CN107710074A

CN107710074A - Solder mask composition, envelope, the manufacture method of coated printed wiring board, the manufacture method of envelope and coated printed wiring board

Info

Publication number: CN107710074A
Application number: CN201680036454.1A
Authority: CN
Inventors: 樋口伦也; 丸泽尚; 荒井贵
Original assignee: Goo Chemical Industries Co Ltd
Current assignee: Goo Chemical Industries Co Ltd
Priority date: 2015-06-24
Filing date: 2016-06-21
Publication date: 2018-02-16
Anticipated expiration: 2036-06-21
Also published as: WO2016208187A1; JPWO2016208187A1; KR20180002887A; CN107710074B; TWI628511B; JP6232168B2; TW201723653A; KR101943934B1

Abstract

The solder mask composition of the present invention contains：The Cristalline epoxy resin (D) and blue dispersions (E) of more than 130 DEG C of photopolymerizable compound (B), Photoepolymerizationinitiater initiater (C), fusing point containing carboxy resin (A), selected from one or more of photopolymerization monomer and photopolymerizing prepolymers.

Description

Solder mask composition, envelope, coated printed wiring board, envelope manufacture method and by Cover the manufacture method of printed wiring board

Technical field

The present invention relates to solder mask composition, envelope, coated printed wiring board, the manufacture method of envelope and coated printing cloth The manufacture method of line plate.

Background technology

Short circuit during in order to protect wiring, prevent that part from installing etc., forms the envelopes such as solder mask layer on printed wiring board. In addition, mark the word for representing product information etc., symbol etc. in printed wiring board sometimes.

The excellent coated wiring plate of identification as mark, it is known to the second quilt is sequentially formed with printed wiring board The coated wiring plate (Japanese Patent No. 5643416) of film and the first envelope.Second envelope plays function as dyed layer.First quilt Film possesses first area and the translucency second area higher than first area.First envelope is by the photonasty containing organic compound Envelope formation formed with composition, the organic compound has specific fusing point and does not have optical polymerism.In this case, only It is partly different to forming light exposure when the film formed with composition is exposed by envelope by making, it becomes possible to produce Possesses the first envelope of first area and second area.

It is coated at this in wiring plate, for example, the first envelope (solder mask layer) is containing viridescent the colouring agent, (resistance of the second envelope Welding flux layer) in the case of the colouring agent containing black, the appearance color of first area looks like green, the outward appearance of second area Color is mixed by the color (green) of the first envelope and the color (black) for the second envelope seen through the first envelope, is seen Get up is black or dirty-green.Thus, the difference of first area and second area can be clearly recognized, the identification of mark becomes It is high.

However, for the coated wiring plate described in patent document 1, due to being formed on printed wiring board by first Two layers of envelope that envelope and the second envelope are formed, so causing the reduction of productivity ratio.Further, since the quilt of covering printed wiring board The overall thickness of film is thicker, so when making coated wiring plate, exposure (UV light) is difficult to fully support from the top layer of two layers of envelope Up to deep.As a result, the solidification of envelope may become insufficient, the adaptation of printed wiring board and two layers of envelope may not fill Point.

The content of the invention

The present invention is to carry out in view of the foregoing, and its object is to provide only light exposure part during by making exposure Ground difference can just produce possess even individual layer also the solder mask composition of the envelope of the mark with excellent identification, by The envelope of solder mask composition making, the coated printed wiring board for possessing the envelope, the manufacture method of envelope and coated printing The manufacture method of wiring plate.

The solder mask composition that the mode of the present invention is related to contains：Containing carboxy resin (A), selected from photopolymerization monomer More than 130 DEG C of photopolymerizable compound (B), Photoepolymerizationinitiater initiater (C), fusing point with one or more of photopolymerizing prepolymers Cristalline epoxy resin (D) and blue dispersions (E).

The envelope that the mode of the present invention is related to is made up of the solidfied material of above-mentioned solder mask composition, including first area The high second area with the above-mentioned first area of light transmittance ratio.

The coated printed wiring board that the mode of the present invention is related to possesses printed wiring board and above-mentioned envelope.Above-mentioned printing Wiring plate possesses insulating barrier and the copper wiring on above-mentioned insulating barrier.It is above-mentioned to cover above-mentioned insulating barrier and above-mentioned cloth Line.

The manufacture method for the envelope that the mode of the present invention is related to includes following process：＜ a ＞ are formed by above-mentioned solder resist The process for the film that composition is formed, the process that above-mentioned film is exposed by ＜ b ＞, and ＜ c ＞ pass through above-mentioned after heating exposure Film and the process for forming envelope.In above-mentioned ＜ b ＞ processes, to the Part I irradiation light in above-mentioned film, to above-mentioned film In the Part II different from above-mentioned Part I irradiation light or do not shone in a manner of light exposure is lower than above-mentioned Part I Light is penetrated, in above-mentioned ＜ c ＞ processes, makes to produce bubble in above-mentioned Part I by using heating, so as to be formed in above-mentioned envelope Bubble is contained in first area and second area, above-mentioned first area, the above-mentioned second area not ratio of bubbles or bubble ratio Above-mentioned first area is low.

The manufacture method for the coated printed wiring board that the mode of the present invention is related to includes following process：

＜ d ＞ by possess insulating barrier and printed wiring board that copper on above-mentioned insulating barrier connects up on in covering The mode for stating insulating barrier and above-mentioned wiring configures the solder mask composition that either type is related in the 1st~the 4th, so as to form film Process,

The process that above-mentioned film is exposed by ＜ e ＞,

＜ f ＞ alkaline-based developers by the process of the above-mentioned painting film development after exposure, and

＜ g ＞ form the process of above-mentioned envelope by heating the above-mentioned film after developing.

In above-mentioned ＜ e ＞ processes, to the Part I irradiation light in above-mentioned film, in above-mentioned film with above-mentioned first The different Part II in part irradiation light in a manner of light exposure is lower than above-mentioned Part I,

In above-mentioned ＜ g ＞ processes, make to produce bubble in above-mentioned Part I by using heating, so as in above-mentioned envelope shape Into first area and second area, bubble is contained in above-mentioned first area, the above-mentioned second area not ratio of bubbles or bubble It is lower than above-mentioned first area.

According to the present invention, the only light exposure by being exposed and making to the film formed by solder mask composition during exposure It is partly different, it becomes possible to even if producing the envelope possessed for the individual layer still mark with excellent identification.

Brief description of the drawings

Fig. 1 is the manufacture for representing envelope and the envelope printed wiring board for possessing envelope in an embodiment of the invention The brief sectional view of method.

Fig. 2 is the manufacture for representing envelope and the envelope printed wiring board for possessing envelope in an embodiment of the invention The brief sectional view of method.

Fig. 3 is the manufacture for representing envelope and the envelope printed wiring board for possessing envelope in an embodiment of the invention The brief sectional view of method.

Embodiment

Hereinafter, embodiments of the present invention are illustrated.Should illustrate, in this specification, sometimes by acryloyl group and/ Or methylacryloyl is expressed as (methyl) acryloyl group.In addition, acrylate and/or methacrylate are expressed as sometimes (methyl) acrylate.In addition, acrylic acid and/or methacrylic acid are expressed as (methyl) acrylic acid sometimes.

{ solder mask composition }

The solder mask composition of present embodiment contains：Containing carboxy resin (A), selected from photopolymerization monomer and optical polymerism The crystallinity ring of more than 130 DEG C of photopolymerizable compound (B), Photoepolymerizationinitiater initiater (C), the fusing point of one or more of prepolymer Oxygen tree fat (D) and blue dispersions (E).

If forming film by the solder mask composition of present embodiment, and the film is exposed and makes the exposure When light exposure it is partly different, even if can then be formed with for the excellent mark of individual layer still identification envelope.If Possess and form envelope on the printed wiring board of copper wiring, then the identification marked is especially excellent.

The composition of solder mask composition is described in more detail.

[(A) containing carboxy resin]

The developability of alkaline solution, i.e. alkali can be assigned to the film formed by solder mask composition containing carboxy resin (A) Property developability.

((A1) containing carboxy resin)

Containing carboxy resin (A) can also contain with optical polymerism functional group containing carboxy resin (A1) (hereinafter also referred to as (A1) composition).Optical polymerism functional group is, for example, ethylenic unsaturated group.

(A1) composition can for example contain the resin (hereinafter referred to as the first resin (a)) with following structures, the structure Be make at least one in the above-mentioned epoxy radicals in a molecule in the epoxide (a1) with the epoxy radicals of more than two and With carboxyl ethylenically unsaturated compounds (a2) reaction, further addition in polybasic carboxylic acid and its acid anhydrides at least one The structure that kind compound (a3) forms.

Epoxide (a1) can for example contain selected from least one of following compounds compound:Cresol novolac is clear Paint shaped epoxy resin, phenol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-A phenolic Type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl-type epoxy resin, isocyanuric acid three contract Water glyceride, alicyclic epoxy resin, bisphenol fluorene type epoxy resin and the ethylenic insatiable hunger comprising the compound with epoxy radicals With the polymer of compound.

Epoxide (a1) can contain the polymer of ethylenically unsaturated compounds (p), the ethylenic unsaturationization Compound (p) contains the compound (p1) for possessing epoxy radicals.Original for the synthesis of the polymer of ethylenically unsaturated compounds (p) Material can also contain the compound (p1) for possessing epoxy radicals and not possess ring only containing the compound (p1) for possessing epoxy radicals The compound (p2) of epoxide.

The compound (p1) for possessing epoxy radicals can contain the compound in appropriate polymer and prepolymer.Specifically For, the compound (p1) for possessing epoxy radicals can contain the epoxycyclohexyl derivative species selected from acrylic acid, methacrylic acid Epoxycyclohexyl derivative species, the alicyclic epoxy derivative of acrylate, the alicyclic epoxy derivative of methacrylate, third The compound of one or more of olefin(e) acid Beta-methyl ethylene oxidic ester and methacrylic acid Beta-methyl ethylene oxidic ester.Especially The compound (p1) of epoxy radicals is preferably provided with containing being widely used and be readily obtained (methyl) glycidyl acrylate.

Do not possess the compound (p2) of epoxy radicals as long as can with possess the compound of epoxy radicals (p1) copolymerization chemical combination Thing.Do not possess the compound (p2) of epoxy radicals, such as the chemical combination selected from one or more of following compounds can be contained Thing：Phthalic acid 2- (methyl) acryloyloxyethyl ester, phthalic acid 2- (methyl) acryloyl-oxyethyl -2- hydroxyls Base ethyl ester, phthalic acid 2- (methyl) acryloxies propyl ester, (methyl) benzyl acrylate, neopentyl glycol benzoic ether (first Base) acrylate, to cumylphenoxy ethylene glycol (methyl) acrylate, EO be modified cresols (methyl) acrylate, ethyoxyl Change (methyl) phenyl acrylate, Nonylphenoxy polyethylene glycol (methyl) acrylate (polymerization degree n=2~17), ECH to be modified (methyl) acrylic acid benzene oxygen ester, phenoxy group diethylene glycol (methyl) acrylate, (methyl) acrylate, phenoxy group Six ethylene glycol (methyl) acrylate, phenoxy group tetraethylene glycol (methyl) acrylate, (methyl) tribromophenyl acrylate, EO change Property (methyl) tribromophenyl acrylate, EO modified bisphenol As two (methyl) acrylate, PO modified bisphenol As two (methyl) acrylic acid Ester, modified bisphenol A two (methyl) acrylate, EO modified bisphenols F bis- (methyl) acrylate, ECH are modified phthalic acid two (methyl) acrylate, trimethylolpropane benzoic ether (methyl) acrylate, EO are modified phthalic acid (methyl) propylene Acid esters, EO, PO be modified phthalic acid (methyl) acrylate, vinyl carbazole, styrene, N-phenylmaleimide, N- benzyl maleimides, 3- maleimidobenzoyl N- succinimide esters, straight-chain or the fat with side chain Race or (methyl) acrylate, (methyl) the acrylic acid hydroxyl of alicyclic (wherein, can have a part of unsaturated bond in ring) Base Arrcostab, (methyl) alkoxyalkyl acrylate and N- substituted maleimides.As N- substituted maleimide amine Class, for example, N- N-cyclohexylmaleimides etc. can be enumerated.

The compound (p2) for not possessing epoxy radicals can be further containing possessing the ethylenic of more than two not in a molecule The compound of saturated group.By using the compound, and its use level is adjusted, so as to be easily adjusted the hardness of envelope and oil Property.Possess the compound of the ethylenic unsaturated group of more than two in one molecule and can for example contain and be selected from polyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate and season penta 4 The compound of one or more of alcohol three (methyl) acrylate.

By by ethylenically unsaturated compounds (p) with such as known to solution polymerization process, emulsion polymerization polymerization It is polymerize and obtains polymer.As the concrete example of solution polymerization process, can enumerate ethylenically unsaturated compounds (p) suitable When organic solvent in, in the presence of polymerization initiator, under nitrogen environment carry out heating stirring method；And azeotropic polymerization Method.

Organic solvent for the polymerization of ethylenically unsaturated compounds (p) can for example contain selected from ketone, aromatic series The compound of one or more of hydro carbons, acetate esters and dialkyl group dihydric alcohol ethers.As ketone, for example, first and second can be enumerated Ketone, cyclohexanone etc..As aromatic hydrocarbon, for example, toluene, dimethylbenzene etc. can be enumerated.As acetate esters, for example, can enumerate Ethyl acetate, butyl acetate, cellosolve acetate, acetic acid butyl cellosolve, carbitol acetate, acetate of butyl carbitol, third Glycol monomethylether acetate etc..

Polymerization initiator for the polymerization of ethylenically unsaturated compounds (p), which can for example contain, is selected from hydroperoxides Class, dialkyl peroxide class, diacyl peroxide class, ketone peroxide class, alkyl super-acid ester class, peroxy dicarbonate The compound of one or more of the initiator of class, azo-compound and redox system.As hydroperoxide type, example Such as, di-isopropylbenzene hydroperoxide etc. can be enumerated.As dialkyl peroxide class, for example, cumyl peroxide, 2 can be enumerated, 5- dimethyl -2,5- two-(tert-butyl peroxide)-hexane etc..As diacyl peroxide class, for example, can enumerate different Bytyry peroxide etc..As ketone peroxide class, for example, methyl ethyl ketone peroxide etc. can be enumerated.As alkyl super-acid ester class, For example, tert-Butyl peroxypivalate etc. can be enumerated.As peroxy dicarbonates, for example, dicetyl peroxydicarbonate can be enumerated Diisopropyl ester etc..As azo-compound, for example, azodiisobutyronitrile etc. can be enumerated.

Ethylenically unsaturated compounds (a2) can contain the compound in appropriate polymer and prepolymer.Ethylene linkage Formula unsaturated compound (a2) can contain the compound only with an ethylenic unsaturated group.Only there is an ethylenic The compound of unsaturated group can for example contain the compound selected from one or more of following compounds：Acrylic acid, methyl Acrylic acid, crotonic acid, cinnamic acid, butanedioic acid 2- acryloyloxyethyl esters, butanedioic acid 2- methacryloyloxyethyls, adjacent benzene Dioctyl phthalate 2- acryloyloxyethyl esters, phthalic acid 2- methacryloyloxyethyls, β-acryloxypropionic acid, amber Acid propylene acyloxy ethyl ester, butanedioic acid methacryloyloxyethyl, 2- acrylic acid 3- (2- Carboxyethoxies) -3- oxygen Propyl ester, tetrahydrophthalic acid 2- acryloyloxyethyl esters, tetrahydrophthalic acid 2- methacryloyloxyethyls, hexahydro Phthalic acid 2- acryloyloxyethyl esters and hexahydrophthalic acid 2- methacryloyloxyethyls.Ethylenic insatiable hunger Can be further containing the compound for possessing multiple ethylenic unsaturated groups with compound (a2).Possess multiple ethylenic insatiable hungers Can for example contain with the compound of group selected from the polyfunctional acrylic ester and multifunctional methacrylate for possessing hydroxyl with The compound of one or more of compound obtained by dibasic acid anhydride reaction.It is used as the polyfunctional acrylic ester that possesses hydroxyl and more Function methacrylate, for example, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, three hydroxyl first can be enumerated Base propane diacrylate, trimethylolpropane dimethylacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol five Methacrylate etc..

Particularly preferred ethylenically unsaturated compounds (a2) contain at least one party in acrylic acid and methacrylic acid.The feelings Under condition, because the photoreactivity from acrylic acid and the ethylenic unsaturated group of methacrylic acid is especially excellent, so first The photoreactivity of resin (a) uprises.

For ethylenically unsaturated compounds (a2) usage amount, relative to 1 mole of the epoxy radicals of epoxide (a1), The carboxyl of preferred ethylenically unsaturated compound (a2) turns into the amount in the range of 0.4~1.2 mole, particularly preferred above-mentioned carboxyl As the amount in the range of 0.5~1.1 mole.

Compound (a3) in polybasic carboxylic acid and its acid anhydrides can for example contain more than dicarboxylic acids, ternary acid The compound of one or more of the acid anhydrides of polybasic carboxylic acid and these polybasic carboxylic acids.As dicarboxylic acids, for example, adjacent benzene can be enumerated Dioctyl phthalate, tetrahydrophthalic acid, methyl tetrahydrophthalic acid, methyl nadic acid, hexahydrophthalic acid, methyl hexahydro Phthalic acid, butanedioic acid, methylsuccinic acid, maleic acid, citraconic acid, glutaric acid, itaconic acid etc..As more than ternary acid more First carboxylic acid, for example, hexamethylene -1,2 can be enumerated, 4- tricarboxylic acids, trimellitic acid, Pyromellitic Acid, benzophenone tetracarboxylic, first Cyclohexene tetracarboxylic acid etc..

The main application target of compound (a3) is by assigning acid number to the first resin (a) so as to solder mask composition Assign the redisperse carried out using dilute alkali aqueous solution, redissolution property.The usage amount of compound (a3) is with the acid of the first resin (a) Value preferably more than 30mgKOH/g, particularly preferably more than 60mgKOH/g mode adjust.In addition, the use of compound (a3) Amount adjusts in a manner of the acid number of the first resin (a) is preferably below 160mgKOH/g, particularly preferably below 130mgKOH/g.

When synthesizing the first resin (a), the addition of epoxide (a1) and ethylenically unsaturated compounds (a2) is being carried out When the product (addition reaction product) of reaction and the addition reaction and the addition reaction of compound (a3), known side can be used Method.Such as in the addition reaction of epoxide (a1) and ethylenically unsaturated compounds (a2), by epoxide (a1) solvent solution adds ethylenically unsaturated compounds (a2), further adds thermal polymerization inhibitor and catalysis as needed Agent is stirred mixing, thus obtains reactive solution.By make the reactive solution conventionally preferably 60~ Reacted under 150 DEG C, particularly preferably 80~120 DEG C of reaction temperature, so as to obtain addition reaction product.Suppress as thermal polymerization Agent, hydroquinones, hydroquinone monomethyl ether etc. can be enumerated.As catalyst, tertiary amines, quaternary ammonium salt, triphenyl phasphine, three can be enumerated Benzene antimony etc..As tertiary amines, for example, benzyl dimethylamine, triethylamine etc. can be enumerated.As quaternary ammonium salt, for example, front three can be enumerated Base benzyl ammonium chloride, methyl triethyl ammonium chloride etc..

It is molten by the solvent to addition reaction product when carrying out the addition reaction of addition reaction product and compound (a3) Compound (a3) is added in liquid, further thermal polymerization inhibitor is added as needed and catalyst is stirred mixing, so as to To reactive solution.By making the reactive solution conventionally react, so as to obtain the first resin (a).Reaction condition It can be the situation identical condition with the addition reaction of epoxide (a1) and ethylenically unsaturated compounds (a2).As Thermal polymerization inhibitor and catalyst, epoxide (a1) and the ethylenic unsaturation chemical combination with carboxyl can be directly used in The compound used during the addition reaction of thing (a2).

(A1) composition can contain the second resin (b).Second resin (b) is by containing the ethylenic insatiable hunger with carboxyl It is unsaturated with a part for the carboxyl in the polymer of the ethylenically unsaturated monomers of compound and the ethylenic with epoxy radicals Obtained from compound reaction.It is unsaturated that ethylenically unsaturated monomers can also contain the ethylenic without carboxyl as needed Compound.

The ethylenically unsaturated compounds with carboxyl for obtaining the second resin (b) can contain appropriate polymer And prepolymer.Such as the ethylenically unsaturated compounds with carboxyl can contain only with ethylenic unsaturated group Compound.More specifically, the ethylenically unsaturated compounds with carboxyl can contain one kind in following compounds Compound above：Acrylic acid, methacrylic acid, ω-carboxyl-polycaprolactone (n ≈ 2) mono acrylic ester, crotonic acid, Chinese cassia tree Acid, butanedioic acid 2- acryloyloxyethyl esters, butanedioic acid 2- methacryloyloxyethyls, phthalic acid 2- acryloyl-oxies Base ethyl ester, phthalic acid 2- methacryloyloxyethyls, β-acryloxypropionic acid, butanedioic acid acryloyloxyethyl ester, Butanedioic acid methacryloyloxyethyl, 2- acrylic acid 3- (2- Carboxyethoxies) -3- oxygen propyl ester, tetrahydrochysene O-phthalic Sour 2- acryloyloxyethyl esters, tetrahydrophthalic acid 2- methacryloyloxyethyls, hexahydrophthalic acid 2- propylene Acyloxy ethyl ester and hexahydrophthalic acid 2- methacryloyloxyethyls.Ethylenically unsaturated compounds with carboxyl The compound with multiple ethylenic unsaturated groups can also be contained.More specifically, the ethylenic with carboxyl is unsaturated Compound can contain polyfunctional (methyl) acrylate with hydroxyl and compound obtained by dibasic acid anhydride reaction.These Compound can be used alone, or and with a variety of.Polyfunctional (methyl) acrylate with hydroxyl is, for example, to select From pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, trimethylolpropane diacrylate, trihydroxy methyl third One or more of alkane dimethylacrylate, Dipentaerythritol Pentaacrylate and dipentaerythritol pentamethacrylates Compound.

As long as obtain the ethylenically unsaturated compounds without carboxyl of the second resin (b) for can with carboxylic The compound that the ethylenically unsaturated compounds of base are copolymerized.Ethylenically unsaturated compounds without carboxyl can be with Contain any of the compound with aromatic rings and the compound without aromatic rings.

Compound with aromatic rings can for example contain the compound selected from one or more of following compounds：Adjacent benzene Dioctyl phthalate 2- (methyl) acryloyloxyethyl ester, phthalic acid 2- (methyl) acryloyl-oxyethyl -2- hydroxy methacrylates, Phthalic acid 2- (methyl) acryloxies propyl ester, (methyl) benzyl acrylate, neopentyl glycol benzoic ether (methyl) propylene Acid esters, cresols (methyl) acrylate, ethoxylation (methyl) are modified to cumylphenoxy ethylene glycol (methyl) acrylate, EO Phenyl acrylate, Nonylphenoxy polyethylene glycol (methyl) acrylate (n=2~17), ECH are modified (methyl) acrylic acid benzene oxygen Ester, phenoxy group diethylene glycol (methyl) acrylate, (methyl) acrylate, the ethylene glycol of phenoxy group six (methyl) third Olefin(e) acid ester, phenoxy group tetraethylene glycol (methyl) acrylate, (methyl) tribromophenyl acrylate, EO are modified (methyl) acrylic acid three Bromobenzene ester, EO modified bisphenol As two (methyl) acrylate, PO modified bisphenol As two (methyl) acrylate, (first of modified bisphenol A two Base) acrylate, EO modified bisphenols F bis- (methyl) acrylate, ECH be modified phthalic acid two (methyl) acrylate, three Hydroxymethyl-propane benzoic ether (methyl) acrylate, EO are modified phthalic acid (methyl) acrylate, EO, PO are modified adjacent benzene Dioctyl phthalate (methyl) acrylate, vinyl carbazole, styrene, vinyl naphthalene and vinyl biphenyl.

Compound without aromatic rings, which can for example contain, is selected from the straight chain either aliphatic of side chain or alicyclic (its In, can have a part of unsaturated bond in ring) (methyl) acrylate, (methyl) hydroxyalkyl acrylates, (methyl) Alkoxyalkyl acrylate；With the compound of one or more of N- substituted maleimides.Substitute Malaysia as N- Acid imide, N- N-cyclohexylmaleimides etc. can be enumerated.Compound without aromatic rings can further contain poly- second two Alcohol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, season penta Compound with the ethylenic unsaturated group of more than 2 in 1 molecules such as tetrol three (methyl) acrylate.These compounds Can be used alone one kind, or and with a variety of.These compounds are preferred in the easily hardness of regulation envelope and oiliness etc..

As for obtaining the ethylenically unsaturated compounds with epoxy radicals of the second resin (b), it is appropriate to enumerate Polymer or prepolymer.As the concrete example of the ethylenically unsaturated compounds with epoxy radicals, can enumerate acrylic acid or The epoxycyclohexyl derivative species of person's methacrylic acid；The alicyclic epoxy derivative of acrylate or methacrylate；Third Olefin(e) acid Beta-methyl ethylene oxidic ester, methacrylic acid Beta-methyl ethylene oxidic ester etc..These compounds can be used alone one kind, Or and with a variety of.Particularly preferably use and be widely used and be readily obtained (methyl) glycidyl acrylate.

(A1) composition can contain the 3rd resin (c).3rd resin (c) is containing the ethylenic unsaturationization with carboxyl Compound and with hydroxyl ethylenically unsaturated compounds ethylenically unsaturated monomers polymer in hydroxyl a part Or all with obtained from the compound addition with ethylenic unsaturated group and NCO.Ethylenic is unsaturated single Body can contain the ethylenically unsaturated compounds without carboxyl and hydroxyl as needed.

The ethylenically unsaturated compounds with carboxyl for obtaining the 3rd resin (c) can for example be used for above-mentioned The ethylenically unsaturated compounds with carboxyl for obtaining the second resin (b) are identical.

As the concrete example of the ethylenically unsaturated compounds with hydroxyl for obtaining the 3rd resin (c), can enumerate (methyl) hydroxyalkyl acrylates, hydroxybutyl vinyl ether, hydroxyethyl vinyl ether and N- hydroxyethyls (methyl) Acrylamide etc..As (methyl) hydroxyalkyl acrylates, for example, (methyl) acrylic acid 2- hydroxy methacrylates, (first can be enumerated Base) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxybutyls, cyclohexanedimethanol list (methyl) acrylate, neighbour Phthalic acid 2- (methyl) acryloyl-oxyethyl -2- hydroxy methacrylates, caprolactone (methyl) acrylate, polyethylene glycol (first Base) acrylate, polypropylene glycol (methyl) acrylate, trimethylolpropane two (methyl) acrylate, (the first of pentaerythrite three Base) acrylate, dipentaerythritol five (methyl) acrylate etc..

Tool as the compound with ethylenic unsaturated group and NCO for obtaining the 3rd resin (c) Style, 2- acryloyloxyethyl isocyanates can be enumerated (as concrete example, Showa Denko K. K；Trade name " Karenz AOI "), 2- methacryloxyethyls isocyanates is (as concrete example, Showa Denko K. K；Commodity Name " Karenz MOI "), methacroyloxyethoxy ethyl isocyanate is (as concrete example, Showa Denko K. K； Trade name " Karenz MOI-EG "), Karenz MOI isocyanate-terminated thing is (as concrete example, Showa electrician's strain formula meeting Society；Trade name " Karenz MOI-BM "), Karenz MOI isocyanate-terminated thing is (as concrete example, Showa electrician's strain formula Commercial firm；Trade name " Karenz MOI-BP ") and 1,1- (double acryloyloxymethyls) ethyl isocyanate) (as specific Example, Showa Denko K. K；Trade name " Karenz BEI ") etc..

(A1) the overall weight average molecular weight of composition is preferably in the range of 800~100000.Within the range, to solder resist Composition assigns especially excellent photonasty and resolution ratio.

(A1) the overall acid number of composition is preferably more than 30mgKOH/g, in this case, being assigned to solder mask composition good Developability.If the acid number is more than 60mgKOH/g, more preferably.In addition, the acid number of (A1) composition entirety is preferably Below 160mgKOH/g, in this case, the residual quantity of the carboxyl in the envelope formed by solder mask composition is reduced, maintain envelope Good electrical characteristics, electric erosion resistance and water resistance etc..If the acid number is below 130mgKOH/g, more preferably.

((A2) containing carboxy resin)

(A2) containing carboxy resin with carboxyl and without optical polymerism functional group can be contained containing carboxy resin (A) (hereinafter also referred to as (A2) composition).

(A2) the composition such as polymer containing ethylenically unsaturated monomers, the ethylenically unsaturated monomers contain with carboxylic The ethylenically unsaturated compounds of base.It is unsaturated that ethylenically unsaturated monomers can further contain the ethylenic without carboxyl Compound.

Ethylenically unsaturated compounds with carboxyl can contain appropriate polymer and prepolymer, such as can contain Only there is the compound of an ethylenic unsaturated group.More specifically, the ethylenically unsaturated compounds with carboxyl can To contain the compound selected from one or more of following compounds：Acrylic acid, methacrylic acid, ω-carboxyl-polycaprolactone (n ≈ 2) mono acrylic ester, crotonic acid, cinnamic acid, butanedioic acid 2- acryloyloxyethyl esters, butanedioic acid 2- methacryloxypropyls Base ethyl ester, phthalic acid 2- acryloyloxyethyl esters, phthalic acid 2- methacryloyloxyethyls, propenoic acid beta- Carboxylic ethyl ester, butanedioic acid acryloyloxyethyl ester, butanedioic acid methacryloyloxyethyl, 2- acrylic acid 3- (2- carboxyethoxies Base) -3- oxygen propyl ester, tetrahydrophthalic acid 2- acryloyloxyethyl esters, tetrahydrophthalic acid 2- methacryloxypropyls Base ethyl ester, hexahydrophthalic acid 2- acryloyloxyethyl esters and hexahydrophthalic acid 2- methacryloyloxyethyls. Ethylenically unsaturated compounds with carboxyl can also contain the compound with multiple ethylenic unsaturated groups.More specifically For, the ethylenically unsaturated compounds with carboxyl can contain polyfunctional (methyl) acrylate and two with hydroxyl Compound obtained by first anhydride reaction.These compounds can be used alone one kind, or and with a variety of.As with the more of hydroxyl (methyl) acrylate of function, for example, from pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, three hydroxyl first Base propane diacrylate, trimethylolpropane dimethylacrylate, Dipentaerythritol Pentaacrylate and dipentaerythritol Selected in pentamethacrylates.

As long as the ethylenically unsaturated compounds without carboxyl is can be with the ethylenic unsaturation chemical combination with carboxyl The compound that thing is copolymerized.Ethylenically unsaturated compounds without carboxyl can contain the chemical combination with aromatic rings Any of thing and compound without aromatic rings.

Compound without aromatic rings, which can for example contain, is selected from the straight chain either aliphatic of side chain or alicyclic (its In, can have a part of unsaturated bond in ring) (methyl) acrylate, (methyl) hydroxyalkyl acrylates, (methyl) Alkoxyalkyl acrylate etc.；With one or more of the N- substituted maleimides such as N- N-cyclohexylmaleimides Compound.Compound without aromatic rings can be further containing the ethylenic unsaturated group in 1 molecule with more than 2 Compound.As the compound of the ethylenic unsaturated group in 1 molecule with more than 2, for example, polyethylene glycol can be enumerated Two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, Ji Wusi Alcohol three (methyl) acrylate etc..These compounds can be used alone one kind, or and with a variety of.These compounds are easily being adjusted Save hardness and oiliness of envelope etc. preferably.

The species of the compound used to obtain (A2) composition, ratio etc. turn into appropriate with the acid number of (A2) composition The mode of value properly selects.(A2) in the range of the acid number of composition is preferably 20~180mgKOH/g, if 35~ In the range of 165mgKOH/g, then more preferably.

[photopolymerizable compound (B)]

Photopolymerizable compound (B) assigns photo-curable to solder mask composition.Photopolymerizable compound (B), which contains, to be selected from The compound of one or more of photopolymerization monomer and photopolymerizing prepolymers.

Photopolymerization monomer is for example with ethylenic unsaturated group.Photopolymerization monomer, which can for example contain, is selected from single official Can one or more of (methyl) acrylate and multifunctional (methyl) acrylate compound.As simple function (methyl) third Olefin(e) acid ester, for example, (methyl) acrylic acid 2- hydroxy methacrylates etc. can be enumerated.As multifunctional (methyl) acrylate, for example, can Enumerate diethylene glycol two (methyl) acrylate, trimethylolpropane two (methyl) acrylate, trimethylolpropane tris (first Base) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, (the first of dipentaerythritol five Base) acrylate, dipentaerythritol six (methyl) acrylate, 6-caprolactone modification acrylate of pentaerythrite six etc..

Photopolymerization monomer is it is also preferred that contain phosphorus-containing compound (phosphorous photopolymerizable compound).In this case, solder resist The anti-flammability of the solidfied material of composition improves.Phosphorous photopolymerizable compound can for example contain one in following compounds The compound of the kind above：2- methacryloxyethyls phosphate ester acid is (as concrete example, Kyoeisha Chemical Co., Ltd. The trade name Light ester P-1M and Light ester P-2M of system), 2- acryloyl-oxyethyl phosphate ester acids (as concrete example, the trade name Light acrylate P-1A of Kyoeisha Chemical Co., Ltd.), diphenyl -2- methyl Acryloyl-oxyethyl phosphate (as concrete example, the trade name MR-260 of big eight Industrial Co., Ltd), and Showa are high The HFA series of molecule Co. Ltd. system is (as concrete example, as dipentaerythritol acrylate and HCA addition reaction Trade name HFA -6003 and HFA-6007, the addition as caprolactone modification dipentaerythritol acrylate and HCA is anti- Answer trade name HFA ー 3003 and HFA-6127 of thing etc.).

As photopolymerizing prepolymers, can enumerate make photopolymerization monomer polymerize obtained by addition ethylenic on prepolymer The prepolymer of unsaturated group, oligomeric (methyl) acrylic ester prepolymer class etc..As oligomeric (methyl) acrylic ester prepolymer Class, for example, epoxy (methyl) acrylate, polyester (methyl) acrylate, polyurethane (methyl) acrylate, alkyd can be enumerated Resin (methyl) acrylate, organic siliconresin (methyl) acrylate, spirane resin (methyl) acrylate etc..

[Photoepolymerizationinitiater initiater (C)]

Photoepolymerizationinitiater initiater (C), which can for example contain, is selected from benzoin and its alkyl ether, acetophenones, Anthraquinones, thiophene Xanthones, benzophenone, xanthene ketone, the compound of nitrogen atom, Alpha-hydroxy alkylbenzene ketone, alpha-aminoalkyl benzophenone In class, monoacylphosphine oxides system Photoepolymerizationinitiater initiater, acylphosphanes system Photoepolymerizationinitiater initiater and oxime ester system Photoepolymerizationinitiater initiater More than one composition.As acetophenones, for example, acetophenone, benzil dimethyl ketal etc. can be enumerated.As Anthraquinones, For example, 2-methylanthraquinone etc. can be enumerated.As thioxanthene ketone class, for example, 2,4- dimethyl thioxanthones, 2,4- diethyls can be enumerated Base thioxanthones, ITX, ITX, 2,4- diisopropylthioxanthones etc..As benzophenone Class, for example, benzophenone, 4- benzoyls -4 '-methyldiphenyl thioether etc. can be enumerated.As xanthene ketone, for example, can lift Go out 2,4- diisopropyl xanthones etc..As the compound of nitrogen atom, for example, 2- methyl isophthalic acids-[4- (first sulphur can be enumerated Base) phenyl] -2- morpholinyl -1- acetone etc..As Alpha-hydroxy alkylbenzene ketone, for example, 1- hydroxy-cyclohexans can be enumerated Base-phenvl-methanone, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 1- [4- (2- '-hydroxyethoxies Base)-phenyl] -2- hydroxy-2-methyl -1- propane -1- ketone, 2- hydroxyls -1- 4- [4- (2- hydroxyls - 2- methyl-propanoyls)-benzyl] phenyl } -2- methyl-propan -1- ketone, phenylglyoxalates methyl esters etc..As α-ammonia Base alkylbenzene ketone, for example, 2- methyl isophthalic acids-(4- methyl mercaptos phenyl) -2- morpholinopropane -1- ketone, 2- can be enumerated Benzyl -2- dimethylaminos -1- (4- morpholino phenyls)-butanone -1,2- (dimethylamino) -2- [(4- first Base phenyl) methyl] -1- [4- (4- morpholinyls) phenyl] -1- butanone etc..Trigger as the photopolymerization of monoacylphosphine oxides system Agent, for example, 2 can be enumerated, 4,6- trimethylbenzoy-diphenies-phosphine oxide, 2,4,6- trimethylbenzoyls-second Base-phenyl-phosphinate etc..As acylphosphanes system Photoepolymerizationinitiater initiater, for example, double-(2,4,6- trimethylbenzenes can be enumerated Formoxyl)-phenyl phosphine oxide, double-(2,6- dichloro-benzoyls base) phenyl phosphine oxide, double-(2,6- dichloro-benzoyls Base) -2,5- 3,5-dimethylphenyls phosphine oxide, double-(2,6- dichloro-benzoyls base) -4- propylphenylphosphine oxides, it is double-(2, 6- dichloro-benzoyls base) -1- naphthyls phosphine oxide, double-(2,6- Dimethoxybenzoyls) phenyl phosphine oxide, it is double-(2, 6- Dimethoxybenzoyls) -2,4,4- trimethylpentylphosphine oxides, double-(2,6- Dimethoxybenzoyls) -2, 5- 3,5-dimethylphenyls phosphine oxide, (2,5,6- trimethylbenzoyls) -2,4,4- trimethylpentylphosphine oxides etc..As oxime Ester system Photoepolymerizationinitiater initiater, for example, can enumerate 1- [4- (thiophenyl)] -1,2- octanediones 2- (О-benzoyl oxime), 1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases]-ethyl ketone 1- (О-acetyl oxime) etc..It is special Not preferred Photoepolymerizationinitiater initiater (C), which is contained, is selected from Alpha-hydroxy alkylbenzene ketone, alpha-aminoalkyl benzophenone class, thioxanthene ketone class and acyl group Composition of more than two kinds in phosphine oxide system Photoepolymerizationinitiater initiater.

[Cristalline epoxy resin (D)]

Cristalline epoxy resin (D) easily forms bubble in the envelope formed by solder mask composition.

The fusing point of Cristalline epoxy resin (D) is more than 130 DEG C, preferably 138 DEG C~230 DEG C.

Cristalline epoxy resin (D) can contain be selected from epoxy radicals and with crystalline monomer, prepolymer and gather The compound of one or more of compound.Such compound is sold, and can be readily available.Such as Cristalline epoxy resin (D) it can contain and be selected from 1,3,5- tri- (2,3- glycidyl) -1,3,5- triazines -2,4,6 (1H, 3H, 5H)-triketone Trade name YDC-1312 (the hydroquinones type crystallinity asphalt mixtures modified by epoxy resin of (high-melting-point type), Nippon Steel ＆ Sumitomo Metal Corporation Fat), in the trade name GTR-1800 (four phenolic group ethane type Cristalline epoxy resins) of Nippon Kayaku K. K it is a kind of with On compound.

[blue dispersions (E)]

Blue dispersions (E) can assign color although being not classified as colouring agent to envelope.Solder mask composition During without colouring agent (F), envelope can utilize blue dispersions (E) to become au bleu.Also, blue dispersions (E) improve crystallization The dispersiveness of property epoxy resin (D).Therefore, in the envelope formed by solder mask composition, and without blue dispersions (E) Situation equably produces bubble compared to easily.Thereby, it is possible to produce the envelope with the excellent mark of identification.

Blue dispersions (E) can contain copper phthalocyanine sulfonate derivatives.As the specific of copper phthalocyanine sulfonate derivatives Example, trade name Solsperse5000, Solsperse12000, Solsperse22000 of Lubrizol company systems can be enumerated ( For copper phthalocyanine sulfonate derivatives) etc..

[colouring agent (F)]

The solder mask composition of present embodiment can contain colouring agent (F).Color thus, it is possible to adjust envelope, especially It is the identification that can further improve the mark when forming envelope on the printed wiring board for possessing copper wiring.It should say Bright, colouring agent (F) can contain any of pigment and dyestuff.

Colouring agent (F) can properly select according to color of the insulating barrier of printed circuit board etc., such as can contain Blue colorant, black colorant, red stain, green colourant, yellow colorants, violet colorant, orange colorant, Dark brown colouring agent etc..

Particularly preferred colouring agent (F) contains at least one party in black colorant and red stain.Thus, possessing copper When making formation envelope on the printed wiring board of wiring, the identification of the mark of envelope is especially high.

It is black colorant that black colorant, which can contain,.Be black colorant for example can contain be selected from color rope Draw the composition of one or more of (C.I.) pigment black 31 and color index (C.I.) pigment black 32.In addition, it is black colorant Agent in addition to above-mentioned composition although can also contain without near infrared ray transmittance black of the color index number as system " the Lumogen Black FK 4280 " and of BASF AG known to toner " in Lumogen Black FK 4281 " at least One side.

Red stain can for example contain selected from anthraquinone system red pigment, azo system red pigment, color lake system red face The composition of one or more of material, quinacridone red pigment and diketo azole series red pigment.Anthraquinone system red pigment Such as color index (C.I.) pigment Red 83, color index (C.I.) paratonere 168, color index (C.I.) paratonere can be enumerated 177th, color index (C.I.) pigment red 21 6 etc..By making red stain be anthraquinone system red stain, it is particularly easy to ensure The disguise for the conductor wiring that the envelope formed by solder mask composition is brought.In addition, dispersiveness and have excellent weather resistance.

Blue colorant can contain the colouring agents such as phthalocyanine system blue colorant, anthraquinone system blue colorant.

Green colourant can for example contain selected from phthalocyanine system green colourant, anthraquinone system green colourant, be green The colouring agent of one or more of colouring agent and the substituted or unsubstituted phthalocyanine compound of metal.As having more for green colourant The example of body, pigment Green 7, pigment green 36 etc. can be enumerated.

[other compositions]

Solder mask composition can be less than 130 DEG C of Cristalline epoxy resin containing fusing point.Fusing point is less than 130 DEG C of crystallization Property epoxy resin can for example contain the compound selected from one or more of following compounds：Aurification strain formula meeting is lived by Nippon Steel The trade name YSLV-80XY (bisphenol type Cristalline epoxy resin) of society, the trade name of Nippon Steel ＆ Sumitomo Metal Corporation YSLV-120TE (thioether-type Cristalline epoxy resin), bisphenol fluorene type Cristalline epoxy resin, Mitsubishi chemical Co., Ltd Trade name YX-4000 (biphenyl type Cristalline epoxy resin) and 1,3,5- tri- (2,3- glycidyl) -1,3,5- triazines - 2,4,6 (1H, 3H, 5H)-triketones (eutectic vertex type).

In addition, solder mask composition can contain amorphism epoxy resin.Amorphism epoxy resin can for example contain choosing From the compound of one or more of following compounds：Non-crystalline cresol novolak type epoxy resin (as concrete example, The trade name EPICLON N-695 of Dainippon Ink Chemicals), non-crystalline phenol novolak type epoxy resin is (as specific Example, the trade name EPICLON N-775 of Dainippon Ink Chemicals), non-crystalline phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin (as Concrete example, the trade name EPICLON N-865 of Dainippon Ink Chemicals), non-crystalline bisphenol A type epoxy resin is (as specific Example, the trade name jER1001 of Mitsubishi chemical Co., Ltd), non-crystalline bisphenol f type epoxy resin is (as concrete example, Mitsubishi The trade name jER4004P of KCC), non-crystalline bisphenol-s epoxy resin is (as concrete example, DIC strain formula meetings The trade name EPICLON EXA-1514 of society), non-crystalline bisphenol-A D-ring oxygen tree fat, non-crystalline hydrogenated bisphenol A type ring Oxygen tree fat, non-crystalline biphenyl phenolic resin varnish type epoxy resin and non-crystalline extraordinary two functional-types epoxy resin are (as specific Example, the trade name YL7175-500 and YL7175-1000 of Mitsubishi chemical Co., Ltd；The trade name of Dainippon Ink Chemicals EPICLON TSR-960, EPICLON TER-601, EPICLON TSR-250-80BX, EPICLON 1650-75MPX, EPICLON EXA-4850, EPICLON EXA-4816, EPICLON EXA-4822 and EPICLON EXA-9726；Newly Day iron lives in the trade name YSLV-120T of aurification Co. Ltd. system) and non-crystalline bis-phenol system epoxy than that described above Resin.

Solder mask composition can contain organic solvent.Organic solvent be used for carry out solder mask composition liquid or The purpose of varnish, viscosity adjustment, the adjustment of coating, adjustment of film forming.

Organic solvent can for example contain selected from straight chain, side chain, 2 yuan or polynary alcohols, ketone, it is aromatic hydrocarbon, Petroleum fragrant family mixed solvent, dioxane, carbitol class, propylene glycol alkyl ethers, polypropylene glycol alkyl ether class, acetic acid The compound of one or more of esters and dialkyl group dihydric alcohol ethers.As straight chain, side chain, 2 yuan or polynary alcohol Class, for example, ethanol, propyl alcohol, isopropanol, hexanol, ethylene glycol etc. can be enumerated.As ketone, for example, MEK, hexamethylene can be enumerated Ketone etc..As aromatic hydrocarbon, for example, toluene, dimethylbenzene etc. can be enumerated.As petroleum fragrant family mixed solvent, for example, Swazole series (ball is apt to petrochemistry company system), Solvesso serial (Exxon Chemical company systems) etc. can be enumerated.Make For dioxane, for example, cellosolve, butyl cellosolve etc. can be enumerated.As carbitol class, for example, carbitol, butyl can be enumerated Carbitol etc..As propylene glycol alkyl ethers, for example, propylene glycol monomethyl ether etc. can be enumerated.As polypropylene glycol alkyl ether class, example Such as, dipropylene glycol methyl ether etc. can be enumerated.As acetate esters, for example, can enumerate ethyl acetate, butyl acetate, cellosolve acetate, Carbitol acetate etc..

The ratio of organic solvent in solder mask composition preferably so that formed by solder mask composition dried coating film when Organic solvent is vaporized rapidly, i.e., the mode that organic solvent is not ended up in desciccator diaphragm is adjusted.Especially with respect to solder resist Composition is overall, in the range of organic solvent is preferably 5~99.5 mass %, if in the range of 15~80 mass % then more It is preferred that.It should illustrate, the preferred proportion of organic solvent is different therefore preferably appropriate according to coating method according to coating method etc. Ground adjusts ratio.

Without departing from the purport of the present invention, then solder mask composition can further containing in addition to the mentioned component into Point.

For example, solder mask composition can contain selected from blocked isocyanate, amino resins, various thermosettings other than the above Property resin, ultra-violet solidified epoxy (methyl) acrylate, on epoxy resin resin obtained by addition (methyl) acrylic acid, And the resin of one or more of high-molecular compound.As blocked isocyanate, for example, can enumerate by caprolactam, oxime, The toluene di-isocyanate(TDI) system of the end-blockings such as malonate, morpholine diisocyanate system, IPDI system, six methylenes Blocked isocyanate of group diisocyanate system etc..As amino resins, for example, melmac, N-butyl can be enumerated Melmac, isobutylated melamine resin, butylation carbamide resin, butylated melamines urea cocondensation resin, benzene And guanamine series cocondensation resin etc..As epoxy resin, for example, bisphenol A-type, phenol novolak type, cresol novolac can be enumerated The epoxy resin etc. of varnish type, alicyclic ring type.As high-molecular compound, for example, can enumerate diallyl phthalate resin, Phenoxy resin, polyurethane resin, fluororesin etc..

When solder mask composition contains epoxide, solder mask composition can further contain and be used to make epoxy compound The curing agent of thing solidification.Curing agent can for example contain selected from imdazole derivatives, amines, hydrazine compound, phosphorus compound, acid Acid anhydride, phenol, mercaptan, lewis acid-amine complex andThe composition of one or more of salt.As imdazole derivatives, for example, Imidazoles, 2-methylimidazole, 2- ethyl imidazol(e)s, 2-ethyl-4-methylimidazole, 2- phenylimidazoles, 4- phenyl miaows can be enumerated Azoles, 1- cyano ethyl -2- phenylimidazoles, 1- (2- cyano ethyls) -2-ethyl-4-methylimidazole etc..As amination Compound, for example, dicyandiamide, benzyl dimethylamine, 4- (dimethylamino)-N, N- dimethyl benzylamine, 4- methoxies can be enumerated Base-N, N- dimethyl benzylamine, 4- methyl-N, N- dimethyl benzylamine etc..As hydrazine compound, for example, adipic acid can be enumerated Two hydrazides, sebacic dihydrazide etc..As phosphorus compound, triphenyl phasphine etc. can be enumerated.As the example of the commercially available product of these compositions, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ that four countries' chemical conversion Co. Ltd. system can be enumerated (are imidazole compound Trade name), U-CAT3503N, U-CAT3502T of San-Apro Co. Ltd. systems (are the end-blocking isocyanic acid of dimethylamine The trade name of ester compounds), DBU, DBN, U-CATSA102, U-CAT5002 (being bicyclic amidine compound and its salt).

Solder mask composition can contain adaptation imparting agent.As adaptation imparting agent, such as guanamines, methyl can be enumerated Guanamines, benzoguanamine, melamine and Striazine derivative.As Striazine derivative, for example, 2,4- diaminos can be enumerated Base -6- methacryloxyethyls-s-triazine, 2- vinyl -4,6- diaminourea-s-triazine, 2- vinyl - 4,6- diaminourea-s-triazine isocyanuric acid adduct, 2,4- diaminourea -6- methacryloxyethyls-equal three Piperazine isocyanuric acid adduct etc..

Solder mask composition can contain selected from curing accelerator, copolymer, levelling agent, adaptation imparting agent, thixotropic agent, Polymerization inhibitor, antihalation agent, fire retardant, defoamer, antioxidant, surfactant, macromolecule dispersing agent and inorganic fill out The composition of one or more of material.As copolymer, for example, organosilicon, acrylate etc. can be enumerated.Assigned as adaptation Agent, for example, silane coupler etc. can be enumerated.As inorganic filler, for example, barium sulfate, crystalline silica, nanometer two can be enumerated Silica, CNT, talcum, bentonite, aluminium hydroxide, magnesium hydroxide, magnesia, calcium carbonate etc..

Solder mask composition can be further containing known photopolymerization promoter, sensitizer etc..Such as solder resist combination Thing can contain to mesitylenic acid ethyl ester, ESCAROL 507 isopentyl ester, 2- dimethyl aminoethyl benzoic acid Ester etc..

[use level and preparation method of each composition contained in solder mask composition]

The amount of composition in solder mask composition is so that solder mask composition has photo-curable and can with alkaline solution The mode of development suitably adjusts.

If the content ratio containing carboxy resin (A) is 20~65 matter relative to the solid constituent amount of solder mask composition Measure in the range of % then preferably, if in the range of 25~55 mass % then it is further preferred that model if 30~50 mass % It is then further preferred in enclosing.It should illustrate, solid constituent amount described herein refers to except forming quilt by solder mask composition The total amount of whole compositions beyond the compositions such as the solvent to be volatilized during film.

If the content ratio of photopolymerizable compound (B) contains carboxy resin relative to what is contained in solder mask composition (A) in the range of being 5~60 mass % then preferably, if in the range of 10~50 mass % then it is further preferred that if 15~ It is then further preferred in the range of 40 mass %.

The content ratio of Photoepolymerizationinitiater initiater (C) is preferred containing carboxy resin (A) relative to containing in solder mask composition In the range of 1~50 mass %, if in the range of 3~40 mass % then it is further preferred that model if 5~25 mass % It is then further preferred in enclosing.

The content ratio of Cristalline epoxy resin (D) is excellent relative to (A) containing carboxy resin contained in solder mask composition In the range of electing 15~200 mass % as, if in the range of 20~100 mass % then it is further preferred that if 25~80 matter In the range of amount % then further preferably, if then particularly preferred in the range of 30~60 mass %.

The content ratio of blue dispersions (E) contains carboxy resin (A) preferably relative to what is contained in solder mask composition 0.1~10 mass %, more preferably 0.5~5 mass %, more preferably 1~3 mass %.If blue dispersions (E) Content ratio is that the adaptation of printed wiring board 1 described later and envelope 3 then can be further improved in above range, and energy Enough make first area 33 described later and the border of second area 34 clearer and more definite.Particularly if blue dispersions (E) contain than Example is below 5 mass %, then the adaptation of printed wiring board 1 and envelope 3 can be made especially high.If blue dispersions (E) Content ratio is below 3 mass %, then the adaptation of printed wiring board 1 and envelope 3 can be made especially high, and can make first Region 33 and the border of second area 34 are especially clear and definite.

When solder mask composition contains colouring agent (F), the content ratio of colouring agent (F) in solder mask composition relative to containing In the range of some (A) containing carboxy resin are preferably 0.01~5 mass %, if in the range of 0.05~1 mass % then more It is preferred that.If the content ratio of colouring agent (F) is in above range, the identification of the mark of envelope can be further improved. The content ratio of black colorant is preferably 0.01~5 matter relative to (A) containing carboxy resin contained in solder mask composition In the range of measuring %, if in the range of 0.05~1 mass % then more preferably.The content ratio of red stain is relative to resistance In the range of (A) containing carboxy resin contained in flux composition is preferably 0.01~5 mass %, if 0.05~1 matter In the range of amount % then more preferably.

By coordinating the raw material of solder mask composition as described above, and utilize and use such as three-roll mill, ball mill, sand The known compounding process of grinding machine etc. is kneaded, and can prepare solder mask composition.By carrying out roller to solder mask composition It is kneaded, Cristalline epoxy resin (D), the good dispersiveness of inorganic pigment can be obtained, improves identification.

In view of storage stability etc., a part for the raw material of solder mask composition can be mixed and prepare first dose, and The remainder of mixed material and prepare second dose.For example, in the raw material of solder mask composition, photopolymerization can be pre-mixed Property compound (B), organic solvent a part and Cristalline epoxy resin (D) make it scattered and prepare first dose, and mix resistance Remainder makes it scattered and prepares second dose in the raw material of flux composition.In this case, by mixing in due course First dose of necessary amount and second dose, solder mask composition can be prepared.

{ envelope and coated printed wiring board }

As shown in figure 3, coated printed wiring board possesses printed wiring board 1 and the envelope 3 formed by solder mask composition.Print Brush wiring plate 1 possesses insulating barrier and the copper wiring on insulating barrier.Coated 3 cover insulating barrier and wiring.

The color of insulating barrier is not particularly limited, for example, it is preferable to be yellow, yellow green, white, cream color, brown, orange Color, green or black.

As printed wiring board 1, for example, can enumerate phenol paper base plate (FR-1, FR-2), epoxy paper base plate (FR-3, Ivory white), epoxy glass substrate (epoxy glass fabric) (FR-4, FR-5), polyester fiberglass felt substrate (FR-6), glass it is compound Substrate (expoxy glass paper) (CEM-1), glass composite base plate (expoxy glass base material) (CEM-3), polyimides glass substrate, Polyimide film, fluororesin (Teflon (registration mark)) substrate, metal substrate (predominantly aluminium), ceramic substrate etc..

Printed wiring board 1 preferably comprises at least one party in rigid material and flexible material.

As shown in figure 3, envelope 3 possesses first area 33 and the light transmittance second area 34 higher than the first area 33.The Contain bubble in one region 33.The ratio of bubbles or bubble is not lower than first area 33 for second area 34.Therefore, first area 33 compared with second area 34 translucency it is low.

From external observation envelope 3 when, the scattering of light caused by bubble is produced in first area 33 and as partially white Tone, and be difficult to pass through and see the substrate i.e. color of printed wiring board 1.On the other hand, in second area 34 without or The scattering of light seldom caused by bubble, so readily penetrating through and seeing the color of printed wiring board 1.Therefore second area 34 Appearance color is the color that the color of second area 34 itself and the blend of colors of printed wiring board 1 form.That is, in first area The difference of outward appearance between 33 and second area 34 be present.In the present embodiment, because envelope 3 contains blue dispersions (E), institute With the appearance color (face that i.e. color of second area 34 itself and the blend of colors of printed wiring board 1 form of second area 34 Color) the tone of tone and the appearance color of first area 33 differ widely.Therefore, first area 33 and second area 34 are utilized The high mark of identification can be obtained.If envelope 3 further contains colouring agent (F), the appearance color of first area 33 and The hue difference of the appearance color of second area 34 is bigger, and the identification of mark is higher.

By so forming first area 33 and second area 34 in envelope 3, identification can be readily formed in envelope 3 High mark.Such as by the way that first area 33 is formed as into the shapes such as appropriate figure, word, so as to be formed by first area 33 Mark.Alternatively, it is also possible to by the way that second area 34 is formed as into the shapes such as appropriate figure, word, so as to by second area 34 Form mark.Therefore, while envelope 3 are formed, it is possible to implement mark.

The thickness of envelope 3 is, for example, in the range of 5~60 μm.So due to envelope 3 and existing two layers of quilt can be made The film thickness overall compared to envelope is thinner, so when making such as coated printed wiring board 1, exposure (UV light) is easily from envelope 3 top layer substantially arrives at deep, it is possible to increase the adaptation of printed wiring board 1 and envelope 3.In addition, in the thickness range, can Clearly recognize the difference of the appearance color of first area 33 and the appearance color of second area 34.

The ratio of bubble in first area 33 is preferably in the range of 3~70%, if in the range of 5~60% then More preferably.In addition, the value of the ratio relative to the bubble in the value of ratio of the bubble in first area 33, second area 34 Ratio be preferably in the range of 0~5%.

Should illustrate, the ratio of the bubble be the surface for grinding envelope 3 and the face that occurs (that is, along the quilt on the surface of envelope 3 The section of film 3) in more than 0.5 μm of major diameter bubble area ratio.The area ratio in film for example based on having 20 μ m²Surface area face in more than 0.5 μm of major diameter bubble area and export.

These ratios are in envelope described later and possess the manufacture method of coated printed wiring board of envelope, can by appropriate The light exposure of Part I 21 and the light exposure of Part II 22 during ground adjustment exposure are controlled.

{ manufacture method of envelope and the printed wiring board for possessing envelope }

The manufacture method of the envelope of 1~3 pair of present embodiment of reference picture and the printed wiring board for possessing envelope illustrates.

The manufacture method of the envelope of present embodiment includes following process：

The process that ＜ a ＞ form the film 2 being made up of the solder mask composition of present embodiment,

The process that film 2 is exposed by ＜ b ＞, and

＜ c ＞ form the process of envelope 3 by the film 2 after heating exposure.

In above-mentioned ＜ b ＞ processes, to the irradiation light of Part I 21 in film 2, in film 2 with Part I 21 not With Part II 22 not irradiation light or the irradiation light in a manner of light exposure is lower than Part I 21.

In above-mentioned ＜ c ＞ processes, make to produce bubble in Part I 21 by heating, contain gas so as to be formed in envelope 3 The first area 33 of bubble and the not ratio of bubbles or the bubble second area 34 lower than first area 33.

In the manufacture method of above-mentioned envelope, after ＜ b ＞ processes, before ＜ c ＞ processes, it can not include film with developer solution The process of 2 developments, the process that film 2 is developed with developer solution can also be included.

The manufacture method of the coated printed wiring board of present embodiment is the method for the coated printed wiring board of manufacture, including such as Lower process：

Solder resists of the ＜ d ＞ configuring present embodiment in a manner of covering insulating barrier and wiring on printed wiring board 5 Composition, so as to form the process of film 2,

The process that film 2 is exposed by ＜ e ＞,

The process that ＜ f ＞ alkaline-based developers develop the film 2 after exposure, and

＜ g ＞ form the process of envelope 3 by heating the film 2 after developing.

In above-mentioned ＜ e ＞ processes, to the irradiation light of Part I 21 in film 2, in film 2 with Part I 21 not Same Part II 22 irradiation light in a manner of light exposure is lower than Part I 21.

In above-mentioned ＜ g ＞ processes, make to produce bubble in Part I 21 by heating, contain gas so as to be formed in envelope 3 The first area 33 of bubble and the not ratio of bubbles or the bubble second area 34 lower than first area 33.

[process ＜ a ＞, ＜ d ＞]

In process ＜ a ＞, ＜ d ＞, the solder mask composition of present embodiment is coated with printed wiring board 1, as shown in Figure 1 Form the film 2 being made up of the solder mask composition of present embodiment.Now, in process ＜ d ＞, by printed wiring board The solder mask composition of present embodiment is configured in a manner of covering insulating barrier and wiring, so as to form film 2.

The coating method of solder mask composition is selected from known method, for example, infusion process, spray-on process, spin-coating method, rolling method, Curtain coating and silk screen print method.

As needed, in order that the organic solvent in solder mask composition volatilizees, heating film 2 (preparation drying).The feelings Heating-up temperature under condition is preferably the low-melting temperature than the Cristalline epoxy resin (D) in solder mask composition, especially excellent Elect as than subtracting the low temperature of the temperature after 30 DEG C by the fusing point of the Cristalline epoxy resin (D) in solder mask composition.It should add Hot temperature is, for example, in the range of 60~100 DEG C.

When forming film 2 on printed wiring board 1, carried out after being coated with solder mask composition on appropriate supporter in advance Dry and form dry film.Drying condition is preferably the low-melting temperature than the Cristalline epoxy resin (D) in solder mask composition Degree, particularly preferably the temperature than being subtracted by the fusing point of the Cristalline epoxy resin (D) in solder mask composition after 30 DEG C is low Temperature.The heating-up temperature is, for example, in the range of 60~100 DEG C.After the dry film can also being overlapped in printed wiring board 1, to dry Film and printed wiring board 1 apply pressure, dry film is transferred on printed wiring board 1 (dry film method).The dry film turns into film 2.Should In the case of, it is convenient to omit preparation drying.

[process ＜ b ＞, ＜ e ＞]

In process ＜ b ＞, ＜ e ＞, as shown in Fig. 2 by via mask 4 to the irradiation light of film 2, so as to be carried out to film 2 Exposure.Thus, photocuring reaction is efficiently carried out from the top layer of film 2 to deep.Especially because film 2 is individual layer, so with Existing two layers of envelope is thin compared to overall thickness, and film 2 is sufficiently solidified from top layer to deep.

Now, to the irradiation light of Part I 21 in film 2, to second different from Part I 21 in film 2 Points 22 in a manner of light exposure is lower than Part I 21 irradiation light.In addition, in film 2 with Part I 21 and Part II 22 different Part III 23 not irradiation light.If such irradiation light, the Part I 21 in film 2 carries out optical polymerism The photopolymerization reaction of compound.On the other hand, in Part II 22, although degree is lower than Part I 21, carries out light and gather The photopolymerization reaction of conjunction property compound.In Part III 23, without the photopolymerization reaction of photopolymerizable compound.

The light exposure of Part I 21 can be uniform, and it is mutually different can also to have light exposure in Part I 21 Some.In addition, during to 22 irradiation light of Part II, the light exposure of Part II 22 can be it is uniform, can also be The mutually different some of light exposure in Part II 22 be present.

The photopolymerization of photopolymerizable compound of the light with the irradiation by the light and in solder mask composition for exposure The mode carried out is reacted to select.Such as the light for exposing, select ultraviolet, visible ray or near infrared ray.Selection During ultraviolet, ultraviolet light source is selected from chemical lamp, low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, xenon Lamp and metal halide lamp.

Mask 4 possesses the mutually different three kinds of parts of degree of translucency.Such as mask 4 possesses：Portion with translucency Divide (hereinafter referred to as transmittance portion 41), there is part (the hereinafter referred to as low transmission portion of the translucency lower than transmittance portion 41 And the part without translucency (hereinafter referred to as non-transmissive portion 43) 42).

If be exposed via the mask 4 to film 2, to part (the corresponding with transmittance portion 41 in film 2 A part of 21) irradiation light.To part (Part II 22) corresponding with low transmission portion 42 in film 2 with than Part I 21 Low exposure light.To part (Part III 23) not irradiation light corresponding with non-transmissive portion 43 in film 2.Should Explanation, it may also be said to the part of irradiation light when Part I 21 is exposure, with than Part I 21 when Part II 22 is exposure The part of low exposure light, the part of not irradiation light when Part III 23 is exposure.Mask 4 is with Part I 21, The mode that two parts 22 and Part III 23 are located at the defined position in film 2 designs.

The light exposure of Part II 22 is relative to the scope that the ratio of the light exposure of Part I 21 is, for example, 1~75% It is interior, in the range of particularly preferably 1.2~60%.

The light exposure of Part I 21 is, for example, 100~5000mJ/cm²In the range of, the light exposure example of Part II 22 Such as it is 20~500mJ/cm²In the range of.

It should illustrate, use mask 4 in the present embodiment, but as long as can be by Part I 21, Part II 22 Control into desired value with the light exposure in Part III 23, then can also be without using mask 4 as described above.It is for example, first First do not cover via masking Part III 23 and the mask (the first mask) of Part I 21 and Part II 22 film 2 is irradiated Light.Then it is overlapping on the first mask to cover Part II 22 and do not cover the mask (the second mask) of Part I 21, via First mask and the second mask, further irradiation light.In this case, also to the irradiation light of Part I 21, to Part II 22 With the exposure light lower than Part I 21, to the not irradiation light of Part III 23.

Since the exposure at the time of film 2 being made up of solder mask composition are formed on printed wiring board 1 to film 2 During untill at the time of end, the temperature of film 2 is preferably maintained into the low-melting temperature than Cristalline epoxy resin (D) Degree.In this case, the ratio of the bubble in first area 33 is higher.Therefore the outward appearance between first area 33 and second area 34 The difference of color becomes apparent from.Speculate this be due to if in Part I 21 photopolymerizable compound polymerization before crystallinity ring Oxygen tree fat (D) melts in Part I 21, then Cristalline epoxy resin (D) becomes stable in Part I 21, therefore Even if film 2 heats Part I 21 after exposing, Part I 21 is not easy to deform.More preferably match somebody with somebody from printed wiring board 1 During untill starting at the time of putting solder mask composition at the time of the end exposure of film 2, the temperature of film 2 is maintained Than subtracting the low temperature of the temperature after 30 DEG C by the fusing point of Cristalline epoxy resin (D).

[process ＜ f ＞]

In process ＜ f ＞, the film 2 after exposure is developed with alkaline-based developer.Thus, by film 2 with it is non-transmissive Property part corresponding to portion 43 be that the Part III 23 of film 2 removes from printed wiring board 1.The Part I 21 of film 2 and Two parts 22 are stayed on printed wiring board 1.

As the concrete example of alkaline-based developer, can enumerate aqueous sodium carbonate, wet chemical, ammonium carbonate solution, Sodium bicarbonate aqueous solution, potassium bicarbonate aqueous solution, ammonium bicarbonate aqueous solution, sodium hydrate aqueous solution, potassium hydroxide aqueous solution, hydrogen Aoxidize aqueous ammonium, tetramethylammonium hydroxide aqueous solution, lithium hydroxide aqueous solution etc..As developer solution, can also use organic Amine etc..As organic amine, for example, can enumerate MEA, diethanol amine, triethanolamine, monoisopropanolamine, diisopropanolamine (DIPA), Triisopropanolamine etc..Solvent in alkaline-based developer can be only water, or the hydrophily such as water and lower alcohols is organic molten The mixture of agent.

[process ＜ c ＞, ＜ g ＞]

In process ＜ c ＞, ＜ g ＞, envelope 3 is formed by heating the film 2 after the exposure on printed wiring board 1.If Film 2 is so heated, then bubble is formed in Part I 21.Especially because the solder mask composition of present embodiment contains Blue dispersions (E), the dispersiveness of Cristalline epoxy resin (D) is high, so holding compared with the situation without blue dispersions (E) Bubble is easily formed in Part I 21.On the other hand, in Part II 22, even if heating does not also form bubble, or i.e. Just bubble is formed, the ratio of the bubble is also lower than Part I 21.Therefore, the translucency of the first area 33 in envelope 3 is than Two regions 34 are low.In addition, first area 33 easily produces the scattering of light compared with second area 34.In addition, if so heating Film 2, then when solder mask composition contains epoxide, carry out the heat cure reaction of epoxide.

Speculate and form the reasons why bubble is due to following in Part I 21 like this.

Due to Part I 21 in the exposure of film 2 illuminated light, so containing being gathered by the light of photopolymerizable compound Close the polymer of reaction generation.If heating film 2 in this condition, Cristalline epoxy resin (D) melting in film 2, Film 2 is intended to deform, but because Part I 21 contains polymer, thus be not easy to follow the melting of Cristalline epoxy resin (D) and Deformation.It is therefore contemplated that bubble is produced in Part I 21.On the other hand, Part II 22 is free of photopolymerizable compound Polymer, or the ratio of the polymer are lower than Part I.Therefore, if heating film 2, Part II 22 and first Divide 21 to compare, easily follow the melting of Cristalline epoxy resin (D) and deform.It is therefore contemplated that do not produced in Part II 22 Anger bubble, or the ratio of bubble is lower than Part I 21 in Part II 22.

The heating-up temperature of film 2 preferably meets Th >=Tm-30 relation, more preferably meets Tm+100 >=Th >=Tm-30 Relation.If the heating-up temperature of film 2 is in above range, being drawn by heat for the composition in solder mask composition can be suppressed The deterioration risen.In the formula, Th (DEG C) is the heating-up temperature of film 2, and Tm (DEG C) is the fusing point of Cristalline epoxy resin (D). Heating-up temperature is, for example, in the range of 100~200 DEG C.The other heat time is in the range of 10 minutes~5 hours.

It should illustrate, even if heating-up temperature during heating film 2 is lower than the fusing point of Cristalline epoxy resin (D), but as long as To be subtracted more than the temperature after 30 DEG C by the fusing point of Cristalline epoxy resin (D), bubble can be just produced in Part I 21.Its Reason still can not clearly know, but speculate that one of reason is that other compounds are mixed into Cristalline epoxy resin in film 2 (D), so the fusing point that Cristalline epoxy resin (D) occurs declines (freezing point decline).

Can be after film 2 be heated, to the overall exposure light of film 2.In this case, in film 2 unreacted and remain Photopolymerizable compound carries out photopolymerization reaction.

Embodiment

Hereinafter, the present invention is specifically described by embodiment.

[preparation of the solution containing carboxy resin]

It is being provided with the four-hole boiling flask of backflow cooling tube, thermometer, air leading-in conduit and mixer, is adding cresol novolac Type epoxy resin (Nippon Steel ＆ Sumitomo Metal Corporation's system, trade name YDCN-700-5, epoxide equivalent 203) 203 matter Measure part, the mass parts of diethylene glycol monoethyl ether acetic acid esters 103, the mass parts of methyl hydroquinone 0.2, the mass parts of acrylic acid 72 and triphen The mass parts of phosphine 1.5, prepare mixture.The mixture is heated under conditions of 110 DEG C of heating-up temperature, 10 hours heat times, So as to carry out addition reaction.Then, the mass parts of tetrabydrophthalic anhydride 60.8 and diethylene glycol list second are added into mixture The mass parts of ether acetic acid ester 78.9, further mixture is heated under conditions of 80 DEG C of heating-up temperature, 3 hours heat times.By This, obtains the 65 mass % solution (solution A containing carboxy resin) containing carboxy resin.

[raw material]

In addition to solution A containing carboxy resin, prepare following raw materials.

Crystallinity epoxide A：1,3,5- tri- (2,3- glycidyl) -1,3,5- triazines -2,4,6 (1H, 3H, 5H)-triketone (high-melting-point type), 150~158 DEG C of fusing point

Crystallinity epoxide B：Hydroquinones type Cristalline epoxy resin, Nippon Steel ＆ Sumitomo Metal Corporation's system Trade name YDC-1312,138~145 DEG C of fusing point

Crystallinity epoxide C：Bisphenol type Cristalline epoxy resin, the business of Nippon Steel ＆ Sumitomo Metal Corporation Name of an article YSLV-80XY, 75~85 DEG C of fusing point

Amorphism epoxide solution：By non-crystalline cresol novolak type epoxy resin, Dainippon Ink Chemicals's system Trade name EPICLON N-695 the solution that diethylene glycol monoethyl ether acetic acid esters form is dissolved in solid constituent 70%

Photopolymerizable compound：Dipentaerythritol acrylate (the trade name of Nippon Kayaku K. K KAYARAD DPHA)

Photoepolymerizationinitiater initiater A：The trade name Irgacure TPO of BASF AG

Photoepolymerizationinitiater initiater B：The trade name Irgacure 184 of BASF AG

Barium sulfate：The trade name BARIACE B30 of Sakai Chemical Industry Co., Ltd.

Fine particle silica：The trade name REOLOSIL MT-10C of Tokuyama Co. Ltd. systems

Melamine：The trade name Melamine HM of Nissan Chemical Ind Ltd

Defoamer：The trade name KS-66 of Shin-Etsu Chemial Co., Ltd

Solvent：Diethylene glycol monoethyl ether acetic acid esters

Blue dispersions：Copper phthalocyanine sulfonate derivatives, the trade name Solsperse5000 of Lubrizol company systems

Blue colorant：Phthalocyanine blue, the trade name Cyanine Blue 4940 of Dainichiseika Color Chem

Black colorant：It is black pigment, the trade name Paliogen Black S 0084 of BASF AG

Red stain：Anthraquinone system red pigment, the trade name Paliogen Red L 4045 of BASF AG

Green colourant：The trade name Lionol Green 6Y-501 of Toyo Ink manufacturing company

[embodiment and comparative example]

Raw material shown in Tables 1 and 2 described later is mixed, makes it scattered using three-roll mill, prepares solder mask composition. It should illustrate, crystallinity epoxide A, B advance with jet pulverizer or mortar is ground into average grain diameter as 20 μm Below.

In embodiment 1~12, comparative example 1~4, prepare following printed wiring boards, with silk screen print method in each printing Obtained solder mask composition is coated with wiring plate, is consequently formed the 1 of covering insulating barrier and the copper wiring on insulating barrier The film of layer.

The copper for possessing 35 μm of thickness connects up and the color of surface of insulating layer is the printed wiring board (expoxy glass of yellow Substrate)

The copper for possessing 35 μm of thickness connects up and the color of surface of insulating layer is printed wiring board (the epoxy glass of yellow green Glass substrate)

The copper for possessing 35 μm of thickness connects up and the color of surface of insulating layer is the printed wiring board of white (cream color) (glass composite base plate)

The copper for possessing 35 μm of thickness connects up and the color of surface of insulating layer is printed wiring board (the phenol paper of fulvescent Substrate)

The copper wiring and surface of insulating layer for possessing 35 μm of thickness are orange printed wiring board (polyimide substrate)

The copper for possessing 35 μm of thickness connects up and the color of surface of insulating layer is the printed wiring board (Darkening process of black Epoxy glass substrate)

In addition, in comparative example 5, the color for preparing the copper wiring and surface of insulating layer for possessing 35 μm of thickness is yellow Printed wiring board (epoxy glass substrate), the negative photosensitive solder resist ink (mixture table 2 of painting black on the printed wiring board Comparative example 5U shown in the material that forms of raw material), heated 15 minutes at 80 DEG C.It is photosensitive in copper wiring after the heating The thickness of the film of solder resist ink is 15 μm.It is coated with what is obtained on the film of the photosensitive solder resist agent ink with silk screen print method Mixture (material that the raw material shown in the comparative example 5T of mixture table 2 forms), form 2 layers of film.

By the film, preparation is heated 30 minutes at 80 DEG C.

Then, via possessing the transmittance portion with translucency, the low transmission with the translucency lower than transmittance portion Portion and the mask in non-transmissive portion without translucency, ultraviolet is irradiated to film, thus film is exposed.Through painting The light exposure for the part that the light in the transmittance portion of film is irradiated is 500mJ/cm²(first area), through the light in low transmission portion The light exposure for the part irradiated is 80mJ/cm²(second area).

60 seconds 1%Na are sprayed with 0.2MPa press atomization to the film after exposure₂CO₃The aqueous solution, developed.

Then, film is heated 1 hour at 160 DEG C.Thus in embodiment 1~12, comparative example 1~4, copper wiring On form the envelopes of 25 μ m thicks.In addition, in comparative example 5, the envelope of 40 μ m thicks is formd in copper wiring.

Should illustrate, dam remain (the residual り of ダ system), adaptation, acid resistance, alkali resistance, resistance to plating, solder heat resistance, In the assessment item of pencil hardness and electric erosion resistance, using surface of insulating layer color be yellow printed wiring board (epoxy Glass substrate) on the envelope that is formed evaluated.

[evaluation]

1. appearance color

The outward appearance of the envelope formed in each embodiment and comparative example is visually observed, is confirmed whether clearly distinguish first Region and second area.As a result, situation about clearly distinguish is evaluated as into " A ", situation about can distinguish is evaluated as " B ", unconspicuous situation will be distinguished and be evaluated as " C ".

2. dam remains

Using with 500mJ/cm²Exposure exposure position and without expose position and the μ of width 40 can be formed M, the mask of 50 μm, 60 μm and 70 μm of solder dam (solder dam), forms dam on the insulating layer.Attached in the solder dam of formation After clear, viscous adhesive tape, enter to be about to the disbonded test (adhesive tape test) of its stripping.The result of the disbonded test：In the solder dam of residual In, the most thin solder dam (dam residual) of measure line width, proceed as described below judgement.

A：The line width of most thin solder dam is 40 μm

B：The line width of most thin solder dam is 50 μm, 60 μm

C：The line width of most thin solder dam is that 70 μm or 70 μm of solder dam is stripped

3. adaptation

According to JIS D0202 test method, 100 lattice are marked with chessboard trellis on the envelope in the copper wiring of test specimen Cross line, then visually observation using transparent adhesive band progress disbonded test after stripping state.According to following Metewand evaluate its result.

A：Cross line residual rate is 81~100%

B：Cross line residual rate is 71~80%

C：Cross line residual rate is less than 70%

4. acid resistance

Test specimen is immersed at room temperature in 10% sulfuric acid after 30 minutes, visually observes the outward appearance of envelope.According to following Metewand evaluate its result.

A：No abnormality seen.

B：See slight variations.

C：See the big change such as the stripping of envelope.

5. alkali resistance

Test specimen is immersed at room temperature in 10% sodium hydroxide after 1 hour, visually observes the outward appearance of envelope.Under The metewand stated evaluates its result.

A：No abnormality seen.

B：See slight variations.

C：See the big change such as the stripping of envelope.

6. resistance to plating

Bathed using the electroless nickel plating bath of commercially available product and electroless gold plating, plating is implemented to test specimen.Observe the state of plating. Clear, viscous adhesive tape disbonded test further is carried out to the envelope after plating.Its result is evaluated according to following metewands.

A：Do not see that cosmetic variation caused by plating, the stripping caused by belt stripping test, plating ooze on envelope Any of enter situation.

B：Do not see the cosmetic variation caused by plating on envelope, but see the stripping caused by the belt stripping test of a part From.

C：Floating caused by plating is seen on envelope, it also seen that the stripping caused by belt stripping test.

7. solder heat resistance

Water-soluble flux (London Chemical company systems, trade name LONCO 3355-11) is coated with test specimen, Then the test specimen is immersed in 260 DEG C of fusion welding bath 10 seconds, next washed.Observation is repeated 3 times The outward appearance of the envelope of test specimen after this series of operation, evaluated according to following metewands.

A：No abnormality seen.

B：See slight variations.

C：See the big change such as the stripping of envelope.

8. pencil hardness

It is hard using Mitsubishi Hi-Uni (Mitsubishi's pencil company system), the pencil of the envelope based on JIS K5400 measure test specimens Degree, and evaluated.

9. electric erosion resistance

On IPC B-25 comb-type electrode B pieces, to form envelope with the situation identical condition of above-mentioned test specimen, thus To the printed wiring board of evaluation.While the bias of the comb-type electrode application DC100V to the printed wiring board of the evaluation, one While the printed wiring board of evaluation is exposed to the open air 500 hours under conditions of 40 DEG C, 90%R.H..Confirm that the evaluation after the experiment is used Printed wiring board in have it is non-migratory.Its result of evaluation as follows.

A：Migration is not confirmed completely.

B：Confirmation has some migrations.

C：Migrate.

10.L values (brightness) are evaluated

Utilize the L values (L of the first area in colour difference meter measure copper wiring_a) with the L values (L of second area_b) difference (Δ L =L_a- L_b), its result of evaluation as follows.L values (brightness) refer to JIS 8781-4：CIE 1976L specified in 2013^*a^* b^*Brightness index " L in color space^*”。

A：Δ L is more than+6

B：Δ L is+4 less than+6

C：Δ L is less than+4

11.Y values are evaluated

Utilize the Y value (Y of the first area in colour difference meter measure copper wiring_a) with the Y value (Y of second area_b) difference (Δ Y =Y_a- Y_b), its result of evaluation as follows.Y value refers to the values " Y " in XYZ colour systems.

A：Δ Y is more than+3

B：Δ Y is+1.5 less than+3

C：Δ Y is less than+1.5

[table 1]

[table 2]

According to Tables 1 and 2, in the Cristalline epoxy resin (D) using more than 130 DEG C of fusing point and blue dispersions (E) In embodiment 1~12, copper wiring is upper, on the insulating barrier of yellow, on the insulating barrier of yellow green, on the insulating barrier of white, brown Insulating barrier on and the appearance color of envelope on orange insulating barrier be evaluated as " A " or " B ".On the other hand, do not having Use the comparative example 1~3 of blue dispersions (E), the comparison without the Cristalline epoxy resin (D) using more than 130 DEG C of fusing point In example 4, on the insulating barrier of yellow, on the insulating barrier of yellow green, on the insulating barrier of white, it is on the insulating barrier of brown and orange exhausted The appearance color of envelope in edge layer is be evaluated as " C ".In comparative example 4, the appearance color on the insulating barrier of black is also commented Valency is " C ".

It is thought that due in embodiment 1~12, due to the Cristalline epoxy resin (D) using blue dispersions (E) Dispersiveness raising, compared with the situation without using blue dispersions (E), in first area, bubble more uniformly produces, i.e., The light transmittance of first area becomes lower, so the color of color i.e. insulating barrier regardless of substrate, first area with The border of second area is all obvious.In addition, in comparative example 4, due to not using the crystallinity asphalt mixtures modified by epoxy resin of more than 130 DEG C of fusing point Fat (D), so in first area almost without generation bubble, first area and second area even on the insulating barrier of black Border also unobvious.

According to Tables 1 and 2, in possessing the embodiment 1~12 of envelope obtained by the curing of coating for making 1 layer, dam residual and Adaptation is be evaluated as " A " or " B ".On the other hand, in possessing the comparative example 5 of envelope obtained by the curing of coating for making 2 layers, Dam is remained and adaptation is be evaluated as " C ".

It is thought that because the envelope of comparative example 5 is to make envelope obtained by 2 layers of curing of coating, so Film Thickness Ratio embodiment 1~12 by thickness, during exposure, film is not cured to deep fully from top layer.

According to Tables 1 and 2, in the embodiment 1~12 of more than 130 DEG C of Cristalline epoxy resin (D) of use fusing point, L Value is evaluated and Y value evaluation is be evaluated as " A " or " B ".On the other hand, the crystallinity ring of more than 130 DEG C of fusing point is not being used In the comparative example 4 of oxygen tree fat (D), the evaluation of L values and Y value evaluation are be evaluated as " C ".

It is thought that due in embodiment 1~12, by using more than 130 DEG C of Cristalline epoxy resin (D) of fusing point, Compared with the situation of Cristalline epoxy resin (D) for not using more than 130 DEG C of fusing point, in the substantial amounts of gas of first area generation Bubble, bubble reflected light, therefore the evaluation of L values and Y value are evaluated as high praise.

According to Tables 1 and 2, in the reality that the content ratio relative to the blue dispersions containing carboxy resin is 1.9 mass % Apply example 2 and for 3 mass % embodiment 8 in, in wiring made of copper, on the insulating barrier of yellow, on the insulating barrier of yellow green, white Insulating barrier on, the appearance color of envelope on the insulating barrier of brown, on orange insulating barrier and on the insulating barrier of black and Dam is remained and adaptation is be evaluated as " A ".It is 5 mass %'s in the content ratio relative to the blue dispersions containing carboxy resin In embodiment 9, on the insulating barrier of yellow, on the insulating barrier of yellow green, on the insulating barrier of white, it is on the insulating barrier of brown and orange Insulating barrier on insulating barrier on appearance color be evaluated as " B ", dam residual and adaptation is be evaluated as " A ".Relative to The content ratio of blue dispersions containing carboxy resin is 9.6 mass % embodiment 10, is 11.5 mass % embodiment 11 In, in wiring made of copper, on the insulating barrier of yellow, on the insulating barrier of yellow green, on the insulating barrier of white, on the insulating barrier of brown It is be evaluated as " B " with the appearance color on orange insulating barrier, dam residual is be evaluated as " B ".

From these results, if relative to the blue dispersions containing carboxy resin content ratio for 5 mass % with Under, then the adaptation of printed wiring board and envelope is especially high, if below 3 mass %, then first area and second area Border becomes especially clear and definite.

Blue dispersions (E) are preferably 0.1~10 matter relative to (A) containing carboxy resin contained in solder mask composition Measure %, more preferably more preferably 0.5~5 mass %, 1~3 mass %.

Claims

1. a kind of solder mask composition, it is characterised in that contain：Containing carboxy resin (A), selected from photopolymerization monomer and photopolymerization The crystallinity of more than 130 DEG C of photopolymerizable compound (B), Photoepolymerizationinitiater initiater (C), the fusing point of one or more of property prepolymer Epoxy resin (D) and blue dispersions (E).

2. solder mask composition according to claim 1, wherein, the blue dispersions (E) contain copper phthalocyanine sulfonate Derivative.

3. solder mask composition according to claim 1 or 2, wherein, containing colouring agent (F), the colouring agent (F) includes black At least one party in chromatic colorant agent and red stain.

4. according to solder mask composition according to any one of claims 1 to 3, wherein, it is described to include tool containing carboxy resin (A) There is (A1) containing carboxy resin of optical polymerism functional group.

5. a kind of envelope, it is made up of the solidfied material of solder mask composition according to any one of claims 1 to 4, includes first The high second area in first area described in region and light transmittance ratio.

6. envelope according to claim 5, wherein, bubble is contained in the first area, the second area not bubbles Or the ratio of bubble is lower than the first area.

7. a kind of coated printed wiring board, possess printed wiring board and the envelope described in claim 5 or 6,

The printed wiring board possesses insulating barrier and the copper wiring on the insulating barrier,

It is described to cover the insulating barrier and the wiring.

8. coated printed wiring board according to claim 7, wherein, the color of the insulating barrier is yellow, yellow green, white Color, cream color, brown, orange, green or black.

9. the coated printed wiring board according to claim 7 or 8, wherein, the printed wiring board include rigid material and At least one party in flexible material.

10. a kind of manufacture method of envelope, it is characterised in that including following process：

The process that ＜ a ＞ form the film being made up of solder mask composition according to any one of claims 1 to 4,

The process that the film is exposed by ＜ b ＞, and

＜ c ＞ form the process of envelope by the film after heating exposure,

In the ＜ b ＞ processes, to the Part I irradiation light in the film, in the film with the Part I Different Part II not irradiation light or the irradiation light in a manner of light exposure is lower than the Part I,

In the ＜ c ＞ processes, make to produce bubble in the Part I by using heating, so as to form the in the envelope Bubble is contained in one region and second area, the first area, and the ratio of bubbles or bubble does not compare institute to the second area It is low to state first area.

11. a kind of manufacture method of coated printed wiring board, it is characterised in that including following process：

＜ d ＞ are described exhausted by being covered on the printed wiring board for possessing insulating barrier and the copper wiring on the insulating barrier Edge layer and the mode of the wiring configure solder mask composition according to any one of claims 1 to 4, so as to form film Process,

The process that the film is exposed by ＜ e ＞,

＜ f ＞ alkaline-based developers by the process of the painting film development after exposure, and

＜ g ＞ form the process of the envelope by heating the film after developing,

In the ＜ e ＞ processes, to the Part I irradiation light in the film, in the film with the Part I Different Part II irradiation light in a manner of light exposure is lower than the Part I,

In the ＜ g ＞ processes, make to produce bubble in the Part I by using heating, so as to form the in the envelope Bubble is contained in one region and second area, the first area, and the ratio of bubbles or bubble does not compare institute to the second area It is low to state first area.