CN106556969A - Photosensitive polymer combination - Google Patents
Photosensitive polymer combination Download PDFInfo
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- CN106556969A CN106556969A CN201610856175.1A CN201610856175A CN106556969A CN 106556969 A CN106556969 A CN 106556969A CN 201610856175 A CN201610856175 A CN 201610856175A CN 106556969 A CN106556969 A CN 106556969A
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- Prior art keywords
- acid
- photosensitive polymer
- polymer combination
- epoxy resin
- fatty acid
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Abstract
The present invention provides photosensitive polymer combination, and the photosensitive polymer combination suitably forms in the case where the fundamental characteristics such as solder heat resistance are not damaged, the soldering-resistance layer that the solder resistant tack, insulation characterisitic and the screening capacity that are produced by extinction effect (low-luster) are excellent etc. is insulation-coated.The photosensitive polymer combination is characterised by containing (A) photoresist containing carboxyl, (B) fatty acid amide, (C) Photoepolymerizationinitiater initiater, the compound of (D) with ethene unsaturated group, (E) epoxide and (F) colouring agent.
Description
Technical field
The present invention relates to be applied to the photosensitive polymer combination of lining material and be coated with make the photoresist group
The wiring plates such as the printed circuit board of solidfied material of compound solidification, the lining material are for example, used for being coated to being formed at printing
The insulation-coated material of the conductor circuit pattern of the substrates such as circuit board.
Background technology
With the miniaturization of the conductor circuit pattern of printed circuit board, there is problems with：Solder sphere when being flowed by solder
Cause welding bridging etc. to insulation-coated surface attachment.In order to prevent the problem, by insulation-coated surface coarsening, delustring, by
Solder resistant tack when this makes solder flow for insulation-coated surface is improved, and prevents the attachment of solder sphere.In addition, attempting logical
Cross insulation-coated delustring to improve insulation-coated screening capacity.
As above-mentioned delustring means, for example, propose in photoresist containing carboxyl, coordinated average primary particle diameter to be 1
The photo-curable of the organic filler of～30 μ ms, the light extinction composition (patent document 1) of Thermocurable.
But, in patent document 1, there are the following problems：In order to obtain good extinction effect, the addition of organic filler is made
When amount increases, thixotropy increase still produces bubble, slip a line (skip) etc., it is impossible to obtain sufficient printing during printing.In addition,
If increasing the addition of organic filler, also there is a problem of causing the insulation-coated electrical insulating property to be formed to reduce.
In addition, use particle diameter big to obtain good extinction effect organic filler when, formed it is insulation-coated
During pattern, organic filler is easy to from film coated surface protrude.As a result, there is water, medicine etc. along organic filler and the boundary of resin
Face is impregnated with, and causes the problem of the reductions such as resistance to chemical reagents, electrical insulating property.In addition, there is masking in the patent document 1 using organic filler
The insufficient problem of ability.
Prior art literature
Patent document
[patent document 1] JP 2006-40935 publication
The content of the invention
Invent technical task to be solved
In view of the foregoing, it is an object of the invention to provide photosensitive polymer combination, the photosensitive polymer combination
It is suitable for forming the resistance to weldering produced in the case where the fundamental characteristics such as solder heat resistance are not damaged, by extinction effect (low-luster)
The excellent soldering-resistance layer of material tack, insulation characterisitic and screening capacity etc. is insulation-coated.For solving the technological means of problem
The solution of the present invention is photosensitive polymer combination, it is characterised in that containing (A) photoresist containing carboxyl, (B)
Fatty acid amide, (C) Photoepolymerizationinitiater initiater, the compound of (D) with ethene unsaturated group, (E) epoxide and (F)
Colouring agent.
The solution of the present invention is photosensitive polymer combination, it is characterised in that above-mentioned (B) fatty acid amide is selected under
State formula (1) compound for representing, the compound represented by following formulas (2) and the compound represented by following formulas (3)
In at least a kind,
R1- C (=O)-NH- (CH2)l- NH-C (=O)-R2 (1)
(in formula, R1、R2It is separately the saturation or unsaturated alkyl of carbon number 14～21, l represents 0 or 1～10
Integer.)；
R3- NH-C (=O)-(CH2)m- C (=O)-NH-R4 (2)
(in formula, R3、R4It is separately the saturation or unsaturated alkyl of carbon number 14～21, m represents 0 or 1～10
Integer.)；
R5- C (=O)-NH-R6 (3)
(in formula, R5、R6The saturation or unsaturated alkyl of carbon number 14～21 are represented separately.).
The solution of the present invention is photosensitive polymer combination, it is characterised in that above-mentioned (B) fatty acid amide with 70 DEG C～
160 DEG C of fusing point.
The solution of the present invention is photosensitive polymer combination, it is characterised in that above-mentioned (B) fatty acid amide is sub- selected from six
Two oleamide of methyl, N- stearylstearic amides, N- oleyl stearamides, N ,-two oil base decanedioic acid acid amides of N ',
N, the N oil base adipic acid acid amides of '-two, N, at least a kind in N '-ethylenebis erucyl amide and ethylene oleamide.
The solution of the present invention is photosensitive polymer combination, it is characterised in that relative to 100 mass parts (A) sense containing carboxyl
Photosensitiveness resin, containing above-mentioned (B) fatty acid amide of 1.0 mass parts～15 mass parts.
The solution of the present invention is photosensitive polymer combination, it is characterised in that above-mentioned (F) colouring agent is black colorant.
The solution of the present invention is the printed circuit board of the photocuring film with above-mentioned photosensitive polymer combination.
Invention effect
Scheme of the invention, by coordinating fatty acid amide, can not damage the fundamental characteristics such as solder heat resistance
In the case of, the solder resistant tack, insulation characterisitic and the screening capacity that obtain being produced by extinction effect (low-luster) it is excellent
Solidfied material.In addition, replacing conventional cooperation organic filler, inorganic filler by coordinating fatty acid amide, can not damage
In the case of excellent extinction effect, reduce the roughness on insulation-coated surface, additionally it is possible to obtain excellent insulation characterisitic, i.e.
Insulating reliability.
Scheme of the invention, is selected from above-mentioned formula (1), formula (2) and formula (3) by making fatty acid amide
At least a kind in the compound of expression, extinction effect, insulation characterisitic and screening capacity are further improved.
According to the present invention, by fatty acid amide with 70 DEG C～160 DEG C of fusing point, extinction effect, insulation characterisitic and screening
The ability of covering harmonious further can be improved well.For extinction effect, insulation characterisitic and screening capacity harmony well
Further improve, it is believed that one of its reason is, in the predry drying process after photosensitive resin coating composition, fatty acid acyl
Dissolve in amine photosensitive polymer combination after coating, so as in the photosensitive polymer combination surface having been coated with, aliphatic acid
Acid amides is easy to equably be orientated.
Scheme of the invention, is stearic selected from two oleamide of hexa-methylene, N- stearyls by fatty acid amide
Sour acid amides, N- oleyl stearamides, N ,-two oil base decanedioic acid acid amides of N ', N ,-two oil base adipic acid acid amides of N ', N, N '-
At least a kind in ethylenebis erucyl amide and ethylene oleamide, can make extinction effect, absolutely with excellent harmony
Edge characteristic and screening capacity are improved.
Specific embodiment
Next, being described in detail for the photosensitive polymer combination of the present invention.The photoresist of the present invention
Composition contains (A) photoresist containing carboxyl, (B) fatty acid amide, (C) Photoepolymerizationinitiater initiater, (D) with ethene insatiable hunger
Compound, (E) epoxide and (F) colouring agent with group.
(A) photoresist containing carboxyl
There is no particular limitation for photoresist containing carboxyl, can for example enumerate it is photosensitive have more than 1 it is unsaturated
Double bond containing carboxy resin.As the example containing carboxyl photoresist, the modified by polyacid epoxy being obtained as below can be enumerated
The free-radical polymerised unsaturated monocarboxylic epoxy resin of the modified by polyacid such as (methyl) acrylate：Make acrylic acid or methyl-prop
Olefin(e) acid is (below, sometimes referred to as " (methyl) acrylic acid ".) etc. there are 2 in free-radical polymerised unsaturated monocarboxylic and 1 molecule
At least a portion reaction of the epoxy radicals of the multi-functional epoxy resin of above epoxy radicals, obtains epoxy (methyl) acrylate etc.
Free-radical polymerised unsaturated monocarboxylic epoxy resin, make generated hydroxyl further with polyacid or its anhydride reaction.
As long as epoxy resin more than above-mentioned 2 sense of multi-functional epoxy resin, can use.Multi-functional epoxy
There is no particular limitation for the epoxide equivalent of resin, and preferably less than 1000, particularly preferably 100～500.Multi-functional asphalt mixtures modified by epoxy resin
Fat can enumerate such as biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene-type epoxy resin, silicon-modified epoxy
The phenolic aldehyde such as the rubber modified epoxy resins such as resin, 6-caprolactone modified epoxy, bisphenol A-type, bisphenol-f type, bisphenol-A D types are clear
Cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, the ring-types such as paint shaped epoxy resin, o-cresol phenol aldehyde type
Aliphatic polyfunctional epoxy resin, glycidyl ester type polyfunctional epoxy resin, glycidyl amine type polyfunctional epoxy resin,
Hetero ring type polyfunctional epoxy resin, bis-phenol modified novolac type epoxy resin, multifunctional modified novolac type epoxy resin,
Phenols and the condensation product type epoxy resin of aromatic aldehyde with phenolic hydroxyl group etc..Alternatively, it is also possible to use in these resins
The material of the halogen atoms such as Br, Cl is imported.These epoxy resin can be used alone, and can also mix two or more in addition makes
With.
There is no particular limitation for free-radical polymerised unsaturated monocarboxylic, can for example enumerate acrylic acid, methacrylic acid,
Crotonic acid, cinnamic acid etc., preferred acrylic acid, methacrylic acid.For epoxy resin and free-radical polymerised unsaturated monocarboxylic
Reaction method, there is no particular limitation, for example, can be existed with free-radical polymerised unsaturated monocarboxylic by making epoxy resin
Heating in appropriate diluent reacts which.
Polyacid, multi-anhydride be by with the reaction by above-mentioned epoxy resin and free-radical polymerised unsaturated monocarboxylic
And the hydroxyl reaction for generating makes free carboxyl import the material in resin.There is no particular limitation for polyacid or its acid anhydrides, satisfies
Sum, undersaturated polyacid or its acid anhydrides can be used.Polyacid can enumerate such as butanedioic acid, maleic acid, adipic acid, lemon
Lemon acid, phthalic acid, tetrahydrophthalic acid, 3- methyl tetrahydrophthalic acids, 4- methyl tetrahydrophthalic acids,
3- ethyl tetrahydrophthalic acids, 4- ethyl tetrahydrophthalic acids, hexahydrophthalic acid, 3- methyl hexahydro neighbour's benzene two
Formic acid, 4- methylhexahydrophthaacid acids, 3- ethyl hexahydrophthalic acids, 4- ethyl hexahydrophthalic acids, methyl four
Hydrogen phthalic acid, methylhexahydrophthaacid acid, methylene tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic tetrahydrochysene neighbour's benzene two
Formic acid, trimellitic acid, PMA and diglycolic acid (Diglycolic acid) etc., as multi-anhydride, can enumerate these
The acid anhydrides of acid.These compounds can be used alone, it is also possible to mix two or more use.
Above-mentioned modified by polyacid unsaturated monocarboxylic epoxy resin is also used as the use of photoresist containing carboxyl, but
Can also as needed, as obtaining photoresist containing carboxyl as follows：By make with more than 1 it is free-radical polymerised not
The carboxylic of the glycidyl compound of saturated group and epoxy radicals and above-mentioned modified by polyacid unsaturated monocarboxylic epoxy resin
Base reacts and further imports free-radical polymerised unsaturated group, so that photonasty is further improved.
For the photoresist containing carboxyl for making photonasty further improve, by above-mentioned glycidyl chemical combination
The side chain key of the reaction of thing, free-radical polymerised unsaturated group and modified by polyacid unsaturated monocarboxylic epoxy backbone
Close, so becoming, photopolymerization reaction is high, there can be the resin of excellent photobehavior.As with the free radical of more than 1
The compound of polymerism unsaturated group and epoxy radicals, can enumerate such as glycidyl acrylate, Glycidyl methacrylate
Glyceride, allyl glycidyl ether, pentaerythritol triacrylate list glycidyl ether etc..It should be noted that 1
There can be multiple glycidyls in molecule.It is above-mentioned that there is more than 1 free-radical polymerised unsaturated group and epoxy radicals
Compound can be used alone, it is also possible to mix two or more use.
Further, as photoresist containing carboxyl, for example, the material for obtaining as follows can be enumerated, i.e. make b) average per 1
The carbon number of carboxyl is the aliphatic acid of at least a kind of more than 10 and carboxylic acid c) containing ethene unsaturated group and a) 1 point
In son, the epoxy reaction of the epoxy resin with more than 2 epoxy radicals, thus obtains reaction product, i.e. LCFA and changes
The modified epoxy containing ethene unsaturated group of property, and then, make d) multi-anhydride add to by LCFA and/
Or the epoxy radicals of the carboxyl of the carboxylic acid containing ethene unsaturated group and epoxy resin reaction and the hydroxyl that generates (mainly
Secondary hydroxyl), so as to free carboxyl, thus obtained material are imported in above-mentioned resin.
A) epoxy resin with more than 2 epoxy radicals in 1 molecule
For the epoxy resin with more than 2 epoxy radicals in 1 molecule, as long as epoxy resin more than 2 senses,
Can use.In 1 molecule, there is no particular limitation for the epoxide equivalent of epoxy resin with more than 2 epoxy radicals, but from preventing
Reduced and caused photonasty and flexibility by the importing ratio of the carboxylic acid containing ethene unsaturated group and LCFA
From the aspect of reducing, epoxide equivalent is preferably less than 1000, particularly preferably 100～500.
For the epoxy resin with more than 2 epoxy radicals in 1 molecule, for example, can enumerate biphenyl aralkyl type epoxy tree
It is fat, phenyl aralkyl-type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene-type epoxy resin, organic
The rubber modified epoxy resins such as silicon modified epoxy resin, 6-caprolactone modified epoxy, bisphenol A-type, bisphenol-f type, bisphenol-A D
The multifunctional ring of cresol novolak type epoxy resin, annular aliphatic such as the phenolic resin varnish type epoxy resins such as type, o-cresol phenol aldehyde type
Oxygen tree fat, glycidyl ester type polyfunctional epoxy resin, glycidyl amine type polyfunctional epoxy resin, the multifunctional ring of hetero ring type
Oxygen tree fat, bis-phenol modified novolac type epoxy resin, multifunctional modified novolac type epoxy resin, phenols with have phenol
The condensation product type epoxy resin of the aromatic aldehyde of hydroxyl, the epoxy resin containing fluorene skeleton, the epoxy for having imported adamantane framework
Resin etc..Material obtained from the halogen atoms such as Br, Cl has been imported alternatively, it is also possible to use in these resins.
Wherein, from photosensitive polymer combination sensitivity, the flexibility of solidfied material and low warpage properties are excellent, and insulate can
From the aspect of by property, heat resistance, preferred biphenyl aralkyl-type epoxy resin, dicyclopentadiene-type epoxy resin.
B) it is average per the aliphatic acid that the carbon number of 1 carboxyl is more than 10
It is average per the aliphatic acid that the carbon number of 1 carboxyl is more than 10, by with 1 molecule in there are more than 2 epoxies
The epoxy reaction of the epoxy resin of base, imports the long-chain hydrocarbon structure from above-mentioned aliphatic acid in the resin, thus enables that
The flexibility (flexibility) of the solidfied material of photosensitive polymer combination and insulating properties are improved.The average carbon per 1 carboxyl is former
Subnumber is that there is no particular limitation for more than 10 aliphatic acid, and saturation, undersaturated aliphatic acid can be used, in addition, straight-chain
, the aliphatic acid of branch-like also can use.Above-mentioned aliphatic acid can enumerate the monoacid that such as carbon number is more than 10, carbon
Atomicity is more than 20 binary acid, from flexibility and dry to touch it is balanced from the aspect of, above-mentioned monoacid and two
The branch-like of first acid preferably straight-chain or the side chain with less than 2 carbon numbers below 2.
In addition, while by LCFA structure importing epoxy resin, further making above-mentioned epoxy resin not
Bond together via aliphatic acid with epoxy radicals, pass through covalent bond thus, it is possible to form the more upright and more outspoken skeleton with epoxy resin
The structure of the long-chain hydrocarbon skeleton crosslinking high with the flexibility from LCFA, and then contribute to cured coating film from the structure
From the aspect of flexibility and solder heat resistance, preferred fatty acid contains at least a kind binary acid.
Further, by importing more from the long-chain hydrocarbon skeleton that the flexibility and insulating properties of LCFA are high, can
The flexibility and insulating properties of cured coating film is made further to improve, now, except the above-mentioned average carbon number per 1 carboxyl is 10
More than binary acid outside, by and with averagely per the monoacid that the carbon number of 1 carboxyl is more than 10, thus, it is possible to improve
From the composition ratio of the composition of LCFA, and moderately control aliphatic acid, polyfunctional epoxy resin and contain ethene
The molecular weight of the reaction product of the carboxylic acid of property unsaturated group.So, by moderately controlling above-mentioned molecular weight, can be balanced
Property positively improves the dry to touch and the dissolubility (i.e. developability) in weak base developer solution of dried film well
And sensitivity.In addition, passing through and using monoacid and binary acid, can reliably contribute to insulating properties and solder heat resistance with good
Harmonious raising.
From by more moderately controlling above-mentioned molecular weight, examine in terms of improving above-mentioned each characteristic better so as to harmony
Consider, particularly preferably containing average per the straight-chain saturation monoacid that the carbon number of 1 carboxyl is more than 18.
From from the aspect of giving cured coating film flexibility and insulating properties, the carbon number averagely per 1 carboxyl be 8 with
On, preferably more than 10.On the other hand, the higher limit of the carbon number averagely having per 1 carboxyl, there is no particular limitation,
From from the aspect of maintaining developability, preferably less than 24, particularly preferably less than 22.
For averagely per the concrete example of the aliphatic acid that the carbon number of 1 carboxyl is more than 10, as monoacid, can
To enumerate capric acid (ten alkanoic acids：C10), hendecanoic acid (C11), laurate (dodecylic acid：C12), tridecanoic acid (C13), Pork and beans
Cool acid (tetradecanoic acid：C14), pentadecanoic acid (C15), palmitic acid (hexadecanoic acid：C16), pearl acid (Heptadecanoic acide：C17 it is), hard
Resin acid (C18), isostearic acid (C18), tuberlostearic acid (Tuberculostearic acid) (C19), arachidic acid (C20), mountain
Yu acid (C22), tricosanic acid (C23), lignoceric acid (C24), hexacosoic acid (C26), octocosoic acid (C28), three
Ten alkanoic acids (C30) etc..
As binary acid, eicosane diacid (C20), ethyl octadecane diacid (C20), 20 carbon, two enedioic acid can be enumerated
(C20), vinyl octadecene diacid (C20), 20 carbon of dimethyl, two enedioic acid (C22), dimethyl eicosane diacid
(C22), diphenyl hexadecandioic acid (hexadecane diacid) (C28), the C36 obtained by the Dimerized reaction of the unrighted acids such as oleic acid (C18)
Dimeric dibasic acid, it is characterised by hydrogenation C36 dimeric dibasic acids that the hydrogenation of the olefinic double bond of the dimeric dibasic acid is formed etc..
It is above-mentioned average per the aliphatic acid that the carbon number of 1 carboxyl is more than 10, can be used alone, it is also possible to 2 kinds with
On be used in mixed way.
With regard in 1 molecule with more than 2 epoxy radicals epoxy resin and the carbon number averagely per 1 carboxyl be 10 with
On at least a kind of aliphatic acid reaction method, known method can be for example enumerated above-mentioned epoxy resin and above-mentioned fat
The reaction method that fat acid is heated in appropriate diluent.
The average carbon number per 1 carboxyl in photoresist containing carboxyl be more than 10 aliphatic acid ratio (plus
Enter ratio), there is no particular limitation, such as, for its lower limit, further improve from the flexibility and insulating properties of solidfied material is made
From the aspect of, preferably 10 mass %, from from the aspect of making flexibility and insulating properties positively improve, particularly preferred 15 matter
Amount %.On the other hand, to limit value thereon, from the import volume by moderately maintaining the carboxylic acid containing ethene unsaturated group
From the aspect of remaining photosensitive, preferably 50 mass %, particularly preferred 40 mass %.
C) carboxylic acid containing ethene unsaturated group
The epoxy of the epoxy resin with more than 2 epoxy radicals in carboxylic acid containing ethene unsaturated group and 1 molecule
Base reacts, and the photo-curable base that can be polymerized by the free free radical produced by Photoepolymerizationinitiater initiater is imported in epoxy resin
Group.As long as the carboxylic acid containing ethene unsaturated group be to confer to epoxy resin photo-curable containing ethene unsaturated group
Carboxylic acid, there is no particular limitation, can for example enumerate acrylic acid, methacrylic acid, β-acryloxy propionic,
Acryloyl group or methylacryloyl can be led by ω-carboxy-polycaprolactone-(methyl) acrylic acid, crotonic acid, cinnamic acid etc.
Enter the carboxylic acid of epoxy resin.Wherein, preferred acrylic acid, methacrylic acid, particularly preferred acrylic acid.They can be used alone,
Can also two or more be used in mixed way.
The ratio of the carboxylic acid containing ethene unsaturated group in photoresist containing carboxyl, there is no particular limitation,
For example the lower limit of (methyl) the acryloyl group equivalent containing carboxyl photoresist is from the side of the flexibility and insulating properties of solidfied material
Face consideration, preferred 800g/eq, particularly preferred 1000g/eq.On the other hand, its higher limit, in terms of photonasty and developability
Consider preferred 3500g/eq, particularly preferred 3000g/eq.
The reaction of the epoxy resin with more than 2 epoxy radicals and the carboxylic acid containing ethene unsaturated group in 1 molecule
Method, there is no particular limitation, for example, can enumerate and above-mentioned epoxy resin and the carboxylic acid containing ethene unsaturated group exist
The reaction method heated in appropriate diluent.
D) multi-anhydride
Multi-anhydride and hydroxyl reaction, enter free carboxyl to above-mentioned epoxy resin derivative, and the hydroxyl is by above-mentioned ring
Hydroxyl that oxygen tree fat is generated with least a kind fatty acid response for averagely per the carbon number of 1 carboxyl being more than 10 and with
Carboxylic acid reaction containing ethene unsaturated group and the hydroxyl that generates.Used as the multi-anhydride for using, there is no particular limitation,
Saturation, undersaturated multi-anhydride can be used.Multi-anhydride can enumerate the acid anhydrides of following acid, such as butanedioic acid, Malaysia
Acid, adipic acid, citric acid, phthalic acid, tetrahydrophthalic acid, 3- methyl tetrahydrophthalic acids, 4- methyl tetrahydrochysenes
Phthalic acid, 3- ethyl tetrahydrophthalic acids, 4- ethyl tetrahydrophthalic acids, hexahydrophthalic acid, 3- methyl
Hexahydrophthalic acid, 4- methylhexahydrophthaacid acids, 3- ethyl hexahydrophthalic acids, 4- ethyls hexahydro neighbour's benzene two
Methylene in formic acid, methyl tetrahydrophthalic acid, methylhexahydrophthaacid acid, methylene tetrahydrophthalic acid, methyl
The polyacids such as base tetrahydrophthalic acid, trimellitic acid, PMA and diglycolic acid.It should be noted that these compounds
Can be used alone, in order to suitably adjust developability can also two or more be used in mixed way.
The ratio (additional proportion) of the multi-anhydride in photoresist containing carboxyl, there is no particular limitation, such as under which
Limit value, preferably 5.0 mass % from from the aspect of improving developability, particularly preferred 8.0 mass %.On the other hand, to thereon
Limit value, remains solid from by suitably maintaining averagely per the import volume of the aliphatic acid that the carbon number of 1 carboxyl is more than 10
From the aspect of the flexibility and insulating properties of compound, preferably 20 mass %, particularly preferred 15 mass %.
Also, as photoresist containing carboxyl, for example can also be using sour modified urethane epoxy radicals (first
Base) acrylate.
Acid number containing carboxyl photoresist, there is no particular limitation, and its lower limit is examined in terms of certain alkali development
Consider, preferred 30mgKOH/g, particularly preferred 40mgKOH/g.On the other hand, the higher limit of acid number is from preventing from causing because of alkaline developer
Exposure portion dissolving from the aspect of, preferred 200mgKOH/g, from prevent the deterioration of moisture-proof and electrical characteristics of solidfied material in terms of
Consider, particularly preferred 150mgKOH/g.
In addition, for the matter average molecular weight containing carboxyl photoresist, there is no particular limitation, and its lower limit is from solidfied material
Obdurability and tack from the aspect of, preferably 3000, particularly preferably 5000.On the other hand, matter average molecular weight
Higher limit from from the aspect of smoothly alkali-developable, preferably 200000, particularly preferably 50000.
For as the commercially available material of photoresist containing carboxyl, for example, can enumerate ZAR-2000, ZFR-1122,
FLX-2089, ZCR-1601H (above by Japanese chemical drug (strain) manufacture), (Daicel is chemical for CYCLOMER P (ACA) Z-250
Industrial (strain) system), Ripoxy SP-4621 (Showa macromolecule (strain) system) etc..These resins can be used alone, it is also possible to mixed
Close two or more use.
(B) fatty acid amide
By coordinating fatty acid amide, the solder resistant tack that can obtain being produced by extinction effect (low-luster), absolutely
The excellent solidfied material of edge characteristic and screening capacity.There is no particular limitation for fatty acid amide, from the resistance to weldering produced by extinction effect
From the aspect of material tack, insulation characterisitic and screening capacity are further improved, the compound for preferably being represented by following formulas (1)
The compound represented by following formulas (2), the compound represented by following formulas (3).
R1- C (=O)-NH- (CH2)l- NH-C (=O)-R2 (1)
(in formula, R1、R2It is separately the saturation or unsaturated alkyl of carbon number 14～21, preferred carbon number 16
～the 18 saturation or unsaturated alkyl with 1 double bond, particularly preferred carbon number 16～18 saturation or has 1
The undersaturated straight-chain alkyl of double bond, l represent 0 or 1～10 integer, preferably represent 4～8 integer.)
R3- NH-C (=O)-(CH2)m- C (=O)-NH-R4 (2)
(in formula, R3、R4It is separately the saturation or unsaturated alkyl of carbon number 14～21, preferred carbon number 16
～the 18 saturation or unsaturated alkyl with 1 double bond, particularly preferred carbon number 16～18 saturation or has 1
The undersaturated straight-chain alkyl of double bond, m represent 0 or 1～10 integer, preferably represent 4～8 integer.)
R5- C (=O)-NH-R6 (3)
(in formula, R5、R6The saturation or unsaturated alkyl of carbon number 14～21, preferred carbon atom are represented separately
The saturation or unsaturated alkyl with 1 double bond of number 16～18, the saturation or tool of particularly preferred carbon number 16～18
There is the undersaturated straight-chain alkyl of 1 double bond.).
It is in addition, wherein, good from solder resistant tack, insulation characterisitic and the screening capacity harmony for making to be produced by extinction effect
From the aspect of further improving well, the fatty acid amide more preferably with 70 DEG C～160 DEG C of fusing point, particularly preferred six is sub-
Two oleamide of methyl (110 DEG C of fusing point), N- stearylstearic amides (95 DEG C of fusing point), N- oleyl stearamides are (molten
Point 74 DEG C), N ,-two oil base decanedioic acid acid amides of N ' (113 DEG C of fusing point), N ,-two oil base adipic acid acid amides of N ' (118 DEG C of fusing point),
N, N '-ethylenebis erucyl amide (120 DEG C of fusing point), ethylene oleamide (119 DEG C of fusing point), di-2-ethylhexylphosphine oxide stearic acid
Acid amides (142 DEG C of fusing point), ethylenebis lauramide (157 DEG C of fusing point).In addition, from extinction effect it is more excellent from the aspect of,
Fatty acid amide more preferably with 70 DEG C～120 DEG C of fusing point, particularly preferred hexa-methylene two oleamides (fusing point 110
DEG C), N- stearylstearic amides (95 DEG C of fusing point), N- oleyl stearamides (74 DEG C of fusing point).Fatty acid amide can be with
It is used alone a kind, it is also possible to which two or more is used in mixed way.
The use level of fatty acid amide has no particular limits, for example its lower limit, from make by extinction effect produce it is resistance to
From the aspect of solder attachment, insulation characterisitic and screening capacity are positively improved, preferably with respect to photoresist containing carboxyl
(solid state component) 100 mass parts are 1.0 mass parts, from the side that the solder resistant tack for making to be produced by extinction effect is further improved
Face considers that more preferably 2.5 mass parts are examined in terms of the especially excellent solder resistant tack produced by extinction effect is obtained
Consider, particularly preferred 3.5 mass parts.On the other hand, its higher limit from be prevented securely from printing reduce from the aspect of, preferred phase
For 100 mass parts of photoresist containing carboxyl (solid state component) are 15 mass parts, from from the aspect of shielding, more preferably
10 mass parts, from from the aspect of film flatness, particularly preferably 8.0 mass parts.
(C) Photoepolymerizationinitiater initiater
What as long as Photoepolymerizationinitiater initiater was usually used, there is no particular limitation, for example, can enumerate 1,2- pungent two
Ketone, 1- (4- (phenylsulfartyl) -2- (O- benzoyl oximes)), ethyl ketone 1- (9- ethyl -6- (2- toluyls
Base) -9H- carbazole -3- bases] -1- (O- acetyl oximes), 2- (acetyl group epoxide iminomethyl) thioxanthene-9-one etc.
Oximes initiator, benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin-n-butyl ether, benzoin are different
Butyl ether, acetophenone, dimethylamino benzoylformaldoxime, 2,2- dimethoxy -2- phenyl acetophenones, 2,2- diethoxy -2- phenyl
Acetophenone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, 1- hydroxycyclohexylphenylketones, 2- methyl isophthalic acids-(4- (methyl mercapto)
Phenyl) it is -2- morpholinyls-propane -1- ketone, 4- (2- hydroxyl-oxethyls) phenyl -2- (hydroxyl -2- propyl group) ketone, benzophenone, p-
Phenyl benzophenone, 4,4 '-diethylamino benzophenone, dichloro benzophenone, 2-methylanthraquinone, 2- EAQs, uncle 2-
Butyl anthraquinone, 2- amino anthraquinones, 2- methyl thioxanthones, 2- ethyl thioxanthones, CTX, 2,4- dimethyl thioxanthones, 2,
4- diethyl thioxanthones, benzyl dimethyl ketal (benzyl dimethyl ketal), acetophenone dimethyl ketal, P- diformazans
Double (2,4, the 6- trimethylbenzene first of base aminobenzoic acid ethyl ester, TMDPO, phenyl
Acyl group) phosphine oxide, ethyl -4- (dimethylamino) benzoic ether, 2- n-butoxyethyl -4- (dimethylamino) benzene
Formic acid esters, methyl -4- (dimethylamino) benzoic ether, isopentyl -4- (dimethylamino) benzoic ether, 2- (diformazans
Base amino) ethylamino benzonitrile acid esters, 2- ethylhexyl -4- (dimethylamino) benzoic ethers etc..They can be used alone,
Can also two or more be used in mixed way.
When the ultraviolet lighting of 300～400nm of wavelength is mapped to the photosensitive polymer combination of the present invention, above-mentioned photopolymerization causes
Agent promotes the photocuring containing carboxyl photoresist.There is no particular limitation for the use level of Photoepolymerizationinitiater initiater, such as preferred phase
For 100 mass parts photoresists containing carboxyl (solid state component) are 2～40 mass parts, particularly preferably 3～30 mass parts.
(D) compound with ethene unsaturated group
Compound with ethene unsaturated group, is for example, that photopolymerization monomer and every 1 molecule have at least 1
The compound of individual polymerism double bond.Using the purpose of the compound with ethene unsaturated group it is, by ultraviolet etc.
The irradiation of active energy ray and photocuring, make the photocuring of photosensitive polymer combination fully, obtain with acid resistance, heat-resisting
The solidfied material of property, alkali resistance etc..
Compound with ethene unsaturated group, there is no particular limitation, for example, can enumerate methacrylic acid 2-
Hydroxy methacrylate, phenoxyethyl methacrylate, diethylene glycol monomethyl acrylate, acrylic acid 2- hydroxyl -3- phenoxy-propyls,
Simple function (methyl) acrylate compounds such as (methyl) stearyl acrylate ester, BDO two (methyl) acrylate, 1,
6- hexylene glycols two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, two (methyl) acrylic acid diethylene glycol (DEG) ester, new penta
Glycol adipic acid two (methyl) acrylate (neopentyladipate di (metha) acrylate), hydroxy new pentane acid new penta
Glycol two (methyl) acrylate, bicyclopentyl two (methyl) acrylate, two (methyl) third of caprolactone modification dicyclopentenyl
Olefin(e) acid ester, ethylene-oxide-modified di(2-ethylhexyl)phosphate (methyl) acrylate, allylation cyclohexyl two (methyl) acrylate, isocyanide urea
Acid esters two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, two trimethylolpropane four (methyl) propylene
Acid esters, dipentaerythritol three (methyl) acrylate, dipentaerythritol three (methyl) acrylate, three (methyl) third of pentaerythrite
Olefin(e) acid ester, epoxy pronane modification trimethylolpropane tris (methyl) acrylate, three (acryloyl-oxyethyl) isocyanuric acid ester,
Propionic acid is modified dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, two season of caprolactone modification
Multifunctional (methyl) acroleic acid esterification such as penta tetrol six (methyl) acrylate, polyfunctional carbamate (methyl) acrylate
Compound (such as 2～6 senses (methyl) acrylate compounds).They can be used alone, it is also possible to which two or more mixing makes
With.
The use level of the compound with ethene unsaturated group, there is no particular limitation, such as relative to 100 mass
Part photoresist containing carboxyl (solid state component), particularly preferably preferably 2.0～500 mass parts, 10～300 mass parts.
(E) epoxide
Epoxide is to improve the crosslink density of solidfied material, obtaining the cured coating film with sufficient mechanical strength
The compound used Deng solidfied material.Epoxide can enumerate such as epoxy resin.As epoxy resin, example can be enumerated
As bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenolic resin varnish type epoxy resin (biphenyl phenolic resin varnish type epoxy resin,
Phenolic resin varnish type epoxy resin, o-cresol phenol aldehyde type epoxy resin, p- tert-butyl group novolac types etc.), make Bisphenol F, bis-phenol
S is with bisphenol-f type, bisphenol-s epoxy resin obtained from epichlorohydrin reaction and with cyclohexene oxide group, three rings of oxidation
The alicyclic epoxy resin of decane group, cyclopentene oxide group etc., three (2,3- glycidyl) isocyanuric acid ester, three are shunk
The triglycidyl group isocyanuric acid esters with triazine ring such as glyceryl three (2- hydroxyethyls) isocyanuric acid ester, two rings penta 2
Ene-type epoxy resin, adamantane type epoxy resin, biphenyl aralkyl-type epoxy resin, phenyl aralkyl-type epoxy resin, biphenyl
Type epoxy resin etc..These compounds may be used alone, can also be two or more kinds in combination.
The use level of epoxide has no particular limits, from the cured coating film for effectively obtaining sufficient mechanical strength
From the aspect of, 10～150 mass parts are preferably relative to 100 mass photoresist containing carboxyl (solid state component) parts, especially
Preferably 20～100 mass parts.
(F) colouring agent
Colouring agent is pigment, pigment etc., and there is no particular limitation, in addition, white color agents, blue colorant, yellow
Toner, black colorant etc. can be used.Above-mentioned colouring agent, can enumerate for example, the titanium oxide of white color agents, for black
Organic system colouring agents such as phthalocyanines, the Anthraquinones such as the inorganic based colorant such as the carbon black of colouring agent, phthalocyanine green and phthalocyanine blue etc..
There is no particular limitation for the use level of colouring agent, such as relative to the 100 mass parts (solid-state of photoresist containing carboxyl
Composition), preferably 1.0～10 mass parts, particularly preferably 2.0～8.0 mass parts.
In the photosensitive polymer combination of the present invention, in addition to above-mentioned (A)～(F) compositions, can also fit as needed
When containing various adding ingredients, such as non-reactive diluent, defoamer, various additives etc..
Non-reactive diluent is the material for adjusting the viscosity of photosensitive polymer combination, drying property.As non-anti-
Answering property diluent, for example, can enumerate organic solvent.Organic solvent can enumerate such as ketone such as methyl ethyl ketone, hexamethylene,
Toluene, dimethylbenzene etc. are aromatic hydrocarbon, the alcohols such as methyl alcohol, isopropanol, cyclohexanol, the ester ring type hydrocarbon such as hexamethylene, hexahydrotoluene
The dioxanes such as petroleum solvents, cellosolve, the butyl cellosolves such as class, petroleum ether, naphtha, carbitol, butyl carbitol etc.
Carbitol class, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl card must
Esters such as alcohol acetic ester, diethylene glycol monomethyl ether acetic acid esters etc..
There is no particular limitation for defoamer, for example, can enumerate silicon-type, hydrocarbon system, acrylic acid series etc..In addition, various add
Plus agent can enumerate the latent curing agents such as dicyandiamide (DICY) and its derivative, melamine and its derivative, antioxidant,
Coupling agent etc..
The manufacture method of the photosensitive polymer combination of the invention described above, is not limited to ad hoc approach, for example can will be upper
It is after each composition is stated with the cooperation of regulation ratio, mixed by kneading devices such as three-roller, ball mill, sand mills or at a high speed at room temperature
The agitating devices such as conjunction machine, planetary stirring machine are kneaded or are mixed to manufacture.In addition, before above-mentioned mixing or mixing, also may be used
To carry out pre- mixing or premixing as needed.
Next, illustrating for the using method of the photosensitive polymer combination of the invention described above.Herein, as example
Son, for the photosensitive polymer combination of the present invention is coated on circuit substrate the situation as soldering-resistance layer, illustrates.
For example, in electricity such as the printed circuit board with the circuit pattern for forming Copper Foil etching, flexible circuit boards
On base board, using serigraphy, spraying process, stick coating method, applicator (applicator), scraper for coating method, air knife coating method,
Coating process known to rolling method, gravure coat method etc., by the photosensitive resin composition of the present invention for obtaining as mentioned above
Thing coating is desired thickness.After coating, when in the photosensitive polymer combination of the present invention containing organic solvent, in order that
Organic solvent is vaporized, and carries out heating at a temperature of 60～80 DEG C or so 15～60 minutes or so predrying, is formed tack-free
(tack-free) film.
Then, on the photosensitive polymer combination having been coated with it is closely sealed with make the bossing (land) of circuit pattern with
The negative film (negative film) of the outer pattern for translucency, from the upper side irradiation ultraviolet radiation (such as 300～400nm's of wavelength
Scope).Then, non-exposed areas corresponding with above-mentioned bossing are removed with dilute aqueous alkali, thus will applies film development.
Developing method for example, can enumerate 0.5～5 matter using spray-on process, spray process etc. as the dilute aqueous alkali for being used
The aqueous sodium carbonate of amount %.Next, being carried out after 20～80 minutes using 130～170 DEG C hot air circulation type drying machine etc.
Solidification (postcure), thus, it is possible to be formed as target on the circuit substrates such as printed circuit board, flexible circuit board
Soldering-resistance layer.
Embodiment
Next, explanation embodiments of the invention, but the present invention is without departing from its purport, is not limited to these examples
Son.
Embodiment 1～17, comparative example 1～4
Each composition shown in table 1 below, table 2 is coordinated according to the mixing ratio shown in table 1 below, table 2, three are used
Roller machine makes its mixing dispersion at room temperature, prepares the photosensitive polymer combination used in embodiment 1～17, comparative example 1～4.
The use level of each composition shown in table 1 below, table 2 is as long as no specified otherwise, then it represents that mass parts.
[table 1]
[table 2]
It should be noted that with regard to the details of each composition in table 1, table 2, it is as follows.
(A) photoresist containing carboxyl
ZFR-1122：The acid anhydrides admixture (65 mass % of solid state component) of bisphenol F type epoxy base acrylate, Japan
Chemical drug (strain) is made.
ZAR-2000：The acid anhydrides admixture (65 mass % of solid state component) of bisphenol type epoxy base acrylate, Japan
Chemical drug (strain) is made.
FLX-2089：Sour modified urethane epoxymethacrylate resin (65 matter of solid state component
Amount %), Japanese chemical drug (strain) system.
ZCR-1601H：Bis-phenol novolac structure with multi-functional epoxy's base containing carboxy resin (solid state component
65 mass %), Japanese chemical drug (strain) system.
Synthetic resin A
In nitrogen/air (2:1) under atmosphere, to the 500mL knockdown type flasks for possessing agitator, backflow cooling tube
TC acetic acid esters (EDGAC) 60g, 8- ethyl octadecane diacid (ridge is added in (separable flask)
Village's liquefaction (strain) SB-20 processed) 25.89g, behenic acid 43.77g, stearic acid 9.32g, acrylic acid 13.79g, triphenylphosphine (TPP)
0.48g, methoxyhydroquinon (MEHQ) 0.40g, with 0.3L/min into reaction vessel in be blown into nitrogen/air (2:1), one
While in 110 DEG C of heating stirrings until dissolving.In addition, being heated to 80 DEG C makes biphenyl aralkyl-type epoxy resin NC-3000 (Japan
Chemical drug (strain) is made, and 277) 132.96g is equably dissolved in 70g EDGAC solvents epoxide equivalent, is added in above-mentioned flask,
In 115 DEG C of heating stirrings 15～17 hours so as to which reaction is until the acid number of reaction solution is the scope of 7～8mgKOH/g.To this
Be dissolved with 10g EDGAC solvents is added in reactant further in hydrogenated trimellitic anhydride (Mitsubishi Gas
Chemical (strain) system, HTMAn) 37.66g solution, air is blown into 0.3L/min, while in 100 DEG C stir 2
～3 hours.Confirm that acid anhydrides disappears by FT-IR (infrared spectrometer).Thus, obtain solid state component acid number 80.7mgKOH/g,
The photoresist containing carboxyl (65 mass % of solid state component) (synthetic resin A) of matter average molecular weight 7000～9000.
(B) fatty acid amide
·Slipacks ZHO、Nikka amide S、Nikka amide OS：Japan's chemical conversion (strain) system.
(C) Photoepolymerizationinitiater initiater
Irgacure OXE-02：BASF AG's system.
·SPEEDCURE EDB：LAMBSON company system.
·Irgacure 907：Ciba Specialty Chemicals (strain) makes.
·SPEEDCURE DETX：LAMBSON company system.
(D) compound with ethene unsaturated group
·KRM 8296：(strain) Daicel systems.
DPCA-120：Japanese chemical drug (strain) system.
·STA：Osaka Organic Chemical Industry (strain) is made.
(E) epoxide
YDF-2004：Dongdu chemical conversion (strain) system.
·EPICLON 860：DIC (strain) makes.
NC-3000：Japanese chemical drug (strain) system.
YX-4000：Japan Epoxy Resins (strain) makes.
(F) colouring agent
Carbon black：Electrochemically industry (strain) is made.
C.I. pigment blue 15：3：Toyo Ink manufacture (strain) system.
With regard to other compositions
Filler
·OK412：EvonikDegussa company systems.
Non-reactive diluent
Diethylene glycol monomethyl ether acetic acid esters：Sanyo's chemical conversion industry (strain) is made.
Test film production process
By the Copper Foil (Cu with resin of polyimide film (Dong Li Du Ponts (strain) system, " kapton100H ", 25 μm of thickness)
It is thick 12.5 μm) circuit pattern is formed, after thus obtained wiring plate is surface-treated with dilute sulfuric acid (5 mass %), adopt
Silk screen print method, is respectively coated the photosensitive polymer combination of the embodiment 1～17 and comparative example 1～4 of above-mentioned preparation.Coating
Afterwards, carried out in 80 DEG C with BOX stoves 20 minutes it is predrying.After predrying, exposure device (OAK company systems, HMW- are used on film
680GW) with 250mJ/cm2It is exposed in the ultraviolet of 300～400nm of wavelength, using the aqueous sodium carbonate of 1 mass %,
30 DEG C of development temperature, the injection pressure of developer pressure 0.2MPa are developed.After development, 60 minute are carried out in 150 DEG C with BOX stoves
Solidify afterwards, thus form cured coating film on wiring plate.The thickness of cured coating film is 20～23 μm.
Evaluate
(1) glossiness
For the cured coating film of above-mentioned test film, using Micro-Tri-Gloss (BYK-Chemie Japan (strain) systems)
Determine 60 degree of glossiness (Gloss Value).It should be noted that 60 degree of glossiness are the 1st after decimal point by mean value
Round up and in round figures.
(2) insulating properties
Wiring plate is changed to the combed of the IPC-SM840B B-25 test specimens (test coupon) of IPC-TM-650
Electrode, based on above-mentioned test film production process, forms cured coating film.Test film to gained, apply DC50V determine in 85 DEG C,
Insulating resistance value of the 85%R.H. humidifications after 200 hours, evaluates to insulating properties according to following benchmark.
◎：5×1012More than Ω
○：1×1012Ω～be less than 5 × 1012Ω
×：Less than 1 × 1012Ω
(3) solder heat resistance
According to the test method of JIS C-6481, the cured coating film of above-mentioned test film is impregnated in 260 DEG C of solder bath
After 30 seconds, by the use of the disbonded test of adhesive tape (cellophane tape) as 1 circulation, to observe by visual observation which is heavy
Painting membrane stage after multiple, is evaluated according to following benchmark.
◎：It is repeated 3 times unconfirmed to change in the film after circulation.
○：Be repeated 2 times circulation after film in it is unconfirmed to change, but be repeated 3 times circulation after film in confirmed
Change.
△：Be repeated 1 times circulation after film in it is unconfirmed to change, but be repeated 2 times circulation after film in confirmed
Change.
×：It is repeated 1 times to confirm in the film after circulation and changes.
(4) screening capacity
Screening capacity of the cured coating film to copper foil circuit pattern is observed by visual observation.Evaluated according to following benchmark.
○：Conductive pattern can not be seen from cured coating film.
×：Conductive pattern can be seen from cured coating film.
Evaluation result is as shown in above-mentioned table 1, table 2.
As shown in above-mentioned table 1, table 2, in the embodiment for having coordinated fatty acid amide, solder heat resistance can not damaged
In the case of, glossiness is reduced to into less than 20, obtain the solder resistant tack obtained by extinction effect.In addition, in above-mentioned reality
Apply in example, in addition to the solder resistant tack obtained by extinction effect, it is also possible to obtain excellent insulating properties and screening capacity.
In addition, the reality of about 7.7 mass parts fatty acid amides is combined with relative to 100 mass parts photoresists containing carboxyl (solid state component)
Apply example 4,16 with coordinated about 1.5 mass parts fatty acid amides embodiment 3,15, coordinated about 4.6 mass parts fatty acid amides
Embodiment 1,2,5～14,17 compare understand, glossiness is further reduced, by extinction effect obtain solder resistant tack
Further improve.
In addition, from the contrast of embodiment 6～9 and embodiment 10～12, during using synthetic resin A, insulating properties enters one
Step is improved, and synthetic resin A is formed as follows：Make b) averagely to contain per the aliphatic acid that the carbon number of 1 carboxyl is more than 10 and c)
Have ethene unsaturated group carboxylic acid and a) have in 1 molecule more than 2 epoxy radicals epoxy resin epoxy reaction, obtain
To the modified epoxy containing ethene unsaturated group that LCFA is modified, d) multi-anhydride and changing obtained by this are made
The hydroxyl addition of property epoxy resin.In addition, from embodiment 11, using synthetic resin A as (A) photonasty containing carboxyl tree
Fat, using biphenyl aralkyl-type epoxy resin as (E) epoxide when, not only insulating properties is further improved, solder heat resistance
Property is also further improved.Further, from the contrast of embodiment 12 and embodiment 13, as (D) with ethene unsaturated group
The compound of group, compared with 3 functional acrylates, in the case of 6 functional acrylate, insulating properties, solder heat resistance are further carried
It is high.
On the other hand, in the comparative example 1,3 of unmated fatty acid amide and filler, glossiness is not reduced, do not obtain by
The solder resistant tack that extinction effect is obtained.In addition, in comparative example 1,3, screening capacity can not be obtained.In addition, replacing fat
Fat acid acid amides and coordinate the comparative example 2,4 of filler, glossiness is reduced to 10, and the solder resistant for having obtained being obtained by extinction effect is attached
The property, but do not obtain insulating properties and screening capacity.
Industrial applicability
The photosensitive polymer combination of the present invention, can be in the case where the fundamental characteristics such as solder heat resistance are not damaged, shape
Into excellent insulation-coated etc. solid of the solder resistant tack, insulation characterisitic and the screening capacity that are obtained by extinction effect (low-luster)
Compound, thus, for example value is high in the field of soldering-resistance layer.
Claims (7)
1. photosensitive polymer combination, it is characterised in that containing (A) photoresist containing carboxyl, (B) fatty acid amide, (C) light
Polymerization initiator, the compound of (D) with ethene unsaturated group, (E) epoxide and (F) colouring agent.
2. photosensitive polymer combination as claimed in claim 1, it is characterised in that (B) fatty acid amide is to be selected from
Compound, the compound represented by following formulas (2) and the chemical combination represented by following formulas (3) that following formulas (1) represent
At least a kind in thing：
R1- C (=O)-NH- (CH2)l- NH-C (=O)-R2 (1)
In formula, R1、R2Separately for carbon number 14～21 saturation or unsaturated alkyl, l represent 0 or 1～10 it is whole
Number；
R3- NH-C (=O)-(CH2)m- C (=O)-NH-R4 (2)
In formula, R3、R4Separately for carbon number 14～21 saturation or unsaturated alkyl, m represent 0 or 1～10 it is whole
Number；
R5- C (=O)-NH-R6 (3)
In formula, R5、R6The saturation or unsaturated alkyl of carbon number 14～21 are represented separately.
3. photosensitive polymer combination as claimed in claim 1, it is characterised in that (B) fatty acid amide has 70 DEG C
～160 DEG C of fusing point.
4. photosensitive polymer combination as claimed in claim 1, it is characterised in that (B) fatty acid amide is selected from six
Two oleamide of methylene, N- stearylstearic amides, N- oleyl stearamides, N ,-two oil base decanedioic acid acyls of N '
Amine, N ,-two oil base adipic acid acid amides of N ', N, at least 1 in N '-ethylenebis erucyl amide and ethylene oleamide
Kind.
5. the photosensitive polymer combination as any one of Claims 1 to 4, it is characterised in that relative to 100 mass parts
(A) photoresist containing carboxyl, containing (B) fatty acid amide described in 1.0 mass parts～15 mass parts.
6. the photosensitive polymer combination as any one of Claims 1 to 5, it is characterised in that (F) colouring agent is
Black colorant.
7. printed circuit board, the photocuring film with the photosensitive polymer combination any one of claim 1～6.
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| JP2015-191657 | 2015-09-29 | ||
| JP2015191657 | 2015-09-29 | ||
| JP2016-173849 | 2016-09-06 | ||
| JP2016173849A JP6346228B2 (en) | 2015-09-29 | 2016-09-06 | Photosensitive resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110297392A (en) * | 2018-03-23 | 2019-10-01 | 株式会社田村制作所 | Photosensitive polymer combination |
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| JP2002244280A (en) * | 2001-02-16 | 2002-08-30 | Hitachi Chem Co Ltd | Photosensitive resin composition |
| US20060240367A1 (en) * | 2005-04-26 | 2006-10-26 | Konica Minolta Medical & Graphic, Inc. | Silver salt photothermographic dry imaging material |
| JP2008250074A (en) * | 2007-03-30 | 2008-10-16 | Fujifilm Corp | Photosensitive resin composition, photosensitive film, photosensitive laminate, method for forming permanent pattern and printed board |
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