CN101169590A - Light solidifying heat curing resin composition and printing circuit board using the same - Google Patents
Light solidifying heat curing resin composition and printing circuit board using the same Download PDFInfo
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- CN101169590A CN101169590A CNA2007101514854A CN200710151485A CN101169590A CN 101169590 A CN101169590 A CN 101169590A CN A2007101514854 A CNA2007101514854 A CN A2007101514854A CN 200710151485 A CN200710151485 A CN 200710151485A CN 101169590 A CN101169590 A CN 101169590A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
The invention provides a white photo-curing heat-curing resin composition which can form a solder mask of high reflectance ratio when is used as a solder resist. A pattern latent image is formed accurately when light irradiates. The invention also provides a pc board with a solder mask of high reflectance ratio formed by using the white photo-curing heat-curing resin composition. The white photo-curing heat-curing resin composition is characterized in comprising: (A) aromatic nucleus-free oxatyl-containing resin, (B) photopolymerization initiating agent comprises at least one oxime ester photopolymerization initiating agent, (C) epoxy compound, (D) rutile type titanium white, and (E) thinning agent.
Description
Technical field
The present invention relates to light solidifying/heat solidifying resin composition, it is suitable as the permanent mask of printed-wiring board (PWB), develop by alkaline aqueous solution and form image in the exposure back, be heating and curing thereafter, thereby can form the soldering-resistance layer of high reflectance, and relate to the printed-wiring board (PWB) that obtains at the print circuit board surface use said composition formation soldering-resistant pattern that is formed with circuit.
Background technology
Printed-wiring board (PWB) is that the unwanted part of usually removing the Copper Foil that is bonded on the laminate by etching forms wiring, and electronic unit is configured in the place of regulation by welding.Use soldering-resistance layer in the making of this printed-wiring board (PWB) always.That is the diaphragm of the circuit when, soldering-resistance layer is as the welding electronic unit is used.When soldering-resistance layer prevents to weld in the unnecessary portions attached solder, and prevent that circuit conductor is directly exposed in the air and with oxygen, the reaction of moist composition.In addition, also play effect as the permanent diaphragm of circuit substrate.Therefore, require to have each performance such as adaptation, electrical insulating property, solder heat resistance, solvent resistance, chemical proofing.
In addition, printed-wiring board (PWB) is explored a road of miniaturization (becoming more meticulous), multiple stratification and a plateization in order to realize densification, and mounting means is also passed to surface mounting technique (SMT).Therefore, soldering-resistance layer also improve become more meticulous, the requirement of high resolution, high precision, high reliability.
As the technology of the pattern that forms this solder resist, can correctly form the photoresist method of fine pattern, particularly from the consideration of environment aspect etc., the photoresist method of alkali developable becomes main flow.
For example, patent documentation 1 and patent documentation 2 disclose a kind of make phenolic resin varnish type epoxy resin and unsaturated monocarboxylic reaction, the addition multi-anhydride obtains reaction product again, but with the liquid etching resisting ink composition of this reaction product as the alkaline aqueous solution development of base polymer.
On the other hand, increased in recent years the backlight liquid crystal display of portable terminal device, PC, TV etc. and the light source of ligthing paraphernalia etc. directly have been installed to the purposes that covers on the printed-wiring board (PWB) that is formed with soldering-resistance layer with the low luminous light emitting diode (LED) of electric power.
Therefore, utilize the light of LED well, require to have the printed-wiring board (PWB) of the soldering-resistance layer of high reflectance for efficient.
Patent documentation 1: Japan special fair 1-54390 number
Patent documentation 2: Japan special fair 7-17737 number
Summary of the invention
Invent problem to be solved
The soldering-resistance layer of high reflectance is considered to use the light solidifying/heat solidifying resin composition of white and forms.Yet the light solidifying/heat solidifying resin composition of white is because himself have high reflectivity, so during irradiates light, can not fully absorb it and solidify needed light, is difficult to correctly form the pattern sub-image, and resolving power is poor.
Therefore the object of the present invention is to provide a kind of light solidifying/heat solidifying resin composition of white, it is the light solidifying/heat solidifying resin composition that can form the soldering-resistance layer of high reflectance, can correctly form the pattern sub-image during irradiates light, and the printed-wiring board (PWB) that a kind of soldering-resistance layer with high reflectance that uses this white light solidifying/heat solidifying resin composition and form is provided.
The method that is used to deal with problems
Found that of people's further investigation of the present invention, by comprising at least a kind of oxime ester is that Photoepolymerizationinitiater initiater is as Photoepolymerizationinitiater initiater, even the resin combination of the white that reflectivity is high also can correctly form the pattern sub-image when irradiates light, has good resolving power.In addition, by use do not have aromatic rings contain carboxy resin and as the Titanium Dioxide Rutile Top grade of Chinese white, deterioration (flavescence) can be suppressed, high reflectance can be reached for a long time always by the photolytic activity resin that cause, that photoconduction causes of the aromatic rings of resin and titanium dioxide.
Promptly, according to the 1st side of the present invention, a kind of light solidifying/heat solidifying resin composition of white can be provided, it is characterized in that it comprises: what (A) do not have aromatic rings contains carboxy resin, (B) Photoepolymerizationinitiater initiater that to comprise at least a kind of oxime ester be Photoepolymerizationinitiater initiater, (C) epoxy compound, (D) Titanium Dioxide Rutile Top grade and (E) thinning agent.
In addition, according to other side of the present invention, can provide a kind of printed-wiring board (PWB), the light solidifying/heat solidifying resin composition of its white by using the 1st side at the print circuit board surface that is formed with circuit forms soldering-resistance layer and obtains.
The effect of invention
A kind of light solidifying/heat solidifying resin composition of white can be provided according to the present invention, this light solidifying/heat solidifying resin composition is by using as solder resist, can form the soldering-resistance layer of high reflectance, can correctly form the pattern sub-image during irradiates light, and have good resolving power, and provide a kind of printed-wiring board (PWB) with the soldering-resistance layer that uses this light solidifying/heat solidifying resin composition and form with high reflectance.
Embodiment
Below, illustrate in greater detail the present invention.
The light solidifying/heat solidifying resin composition of white of the present invention comprises: what (A) do not have aromatic rings contains carboxy resin, (B) Photoepolymerizationinitiater initiater that to comprise at least a kind of oxime ester be Photoepolymerizationinitiater initiater, (C) epoxy compound, (D) Titanium Dioxide Rutile Top grade and (E) thinning agent.
The carboxy resin that contains that does not have aromatic rings as (A), so long as do not have the resin with carboxyl of aromatic rings, just can use photosensitive in the carboxy resin any that contain that contains carboxy resin and do not have photosensitive unsaturated double-bond that himself has photosensitive unsaturated double-bond more than 1, be not limited to specific material.The carboxy resin that contains that (A) so do not have aromatic rings preferably contains carboxy resin by what aliphatics polymerization monomer generated.In addition, in the resin of enumerating especially below, can suitably use material with aromatic rings (oligomer or polymkeric substance all can).That is,
(1) by unsaturated carboxylic acid with have a carboxy resin that contains that the copolymerization of the compound of unsaturated double-bond obtains;
(2) contain the photosensitive carboxy resin that contains that the compound reaction that has oxirane ring and ethylenically unsaturated group in carboxyl (methyl) acrylate based copolymerized resin and 1 molecule obtains by making;
(3) make compound that has 1 epoxy radicals and unsaturated double-bond in 1 molecule respectively and compound copolymerization with unsaturated double-bond, make the reaction of this multipolymer and unsaturated monocarboxylic, the secondary hydroxyl that is generated and saturated or unsaturated multi-anhydride react and obtain the photosensitive carboxy resin that contains;
(4) make the reaction of hydroxyl polymer-containing and saturated or unsaturated multi-anhydride, the compound that has 1 epoxy radicals and unsaturated double-bond in the carboxylic acid that makes generation then and 1 molecule respectively reacts and obtains the resin of photosensitive hydroxyl and carboxyl.
In the middle of these, the photosensitive carboxy resin that contains of preferably above-mentioned (2), that is, containing the copolymerization with carboxyl that the reaction that has the compound of oxirane ring and ethylenically unsaturated group in carboxyl (methyl) acrylate based copolymerized resin and (b) 1 molecule obtains by (a) is resin.
(a) containing carboxyl (methyl) acrylate based copolymerized resin obtains by making the compound copolymerization that has 1 unsaturated group and 1 carboxyl in (methyl) acrylate and 1 molecule at least.(methyl) acrylate as constituting copolymer resins (a) can list (methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate; Hydroxyl (methyl) esters of acrylic acids such as (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid hydroxy butyl ester, caprolactone modification (methyl) acrylic acid 2-hydroxyl ethyl ester; Glycol modification (methyl) esters of acrylic acids such as methoxyl diethylene glycol (methyl) acrylate, ethoxy diethylene glycol (methyl) acrylate, different octyloxy diethylene glycol (methyl) acrylate, methoxyl triethylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate etc.These can use separately, also can mix more than 2 kinds and use.In addition, in this manual, (methyl) acrylate is meant the term of general name acrylate and methacrylate, and other similar expression too.
In addition, as the compound that has 1 unsaturated group and at least 1 carboxyl in 1 molecule, can list between acrylic acid, methacrylic acid, unsaturated group and the carboxylic acid by the modification unsaturated monocarboxylic of chain elongation, for example (methyl) propenoic acid beta-carboxylic ethyl ester, 2-acrylyl oxy-ethyl succinic acid, 2-acrylyl oxy-ethyl hexahydrophthalic acid, by interior material that comprises 2 above carboxyls in the unsaturated monocarboxylic of ester bond, modification unsaturated monocarboxylic and the maleic acid equimolecular etc. that has such as ester modified with ehter bond.These can use separately, also can mix more than 2 kinds and use.
As the compound that has oxirane ring and ethylenically unsaturated group in (b) 1 molecule, get final product so long as have the compound of ethylenically unsaturated group and oxirane ring in 1 molecule, for example, can list (methyl) glycidyl acrylate, (methyl) acrylic acid Alpha-Methyl ethylene oxidic ester, (methyl) acrylic acid 3,4-epoxycyclohexyl methyl esters, (methyl) acrylic acid 3,4-epoxycyclohexyl ethyl ester, (methyl) acrylic acid 3,4-epoxycyclohexyl butyl ester, acrylic acid 3,4-epoxycyclohexyl methylamine ester etc.Wherein, preferred (methyl) acrylic acid 3,4-epoxycyclohexyl methyl esters.The compound that has oxirane ring and ethylenically unsaturated group in these (b) 1 molecules can use separately, also can mix more than 2 kinds and use.
(A) do not have the carboxy resin that contains of aromatic rings, its acid number must be in the scope of 50～200mgKOH/g.During acid number deficiency 50mgKOH/g, utilize weak alkaline aqueous solution to be difficult to remove unexposed portion.When surpassing 200mgKOH/g, there are the problems such as water tolerance, electrical characteristics difference of curing overlay film.In addition, the weight-average molecular weight that (A) contains carboxy resin is preferably in 5000～100000 scope.During weight-average molecular weight less than 5000, there is the tendency of the remarkable variation of dry to touch.In addition, weight-average molecular weight surpasses at 100000 o'clock, produces the significantly problem of deterioration of development, bin stability, so not preferred.
Oxime ester in the Photoepolymerizationinitiater initiater (B) that to comprise at least a kind of oxime ester be Photoepolymerizationinitiater initiater used in the present invention is a Photoepolymerizationinitiater initiater, get final product so long as have the compound of the represented group of following formula (I), wherein, the compound that preferably has the thioxanthones structure.As such compound, can list the compound of following formula (II) with thioxanthones structure.
In the formula, R1 represents that hydrogen atom, carbon number are 1～7 alkyl or aryl, and R2 represents that carbon number is 1～7 alkyl or aryl.
By comprise the oxime ester in the contained Photoepolymerizationinitiater initiater of resin combination of the present invention is Photoepolymerizationinitiater initiater, even the light solidifying/heat solidifying resin composition of white also can correctly form the pattern sub-image when irradiates light.As Photoepolymerizationinitiater initiater of the present invention, can use the oxime ester separately is Photoepolymerizationinitiater initiater, is Photoepolymerizationinitiater initiater as long as comprise at least a kind of oxime ester, then can also be used in combination other Photoepolymerizationinitiater initiater.As being other Photoepolymerizationinitiater initiater that Photoepolymerizationinitiater initiater uses with the oxime ester in the present invention, for example, can list benzoin and benzoin alkylether classes such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether; Acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1, acetophenones such as 1-dichloroacetophenone; 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-1-butanone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-aminoalkyl benzophenone classes such as 1-butanone; Anthraquinone classes such as 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone; Ketal classes such as acetophenone dimethyl ketal, benzil dimethyl ketal; Benzophenones such as benzophenone; The xanthene ketone; (2,6-dimethoxy benzoyl)-2,4,4-amyl group phosphine oxide, two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxide, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, ethyl-2,4, phosphinoxidess such as 6-trimethylbenzoyl phenyl phosphites; Various peroxides; Luxuriant titanium series initiators etc.These are that other Photoepolymerizationinitiater initiater that Photoepolymerizationinitiater initiater uses can use a kind with the oxime ester, also can make up more than 2 kinds and use.
The Photoepolymerizationinitiater initiater (B) that to comprise at least a kind of oxime ester be Photoepolymerizationinitiater initiater of the present invention can with N, N-dimethylamino ethyl benzoate, N, the photosensitizer that tertiary amines such as N-dimethylamino benzoic acid isopentyl ester, amyl group-4-dimethylaminobenzoic acid ester, triethylamine, triethanolamine are such etc. is used in combination.
Do not contain carboxy resin (A) with respect to what 100 mass parts did not have an aromatic rings, the use level of the Photoepolymerizationinitiater initiater (B) that to comprise at least a kind of oxime ester be Photoepolymerizationinitiater initiater is preferably 1～30 mass parts, more preferably 2～25 mass parts.During use level less than 1 mass parts of the Photoepolymerizationinitiater initiater (B) that to comprise at least a kind of oxime ester be Photoepolymerizationinitiater initiater, photo-curable reduces, and the pattern behind the exposure imaging forms and becomes difficulty, so not preferred.On the other hand, when surpassing 30 mass parts, the thick film curable reduces, and causes the cost height in addition, so not preferred.
Then, (C) can use various epoxy resin as epoxy compound, bisphenol-s epoxy resin for example, the o-phthalic acid diglycidyl ester resin, triglycidyl isocyanurate (is for example produced the TEPIC-H (having 3 epoxy radicals along the β body of same direction to the structure of s-triazine ring skeleton face combination) that chemistry (strain) is produced daily, TEPIC (potpourri of β body and α body, this α body have 1 epoxy radicals along the structure of the direction different with other 2 epoxy radicals to the combination of s-triazine ring skeleton face) etc.) heterocyclic ring epoxy resins such as, di-toluene phenol-type epoxy resin, united phenol-type epoxy resin, four glycidyl group xylenols ethane resin etc. is insoluble in the epoxy resin of thinning agent, bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol f type epoxy resin, brominated bisphenol a type epoxy resin, phenol phenolic varnish type or cresols phenolic resin varnish type epoxy resin, alicyclic epoxy resin, the phenolic resin varnish type epoxy resin of bisphenol-A, chelating type epoxy resin, glyoxal type epoxy resin, contain aminoepoxy resin, rubber modified epoxy resin, the bicyclopentadiene phenol aldehyde type epoxy resin, the silicone modified epoxy, 6-caprolactone modified epoxy etc. dissolves in the epoxy resin of thinning agent etc.These epoxy resin can be used alone or in combination of two or more kinds.
Do not contain carboxy resin (A) with respect to what 100 mass parts did not have an aromatic rings, the use level of epoxy compound (C) is preferably 5～70 mass parts, 5～60 mass parts more preferably.When the use level of epoxy compound (C) surpassed 70 mass parts, the dissolubility of unexposed portion in developer solution reduced, and it is residual easily to take place to develop, and was difficult to use on actual the use.Therefore on the other hand, during less than 5 mass parts, the carboxyl that contains carboxy resin (A) is residual with unreacted state, has the tendency of the electrical characteristics that are difficult to fully obtain cured coating film, solder heat resistance, chemical proofing.
Not having the carboxyl that contains carboxy resin (A) of aromatic rings and the epoxy radicals of epoxy compound (C) reacts by ring-opening polymerization, when using ease of solubility epoxy resin in other material in thinning agent (E), composition, the crosslinked because heat when dry and easily carrying out.Therefore, want to suppress cross-linking reaction and when prolonging drying time, it is desirable to use separately the epoxy resin of slightly solubility or use with the epoxy resin of ease of solubility.
In the present invention, one of feature is to use Titanium Dioxide Rutile Top grade (D) as Chinese white.Anatase-type titanium oxide is compared the whiteness height with rutile-type, therefore often used.But,, therefore cause the variable color of the resin in the light solidifying/heat solidifying resin composition because anatase-type titanium oxide has photocatalytic activity.Relative therewith, Titanium Dioxide Rutile Top grade is compared with Detitanium-ore-type, and whiteness is weaker, but because almost there is not photolytic activity, therefore can obtain stable soldering-resistance layer.As Titanium Dioxide Rutile Top grade (D), can use the material of known rutile-type.Particularly, can use FUJITITANIUM INDUSTRY CO., KR-270, the KR-310 that R-550, the R-580 that the former industry of TR-600, TR-700, TR-750, TR-840, stone (strain) that LTD. produces is produced, R-630, R-820, CR-50, CR-60, CR-90, titanium industry (strain) are produced, KR-380 etc.
Do not contain carboxy resin (A) with respect to what 100 mass parts did not have an aromatic rings, the use level of Titanium Dioxide Rutile Top grade (D) is preferably 50～300 mass parts, 60～260 mass parts more preferably.When use level surpassed 300 mass parts, photo-curable reduced, and the curing depth step-down is not preferred.On the other hand, during less than 50 mass parts, covering power is little, can not obtain the soldering-resistance layer of high reflectance.
In addition, in the present invention, when being used in combination silica granule (F), can obtain having the light solidifying/heat solidifying resin composition of darker curing depth.This think since the refractive index of silica with do not have aromatic rings to contain carboxy resin (A) more approaching.
As such silica granule (F), can use known material.For example, can list spherical silica (ADMAFINE SO-E1, the SO-E2 that admatechs company produces, SO-E5 etc.), fine-powdered monox, amorphous silica, crystalline silica, fused silica etc.These silica granules can be used singly or in combination of two or more thereof.Do not contain carboxy resin (A) with respect to what 100 mass parts did not have an aromatic rings, the use level of silica granule (F) is preferably 50～200 mass parts.
As thinning agent used in the present invention (E), can list photopolymerization monomer and/or organic solvent.As photopolymerization monomer, can list acrylic acid hydroxy alkyl ester classes such as acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxy butyl ester; The list or the diacrylate class of glycol such as ethylene glycol, methoxyl TEG, polyglycol, propylene glycol; Acrylic amide such as N,N-DMAA, N hydroxymethyl acrylamide; Acrylic acid N, acrylic-amino alkyl esters such as N-dimethylaminoethyl; The multicomponent methacrylate class of polyvalent alcohols such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate or their ethylene oxide adduct or propylene oxide adduct; The esters of acrylic acid of the ethylene oxide adduct of phenoxy group acrylate, bisphenol a diacrylate and these phenol or propylene oxide adduct etc.; The esters of acrylic acid of glycidol ethers such as glycerine diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether; And melamine acrylate; And/or the methyl acrylic ester corresponding with the aforesaid propylene esters of gallic acid etc.
On the other hand, as organic solvent, can use ketones such as MEK, cyclohexanone; Toluene, dimethylbenzene, tetramethylbenzene etc. are aromatic hydrocarbon based; Glycol ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, the single ether of dipropylene glycol, Triethylene glycol ethyl ether; The ester classes such as carboxylate of ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol ether acetate alone and above-mentioned glycol ethers; Alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; Aliphatic hydrocarbon such as octane, decane; Oil series solvents such as sherwood oil, naphtha, hydrogenated naphtha, solvent naphtha etc.
Above-mentioned such thinning agent (E) can use separately or use as potpourri more than 2 kinds.Do not contain carboxy resin (A) with respect to what 100 mass parts did not have an aromatic rings, preferably use the thinning agent (E) of 20～300 mass parts.The application target of aforementioned thinning agent is, photopolymerization monomer not only makes composition be in the state of easy coating, and dilution active energy ray-curable resin, and strengthens optical polymerism, and on the other hand, organic solvent is used for by the dry film of making.Therefore, according to the thinning agent that uses, can use the photomask and the way of contact that contacts or the not way of contact Exposure mode arbitrarily of filming.
In addition, by in the light solidifying/heat solidifying resin composition of white of the present invention, containing antioxidant and hindered amine light stabilizer, can further reduce hot deterioration, light deterioration.As antioxidant, be not particularly limited, but be preferably hindered phenol compound.As hindered phenol compound, for example can list NOCRAC 200, NOCRAC M-17, NOCRAC SP, NOCRAC SP-N, NOCRACNS-5, NOCRAC NS-6, NOCRAC NS-30, NOCRAC 300, NOCRAC NS-7, NOCRAC DAH (more than be the emerging chemical industry of imperial palace (strain) production); MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK AO616, MARK AO-635, MARKAO-658, MARK AO-15, MARK AO-18, MARK 328, MARKAO-37 (more than be ADEKA ARGUS CHEMICAL CO., LTD. produces); IRGANOX 245, IRGANOX 259, IRGANOX 565, IRGANOX1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1081, IRGANOX 1098, IRGANOX 1222, IRGANOX 1330, IRGANOX1425WL (more than be Ciba Specialty Chemicals company produce) etc.
In addition, as hindered amine light stabilizer, for example can list TINUVIN622LD, TINUVIN 144; CHIMASSORB 944LD, CHIMASSORB119FL (more than be Ciba Specialty Chemicals company produce), MARK LA-57, LA-62, LA-67, LA-63, LA-68 (more than be ADEKAARGUS CHEMICAL CO., LTD. gives birth to tight); SANOL LS-770, LS-765, LS-292, LS-2626, LS-1114, LS-744 (more than be SankyoLifetech Co., Ltd. produces) etc.
Do not contain carboxy resin (A) with respect to what 100 mass parts did not have an aromatic rings, above-mentioned antioxidant and light stabilizer preferably add 0.1～10 mass parts.
Further, as required, can use curing accelerator, hot polymerization inhibitor, thickening agent, defoamer, levelling agent, coupling agent, flame retardant etc.
The light solidifying/heat solidifying resin composition of white of the present invention can provide with form liquid, pasty state.
With the light solidifying/heat solidifying resin composition of white of the present invention, dilute as required and be adjusted into the viscosity that is suitable for coating process.By methods such as silk screen print method, curtain formula curtain coating, spraying process, rolling methods it is applied on the printed-wiring board (PWB) that is formed with circuit, for example make organic solvent volatile dry contained in the composition under 70～90 ℃ the temperature, thereby can form filming of not touching with one's hand.Then, utilize the exposure of active energy beam selectivity, utilize buck solution unexposed portion to be developed and the formation corrosion-resisting pattern, thereby can obtain printed-wiring board (PWB) of the present invention by photomask.As at this employed alkaline aqueous solution, the aqueous sodium carbonate of 0.5～5 weight % normally, but also can use other alkaline aqueous solution.As other alkaline aqueous solution, for example, can list the alkaline aqueous solution of potassium hydroxide, NaOH, sal tartari, sodium phosphate, sodium silicate, ammonia, amine etc.In addition, as the radiation source that is used to expose, can use low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, xenon lamp or metal halide lamp etc.In addition, laser beam etc. also can be used as active ray and uses.
In order to improve the thermotolerance of the resulting soldering-resistance layer of such operation, it is desirable to utilize 100～200 ℃ heat, ultraviolet ray or far infrared to make the soldering-resistance layer regelate.
Use the formed soldering-resistance layer of light solidifying/heat solidifying resin composition of the present invention to have high reflectance, in addition, have the desired character of solder resist such as thermotolerance, solvent resistance and electrical characteristics.Behind activated deterioration test, also keep high reflectivity by the formed solder resist of the present invention.
Embodiment
Below, by embodiment the present invention is described, but the present invention is not limited to these embodiment.
What do not have aromatic rings contains the synthetic of carboxy resin
In possessing 2 liters of removable flasks of stirrer, thermometer, reflux condenser, tap funnel and nitrogen ingress pipe, add 900g as the diethylene glycol dimethyl ether of solvent and 21.4g as the tert-butyl peroxide-2 ethyl hexanoic acid ester (the Perbutyl O that Japanese grease (strain) is made) of polymerization initiator, be heated to 90 ℃.After the heating, to wherein, with 3 hours ester modified in 309.9g methacrylic acid, 116.4g methyl methacrylate and the 109.8g (methyl) acrylic acid 2-hydroxyl ethyl ester (the PLACCEL FM1 that Daicel chemical industry (strain) is made) is added as two (4-tert-butylcyclohexyl) peroxy dicarbonates (PEROYLTCP that Japanese grease (strain) is made) dropping of polymerization initiator with 21.4g, slaking is 6 hours again, thereby obtains containing the carboxyl copolymer resins.In addition, be reflected under the nitrogen atmosphere and carry out.
Then, add 363.9g acrylic acid 3 in the carboxyl copolymer resins in containing of gained, 4-epoxycyclohexyl methyl esters (Daicel chemical industry (strain) make Cyclomer A200), 3.6g are as the dimethyl benzylamine of ring opening catalyst, the 1.80g hydroquinone monomethyl ether as polymerization inhibitor, be heated to 100 ℃ and stirring, thereby carry out the opening of epoxy.After 16 hours, obtain comprising the solution that contains carboxy resin that 53.8 weight % (nonvolatile component) do not have aromatic rings, the acid number of the solid constituent of this resin is that 108.9mgKOH/g, weight-average molecular weight are 25000.Below, claim that this reaction solution is an A-1 varnish.
Embodiment 1～6, comparative example 1～6
Cooperate, stir each composition by table 1 and table 2, disperse, prepare light solidifying/heat solidifying resin composition respectively with the three-roller type roller mill.Numeral mass parts in the table.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| A-1 varnish | 186 | 186 | 186 | 186 | 186 | 186 |
| R820 | 180 | 180 | 180 | 180 | 180 | 180 |
| 828 | 37 | 37 | 37 | 37 | 37 | 37 |
| SO-E5 | 110 | 110 | 110 | 110 | 110 | 110 |
| Initiating agent 1 | 1 | 1 | 1 | 1 | 1 | |
| Initiating agent 2 | 1 | |||||
| Initiating agent 3 | 9 | 18 | ||||
| Initiating agent 4 | 9 | 9 | 18 | |||
| Initiating agent 5 | 9 | 9 | 9 | 18 | ||
| Monomer | 15 | 15 | 15 | 15 | 15 | 15 |
| KS-66 | 3 | 3 | 3 | 3 | 3 | 3 |
| Solvent | 20 | 20 | 20 | 20 | 20 | 20 |
Table 2
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| A-1 varnish | 186 | 186 | 186 | 186 | 186 | 186 |
| R820 | 180 | 180 | 180 | 180 | 180 | 180 |
| 828 | 37 | 37 | 37 | 37 | 37 | 37 |
| SO-E5 | 110 | 110 | 110 | 110 | 110 | 110 |
| Initiating agent 1 | ||||||
| Initiating agent 2 | ||||||
| Initiating agent 3 | 19 | 38 | ||||
| Initiating agent 4 | 19 | 38 | ||||
| Initiating agent 5 | 19 | 38 | ||||
| Monomer | 15 | 15 | 15 | 15 | 15 | 15 |
| KS-66 | 3 | 3 | 3 | 3 | 3 | 3 |
| Solvent | 20 | 20 | 20 | 20 | 20 | 20 |
R820: the Titanium Dioxide Rutile Top grade that the former industry of stone company produces
828:Japan Epoxy Resins Co., the bisphenol A type epoxy resin that Ltd. produces
The spherical silica that SO-E5:admatechs produces
Initiating agent 1:2-(acetyl oxyimino group methyl) thioxanthene-9-one (the oxime ester is a Photoepolymerizationinitiater initiater)
The OXE02 (the oxime ester is a Photoepolymerizationinitiater initiater) that initiating agent 2:Ciba Specialty Chemicals company produces
The IRGACURE907 that initiating agent 3:Ciba Specialty Chemicals company produces
The IRGACURE369 that initiating agent 4:Ciba Specialty Chemicals company produces
The DAROCURTPO that initiating agent 5:Ciba Specialty Chemicals company produces
Monomer: dipentaerythritol acrylate
The silicone oil that KS-66:Shin-Etsu Silicones produces
Solvent: carbitol acetic acid esters
In order to study each character of the soldering-resistance layer that uses each light solidifying/heat solidifying resin composition and form, the following test estimated.
(1) resolving power
Utilize silk screen print method, using 100 order polyester twill versions is that the amount of 40 μ m is printed onto the full version of each light solidifying/heat solidifying resin composition on the FR-4 copper clad laminate of 100mm * 150mm size, 1.6mm thickness with thickness, utilizes the heated air circulation type drying oven in 80 ℃ of dryings 10 minutes.Again to each above-mentioned dry coating with the overlapping printing light solidifying/heat solidifying resin composition of same method, utilize the heated air circulation type drying oven in 80 ℃ of dryings 20 minutes.Use the HMW-680GW of printed-wiring board (PWB), use the mask pattern of the line of describing 80 μ m and 100 μ m, with 500mJ/cm with exposure machine Oak making manufacturing
2The accumulative total light quantity carry out ultraviolet exposure.Then, as developer solution, utilize printed-wiring board (PWB) to develop for 60 seconds 30 ℃, 1% aqueous sodium carbonate, then carry out heat curing in 60 minutes in 150 ℃, make test film with the heated air circulation type drying oven with developing machine.Confirm to residue in the live width on this test film, estimate resolving power.The result is shown in table 3 and the table 4.Wherein, the result of the line of residual 80 μ m is designated as two circles, the result of the line of residual 100 μ m is designated as round mark, the result of the line of not residual 100 μ m is designated as the fork mark.
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Resolving power | ◎ | ◎ | ◎ | ○ | ◎ | ○ |
Table 4
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| Resolving power | × | × | × | × | × | × |
As shown in Table 3, used among the embodiment 1～6 of the light solidifying/heat solidifying resin composition of the present invention that to comprise at least a kind of oxime ester be Photoepolymerizationinitiater initiater, can obtain good resolving power.On the other hand, though the oxime ester that do not contain of table 4 is that the comparative example 1～3 of Photoepolymerizationinitiater initiater comprises and the initiating agent of the contained Photoepolymerizationinitiater initiater amount of embodiment with amount, residual wires not after developing does not have good resolving power as can be known.Therefore, in comparative example 4～6, use the Photoepolymerizationinitiater initiater of doubled amount in order to improve resolving power, but also residual wires not after developing this moment.
(2) photostability
Utilize silk screen print method, using 100 order polyester twill versions is that the amount of 40 μ m is printed onto the full version of the light solidifying/heat solidifying resin composition of embodiment 1～6 pattern on the FR-4 copper clad laminate of 100mm * 150mm size, 1.6mm thickness with thickness, utilizes the heated air circulation type drying oven in 80 ℃ of dryings 30 minutes.Use the HMW-680GW of printed-wiring board (PWB), with 500mJ/cm with exposure machine Oak making manufacturing
2The accumulative total light quantity carry out ultraviolet exposure, make the negative pattern that residual 30mm is square.Then, as developer solution, utilize printed-wiring board (PWB) to develop for 60 seconds 30 ℃, 1% aqueous sodium carbonate, then carry out heat curing in 60 minutes in 150 ℃, make the test film that attribute testing is used with the heated air circulation type drying oven with developing machine.
Measure the test film of gained in the color colour difference meter CR-400 of Minolta production.Then, with UV conveyor oven (output power is 150W/cm, metal halide lamp, Cold Mirrors) irradiation 50J/cm
2, 100J/cm
2, 150J/cm
2Light and accelerated deterioration.The result is shown in table 5 and 6.
Table 5
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | ||
| Initial value | Y | 77.06 | 78.29 | 79.17 | 76.24 | 77.24 | 76.82 |
| L * | 90.36 | 90.91 | 91.31 | 89.97 | 90.43 | 90.24 | |
| a * | 0.33 | 0.03 | 0.53 | 0.05 | 0.72 | 0.52 | |
| b * | 3.96 | 3.02 | 4.26 | 3.97 | 4.63 | 3.46 | |
| 1 5 0 J / c m 2Irradiation | Y | 72.15 | 72.90 | 72.80 | 75.11 | 74.37 | 77.35 |
| L * | 89.52 | 89.68 | 90.95 | 88.94 | 89.10 | 89.19 | |
| a * | 0.82 | 0.67 | 0.08 | 0.13 | 0.93 | 0.39 | |
| b * | 3.18 | 3.39 | 3.16 | 4.40 | 5.96 | 3.50 | |
| ΔE *ab | 1.25 | 1.44 | 1.24 | 1.12 | 1.89 | 1.06 | |
| Visual valuation | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ |
Table 6
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | ||
| Initial value | Y | 72.15 | 72.90 | 72.80 | 72.80 | 66.77 | 73.26 |
| L * | 88.04 | 88.40 | 88.35 | 88.35 | 85.39 | 88.57 | |
| a * | 0.32 | 0.60 | 0.57 | 0.59 | 0.92 | 0.44 | |
| b * | 4.02 | 4.22 | 2.96 | 3.05 | 6.74 | 3.09 | |
| 1 5 0 J / c m 2Irradiation | Y | 69.11 | 71.48 | 78.83 | 68.13 | 60.37 | 67.81 |
| L * | 86.56 | 87.72 | 86.42 | 86.07 | 82.04 | 85.91 | |
| a * | 1.21 | 0.90 | 0.89 | 0.99 | 1.48 | 1.09 | |
| b * | 5.89 | 6.52 | 4.32 | 11.24 | 14.67 | 9.57 | |
| ΔE *ab | 2.55 | 2.42 | 2.38 | 8.51 | 8.63 | 7.03 | |
| Visual valuation | ◎ | ◎ | ◎ | × | × | × |
In table 5, Y represents the reflectivity of XYZ colorimetric system, L
*Expression L
*a
*b
*The lightness of colorimetric system.a
*The expression red is to ,-a
*Represent green direction, b
*Represent yellow direction ,-b
*Represent blue direction, do not have chroma more near null representation more.Δ E
*Ab represents change in color.The more little expression change in color of this value is more little.About the visual valuation project, the imperceptible variable color of two circle expressions, the circle mark represents almost not have variable color, and the triangle mark represents to have a little variable color, and the fork mark represents to have tangible variable color.
As shown in Table 5, in the embodiment 1～6 that has used composition of the present invention, accelerated deterioration back reflection rate reduces not significantly, and the variation of lightness is also little, and as the Δ E of change in color
*The value of ab is little.In addition, in the visual valuation, not variable color, perhaps variable color hardly.
As shown in Table 6, the comparative example 4～6 of Photoepolymerizationinitiater initiater of doubled amount that uses embodiment behind accelerated deterioration, reflectivity Y and lightness L
*All become low value, and, as the Δ E of change in color
*The value of ab is also big.In addition, in visual valuation, can see variable color.Hence one can see that, even use the Photoepolymerizationinitiater initiater of doubled amount can not improve resolving power, and photostability is also poor.
(3) thermotolerance
With (2) same each test film of making on coating rosin series solder flux, 10 seconds of circulation in 260 ℃ weld groove.With after propylene glycol monomethyl ether acetate washing and the drying, utilize the viscose paper adhesive tape to carry out disbonded test then, peeling off of filming estimated.The result is shown in table 7 and the table 8.At this, circle is represented to film and is not peeled off, and the fork expression has been filmed and peeled off.
(4) solvent resistance
To in propylene glycol monomethyl ether acetate, flood 30 minutes with (2) same each test film of making, and after the drying, utilize the viscose paper adhesive tape to carry out disbonded test, peeling off of filming and variable color will be estimated.The result illustrates in table 7 and table 8 together.At this, circle represent to film do not peel off, variable color, fork expression has been filmed and has been peeled off, variable color.
(5) pencil hardness test
With (2) same each test film of making on, the B that the nib of pen core is polished is to the pencil of 9H, by giving as security, writing down films does not produce the hardness of the pencil of peeling off with about 45 ° angle.The result illustrates in table 7 and table 8 together.
(6) insulation resistance test
Except the comb-type electrode B test sheet of using IPC B-25 test pattern replaces the FR-4 copper clad laminate, similarly making test film under the condition with (2).This test film is applied the bias voltage of DC500V and measures insulating resistance value.The result illustrates in table 7 and table 8 together.
Table 7
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Thermotolerance | ○ | ○ | ○ | ○ | ○ | ○ |
| Solvent resistance | ○ | ○ | ○ | ○ | ○ | ○ |
| Pencil hardness test | 7H | 7H | 7H | 7H | 7H | 7H |
| Insulation resistance test (Ω) | 1×10 13More than | 1×10 13More than | 1×10 13More than | 1×10 13More than | 1×10 13More than | 1×10 13More than |
Table 8
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| Thermotolerance | ○ | ○ | ○ | ○ | ○ | ○ |
| Solvent resistance | ○ | ○ | ○ | ○ | ○ | ○ |
| Pencil hardness test | 7H | 7H | 7H | 7H | 7H | 7H |
| Insulation resistance test (Ω) | 1×10 13More than | 5×10 12 | 1×10 13More than | 1×10 13More than | 1×10 13More than | 1×10 13More than |
As shown in Table 7, in the embodiment 1～6 that has used light solidifying/heat solidifying resin composition of the present invention, have the desired good thermotolerance of soldering-resistance layer, solvent resistance, adaptation and electrical insulating property.
By The above results as can be known, be Photoepolymerizationinitiater initiater by in Photoepolymerizationinitiater initiater, comprising the oxime ester, can keep the character of good photostability, thermotolerance, solvent resistance, adaptation and electrical insulating property, obtain high resolving power.
As above detailed description,, can obtain to form the light solidifying/heat solidifying resin composition of white of the soldering-resistance layer of high reflectance according to the present invention.The light solidifying/heat solidifying resin composition of white of the present invention can correctly form the pattern sub-image when irradiates light, have good resolving power.
Claims (7)
1. the light solidifying/heat solidifying resin composition of a white, it is characterized in that it comprises: what (A) do not have aromatic rings contains carboxy resin, (B) Photoepolymerizationinitiater initiater that to comprise at least a kind of oxime ester be Photoepolymerizationinitiater initiater, (C) epoxy compound, (D) Titanium Dioxide Rutile Top grade and (E) thinning agent.
2. the light solidifying/heat solidifying resin composition of white according to claim 1, it is characterized in that the carboxy resin that contains that described (A) do not have aromatic rings is that to contain the copolymerization with carboxyl that the reaction that has the compound of oxirane ring and ethylenically unsaturated group in carboxyl (methyl) acrylate based copolymerized resin and (b) 1 molecule obtains by (a) be resin.
3. the light solidifying/heat solidifying resin composition of white according to claim 1 is characterized in that, the carboxy resin that contains that described (A) do not have aromatic rings is to contain carboxy resin by what aliphatics polymerization monomer generated.
4. the light solidifying/heat solidifying resin composition of white according to claim 1 is characterized in that, described oxime ester is that Photoepolymerizationinitiater initiater has the thioxanthones structure.
5. the light solidifying/heat solidifying resin composition of white according to claim 1 is characterized in that, also comprises (F) silica granule.
6. according to the light solidifying/heat solidifying resin composition of each described white of claim 1～4, wherein, described light solidifying/heat solidifying resin composition is the solder resist composition.
7. printed-wiring board (PWB), it forms soldering-resistance layer by the light solidifying/heat solidifying resin composition that uses each described white of claim 1～5 at the print circuit board surface that is formed with circuit and obtains.
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| JP2006288943 | 2006-10-24 | ||
| JP2006288943 | 2006-10-24 |
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| CNA2007101514854A Pending CN101169590A (en) | 2006-10-24 | 2007-10-24 | Light solidifying heat curing resin composition and printing circuit board using the same |
| CN201310449469.9A Pending CN103558735A (en) | 2006-10-24 | 2007-10-24 | Photocurable thermosetting resin composition and printed wiring board using the same |
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| KR (1) | KR100904348B1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN103558735A (en) | 2014-02-05 |
| TW200830047A (en) | 2008-07-16 |
| KR20080036920A (en) | 2008-04-29 |
| KR100904348B1 (en) | 2009-06-23 |
| TWI356280B (en) | 2012-01-11 |
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