CN109388026A

CN109388026A - The forming method of photoresist, the forming method of corrosion-resisting pattern and conductive pattern

Info

Publication number: CN109388026A
Application number: CN201710685298.8A
Authority: CN
Inventors: 横道清; 横道清一
Original assignee: Nikko Materials Co Ltd
Current assignee: Changxing Materials Industry Co ltd
Priority date: 2017-08-11
Filing date: 2017-08-11
Publication date: 2019-02-26
Also published as: TW201910116A

Abstract

This application involves the forming methods of a kind of photoresist, the forming method of corrosion-resisting pattern and conductive pattern.The present invention provides a kind of photoresist, and air gap is not likely to produce when being laminated on processed substrate, and the protective film being even coated with through non-silicone release agent is also excellent from the fissility of photosensitive polymer combination layer removing.Photoresist of the invention is characterized in that: it is that have (II) photosensitive polymer combination layer/(III) protective film lamination construction on (I) support membrane; and (II) photosensitive polymer combination layer with a thickness of 33 μm of photoresists below, (III) protective film is that the maximum height (Rz) in the lamination face on (II) photosensitive polymer combination layer is the polyester film that 1.2 μm or less and adhesive tape peel strength are 450~1500mN/cm.

Description

The forming method of photoresist, the forming method of corrosion-resisting pattern and conductive pattern

Technical field

The present invention relates to one kind to have (II) photosensitive polymer combination layer/(III) protective film product on (I) support membrane The photoresist of layer construction, the method and use for forming corrosion-resisting pattern on being processed substrate using the photoresist The method that the photoresist forms conductive pattern on being processed substrate.

Background technique

In recent years, for the pattern processing anticorrosive additive material of display components, constantly expect to cope with higher and higher solution As property.Especially in the processing method for etching processed substrate, it is known that by reducing the thickness of resist layer, etching solution flow direction can be improved Small space portion, and improve machining accuracy, so that the requirement for reducing resist thickness is very high.

On the other hand, for the easiness of step management, there is support membrane/photosensitive polymer combination layer/protective film The photoresist of composition be industrially widely used.Contain and claimed commonly used in the polyethylene protective film of photoresist For the foreign matter or undissolved object of flake (fisheye), the lobe shape due to the flake in film surface can be transferred to photonasty tree Oil/fat composition layer, therefore when being depressed into photosensitive polymer combination processed substrate layer by layer, sometimes in processed substrate and sense The case where gap (air gap) is generated between photosensitive resin composition layer.The air gap can be after the exposure of next step, development Cause generation pattern defect, broken string etc. bad.

Especially in the case where photosensitive polymer combination layer is thin, due to can fill recess portion resin combination amount not Foot becomes problem when resist thickness reduces so pattern defect, broken string etc. are bad to become more significant.In addition, being processed In the case that substrate is membranaceous flexible substrate, pressure when lamination is not applied sufficiently, therefore has air gap to generate increased tendency.

It is known to become the air gap of poor prognostic cause in order to reduce and generate number, use the polyolefin films such as polyethylene film flat as surface Sliding and few flake protective film, such as disclosing in patent document 1 can be by making to contact with photosensitive polymer combination layer Smoothly reduce air gap in the face of protective film.

But usually used polyethylene film is difficult to realize smooth.Although the polypropylene screen equally as polyolefin film It is able to achieve surface smoothness, but there is the property for penetrating organic matter, therefore photoresist is being rolled into a roll to take care of In the case where, there is photosensitive polymer combination to be attached on the support membrane contacted with polypropylene screen through polypropylene screen, uses When contaminated equipment worry.

Polyethylene terephthalate (PET) film as polyester film can similarly form smooth surface, although being not easy The transmission of photosensitive polymer combination is generated, but its material is identical as support membrane under normal circumstances, therefore in lamination step It can not steadily be removed when removing, there is photosensitive polymer combination layer to be transferred to the worry of protective film.

Implemented at demoulding as being disclosed in countermeasure of the situation, such as patent document 2 etc. by the surface to PET film The technology for managing to ensure the release property of protective film.

But have and handled by demoulding, the release property of protective film is simultaneously inadequate, and generates turning for photosensitive polymer combination The case where print.In addition, there is the case where release agent carries out contact transfer, the table of photosensitive polymer combination layer is transferred in release agent In the case where face, because photoresist is laminated to processed substrate, cause release agent that can be transferred to processed substrate surface.By Be attached to the surface of processed substrate in release agent transfer, and there is the adhesion for causing photosensitive polymer combination layer to reduce, because The wetability for being processed substrate surface reduces the worry for causing etching to reduce.

In addition, silicone release agent was widely used in the past as release agent, but transferred to processed substrate surface In the case of, also have except etching or plating and etc. in addition to, the surface wettability in following process such as surface coating or part installation It is significantly reduced, the worry for causing product yield to reduce.Moreover, being mixed into silicon in electronic industry circle deterrent due to it influences intensity Ketone.Therefore, it is necessary to which photosensitive polymer combination layer is made using the protective film for being coated with non-silicone-based and the few release agent of transfer The excellent photoresist with the fissility of protective film.

[background technology document]

[patent document]

[patent document 1] Japanese Patent Laid-Open 2000-330291 bulletin

[patent document 2] Japanese Patent Laid-Open 2003-241369 bulletin

Summary of the invention

[problems to be solved by the invention]

In this background, the purpose of the present invention is to provide a kind of photoresists, are being laminated to processed substrate Air gap was not likely to produce when upper, the protective film being even coated with through non-silicone release agent is removed from photosensitive polymer combination layer Fissility it is also excellent.

[technical means to solve problem]

But present inventor has carried out various researchs to the protective film for being coated with non-silicone-based and the few release agent of transfer, As a result, it has been found that the maximum height (Rz) by using lamination in the lamination face of photosensitive polymer combination layer meets rated condition, And adhesive tape peel strength is the protective film in prescribed limit, can obtain the photoresist consistent with the purpose, from And complete the present invention.

That is, photoresist of the invention is characterized in that: it is that have (II) photoresist group on (I) support membrane Nitride layer/(III) protective film lamination construction is closed, and (II) photosensitive polymer combination layer is below photic anti-with a thickness of 33 μm Lose film, (III) protective film be the lamination face on (II) photosensitive polymer combination layer maximum height (Rz) be 1.2 μm with Under and adhesive tape peel strength be 450~1500mN/cm polyester film.

In addition, the present invention also provides a kind of forming method of corrosion-resisting pattern using photoresist of the invention, this hair The forming method of bright corrosion-resisting pattern be characterized in that the following steps are included:

By the way that (III) of photoresist of the invention is protected film stripping, and by (II) photonasty of photoresist Resin composition layer, which is laminated to surface, to be had on the processed substrate of metal film, and (II) sense is formed on the processed substrate Photosensitive resin composition layer；And

(II) photosensitive polymer combination layer on the processed substrate is exposed, is developed and forms resist pattern Case.

In addition, the present invention also provides a kind of forming method of conductive pattern using photoresist of the invention, this hair The forming method of bright conductive pattern be characterized in that the following steps are included:

By the way that (III) of photoresist of the invention is protected film stripping, and by (II) photonasty of photoresist Resin composition layer, which is laminated to surface, to be had on the processed substrate of metal film, and (II) sense is formed on the processed substrate Photosensitive resin composition layer；

(II) photosensitive polymer combination layer on the processed substrate is exposed, is developed and forms resist pattern Case；And

The metal film on the processed substrate for being formed with the corrosion-resisting pattern is etched or plating, by institute State corrosion-resisting pattern removing.

[invention effect]

Photoresist according to the present invention can obtain following effect: be not easy to produce when being laminated on processed substrate Angry gap, (III) protective film being even coated with through non-silicone release agent are removed from (II) photosensitive polymer combination layer Fissility is also excellent.

In the present invention, especially in roll-to-roll (the Roll To Roll) processing method of utilization to flexibility printed circuit board or metal In the case that film is handled, by improving the step of photoresist is laminated processed substrate, it is able to suppress subsequent step It is bad when the etching of rapid processed substrate or plating (electroforming) on substrate, improve product yield.

Therefore, by using photoresist of the invention, being able to produce property forms in processed substrate against corrosion well Pattern forms conductive pattern, and also can prevent photoresist from polluting to (I) support membrane or manufacturing equipment.

Specific embodiment

Hereinafter, the sequentially forming method to photoresist of the invention, corrosion-resisting pattern and the forming method of conductive pattern Each embodiment be illustrated.

In addition, "~" being clipped between 2 numerical value indicates the range comprising the numerical value in this specification.Such as " 0~2 " table Show 0 or more and 2 or less.

[photoresist]

Photoresist of the invention is that have (II) photosensitive polymer combination layer/(III) protection on (I) support membrane The lamination of film constructs, typically the sequentially lamination in such a way that (II) photosensitive polymer combination layer is contacted with (I) support membrane (II) photosensitive polymer combination layer and (III) protective film.But it is also possible in (I) support membrane and (II) photoresist group Close nitride layer between be interposed 1 layer or 2 layers or more for example to keep (I) support membrane bonding with (II) photosensitive polymer combination layer Other layers such as stronger bonding and reinforcing layer.

< (I) support membrane >

In order to be exposed to (II) photosensitive polymer combination layer, (I) support membrane preferably makes to project from exposure light source Light penetrate hyaline membrane.

As this (I) support membrane, such as can enumerate: using polyethylene terephthalate film as the polyester film of representative, Polyvinyl alcohol film, PA membrane etc., wherein being suitably polyethylene terephthalate film.These films preferably film through extending, The film without extension can be used.

(I) thickness of support membrane is thinner, more advantageous in terms of image formative and economy, since intensity must be maintained, It is advantageous to use 10~30 μm of support membrane.

For the ease of processing of photoresist, the preferred 2.0GPa or more of young's modulus of (I) support membrane.In addition, (I) young's modulus of support membrane can use the stretchings such as ultraprecise Material Testing Machine MODEL5848 (manufacture of Instron company) examination The machine of testing is measured.

In addition, the mist degree preferably 5 or less of (I) support membrane.In addition, the mist degree of (I) support membrane can use NDH-1001DP Haze meters such as (Japanese electricity Se industrial group manufactures) etc. are measured.

In order to cope with heating crimping when heat drying or the lamination when manufacture, the preferred percent thermal shrinkage of (I) support membrane is small Film, such as shrinking percentage preferably when heating 30 minutes at 150 DEG C under zero load are 4% or less.

< (II) photosensitive polymer combination layer >

(II) photosensitive polymer combination layer is the photosensitive polymer combination institute structure by that can irradiate hardening by light At layer, and the layer is the bonding force for showing the degree that can be easily peeled off relative to (III) protective film upon hardening, and And the bonding force that the degree removed is difficult to relative to (I) support membrane is shown after curing.

In addition, " light " refers to the light such as ultraviolet light, near ultraviolet ray, luminous ray, infrared ray in this specification.

As the photosensitive polymer combination, preferably with the alkalinity of high-resolution needed for being realized with a low cost photoresist Developable acrylic acid series resist, such as it can be listed below composition, contain (A) with (methyl) acrylic acid with carboxyl Based polymer is able to carry out monomer and the producing agent conduct of (C) optical free radical of free radical polymerization as polymer, (B) of main body Essential component.

In addition, (methyl) acrylic acid refers to acrylic acid or corresponds to its methacrylic acid, (methyl) propylene in this specification Acid esters refers to acrylate or corresponds to its methacrylate, and (methyl) acryloyl refers to acryloyl or corresponds to its methyl-prop Alkene acyl.

(A) polymer using (methyl) acrylic acid series polymeric compounds with carboxyl as main body contains in (A) polymer (methyl) acrylic acid series with carboxyl of at least 90 weight %, preferably 95 weight % or more, particularly preferred 98 weight % or more Polymer (hereinafter also referred to contains carboxyl (methyl) acrylic acid series polymeric compounds).

It can be used alone containing carboxyl (methyl) acrylic acid series polymeric compounds or combine two or more and use.As combination Two or more and contain carboxyl (methyl) acrylic acid series polymeric compounds in the case where use, such as can enumerate comprising different copolymerization Of more than two kinds containing the carboxyl (first different containing carboxyl (methyl) acrylic acid series polymeric compounds, weight average molecular weight of more than two kinds of ingredient Base) different of more than two kinds containing carboxyl (methyl) acrylic acid series polymeric compounds etc. of acrylic acid series polymeric compounds, dispersion degree.

It (A) can also be containing containing carboxyl as the polymer of main body using (methyl) acrylic acid series polymeric compounds with carboxyl Other based polymers containing carboxyl other than (methyl) acrylic acid series polymeric compounds as the based polymer containing carboxyl, such as can arrange Lift: maleic acid based polymer, vinyl acetate based polymer etc. can be used alone a kind in these polymer or group It closes two or more and uses.

It is described to contain in carboxyl (methyl) acrylic acid series polymeric compounds, it is preferable to use making (methyl) acrylate and ethylene insatiable hunger With carboxylic acid so other monomers that can be copolymerized as needed be copolymerized made of acrylic acid series polymeric compounds.

It as (methyl) acrylate, such as can enumerate: (methyl) methyl acrylate, (methyl) acrylic acid second Ester, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-EHA, Aliphatic (methyl) acrylate that the carbon number of the alkyl such as (methyl) cyclohexyl acrylate is 1~20, preferably 1~10；(methyl) The aromatic series such as benzyl acrylate (methyl) acrylate；(methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylic acid diformazan Base amino ethyl ester etc. contains amino (methyl) acrylate；(methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate etc. Hydroxyl (methyl) acrylate；(methyl) glycidyl acrylate etc. contains epoxy group (methyl) acrylate, (methyl) third Olefin(e) acid 2,2,2- trifluoro ethyl ester, (methyl) tetrahydrofurfuryl acrylate etc.；These can be used alone or combine two or more and make With.

It as the ethylene unsaturated carboxylic acid, such as is suitable for using acrylic acid, methacrylic acid, butenoic acid, acetic acid second The dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid or these acid anhydrides or half also can be used in the monocarboxylic acids such as enester Ester, these can be used alone or combine two or more and use.Wherein, particularly preferred acrylic acid, methacrylic acid.

As the monomer that other can be copolymerized, such as can enumerate: (methyl) acrylamide, (methyl) acrylic acid 2, 2,3,3- tetrafluoro propyl ester, acrylamide, diacetone acrylamide, styrene, α-methylstyrene, vinyl naphthalene, ethylene basic ring Hexane, vinyltoluene, alkyl vinyl ether, (methyl) acrylonitrile etc., these can be used alone or combine two or more and make With.

Just make for alkali development, resolution and the good viewpoint of peel property, based on described (methyl) acrylate Structural unit content (ratio of (methyl) acrylate relative to all polymerizable monomers used) preferably 10~70 weights Measure %, particularly preferred 20~60 weight %, further preferred 30~50 weight %.

Inhibit, for the viewpoint of fissility in addition, being generated with regard to resolution and adhesion, crimping, it is unsaturated based on ethylene The content (ratio of the ethylene unsaturated carboxylic acid relative to all polymerizable monomers used) preferably 12 of the structural unit of carboxylic acid ~50 weight %, particularly preferred 15~40 weight %, further preferred 18~30 weight %.If ethylene unsaturated carboxylic acid Content is very few, then has that alkaline reaction is poor, the elongated tendency of developing time, splitting time, if excessively, there is developer solution patience It reduces, the tendency that adhesion reduces.

In addition, the structural unit based on other monomers that can be copolymerized content (other monomers that can be copolymerized relative to The ratio of all polymerizable monomers used) preferably 10~80 weight %, particularly preferred 20~70 weight %, further preferred 30 ~60 weight %.

Contain carboxyl (methyl) acrylic acid series polymeric compounds, for the viewpoint of resolution and adhesion, Weight-average molecular about this Amount preferably 0.5 ten thousand~200,000, particularly preferred 10,000~100,000, acid value preferably 100~300mgKOH/g, particularly preferred 120~ 250mgKOH/g, further preferred 140~190mgKOH/g.

In addition, weight average molecular weight (Mw) is to be measured using GPC (gel permeation chromatograph) device based on polystyrene benchmark It is worth obtained by THF (tetrahydrofuran) lysate of dry polymer.In addition, acid value is to neutralize (A) binder polymer (such as third Olefin(e) acid based polymer) KOH (potassium hydroxide) needed for 1g weight, such as by be dissolved in the alcohols such as methanol, isopropanol or The ketones such as acetone, methyl ethyl ketone or the polymer of these in the mixed solvent carry out acid-base titration and measure.

If the weight average molecular weight is too small, the photosensitive polymer combination after having the tendency that hardening becomes fragile, whereas if It is excessive, then have the tendency that resolution or resist fissility reduce.In addition, having resolution or anti-if the acid value is too small The tendency that agent fissility reduces is lost, whereas if it is excessive, then have the tendency that the filament adhesion for hardening resist reduces.

The range of preferably 30~150 DEG C of the glass transition temperature (Tg) containing carboxyl (methyl) acrylic acid series polymeric compounds, Particularly preferred 60~120 DEG C of range.If glass transition temperature is too low, there is photosensitive polymer combination to be easy flowing, with The form of photoresist causes the tendency of Fusion Edges when web-like is made, on the other hand, if glass transition temperature is excessively high, The concave-convex tracing ability of substrate surface is reduced when having the tendency that being used as photoresist.

The glass transition temperature (Tg) can (Differential Scanning Calorimetry, shows difference by DSC Scanning calorimetry) it is measured, or at known (A) by constituting being copolymerized into for (methyl) acrylic acid series polymeric compounds with carboxyl In the case where the glass transition temperature for the homopolymer for dividing (monomer) to constitute, the calculating of Fox formula can be used.

It is able to carry out the monomer of free radical polymerization as (B), such as the list with 1 polymerism unsaturated group can be enumerated Body, the monomer with 2 polymerism unsaturated groups, the monomer with 3 or more polymerism unsaturated groups, can be used alone this It a kind in a little monomers or combines two or more and uses.

As the monomer with 1 polymerism unsaturated group, such as can enumerate: (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (methyl) acrylic acid 2- phenoxy group -2- hydroxyl third Ester, phthalic acid 2- (methyl) acryloxy -2- hydroxy propyl ester, (methyl) acrylic acid 3- chlorine-2-hydroxyl propyl ester, glycerol list (methyl) acrylate, half (methyl) acrylate of phthalic acid derivatives etc. have the monomer of hydroxyl；Acid phosphate 2- The phosphates system such as (methyl) acryloyloxyethyl ester monomer；Diethyl aminoethyl methacrylate etc. has the list of amine structure Body；(methyl) acrylic acid 2- hydroxy methacrylates, 2- ethylhexyl carbitol acrylate etc. have the monomer etc. of ether structure；These It can be used alone or combine two or more and use.

In addition, as the monomer with 2 polymerism unsaturated groups, such as can enumerate: ethylene glycol two (methyl) propylene Acid esters, diethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylic acid Ester, propylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polyethylene glycol propylene glycol two (methyl) Acrylate, butanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, the bisphenol A-type containing oxyethylene group It is two (methyl) acrylate, bisphenol A-type two (methyl) acrylate containing oxypropylene group, double containing oxyethylene group-oxypropylene group Phenol A type two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, glycerol two (methyl) acrylate, Ji Wusi Alcohol two (methyl) acrylate, ethylene glycol diglycidylether two (methyl) acrylate, diethylene glycol diglycidyl glycerin ether two The modified neopentyl glycol of (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) acrylate, hydroxy new pentane acid Two (methyl) acrylate etc., these can be used alone or combine two or more and use.Wherein, particularly preferably using oxygen-containing Bisphenol A-type two (methyl) acrylate, polyethylene glycol propylene glycol two (methyl) acrylate of vinyl.

In addition, as the monomer with 3 or more polymerism unsaturated groups, such as can enumerate: trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, three (methyl) third Poly- (methyl) acrylate of alkene oyloxyethoxy trimethylolpropane, glycerine polyglycidyl ether etc., these can individually make With or combine two or more and use.

Alternatively, it is also possible to enumerate (methyl) propenoic methyl carbamate.It, can be with as (methyl) propenoic methyl carbamate Enumerating makes the diisocyanate such as hexamethylene diisocyanate, toluene di-isocyanate(TDI) and such as acrylic acid 2- hydroxyl second There is hydroxyl and (methyl) acrylic acid in one molecules such as ester, acrylic acid 2- hydroxy propyl ester, low polypropylene glycol monomethacrylate Hydroxyl (methyl) acrylate of base and polyalcohol as needed are reacted and the compound that obtains.These can be single It solely uses, also two or more kinds may be used.

In the present invention, the molecular weight that photosensitive polymer combination contains the monomer that (B) is able to carry out free radical polymerization is 180 The side of resolution of~600 monomer when realizing that air gap when being laminated to processed substrate is reduced and corrosion-resisting pattern is formed On face preferably.(B) content for the monomer that the molecular weight for being able to carry out the monomer of free radical polymerization is 180~600 is relative to (B) energy 100 parts by weight of monomer total amount of free radical polymerization are enough carried out, preferably 10~100 parts by weight contain carboxyl (methyl) third relative to (A) 100 parts by weight of olefin(e) acid based polymer, preferably 5~120 parts by weight.It is photosensitive in formation (II) in the case where the molecular weight is too small It is readily volatilized when property resin composition layer, have the tendency that because condensing oil droplet due to polluted membrane.Free radical polymerization is able to carry out at (B) In the case that the excessive situation of the molecular weight of monomer or content are very few, have the tendency that the effect can not be obtained.

In the present invention, (B) in photosensitive polymer combination be able to carry out the content of the monomer of free radical polymerization relative to (A) 100 parts by weight containing carboxyl (methyl) acrylic acid series polymeric compounds, preferably 10~200 parts by weight, particularly preferred 30~160 weight Part, further preferred 50~120 parts by weight, particularly preferred 60~100 parts by weight.If the content is very few, there is hardening to become Insufficient tendency, if excessively, having the tendency that being easy to produce cold flow.

It as (C) optical free radical producing agent, such as can enumerate: (C1) six aryl united imidazole derivative, (C2) alkyl ammonia The anthraquinones such as base benzophenone derivates, N- aryl glycine derivative, acridine derivatives, acridone derivatives, diamino-anthraquinone Derivative, N, N, N', N'- tetra-aryl biphenyl amine derivative, triacetic acid riboflavin, benzophenone, benzil dimethyl ketal, thiophene Coumarin derivatives such as ton ketone derivatives, alkyl amino benzoic acid alkyl base ester, pyrrolotriazine derivatives, coumarin 6 etc., these can be single Solely uses or combine two or more and use.

As (C1) six aryl united imidazole derivative, such as can enumerate: 2,2'- bis- (2,3- dichlorophenyls) -4,4', 5, Bis- (2,3- dichlorophenyl) -4,4', 5,5'- tetra- (4- methoxyphenyl) connection of 5'- tetra- (3- methoxyphenyl) bisglyoxaline, 2,2'- Bis- (2,4 dichloro benzene base) -4,4', 5,5'- tetra- (3- methoxyphenyl) the phenyl bisglyoxalines of imidazoles, 2,2'-, the bis- (2,5- of 2,2'- Dichlorophenyl) -4,4', 5,5'- tetra- (3- methoxyphenyl) bisglyoxaline, 2,2'- bis- (2,6- dichlorophenyl) -4,4', 5,5'- tetra- (3- methoxyphenyl) bisglyoxaline, 2,2', 4,4'- tetra- (2- chlorphenyl) -5,5'- bis- (3- methoxyphenyl) bisglyoxalines, 2,2'- Bis- (2- chlorphenyl) -4,4', 5,5'- tetraphenyl bisglyoxaline, 2,2', bis- (the 4- methoxybenzenes of 4,4'- tetra- (2- chlorphenyl) -5,5'- Base) bisglyoxaline, 2,2', 4,4'- tetra- (2- chlorphenyl) -5,5'- bis- (2,3- Dimethoxyphenyl) bisglyoxalines, 2,2', 4,4'- tetra- Bis- (3,4- Dimethoxyphenyl) bisglyoxalines of (2- chlorphenyl) -5,5'-, tetra- (4- of bis- (2- the chlorphenyl) -4,4', 5,5'- of 2,2'- Methoxyphenyl) bisglyoxaline, 2,2'- bis- (2- chlorphenyl) -4,4', 5,5'- tetra- (3,4- Dimethoxyphenyl) bisglyoxalines, 2, Bis- (2- chlorphenyl) -4,4', 5,5'- tetra- (3,4,5- trimethoxyphenyl) bisglyoxalines of 2'-, bis- (2- the chlorphenyl) -4,5- of 2,2'- Bis- (the 3,4- dimethoxy benzenes of bis- (3- methoxyphenyl) -4', bis- (2- the chlorphenyl) -4,5- of 5'- diphenyl bisglyoxaline, 2,2'- Base) -4', bis- (2- chlorphenyl) -4- (3,4- the Dimethoxyphenyl) -4' of 5'- diphenyl bisglyoxaline, 2,2'-, 5,5'- triphenyl Bisglyoxaline etc., wherein it is suitably 2,2', 4,4'- tetra- (2- chlorphenyl) -5,5'- bis- (3- methoxyphenyl) bisglyoxalines, 2,2', Bis- (2,3- Dimethoxyphenyl) bisglyoxalines of 4,4'- tetra- (2- chlorphenyl) -5,5'-, bis- (the 2- chlorphenyl) -4- (3,4- bis- of 2,2'- Methoxyphenyl) -4', -4,4', 5,5'- tetraphenyl bisglyoxaline of 5,5'- triphenyl bisglyoxalines, 2,2'- bis- (2- chlorphenyls), this It can be used alone or combine two or more and use.

It as (C2) alkyl amino benzophenone derivates, such as can enumerate: 4,4'- bis- (diethylamino) hexichol first Bis- (dimethylamino) benzophenone of ketone, 4,4'- etc., wherein particularly preferred bis- (diethylamino) benzophenone of 4,4'-, this It can be used alone or combine two or more and use.

For the viewpoint of high sensitivity, photosensitive polymer combination of the invention preferably at least contains (C1) six aryl connection Imdazole derivatives are used as (C) optical free radical producing agent, particularly preferably poly- containing (C1) six aryl united imidazole derivative and other light Close initiator, further preferably (C1) six aryl united imidazole derivative and (C2) alkyl amino benzophenone derivates.

In the present invention, the content of (C) optical free radical producing agent in photosensitive polymer combination contains carboxyl relative to (A) 100 parts by weight of (methyl) acrylic acid series polymeric compounds, preferably 1~20 parts by weight, particularly preferred 1.5~16 parts by weight are further excellent Select 2~12 parts by weight.If the content of (C) optical free radical producing agent is very few, have can not obtain required sensitivity, resolution and The tendency of adhesion, in addition, if excessive, have the tendency that generating insoluble matter in photosensitive polymer combination.

In the case where (C1) six aryl united imidazole derivative and other Photoepolymerizationinitiater initiaters are used in combination, such as and with (C1) In the case where six aryl united imidazole derivatives and (C2) alkyl amino benzophenone derivates, relative to (A) (methyl) containing carboxyl 100 parts by weight of acrylic acid series polymeric compounds, (C1) six aryl united imidazole derivative preferably 0.5~16 parts by weight, particularly preferred 1~13 Parts by weight, further preferred 2~10 parts by weight, (C2) alkyl amino benzophenone derivates preferably 0.01~4 parts by weight, especially It is preferred that 0.01~3 parts by weight, further preferred 0.02~2 parts by weight.

Photosensitive polymer combination of the invention also contains and has illicit sexual relations it is also preferred that in addition to the compound containing (A)~(C) Material.It as the dyestuff, such as can enumerate: crystal violet, malachite green, malachite green shallow lake, brilliant green, diamond green, patent blue, thyl The colorings dyes such as violet, Victoria blue, Victoria pure blue, oil blue, alkali blue 20, rosaniline, paramagenta, sub- second purple Material, three (4- dimethylamino -2- aminomethyl phenyl) methane [leuco crystal violet], three (4- dimethylamino -2- aminomethyl phenyl) first Leuco dyes such as alkane [leucogentian violet], fluoran dyes etc..

In addition, halogen compounds can also be contained in photosensitive polymer combination of the invention.As halogen compounds, example Can such as enumerate: bromo pentane silane, bromine isopentane, brominated isobutylene, ethylene bromide, hexichol bromomethane, benzyl bromide, methylene bromide, Trisbromomethyl phenyl sulfone, carbon tetrabromide, tricresyl phosphate (2,3- dibromopropyl) ester, trichloroacetamide, iodopentane, iodo isobutane, Bis- (rubigan) ethane of the chloro- 2,2- of 1,1,1- tri-, chlorination triaizine compounds etc..

In addition, also can according to need in photosensitive polymer combination of the invention containing additives such as plasticizer.As This additive, such as can enumerate: polyethylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene ether, polyoxyethylene monomethyl ether, Polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene list ether, polyoxypropylene list ether, polyoxyethylene Phthalates, the orthotoluene sulfonamides such as diol-lipids, the diethyl phthalates such as polyoxypropylene list ether, to toluene Sulfonamide, tributyl citrate, triethyl citrate, CitroflexA-2, three n-propyl of acetyl citrate, acetyl Base tri-n-butyl citrate etc..

In order to improve thermal stability, the storage stability of photosensitive polymer combination of the invention, photonasty can also be made Resin combination contains radical polymerization inhibitor.It as radical polymerization inhibitor, such as can enumerate: to methoxybenzene Phenol, hydroquinone, pyrogallol, naphthylamines, tert-butyl catechol, stannous chloride, DBPC 2,6 ditertiary butyl p cresol, 2,2'- methylene Base bis- (4- methyl-6-tert-butylphenols), 2,2' methylene bis (4- ethyl -6- tert-butyl phenol), nitroso phenylhydroxylamine Aluminium salt and N nitrosodiphenyl amine etc..

Photosensitive polymer combination of the invention, which also can according to need, is dissolved in methanol, ethyl alcohol, propyl alcohol, acetone, methyl Ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol monomethyl ether equal solvent or these The solution of 30~60 weight % of solid component or so is made in the mixed solvent.The solution can be used to form aftermentioned light Cause the coating fluid of the photosensitive polymer combination layer of etchant resist.

In addition, can also suitably contain adhesion imparting agent, antioxidant, heat in photosensitive polymer combination of the invention The additives such as polymerization inhibitor, surface tension modification agent, stabilizer, chain-transferring agent, defoaming agent, fire retardant.Contain the additive When solid component total amount 100 parts by weight of the content relative to (A)~(C) ingredient, preferably 0.01~20 parts by weight respectively, into one Walk preferably 0.02~15 parts by weight, particularly preferred 0.03~10 parts by weight.These additives can be used alone or combine 2 kinds with Above use.

(II) photosensitive polymer combination layer comprising the photosensitive polymer combination with a thickness of 33 μm hereinafter, it is preferred that 5 ~25 μm, particularly preferred 7~20 μm.If (II) photosensitive polymer combination layer is excessively thin, when being laminated to processed substrate It is easy to produce the tendency of air gap, if blocked up, has the tendency that adhesion, sensitivity, resolution reduce.

< (III) protective film >

(III) protective film for contacting (II) photosensitive polymer combination layer and lamination is polyester film, in (II) photonasty tree The maximum height (Rz) in the lamination face on oil/fat composition layer is 1.2 μm or less.

In addition, the maximum height (Rz) in the lamination face of (III) protective film is measured according to JIS B0601-2001.

In addition, in the case where (III) protective film is implemented to state surface demoulding processing later, the lamination face of (III) protective film Maximum height (Rz) be through surface demoulding processing face maximum height (Rz).

In addition, the adhesive tape peel strength of (III) protective film is 450~1500mN/cm, preferably 800~1400mN/cm.Such as Pectin band peel strength is too low, then has the release agent for being present in (III) protection film surface to be transferred to photosensitive polymer combination Worry, in addition, thering is demoulding process layer to pass through at any time with (II) photosensitive polymer combination layer after (III) protective film lamination And the tendency of migration (Migration) is generated, such as have the demoulding of (III) protective film after 1 month or more after lamination Property impaired worry.If adhesive tape peel strength is excessively high, there is photosensitive polymer combination to be transferred to the load of (III) protective film Sorrow.

By using (III) protective film for meeting these necessary conditions, it can be realized improvement and added using film resist film Workability in the step of work film substrate, and improve product yield.

In addition, in the present invention, adhesive tape peel strength is the roller by using 2kg by Nitto Denko Corp.'s system The acrylic acid series adhesive tape " 31B " (wide 25mm) made is attached to the aspect of measure of (III) protective film, the peeling force after measurement 24 hours (band removing, 90 ° of peel angle, peeling rate 300mm/ minutes) and find out.

In addition, the measurement of adhesive tape peel strength is in the case where (III) protective film is implemented to state surface demoulding processing later Surface demoulding process face is carried out.

Adhesive tape peel strength can by adjusting the resin molecular weight of mold release component, monomeric species, release layer thickness And appropriate adjustment.In addition, passing through the carbon for increasing the alkyl in the monomer with chain alkyl for constituting the resin of mold release component Number, is capable of increasing adhesive tape peel strength.

It is preferred that implementing silicone-treated to the face of (III) protective film of the side contacted with (II) photosensitive polymer combination layer In addition surface demoulding processing, can also to the side and its opposite side contacted with (II) photosensitive polymer combination layer the two Implement the surface demoulding processing other than silicone-treated in face.

It is handled as the surface demoulding, the surface in (III) protective film can be enumerated and form the release layer comprising release agent Method.As release agent used in release layer is formed, as long as can be by (III) protective film easily from presclerotic (II) The removing of photosensitive polymer combination layer, is not particularly limited, such as can to enumerate alkyd resin system release agent or silicone-based de- Mould agent etc..

But if silicone release agent is transferred to (II) photosensitive polymer combination layer, the influence to product is very big, Therefore usual deterrent brings silicone release agent in step in itself into especially in electronic industry.In contrast, alkyd resin system Release agent is suitable for the mold release treating agent few as the transfer for the release property and release agent for ensuring (III) protective film.

Also the commercially available polyester film that surface is formed with release layer can be used, such as also can be used with alkyd resin It is the PET film for the release layer that release agent is principal component.

In addition, in the case where (III) protective film has release layer, it can also (II) photonasty to (III) protective film Antistatic treatment or sided corona treatment are implemented in the face of resin composition layer side, form release layer in the process face.In addition, also can Implement the processing that setting has the release layer of antistatic property in the range of meeting regulation of the invention.

(III) protective film sufficiently few as certainly transfer of the selection release agent to (II) photosensitive polymer combination layer Index, preferably following method: make (III) protective film demoulding process face and untreated face strong contact, according to water contact angle Micro transfer of the variation confirmation release agent to untreated face.

Such as preferred single side is carried out (III) protective film that the demoulding of the surface other than silicone-treated is handled and meets following (a) Necessary condition.

(a) by 2 (III) protective films with the surface demoulding process face of a protective film and being taken off without surface for another protective film The mode lamination of the non-demoulding processing face contact of mould processing.In the environment of 22 DEG C, 60%RH, pressurizeed with the pressure of 0.056MPa Keeping 2 days, the water contact angle variable quantity of the non-demoulding process face before and after lamination is 7 ° or less at this time.

The water contact angle variation of the non-demoulding process face of lamination pressurization front and back is suitably 7 ° hereinafter, particularly preferred 5 ° or less. If water contact angle variation is excessive, have mold release treating agent be transferred to (II) photosensitive polymer combination level or manufacturing equipment and It pollutes, and is transferred to the surface of processed substrate again, thus cause the contiguity of photosensitive resin pattern bad or processed The etching of substrate is bad, the undesirable worry of plating.

In addition, the water contact angle of non-demoulding process face is the static state of water droplet when non-demoulding process face being added dropwise 2 μ L pure water Contact angle.

In the present invention, face (the photoresist phase not contacted with (II) photosensitive polymer combination layer of (III) protective film Reverse side) preferably 3~30 μm of maximum height (Rz) (3.0~30.0 μm), it is 5~15 μm particularly preferred (5.0~15.0 μm).If Maximum height (Rz) is too low, then film when having film bending when being rolled into a roll photoresist of the invention or being taken care of in the form of roller It generates fold or rolls up inclined worry.In addition, having if maximum height (Rz) is excessively high and generating unwinding or film when taking care of in the form of roller The worry of fold, in addition, also having the worry for the defect for being difficult to detect by film when manufacture since translucency reduces.

As by the face not contacted with (II) photosensitive polymer combination layer of (III) protective film, (photoresist is opposite Face) maximum height (Rz) method that is set as 3~30 μm, can be used is locally present lubricant particle in (III) protective film Photosensitive resin opposite side, furthermore can be used coating be dispersed with lubricant particle resin or implement delustring processing etc. side Method.

In addition, the maximum height (Rz) of the photoresist opposing face of (III) protective film is according to JIS B0601-2001 It is measured.

By the face not contacted with (II) photosensitive polymer combination layer to (III) protective film, (photoresist is opposite Face) implement antistatic treatment, it is possible to reduce (III) protective film stripping charge in lamination step.The film in step is mobile as a result, Friction is reduced, therefore film moves stabilization and can prevent lamination fold.Further, since the absorption of foreign matter is reduced, therefore can subtract It is bad caused by lacking because of foreign matter.Antistatic treatment without transfer process, must implement the sheet resistance value in the face of antistatic treatment It is preferred that 5.0 × 10¹⁰Ω/ or less.Sheet resistance value can be for example measured by method shown in JIS K7194.

Photoresist of the invention can by will the coating liquid containing photosensitive polymer combination (I) support The single side of film is simultaneously subject to drying, and then is coated the applicator surface by (III) protective film and is manufactured.It more specifically, can be by such as Under type manufacture, that is, utilize the known method such as roll coater method or rod coater method, industrial upper mold mouth coater Coating fluid containing photosensitive polymer combination is uniformly coated to the single side of (I) support membrane, in 50~120 DEG C or temperature It is dried in the baking oven gradually got higher and forms (II) photosensitive polymer combination layer, then pressurizeed and accumulate in the upper surface of this layer Layer (III) protective film.

(III) the pressurization lamination of protective film generally uses pressure roller, and preferably 20~80 DEG C of the temperature of roller, just certainly lamination Aspect for, particularly preferred 40~70 DEG C.In the case where the temperature is too low, (III) protective film after having lamination generates grand The tendency risen, in the case where temperature is excessively high, (II) photosensitive polymer combination layer after having the tendency that lamination is deformed.

(III) preferably 15~40 μm of the thickness of protective film, particularly preferred 19~38 μm.

[forming method of corrosion-resisting pattern]

Each step for using photoresist of the invention to form corrosion-resisting pattern on being processed substrate is said It is bright.

It can be by including layering steps, step of exposure and development using the corrosion-resisting pattern of photoresist of the invention The step of step, is formed.Following an examples for indicating specific method.

As processed substrate, for the purpose of manufacturing printed wiring board, can enumerate copper-cover laminated plate or Flexible substrate, in addition, about sheet metals such as metal mask or metal parts, except enumerating with SUS (Steel Use Stainless, stainless steel) material be representative ferroalloy other than, nickel alloy, copper alloy etc. can also be enumerated.

Firstly, carrying out layering steps using make-up machine.After (III) of photoresist is protected film stripping, patch is utilized The heating of (II) photosensitive polymer combination layer is crimped to processed substrate surface and carries out lamination by conjunction machine.In this case, (II) photosensitive polymer combination layer can only lamination substrate surface single side, can also lamination on two sides.Heating temperature at this time Generally 40~160 DEG C of degree.

Then, step is exposed using exposure machine.(I) is supported into film stripping as needed, work is utilized by photomask Property light is exposed.Light exposure is determined according to light illumination and time for exposure, can also be also measured using quantometer.

In step of exposure, usually using the contact exposure machine or projection exposure machine using extra-high-pressure mercury vapour lamp.Contact exposure It is to be exposed after the pattern mask for drawing depicting pattern to be overlapped in the substrate after being laminated lamination.Projection exposure is to pass through utilization Lens are exposed pattern mask image projection in lamination lamination rear substrate face.

Directly describe exposure method in addition, also can be used in step of exposure.Directly describing exposure method is not use Photomask and the mode directly described on substrate and be exposed.As light source, such as use the half of 350~410nm of wavelength Conductor Laser or LED (Light Emitting Diode, light emitting diode), extra-high-pressure mercury vapour lamp.Depicting pattern is by calculating Machine control, light exposure in this case is determined according to the movement speed of light illumination and substrate.

Then, will develop after (I) support film stripping removal as needed.In (II) photosensitive polymer combination layer In the case that photosensitive polymer combination is diluted alkaline developable, development is using comprising sodium carbonate, potassium carbonate, tetramethylphosphonihydroxide hydroxide The alkaline aqueous solution of 0.1~5 weight % of the alkali compounds such as base ammonium carries out.The pH value of the alkaline aqueous solution is preferably set to The temperature of 9~11 range, the alkaline aqueous solution is adjusted according to the developability of (II) photosensitive polymer combination layer.It is logical The development is crossed, the unexposed portion (region except required pattern image) in (II) photosensitive polymer combination layer is removed, Form corrosion-resisting pattern.In addition, surfactant, defoaming agent can also be mixed into the alkaline aqueous solution or for promoting development A small amount of organic solvent etc..

By the step obtain corrosion-resisting pattern, optionally can also with 100~300 DEG C of further progress of heating stepses, Or UV (ultraviolet, ultraviolet light) curing schedule.By implementing these steps, chemical-resistant can be further increased.

[forming method of conductive pattern]

The forming method of conductive pattern of the invention is to be formed to use by using circuits such as copper-cover laminated plate or flexible substrates Substrate carry out by following steps after the corrosion-resisting pattern formed as substrate is processed.Firstly, using plating method Or the known methods such as etching method form conductive pattern in the substrate surface exposed by development.

In addition, the processing of sheet metal also uses identical step.

Coating method when as progress plating, such as can enumerate: the copper facing, Gao Jun such as plating copper sulphate, plating cupric pyrophosphate The nickel plating such as the scolding tin such as one property scolding tin, plating watt bath (nickel sulfate-nickel chloride), plating nickel sulfamic acid, the hard gold of plating, the soft gold of plating etc. are gold-plated Deng., it is preferable to use the plating pretreating reagent such as degreasing agent, soft etching agent is pre-processed when progress plating.In addition, etching usually makes With the acidic etching liquids such as copper chloride-hydrochloric acid aqueous solution or iron chloride-aqueous hydrochloric acid solution, carried out according to well-established law.In few situation Ammonia system alkaline etching liquid can be used.

After plating or etching, using including 0.1~10 weight containing alkali compounds such as sodium hydroxide, potassium hydroxide Organic amine system stripper of amount % or so the alkaline stripper of the alkaline aqueous solution of concentration or 3~15 weight % aqueous solutions is (especially Using monoethanolamine as the stripper of principal component), carry out the removing removal of corrosion-resisting pattern.

In addition, then carrying out fast-etching using half addition processing method of plating.By above step, The conductive pattern in the circuitry substrates such as printed wiring board can be formed.

[embodiment]

Hereinafter, enumerating embodiment further illustrates the present invention, but as long as then the present invention does not limit without departing from its purport In embodiment below.In addition, following " % " " part " refers to weight basis.

1) preparation of photosensitive polymer combination

Allotment following compositions are simultaneously heated up to 40 DEG C, after mixing 1 hour, and standing slow cooling to room temperature prepares and is used as photonasty tree The photosensitive liquid of oil/fat composition.

(A) using (methyl) acrylic acid series polymeric compounds with carboxyl as the polymer of main body

(A1) methyl methacrylate/acrylic acid 2- ethylhexyl/styrene/methacrylic acid copolymer (copolymerization ratio 30/10/35/25, weight average molecular weight 52,000): 55.0 parts

(B) it is able to carry out the monomer of free radical polymerization

(B1) tetraethylene glycol dimethylacrylate: 25.0 parts

(B2) ethylene-oxide-modified (4 moles) bisphenol a dimethacrylate: 20.0 parts

(C) optical free radical producing agent

(C1) bis- (2- chlorphenyl) -4,4', the 5,5'- tetraphenyl -1,2'- bisglyoxalines of 2,2'-: 6.0 parts

(C2) bis- 0.12 parts of (diethylamino) benzophenone of 4,4'-

(D) other compositions

(D1) leuco crystal violet: 0.3 part

(D2) malachite green: 0.04 part

(E) solvent

(E1) methyl ethyl ketone: 85 parts

(E2) isopropanol: 15 parts

2) preparation of photoresist

The apparatus for coating manufactured using open country (Hirano Tecseed) limited liability company, as (I) support membrane 16 μm of thickness, width 1000mm PET film (Dong Li limited liability company manufacture, FB40, Rz=0.12 μm) on, with width After 970mm is coated with the photosensitive liquid, by 3 arid regions be successively adjusted for 60 DEG C, 90 DEG C, 100 DEG C of drying oven and By the dry removal of solvent composition, (II) photosensitive polymer combination layer is formd.

It is each documented by lamination table 1~4 on (II) photosensitive polymer combination layer using the laminating roll for being heated up to 40 DEG C Kind (III) protective film, thereby is achieved various photoresists.

In addition, by gas chromatograph to the solvent composition (E1) and (E2) of (II) photosensitive polymer combination layer at this time It is determined, as a result respectively less than 0.01%.

3) adhesive tape peel strength

By following methods, adhesive tape peel strength is measured to various (III) protective films documented by table 1~4.

Day is attached in the predetermined face (demoulding process face) contacted with (II) photosensitive polymer combination layer of (III) protective film The acrylic acid series adhesive tape " 31B " (25mm width) of eastern electrician limited liability company manufacture, be cut into 27~29mm of size × 200mm is fixed on CCL plate then in the attached double faced adhesive tape of face paste of (III) protective film for not attaching the acrylic acid series adhesive tape (copper-cover laminated plate).

After fixing 24 hours, Material Testing Machine STA-1150 type on the table of Orientec limited liability company manufacture is utilized (90 ° of removing attachmentes of band) determine peel strength with 90 ° of direction removings.

4) transfer stability (demoulding processing transfer stability) of the release agent in process face is demoulded

(III) protective film is cut out 2 with the size of 15cm × 10cm, with the stripping surface of (III) protective film cut out It is be overlapped with the mode of rear-face contact of another (III) protective film, it is inserted between the copper-cover laminated plate of identical size, with the weight of 85kg Code is pressurizeed (duration of load application: 2 days, 22 DEG C, 60%RH, pressure: 0.056MPa).

Using the surface tensometer CA-XE type of consonance interface science limited liability company manufacture, before pressurization (III) water (pure water) contact angle of protection back of the membrane and (III) protection back of the membrane after pressurization, thus determines turning for release agent Print stability.

Back of the membrane is protected about (III) protection back of the membrane before pressurization and (III) after pressurization, by the number of pure water contact angle Value difference is that 5 ° of protective films below are judged as excellent product, is denoted as "○" in table 1~4, is more than 5 ° by numerical difference and is 7 ° below Protective film is judged as non-defective unit, and " △ " is denoted as in table 1~4, the protective film that numerical difference is more than 7 ° is judged as defective products, in table 1~4 It is denoted as "×".

[table 1]

[table 2]

[table 3]

[table 4]

PET: extend polyethylene terephthalate

OPP: extended polypropylene

PE: low density polyethylene (LDPE) (the inflation formed products of Tamapoly company manufacture)

5) protective film fissility

By various photoresists documented by table 1~4 in the environment of 22 DEG C, 50~60%RH, taken care of under shading After 90 days, (III) protective film is removed with hand.In the case where unquestionably removing, it is denoted as "○" in table 1~4, is judged to closing Lattice are denoted as "×" in table 1~4 in the case where a part of photosensitive polymer combination is transferred to (III) protective film, determine It is unqualified.

6) stability is batched

Various photoresists documented by table 1~4 are rolled into a roll, in the environment of 22 DEG C, 50~60%RH, are being hidden After being taken care of 90 days under light, the photoresist of web-like is rolled out, visual confirmation photoresist there are the appearances such as corrugationless generation different Often.

In table 1~4, it is denoted as "○" in the case where no abnormal appearance, is determined as qualification, generated outside fold etc. confirming It is denoted as "×" in the case where seeing exception, is determined as unqualified.

7) exudation of photoresist ingredient

Various photoresists documented by table 1~4 are cut out 2 with the size of 15cm × 10cm, with cut out one (I) support film surface of photoresist is be overlapped with the mode of (III) protective film face contact of another photoresist, is inserted in identical Between the copper-cover laminated plate of size, pressurizeed with the counterweight of 85kg (duration of load application: 2 days, 22 DEG C, 60%RH, pressure: 0.056MPa)。

For (I) branch of a photoresist of (III) protective film face contact with another photoresist Film surface is supportted, the surface tensometer CA-XE type of consonance interface science limited liability company manufacture is utilized respectively before and after pressurization Measure water (pure water) contact angle.

Film surface is supported about (I) support film surface before pressurization and (I) after pressurization, is 5 ° by the numerical difference of pure water contact angle Photoresist below is judged as excellent product, is denoted as "○" in table 1~4, is more than 5 ° by numerical difference and is 7 ° below photic Etchant resist is judged as non-defective unit, and " △ " is denoted as in table 1~4, and the photoresist that numerical difference is more than 7 ° is judged as defective products, table 1 "×" is denoted as in~4.

8) patternability

Roll-to-roll (Roll To Roll) the mode make-up machine manufactured using MCK limited liability company, to be laminated roll temperature The table 1~4 that severing is width 440mm by 100 DEG C, speed 2m/ minutes, lamination pressure 0.2MPa and is rolled into a roll it is photic anti- Erosion film layer is depressed into the copper vapor deposition PET base material of width 470mm (base material thickness: 100 μm, copper is thick: about 1 μm, Ra:0.02 μm).

(manufacture of Orc production limited liability company, institute, directional light are exposed to the copper vapor deposition PET base material being laminated Exposure device " EXM-1201 " type, 20 μm of line width, 200 μm of gap width of pattern of parallel lines mask), by with 27 DEG C, 0.15MPa mist sprays 0.7% aqueous sodium carbonate, carries out the development of 2 times of minimum developing times.

Then, chloride series etching solution 10 seconds of 42 Baumes are sprayed with 45 DEG C, 0.15MPa mist.It is saturating in optical microscopy (viewing area is 250mm × 200mm) is counted to the position of bad (broken string) of copper pattern under light.

[industrial availability]

Photoresist of the invention being capable of manufacture in printed wiring board, lead frame, semiconductor package body etc., metal The fields such as Precision Machining be suitably used as the anticorrosive additive materials such as etching resist, plating resist.

Claims

1. a kind of photoresist, it is characterised in that: its be on (I) support membrane have (II) photosensitive polymer combination layer/ (III) the lamination construction of protective film, and (II) photosensitive polymer combination layer with a thickness of 33 μm of photoresists below,

(III) protective film be the lamination face on (II) photosensitive polymer combination layer maximum height (Rz) be 1.2 μm or less, And adhesive tape peel strength is the polyester film of 450~1500mN/cm.

2. photoresist according to claim 1, it is characterised in that: implement silicon at least single side of (III) protective film Surface demoulding processing other than ketone processing, and with the surface of (III) protective film demoulding process face and (II) photosensitive resin composition The mode lamination of nitride layer contact.

3. photoresist according to claim 2, it is characterised in that: it is de- that single side implemented the surface other than silicone-treated (III) protective film of mould processing meets the necessary condition of following (a):

(a) by 2 (III) protective films with the surface of protective film demoulding process face and another protective film without surface demoulding at The mode lamination of the non-demoulding processing face contact of reason, with the pressure pressurization keeping 2 of 0.056MPa in the environment of 22 DEG C, 60%RH It, the water contact angle variable quantity of the non-demoulding process face before and after lamination is 7 ° or less at this time.

4. photoresist according to any one of claim 1 to 3, it is characterised in that: (III) protective film not with (II) maximum height (Rz) in the face of photosensitive polymer combination layer contact is 3~30 μm.

5. photoresist according to any one of claim 1 to 3, it is characterised in that: (II) photosensitive resin composition Nitride layer contains polymer, (B) of (A) using (methyl) acrylic acid series polymeric compounds with carboxyl as main body and is able to carry out free radical The monomer of polymerization and (C) optical free radical producing agent.

6. photoresist according to claim 4, it is characterised in that: (II) photosensitive polymer combination layer contains (A) Using (methyl) acrylic acid series polymeric compounds with carboxyl as the polymer of main body, (B) be able to carry out free radical polymerization monomer, And (C) optical free radical producing agent.

7. a kind of forming method of corrosion-resisting pattern, it is characterised in that the following steps are included: by will be according to claim 1 in 6 (III) of described in any item photoresists protects film stripping, and by (II) photosensitive polymer combination of photoresist Being depressed into surface layer by layer has on the processed substrate of metal film, and (II) photoresist group is formed on the processed substrate Close nitride layer；And

(II) photosensitive polymer combination layer on the processed substrate is exposed, is developed and forms corrosion-resisting pattern.

8. a kind of forming method of conductive pattern, it is characterised in that the following steps are included: by will be according to claim 1 in 6 (III) of described in any item photoresists protects film stripping, and by (II) photosensitive polymer combination of photoresist Being depressed into surface layer by layer has on the processed substrate of metal film, and (II) photoresist group is formed on the processed substrate Close nitride layer；

(II) photosensitive polymer combination layer on the processed substrate is exposed, is developed and forms corrosion-resisting pattern；And

The metal film on the processed substrate for being formed with the corrosion-resisting pattern is etched or plating, it will be described anti- The removing of corrosion figure case.