CN1779568B - Hardenable resin composition, hardened body thereof, and printed wiring board - Google Patents
Hardenable resin composition, hardened body thereof, and printed wiring board Download PDFInfo
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- CN1779568B CN1779568B CN2004100954406A CN200410095440A CN1779568B CN 1779568 B CN1779568 B CN 1779568B CN 2004100954406 A CN2004100954406 A CN 2004100954406A CN 200410095440 A CN200410095440 A CN 200410095440A CN 1779568 B CN1779568 B CN 1779568B
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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
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The present invention provides a hardenable resin composition which can have superior surface hardenable property by irradiation with an active energy beam of 350 to 420 nm in wavelength. The hardenable resin composition contains a compound (A) having at least one unsaturated double bond, a compound (B) having an oxime ester group, and a benzophenone compound (C) containing sulfur atoms and hardened with an active energy beam of 350 to 420 nm in wavelength.
Description
Technical field
The present invention relates to the hardening resin composition that active energy ray solidified, its solidfied material and the printed circuit board (PCB) thereof by 350nm～420nm.
Background technology
In recent years, along with electronic equipment to miniaturization, high performance development, for the demand of employed light curing resin composition in these electronic equipments also in continuous increase.No matter be at the soldering-resistance layer (solder resist) that uses Photocurable resin composition, interlayer dielectic, electro-cladding, sandblast resistant durable with printing ink, polymkeric substance light-guide wave path, flat-panel monitor (FPD) with the raising of the densification of the raising of the irrelevant for example reliability of insulating cells such as parts, coating diaphragm, color filter protecting layer, contact type panel etc. and purposes, circuit pattern, pattern precision requirement to some extent aspect these.
Photocurable resin composition is general when being cured to use ultraviolet (UV) light source, and is widely used in relief printing plate, matrix and photoresist.Such Photocurable resin composition contains the organic principle that forms the portrait main body and the formed Photoepolymerizationinitiater initiater of polymerization activity kind to light sensitization such as ultraviolet rays.
In addition, consider environmental problem in recent years, and, use the Photocurable resin composition of alkali developable, be widely known by the people by exposure, the photo-engraving process that forms pattern that develops as the technology that improves this pattern precision.The example of the light curing resin composition of this alkali developable can list and comprise by adding the resulting photonasty prepolymer of multi-anhydride as the composition of raw polymer (consult the spy opens clear 61-243869 communique, the spy opens flat 7-50473 communique, special fair 7-17737 communique) in the reaction product of phenolic resin varnish type epoxy resin and unsaturated monocarboxylic acid.
And, recently, save resource or save energy and photo-engraving process that considered environmental problem as a kind of, be that the direct tracing method (laser direct image) of light source has been practical with laser.Directly the tracing method has been omitted the mask manufacturing step, can carry out proportional zoom to each substrate, therefore be a kind of be fit to many kinds few, in batches, dilivery date short, high multilager base plate the method for manufacturing.
Directly employed light source and wavelength in the tracing method change according to the difference of the purposes of employed Photocurable resin composition, and light source is broadly divided into the type of using gases ion laser and uses the type of Solid State Laser.What use in gaseous ion laser is argon gas, general semiconductor laser and the YAG laser of using in Solid State Laser.In addition,, it can be divided into ultraviolet region type and visible region type, generally use 365nm, 405nm and 488nm if according to the Wavelength of Laser scope division of being radiated.
Consider the price of operating environment and protective seam simultaneously, Wavelength of Laser just turns to ultraviolet light by visible light, in addition, considers that from operating cost light source also just turns to Solid State Laser by gas laser.Semiconductor laser as Solid State Laser is widely used in the communications field and photoelectric field, the laser of it and other type is compared, have advantages such as miniaturization, high-level efficiency, low-voltage, low power consumption, life-span length, therefore be used as the light source of direct tracing method.
At photoelectric field, use the wavelength that is adopted in the direct tracing method of semiconductor laser to be 405nm, 650nm, 780nm.Because wherein the wavelength of 405nm is short, energy is high, thereby can improve curable, resolution, therefore, often is used recently.
But, soldering-resistance layer as one of employed Photocurable resin composition in the prior art, when the direct tracing device that use is mounted with semiconductor laser exposes to it,, just can not obtain enough surface cures because it is imperfect to solidify the not enough development that causes under 405nm.Promptly, owing to can not obtain surface cure, cause producing following problem: as the patience to scolder of the fundamental characteristics of soldering-resistance layer, test the reliability reduction that (HAST) estimated to the reduction of gold-plated patience and by pressure-cooking (PCT) and height accelerated aging.
A main cause of this surface cure reduction is considered to, because directly the tracing method expose as a kind of noncontact, and because the obstruction of oxygen in the air, makes the cause that near the free-radical generating number of film coated surface has reduced.Other reason is considered to, the component of the Photoepolymerizationinitiater initiater of prior art is for example used photosensitive polymer combination (opening the 2001-235858 communique with reference to the spy) and the styrax and the derivant thereof of oxime ester (oxime ester) compound, many materials such as benzoquinones class of replacement or non-replacement are known (Off オ ト Port リ マ one Ken Words meeting Knitting, Off オ ト Port リ マ one Ha Application De Block Star Network, the 6th chapter (Gong Ye Tone looks into meeting, version in 1989)), wherein any all being difficult to has sufficient light sensitivity in 350nm or above low-yield scope, the film coated surface after therefore developing produces incomplete phenomenon.And think that last cause is that then a reason is bigger generation of influence by the light-cured resin solidfied material because the influence of device produces.
Summary of the invention
Therefore, because the shortcoming that influence caused of above-mentioned light-cured resin solidfied material, its fundamental purpose is to provide a kind of activation evergy line by 350nm～420nm to obtain the good hardening resin composition of surface cure in order to solve particularly in the present invention.
The present inventor has carried out research energetically for achieving the above object, found that, as Photoepolymerizationinitiater initiater, contain the compound of specific oxime ester base and specific benzophenone by using simultaneously with the compound that contains unsaturated double-bond, just can achieve the above object, thereby finish the present invention.
Promptly, the invention provides a kind of hardening resin composition, it contains: have the compound (A) of at least one unsaturated double-bond, the benzophenone cpd (C) that has oxime ester base compound (B) and contain sulphur atom shown in the following formula (1), and be the activation evergy line curing of 350nm～420nm by wavelength.
In formula (1), R represents to have the alkyl or the phenyl of 1～7 carbon atom, and R ' represents hydrogen atom or has the alkyl or the phenyl of 1～7 carbon atom.
In addition, the invention provides a kind of printed circuit board (PCB) that forms the solidfied material of hardening resin composition of the present invention and be formed with the pattern of this solidfied material.
Hardening resin composition of the present invention can be good by the surface cure that light produced of 350nm～420nm wavelength, and can be cured by semiconductor laser.
Description of drawings
Fig. 1 represents the synoptic diagram of the resin combination of embodiment 1 by the spectrum sensitivity of the surface cure state that rayed produced of each wavelength.
Fig. 2 represents the synoptic diagram of the resin combination of comparative example 1 by the spectrum sensitivity of the surface cure state that rayed produced of each wavelength.
Fig. 3 represents to form by the pattern of the device that directly traces designs by the resin combination of the embodiment 1 of electron microscope demonstration the synoptic diagram of state.
Fig. 4 represents to form by the pattern of the device that directly traces designs by the resin combination of the comparative example 1 of electron microscope demonstration the synoptic diagram of state.
Embodiment
Hardening resin composition of the present invention contains: have (organic) compound (A) of at least one unsaturated double-bond, the benzophenone cpd (C) that has oxime ester base compound (B) and contain sulphur atom shown in the following formula (1).
The compound that contains at least one unsaturated double-bond (A) that is had in the hardening resin composition of the present invention is a kind of compound that solidifies by the effect of Photoepolymerizationinitiater initiater, and can be any form in monomer, oligomer, prepolymer, the resin.Preferred compound (A) is: (i) contain the compound (A-1) of 1 or above unsaturated double-bond and 1 or above carboxyl, and the compound (A-2) that (ii) has 1 or above unsaturated double-bond.
When compound (A-1) has 1 or above unsaturated double-bond, also contain at least one carboxyl.By activation evergy line irradiation curing compound (A-1), owing to have carboxyl in its solidfied material, thereby can carry out alkali and develop.Can use various photo-curable composition commonly known in the art, for example special clear 51-131706 communique, spy opened opened clear 52-94388 communique, spy and opened clear 64-62375 communique, spy and open flat 2-97513 communique, spy and open flat 2-113252 communique, spy and open flat 3-253093 communique, spy and open flat 3-289656 communique, special public clear 63-46791 communique, special fair 1-54390 communique, special fair 1-32868 communique, spy and open the photoresist of being put down in writing in the 2002-363231 communique.
Compound (A-1) can be the following compound of enumerating particularly.
That is, (1) by in unsaturated carboxylic acid and the multipolymer of compound that contains unsaturated double-bond, adduction olefinic unsaturated group is as the resulting carboxylic photoresist of side chain;
(2) multipolymer and unsaturated carboxylic acid reaction of the compound that will contain epoxy radicals and unsaturated double-bond and the compound that contains unsaturated double-bond make the secondary hydroxyl and the polybasic acid anhydride (a) that are generated react resulting carboxylic photoresist then;
(3) will have the acid anhydrides of unsaturated double-bond and the multipolymer of the compound that contains unsaturated double-bond and react resulting carboxylic photoresist with the compound that contains hydroxyl and unsaturated double-bond;
(4) with epoxy compound and unsaturated monocarboxylic reaction, the secondary hydroxyl that is generated reacts resulting carboxylic photoresist with polybasic acid anhydride (a) again;
(5) polymkeric substance and the polynary carboxylic anhydride reactant with hydroxyl obtains carboxylic resin, makes itself and the compound with epoxy radicals and unsaturated double-bond further react resulting carboxylic photoresist;
(6) polyfunctional group oxetane compound and unsaturated monocarboxylic are reacted the primary hydroxyl of the oxetane resin of resulting modification, further with the resulting carboxylic photoresist of polynary carboxylic acid anhydride (a) reaction;
(7) with the hydroxyl of the reaction product of polycyclic ring oxygen compound and unsaturated monocarboxylic, further with the resulting carboxylic photoresist of polynary carboxylic acid anhydride (a) reaction;
(8) in a part of acidic group of the formed multipolymer of monomer that contains ethylenically unsaturated carboxylic acids and (methyl) acrylate to following general formula (I) or (II), adduction contains the formed carboxylic photoresist of unsaturated compound of epoxy radicals etc.
Formula (I):
CH
2＝C(R)-CO[O(CH
2)
5CO]
n-OH
Formula (II):
CH
2＝C(R)-COOCH
2CH
2O[CO(CH
2)
5O]
n-CO-X-COOH
In formula (I), formula (II), n is 1～10 integer, and R represents hydrogen atom or methyl, and X represents that carbon number is 1～4 carboxylic acid (acid anhydride) base.
And (methyl) acrylate described in this instructions is meant the general name of acrylate and methacrylate, and the situation of other similar expression is identical therewith.
In the above-mentioned carboxylic resin, preferred per molecule contains olefinic unsaturated group and at least 2 carboxyls simultaneously, and the acid number of solid constituent is preferably 10～150mg KOH/g, more preferably 30～130mg KOH/g.When acid number deficiency 10mg KOH/g, be difficult to remove uncured film by dilute alkaline aqueous solution, on the other hand, and if acid number has surpassed 150mg KOH/g, the water tolerance of cured film and electrical property possible deviation.In addition, the weight average molecular weight range of above-mentioned carboxylic resin is preferably 5000～150000, and more preferably 5000～100000.If weight-average molecular weight less than 5000, the film moisture-proof variation after dry to touch (tackfree) variation, the exposure, the back of developing produce the film loss, resolution greatly reduces.On the other hand, if weight-average molecular weight surpasses 150000, then development property significantly worsens, the storage stability variation.
As the instantiation of above-mentioned polynary carboxylic acid anhydride, representational have: dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, first bridge tetrabydrophthalic anhydride, methyl first bridge tetrabydrophthalic anhydride, hexachloro bridge methylene tetrahydrochysene phthalic anhydride, methyl tetrahydrophthalic anhydride; Aromatic series multi-anhydrides such as trimellitic anhydride, pyromellitic acid dianhydride, benzophenone tetracarboxylic dianhydride; In addition, what can also give an example is 5-(2,5-dioxy tetrahydrofuran base)-3-methyl-3-cyclopentene-1, the polybasic acid anhydride derivant that the 2-dicarboxylic anhydride is such, preferred especially tetrabydrophthalic anhydride or hexahydrophthalic anhydride.
Compound (A-2) is the compound that contains olefinic unsaturated ends group of being derived by propylene class monomer.Propylene class monomer described here for example is meant derivants such as (methyl) acrylic acid, β-furfuryl group acrylic acid, β-styrene acrylic, cinnamic acid, crotonic acid, alpha-cyano cinnamic acid etc. or their Arrcostab, hydroxyalkyl acrylate, derivants such as wherein preferred especially (methyl) acrylic acid or its Arrcostab, hydroxyalkyl acrylate.
That can enumerate specifically, has: (methyl) alkyl acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid-2-ethyl caproite, (methyl) decyl acrylate, (methyl) lauryl acrylate, (methyl) acrylic acid stearyl;
(methyl) acrylate cyclic group esters such as (methyl) cyclohexyl acrylate, (methyl) acrylic acid norbornene ester, (methyl) isobornyl acrylate, (methyl) acrylic acid two cyclopentene esters, (methyl) acrylic acid dicyclopentenyl hydroxyethyl ester;
(methyl) acrylic acid aromatic radical esters such as (methyl) acrylic acid benzyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid phenyl carbitol ester, (methyl) acrylic acid nonyl phenylester, (methyl) acrylic acid nonyl phenyl carbitol ester, (methyl) acrylic acid Nonylphenoxy ester;
(methyl) 2-hydroxyethyl acrylate, (methyl) acrylic acid hydroxypropyl ester, (methyl) hydroxybutyl acrylate, butylene glycol list (methyl) acrylate, glycerine (methyl) acrylate, phenoxy group hydroxypropyl (methyl) acrylate, polyglycol (methyl) acrylate and ethylene glycol bisthioglycolate (methyl) acrylate etc. have (methyl) acrylate of hydroxyl;
2-dimethyl aminoethyl (methyl) acrylate, 2-diethylamino ethyl (methyl) acrylate, 2-tert-butyl group amino-ethyl (methyl) acrylate etc. have amino (methyl) acrylate;
Phosphoric acid methacryl hydroxyethyl ester, two methacryloxy second phosphate, methacryl hydroxyethyl phenyl azido acid ester (phenyl P) etc. contain the methacrylate of phosphorus atoms;
Ethylene glycol bisthioglycolate (methyl) acrylate, diglycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, polyglycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, 1,4-butylene glycol two (methyl) acrylate, 1,3-butylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, diacrylates such as bisglycidyl base (methyl) acrylate;
Many acrylate such as trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate;
The many acrylate of polyvalent alcohols such as triacrylate of the triacrylate of the epoxy pronane modification of the diacrylate of the diacrylate of the oxirane modification of bisphenol S, the oxirane modification of bisphenol-A, fatty acid modified pentaerythritol diacrylate, trimethylolpropane, the epoxypropane sex change of trimethylolpropane;
Three (acryloyl group hydroxyethyl) isocyanuric acid ester etc. of two (acryloyl group hydroxyethyl) single hydroxyethyl isocyanuric acid ester, three (acryloyl group hydroxyethyl) isocyanuric acid ester, 6-caprolactone modification has many acrylate of isocyanuric acid skeleton; α, ω-two acryloyl group-(two ethylene glycol)-phthalic ester, α, ω-tetrapropylene acyl group-polyester acrylates such as (double trimethylolpropane)-tetrahydrophthalic acid ester;
(methyl) glycidyl acrylate;
(methyl) allyl acrylate;
ω-hydroxyl six nonyl hydroxyethyl (methyl) acrylate; Many caprolactones (methyl) acrylate;
(methyl) acryloyl group hydroxyethyl phthalic ester; (methyl) acryloyl group hydroxyethyl succinate;
2-hydroxyl-3-benzene hydroxypropyl acrylate;
Benzene hydroxy ethyl methacrylate etc.
In addition, N-vinyl compound, polyester acrylate, urethane acrylate, epoxy acrylate etc. such as N-vinyl pyrrolidone, N-vinyl formamide, N-vinyl acetamide have also suitable use of compound of olefinic unsaturated group.
Preferred in these compounds (A-2): (methyl) acrylate, glycidyl (methyl) acrylate and urethane acrylate with hydroxyl, (methyl) acrylate as having hydroxyl can list: (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid hydroxy butyl ester and urethane acrylate.In addition, consider the preferred compound that uses with 3 or above olefinic unsaturated group from improving the thermotolerance aspect.
Compound (A-2) uses as thinning agent described later and also is fine.For example, while can be with the viscosity of adjusting hardening resin composition, physical propertys such as the thermotolerance when being adjusted at hardening resin composition and forming solidfied material, pliability are that purpose is used.
Secondly, employed compound (B) is the compound with oxime ester base shown in following formula (1) among the present invention, and can use wherein any one.For example can be 1,2-acetyl caproyl, 1-[4-(benzene sulphur)-2-(O-benzoyl oxime)] (IRGACURE-OXE that Ciba Specialty Chemicals company makes), 1-phenyl-1,2-propanedione-2-(O-ethoxy carbonyl) oxime (the Quantacure PDO of イ Application タ one Na シ ヨ Na Le バ イ オ one シ Application セ エ テ イ Star Network ス company manufacturing).Wherein, preferred compositions (B) is the thioxanthones compound, especially preferably has as shown in the formula the thioxanthones compound shown in (1-1):
In the formula (1-1), 1 or 2 R
1Be the represented oxime ester base of formula (1), other R
1Expression hydrogen, methyl, phenyl or halogen atom.Particularly preferred compound (B) is as shown in the formula the thioxanthones compound shown in (1-2):
Preferably in curable resin potpourri of the present invention, contain the compound (B) of the ratio of 0.01～50 weight portion with respect to the compound (A) of 100 weight portions.If compound (A) with respect to 100 weight portions, compound (B) contain quantity not sufficient 0.01 weight portion, the curing of the compound (A) that the light by 350nm～420nm wavelength coverage carries out is just insufficient, the hydroscopicity of cured film uprises and PCT patience reduces, and solder heat resistance and anti-electroless plating also reduce easily.On the other hand, if with respect to the compound (A) of 100 weight portions, the content of compound (B) surpasses 50 weight portions, the development of filming and the degradation of anti-electroless plating of cured film, and demonstrate the tendency of PCT patience variation.More preferably the content with respect to compound (A) compound (B) of 100 weight portions is 0.1～30 weight portion.
Benzophenone cpd (C) is a kind of light sensitizer, if it is a kind of benzophenone cpd that contains sulphur atom, then to its restriction and without particular limitation.In this benzophenone cpd (C), comprise 4-benzoyl diphenyl sulfide compound.The phenyl ring of combination can be selected from chlorine atom, methoxyl, ethoxy and be contained in the alkyl of 1～5 carbon atom 1 or 2 substituting groups and be replaced in the 4-benzoyl of this compound, and/or can be selected from chlorine atom, methoxyl, ethoxy in conjunction with the phenyl ring of benzoyl and 1 substituting group containing in the alkyl of 1～5 carbon atom replaces.The instantiation of this 4-benzoyl diphenyl sulfide compound is: 4-benzoyl diphenyl sulfide; 4-benzoyl-4 '-methyldiphenyl thioether (the カ ヤ キ ユ ア that makes of Japanese chemical drug corporate system-BMS); 4-benzoyl-4 '-the ethyl diphenyl sulfide; 4-benzoyl-4 '-propyl group diphenyl sulfide; 4-o-methyl-benzene formoxyl diphenyl sulfide; 4-is to the methyl benzoyl diphenyl sulfide; methyl benzoyl diphenyl sulfide between 4-; between 4-, '-the dimethylbenzoyl diphenyl sulfide; the adjacent chlorobenzene formacyl diphenyl sulfide of 4-; 4-is to the chlorobenzene formacyl diphenyl sulfide; 4-is to tert-butyl benzene formoxyl diphenyl sulfide; 4-meta-methoxy benzoyl diphenyl sulfide etc.These benzophenone cpds (C) can use or use two or more potpourri separately.
Preferably in hardening resin composition of the present invention, contain the benzophenone cpd (C) of 0.01～40 weight portion ratio with respect to the compound (A) of per 100 weight portions.If compound (A) with respect to 100 weight portions, benzophenone cpd (C) contain quantity not sufficient 0.01 weight portion, light by 350nm～420nm wavelength coverage, the surface cure of hardening resin composition is insufficient, the gloss of cured coating film just is difficult to realize, and the hydroscopicity of cured film uprises and PCT patience, solder heat resistance and anti-electroless plating also reduce easily.On the other hand, if with respect to the compound (A) of 100 weight portions, the content of benzophenone cpd (C) surpasses 40 weight portions, the development of filming and the degradation of anti-electroless plating of cured film, and demonstrate the tendency of PCT patience variation.More preferably with respect to the photoresist composition of 100 weight portions, the content of benzophenone cpd (C) is 0.1～20 weight portion.
Hardening resin composition of the present invention can contain as the tertiary amine compound of photocuring promoter (D).These tertiary amine compounds (D) can list ethanolamines, 4,4 '-dimethylamino benzophenone (the Nisso cure-MABP that Japanese Cao Da company makes), 4-dimethylamino ethyl benzoate (the カ ヤ キ ユ ア that makes of Japanese chemical drug corporate system-EPA), 2-dimethylamino ethyl benzoate (the Quantacure DMB of イ Application タ one Na シ ヨ Na Le バ イ オ one シ Application セ エ テ イ Star Network ス company manufacturing), 4-dimethylamino ethyl benzoate (the Quantacure BEA of イ Application タ one Na シ ヨ Na Le バ イ オ one シ Application セ エ テ イ Star Network ス company manufacturing), to methylamino benzoic acid isopentyl ethyl ester (the カ ヤ キ ユ ア that Japanization Drug company makes-DMBI), (Van Dyk company makes 4-dimethylamino benzoic acid 2-Octyl Nitrite, Esolol507), 4,4 '-diethylamino benzophenone (protecting the EAB that native ケ paddy chemical company makes), 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butane-1-ketone (IRGACURE-369 that Ciba Specialty Chemicals company makes), N, N-dimethylamino benzaldehyde, N, N-dimethylamino benzoylformaldoxime etc.Preferred tertiary amine compound (D) is a triethanolamine, 4,4 '-diethylamino benzophenone and 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butane-1-ketone, and the latter's compound has the effect as Photoepolymerizationinitiater initiater.
In the hardening resin composition of the present invention, use 0.01～40 weight portion, the tertiary amine compound of the ratio of preferred 0.1～20 weight portion (D) with respect to the compound (A) of per 100 weight portions.At compound (A) with respect to 100 weight portions, tertiary amine compound (D) contain quantity not sufficient 0.01 weight portion the time, just can not give full play to the raising curable of tertiary amine compound in 350nm～420nm wavelength coverage, reduce cured film hydroscopicity, improve PCT patience, improve the effect of thermotolerance and anti-electroless plating.On the other hand, if with respect to the compound (A) of 100 weight portions, the content of tertiary amine compound (D) surpasses 40 weight portions, the development of filming and the degradation of anti-electroless plating of cured film, and also variation of PCT patience.
Hardening resin composition of the present invention can contain ring (sulphur) ether compound (E) as ring (sulphur) ether of 3,4 or 5 yuan of rings that contain oxygen atom or sulphur atom of heat curing composition.Ring (sulphur) ether compound (E) improves the adhesiveness of solidfied material, thermotolerance.Ring (sulphur) ether compound (E) preferably contains 2 or above ring (sulphur) ether, the compound that for example in each molecule, contains 2 or above epoxy radicals at least, be polyfunctional group epoxy compounds (E-1), and/or contain the compound of 2 or above oxetane groups in each molecule at least, promptly polyfunctional group oxetane compound (E-2) also is suitable use.In addition, contain the compound of at least 2 or above thia propane ring at each molecule, promptly episulfide resin (E-3) also is suitable use.
As polyfunctional group epoxy compounds (E-1), for example can list, the epikote 828 that japan epoxy resin company makes, epikote 834, epikote 1001, epikote 1004, the epiclon 840 that big Japanese ink chemical industrial company makes, epiclon 850, epiclon 1050, epiclon 2055, Dongdu changes into the Epo TohtoYD-011 that company makes, YD-013, YD-127, YD-128, the D.E.R.317 that Dow Chemical company makes, D.E.R.331, D.E.R.661, D.E.R.664, the Araldite 6071 that Ciba Specialty Chemicals company makes, Araldite6084, Araldite GY 250, Araldite GY 260, the Sumi-epoxy ESA-011 that Sumitomo Chemical Co. Ltd. makes, ESA-014, ELA-115, ELA-128, the A.E.R.330 that industrial group of Asahi Chemical Industry makes, A.E.R.331, A.E.R.661, the bisphenol A type epoxy resin of A.E.R.664 etc. (all being trade name); The epikote YL903 that japan epoxy resin company makes, epiclon 152, epiclon 165 that big Japanese ink chemical industrial company makes, Dongdu changes into Epo Tohto YDB-400, the YDB-500 that company makes, the D.E.R.542 that Dow Chemical company makes, the Araldite 8011 that Ciba Specialty Chemicals company makes, Sumi-epoxy ESB-400, ESB-700 that Sumitomo Chemical Co. Ltd. makes, the brominated epoxy resin of (all being trade name) such as A.E.R.711, A.E.R.714 that industrial group of Asahi Chemical Industry makes; The epikote152 that japan epoxy resin company makes, epikote154, the D.E.N.431 that Dow Chemical company makes, D.E.N.438, the epiclonN-730 that big Japanese ink chemical industrial company makes, epiclon N-770, epiclon N-865, Dongdu changes into the Epo TohtoYDCN-701 that company makes, YDCN-704, the AralditeECN 1235 that Ciba Specialty Chemicals company makes, Araldite ECN 1273, Araldite ECN 1299, Araldite XPY 307, the EPPN-201 that Japan's chemical drug corporate system is made, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, the Sumi-epoxy ESCN-195X that Sumitomo Chemical Co. Ltd. makes, ESCN-220, the A.E.R.ECN 235 that industrial group of Asahi Chemical Industry makes, the phenolic resin varnish of ECN 299 grades (all being trade name); The epiclon 830 that big Japanese ink chemical industrial company makes, the epikote 807 that japan epoxy resin company makes, Dongdu changes into Epo Tohto YDF-170, YDF-175, the YDF-2004 that company makes, the bisphenol f type epoxy resin of (all being trade name) such as AralditeXPY306 that Ciba Specialty Chemicals company makes; The Epo Tohto ST-2004 that Dongdu company that changes into makes, the hydrogenation bisphenol A type epoxy resin of (trade names) such as ST-2007, ST-3000; The glycidyl group amine type epoxy resin of (all being trade name) such as Sumi-epoxyELM-120 of the Epo TohtoYH-434 that epikote 604, Dongdu that japan epoxy resin company makes company that changes into makes, the AralditeMY720 that Ciba Specialty Chemicals company makes, Sumitomo Chemical Co. Ltd.'s manufacturing; The Araldite CY-350 hydantoins epoxy resin such as (all being trade name) that Ciba Specialty Chemicals company makes; The セ ロ キ サ イ De 2021 that DAICEL chemical industrial company makes, the alicyclic epoxy resin of (all being trade name) such as Araldite CY-175, CY-179 that Ciba Specialty Chemicals company makes; The trihydroxy benzene methylmethane type epoxy resin of (all being trade name) such as T.E.N., the EPPN-501 that the YL-933 that japan epoxy resin company makes, Dow Chemical company make, EPPN-502; The EXA-1514 bisphenol-s epoxy resins such as (trade names) that the EBPS-200 that two dimethyl phenols of (all being trade name) such as YL-6056, the YX-4000 that japan epoxy resin company makes, YL-6121 or bisphenol-type epoxy resin and their potpourri Japan chemical drug corporate system are made, the EPX-30 that Asahi Electro-Chemical Co. Ltd makes, big Japanese ink chemical industrial company make; The epikote 157S bisphenol-A phenolic varnish type epoxy resin such as (trade names) that japan epoxy resin company makes; The four phenylol ethane type epoxy resin of (all being trade name) such as Araldite 163 that the epikote YL-931 that japan epoxy resin company makes, Ciba Specialty Chemicals company make; The heterocyclic ring epoxy resins of (all being trade name) such as TEPIC that the AralditePT810 that Ciba Specialty Chemicals company makes, daily output chemical industrial company make; The o-phthalic acid diglycidyl ester resins such as Block レ Application マ-DGT that Nof Corp. makes; Dongdu changes into the four glycidyl group dimethylbenzene phenolic group ethane resin such as ZX-1063 that company makes; ESN-190, ESN-360 that chemical company of Nippon Steel makes, HP-4032, the EXA-4750 that big Japanese ink chemical industrial company makes, EXA-4700 etc. contain the epoxy resin of naphthyl; HP-7200, the HP-7200H etc. that big Japanese ink chemical industrial company makes have the epoxy resin of bicyclopentadiene skeleton; The copolymerization based epoxy resin of the glycidyl methacrylate of CP-50S, CP-50M etc. that Nof Corp. makes; And the copolymerization epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; The epoxy resin (for example Dongdu changes into YR-102, the YR-450 etc. that company makes) of epoxide modified polybutadiene rubber derivant (for example the PB-3600 that makes of DAICEL chemical industrial company etc.), CTBN modification etc., but be not limited to these examples.These resins can use separately or be used in combination its two or more.This wherein preferred especially phenolic resin varnish, hetero ring type epoxy resin, bisphenol A type epoxy resin or their potpourri.
As multifunction group epoxy based compound (E-2), can list two [(3-methyl-3-oxa-cyclobutyl methoxy base) methyl] ethers, two [(3-ethyl-3-oxa-cyclobutyl methoxy base) methyl] ether, 1, two [(3-methyl-3-oxa-cyclobutyl methoxy base) methyl] benzene of 4-, 1, two [(3-ethyl-3-oxa-cyclobutyl methoxy base) methyl] benzene of 4-, acrylic acid (3-methyl-3-oxa-cyclobutyl) methyl esters, acrylic acid (3-ethyl-3-oxa-cyclobutyl) methyl esters, methacrylic acid (3-methyl-3-oxa-cyclobutyl) methyl esters, methacrylic acid (3-ethyl-3-oxa-cyclobutyl) methyl esters and oxetanes classes such as their oligomer or multipolymer, and oxetanes and phenolic resin varnish, poly-(para hydroxybenzene ethene), cardo (カ Le De) type bisphenols, calixarenes (Calixarene) class, resorcinol calixarenes (Calixresorcinearene) class, perhaps silsesquioxane (Silsesquioxanes) etc. has the etherate of hydroxy resin.Other example also has the unsaturated monomer of oxygen heterocycle butane ring and the multipolymer of (methyl) alkyl acrylate.
As episulfide compounds (E-3), can list the bisphenol A-type episulfide resin YL7000 of japan epoxy resin company manufacturing etc.In addition, using same synthetic method, also is operable with the resulting episulfide resin of oxygen atom of the epoxy radicals of sulphur atom displacement phenolic resin varnish type epoxy resin kind etc.
With respect to the compound (A) of 100 weight portions, can use 10～100 weight portions, preferably use ring (sulphur) ether compound (E) of the ratio of 25～60 weight portions.In compound (A) with respect to 100 weight portions, ring (sulphur) ether compound (E) contain quantity not sufficient 10 weight portions the time, just can not give full play to the effect of ring (sulphur) the reduction cured film hydroscopicity that ether compound had, raising PCT patience, raising solder heat resistance and anti-electroless plating.On the other hand, if in the compound (A) with respect to 100 weight portions, the content of ring (sulphur) ether compound (E) surpasses 100 weight portions, the anti-electroless plating variation of development of filming and cured film, and demonstrate also variation of PCT patience.
When stating ring (sulphur) ether compound (E) in the use, preferably use the catalyzer of heat curing.This thermal curing catalyst can list imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano ethyl-2-phenylimidazole, 1-(2-cyano ethyl)-imdazole derivatives such as 2-ethyl-4-methylimidazole; The dicyano diamides, benzyl dimethylamine, 4-(dimethylamino)-N, the N-dimethyl benzylamine, 4-methoxyl-N, the N-dimethyl benzylamine, 4-methyl-N, amines such as N-dimethyl benzylamine, the hexane diacid hydrazides, hydrazide compounds such as decanedioic acid hydrazides, phosphorus compounds such as triphenylphosphine etc., and commercially available compound for example four countries change into the 2MZ-A that industrial group makes, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (being the trade name of glyoxaline compound all), the U-CAT3503N that SUN APOLLOSUN APOLLO company makes, U-CAT3502T (being the trade name of dimethylamine block isocyanate compound all), DBU, DBN, U-CATSA102, U-CAT5002 (being bicyclic amidine compound and salt thereof all) etc.; And be not limited to above-mentioned these, can promote ring (sulphur) ether and ring (sulphur) ether or get final product that these compounds can use separately or with its two or more mixing use with the compound of the reaction of carboxyl.In addition, as the Thermocurable catalyzer, can use the guanamine, acetyl guanamine, benzo guanamine, the melamine, 2 that also have the adhesiveness additives function, 4-diamido-6-methacryl hydroxyethyl-S-triazine, 2-vinyl-4,6-diamido-S-triazine, 2-vinyl-4,6-diamido-S-triazine isocyanuric acid adduct, 2,4-diamido-6-methacryl hydroxyethyl-S-pyrrolotriazine derivatives such as S-triazine isocyanuric acid adduct.The compound and the above-mentioned thermal curing catalyst that preferably these are also had the adhesiveness additives function use simultaneously.
The combined amount of thermal curing catalyst is that the ratio of amount usually is just enough, and for example with respect to compound (A) or ring (sulphur) ether compound (E) of 100 weight portions, the amount of thermal curing catalyst is 0.1～20 weight portion, the ratio of preferred 0.5～15.0 weight portion.
In addition, hardening resin composition of the present invention can contain the sensitizer that is useful on photocuring, in such sensitizer, contains the thioxanthones compound.Specifically can listing of thioxanthones compound: 1-chloro-4-propoxyl group thioxanthones (Nihon SiberHegner company make SpcedcureCPTX), 2-clopenthixal ketone (the カ ヤ キ ユ ア that makes of Japanese chemical drug corporate system-CTX), diisopropyl thioxanthones (the カ ヤ キ ユ ア that makes of Japanese chemical drug corporate system-DITX), 2,4-dimethyl thioxanthones (the カ ヤ キ ユ ア that makes of Japanese chemical drug corporate system-RTX), 2-isopropyl thioxanthone (the カ ヤ キ ユ ア that makes of Japanese chemical drug corporate system-ITX) etc.
Can be that ratio 0.01 weight portion～50 weight portions, preferred 0.1～30 weight portion is used the thioxanthones compound with compound (A) with respect to 100 weight portions.In the ratio of thioxanthones compound during with respect to compound (A) less than 0.01 weight portion of 100 weight portions, that just can not give full play to that the thioxanthones compound had improves curable, reduces the cured film hydroscopicity, improves PCT patience, improves the effect of solder heat resistance and anti-electroless plating in 350nm～420nm scope.On the other hand, if surpass 50 weight portions with respect to the content of compound (A) the thioxanthones compound of 100 weight portions, the development of filming and the degradation of anti-electroless plating of cured film, and also variation of PCT patience.
In addition, hardening resin composition of the present invention can contain various thinning agents.The example of such thinning agent is ketone, arene, gylcol ether, glycol ether acetates, ester class, alcohols, aliphatic hydrocarbon, petroleum-type solvent etc.More specifically, be arenes such as ketones such as methyl ethyl ketone, cyclohexanone, toluene, dimethylbenzene, tetramethylbenzene; Gylcol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, Triethylene glycol ethyl ether; Glycol ether acetates such as dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethylether acetate, propylene glycol butyl ether acetate; Ester classes such as the acetate compound of ethyl acetate, butyl acetate and above-mentioned gylcol ether; Alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; Aliphatic hydrocarbon such as octane, decane; Oil series solvents such as sherwood oil, naphtha, hydrotreated naphtha, solvent naphtha.
Such thinning agent can use separately or use with its two or more potpourri, and the scope of the use amount that it is suitable is that the compound (A) with respect to 100 weight portions is 10～60 weight portions, the ratio of preferred 15～50 weight portions.Because so dry to touch variation when using than this more amount is not preferred.
In addition, hardening resin composition of the present invention can contain filling material.Known inorganic fillers commonly used such as the example of filling agent can list spherical monox (for example Admatechs company make ア De マ Off ア イ Application SO-E2), contains organic filling material of urethane particle, other barium sulphate, barium titanate, silicon oxide powder (micro mist shape monox, amorphous silicon oxide, crystallinity monox, fused silica, spherical monox), talcum, clay, magnesium carbonate, lime carbonate, aluminium oxide, aluminium hydroxide, mica.These filling materials can use separately or with its 2 kinds or above being used in combination.
Hardening resin composition of the present invention as required can be further and phthalocyanine blue, phthalocyanine green, iodine is green, two diazonium Huangs, crystal violet, titanium dioxide, carbon black, known colorants commonly used such as naphthalene is black are used, with quinhydrones, hydroquinone monomethyl ether, tert-butyl catechol, 1,2,3,-thrihydroxy-benzene, known thermal polymerization inhibitor commonly used such as phenothiazine is used, with the micro mist monox, organobentonite, known tackifier commonly used such as polynite are used, with silicone, the fluorine class, macromolecule defoamer and/or levelling agent are used, with imidazoles, thiazoles, known additive kind commonly used such as silane coupling agents such as triazole type mixes use.
In addition, hardening resin composition of the present invention can be the form of aqueous, pasty state or dry film.
Hardening resin composition of the present invention is suitable for printing ink; plastics; the paper printing; film coating; the various coating of coatings for furniture etc.; FRP; wadding, and the insulating varnish of electronic applications; insulating base; laminate; printed base plate; aqueous protective seam; dry film; resist protective seam printing ink; color filter that LCD is used or black matrix" pigment diaphragm; perhaps coating diaphragm composition; semiconductor encapsulant; soldering-resistance layer; interlayer dielectic; the coating protective seam; etch protection layer; sandblast resistant durable printing ink; the polymkeric substance light-guide wave path; flat-panel monitor (FPD) is used parts; the color filter diaphragm; insulating cells such as contact type panel.
On base material, can be coated with method by silk screen print method, curtain formula rubbing method, spraying process, rolling method, mould, revolve tumbling barrel process, coating processes such as rod is coated with method, infusion process are coated with hardening resin composition of the present invention, the organic diluent volatile dry (temporary transient dry) that is contained by for example making in the composition under 60～100 ℃ temperature can form good, long the filming of life-span of developing of dry to touch.
As base material, the copper foil laminate of (FR-4) of all grades of having of can the enumerating copper foil laminate that high-frequency circuits such as using paper phenol, paper epoxy resin, glass cloth epoxy resin, glass polyimide, glass cloth/nonwoven fabrics epoxy resin, glass cloth/paper epoxy resin, synthon epoxy resin, fluorine tygon PPO cyanate use etc., other Kapton, PET film, glass substrate, ceramic substrate, chip plate etc.
Before coating hardening resin composition of the present invention, can to base material by polishing grind, float stone is cleaned and is ground, spray clean grind, physical grindings such as brush grindings, melanism is handled, the System of institute of MEC A/S make CZ-5480, CZ-8100 (preferably), マ Le チ ボ Application De that マ Network ダ ミ Star De company makes, テ Star Network A-7, テ Star Network F-1 etc. that electrochemical industry company in the East Sea makes are independent or make up the pre-treatment of carrying out chemical grinding etc.
The volatile dry that is carried out after the hardening resin composition of the present invention in coating can use heated air circulation type drying oven, IR stove, electric hot plate, convection oven (make the hot blast of exsiccator carry out the mode that convection current contacts in the device of the thermal source of the method for air heat by using to be equipped with by steam, perhaps be blown into the mode of hot blast by nozzle) to carry out.
As mentioned above, can behind coating hardening resin composition of the present invention, volatile dry, filming of gained be exposed (irradiation of activation evergy line), for example can carry out image exposure.The exposed portion of coated film (by the part of activation evergy line irradiation) is cured.
When exposure, can use direct tracing device (for example using the laser direct image device of direct laser tracing image), substep exposure machine, close induction type exposure machine etc. as exposure device by the cad data of computing machine.In addition, can use laser, near ultraviolet ray, ultraviolet ray, electron beam, X ray etc. is that main electromagnetic wave is as the activation evergy line.Can using gases laser, visible light laser, ultraviolet laser etc. such as Solid State Laser are as laser, can use argon laser, CO
2Laser, YAG laser, variable wavelength laser, fibre laser, slave mode Q-switch laser, semiconductor laser are as lasing light emitter.As the radiation source except that laser, can use Cooper-Hewitt lamp, middle medium pressure mercury lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, excimer laser (エ キ シ マ ラ) lamp, argon incandescent lamp, X-flash, photograph flood lighting lamp, xenon lamp or metal halide lamp etc.But the composition of hardening resin composition of the present invention is characterised in that it especially by the activation evergy line curing of 350nm～420nm, and therefore preferred use laser is as the activation evergy line.Wherein, under near the wavelength 355nm, 360nm, the 405nm, hardening resin composition of the present invention demonstrates fabulous surface cure.Above-mentioned direct tracing device also can use for example Japanese オ Le Port テ Star Network company makes, rising sun optics industry company any device that make, ボ one Le セ ミ コ Application ダ Network タ one manufacturing.
After the exposure,, can obtain hardening resin composition pattern of the present invention by unexposed portion is developed.Can develop by infusion process, spray process, spraying, brushing method.As developer solution,, can use alkaline aqueous solutions such as potassium hydroxide, NaOH, sodium carbonate, sal tartari, sodium phosphate, sodium silicate, ammonia, amine when compound (A) when having carboxyl.In addition, when developing, can use organic solvents such as acetone, toluene, methyl ethyl ketone by organic solvent.
When hardening resin composition of the present invention contains the heat curing composition, after above-mentioned development, can make its heat curing by for example under about 140～180 ℃ temperature, heating, form insulating coating film with fabulous adhesiveness, hardness, solder heat resistance, resistance to chemical reagents, chemical reagent resistance, electrical insulating property, electrocorrosion-resisting.
When making printed circuit board (PCB) of the present invention, in the formation method of above-mentioned pattern,, use the base material that is printed with circuit-line as base material.
Embodiment
Below by providing specific embodiment and comparative example specifies the present invention, the present invention is not limited to the described content of following embodiment.
Synthesis example 1
In a detachable flask of 2 liters that is equipped with stirrer, thermometer, reflux condensing tube, tap funnel and nitrogen ingress pipe, add 508g dipropylene glycol monomethyl ether (the Japanese emulsifying agent manufacturing MFDG of company), be heated to after 110 ℃, splash into 174g in total in 3 hours time and contain the carboxylic acid of olefinic unsaturated group (in the following formula (I), R is a methyl, and n is 2 compound), 174g methacrylic acid, 77g Jia Jibingxisuanyizhi, 222g MFDG and 12.0g t-butyl peroxy-2 ethyl hexanoic acid ester (Nof Corp. makes パ one Block チ Le O).Add post curing 3 hours, the synthetic dry polymer (multipolymer) that contains carboxyl, then in this dry polymeric, add 289g 3, (the サ イ Network ロ マ that DAICEL chemical industrial company makes-A200), 3.0g triphenylphosphine, 1.3g methylnaphthohydroquinone, reaction is 10 hours under 100 ℃ of temperature for 4-epoxycyclohexyl methacrylate.Reaction is to carry out under the mixed atmosphere of air/nitrogen.Thus, obtaining acid number is the solution of the activation evergy line curable resin A (unsaturated compound that contains epoxy radicals that contains carboxylic acid/(methyl) acrylate copolymer of olefinic unsaturated group) of 80mg KOH/g, two key equivalent (quality of the resin of per 1 mole of unsaturated group (g)) 450, weight-average molecular weight 25,000.
Synthesis example 2
In a detachable flask of 2 liters that is equipped with stirrer, thermometer, reflux condensing tube, tap funnel and nitrogen ingress pipe, (Japanese chemical drug strain formula can company be made EOCN-104S to add 660g cresols phenolic resin varnish type epoxy resin, 92 ℃ of softening points, epoxide equivalent 220), 421.3g carbitol acetate and 180.6g solvent naphtha, heat, be stirred to 90 ℃, make it dissolving.Then, after being cooled to 60 ℃ of temperature, add 216g acrylic acid, 4.0g triphenylphosphine, 1.3g methylnaphthohydroquinone, reaction is 12 hours under 100 ℃ of temperature.Thus, obtain the reaction product that acid number is 0.2mgKOH/g.Then add the 241.7g tetrahydrophthalic acid, be heated to 90 ℃ of stirrings and make it dissolving, reacted 6 hours, obtaining acid number thus is the solution of the activation evergy line curable resin B (the multi-anhydride adduct of the acrylate resin that the cresols phenolic varnish type is epoxide modified) of 50mg KOH/g, two key equivalent (quality of the resin of per 1 mole of unsaturated group (g)) 400, weight-average molecular weight 7,000.
The resin solution of the synthesis example 1,2 that obtains is like this mixed according to the ratio shown in the table 1 (weight portion) with the various compositions shown in the table 1, in stirring machine, after the ready-mixed, use 3 roll-type roll squeezers mixing, preparation soldering-resistance layer photosensitive resin composition.Then, fixed its granularity of the lapping degree instrumentation that uses Eriksen company to make, the result is 15 μ m or following.
Then, on substrate, be coated with the as above photosensitive polymer combination of preparation of 20 μ m thickness by silk screen print method, drying is after 30 minutes in 80 ℃ heated air circulation type drying oven, use spectrograph (RM-23 that MESSTEK makes) to use activation evergy line irradiation 60 minutes (light source: xenon lamp, the XB-10201AA-A that USHIO makes) while carrying out the nitrogen cleaning.Then, obtain cured coating film by the aqueous sodium carbonate development of using 30 ℃ 1 quality %.
Then carry out according to the methods below the spectrum sensitivity of gained soldering-resistance layer with the cured coating film of photosensitive polymer combination experimentized.That is, in the illumination wavelength of 200nm～800nm, measure, when wavelength is 405nm, the surface gloss under the visual observation 405nm.Even the standard of estimating also is designated as well for only showing surface gloss seldom, and not display surface gloss just be designated as bad.Evaluation result is recorded in the table 1 in the lump.
In addition, measure by the light-struck embodiment 1 of various wavelength and the resin combination surface cure state of comparative example 1 by spectrum sensitivity, its result separately as depicted in figs. 1 and 2.As shown in Figure 1, the resin combination of embodiment 1 demonstrates surface gloss by the rayed of 405nm, the surface cure excellence.On the other hand, as shown in Figure 2, the resin combination of comparative example 1 does not demonstrate surface gloss by the rayed of 405nm.
In addition, on substrate, be coated with the above-mentioned photosensitive polymer combination of 20 μ m thickness by silk screen print method, in 80 ℃ heated air circulation type drying oven, after dry 30 minutes, use the direct tracing device (DE-S that the ピ ア メ カ ニ of Hitachi Network ス company makes) that the 405nm semiconductor laser is installed to expose.Then, obtain cured coating film by the aqueous sodium carbonate development of using 30 ℃ 1 quality %.
Then using direct tracing device that the soldering-resistance layer that as above obtains is carried out pattern with the cured coating film of photosensitive polymer combination forms and tests.That is, pattern is that the wavelength of lines/gap=50/50 (μ m), 405nm carries out 80mJ/cm
2Irradiation, the image after form developing is checked the lines that noresidue is arranged immediately.Even the standard of estimating just is designated as well for the residual situation that only demonstrates seldom, and do not have residual be designated as bad.Evaluation result is recorded in the table 1 in the lump.
Table 1
In table 1, each component is as described below:
Photoepolymerizationinitiater initiater A: the compound of following formula (1-2) (2-acetoxyl group oximido methyl) thioxanthene-9-one
Photoepolymerizationinitiater initiater B:2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butane-1-ketone (IRGACURE-369 that Ciba Specialty Chemicals company makes)
Sensitizer A:4-dimethyl ethyl benzoate (the カ ヤ キ ユ ア that makes of Japanese chemical drug corporate system-EPA)
Sensitizer B:4,4 '-lignocaine benzophenone (protecting the EAB that native ケ paddy chemical company makes)
Sensitizer C: two (η
5-2,4-cyclopentadiene-1-yl)-two-(2,6-two fluoro-3-(1H-pyrroles-1 base) phenyl) titanium (IRGACURE-784 that Ciba Specialty Chemicals company makes)
Sensitizer D: two (2,4, the 6-trimethylbenzoyl)-phenylphosphine oxide (IRGACURE-819 that Ciba Specialty Chemicals company makes)
Sensitizer E:4-benzoyl-4 '-methyldiphenyl thioether (the カ ヤ キ ユ ア that makes of Japanese chemical drug corporate system-BMS)
Epoxy resin A: phenolic resin varnish type epoxy resin (EPPN-201 that Japanese chemical drug corporate system is made)
Epoxy resin B: cresols phenolic resin varnish type epoxy resin (RN695 that big Japanese ink company makes)
Epoxy resin C: to diformazan phenol-type epoxy resin (YX-4000 that japan epoxy resin company makes)
Polymerizable monomer A: dipentaerythritol acrylate (DPHA that Japanese chemical drug corporate system is made)
Polymerizable monomer B: trimethylolpropane triacrylate (TMPTA that Japanese chemical drug corporate system is made)
Thermal curing catalyst A: dicyano diamides (manufacturing of oiling シ エ Le エ ボ キ シ company)
Thermal curing catalyst B:2,4-diamido-6-[2 '-methylimidazole-(1 ')]-ethyl-S-triazine (four countries change into the 2MZ-AP that industrial group makes)
Pigment A: phthalocyanine blue
Pigment B: anthraquinone class pigment
Adjuvant: silicone defoamer (KS-66 that chemical industrial company of SHIN-ETSU HANTOTAI makes)
Filling agent A: fused silica (ヒ ユ-ズ レ Star Network ス WX that the gloomy company of Long makes).
By the result shown in the table 1 as can be known: the present invention mixes the photopolymerization initiator composition that obtains by using simultaneously by the benzophenone cpd that contains sulphur atom (C) with the compound that contains oxime ester base (B), use the rayed of 405nm to obtain the surface coating glossiness, i.e. the surface of good curable.And, be used for this polymerization initiator and the skeleton of resin (compound (A)) do not exerted an influence, use the rayed of 405nm, can realize the film coated surface glossiness, promptly good surface cure.
Claims (5)
1. hardening resin composition, it contains: the compound (A) with at least one unsaturated double-bond, compound (B) with oxime ester base, and the benzophenone cpd (C) that contains sulphur atom, and further contain the ring-type ether that has more than 2 or the cyclic ether compound or the cyclic thioether compound (E) of cyclic thioether base, described hardening resin composition is the activation evergy line curing of 350nm～420nm by wavelength, described compound (B) with the ratio that cooperates of described benzophenone cpd (C) is, described compound (A) with respect to 100 weight portions, described compound (B) is 0.01～50 weight portion, and described benzophenone cpd (C) is 0.01～40 weight portion, the cooperation ratio of described cyclic ether compound or cyclic thioether compound (E) is, described compound (A) with respect to 100 weight portions, this cyclic ether compound or cyclic thioether compound (E) are 10～100 weight portions
Described compound (B) is to be selected from 1,2-acetyl caproyl, 1-[4-(benzene sulphur)-2-(O-benzoyl oxime)], 1-phenyl-1, the Photoepolymerizationinitiater initiater in the thioxanthones compound shown in 2-propanedione-2-(O-ethoxy carbonyl) oxime and the formula (1-1),
In the formula (1-1), 1 or 2 R
1Be the represented oxime ester base of formula (1), other R
1Expression hydrogen, methyl, phenyl or halogen atom,
In formula (1), R represents to have the alkyl or the phenyl of 1～7 carbon atom, and R ' represents hydrogen atom or has the alkyl or the phenyl of 1～7 carbon atom.
2. the hardening resin composition of putting down in writing according to claim 1, it also contains tertiary amine compound (D), and the cooperation ratio of this tertiary amine compound (D) is that with respect to the described compound (A) of 100 weight portions, this tertiary amine compound (D) is 0.01～40 weight portion.
3. according to claim 1 or 2 hardening resin compositions of being put down in writing, it can be cured by laser.
4. the solidfied material of each hardening resin composition of putting down in writing in the claim 1～3.
5. printed circuit board (PCB), it is formed with the pattern of the solidfied material of each hardening resin composition of putting down in writing in the claim 1～3.
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| Application Number | Priority Date | Filing Date | Title |
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| JP398088/2003 | 2003-11-27 | ||
| JP2003398088 | 2003-11-27 |
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| JP (1) | JP4865044B2 (en) |
| KR (1) | KR101048940B1 (en) |
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|---|---|---|---|---|
| JP4849860B2 (en) * | 2005-10-04 | 2012-01-11 | 太陽ホールディングス株式会社 | Photocurable / thermosetting resin composition, cured product thereof, and printed wiring board obtained using the same |
| KR100781873B1 (en) * | 2006-01-02 | 2007-12-05 | 주식회사 엘지화학 | Photoactive oxime ester based compounds and photosensitive composition comprising the same |
| JP4864545B2 (en) * | 2006-05-26 | 2012-02-01 | 太陽ホールディングス株式会社 | Thermosetting solder resist composition for flexible substrate, flexible substrate and method for producing flexible substrate |
| KR100904348B1 (en) * | 2006-10-24 | 2009-06-23 | 다이요 잉키 세이조 가부시키가이샤 | Photocurable thermosetting resin composition and printed wiring board using same |
| JP5079310B2 (en) * | 2006-11-15 | 2012-11-21 | 太陽ホールディングス株式会社 | PHOTO TOOL FOR SOLDER RESIST EXPOSURE AND METHOD FOR FORMING SOLDER RESIST PATTERN EXPOSED BY USING THE SAME |
| KR20080044184A (en) * | 2006-11-15 | 2008-05-20 | 다이요 잉키 세이조 가부시키가이샤 | Alkali development type paste composition, method for conductive pattern and black matrix pattern formation using the same, and the conductive pattern and the black matrix pattern |
| KR100996046B1 (en) * | 2007-03-29 | 2010-11-22 | 도쿄 오카 고교 가부시키가이샤 | Colored photosensitive resin composition, black matrix, color filter, and liquid crystal display |
| KR101277020B1 (en) * | 2010-09-30 | 2013-06-24 | 다이요 홀딩스 가부시키가이샤 | Photosensitive conductive paste |
| JP5744528B2 (en) * | 2011-01-11 | 2015-07-08 | 東京応化工業株式会社 | Colored photosensitive resin composition for touch panel, touch panel, and display device |
| JP2012163735A (en) * | 2011-02-07 | 2012-08-30 | Toyo Ink Sc Holdings Co Ltd | Photosensitive resin composition, and protective film and insulating film for touch panel using the composition |
| KR101692003B1 (en) * | 2013-12-24 | 2017-01-03 | 코오롱인더스트리 주식회사 | Photosensitive Resin Composition for Dry Film Photoresist |
| TW201940615A (en) * | 2014-12-26 | 2019-10-16 | 日商太陽油墨製造股份有限公司 | Curable resin composition, dry film, cured product and printed circuit board |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR101048940B1 (en) | 2011-07-12 |
| JP2010160495A (en) | 2010-07-22 |
| JP4865044B2 (en) | 2012-02-01 |
| TW200519535A (en) | 2005-06-16 |
| KR20050051574A (en) | 2005-06-01 |
| CN1779568A (en) | 2006-05-31 |
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