesion, an extremely small fringe on the cured resist after development, and excellent release properties.

Description

The formation method of photosensitive polymer combination, the photoresist that uses it, corrosion-resisting pattern and the formation method of conductive pattern
Technical field
The photosensitive polymer combination that the present invention relates to can to develop by alkaline aqueous solution, the photoresist that comprises the photosensitive polymer combination layer that formed by this photosensitive polymer combination and supporting layer, use this photoresist to form the method for corrosion-resisting pattern on base material and use this photoresist conductive pattern form method.More specifically, the present invention relates to give the manufacture that is suitable for printed circuit board (PCB), the manufacture of flexible print wiring board, IC lead frame for chip carrying (below, be called lead frame) manufacture, the metal forming Precision Machining such as metal mask manufacture, BGA (ball grid array) and CSP (chip size packages, Chip size package) the semiconductor package body manufacture such as, TAB (Tape Automated Bonding, belt engages automatically) and the manufacture of the belt substrate of COF (Chip On Film: semiconducter IC is equipped on to the chip formed on the fine circuits plate of film-form) representative, the manufacture of semiconductor projection, ITO electrode in field of flat panel displays, addressing electrode, the perhaps photosensitive polymer combination of the corrosion-resisting pattern of the manufacture of electromagnetic wave shielding body component and correlation technique thereof.
Background technology
All the time, printed circuit board (PCB) adopts the photoetching process manufacture.Photoetching process refers to following method: photosensitive polymer combination is coated on substrate, carry out pattern exposure, and make the exposure section polymerizing curable of this photosensitive polymer combination, by unexposed, adopt developer solution to remove, form corrosion-resisting pattern on substrate, implement etching or plating, after forming conductive pattern, by this corrosion-resisting pattern is peeled off to removal from this substrate, thereby form conductive pattern on substrate.
In above-mentioned photoetching process, can optionally use following method: when being coated on substrate by photosensitive polymer combination, the photoresist solution coat is made it to dry method on substrate; Perhaps use by supporting layer, by photosensitive polymer combination, formed the layer (below, also referred to as " photosensitive polymer combination layer ".) and the protective seam used as required stack gradually the photoresist formed, its photosensitive polymer combination layer side is layered in to the method on substrate.In the manufacture of printed circuit board (PCB), mostly use the latter's photoresist.
For using above-mentioned photoresist to manufacture the method for printed circuit board (PCB), below narration simply.
At first, photoresist has protective seam for example during polyethylene film, from the photosensitive polymer combination layer, it is peeled off.Then, use laminating machine at substrate for example on copper-clad laminated board, with sequential cascade photosensitive polymer combination layer and the supporting layer of this substrate, photosensitive polymer combination layer, supporting layer.Then, be situated between by the mask with wiring pattern, to this photosensitive polymer combination layer, adopt the ultraviolet isoreactivity energy-ray of the i ray (365nm) that comprises the ultrahigh pressure mercury lamp generation to be exposed, make thus the exposed portion polymerizing curable.Then, peel off for example pet film of supporting layer.Then, adopt developer solution for example to there is weakly alkaline aqueous solution and the unexposed portion of photosensitive polymer combination layer is dissolved or disperse removal, form corrosion-resisting pattern on substrate.After corrosion-resisting pattern forms, the technique that forms circuit is divided into 2 kinds of methods substantially.After the copper face etching that first method is the substrate by not covered by corrosion-resisting pattern is removed, the method (etching method) that partly adopts the alkaline aqueous solution stronger than developer solution to remove corrosion-resisting pattern.Second method, for using on the copper face of substrate after copper, scolding tin, nickel carries out plating, is removed the corrosion-resisting pattern part, and then by the copper face etching method (plating method) of the substrate that exposes.
On the other hand, in order to make the highdensity wiring of conductor shape homogeneous, adopt semi-additive process.In semi-additive process, at first, on the seed copper film, adopt above-mentioned method to form corrosion-resisting pattern.Then, implement plating and form the copper facing wiring between corrosion-resisting pattern, after resist is peeled off, adopt and be called as the method for dodging erosion (flash etching), by this copper facing wiring and the etching simultaneously of seed copper film.Semi-additive process is different from above-mentioned plating method, and the seed copper film is thin, and the impact almost do not produced by etching, can make rectangle and highdensity wiring.
Yet, after development, in the boundary member generation of solidifying resist layer and substrate, be called as the semi-solid preparation resist layer of foot (foot) (solidifying resist layer foot) (with reference to Fig. 1.)。Particularly, between highdensity corrosion-resisting pattern, due to foot, the surface area of the seed copper film exposed after development reduces, and the copper facing wiring therefore formed by plating method and the contact area of copper film reduce.The problem that therefore, may cause the copper facing wiring to become and easily peel off.In addition, because foot is present in below copper facing wiring, when resist is peeled off, also can become and be stumbled, peel off bad reason.And then, in etching method, due to foot, the surface area of the copper film exposed after development reduces, and therefore exists etching to remove inadequate worry.Therefore, the minimum photoresist of foot of the curing resist layer after seeking to develop.
Method as solving these problems, for example proposed in patent documentation 1 by preventing that with triaizine compounds transmitted light from producing halation on substrate surface, suppresses the method for the generation of foot; In addition, proposed to suppress by the optical polymerism compound with thering is fluorene skeleton in molecule the method for the generation of semi-solid preparation resist layer (foot) in patent documentation 2.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2007-114452 communique
Patent documentation 2: TOHKEMY 2009-53388 communique
Summary of the invention
The problem that invention will solve
Yet, although the triaizine compounds described in above-mentioned patent documentation 1 to reducing foot, produce effect, still not talkative fully; There is the significantly problem of variation of resist fissility in the optical polymerism compound that has fluorene skeleton in molecule described in above-mentioned patent documentation 2 because of its strong-hydrophobicity.
Under such background, the object of the present invention is to provide resolution and adaptation good and develop after minimum, the fissility of the foot of curing resist layer also good photosensitive polymer combination, the photoresist that comprises the photosensitive polymer combination layer that formed by this photosensitive polymer combination and supporting layer, use this photoresist to form the method for corrosion-resisting pattern on base material and use this photoresist conductive pattern form method.
For the scheme of dealing with problems
The inventor etc. conduct in-depth research in order to solve above-mentioned problem, found that, by containing binder polymer as principal ingredient, and containing can photopolymerisable monomer, in the photosensitive polymer combination of Photoepolymerizationinitiater initiater, contain and there is amino monomer as can photopolymerisable monomer component, with the benzotriazole derivatives with carboxyl as the composition of giving fissility, can show high resolving power and high adhesion, and the foot of the curing resist layer after developing is minimum, fissility is also good, can achieve the above object, thereby completed the present invention.
; purport of the present invention relates to a kind of photosensitive polymer combination; it is characterized in that, its contain (A) binder polymer, (B) have amino can photopolymerisable monomer, (C) Photoepolymerizationinitiater initiater and the benzotriazole derivatives that (D) there is carboxyl.
In addition, the present invention relates to comprise the photosensitive polymer combination layer that formed by photosensitive polymer combination of the present invention and the photoresist of supporting layer.
And then, the invention still further relates to the formation method of corrosion-resisting pattern, it has the photoresist of the present invention of use and form the photosensitive polymer combination layer on base material, and the operation of being exposed, developing.
In addition, the present invention relates to the formation method of conductive pattern, it has following operation: use photoresist of the present invention to form with forming the photosensitive polymer combination layer on substrate at circuit, and exposed, develop, form the operation of corrosion-resisting pattern; Carry out etching or plating with the aforementioned circuit formation to being formed with aforementioned corrosion-resisting pattern with substrate, peel off the operation of aforementioned corrosion-resisting pattern.
The present invention comprises following mode.
[1] a kind of photosensitive polymer combination, is characterized in that, its contain (A) binder polymer, (B) have amino can photopolymerisable monomer, (C) Photoepolymerizationinitiater initiater and the benzotriazole derivatives that (D) there is carboxyl.
[2] according to [1] described photosensitive polymer combination, it is characterized in that, (B) have amino can photopolymerisable monomer be following general formula (I) represented can photopolymerisable unsaturated compound.
Figure BDA00003766665400041
(wherein, the R in formula 1For H or CH 3.R 2And R 3Group in the group that means independently respectively to select free hydrogen atom, alkyl, alkoxy and halogen group to form, R 2And R 3Bonding and form the ring that comprises N mutually.The alkylidene that X is carbon number 1～10, or (C 2H 4O) m or (C 3H 6O) n mean, m, n be respectively the polyoxy alkylidene of 1～10 integer; Polyoxy alkylidene is atactic polymerization or block polymerization.)
[3] according to [1] or [2] described photosensitive polymer combination, it is characterized in that, with respect to 100 weight portions (A) binder polymer, contain 0.01～30 weight portion (B) have amino can photopolymerisable monomer.
[4] according to the described photosensitive polymer combination of any one of [1]～[3], it is characterized in that, with respect to 100 weight portions (A) binder polymer, contain the benzotriazole derivatives that 0.01～2 weight portion (D) has carboxyl.
[5] according to the described photosensitive polymer combination of any one of [1]～[4], it is characterized in that, (A) binder polymer has carboxyl, and its acid number is 100～300mgKOH/g.
[6] a kind of photoresist, is characterized in that, it comprises photosensitive polymer combination layer and supporting layer that the described photosensitive polymer combination of any one by [1]～[5] forms.
[7] a kind of formation method of corrosion-resisting pattern, it comprises: use [6] described photoresist to form the photosensitive polymer combination layer on base material, and exposed, develop.
[8] a kind of formation method of conductive pattern, it comprises: use [6] described photoresist to form with forming the photosensitive polymer combination layer on substrate at circuit, and exposed, develop, form corrosion-resisting pattern; And the aforementioned circuit that is formed with aforementioned corrosion-resisting pattern is formed and carries out etching or plating with substrate, peel off aforementioned corrosion-resisting pattern.
The effect of invention
Photosensitive polymer combination of the present invention and photoresist have resolution and adaptation good and develop after also good effect of minimum, the fissility of the foot of curing resist layer.Therefore, adopt to use the formation method of corrosion-resisting pattern of photoresist of the present invention and the formation method of conductive pattern, can access that peeling off of corrosion-resisting pattern is bad, the effect of peeling off minimizing of conductive pattern (wiring).
The accompanying drawing explanation
Fig. 1 schematically shows using photoresist in the past to solidify resist layer upper formation of substrate (copper film), produces foot (curing resist layer foot) while forming coating layer (copper wiring) and the sectional view of the problem that causes.Sectional view, B after A means to develop means the sectional view after sectional view, the C after plating means to peel off.
Embodiment
Below, the present invention is specifically described.
It should be noted that, in this instructions, (methyl) acrylic acid refers to acrylic acid or methacrylic acid corresponding thereto; (methyl) acrylate refers to acrylate or methacrylate corresponding thereto; (methyl) acryloyl refers to acryloyl or methacryl corresponding thereto.
[photosensitive polymer combination]
Photosensitive polymer combination of the present invention is characterised in that, its contain (A) binder polymer, (B) have amino can photopolymerisable monomer, (C) Photoepolymerizationinitiater initiater and the benzotriazole derivatives that (D) there is carboxyl.
As (A) binder polymer, can list such as acrylic polymers, styrenic polymer, epoxide polymer, acylamide polymer, acid amides epoxide polymer, alcohol acids polymkeric substance, phenol polymer etc., can use separately a kind of in these polymkeric substance or be used in combination wherein two or more.In these polymkeric substance, preferred carbonyl bearing polymer.
As carbonyl bearing polymer, but illustration acrylic polymers, polyester polymer, polyamide polymers, epoxide polymer etc.; Wherein, preferably make (methyl) but acrylic polymers that the monomer copolymerization of acrylate and ethene unsaturated carboxylic acid and other copolymerization as required forms.
The content (ratios of whole polymerizable monomers of (methyl) acrylate and use) of the structural unit based on above-mentioned (methyl) acrylate, from realizing well the opinion of alkali-developable, resolution and peel property, preferably contain 10～70 mass parts, more preferably contain 20～60 mass parts, particularly preferably contain 30～50 mass parts.
In addition, the content of the structural unit based on the ethene unsaturated carboxylic acid (ratios of whole polymerizable monomers of ethene unsaturated carboxylic acid and use), the inhibition produced from resolution and adaptation, foot, the viewpoint of fissility, be preferably 12～50 mass parts, more preferably 15～40 mass parts, be particularly preferably 18～30 mass parts.If the content of ethene unsaturated carboxylic acid is very few, have that alkali reaction is poor, a development time, the elongated tendency of splitting time; If the content of ethene unsaturated carboxylic acid is too much, the tendency that the developer solution tolerance reduces, adaptation reduces is arranged.
And then, but the content of the structural unit of the monomer of the copolymerization based on other (but ratio of whole polymerizable monomers of the monomer of other copolymerization and use) preferably contains 10～80 mass parts, more preferably contain 20～70 mass parts, particularly preferably contain 30～60 mass parts.
These polymkeric substance that contain carboxyl may be used singly or two or more in combination.The polymkeric substance that contains carboxyl when being used in combination, can list such as the two or more polymkeric substance that contains carboxyl of the two or more polymkeric substance that contains carboxyl of the two or more polymkeric substance that contains carboxyl formed by different copolymer compositions, different weight-average molecular weight, different dispersion degree etc.
Below, described acrylic polymers is described.But the acrylic polymers used in the present invention is not limited to following acrylic polymers.
As above-mentioned (methyl) acrylate, can list such as: the carbon number of the alkyl such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate and be 1～20, be preferably 1～10 aliphatics (methyl) acrylate; Aromatic series (methyl) acrylate such as (methyl) acrylic acid benzyl ester; (methyl) acrylic acid lignocaine ethyl ester, (methyl) dimethylaminoethyl acrylate etc. are containing amino (methyl) acrylate; Hydroxyl (methyl) acrylate such as (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate; (methyl) glycidyl acrylates etc. are containing epoxy radicals (methyl) acrylate; (methyl) acrylic acid 2,2,2-trifluoro ethyl ester, (methyl) acrylic acid tetrahydro furfuryl ester etc., these (methyl) acrylate may be used singly or in combination of two or more.
As above-mentioned ethene unsaturated carboxylic acid, for example, can preferably use the monocarboxylic acids such as acrylic acid, methacrylic acid, butenoic acid, also can use dicarboxylic acid, their acid anhydrides, the half esters such as maleic acid, fumaric acid, itaconic acid, these ethene unsaturated carboxylic acids may be used singly or in combination of two or more.Wherein, particularly preferably acrylic acid, methacrylic acid.
But the monomer as above-mentioned other copolymerization, can list for example (methyl) acrylamide, (methyl) acrylic acid 2,2,3,3-tetrafluoro propyl ester, acrylamide, diacetone acrylamide, styrene, α-methyl styrene, vinyl naphthalene, vinyl cyclohexane, vinyltoluene, vinyl-acetic ester, alkyl vinyl ether, (methyl) vinyl cyanide etc., these monomers may be used singly or in combination of two or more.
For described acrylic polymers, the inhibition produced from resolution and adaptation, foot, the viewpoint of fissility, weight-average molecular weight is preferably 0.5 ten thousand～200,000, and more preferably 10,000～100,000; Acid number is preferably 100～300mgKOH/g, more preferably 120～250mgKOH/g, be particularly preferably 140～190mgKOH/g.It should be noted that, weight-average molecular weight (Mw) is use GPC (gel permeation chromatograph) device, the value obtained with THF (tetrahydrofuran) lysate of polystyrene benchmark mensuration dry polymer.
Described acid number be in and the weight of the needed KOH of 1g polymkeric substance (potassium hydroxide); By to being dissolved in polymkeric substance in ketones such as the alcohols such as methyl alcohol, acetone, methyl ethyl ketone or their mixed solvent, carrying out acid-base titration and measure.
If described weight-average molecular weight is too low, the tendency that has the photosensitive polymer combination after solidifying to become fragile; If excessive on the contrary, as to have resolution, resist layer fissility to descend tendency.In addition, if above-mentioned acid number is too small, the tendency that the effect that has inhibition resolution, resist layer fissility to reduce dies down; If excessive on the contrary, as to have effect that the fine rule adaptation of suppress solidifying resist layer reduces to die down tendency.
The glass transition temperature (Tg) of aforesaid propylene acids polymkeric substance preferably the scope of 30～150 ℃, further preferably the scope of 60～120 ℃.If glass transition temperature is too low, there is photosensitive polymer combination easily to flow, the tendency of edge-melting occurs while as photoresist, making web-like; On the other hand, if glass transition temperature is too high, the tendency while having as photoresist, the concavo-convex tracing ability of substrate surface descended.
Described glass transition temperature (Tg) can adopt DSC (Differential Scanning Calorimetry) to measure, in the situation that the glass transition temperature of the homopolymer of the comonomer of known binder polymer can be used the Fox formula to calculate.In the present invention, glass transition temperature is calculated by the Fox formula.
[mathematical expression 1]
The FOX formula
1 Tg = Wa Ta + Wb Tb + . . .
(Tg means the glass transition temperature of multipolymer.Wa, Wb ... mean a composition, b composition ... weight fraction.Ta, Tb ... mean a composition, b composition ... the glass transition temperature of homopolymer.)
As (B) have amino can photopolymerisable monomer, for example, except N, N-dimethyl (methyl) acrylamide, N, outside N-diethyl (methyl) acrylamide, dimethylamino-propyl (methyl) acrylamide, lignocaine propyl group (methyl) acrylamide, n-pro-pyl (methyl) acrylamide, isopropyl (methyl) acrylamide, N-(methyl) acryloyl morpholine etc., also can list at least one that be selected from the represented group of following general formula (I) can photopolymerisable unsaturated compound.Wherein, from the viewpoint of the effect that reduces foot, preferably use following general formula (I) represented can photopolymerisable unsaturated compound.
Figure BDA00003766665400091
(wherein, the R in formula 1For H or CH 3.R 2And R 3Group in the group that means independently respectively to select free hydrogen atom, alkyl, alkoxy and halogen group to form, R 2And R 3Bonding forms the ring that comprises N mutually.The alkylidene that X is carbon number 1～10, or (C 2H 4O) m or (C 3H 6O) n represented, m, n be respectively the polyoxy alkylidene of 1～10 integer; Polyoxy alkylidene is atactic polymerization or block polymerization.)
In above-mentioned general formula (I), the R in formula 1For H or CH 3.R 2And R 3Group in the group that means independently respectively to select free hydrogen atom, alkyl, alkoxy and halogen group to form, R 2And R 3Bonding forms the ring that comprises N mutually.The carbon number of alkyl and alkoxy is generally 1～10, is preferably 1～6.X is carbon number 1～10, preferably 1～6 alkylidene, or (C 2H 4O) m or (C 3H 6O) n represented, m, n be respectively the polyoxy alkylidene of 1～10 integer.Polyoxy alkylidene both can atactic polymerization, also can block polymerization.
As the represented compound of above-mentioned general formula (I), particularly, for example can list (methyl) acrylic acid N, N-dimethylamino methyl esters, (methyl) acrylic acid N, the N-dimethylaminoethyl, (methyl) acrylic acid N, N-dimethylamino propyl ester, (methyl) acrylic acid N, N-dimethylamino butyl ester, (methyl) acrylic acid N, N-dimethylamino pentyl ester, (methyl) acrylic acid N, the own ester of N-dimethylamino, (methyl) acrylic acid N, N-dimethylamino heptyl ester, (methyl) acrylic acid N, N-dimethylamino monooctyl ester, (methyl) acrylic acid N, N-dimethylamino ester in the ninth of the ten Heavenly Stems, (methyl) acrylic acid N, N-dimethylamino ester in the last of the ten Heavenly stems, (methyl) acrylic acid N, N-lignocaine methyl esters, (methyl) acrylic acid N, the N-lignocaine ethyl ester, (methyl) acrylic acid N, N-lignocaine propyl ester, (methyl) acrylic acid N, N-lignocaine butyl ester, (methyl) acrylic acid N, N-lignocaine pentyl ester, (methyl) acrylic acid N, the own ester of N-lignocaine, (methyl) acrylic acid N, N-lignocaine heptyl ester, (methyl) acrylic acid N, N-lignocaine monooctyl ester, (methyl) acrylic acid N, N-lignocaine ester in the ninth of the ten Heavenly Stems, (methyl) acrylic acid N, (methyl) acrylic acid dialkylaminoalkyl esters such as N-lignocaine ester in the last of the ten Heavenly stems, (methyl) acrylic acid list alkyl amino alkyl esters such as (methyl) acrylic acid N-n-propylamine base ethyl ester, (methyl) acrylic acid N-isopropylamino ethyl ester, the tertiary fourth amino ethyl ester of (methyl) acrylic acid N-, (methyl) acrylic acid N-n-butyl amine base ethyl ester, (methyl) acrylic acid N, N-dimethylamino macrogol ester, (methyl) acrylic acid N, N-lignocaine macrogol ester, (methyl) acrylic acid N, N-dimethylamino polypropylene glycol ester, (methyl) acrylic acid N, dialkylamino polyethers (methyl) acrylate such as N-lignocaine polypropylene glycol ester, (methyl) acrylic acid cyclic amino Arrcostabs such as (methyl) acrylic acid morpholine ethyl ester.Wherein, preferably (methyl) acrylic acid dialkylaminoalkyl ester, particularly preferably used (methyl) acrylic acid lignocaine Arrcostab.
It should be noted that, from the easness of starting with, R in above-mentioned general formula most preferably 1For CH 3, R 2And R 3Be C 2H 5, X is C 2H 5Compound, i.e. methacrylic acid N, the N-lignocaine ethyl ester (for example, manufacture, trade name: LIGHT ESTER DE) by common prosperity society chemistry (Zhu Shi commercial firm).
Herein, the generation of solidifying the foot of resist layer be presumably due to, solidify acidic-group and the developer solution partial reaction of weak semi-solid preparation resist layer, be not removed and during dry after development, the semi-solid preparation resist layer moves and be attached to the resist layer bottom.(B) can photopolymerisable monomer amino in photosensitive polymer combination with (A) binder polymer in acidic-group generation neutralization reaction; (A) acidic-group of binder polymer is protected; thereby anti-development fluidity improves; the semi-solid preparation resist layer adhere to again minimizing; that is, may be thought of as foot diminishes.In addition, due to the monomer of (B) has can photopolymerisable structure, therefore can expect that degree of cure improves, the raising of adaptation.Therefore, as the monomer of (B), so long as there is amino and can photopolymerisable structure, just can expect same effect.
It should be noted that, consider the worry of the unfavorable condition of the acid solutions such as the bath of pollution plating, etching solution can occur, for the photosensitive polymer combination of the purposes of photoresist, use never (B) have amino can photopolymerisable monomer as can photopolymerisable monomer component.But, in the present invention, dare to use and there is amino monomer, and not produce above-mentioned unfavorable condition unexpectedly, can reach purpose of the present invention.
In the present invention, above-mentioned (B) has amino content that can photopolymerisable monomer with respect to (A) binder polymer 100 weight portions, be preferably 0.01～30 weight portion, 0.1～25 weight portion more preferably, more preferably 0.5～20 weight portion, be particularly preferably 1～15 weight portion.If described content is very few, effect that foot the reduces inadequate tendency that becomes is arranged; If cross the tendency that decrease resolution is arranged at most.
Also can with (B) have amino can photopolymerisable monomer together with, use shown in following can photopolymerisable monomer.For example, as the monomer with 1 polymerism unsaturated group, can list: half (methyl) acrylate of (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 2-hydroxy butyl ester, (methyl) acrylic acid 2-phenoxy group-2-hydroxypropyl acrylate, phthalic acid 2-(methyl) acryloxy-2-hydroxypropyl acrylate, the chloro-2-hydroxypropyl acrylate of (methyl) acrylic acid 3-, list (methyl) acrylic acid glyceride, 2-(methyl) acrylyl oxy-ethyl phosphate ester acid, phthalic acid derivatives etc., these monomers may be used singly or in combination of two or more.
In addition, as the monomer with 2 polymerism unsaturated groups, can list for example ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, polyglycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polyglycol polypropylene glycol two (methyl) acrylate, butylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, bisphenol A-type two (methyl) acrylate containing the oxygen ethylidene, bisphenol A-type two (methyl) acrylate containing the oxygen propylidene, bisphenol A-type two (methyl) acrylate containing oxygen ethylidene oxygen propylidene, 1,6-hexanediol two (methyl) acrylate, two (methyl) acrylic acid glyceride, pentaerythrite two (methyl) acrylate, ethylene glycol diglycidylether two (methyl) acrylate, diethylene glycol diglycidyl ether two (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) acrylate, hydroxy new pentane acid modification neopentyl glycol two (methyl) acrylate etc., these monomers may be used singly or in combination of two or more.Wherein, particularly preferably use bisphenol A-type two (methyl) acrylate, polyglycol polypropylene glycol two (methyl) acrylate containing the oxygen ethylidene.
And then, as the monomer with 3 above polymerism unsaturated groups, can list such as trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, three (methyl) acryloyl-oxy base oxethyl trimethylolpropane, poly-(methyl) acrylate of glycerine poly epihydric alcohol base ether etc., these monomers may be used singly or in combination of two or more.
In addition, also can list urethane (methyl) acrylate.As urethane (methyl) acrylate, can enumerate the compound of sening as an envoy to diisocyanate such as hexamethylene diisocyanate, toluene diisocyanate and obtaining such as hydroxyl (methyl) acrylate that there is hydroxyl and (methyl) acryloyl group in a part such as the few propylene glycol ester of acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl fat, monomethyl acrylic acid (oligopropylene glycol monoacrylate) and polyol reaction as required.These compounds both can be used separately, also can be used in combination.
In the present invention, for (B) have amino can photopolymerisable monomer and (B) in addition can photopolymerisable monomer total amount, with respect to (A) binder polymer 100 weight portions, be preferably 10～200 weight portions, be particularly preferably 30～160 weight portions, more preferably 50～120 weight portions, be particularly preferably 60～100 weight portions.If described content is very few, has and solidify the inadequate tendency that becomes; If cross the tendency that easy generation cold deformation (cold flow) arranged at most.
As (C) Photoepolymerizationinitiater initiater, can list such as (C1) anthraquinone derivatives such as hexa-aryl bi-imidazole derivant, (C2) alkylamino benzophenone derivates, N-aryl glycine derivant, acridine derivatives, diamino-anthraquinone; N, N, N ', the triaryl phosphines such as the coumarin derivatives such as N '-tetra-aryl biphenyl amine derivative, triacetic acid lactochrome, benzophenone, benzil dimethyl ketal, thioxanthone derivates, alkylamino benzoic acid alkyl ester, pyrrolotriazine derivatives, coumarin 6, triphenylphosphine, trimethylphenyl phosphine, three (xylyl) phosphine, terphenyl phosphine, three naphthyl phosphines, three anthryl phosphines, three phenanthryl phosphines etc., these Photoepolymerizationinitiater initiaters may be used singly or in combination of two or more.
As (C1) hexa-aryl bi-imidazole derivant, for example can list: 2, 2 '-bis-(2, the 3-dichlorophenyl)-4, 4 ', 5, 5 '-tetra-(3-methoxyphenyl) two imidazoles, 2, 2 '-bis-(2, the 3-dichlorophenyl)-4, 4 ', 5, 5 '-tetra-(4-methoxyphenyl) two imidazoles, 2, 2 '-bis-(2, the 4-dichlorophenyl)-4, 4 ', 5, the two imidazoles of 5 '-tetra-(3-methoxyphenyl) phenyl, 2, 2 '-bis-(2, the 5-dichlorophenyl)-4, 4 ', 5, 5 '-tetra-(3-methoxyphenyl) two imidazoles, 2, 2 '-bis-(2, the 6-dichlorophenyl)-4, 4 ', 5, 5 '-tetra-(3-methoxyphenyl) two imidazoles, 2, 2 ', 4, 4 '-tetra-(2-chlorphenyls)-5, 5 '-bis-(3-methoxyphenyl) two imidazoles, 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-tetraphenyl double imidazole, 2, 2 ', 4, 4 '-tetra-(2-chlorphenyls)-5, 5 '-bis-(4-methoxyphenyl) two imidazoles, 2, 2 ', 4, 4 '-tetra-(2-chlorphenyls)-5, 5 '-bis-(2, the 3-Dimethoxyphenyl) two imidazoles, 2, 2 ', 4, 4 '-tetra-(2-chlorphenyls)-5, 5 '-bis-(3, the 4-Dimethoxyphenyl) two imidazoles, 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-tetra-(4-methoxyphenyl) two imidazoles, 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-tetra-(3, the 4-Dimethoxyphenyl) two imidazoles, 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-tetra-(3, 4, the 5-trimethoxyphenyl) two imidazoles, 2, 2 '-bis-(2-chlorphenyls)-4, two (the 3-methoxyphenyls)-4 ' of 5-, the two imidazoles of 5 '-diphenyl, 2, 2 '-bis-(2-chlorphenyls)-4, 5-two (3, the 4-Dimethoxyphenyl)-4 ', the two imidazoles of 5 '-diphenyl, 2, 2 '-bis-(2-chlorphenyl)-4-(3, the 4-Dimethoxyphenyl)-4 ', 5, the two imidazoles of 5 '-triphenyl etc., wherein, preferably 2,2 ', 4,4 '-tetra-(2-chlorphenyls)-5,5 '-bis-(3-methoxyphenyl) two imidazoles, 2,2 ', 4,4 '-tetra-(2-chlorphenyls)-5,5 '-bis-(2,3-Dimethoxyphenyl) two imidazoles, 2,2 '-bis-(2-chlorphenyl)-4-(3, the 4-Dimethoxyphenyl)-4 ', 5, the two imidazoles, 2 of 5 '-triphenyl, 2 '-bis-(2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl double imidazole, these hexa-aryl bi-imidazole derivants may be used singly or in combination of two or more.
As (C2) alkylamino benzophenone derivates, can list for example 4,4 '-bis-(lignocaine) benzophenone, 3,3 '-dimethylamino-4-methoxy benzophenone, 4,4 '-bis-(dimethylamino) benzophenone etc.; Wherein, 4,4 '-bis-(lignocaine) benzophenone particularly preferably, these alkylamino benzophenone may be used singly or in combination of two or more.
For photosensitive polymer combination of the present invention, from the viewpoint of high-sensitivity, consider, as Photoepolymerizationinitiater initiater (C), preferably at least contain (C1) hexa-aryl bi-imidazole derivant, particularly preferably contain (C1) hexa-aryl bi-imidazole derivant and other Photoepolymerizationinitiater initiaters, further preferably contain (C1) hexa-aryl bi-imidazole derivant and reach (C2) alkylamino benzophenone derivates.
For the content of (C) Photoepolymerizationinitiater initiater, with respect to (A) binder polymer 100 weight portions, be preferably 1～20 weight portion, be particularly preferably 2～16 weight portions, more preferably 3～12 weight portions.(C) if the content of Photoepolymerizationinitiater initiater is very few, the tendency that can't obtain necessary sensitivity, resolution and adaptation is arranged; If too much in addition, the tendency that produces insolubles in photosensitive polymer combination is arranged.
In the situation that be used in combination (C1) hexa-aryl bi-imidazole derivant and other Photoepolymerizationinitiater initiaters, for example, reach (C2) alkylamino benzophenone derivates in the situation that be used in combination (C1) hexa-aryl bi-imidazole derivant, with respect to (A) binder polymer 100 weight portions, (C1) the hexa-aryl bi-imidazole derivant is preferably 1～16 weight portion, be particularly preferably 2～13 weight portions, more preferably 3～10 weight portions; (C2) the alkylamino benzophenone derivates is preferably 0.01～4 weight portion, is particularly preferably 0.02～3 weight portion, more preferably 0.06～2 weight portion.
The benzotriazole derivatives that there is carboxyl as (D), preferably use for example 4-carboxyl benzotriazole, 5-carboxyl benzotriazole, 1-(1 ', 2 '-bis-carboxyethyls) benzotriazole, 1-(2 ', 3 '-dicarboxyl propyl group) benzotriazole, 1-((two (2-ethylhexyl) amino) methyl)-1H-benzotriazole carboxylic acid, they can use separately or combine two or more uses.It should be noted that, from the easness of starting with, particularly preferably 4-carboxyl benzotriazole, 5-carboxyl benzotriazole.
The compatibility of known benzotriazole derivatives and copper metal is good, can think that benzotriazole derivatives is coordinated on the copper base material after the press polish of copper layers on substrates causes etchant resist.The known benzotriazole derivatives with carboxyl strong alkali aqueous solution and this carboxyl generation neutralization reaction owing to peeling off, the therefore interface peel from the copper base material by resist layer easily.
The content that has the benzotriazole derivatives of carboxyl for (D), with respect to (A) binder polymer 100 weight portions, be preferably 0.01～2 weight portion, is particularly preferably 0.04～1.6 weight portion, more preferably 0.08～1 weight portion.(D) very few if having the content of benzotriazole derivatives of carboxyl, the tendency that has fissility to reduce, if too much in addition, have that adaptation reduces, foot also becomes large tendency.
In addition, in the present invention, all obtain from minimizing and the fissility of foot the viewpoint of taking into account, be used in combination aforementioned (B) composition and aforementioned (D) composition is important, preferably the weight rate (B)/(D) of aforementioned (B) composition and aforementioned (D) composition is in the scope more than 1 and below 500.Particularly preferably weight rate (B)/(D) is in the scope more than 3 and below 200, and further preferred weight ratio (B)/(D) is in the scope more than 5 and below 50.If described ratio fruit is too low, has and can easily peel off but foot becomes large tendency; If too high, the generation that can suppress foot arranged but peel off the tendency that becomes difficult.
In photosensitive polymer combination of the present invention, on the basis of the compound of above-mentioned (A)～(D), preferably further contain dyestuff, and then, as described dyestuff, can list painted dyestuffs such as crystal violet, malachite green, malachite green color lake, BG, diamond green, patent blue, methyl violet, Victoria blue, Victoria's ethereal blue, solvent blue, alkali blue 20, rosaniline, paramagenta, ethyl violet; The leuco dyes such as three (4-dimethylamino-2-tolyl) methane ［ leuco crystal violet ］, three (4-dimethylamino-2-aminomethyl phenyl) methane ［ procrypsis malachite green ］, Material of Fluoran dyestuff (FluoranDye) etc.
In addition, also can contain halogenide in photosensitive polymer combination of the present invention.As halogenide, can list for example amyl bromide, isoamyl bromide, bromination isobutylene, 1,2-ethylene dibromide, benzhydryl bromide, benzyl bromide a-bromotoluene, methylene bromide, trisbromomethyl phenyl sulfone, carbon tetrabromide, three (2, the 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-tri-is chloro-2, two (rubigan) ethane of 2-, chloro triaizine compounds etc.
And then, in photosensitive polymer combination of the present invention, also can contain as required the adjuvants such as plastifier.As such adjuvant, can list for example polyglycol, polypropylene glycol, polyoxy propylidene polyoxyethylene ether, the polyoxyethylene monomethyl ether, polyoxy propylidene monomethyl ether, polyoxyethylene polyoxy propylidene monomethyl ether, the single ethylether of polyoxyethylene, polyoxy propylidene list ethylether, the diol-lipids such as polyoxyethylene polyoxy propylidene list ethylether, the phthalates such as diethyl phthalate, orthotoluene sulfonamide, para toluene sulfonamide, tributyl citrate, triethyl citrate, CitroflexA-2, acetyl group citric acid three n-propyls, acetyl tributyl citrate etc.
Thermal stability, storage stability in order to improve photosensitive polymer combination of the present invention, also can contain radical polymerization inhibitor in photosensitive polymer combination.As radical polymerization inhibitor, can list for example p methoxy phenol, quinhydrones, 1,2,3,-thrihydroxy-benzene, naphthylamines, tert-butyl catechol, stannous chloride, 2,6-di-t-butyl-paracresol, 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), nitroso-phenyl azanol aluminium salt and diphenyl nitrosamine etc.
Photosensitive polymer combination of the present invention can be dissolved in as required the mixed solvent of methyl alcohol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, DMF, propylene glycol monomethyl ether equal solvent or these solvents and make the solution of solid constituent 30～60 % by weight left and right.Can use the coating fluid of this solution as the photosensitive polymer combination layer that is used to form photoresist described later.It should be noted that, also Gai Tu cloth liquid can be coated on to circuit and form with on the substrates such as substrate, make its drying, form the photosensitive polymer combination layer, but, from viewpoints such as operating efficiencies, be preferred for forming the photosensitive polymer combination layer of photoresist described later.
And then, in photosensitive polymer combination of the present invention, also can contain aptly the adjuvants such as adaptation imparting agent, antioxidant, thermal polymerization inhibitor, surface tension modifier, stabilizing agent, chain-transferring agent, defoamer, fire retardant, while containing these adjuvants, the content of described adjuvant is with respect to solid constituent total amount 100 mass parts of (A)～(D) composition, preferably contain respectively 0.01～20 mass parts, further preferably contain 0.02～15 mass parts, particularly preferably contain 0.03～10 mass parts.These adjuvants may be used singly or two or more in combination.
[photoresist]
Photoresist of the present invention contains photosensitive polymer combination layer and the supporting layer formed by photosensitive polymer combination.As supporting layer used herein, preferably see through the clear support layer by the light of exposure light source radiation.
As such supporting layer, can list such as pet film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, Vingon film, vinylidene chloride copolymerization film, polymethyl methacrylate copolymer film, plasticon, polyacrylonitrile film, styrol copolymer film, polyamide film, cellulose derivative film etc.; Wherein, preferred pet film.These films can be used the film stretched as required.
Preferably the mist degree of supporting layer is below 5.During the thin thickness of supporting layer, from the aspect of image formative and economy, consider it is favourable, from maintain intensity need consider, preferably use the supporting layer of 10～30 μ m.The thickness of the photosensitive polymer combination layer in photoresist is according to purposes and difference is preferably 5～100 μ m, and more preferably 7～60 μ m, be particularly preferably 10～50 μ m.If the photosensitive polymer combination layer is excessively thin, the tendency that has film strength to become too low; If blocked up, the tendency of adaptation, sensitivity, decrease resolution is arranged.
Photoresist of the present invention also can have protective seam as required on the surface of the opposition side of the supporting layer side of photosensitive polymer combination layer.One of key property of the protective seam used in photoresist is: can from the photosensitive polymer combination layer, easily peel off in use; Therefore, for and the photosensitive polymer combination layer between closing force, require than supporting layer, one side is enough little for protective seam.As protective seam, can preferably use for example polyethylene film, polypropylene film.The thickness of protective seam is preferably 10～100 μ m, more preferably 10～50 μ m.
Photoresist of the present invention can be as the manufacture of getting off, that is, the coating fluid that will contain photosensitive polymer combination of the present invention is coated in the single face of supporting layer, carries out drying, and then covers its coated side with protective seam as required.More specifically; can be as the manufacture of getting off;; single face at supporting layer; with the coating fluid that evenly coating contains photosensitive polymer combination of the present invention such as rolling method, excellent Tu Fa, carry out drying in the baking oven that 50～120 ℃ or temperature raise successively, form the photosensitive polymer combination layer; then, at the upper surface of this layer stacked protective seam that pressurizes.
[the formation method of corrosion-resisting pattern]
To for using photoresist of the present invention, each operation that forms corrosion-resisting pattern on base material describes.
With the corrosion-resisting pattern of photoresist of the present invention, can form by comprising following operation: stacked operation, exposure process and developing procedure.Below mean an example of concrete grammar.
As processed base material, take and manufacture in the situation that printed circuit board (PCB) is purpose, can list copper-clad laminated board; In addition, take and manufacture in the situation that concavo-convex base material is purpose, can list glass baseplate (for example, for Plasmia indicating panel, base material, surperficial electrolysis show base material), the Silicon Wafer that is formed with through hole and ceramic base material etc.The Plasmia indicating panel base material is following base material: form electrode on glass baseplate after, form dielectric layer, then be coated with partition glass paste, partition is partly implemented to sandblast processing with the glass paste, form partition.
At first, use laminating machine to carry out stacked operation.Photoresist has in the situation of protective seam, after protective seam is peeled off, adopts laminating machine that the photosensitive polymer combination layer is added to thermo-compressed and is layered on processed substrate surface.Now, the photosensitive polymer combination layer both can only be layered on the single face of substrate surface, also can be layered in two-sided on.Heating-up temperature now is generally 40～160 ℃.
Then, use exposure machine to carry out exposure process.In case of necessity, supporting layer is peeled off, seen through photomask and adopt active light to be exposed.Exposure is determined by light illumination and time shutter, also can use quantometer to measure.
In addition, in exposure process, also can use and directly describe exposure method.Directly describe exposure method for not using photomask directly to describe the mode of being exposed on base material.As light source, can use for example semiconductor laser, the ultrahigh pressure mercury lamp of wavelength 350～410nm.Describe pattern by computer control, exposure is now determined by the translational speed of light illumination and substrate.
Then, peel off as required after removing supporting layer and developed.Because photosensitive polymer combination of the present invention is the diluted alkaline developable, therefore, during development, use the alkaline aqueous solution of 0.1～5 % by weight that comprises the alkali cpds such as sodium carbonate, sal tartari, Tetramethylammonium hydroxide to carry out.The pH of above-mentioned alkaline aqueous solution is preferably in 9～11 scope, and its temperature can be regulated according to the developability of photosensitive polymer combination layer.By this development, in the photosensitive polymer combination layer, unexposed (removing the zone of target pattern image) is removed, and forms corrosion-resisting pattern.It should be noted that, in above-mentioned alkaline aqueous solution, can sneak into surfactant, defoamer, for a small amount of organic solvent of promoting to develop etc.
Can access corrosion-resisting pattern by above-mentioned operation, but difference according to circumstances also can further be carried out heating process or the UV curing process of 100～300 ℃.By implementing these operations, can further improve chemical reagent resistance.
[the formation method of conductive pattern]
The formation method of conductive pattern of the present invention is used the circuit such as copper-clad laminated board, flexible substrate to form with substrates as base material, carries out after above-mentioned corrosion-resisting pattern forms, through following operation, carrying out.At first, on the face of the substrate exposed by development, use the method that plating method or etching method etc. are known to form conductive pattern.
Coating method when carrying out plating, such as enumerating: the solder platings such as the copper plating such as copper sulphate plating, cupric pyrophosphate plating, high homogeneity (high throw) solder plating, watt are bathed the golden plating such as nickel plating, hard golden plating, soft golden plating such as (nickelous sulfate-nickel chloride) plating, nickel sulfamic acid etc.When carrying out plating, preferably use the plating pretreating agents such as degreasing agent, soft etchant to carry out pre-service.In addition, etching is carried out according to common method with acidic etching liquids such as cupric chloride-aqueous hydrochloric acid solution, iron chloride-aqueous hydrochloric acid solutions usually.Also use once in a while the Ammonia alkali etching liquid.
After plating or etching finish, with the alkali stripper that comprises aqueous alkali alkali cpds such as containing NaOH, potassium hydroxide, that concentration is 0.1～10 % by weight left and right; Or the organic amine of 3～15 % by weight aqueous solution is stripper (liquid that the monoethanolamine of particularly take is principal ingredient), carry out the removal of peeling off of corrosion-resisting pattern.
It should be noted that, while with corrosion-resisting pattern, filling plating etc. in through hole, sometimes also in the situation that do not remove corrosion-resisting pattern stacked electrically conductive film on corrosion-resisting pattern.In the situation of plating, then dodge erosion.Through above operation, can form the conductive pattern on the circuit substrate such as printed circuit board (PCB).
Embodiment
Below, enumerate embodiment and further specifically describe the present invention, but the present invention is only otherwise exceeding its purport just is not limited to the following examples.It should be noted that, below " % " " part " refer to weight basis.
1) estimate the making with sample
The photoresist of embodiment and comparative example is made as follows.The solution of the photosensitive polymer combination shown in the mode preparation table 1 that the solid constituent amount of take is 55 % by weight, fully stir and mix, use applicator, the mode that the dried coating thickness of usining becomes 25 μ m is coated on polyethylene terephthalate (PET) film thick as 16 μ m of support film.Carry out respectively 2 minutes dryings in the baking oven of 60 ℃, 90 ℃, and then, from the top of described photosensitive polymer combination layer, cover with the polyethylene film of thickness 21 μ m, obtain photoresist.For the photoresist obtained, evaluation following items as described below.
[table 1]
Figure BDA00003766665400201
Symbol in table 1 means following material.
((A) binder polymer)
P-1: polymerization obtains, 40% methyl ethyl ketone solution of weight-average molecular weight 42,000 to make methacrylic acid/methyl methacrylate/styrene (weight ratio 22/38/40).Solid constituent acid number=143.4mgKOH/g.Glass transition temperature=113.9 ℃.
P-2: polymerization obtains, 40% methyl ethyl ketone solution of weight-average molecular weight 34,000 to make methacrylic acid/methyl methacrylate/styrene (weight ratio 28/32/40).Solid constituent acid number=182.5mgKOH/g.Glass transition temperature=118.1 ℃.
(can photopolymerisable monomer)
M-1: methacrylic acid N, N-lignocaine ethyl ester CH 2=CH (CH 3) COOC 2H 5N(C 2H 5) 2(chemistry society of common prosperity society manufactures, trade name: LIGHT ESTER DE)
M-2: the tertiary fourth amino ethyl ester of methacrylic acid N-CH 2=CH (CH 3) COOC 2H 5NH (t-C 4H 9)
M-3: in the both sides of bisphenol-A respectively the oxygen ethylidene of average 5 moles of addition and the bisphenol A-type dimethylacrylate containing the oxygen ethylidene that obtains (Xin Zhong village chemical industry society manufactures, trade name: BPE-500)
M-4: nine ethylene glycol dimethacrylate 〔Xin Zhong village chemical industry societies manufacture, trade name: 9G)
(Photoepolymerizationinitiater initiater)
I-1:2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole
I-2:4,4 '-bis-(lignocaine) benzophenone
(dyestuff)
D-1: malachite green
D-2: leuco crystal violet
(benzotriazole derivatives)
The T-1:4-carboxyl benzotriazole
T-2:1-(1 ', 2 '-bis-carboxyethyls) benzotriazole
T-3:1-((two (2-ethylhexyl) amino) methyl)-1H-benzotriazole carboxylic acid
T-4: benzotriazole
(solvent)
F-1: methyl ethyl ketone
2) evaluation method
After peeling off the polyethylene film of above-mentioned photoresist, the mode of joining with photosensitive polymer combination aspect and copper-clad base plate is carried out lamination under 100 ℃ of laminating roll temperature, laminating roll pressure 0.3MPa, laminate speed 1.2m/min.Thereafter, the negative film that the mode that use gradually reduces with light transmission capacity is made (21 sections stage metraster of Si Tuofu (stouffer 21 step tablet)), utilization have parallel exposing machine (the ORC MANUFACTURING CO. of ultrahigh pressure mercury lamp, LTD. manufacture trade name: EXM-1201)) 21 sections whole faces of stage metraster of Si Tuofu are carried out to uniform exposure.After exposure, peeled off the PET film after 15 minutes, the development time of 2 times with development point (break point) (consoluet time of unexposed portion) under 27 ℃ sprays 0.7 % by weight aqueous sodium carbonate, and dissolving is removed unexposed portion and obtained solidifying the resist layer image thus.By each exposure and the rear residual hop count that develops, the exposure (mJ/cm that the residual classification hop count after 21 sections stage metraster of research Si Tuofu develop is 6 sections 2).
(resolution)
As the glass chrome mask in when exposure, using exposure section and the wide of unexposed section is the line image mask (Line pattern mask) of 1:1 ratio, and the hop count of stage metraster of take is exposed and develops as the exposure of 6 sections.The value of the minimum mask wide (μ m) of curing corrosion-resisting pattern as resolution will normally be formed.
(adaptation)
As the mask film in when exposure, use the line image mask that only has exposure section, the hop count of stage metraster of take is exposed and is developed as the exposure of 6 sections.The value of the minimum mask wide (μ m) of curing corrosion-resisting pattern as adaptation will normally be formed.
(foot of the curing resist layer after development)
To being laminated on the photoresist on substrate, see through the chromium glass mask and take the hop count of stage metraster and exposed and develop as the exposure of 6 sections.The following mark grade of foot to the live width/line-spacing of the corrosion-resisting pattern that obtains=10/10 μ m line.Foot length (foot length) adopts SEM, and (NEC society manufactures, trade name: foot's width of JSM-6390) measuring the foot (foot section) of solidifying corrosion-resisting pattern.
◎: in the foot of solidifying corrosion-resisting pattern, confirm to have the foot length below 1 μ m.
Zero: in the foot of solidifying corrosion-resisting pattern, confirm that the 1 μ m of surpassing is arranged and be the foot length below 3 μ m.
*: confirm that in the foot of solidifying corrosion-resisting pattern the foot length that surpasses 3 μ m is arranged.
(fissility)
To being laminated to the photoresist on substrate, become the exposure exposure 4cm * 4cm square pattern of 6 sections with the hop count of stage metraster.After the development time development of 2 times with minimum development time, carry out the copper sulphate plating.And then under 50 ℃, adopt the sodium hydroxide aqueous solution of 3 % by weight to be sprayed, measure the splitting time that solidifies resist layer, by the fissility that solidifies resist layer mark grade as described below.
◎: the resist layer splitting time is below 50 seconds.
Zero: the resist layer splitting time surpasses 50 seconds and is below 60 seconds.
*: the resist layer splitting time was over 60 seconds.
3) evaluation result
The evaluation result of embodiment and comparative example is shown in to table 2.
[table 2]
Figure BDA00003766665400241
As shown in table 2, the resolution of the photosensitive polymer combination of embodiment 1～7, adaptation excellence.And then, because the foot of solidifying resist layer is little, be difficult for producing obstacle when the etching of subsequent handling, plating.In addition, because fissility is also good, can guarantee stable throughput rate.
On the other hand, the resolution of the photosensitive polymer combination of comparative example 1～4, the equal variation of adaptation.In addition,, because the foot of solidifying resist layer is large, there is the worry that produces obstacle in the photosensitive polymer combination of comparative example 1,3,4 when the etching of subsequent handling, plating.And then, because the fissility of the photosensitive polymer combination of comparative example 1,2 is also poor, be difficult to obtain stable turnout.
Describe the present invention in detail and with reference to specific embodiment, but the those skilled in the art is clear, in the situation that do not depart from the spirit and scope of the invention in addition various changes or modification.
The Japanese patent application (Japanese Patent Application 2011-046373) of the application based on application on March 3rd, 2011, its content is introduced in the application as reference.
Utilizability on industry
Photosensitive polymer combination of the present invention and photoresist have resolution and adaptation good and develop after also good effect of minimum, the fissility of the foot of curing resist layer.Therefore, photosensitive polymer combination of the present invention and photoresist, in the fields such as Precision Machining of the manufacture of printed circuit board (PCB), lead frame, semiconductor package body etc., metal, can be used as the anticorrosive additive materials such as etching resist, plating resist aptly.
Description of reference numerals
1 solidifies resist layer
2 substrates (copper film)
3 foots
4 coating layers (copper wiring)

Claims (8)

1. a photosensitive polymer combination, is characterized in that, its contain (A) binder polymer, (B) have amino can photopolymerisable monomer, (C) Photoepolymerizationinitiater initiater and the benzotriazole derivatives that (D) there is carboxyl.
2. photosensitive polymer combination according to claim 1, is characterized in that, (B) have amino can photopolymerisable monomer be following general formula (I) mean can photopolymerisable unsaturated compound,
Figure FDA00003766665300011
Wherein, the R in formula (I) 1For H or CH 3R 2And R 3Group in the group that means independently respectively to select free hydrogen atom, alkyl, alkoxy and halogen group to form, R 2And R 3Bonding forms the ring that comprises N mutually; The alkylidene that X is carbon number 1～10, or (C 2H 4O) m or (C 3H 6O) n represented, m, n be respectively the polyoxy alkylidene of 1～10 integer; Polyoxy alkylidene is atactic polymerization or block polymerization.
3. photosensitive polymer combination according to claim 1 and 2, is characterized in that, with respect to 100 weight portions (A) binder polymer, contain 0.01～30 weight portion (B) have amino can photopolymerisable monomer.
4. according to the described photosensitive polymer combination of any one of claim 1～3, it is characterized in that, with respect to 100 weight portions (A) binder polymer, contain the benzotriazole derivatives that 0.01～2 weight portion (D) has carboxyl.
5. according to the described photosensitive polymer combination of any one of claim 1～4, it is characterized in that, (A) binder polymer has carboxyl, and its acid number is 100～300mgKOH/g.
6. a photoresist, is characterized in that, it comprises photosensitive polymer combination layer and the supporting layer formed by the described photosensitive polymer combination of any one of claim 1～5.
7. the formation method of a corrosion-resisting pattern, it comprises: right to use requires 6 described photoresists to form the photosensitive polymer combination layer on base material, and is exposed, develops.
8. the formation method of a conductive pattern, it comprises: right to use requires 6 described photoresists to form the photosensitive polymer combination layer at circuit on substrate for forming, and is exposed, develops, the formation corrosion-resisting pattern; And
The described circuit that is formed with described corrosion-resisting pattern is formed and carries out etching or plating with substrate, peel off described corrosion-resisting pattern.
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CN109388026A (en) * 2017-08-11 2019-02-26 日兴材料株式会社 The forming method of photoresist, the forming method of corrosion-resisting pattern and conductive pattern
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CN111316164A (en) * 2017-11-06 2020-06-19 旭化成株式会社 Photosensitive resin laminate and method for producing resist pattern
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CN110531583A (en) * 2019-09-14 2019-12-03 浙江福斯特新材料研究院有限公司 Photosensitive polymer combination, dry film resist layer
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