CN110320753A - Photosensitive polymer combination - Google Patents

Photosensitive polymer combination Download PDF

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Publication number
CN110320753A
CN110320753A CN201910247326.7A CN201910247326A CN110320753A CN 110320753 A CN110320753 A CN 110320753A CN 201910247326 A CN201910247326 A CN 201910247326A CN 110320753 A CN110320753 A CN 110320753A
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China
Prior art keywords
mass
reactive diluent
photosensitive polymer
polymer combination
surface tension
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CN201910247326.7A
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Chinese (zh)
Inventor
斋藤隆英
上杉尚之
木村健人
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Tamura Corp
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Tamura Corp
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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
    • 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
    • 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
    • H05K3/0094—Filling or covering plated through-holes or blind plated vias, e.g. for masking or for mechanical reinforcement
    • 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
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

The purpose of the present invention is to provide a kind of photosensitive polymer combinations, can obtain the excellent solidfied material of blind hole landfill property, film thickness uniformity, spreadability.The photosensitive polymer combination includes the photoresist of (A) containing carboxyl, (B) Photoepolymerizationinitiater initiater, (C) reactive diluent, (D) epoxide and (E) non-reactive diluent, (E) non-reactive diluent includes the organic compound at a variety of 25 DEG C for liquid phase, and surface tension when including 10 mass % or more and 60 mass % 25 DEG C below in (E) non-reactive diluent is less than the organic compound of 30.0mN/m.

Description

Photosensitive polymer combination
Technical field
The present invention relates to the photosensitive polymer combination for lining material, the lining material is for example for shape At in forming protective film on the printing distributing board of the conductor circuit pattern of rigid substrates, flexible base board.
Background technique
The circuit pattern that conductor (such as copper foil) is formed on printing distributing board, by welding electro part carrying in this The pad of circuit pattern utilizes the circuit part covered in addition to pad as the insulating film of protective film.For the insulation quilt Film requires to apply film uniformity, in order to adjust the raw material i.e. viscosity of hardening resin composition of insulating film, sometimes in curability Cooperate non-reactive diluent in resin combination.
As being combined with the hardening resin composition of non-reactive diluent, such as propose active energy ray-curable Resin combination contains 0.5~30.0 mass %, N- of (methyl) acrylamide oligourethane (A) and replaces (first Base) 10.0~69.0 mass % and 1.0~80.0 mass % (patent document 1) of non-reactive diluent (C) of acrylamide (B).
On the other hand, the via hole being not penetrated, i.e. blind hole are formed in printing distributing board sometimes.It is required that even if matching in printing Blind hole is formed in line plate, insulating film also reliably fills blind hole；The wetting resistant expansibility excellent of film has uniform film thickness Property；Circuit part in addition to pad is fully coated.
But the existing photosensitive polymer combination such as patent document 1 fills property without fully obtaining blind hole, in addition, The wetting scalability of film is insufficient, is fully coated in the film thickness uniformity of film and by the circuit part in addition to pad There is room for improvement in terms of (spreadability).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2016-113518 bulletin
Summary of the invention
Subject to be solved by the invention
In view of above-mentioned actual conditions, the purpose of the present invention is to provide can obtain blind hole landfill property, film thickness uniformity, cover The photosensitive polymer combination of the excellent solidfied material of lid.
Means for solving the problems
Embodiments of the present invention are a kind of photosensitive polymer combination, photoresist it includes (A) containing carboxyl, (B) Photoepolymerizationinitiater initiater, (C) reactive diluent, (D) epoxide and (E) non-reactive diluent, (E) are non-anti- It is the organic compound of liquid phase at 25 DEG C that answering property diluent, which includes a variety of, includes 10 in (E) non-reactive diluent Quality % or more and surface tension when 60 mass % 25 DEG C below are less than the organic compound of 30.0mN/m.
Embodiments of the present invention are a kind of photosensitive polymer combination, wherein in (E) non-reactive diluent Surface tension comprising 10 mass % or more and when 60 mass % 25 DEG C below is less than the organic compound of 28.0mN/m.
Embodiments of the present invention are a kind of photosensitive polymer combination, wherein surface tension at 25 DEG C is less than The organic compound of 30.0mN/m includes diethyl carbitol and/or dipropylene glycol monomethyl ether.
Embodiments of the present invention are a kind of photosensitive polymer combination, wherein including 20 mass % or more and 30 mass % Described (E) non-reactive diluent below.
Embodiments of the present invention are a kind of photosensitive polymer combination, wherein relative to (A) described in 100 mass parts Photoresist containing carboxyl, comprising it is more than 80 mass parts and 120 below the mass described in (E) non-reactive diluent.
The effect of invention
Embodiment according to the present invention, by containing 10 mass % or more and 60 matter in (E) non-reactive diluent Surface tension when amount % is 25 DEG C below is less than the organic compound of 30.0mN/m, and blind hole landfill can be obtained so as to be made The photosensitive polymer combination of the excellent solidfied material of property, film thickness uniformity, spreadability.
Embodiment according to the present invention, by making surface tension at 25 DEG C be less than the above-mentioned organic compound of 30.0mN/m Object includes diethyl carbitol and/or dipropylene glycol monomethyl ether, so as to obtain blind hole landfill property, film thickness uniformity, covering The solidfied material of the superior photosensitive polymer combination of property.
Specific embodiment
Next, being explained in detail to photosensitive polymer combination of the invention.Photosensitive polymer combination of the invention Be comprising the photoresist of (A) containing carboxyl, (B) Photoepolymerizationinitiater initiater, (C) reactive diluent, (D) epoxide and (E) photosensitive polymer combination of non-reactive diluent, it is liquid at 25 DEG C that above-mentioned (E) non-reactive diluent, which includes a variety of, The organic compound of phase includes 10 mass % or more and 25 DEG C below of 60 mass % in above-mentioned (E) non-reactive diluent When surface tension be less than 30.0mN/m the organic compound.
(A) containing the photoresist of carboxyl
As long as the photoresist containing carboxyl has the photoresist of free carboxyl, then spy is had no to its chemical structure It does not limit, such as the resin with 1 or more photonasty unsaturated double-bond can be enumerated.As the photonasty tree containing carboxyl Rouge, for example, the free-radical polymerised unsaturated single carboxylic of the modified by polyacid such as modified by polyacid epoxy (methyl) acrylate Be acidified epoxy resin, modified by polyacid epoxy (methyl) acrylate obtains as follows: make acrylic acid, methacrylic acid (with Down sometimes referred to as " (methyl) acrylic acid ".) etc. there are 2 or more epoxies in free-radical polymerised unsaturated monocarboxylic and 1 molecule At least part of the epoxy group of the polyfunctional epoxy resin of base is reacted, and the free radical polymerizations such as epoxy (methyl) acrylate are obtained Property unsaturated monocarboxylic epoxy resin, and then react polyacid or its acid anhydrides with the hydroxyl of generation.
As long as multi-functional epoxy resin is the epoxy resin of 2 functions or more, its chemical structure is not particularly limited.It is right The epoxide equivalent of multi-functional epoxy resin is not particularly limited, upper limit value preferred 3000g/eq, more preferable 1000g/eq, especially excellent Select 500g/eq.On the other hand, the preferred 100g/eq of the lower limit value of the epoxide equivalent of multi-functional epoxy resin, particularly preferred 200g/eq.
In multi-functional epoxy resin, such as biphenyl aralkyl-type epoxy resin, phenyl aralkyl-type can be enumerated It is epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol A type epoxy resin, double Phenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolac type ring Oxygen resin, annular aliphatic polyfunctional epoxy resin, glycidyl ester type polyfunctional epoxy resin, glycidic amine type polyfunctional Epoxy resin, hetero ring type polyfunctional epoxy resin, bis-phenol modified novolac type epoxy resin, multifunctional modified novolac type Epoxy resin etc..These epoxy resin can be used alone, and also two or more kinds may be used.
Free-radical polymerised unsaturated monocarboxylic is not particularly limited, for example, can enumerate (methyl) acrylic acid, bar Beans acid, cinnamic acid etc..These free-radical polymerised unsaturated monocarboxylics can be used alone, and also two or more kinds may be used.
The reaction method of epoxy resin and free-radical polymerised unsaturated monocarboxylic is not particularly limited, such as can be led to It crosses and epoxy resin is heated in a suitable organic solvent with free-radical polymerised unsaturated monocarboxylic and reacts it.
Polyacid or multi-anhydride and reacting by above-mentioned epoxy resin and free-radical polymerised unsaturated monocarboxylic The hydroxyl of generation reacts, so that free carboxyl is introduced photoresist.By the way that the carboxyl to dissociate is introduced photoresist, from And alkali-developable is assigned to photoresist.Polyacid or multi-anhydride are not particularly limited, in polyacid, such as can be enumerated Succinic acid, maleic acid, adipic acid, citric acid, phthalic acid, tetrahydrophthalic acid, 3- methyl tetrahydrophthalic acid, 4- out Methyl tetrahydrophthalic acid, 3- ethyl tetrahydrophthalic acid, 4- ethyl tetrahydrophthalic acid, hexahydrophthalic acid, 3- Methylhexahydrophthaacid acid, 4- methylhexahydrophthaacid acid, 3- ethyl hexahydrophthalic acid, 4- ethyl hexahydro O-phthalic Acid, methyl tetrahydrophthalic acid, methylhexahydrophthaacid acid, endo-methylene group tetrahydrophthalic acid, methylendomethylene It is polynary can to enumerate these as multi-anhydride for tetrahydrophthalic acid, trimellitic acid, Pyromellitic Acid and diglycolic acid etc. The acid anhydrides of acid.These compounds can be used alone, and also two or more kinds may be used.To free-radical polymerised unsaturated monocarboxylic The reaction method for changing epoxy resin and polyacid or multi-anhydride is not particularly limited, such as can be by will be free-radical polymerised Unsaturated monocarboxylic epoxy resin heats in a suitable organic solvent with polyacid or multi-anhydride and reacts it.
In the present invention, the above-mentioned free-radical polymerised unsaturated monocarboxylic epoxy resin of modified by polyacid can be used as containing There is the photoresist of carboxyl to use, but as needed, can by make to have 1 or more free-radical polymerised unsaturated group with The glycidyl compound of epoxy group and the free-radical polymerised unsaturated monocarboxylic epoxy resin of above-mentioned modified by polyacid Carboxyl carries out addition reaction, to further introduce free-radical polymerised unsaturated group in the photoresist containing carboxyl Group, is made the photoresist containing carboxyl for further increasing photonasty.
The photoresist containing carboxyl for further increasing photonasty is due to passing through above-mentioned glycidyl chemical combination The reaction of object and so that free-radical polymerised unsaturated group is incorporated into the free-radical polymerised unsaturated monocarboxylic of modified by polyacid The side chain of epoxy backbone, therefore photopolymerization reaction is high, can play superior photobehavior.As have 1 with The compound of upper free-radical polymerised unsaturated group and epoxy group, such as glycidyl acrylate, methyl-prop can be enumerated Olefin(e) acid ethylene oxidic ester, allyl glycidyl ether, pentaerythritol triacrylate monoglycidyl ether, pentaerythrite front three Base acrylate monoglycidyl ether etc..The above-mentioned chemical combination with 1 or more free-radical polymerised unsaturated group and epoxy group Object can be used alone, and also two or more kinds may be used.
The acid value of photoresist containing carboxyl is not particularly limited, is examined in terms of obtaining reliable alkali-developable Consider, lower limit value preferred 30mgKOH/g, particularly preferred 40mgKOH/g.On the other hand, from preventing alkaline developer from causing exposure portion From the aspect of dissolution, the preferred 200mgKOH/g of the upper limit value of the acid value of the photoresist containing carboxyl, from preventing containing carboxylic From the aspect of the reduction of the moisture-proof and insulating properties of the solidfied material of the photoresist of base, particularly preferred 150mgKOH/g.
The matter average molecular weight of photoresist containing carboxyl is not particularly limited, obdurability, machinery from solidfied material From the aspect of intensity and dry to touch, lower limit value preferably 6000, particularly preferred 7000.On the other hand, from reliably obtaining From the aspect of obtaining alkali-developable, the upper limit value of the matter average molecular weight of the photoresist containing carboxyl preferably 200000 is more excellent Select 100000, particularly preferred 50000.
Above-mentioned each raw material can be used to synthesize by above-mentioned reaction process for photoresist containing carboxyl, it is possible to use city The photoresist containing carboxyl sold.As the commercially available photoresist containing carboxyl, such as " SP- can be enumerated 4621 " (Showa Denko K. K), " ZAR-2000 ", " ZFR-1122 ", " FLX-2089 ", " ZCR-1569H " (the above are days The manufacture of this chemical drug Co., Ltd.), " CYCLOMER P (ACA) Z-250 " (Daicel-Allnex Ltd.) etc..These resins can be with It is used alone, also two or more kinds may be used.
(B) Photoepolymerizationinitiater initiater
Photoepolymerizationinitiater initiater is not particularly limited, well known Photoepolymerizationinitiater initiater is able to use.As Photoepolymerizationinitiater initiater, example Bis- (2,4,6- trimethylbenzoyl) phenyl phosphine oxides, the oxidation of 2,4,6- trimethyl benzoyl diphenyl base can such as be enumerated Phosphine, benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin n-butylether, benzoin isobutyl ether, benzene second Ketone, dimethylamino benzoylformaldoxime, 2,2- dimethoxy -2- phenyl acetophenone, 2,2- diethoxy -2- phenyl acetophenone, 2- first Base -4 '-(methyl mercapto) -2- morpholino propiophenone, 2- benzyl -2- dimethylamino -1- (4- morphlinophenyl)-butanone -1,2- Methyl-1-(4- methyl mercapto phenyl)-2- morpholino propane-1- ketone, 2- hydroxy-2-methyl-1- phenyl-propane-1- ketone, 1- hydroxyl Cyclohexyl-phenyl ketone, 4- (2- hydroxyl-oxethyl) phenyl -2- (hydroxyl -2- propyl) ketone, benzophenone, to phenyl benzophenone, 4,4 '-bis- (diethylamino) benzophenone, dichloro benzophenone, 2-methylanthraquinone, 2- ethyl hydrazine, 2- tert-butyl anthraquinone, 2- amino anthraquinones, 2- methyl thioxanthones, 2- ethyl thioxanthones, 2-chlorothioxanthone, 2,4- dimethyl thioxanthone, 2,4- diethyl thiophene Ton ketone, benzil dimethyl ketal, acetophenone dimethyl ketal, p- dimethyl amino benzoate etc..Alternatively, it is also possible to Use 1,2- acetyl caproyl, 1- [4- (thiophenyl) -2- (O- benzoyl oximes)], ethyl ketone 1- [9- ethyl -6- (2- toluyl Base) -9H- carbazole -3- base] the oximes ester system Photoepolymerizationinitiater initiater such as -1- (O- acetyl group oxime).Above-mentioned Photoepolymerizationinitiater initiater can be independent It uses, also two or more kinds may be used.
The content of Photoepolymerizationinitiater initiater is not particularly limited, relative to 100 mass parts of photoresist containing carboxyl (solid component, similarly hereinafter), preferably 5 mass parts~50 mass parts, particularly preferred 10 mass parts~30 mass parts.
(C) reactive diluent
Reactive diluent is, for example, photopolymerization monomer, be every 1 molecule at least one, preferably every 1 molecule have at least 2 The compound of a polymeric double bond.Reactive diluent keeps the photocuring of photosensitive polymer combination abundant, to be had The solidfied material of acid resistance, heat resistance, alkali resistance etc..At least there is unglazed gather with the non-reactive diluent for not having optical polymerism The aspect of conjunction property is different.
As long as reactive diluent is above compound, it is not particularly limited, such as list (methyl) third can be enumerated Multifunctional (methyl) acrylate monomer class more than olefin(e) acid ester monomer class, 2 functions etc..Specifically, such as (first can be enumerated Base) acrylic acid 2- hydroxy methacrylate, (methyl) phenoxyethyl acrylate, diglycol monotertiary (methyl) acrylate, (methyl) propylene Sour 2- hydroxyl -3- phenoxy-propyl, 1,4- butanediol two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, Neopentyl glycol two (methyl) acrylate, diethylene glycol (deg) two (methyl) acrylate, NPGA neopentyl glycol adipate two (methyl) propylene Acid esters, hydroxy new pentane acid neopentyl glycol two (methyl) acrylate, Bicvclopentyl two (methyl) acrylate, allylation hexamethylene Base two (methyl) acrylate, isocyanuric acid ester two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, two (trimethylolpropane) four (methyl) acrylate, dipentaerythritol three (methyl) acrylate, dipentaerythritol three (methyl) It is acrylate, pentaerythrite three (methyl) acrylate, epoxy pronane modification trimethylolpropane tris (methyl) acrylate, different Cyanurate three (acryloyl-oxyethyl) ester, dipentaerythritol six (methyl) acrylate, carbamate (methyl) acrylic acid Esters etc..These reactive diluents can be used alone, and also two or more kinds may be used.
The content of reactive diluent is not particularly limited, for example, containing the photosensitive of carboxyl relative to 100 mass parts Property resin, preferably 5 mass parts~100 mass parts, particularly preferred 10 mass parts~50 mass parts.
(D) epoxide
Epoxide is used to improve the crosslink density of cured coating film, obtains the cured coating film with enough intensity.As ring Oxygen compound, such as epoxy resin can be enumerated.As epoxy resin, such as the above-mentioned sense containing carboxyl can be enumerated Epoxy resin used in the preparation of photosensitiveness resin specifically can enumerate biphenyl aralkyl-type epoxy resin, phenyl aralkyl Type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol type epoxy tree Rouge, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol-A phenolic are clear Paint shaped epoxy resin, annular aliphatic polyfunctional epoxy resin, glycidyl ester type polyfunctional epoxy resin, glycidic amine type Polyfunctional epoxy resin, hetero ring type polyfunctional epoxy resin, bis-phenol modified novolac type epoxy resin, multifunctional modified phenolic Type epoxy resin etc..These epoxy resin can be used alone, and also two or more kinds may be used.
The content of epoxide is not particularly limited, the film of sufficient intensity is obtained after solidification and prevents photonasty Reduction from the aspect of, relative to 100 mass parts of photoresist containing carboxyl, preferably 10~70 mass parts are especially excellent Select 20~60 mass parts.
(E) non-reactive diluent
Non-reactive diluent is comprising being the mixture of the non-reactive diluent of liquid phase at a variety of 25 DEG C, non-reacted dilute It releases in agent, the surface tension containing 10 mass % or more and when 60 mass % 25 DEG C below is non-reacted less than 30.0mN/m's Diluent.Pass through the surface tension in non-reactive diluent containing 10 mass % or more and when 60 mass % 25 DEG C below Non-reactive diluent less than 30.0mN/m, so as to be made, that blind hole landfill property, film thickness uniformity, spreadability can be obtained is excellent The photosensitive polymer combination of different solidfied material.
As long as the non-reacted dilution contained in non-reactive diluent with 10 mass % or more and 60 mass % or less Surface tension of the agent at 25 DEG C is less than 30.0mN/m, then is not particularly limited, and surface tension at preferably 25 DEG C is less than 29.0mN/m, surface tension at particularly preferred 25 DEG C are less than 28.0mN/m.Surface tension when for 25 DEG C is less than 30.0mN/ The non-reactive diluent of m is not particularly limited the lower limit value of the surface tension, from the aspect of coating, preferably 10.0mN/m.As non-reactive diluent, such as the organic compounds such as organic solvent can be enumerated.
Surface tension when as 25 DEG C is less than the organic solvent of 30.0mN/m, such as is preferably indicated, simultaneously by following formula (1) And above-mentioned surface tension is less than the organic compound of 30.0mN/m；It is indicated by following formula (2) and above-mentioned surface tension is less than 30.0mN/m organic compound.
R1-O-R2-O-R3-O-R4 (1)
(in formula: R1、R2、R3、R4Each independently represent the alkyl of carbon atom number 1~3.)
HO-R5-O-R6-O-R7 (2)
(in formula: R5、R6、R7Each independently represent the alkyl of carbon atom number 1~3.)
Wherein, as the organic compound indicated by formula (1), (surface tension at 25 DEG C is for particularly preferred diethyl carbitol 25mN/m), as the organic compound indicated by formula (2), (surface tension at 25 DEG C is for particularly preferred dipropylene glycol monomethyl ether 27.9mN/m)。
As described above, organic compound of the surface tension less than 30.0mN/m at 25 DEG C is in whole non-reactive diluents In (non-reactive diluent total 100 mass % in) contain 10 mass % or more and 60 mass % or less.If at 25 DEG C Surface tension less than 30.0mN/m organic compound in whole non-reactive diluents be lower than 10 mass %, then cannot get Blind hole landfill property, if it exceeds 60 mass %, then cannot get spreadability.Surface tension having less than 30.0mN/m when with regard to 25 DEG C For the mixing ratio of machine compound, if in whole non-reactive diluents for 10 mass % or more and 60 mass % with Under, then it is not particularly limited, it is excellent from the aspect of further balancedly improving blind hole landfill property, film thickness uniformity, spreadability It is selected in whole non-reactive diluents as 15 mass % or more and 55 mass % hereinafter, particularly preferably all non-reacted dilute It releases in agent as 20 mass % or more and 50 mass % or less.
The mixing ratio of whole non-reactive diluents in photosensitive polymer combination is not particularly limited, from obtaining Blind hole moderately adjusts the viscous of photosensitive polymer combination while filling property, film thickness uniformity, spreadability excellent solidfied material Degree, from the aspect of drying property, preferably 10 mass % or more and 100 mass % are hereinafter, more preferable 15 mass % or more and 50 matter % is measured hereinafter, particularly preferred 20 mass % or more and 30 mass % or less.
The content of whole non-reactive diluents is not particularly limited, from obtain blind hole landfill property, film thickness uniformity, cover From the aspect of moderately adjusting the viscosity of photosensitive polymer combination, drying property while lid excellent solidfied material, relatively More than 100 mass parts of photoresist containing carboxyl, preferably 40 mass parts and 400 below the mass, more preferable 60 mass Part or more and 200 below the mass, more than particularly preferred 80 mass parts and 120 below the mass.
Surface tension when surplus in non-reactive diluent is 25 DEG C is the non-reacted dilution of 30.0mN/m or more Agent.Therefore, the surface tension in non-reactive diluent containing 40 mass % or more and when 90 mass % 25 DEG C below is The non-reactive diluent of 30.0mN/m or more.The non-reactive diluent that surface tension when to 25 DEG C is 30.0mN/m or more It is not particularly limited, surface tension when can enumerate 25 DEG C is the organic compounds such as the organic solvent of 30.0mN/m or more. Surface tension when as 25 DEG C is the organic solvent of 30.0mN/m or more, such as can enumerate diethylene glycol monoethyl ether acetic acid esters (surface tension 31mN/m at 25 DEG C), propylene-glycol diacetate (surface tension 31mN/m at 25 DEG C), diethylene glycol monoethyl ether (surface tension 31mN/m at 25 DEG C) etc..
It, being capable of basis other than above-mentioned (A) ingredient~(E) ingredient in photosensitive polymer combination of the invention Need suitably to contain various composition, for example, colorant, extender pigment, various additives (such as curing catalysts, organic filler, Thixotropy conferring agents etc.), fire retardant etc..
Colorant is pigment, pigment etc., is not particularly limited, further, it is possible to use white color agents, blue colorant, The colorant of any color such as green colourant, yellow colorants, violet colorant, black colorant, orange colorant.Upper It states in colorant, such as the inorganic systems such as the titanium oxide as white color agents, the carbon black as black colorant can be enumerated Colorant, the phthalocyanine green as green colourant and the phthalocyanine blue as blue colorant, thunder Austria Nore are blue (LIONOL BLUE) Wait phthalocyanines system, as organic systems colorants such as the anthraquinones systems such as the Chromophthal Huang of yellow colorants etc..
In extender pigment, talcum, barium sulfate, hydrophobic silica, aluminium oxide, aluminium hydroxide, cloud can be enumerated Mother, polyurethane bead etc..In various additives, mercaptobenzoxazole and its derivative, dicyandiamide (DICY) can be enumerated And its derivative, melamine and its derivative, boron trifluoride-amine complex, organic acid hydrazides, diaminomaleonitrile (DAMN) And its curing catalysts such as derivative, guanamines and its derivative, amine acid imide (AI) and polyamines etc..It, can in defoaming agent Enumerate organic silicon-type, hydrocarbon system and acrylic acid series etc..
Fire retardant is used to assign anti-flammability to the photocured product of photosensitive polymer combination.As fire retardant, such as can be with Enumerate phosphorus flame retardant.Specifically, tricresyl phosphate (chloroethyl) ester, tricresyl phosphate (2,3- bis- chloropropyl) ester, phosphoric acid can be enumerated Three (2- chloropropyl) esters, tricresyl phosphate (2,3- bromopropyl) ester, tricresyl phosphate (bromine chloropropyl) ester, phosphoric acid 2,3- dibromopropyl -2,3- The phosphorus containing halogen system such as chlorine propyl ester, tricresyl phosphate (tribromo phenyl) ester, tricresyl phosphate (dibromo phenyl) ester, tricresyl phosphate (tribromo neopentyl) ester Acid esters；The non-halogens rouge such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate Fat race phosphate；Triphenyl phosphate, tricresyl phosphate base diphenyl, di(2-ethylhexyl)phosphate (tolyl) phenylester, tricresyl phosphate (toluene) ester, Tricresyl phosphate (dimethylbenzene) ester, di(2-ethylhexyl)phosphate cresyl diphenyl phosphate, tricresyl phosphate (isopropyl phenyl) ester, p isopropylbenzoic acid base phenyl hexichol Base ester, phosphoric acid diisopropyl phenyl phenylester, tricresyl phosphate (trimethylphenyl) ester, tricresyl phosphate (tert-butyl phenyl) ester, phosphoric acid hydroxyl The non-halogens aromatic phosphoric esters such as base phenyl diphenyl, octyl diphenyl phosphate；Three (diethyl phosphinic acids) aluminium, three (Methylethyl phosphinic acids) aluminium, three (diphenyl phosphonic acid) aluminium, bis- (diethyl phosphinic acids) zinc, bis- (Methylethyl phosphinic acids) Zinc, bis- (diphenyl phosphonic acid) zinc, bis- (diethyl phosphinic acids) oxygen titaniums, four (diethyl phosphinic acids) titaniums, bis- (Methylethyl time phosphines Acid) phosphinic acids such as oxygen titanium, four (Methylethyl phosphinic acids) titaniums, bis- (diphenyl phosphonic acid) oxygen titaniums, four (diphenyl phosphonic acid) titaniums Miscellaneous -10- phospho hetero phenanthrene -10- the oxide of metal salt, 9,10- dihydro-9-oxy, diphenylacetylene phosphine oxide, triphenylphosphine oxide, Phosphine oxides based compounds such as trialkyl phosphine, three (hydroxy alkyl) phosphine oxides etc..Wherein, preferred organic phosphate system.
The manufacturing method of the photosensitive polymer combination of aforementioned present invention is not limited to specific method, such as can be With regulated proportion will after above-mentioned each components matching, at room temperature using the kneading devices such as three rollers, ball mill, sand mill or The agitating devices such as super mixing machine, planetary-type mixer are kneaded or are mixed and manufactured.In addition, before above-mentioned mixing or mixing, As needed, it can be kneaded or be pre-mixed in advance.In addition, can also first with regulated proportion by other than (E) non-reactive diluent at It after distribution is closed, is kneaded or is mixed, after resin combination is made, add (E) non-reactive diluent, further mixing or mixing.
Next, being illustrated for user's rule of the photosensitive polymer combination of aforementioned present invention.Here, first It is illustrated for forming the method for solder mask to be coated with photosensitive polymer combination of the invention on printing distributing board, institute The circuit pattern that printing distributing board has etching copper foil and formed is stated, and is provided with blind hole.
Copper foil is etched on the circuit pattern of formation, the printing distributing board provided with blind hole having, uses screen printing Method well known to brush, spray coating method, stick coating method, spreader method, scraper coating method, scraper for coating method, rolling method, gravure coating process etc. The photosensitive polymer combination manufactured as described above is coated into desired thickness, in addition, filling photonasty inside blind hole Resin combination.Next, in order to make the non-reactive diluent (such as organic solvent) in photosensitive polymer combination volatilize, The at a temperature of heating predrying in 15~60 minutes or so at 60~90 DEG C or so is carried out, makes non-reactive diluent from photonasty It volatilizees in resin combination, the surface of film is made to become tack-free state.It is bonded on the photosensitive polymer combination of coating Minus film with the pattern for making to become other than the pad of foregoing circuit pattern translucency, and from irradiate thereon ultraviolet light (such as The range of 300~400nm of wavelength).Then, by being removed non-exposed areas corresponding with above-mentioned pad with dilute alkaline aqueous solution, To make film develop.Using spray-on process, spray process etc. in developing method, as the dilute alkaline aqueous solution used, such as can arrange Enumerate the aqueous sodium carbonate of 0.5~5 mass %.Next, by using hot air circulation type drying machine etc. at 130~170 DEG C Solidify after carrying out 20~80 minutes, so as to form the cured coating film with target pattern on printing distributing board, that is, blind hole Also the solder mask of the film that is cured filling.
Embodiment
Next, the embodiment of the present invention is illustrated, as long as but it is of the invention no more than its purport, it is not limited to These examples.
Examples 1 to 6, comparative example 1~3
Cooperate each ingredient shown in the following table 1 other than non-reactive diluent with mixing ratio shown in following table 1, makes Make its mixing dispersion at room temperature with three rollers, prepares resin combination.Then, by being added in obtained resin combination Non-reactive diluent, and make its mixing dispersion as described above, to be prepared for Examples 1 to 6, make in comparative example 1~3 Photosensitive polymer combination.The use level of each ingredient shown in following table 1 is as long as no special instructions, then it represents that quality Part.It should be noted that the empty column portion of the use level in following table 1 indicates unmated.
It should be noted that the details about each ingredient in table 1,2 is as described below.
(A) containing the photoresist of carboxyl
FLX-2089: 65 mass % of solid component (resin component), diethylene glycol monoethyl ether acetic acid esters (surface tension at 25 DEG C It is a kind of modified by polyacid epoxy acrylate, and be by making acrylic acid and epoxy resin for 35 mass % of 31mN/m) At least part of epoxy group is reacted, and epoxy acrylate is obtained, and knot obtained from reacting polyacid with the hydroxyl of generation Structure.Nippon Kayaku K. K
(B) Photoepolymerizationinitiater initiater
Chemcure DETX:Nihon Siber Hegner Co., Ltd.
Irgacure 907: BASF AG
(C) reactive diluent
KRM 8296:Daicel-Allnex Ltd.
(D) epoxide
EPICRON 860:DIC Co., Ltd.
Colorant
LIONOL BLUE FG7351:TOYOCOLOR CO., LTD.
YELLOW: Qi Ba Specialty Chemicals of CHROMOPHTHAL
Extender pigment
RHC-730CLEAR: Dainichiseika Color Chem
HIGILITE H-42STV: Showa Denko K. K
Additive
DICY-7: Mitsubishi chemical Co., Ltd
Melamine: Nissan Chemical Ind Ltd
Defoaming agent
KS-66: Shin-Etsu Chemial Co., Ltd
Fire retardant
Exolit OP-935: Clariant Amada Co., Ltd.
(E) non-reactive diluent
Surface tension when HIGHSOLV EDE:25 DEG C is 25mN/m, eastern nation Chemical Co., Ltd.
Surface tension when HIGHSOLV DPM:25 DEG C is 28mN/m, eastern nation Chemical Co., Ltd.
Surface tension at EDGAC:25 DEG C is 31mN/m, Sanyo is melted into product Co., Ltd..
Test film production process
Substrate: it is provided withThe substrate in deep 70 μm of blind hole portion and thick 18 μm of the Wiring pattern of conductor
Surface treatment: acid processing (sulfuric acid solutions of 5 mass %)
Print process: silk-screen printing
Dried film thickness: 20~23 μm
Predrying: 80 DEG C, 20 minutes
Exposure: with 250mJ/cm on film2(ORC MANUFACTURING CO.,LTD.、HMW-680GW)
Development: 1 mass % aqueous sodium carbonate, developing time 60 seconds, injection pressure 0.2MPa
Solidify afterwards: 150 DEG C, 30 minutes
Assessment item
(1) blind hole landfill property
Whether filled using (× 40 times) observation photosensitive polymer combinations of optical microscopy in the test film obtained as described above Blind hole portion 100 at, calculate the blind hole portion of landfill, it is as described below to evaluate.
Blind hole portion at ◎: 100 is all landfilled.
Blind hole portion at zero: 90~99 is landfilled.
Blind hole portion at △: 80~89 is landfilled.
×: blind hole portion below is landfilled at 79.
(2) film thickness uniformity
After the cross section sealing of the cured coating film between the Wiring pattern of the test film obtained as described above, grinding, optical microphotograph is used Mirror (× 40 times) is observed with N=9, measures film thickness, as described below to evaluate.
Zero: the maximum of film thickness, minimum difference are less than 3 μm.
△: the maximum of film thickness, minimum difference are 3 μm more than and less than 5 μm.
×: the maximum of film thickness, minimum difference are 5 μm or more.
(3) spreadability
After the section sealing of the cured coating film on a Wiring pattern of the test film obtained as described above, grinding, optics is used Microscope (× 40 times) is observed with N=9, measures film thickness, as described below to evaluate.
Zero: the film thickness of the cured coating film of wiring upper edge is 15 μm or more.
△: the film thickness of the cured coating film of wiring upper edge is 10 μm more than and less than 15 μm.
×: the film thickness of the cured coating film of wiring upper edge is less than 10 μm.
It shows the results of the evaluation in following table 1.
[table 1]
As shown in table 1 like that, when 25 DEG C containing 15 mass of mass %~50 % in whole non-reactive diluents Surface tension less than 30mN/m non-reactive diluent Examples 1 to 6 in, can obtain blind hole landfill property, film thickness it is equal The excellent cured coating film of even property, spreadability.Especially by embodiment 4,5 it is found that the surface tension when being combined with 25 DEG C is When the non-reactive diluent of 25mN/m, even a small amount of mixing ratio, blind hole landfill property, uniform film thickness can be also obtained The excellent cured coating film of property, spreadability.
On the other hand, surface tension when 25 DEG C containing 0 mass of mass %~8 % in whole non-reactive diluents In the Comparative Examples 1 and 2 of non-reactive diluent less than 30mN/m, there is no blind hole landfill property, in all non-reacted dilutions In the comparative example 3 of non-reactive diluent of the surface tension less than 30mN/m when 25 DEG C containing 61 mass % in agent, do not have Obtain spreadability.
Industrial availability
Photosensitive polymer combination of the invention is excellent due to that can obtain blind hole landfill property, film thickness uniformity, spreadability Solidfied material, thus, for example on the printing distributing board with desired circuit pattern formed insulating film field in benefit It is high with value.

Claims (5)

1. a kind of photosensitive polymer combination is comprising the photoresist of (A) containing carboxyl, (B) Photoepolymerizationinitiater initiater, (C) The photosensitive polymer combination of reactive diluent, (D) epoxide and (E) non-reactive diluent, (E) the non-reaction Property diluent to include a variety of be at 25 DEG C liquid phase organic compound, include 10 matter in (E) non-reactive diluent Surface tension when measuring % or more and 60 mass % 25 DEG C below is less than the organic compound of 30.0mN/m.
2. photosensitive polymer combination according to claim 1, wherein include in (E) non-reactive diluent 10 mass % or more and surface tension when 60 mass % 25 DEG C below are less than the organic compound of 28.0mN/m.
3. photosensitive polymer combination according to claim 1 or 2, wherein surface tension at 25 DEG C is less than 30.0mN/ The organic compound of m includes diethyl carbitol and/or dipropylene glycol monomethyl ether.
4. photosensitive polymer combination described in any one of claim 1 to 3, it includes more than 20 mass % and 30 matter Measure % described (E) non-reactive diluent below.
5. photosensitive polymer combination described in any one of claim 1 to 3, wherein the institute relative to 100 mass parts State the photoresist of (A) containing carboxyl, comprising it is more than 80 mass parts and 120 below the mass described in (E) it is non-reacted dilute Release agent.
CN201910247326.7A 2018-03-29 2019-03-29 Photosensitive polymer combination Pending CN110320753A (en)

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