CN104678702A - Photosensitive resin composition, dry film, cured product and printed circuit board - Google Patents
Photosensitive resin composition, dry film, cured product and printed circuit board Download PDFInfo
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- CN104678702A CN104678702A CN201410723063.XA CN201410723063A CN104678702A CN 104678702 A CN104678702 A CN 104678702A CN 201410723063 A CN201410723063 A CN 201410723063A CN 104678702 A CN104678702 A CN 104678702A
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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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- 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
- G03F7/0275—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with dithiol or polysulfide compounds
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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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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a photosensitive resin composition, a dry film, a cured product and a printed circuit board and provides a technology capable of restraining the generation of developing residue in hole portions such as through holes in a solder mask composition containing titanium oxide. The invention relates to the photosensitive resin composition, the dry film using the same and the cured product thereof. The photosensitive resin composition contains (A) carboxyl-containing resin, (B) an epoxy series thermocuring component, (C) inorganic filler, and (D) a photopolymerization initiator. Relative to the equivalent of 1 of carboxyl contained in the (A) carboxyl-containing resin, the equivalent of epoxy groups contained in the (B) epoxy series thermocuring component is below 1.0; the (C) inorganic filler contains titanium oxide.
Description
Technical field
The present invention relates to photosensitive polymer combination (being also simply called below " composition "), dry film, solidfied material and printed circuit board (PCB), specifically, the alkali development-type photosensitive resin composition of improvement Photoepolymerizationinitiater initiater, dry film, solidfied material and printed circuit board (PCB) is related to.
Background technology
Generally speaking, printed circuit board (PCB) removes the unwanted part of the Copper Foil being pasted on plywood by etching and is formed with wiring, and electronic unit is configured in the position of regulation by welding.In such printed circuit board (PCB); as for prevent solder to the attachment of required part and oxidized for preventing the conductor of circuit from exposing, the diaphragm that corrodes by moisture, the region except connecting hole on the substrate being formed with circuit pattern forms solder mask.Solder mask also plays function as the permanent diaphragm of circuit substrate, therefore requires to possess the various performances such as adaptation, electrical insulating property, resistance to soldering heat performance, solvent resistance, chemical proofing to solder resist.
As one of the method for solder mask of pattern forming expectation on substrate, employ the formation method utilizing photoetching technique.Such as, after being exposed by pattern mask by the photonasty solder mask that the photosensitive polymer combination by alkali developable is formed, carry out alkali development, thus the deliquescent difference to alkaline developer that produces in exposure portion and non-exposed portion can be utilized and form pattern.
Such as, in order to provide containing Chinese white and light quantity needed for exposing is suppressed and can form the solder mask composition of the solder mask with high light reflectivity in patent documentation 1, the light disclose a kind of solder mask composition, described solder mask composition is compounding photoresist, Chinese white, utilizing more than wavelength 400nm carries out the Photoepolymerizationinitiater initiater that activates and fluorescent dye.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2011-227343 publication (claims etc.)
Summary of the invention
the problem that invention will solve
Therefore, in solder mask composition, in order to composition is colored as white, sometimes in large quantities containing titanium dioxide.But the fluidity of the composition in large quantities containing titanium dioxide is low, exists when therefore entering into the hole portions such as through hole and be difficult to remove and the problem of residual development residue.
The object of the present invention is to provide the technology that can suppress the generation of the development residue in the hole portions such as through hole in containing the solder mask composition of titanium dioxide.
for the scheme of dealing with problems
The present inventor etc. further investigate, found that, by making the equivalent of epoxy radicals contained in composition be less than 1.0 relative to carboxyl 1 equivalent contained in composition, even if in the generation in large quantities containing the development residue that also can suppress when titanium dioxide in through hole etc., thus complete the present invention.
That is, photosensitive polymer combination of the present invention, is characterized in that, it contains (A) containing carboxy resin, (B) epoxy Thermocurable composition, (C) inorganic filler and (D) Photoepolymerizationinitiater initiater,
Relative to aforementioned (A) containing carboxyl 1 equivalent contained in carboxy resin, the equivalent of epoxy radicals contained in aforementioned (B) epoxy Thermocurable composition is less than 1.0, and aforementioned (C) inorganic filler contains titanium dioxide.
In composition of the present invention, preferably, aforementioned (B) epoxy Thermocurable composition contain at 20 DEG C for liquid epoxy resin and at 40 DEG C for more than at least one in solid-state solid epoxy.In addition, in composition of the present invention, aforementioned (A) is suitably for less than 0.8 containing the ratio of the equivalent of the epoxy radicals contained by equivalent and aforementioned (B) epoxy Thermocurable composition of carboxyl contained in carboxy resin.And then, in composition of the present invention, preferably, aforementioned (A) containing carboxy resin derived from styrene or styrene derivative.
In addition, the feature of dry film of the present invention is, has the photosensitive polymer combination being coated with the invention described above on a carrier film and the resin bed making it dry and obtain.
And then the feature of solidfied material of the present invention is, it utilizes illumination to penetrate and the aforementioned resin layer solidification of the photosensitive polymer combination of the invention described above or the dry film of the invention described above is obtained.
And then the feature of printed circuit board (PCB) of the present invention is, there is the solidfied material of the invention described above.
the effect of invention
According to the present invention, can be implemented in the technology that can suppress the generation of the development residue in the hole portions such as through hole in the solder mask composition containing titanium dioxide.
Accompanying drawing explanation
Fig. 1 is the summary lateral view that 2 developmental tubes used are shown during the liquid state of epoxy resin judges.
Embodiment
Below, embodiments of the present invention are described in detail.
First, each composition of photosensitive polymer combination of the present invention is described.It should be noted that, in this instructions, (methyl) acrylate refers to the term being referred to as acrylate, methacrylate and their potpourri, to other similar performance too.
[(A) is containing carboxy resin]
Photosensitive polymer combination of the present invention contains (A) containing carboxy resin.As (A) containing carboxy resin, the carboxylic resin of known bag can be used.Due to the existence of carboxyl, composition can be made to be alkali-developable.In addition, from the view point of making composition of the present invention be photo-curable, resistance to developability, except carboxyl, also preferred have ethylenic unsaturated bond in molecule, but also can only use do not have ethylenical unsaturated double bonds containing carboxy resin.(A) aromatic rings can be had containing carboxy resin and also can not have aromatic rings.(A) when there is aromatic rings containing carboxy resin, the effect of the deterioration caused by heat, photoconduction that can be inhibited, therefore preferably.
As can use in composition of the present invention containing the concrete example of carboxy resin, can enumerate and enumerate such compound (oligomer and polymkeric substance) below.
(1) by the unsaturated carboxylic acids such as (methyl) acrylic acid, with styrene, α-methyl styrene, (methyl) lower alkyl acrylate, isobutylene etc. containing the copolymerization of unsaturated group compound obtain containing carboxy resin.When should have aromatic rings containing carboxy resin, unsaturated carboxylic acid and at least a kind of containing in unsaturated group compound have aromatic rings.
(2) aliphatic diisocyanate is utilized, Branched fatty (cyclo) aliphatic diisocyanates, ester ring type diisocyanate, the diisocyanate such as aromatic diisocyanate, and dihydromethyl propionic acid, dimethylolpropionic acids etc. are containing carboxyl diatomic alcohol compounds, and polycarbonate-based polyvalent alcohol, polyethers system polyvalent alcohol, polyester-based polyols, polyolefin polyvalent alcohol, acrylic polyol, bisphenol-A system alkylene oxide addition product glycol, have the diol compounds such as the compound of phenolic hydroxyl group and alcohol hydroxyl group addition polymerization and obtain containing carboxyl urethane resin.When should have aromatic rings containing carboxyl urethane resin, diisocyanate, containing at least a kind in carboxyl diatomic alcohol compounds and diol compound, there is aromatic rings.
(3) utilize the diisocyanate cpds such as aliphatic diisocyanate, Branched fatty (cyclo) aliphatic diisocyanates, ester ring type diisocyanate, aromatic diisocyanate and polycarbonate-based polyvalent alcohol, polyethers system polyvalent alcohol, polyester-based polyols, polyolefin polyvalent alcohol, acrylic polyol, bisphenol-A system alkylene oxide addition product glycol, have the diol compound such as compound of phenolic hydroxyl group and alcohol hydroxyl group addition polymerization and obtain urethane resin, make the end of this urethane resin and anhydride reaction containing terminal carboxyl group urethane resin.When should have aromatic rings containing carboxyl urethane resin, at least a kind in diisocyanate cpd, diol compound and acid anhydrides had aromatic rings.
(4) utilize (methyl) acrylate of 2 functional epoxy resins such as diisocyanate and bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, di-first phenol-type epoxy resin, united phenol-type epoxy resin or the anhydride modified thing of its part, the photonasty that obtains containing the addition polymerization of carboxyl diatomic alcohol compounds and diol compound containing carboxyl urethane resin.When this photonasty has aromatic rings containing carboxyl urethane resin, (methyl) acrylate or the anhydride modified thing of its part of diisocyanate, 2 functional epoxy resins, containing at least a kind in carboxyl diatomic alcohol compounds and diol compound, there is aromatic rings.
(5) add the compound in (methyl) hydroxyalkyl acrylates equimolecular with 1 hydroxyl and more than 1 (methyl) acryloyl group in the synthesis of the resin of above-mentioned (2) or (4) and carried out end (methyl) acrylated containing carboxyl urethane resin.When this photonasty has aromatic rings containing carboxyl urethane resin, the compound in molecule with 1 hydroxyl and more than 1 (methyl) acryloyl group can have aromatic rings.
(6) add the compound in the reaction with same mole thing of isophorone diisocyanate and pentaerythritol triacrylate etc., molecule with 1 isocyanate group and more than 1 (methyl) acryloyl group in the synthesis of the resin of above-mentioned (2) or (4) and carried out end (methyl) acrylated containing carboxyl urethane resin.When this photonasty has aromatic rings containing carboxyl urethane resin, the compound in molecule with 1 isocyanate group and more than 1 (methyl) acryloyl group can have aromatic rings.
(7) make polyfunctional epoxy resin and (methyl) acrylic acid react, on the hydroxyl being present in side chain, the photonasty of the dibasic acid anhydride such as addition phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride contains carboxy resin.When this photonasty has aromatic rings containing carboxy resin, at least a kind in polyfunctional epoxy resin and dibasic acid anhydride has aromatic rings.
(8) make the polyfunctional epoxy resin of the hydroxyl epoxidation of 2 functional epoxy resins and (methyl) acrylic acid to be reacted with chloropropylene oxide further, on the hydroxyl generated, the photonasty of addition dibasic acid anhydride is containing carboxy resin.When this photonasty has aromatic rings containing carboxy resin, at least a kind in 2 functional epoxy resins and dibasic acid anhydride has aromatic rings.
(9) make multifunctional oxetane resin and dicarboxylic acid react, on the primary hydroxyl generated, addition dibasic acid anhydride contains carboxyl polyester resin.When this photonasty has aromatic rings containing carboxyl polyester resin, at least a kind in multifunctional oxetane resin, dicarboxylic acid and dibasic acid anhydride has aromatic rings.
(10) compound and the alkylene oxide such as oxirane, epoxypropane that make to have in 1 molecule multiple phenolic hydroxyl group react and obtain reaction product, make this reaction product and react containing unsaturated group monocarboxylic acid, what make the reaction product that obtains thus and multi-anhydride react and obtain contains carboxyl photoresist.
(11) compound and the cyclic carbonate compound such as ethylene carbonate, propylene carbonate that make to have in 1 molecule multiple phenolic hydroxyl group react and obtain reaction product, make this reaction product and react containing unsaturated group monocarboxylic acid, what make the reaction product that obtains thus and multi-anhydride react and obtain contains carboxyl photoresist.
(12) make to have in 1 molecule the compound in 1 molecules such as the epoxy compound of multiple epoxy radicals and p-hydroxyphenylethanol with at least 1 alcohol hydroxyl group and 1 phenolic hydroxyl group and (methyl) acrylic acid etc. react containing unsaturated group monocarboxylic acid, the multi-anhydride such as the alcohol hydroxyl group of the reaction product obtained and maleic anhydride, tetrabydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, adipic anhydride is reacted and obtain contain carboxyl photoresist.When this photonasty has aromatic rings containing carboxyl polyester resin, there is in epoxy compound, 1 molecule the compound of at least 1 alcohol hydroxyl group and 1 phenolic hydroxyl group, containing at least a kind in unsaturated group monocarboxylic acid and multi-anhydride, there is aromatic rings.
(13) any one resin in above-mentioned (1) ~ (12) has the photonasty of the compound of 1 epoxy radicals and more than 1 (methyl) acryloyl group in further addition (methyl) glycidyl acrylate, (methyl) acrylic acid Alpha-Methyl ethylene oxidic ester equimolecular containing carboxy resin.When this photonasty has aromatic rings containing carboxyl urethane resin, the compound in molecule with 1 epoxy radicals and more than 1 (methyl) acryloyl group can have aromatic rings.
As described above containing carboxy resin owing to there is multiple carboxyl at the side chain of trunk polymer, so utilize the development of dilute alkaline aqueous solution to become possibility.
In addition, in above-mentioned, when using (A) derived from styrene or styrene derivative containing carboxy resin, the composition of resistance to soldering heat excellent performance can be obtained, therefore preferably.
The above-mentioned acid number containing carboxy resin expect be 20 ~ 200mgKOH/g scope, be more preferably the scope of 40 ~ 180mgKOH/g.When being the scope of 20 ~ 200mgKOH/g, can obtain the adaptation of film, alkali development becomes easy, and the dissolving in the exposure portion caused by developer solution is suppressed, and line can not narrow to more than necessity, and the description transfiguration of normal corrosion-resisting pattern is easy, therefore preferably.
In addition, the weight-average molecular weight containing carboxy resin used in the present invention is different according to resin matrix, is preferably the scope of 2000 ~ 150000.During for this scope, non-adhesion behavior is good, and the moisture-proof of the film after exposure is good, not easily produces film and reduce during development.In addition, during scope for above-mentioned weight-average molecular weight, resolution improves, and developability is good, and storage-stable becomes good.Be more preferably 5000 ~ 100000.Weight-average molecular weight can utilize gel permeation chromatography to measure.
[(B) epoxy Thermocurable composition]
(B) epoxy Thermocurable composition is contained in order to give thermotolerance in photosensitive polymer combination of the present invention.As (B) epoxy Thermocurable composition, the material used as Thermocurable composition in hot curing resin composition can be used in arbitrarily, specifically, compound, the i.e. known multi-functional epoxy compound with multiple epoxy radicals can be used arbitrarily in molecule.
As above-mentioned multi-functional epoxy compound, such as, can enumerate the bisphenol A type epoxy resins such as the jER828 of Mitsubishi chemical Co., Ltd's manufacture, brominated epoxy resin, phenolic resin varnish type epoxy resin, bisphenol f type epoxy resin, bisphenol-A epoxy resin, glycidyl amine type epoxy resin, hydantoins type epoxy resin, alicyclic epoxy resin, trihydroxy benzene methylmethane type epoxy resin, the di-cresols type such as YX-4000 that Mitsubishi chemical Co., Ltd manufactures or united phenol-type epoxy resin or their potpourri, bisphenol-s epoxy resin, bisphenol A novolac type epoxy resin, the cresol novolak type epoxy resins such as the RN-695 that Dainippon Ink Chemicals manufactures, four hydroxy phenyl ethane type epoxy resin, the hetero ring type epoxy resin such as the TEPIC that Nissan Chemical Ind Ltd manufactures, terephthalic acid diglycidyl ester resin, four glycidyl group dimethylbenzene acyl group ethane resin, containing Naphthol-based Epoxy Resin, there is the epoxy resin of bicyclopentadiene skeleton, soft tough epoxy resin, glycidyl methacrylate copolymerization system epoxy resin, the copolymerization epoxy resin etc. of N-cyclohexylmaleimide and glycidyl methacrylate, but be not limited to these.These epoxy resin can be used alone or in combination of two or more kinds.Wherein, from the view point of flexibility, be preferably the epoxy resin of 2 officials' energy.From the view point of anti-flammability, be particularly preferably biphenyl phenolic resin varnish type epoxy resin, di-first phenol-type epoxy resin or their potpourri.
In the present invention, (B) the compounding amount of epoxy Thermocurable composition needs to be set to: relative to (A) containing carboxyl 1 equivalent contained in carboxy resin, and the equivalent of epoxy radicals contained in (B) epoxy Thermocurable composition is the scope of less than 1.0.Preferably be set to: (A) be more than 0.1 containing the ratio of the equivalent of epoxy radicals contained in equivalent and (B) epoxy Thermocurable composition of carboxyl contained in carboxy resin and less than 0.8, be particularly preferably less than more than 0.2 0.6 scope.Herein, in the present invention, the equivalent of carboxyl and epoxy radicals refers to respectively, as the carboxyl of reactive group and the chemical equivalent of epoxy radicals.That is, in the present invention, epoxy radix contained by making in composition (dry coating), (B) epoxy Thermocurable composition is less than (A) carboxyl number containing carboxy resin.
Usually, (B) the compounding amount of epoxy Thermocurable composition is set to the residual scope of the carboxyl that can prevent in curing overlay film, but in the present invention, by the compounding amount of (B) epoxy Thermocurable composition in composition is set to above-mentioned scope, make the negligible amounts of quantity relative to carboxyl of the epoxy radicals reacted, thus the carboxyl being conducive to developability can be made also more to remain after heat curing.Thus, even the curing overlay film containing titanium dioxide, also can improve the dissolubility for developer solution, in the hole portions such as through hole, also can suppress the generation of development residue.It should be noted that, in the present invention, the hole portions such as through hole refer to, are not limited to through hole, also comprise other hole portions such as via.Hole portion diameter is less, and residue more easily blocks, but according to the present invention, even if be such as below internal diameter 300mm, specifically for more than internal diameter 200mm and the little hole portion of the diameter of below 300mm, also can carry out developing and can not producing residue.
In the present invention, as (B) epoxy Thermocurable composition, preferably containing be liquid epoxy resin at 20 DEG C and being more than at least one in solid-state solid epoxy at 40 DEG C.Herein, in the present invention, solid-stately refer to the concept comprising powder.As (B) epoxy Thermocurable composition, containing when be liquid epoxy resin at 20 DEG C, viscosity is low, become and be easy to flowing, therefore, becomes the development residue in not easily generation through hole.In addition, as (B) epoxy Thermocurable composition, containing when be the solid epoxy of powder at 40 DEG C, for granular, not easily block in through hole, therefore still become and not easily produce the residue that develops.And then, as (B) epoxy Thermocurable composition, containing be solid-state solid epoxy at 40 DEG C time, also in the same manner as the situation of powder for granular, not easily block in through hole, therefore become not easily produce develop residue.On the other hand, at the temperature when developing, during containing semi-solid epoxy resin, be solid-state and liquid intermediateness, viscosity is high, therefore thinks that development residue easily enters in through hole, becomes the state being difficult to discharge.In recent years, along with the miniaturization of substrate, the size of through hole also becomes less, therefore especially easily produces such phenomenon.
Herein, the decision method of " liquid state " in the present invention is described.
Liquid judgement is carried out according to making " the liquid confirmation method " of the attached sheet the 2nd of (Heisei autonomous province in the first year makes No. 1) about the test of danger and the province of proterties.
(1) device
Water Tank with Temp.-controlled:
Use possesses stirring machine, well heater, thermometer, automatic temperature regulator (can carry out temperature control with ± 0.1 DEG C) and the Water Tank with Temp.-controlled of more than degree of depth 150mm.
It should be noted that, in the judgement of the epoxy resin used in embodiment described later, all use Yamato Scientific Co., Ltd. the Low Constant Temperature Water Baths (model BU300) made and the combination of Constant Temperature Devices Thermo-Mate (model BF500), about 22 liters, tap water is joined in Low Constant Temperature Water Baths (model BU300), connect the power supply of the Thermo-Mate (model BF500) be mounted thereon, be set as design temperature (20 DEG C or 40 DEG C), with Thermo-Mate (model BF500) by water temperature inching to design temperature ± 0.1 DEG C, as long as but for the device of same adjustment can be carried out, then can use arbitrarily.
Developmental tube:
As developmental tube, as shown in Figure 1, use the flat cylinder type clear glass of internal diameter 30mm, height 120mm, to mark respectively in the position of the height of 55mm and 85mm at the bottom of pipe graticule 31,32, by liquid state judgement developmental tube 30a airtight for the mouth rubber plug 33a of developmental tube, and same size and similarly mark graticule, be used in central authorities and have for inserting and the mouth of the rubber plug 33b closed test tube in the hole of support temperature meter insert the temperature measuring developmental tube 30b of thermometer 34 in rubber plug 33b.Below, the graticule of the height of 55mm at the bottom of pipe is called " A line ", the graticule of the height of 85mm is called " B line " at the bottom of pipe.
As thermometer 34, use the thermometer (SOP-58 range ability 20 ~ 50 DEG C) of the kryoscopy of regulation in JIS B7410 (1982) " petroleum-type test glass thermometer ", as long as but the temperature range of 0 ~ 50 DEG C can be measured.
(2) the enforcement order tested
The sample placing more than 24 hours under the atmospheric pressure of temperature 20 ± 5 DEG C is put into respectively the temperature measuring developmental tube 30b shown in (b) of liquid state judgement developmental tube 30a and Fig. 1 shown in (a) of Fig. 1 till A line.2 developmental tubes 30a, 30b are erectly rested in Low Constant Temperature Water Baths in undersurface mode with B line.Thermometer is arranged in the mode of its lower end than A line 30mm on the lower.
Specimen temperature keeps this state constant 10 minutes after reaching design temperature ± 0.1 DEG C.After 10 minutes, liquid state judgement developmental tube 30a is taken out from Low Constant Temperature Water Baths, flatly fell on the testing table of level immediately, move to time of B line and record with the front end of the liquid level in stopwatch determination test pipe from A line.For sample, be that situation within 90 seconds is judged to be liquid state, situation more than 90 seconds is judged to be solid-state by the time measured at a set temperature.
As being liquid epoxy resin at 20 DEG C, bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, the tert-butyl group-catechol type epoxy resin, glycidyl amine type epoxy resin, aminobenzene phenol-type epoxy resin, the alicyclic epoxy resins etc. such as the jER828 of Mitsubishi chemical Co., Ltd's manufacture can be enumerated.It should be noted that, be that the epoxy resin of liquid state can certainly be liquid state at lower than 20 DEG C at 20 DEG C.In addition, as epoxy resin, from viewpoints such as the preferred physical property of solidfied material, be preferably fragrant family epoxy resin.It should be noted that, in this instructions, fragrant family epoxy resin refers to the epoxy resin in its molecule with aromatic rings skeleton.Therefore, as being liquid epoxy resin at 20 DEG C, be more preferably liquid fragrant family epoxy resin at 20 DEG C.These epoxy resin can be used alone or also can combine two or more and use.
As being solid-state solid epoxy at 40 DEG C, can enumerate 4 officials can naphthalene type epoxy resin, the naphthalene type epoxy resin such as multifunctional solid epoxy containing naphthalene skeleton; Phenols and there is the epoxide (triphen phenol-type epoxy resin) of condensation product of aromatic aldehyde of phenolic hydroxyl group; Containing the bicyclopentadiene aralkyl-type epoxy resin such as multifunctional solid epoxy of bicyclopentadiene skeleton; Containing the biphenyl aralkyl-type epoxy resin such as multifunctional solid epoxy of biphenyl backbone; Phenolic resin varnish type epoxy resin; The di-cresols type such as YX-4000 that Mitsubishi chemical Co., Ltd manufactures or united phenol-type epoxy resin or their potpourri; The cresol novolak type epoxy resins such as the RN-695 that Dainippon Ink Chemicals manufactures; The hetero ring type epoxy resin etc. such as the TEPIC that Nissan Chemical Ind Ltd manufactures.These epoxy resin can individually use, and also can combine two or more and use.In order to give low heat swollen Zhang, particularly preferably use the epoxy resin containing naphthalene skeleton.
As at 20 DEG C be solid-state, be liquid semi-solid epoxy resin (C) at 40 DEG C, bisphenol A type epoxy resin can be enumerated; Naphthalene type epoxy resin; Phenol novolak type epoxy resin etc.These epoxy resin can individually use, and also can combine two or more and use.
[(C) inorganic filler]
Alkali development-type photosensitive resin composition of the present invention contains (C) inorganic filler.As (C) inorganic filler, calcium carbonate can be enumerated, magnesium carbonate, flying dust, dewatered sludge, native silicon dioxide, synthetic silica, porcelain earth, clay, calcium oxide, magnesium oxide, titanium dioxide, zinc paste, barium sulphate, aluminium oxide, talcum, mica, hydrotalcite, alumina silicate, magnesium silicate, calcium silicate, sintering talcum, wollastonite, potassium titanate, magnesium sulfate, calcium sulphate, magnesium phosphate, sepiolite, xonolite, boron nitride, aluminium borate, hollow silica ball, glass flake, glass bead, amorphous silica, crystallinity silicon dioxide, fused silica, spherical silicon dioxide, iron blast furnace slag processed, copper, iron, iron oxide, carbon black, sendust, alnico magnet, the magnetic powder such as various ferrites, cement, glass powder, Nuo Yibao tripoli, zeyssatite, antimony trioxide, alkali magnesium sulfate (magnesium oxysulfate), hydrated aluminum, hydrated gypsum, alum etc.These inorganic fillers can be used alone a kind, also can combine two or more and use.
In above-mentioned, in the present invention, as (C) inorganic filler, containing titanium dioxide.By containing titanium dioxide as (C) inorganic filler, thus the solidfied material of composition can be made for white, high reflectivity can be obtained.On the other hand, as described above, the fluidity of the composition containing titanium dioxide reduces, therefore the problem being easy to produce development residue in through hole etc. is had, but in the present invention, by (A) to be set to the scope of afore mentioned rules containing the equivalent proportion of epoxy radicals contained in carboxyl contained in carboxy resin and (B) epoxy Thermocurable composition, thus the high curing overlay film of reflectivity can be obtained when there is not the problem of development residue.
Titanium dioxide can be the titanium dioxide of the arbitrary structures in rutile-type, Detitanium-ore-type, ramsdellite type.Ramsdellite type titanium dioxide is by ramsdellite type Li
0.5tiO
2the de-lithium process implemented based on chemical oxidation obtains.Titanium Dioxide Rutile Top grade not easily causes and results from light-struck variable color, therefore preferably.
The compounding amount of titanium dioxide as (C) inorganic filler of essential component is comprised for such, relative to the solid constituent in photosensitive polymer combination (when photosensitive polymer combination contains organic solvent, composition relative to except organic solvent), be preferably the scope of 5 ~ 80 quality %, be more preferably the scope of 10 ~ 70 quality %.
[(D) Photoepolymerizationinitiater initiater]
Alkali development-type photosensitive resin composition of the present invention contains (D) Photoepolymerizationinitiater initiater.As (D) Photoepolymerizationinitiater initiater, as long as produce agent and known Photoepolymerizationinitiater initiater as Photoepolymerizationinitiater initiater, optical free radical, then can use arbitrarily.
As (D) Photoepolymerizationinitiater initiater, such as can enumerate two-(2, 6-dichloro-benzoyl base) phenyl phosphine oxide, two-(2, 6-dichloro-benzoyl base)-2, 5-3,5-dimethylphenyl phosphine oxide, two-(2, 6-dichloro-benzoyl base)-4-propylphenylphosphine oxide, two-(2, 6-dichloro-benzoyl base)-1-naphthyl phosphine oxide, two-(2, 6-Dimethoxybenzoyl) phenyl phosphine oxide, two-(2, 6-Dimethoxybenzoyl)-2, 4, 4-trimethylpentylphosphine oxide, two-(2, 6-Dimethoxybenzoyl)-2, 5-3,5-dimethylphenyl phosphine oxide, two-(2, 4, 6-trimethylbenzoyl) (BASF Japan Ltd. manufactures-phenyl phosphine oxide, two acylphosphine oxide class such as IRGACURE819), 2,6-Dimethoxybenzoyl diphenyl phosphine oxide, 2,6-dichloro-benzoyl base diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl phenyl methyl-phosphonate, 2-methyl benzoyl diphenyl phosphine oxide, valeryl phenyl-phosphonic acid isopropyl ester, 2, the monoacylphosphine oxides classes such as 4,6-trimethyl benzoyl diphenyl base phosphine oxide (BASF Japan Ltd. manufactures, DAROCUR TPO), 1-hydroxy-cyciohexyl Benzophenone, 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone, 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propiono)-benzyl] phenyl } the hydroxy acetophenone class such as-2-methyl-propan-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, the benzoin classes such as benzoin, benzil, benzoin methylether, benzoin ethyl ether, benzoin positive propyl ether, benzoin iso-propylether, benzoin n-butylether, benzoin alkyl ethers, benzophenone, to methyl benzophenone, michaelis ketone (Michler's ketone), methyl benzophenone, 4,4 '-dichloro benzophenone, 4, the benzophenones such as 4 '-bis-diethylamino benzophenone, acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1, the acetophenones such as 1-dichloroacetophenone, 1-hydroxy cyclohexyl phenylketone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1, N, N-dimethylamino benzoylformaldoxime, the thioxanthene ketones such as thioxanthones, 2-ethyl thioxanthones, ITX, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthones, CTX, 2,4-diisopropylthioxanthone, the Anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone, 2-amyl anthraquinone, 2-amino anthraquinones, the ketal classes such as acetophenone dimethyl ketal, benzil dimethyl ketal, EDMAB, benzoic acid 2-(dimethylamino) ethyl ester, to benzoates such as mesitylenic acid ethyl esters, the oxime ester classes such as 1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oxime) 1,2-octanedione, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl oxime) ethyl ketone, two (η
5-2,4-cyclopentadiene-1-base)-bis-(2, the fluoro-3-of 6-bis-(1H-pyrroles-1-base) phenyl) the two luxuriant titanium classes such as titanium, two (cyclopentadienyl group)-bis-[the fluoro-3-of 2,6-bis-(2-(1-pyrroles-1-base) ethyl) phenyl] titanium, phenyl curing 2-nitrofluorene, butyroin, anisoin ethyl ether, azoisobutyronitrile, tetramethylthiuram disulfide etc.Above Photoepolymerizationinitiater initiater all can be used alone a kind, also can combine two or more and use.
(D) the compounding amount of Photoepolymerizationinitiater initiater converts relative to 100 mass parts (A) in solid constituent is 0.1 ~ 50 mass parts containing carboxy resin.By with this scope compounding (D) Photoepolymerizationinitiater initiater, thus the photo-curable on copper becomes abundant, and the curability of film becomes good, and the coating characteristics such as chemical proofing improve, and deep curability also improves.More preferably be 5 ~ 40 mass parts relative to 100 mass parts (A) containing carboxy resin.
(thinning agent)
Photosensitive polymer combination of the present invention can contain thinning agent.The thinning agent used in the present invention is viscosity in order to adjust composition to improve operability and improve cross-linking density or improve adaptation etc. and use, and can use photo-curable monomer isoreactivity thinning agent, known conventional organic solvent.
As photo-curable monomer, (methyl) alkyl-acrylates such as (methyl) 2-EHA, (methyl) cyclohexyl acrylate can be enumerated; (methyl) hydroxyalkyl acrylates classes such as (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester; The list of the alkylene oxide derivative of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol etc. or two (methyl) esters of acrylic acid; Polynary (methyl) esters of acrylic acid of the polyvalent alcohol such as hexanediol, trimethylolpropane, pentaerythrite, two (trimethylolpropanes), dipentaerythritol, three (hydroxyethyl) isocyanuric acid ester or their oxirane or propylene oxide adduct; The oxirane of phenols or (methyl) esters of acrylic acids of propylene oxide adduct such as polyethoxy two (methyl) acrylate of (methyl) acrylate, bisphenol-A; (methyl) esters of acrylic acid of the glycidol ethers such as glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl isocyanurate; With melamine (methyl) acrylate etc.
The compounding rate of such photo-curable monomer is preferably 5 ~ 100 mass parts relative to 100 mass parts containing carboxy resin (A), is more preferably the ratio of 5 ~ 70 mass parts.During scope for above-mentioned compounding rate, photo-curable improves, and it is easy that pattern forms transfiguration, and solidification film strength also can improve.
As organic solvent, the ketone such as MEK, cyclohexanone can be used; Toluene, dimethylbenzene, tetramethylbenzene etc. are aromatic hydrocarbon based; The glycol 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, Tripropylene glycol monomethyl Ether; The ester classes such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, acetate of butyl carbitol, propylene glycol methyl ether acetate, dipropylene glycol monomethyl ether acetic acid esters, propylene carbonate; The aliphatic hydrocarbon such as octane, decane; The known conventional organic solvents such as petroleum solvent such as sherwood oil, naphtha, solvent naphtha.These organic solvents may be used singly or in combination of two or more kinds.
(other any composition)
In the present compositions can known conventional adjuvant in compounding field of electronic materials.As adjuvant, thermal curing catalyst, thermal polymerization inhibitor, ultraviolet light absorber, silane coupling agent, plastifier, fire retardant, antistatic agent, aging resister, antibacterial/mildewproof agent, defoamer, levelling agent, filling agent other than the above, tackifier, adaptation imparting agent, thixotropy conferring agents, colorant, light-initiated auxiliary agent, sensitizer etc. can be enumerated.
(fire retardant)
Photosensitive polymer combination of the present invention can comprise the fire retardants such as phosphorus-containing compound.Photosensitive polymer combination of the present invention, when comprising the fire retardant of solid, also can suppress the generation of the development residue in the portion of hole.As fire retardant, metal hydroxides, phosphorus-containing compound etc. can be used to commonly use known material.As metal hydroxides, such as, can enumerate aluminium hydroxide, calcium hydroxide, magnesium hydroxide etc.As phosphorus-containing compound, phosphate, condensed phosphoric acid esters, cyclic phosphazene compound, the phosphorus-containing compound with phenolic hydroxyl group, the phosphorus-containing compound as oligomer or polymkeric substance, Phosphazene oligomers, phosphonic acid metal salt, the compound etc. shown in following general formula can be enumerated.
In above-mentioned general formula, R
7, R
8and R
9separately represent the substituting group except halogen atom.In general formula, R
7, R
8be preferably the alkyl of hydrogen atom or carbon number 1 ~ 4, R
9be preferably hydrogen atom, the alkyl of carbon number 1 ~ 4 optionally replaced by cyano group, 2,5-dihydroxy phenyls or 3,5-, bis--tert-butyl-hydroxy phenyl.
As Phosphazene oligomers, phenoxy phosphazene compound is effective, has the ring of replacement or unsubstituting phenoxy Phosphazene oligomers or tripolymer, the tetramer, pentamer.
The compounding amount of fire retardant converts relative to above-mentioned 100 mass parts (A) containing carboxy resin in solid constituent, is preferably the scope of 5 ~ 50 mass parts, is particularly preferably 10 ~ 40 mass parts.
Dry film of the present invention has at carrier film (supporter) upper coating composition of the present invention and the resin bed making it dry and obtain.About the formation of dry film, the above-mentioned organic solvent diluting of composition of the present invention is adjusted to applicable viscosity, then, be applied in carrier film with uniform thickness with comma coater, knife type coater, lip coating machine, bar coater, extrusion coating machine, inverse formula coating machine, delivery roll coating machine, gravure coater, flush coater etc.Afterwards, by the composition that is coated with at the temperature of 50 ~ 130 DEG C dry 1 ~ 30 minute usually, thus resin bed can be formed.Coating film thickness is not particularly limited, generally speaking, with dried film thickness gauge, suitably selects in the scope of 10 ~ 150 μm, preferably 20 ~ 60 μm.
As carrier film, can plastic sheeting be used, preferably use the plastic sheetings such as mylar, Kapton, polyamidoimide film, polypropylene film, plasticon such as polyethylene terephthalate.Thickness for carrier film is not particularly limited, and generally speaking, suitably selects in the scope of 10 ~ 150 μm.
After forming the resin bed formed by composition of the present invention on a carrier film, in order to prevent the surface attachment dust etc. at film, the coverlay that preferably stacked energy is peeled off on the surface of film further.As the coverlay that can peel off, such as, can use polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper etc.As coverlay, if when peeling off coverlay and the bonding force of resin bed be less than the bonding force of resin bed and carrier film.
In addition, above-mentioned organic solvent is such as used to be adjusted to the viscosity being suitable for coating process composition of the present invention, be applied on base material by methods such as dip coating, flow coat method, rolling method, stick coating method, silk screen print method, curtain Tu Fa, then at the temperature of about 60 ~ 100 DEG C, make organic solvent volatile dry (temporarily dry) contained in composition, thus the resin bed that can cannot do not formed stickyly.In addition, by above-mentioned composition coating on a carrier film and the dry film making it dry and coil into the form of film when, laminating machine etc. is utilized to be pasted on base material by this dry film in the mode that the layer of composition of the present invention contacts with base material, peel off carrier film afterwards, thus can resin bed be formed.
As above-mentioned base material, except being pre-formed with the printed circuit board (PCB) of circuit, outside flexible printed circuit board, can also enumerate: all copper-clad laminated boards of grade (FR-4 etc.), and Kapton, PET film, glass substrate, ceramic substrate, wafer board etc., described copper-clad laminated board employs paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven fabrics epoxy, glass cloth/paper epoxy, synthon epoxy, employ the material of the high-frequency circuit copper-clad laminated board of fluorine tygon polyphenylene oxide (polyphenylene oxide) cyanate etc. etc.
The volatile dry carried out after being coated with composition of the present invention can utilize heated air circulation type drying oven, IR stove, hot plate, convection oven etc. (use possesses the device of the thermal source of the air heat mode utilizing steam, the method that the hot air convection in dryer is contacted and utilize nozzle to be blown into mode on supporter) to carry out.
The temperature that composition of the present invention is such as heated to about 140 ~ 180 DEG C makes its heat curing, thus can form the cured coating film of the various excellents such as thermotolerance, chemical proofing, resistance to hydroscopicity, adaptation, electrical characteristics.
In addition, by coating composition of the present invention, exposed (illumination is penetrated) by the resin bed obtained after solvent volatile dry, thus exposure portion (part that illumination is emitted through) solidifies.Specifically, with contact or cordless, active energy beam is optionally utilized to expose by forming figuratum photomask, or utilize the direct exposure machine of laser directly to carry out pattern exposure, unexposed portion dilute alkaline aqueous solution (such as 0.3 ~ 3wt% aqueous sodium carbonate) is developed, thus can corrosion-resisting pattern be formed.
The exposure machine used in irradiating as above-mentioned active energy beam, as long as carrying high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, mercury short arc lamp etc. and at the ultraviolet device of scope internal radiation of 350 ~ 450nm, and then direct drawing apparatus (such as utilizing the cad data from computing machine directly to use the laser direct imaging device of laser rendering image) also can be used.As the LASER Light Source of directly retouching machine, if use maximum wavelength is in the laser in the scope of 350 ~ 410nm, then gas laser and Solid State Laser.The exposure formed for image is different according to thickness etc., generally speaking, can be set to 20 ~ 800mJ/cm
2, be preferably set to 20 ~ 600mJ/cm
2scope in.
As above-mentioned developing method, infusion process, spray process, spray-on process, spread coating etc. can be utilized, as developer solution, the aqueous alkali of potassium hydroxide, NaOH, sodium carbonate, sal tartari, sodium phosphate, sodium silicate, ammonia, amine etc. can be used.
Composition of the present invention is suitable for the formation of the cured film such as solder mask, interlayer insulating film of printed circuit board (PCB), flexible printed circuit board.In addition, by making composition of the present invention for white, be suitable in the backlight etc. of the liquid crystal display such as ligthing paraphernalia, portable terminal device, personal computer, televisor reflection from being used as the light emitting diode (LED) of its light source, the reflecting plate of light that electroluminescent cell (EL) sends.
embodiment
Below, embodiment is utilized to illustrate in greater detail the present invention.
According to the formula shown in following table, by compounding for each composition, in stirring machine, carry out premixed, make it disperse with triple-roller mill afterwards and mixing, prepare composition respectively.It should be noted that, the compounding amount in table represents mass parts.
< synthesis example 1 (preparation containing carboxy resin) >
Methacrylic acid 42 mass parts, methyl methacrylate 43 mass parts, styrene 35 mass parts, benzyl acrylate 35 mass parts, carbitol acetate 100 mass parts, lauryl mercaptan 0.5 mass parts and azoisobutyronitrile 4 mass parts is added in the four-hole boiling flask that reflux condenser, thermometer, nitrogen displacement glass tube and stirring machine be housed, under stream of nitrogen gas, in 75 DEG C of heating 5 hours, carry out polyreaction, obtain copolymer solution (solid component concentration 50 quality %).Add quinhydrones 0.05 mass parts, glycidyl methacrylate 23 mass parts and dimethyl benzyl amine 2.0 mass parts wherein, addition reaction in 24 hours is carried out at 80 DEG C, then add carbitol acetate 35 mass parts, obtain the copolymer resins solution (solid component concentration 50 quality %) with aromatic rings.
< developability (through hole developability) >
With φ 300 μm of drill bit punchings on the copper-clad laminated board that 1.0mm is thick, carry out through hole plating by conventional method, make the substrate that the measured value being formed with 100 holes is about the through hole of φ 260 μm.Utilize serigraphy, the composition of each embodiment and comparative example is printed 2 times on the substrate, in the heated air circulation type drying oven of 80 DEG C, make its dry 30 minutes, naturally cool to room temperature.Use the 1 quality % aqueous sodium carbonate of 30 DEG C, development in 90 seconds is carried out under the condition spraying 0.2MPa to this substrate, washing, obtain the substrate after developing.Observe in the through hole of gained substrate by visual and observer (scope), carry out the evaluation of the developability in through hole.The situation of the residue that do not develop is designated as ◎, will only has the situation of a small amount of development residue to be designated as zero, development residue will be had but the through situation of through hole is designated as △, development residue is entered into through hole and do not have through situation be designated as ×.
< reflectivity >
Utilize silk screen print method, use the version of 100 object polyester (BIAS system), for the size of 100mm × 150mm and the FR-4 copper-clad laminated board of the thickness of 1.6mm, with the composition of each embodiment and comparative example with the mode of thickness 40 μm solid (the whole face of substrate) ground printed patterns.Make they at 80 DEG C through 30 minutes at heated air circulation type drying oven inner drying.And then, use use in printed circuit board exposure machine HMW-680GW (Co., Ltd. O rc makes manufactured), in the mode of the square negative image pattern of residual 30mm with 900mJ/cm
2accumulated light carry out ultraviolet exposure.Afterwards, at 30 DEG C, using the aqueous sodium carbonate of 1% as developer solution, they are carried out in printed-wiring board (PWB) developing machine development in 60 seconds, then, at 150 DEG C, in heated air circulation type drying oven, carry out heat curing in 60 minutes, make the test film of attribute testing.
Gained test film color evaluating CR-400 (KONICA MINOLTA SENSING, INC. manufacture) is measured, by the value of Y value is that the situation of more than 85 is designated as zero, more than 80 and the situation being less than 85 is designated as △, the situation of 80 that is less than is designated as ×.
< resistance to soldering heat performance >
By the test film being coated with rosin series scaling powder being redefined in the solder bath of 260 DEG C with 30 seconds dippings 1 time, with modification alcohol cleaning scaling powder, utilize the stripping of visual valuation resist layer afterwards.Being designated as zero by there is no situation about peeling off, producing a little situation about peeling off and be designated as △, produce situation about obviously peeling off and be designated as ×.
Above-mentioned each evaluation result is shown in following table.
table 1
※ 1) obtain in synthesis example 1 derived from cinnamic containing carboxy resin (carboxyl equivalent=960)
※ 2) be diluted to 44 quality % (manufacture of Daicel chemical industry Co., Ltd.) (containing carboxy resin, carboxyl equivalent=806) with DPM (dipropylene glycol monomethyl ether)
※ 3) bisphenol A type epoxy resin, Mitsubishi chemical Co., Ltd manufactures (being liquid at 20 DEG C, epoxide equivalent=185)
※ 4) Nissan Chemical Ind Ltd's manufacture (being powder (solid-state) at 40 DEG C, epoxide equivalent=100)
※ 5) biphenyl type epoxy resin (Mitsubishi chemical Co., Ltd's manufacture) (being powder (solid-state) at 40 DEG C, epoxide equivalent=182)
※ 6) cresol novolak type epoxy resin (Dainippon Ink Chemicals's manufacture) (being solid-state at 40 DEG C, epoxide equivalent=210)
※ 7) Ishihara Sangyo Kaisha, Ltd.'s manufacture
※ 8) Showa Denko K. K's manufacture
※ 9) phosphonic acids aluminium salt, Clarian Japan Co., Ltd. manufactures
※ 10) monoacylphosphine oxides system Photoepolymerizationinitiater initiater, Lucirin TPO (2,4,6-trimethylbenzoy-dipheny-phosphine oxide), BASF Japan Ltd. manufactures
※ 11) two acylphosphine oxide systems Photoepolymerizationinitiater initiater, IRGACURE819 (two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide), BASF Japan Ltd. manufactures
※ 12) imidazole compound, Shikoku Chem manufactures
※ 13) diethylene glycol monomethyl ether acetic acid esters
※ 14) aromatic hydrocarbon (Solvesso150)
※ 15) dipentaerythritol acrylate, Kyoeisha Chemical Co., Ltd. manufactures
※ 16) under drying regime (solid constituent conversion), (A) in composition containing carboxyl contained in carboxy resin equivalent (number), with (B) epoxy Thermocurable composition in contained by the ratio (epoxy radix/carboxyl number) of equivalent (number) of epoxy radicals.
table 2
From the result in above-mentioned table, in the composition of each embodiment, even if when containing the development residue also do not produced when titanium dioxide in through hole, resistance to soldering heat performance is also good.Confirm thus, according to the present invention, can obtain guaranteeing good through hole developability and the photosensitive polymer combination with high reflectance.
Claims (8)
1. a photosensitive polymer combination, it contains (A) containing carboxy resin, (B) epoxy Thermocurable composition, (C) inorganic filler and (D) Photoepolymerizationinitiater initiater,
Relative to described (A) containing carboxyl 1 equivalent contained in carboxy resin, the equivalent of epoxy radicals contained in described (B) epoxy Thermocurable composition is less than 1.0, and described (C) inorganic filler contains titanium dioxide.
2. photosensitive polymer combination according to claim 1, wherein, described (B) epoxy Thermocurable composition contain at 20 DEG C for liquid epoxy resin and at 40 DEG C for more than at least one in solid-state solid epoxy.
3. photosensitive polymer combination according to claim 1 and 2, wherein, described (A) is less than 0.8 containing the ratio of the equivalent of the epoxy radicals contained by equivalent and described (B) epoxy Thermocurable composition of carboxyl contained in carboxy resin.
4. photosensitive polymer combination according to claim 1 and 2, wherein, described (A) containing carboxy resin derived from styrene or styrene derivative.
5. photosensitive polymer combination according to claim 3, wherein, described (A) containing carboxy resin derived from styrene or styrene derivative.
6. a dry film, is characterized in that, has and is coated with the photosensitive polymer combination according to any one of Claims 1 to 5 on a carrier film and the resin bed making it dry and obtain.
7. a solidfied material, is characterized in that, it utilizes illumination to penetrate and the described resin bed solidification of the photosensitive polymer combination according to any one of Claims 1 to 5 or dry film according to claim 6 is obtained.
8. a printed circuit board (PCB), is characterized in that, has solidfied material according to claim 7.
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| CN109791354A (en) * | 2017-06-09 | 2019-05-21 | 互应化学工业株式会社 | Photosensitive polymer combination, dry film and printing distributing board |
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| CN110320753A (en) * | 2018-03-29 | 2019-10-11 | 株式会社田村制作所 | Photosensitive polymer combination |
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| JP6742796B2 (en) * | 2015-07-21 | 2020-08-19 | 太陽インキ製造株式会社 | Curable resin composition, dry film, cured product and printed wiring board |
| US9799534B1 (en) | 2017-01-04 | 2017-10-24 | International Business Machines Corporation | Application of titanium-oxide as a patterning hardmask |
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Application publication date: 20150603 |