CN101529333A - Photosensitive resin composition and photosensitive element using the same - Google Patents
Photosensitive resin composition and photosensitive element using the same Download PDFInfo
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- CN101529333A CN101529333A CNA2007800395894A CN200780039589A CN101529333A CN 101529333 A CN101529333 A CN 101529333A CN A2007800395894 A CNA2007800395894 A CN A2007800395894A CN 200780039589 A CN200780039589 A CN 200780039589A CN 101529333 A CN101529333 A CN 101529333A
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Abstract
The invention provides a photosensitive resin composition comprising (A) a novolac-type acid-modified, vinyl-group-containing epoxy resin having a biphenyl skeleton, (B) a phosphorus-containing compound, (C) a photopolymerizable compound having at least one ethylenically unsaturated group in the molecule, and (D) a photopolymerization initiator.
Description
Technical field
The present invention relates to the photosensitive element of photosensitive polymer combination and use said composition.
Background technology
In the manufacturing industry of printed circuit board (PCB), on printed circuit board (PCB), form the scolder resist so far always.This scolder resist is in the solder technology that is used for engaging to printed circuit board (PCB) installing component, have and prevent that scolding tin is attached to the effect of the part that does not need conductor layer of printed circuit board (PCB), have in addition to engage and prevent the corrosion of conductor layer or the effect that keeps the permanent veil of conduct of the electrical insulating property between conductor layer when printed circuit board (PCB) is used in the back at installing component.
About the formation method of scolder resist, the known for example method of serigraphy thermoset resin on the conductor layer of printed circuit board (PCB).But for this method, the high resolving powerization of resist pattern is limited, therefore is difficult to tackle the densification of printed circuit board (PCB) in recent years.
Therefore, in order to realize the high resolving powerization of resist pattern, adopted the photoresist method widely.This photoresist method is: form the photosensitive polymer combination layer that comprises photosensitive polymer combination on substrate, exposure by predetermined pattern is solidified this photosensitive polymer combination layer, removes the cured film that unexposed portion forms predetermined pattern by development again.
In addition, consider that for the photosensitive polymer combination that uses in the said method, the composition of the alkali developable that can develop with dilute alkaline aqueous solutions such as aqueous sodium carbonates becomes main flow gradually from the angle of operating environment protection, earth environment protection.
Photosensitive heat curing resin combination etc. as record in the liquid resist ink composite of record in the known for example following patent documentation 1 of this photosensitive polymer combination and the following patent documentation 2.
Patent documentation 1: Japanese kokai publication sho 61-243869 communique
Patent documentation 2: Japanese kokai publication hei 01-141904 communique
Summary of the invention
Yet various in recent years industrial products become strict at the fire-retardantization standard of fire, and the material that is used for printed circuit board (PCB) etc. is no exception.As the method for adding halogen based compound, antimony based compound, phosphorus series compound, borate compounds, inorganic filler etc. in the common known oriented material of flame resistant method.
But, recently to the care of environmental problem, human safety problem surging the time, emphasis to non-Hazardous, low toxic, security is shifted, and is not only to be difficult to burning, also expects the minimizing of harmful gas and smokiness material.Thus, begun to the fire-retardant substrate that does not use halogen based compound and antimony based compound develop, practicability.
Yet, by discovering of the inventor, on aforesaid fire-retardant substrate, use when the photosensitive polymer combination in the past of record forms cured film in the above-mentioned patent documentation 1 and 2, can not guarantee sufficient anti-flammability (preferred UL94 VTM-0 standard).
The present invention In view of the foregoing finishes, and its purpose is to provide the photosensitive polymer combination that can form the cured film of excellent in flame retardance when having excellent alkali-developable.In addition, the object of the present invention is to provide, have the photosensitive element of the photosensitive polymer combination layer that comprises such photosensitive polymer combination.
To achieve these goals, what people of the present invention studied repeatedly with keen determination found that, by comprise resin and the phosphorus-containing compound with ad hoc structure in photosensitive polymer combination, can realize above-mentioned purpose, thereby finish the present invention.
Promptly, the invention provides a kind of photosensitive polymer combination, contain phenolic varnish type acid modification that (A) have biphenyl backbone and contain vinyl epoxy resin, (B) phosphorus-containing compound, (C) and in molecule, have the optical polymerism compound of at least one alkene class unsaturated group and (D) Photoepolymerizationinitiater initiater.
Utilize such photosensitive polymer combination, by having above-mentioned formation, can have excellent alkali-developable, its cured film can obtain excellent flame simultaneously.Therefore, above-mentioned photosensitive polymer combination can be used for the manufacturing of the printed circuit board (PCB) etc. of requirement anti-flammability aptly.
In addition, in the photosensitive polymer combination of the present invention, the sour modification that above-mentioned (A) epoxy resin preferably includes as following resultant of reaction contains vinyl epoxy resin, to be (a) contain the monocarboxylic acid of unsaturated group and (c) resultant of reaction of polybasic acid anhydride by epoxy resin, (b) of following general formula (1) expression to described resultant of reaction
[changing 1]
[in the formula (1), R
1And R
2Represent the alkyl or the aryl of hydrogen atom, carbon number 1～8 independently of one another, n represents 0～50 integer.In addition, a plurality of R that exist in the formula (1)
1And R
2Can be mutually the same, also can be different].
Contain vinyl epoxy resin as (A) epoxy resin by comprising above-mentioned specific sour modification, make photosensitive polymer combination can obtain excellent alkali-developable, the while can form and have the more cured film of excellent flame.
In addition, photosensitive polymer combination of the present invention preferably further contains (E) thermal curing agents.Contain (E) thermal curing agents by photosensitive polymer combination, make that photosensitive polymer combination carries out photocuring after, further carry out heat curing, thus, can further improve the insulating reliability of the cured film that obtains.
In addition, in the photosensitive polymer combination of the present invention, above-mentioned (B) phosphorus-containing compound preferably includes the phosphinates by following general formula (2) expression,
[changing 2]
[in the formula (2), A and B represent the alkyl or the aryl of the carbon number 1～6 of a straight chain shape or a chain independently of one another, M represents to be selected from least a metal in the group that is made of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na and K, and m represents 1～4 integer].
Comprise the phosphinates of representing by above-mentioned general formula (2) by photosensitive polymer combination, can further improve the anti-flammability of the cured film that obtains.
In addition, in the photosensitive polymer combination of the present invention, above-mentioned (B) phosphorus-containing compound preferably includes phosphate.Comprise phosphate by photosensitive polymer combination, can further improve the anti-flammability of the cured film that obtains and flexible.In addition, in the photosensitive polymer combination of the present invention, above-mentioned (B) phosphorus-containing compound preferably contain simultaneously above-mentioned by general formula (2) expression phosphinates and above-mentioned phosphate the two, thus can be so that the anti-flammability of the cured film that arrives and flexible all excellent especially.
In addition, in the photosensitive polymer combination of the present invention, above-mentioned (B) phosphorus-containing compound preferably includes phenoxy phosphazene compound.Comprise phenoxy phosphazene compound by photosensitive polymer combination, can further improve the anti-flammability of the cured film that obtains and flexible, can make exudative (photosensitive polymer combination exudative) better simultaneously.In addition, in the photosensitive polymer combination of the present invention, (B) phosphorus-containing compound preferably contain simultaneously above-mentioned by general formula (2) expression phosphinates and above-mentioned phenoxy phosphazene compound the two, thus can be so that the anti-flammability of the cured film that arrives, flexible and exudative all excellent especially.
And then photosensitive polymer combination of the present invention is preferably the composition that is used for forming as the cured film of permanent veil on flexible base, board.
The present invention also provides a kind of photosensitive element, and this photosensitive element has support and the photosensitive polymer combination layer of the photosensitive polymer combination that comprises the invention described above that forms on this support.Utilize such photosensitive element,, can obtain excellent alkali-developable, can form cured film simultaneously with excellent flame by having the photosensitive polymer combination layer that comprises above-mentioned photosensitive polymer combination.
According to the present invention, can provide the photosensitive polymer combination of the cured film that can form excellent in flame retardance when having excellent alkali-developable and the photosensitive element that uses said composition.
Description of drawings
Fig. 1 is the schematic cross-section of a preferred embodiment of expression light-sensitive surface of the present invention.
Symbol description
1... photosensitive element, 10... support, 14... photosensitive polymer combination layer
Embodiment
Following one side according to circumstances, at length describe preferred implementation of the present invention on one side with reference to accompanying drawing.In addition, identical or considerable part is given prosign in the accompanying drawing, and the repetitive description thereof will be omitted.And; (methyl) acrylic acid is meant acrylic acid and the methacrylic acid corresponding with it among the present invention; (methyl) acrylate is meant acrylate and the methacrylate corresponding with it, and (methyl) acryloyl group is meant acryloyl group and the methacryl corresponding with it.
(photosensitive polymer combination)
Photosensitive polymer combination of the present invention contains phenolic varnish type acid modification that (A) have biphenyl backbone and contains vinyl epoxy resin (below be sometimes referred to as " (A) composition "), (B) phosphorus-containing compound (below be sometimes referred to as " (B) composition "), (C) have at least one alkene class unsaturated group in molecule optical polymerism compound (below be sometimes referred to as " (C) composition ") and (D) Photoepolymerizationinitiater initiater (below be sometimes referred to as " (D) composition ").And photosensitive polymer combination of the present invention also preferably further contains (E) thermal curing agents (below be sometimes referred to as " (E) composition ").
Photosensitive polymer combination of the present invention above-mentioned by containing (A)～(D) composition can utilize dilute alkaline aqueous solution to develop, and solidifies this photosensitive polymer combination simultaneously and the cured film that obtains can make anti-flammability satisfy with high level.Therefore, according to photosensitive polymer combination of the present invention, can form cured film effectively with high resolving power with abundant anti-flammability.
In addition, according to photosensitive polymer combination of the present invention, make the anti-flammability of cured film enough high owing to can not comprising halogen based compound and antimony based compound, thereby can reduce for example carrying capacity of environment and the toxicity of printed circuit board (PCB).Particularly, photosensitive polymer combination of the present invention is applicable to the situation of the fire-retardant substrate of non-halogen system or non-antimony system can more effectively realizes above-mentioned effect.
Describe at each composition that is included in the photosensitive polymer combination of the present invention below.
＜(A) composition: sour modification contains vinyl epoxy resin 〉
Contain vinyl epoxy resin as the phenolic varnish type acid modification with biphenyl backbone of (A) composition and be preferably the resin that obtains as following resultant of reaction, to be (a) contain the monocarboxylic acid of unsaturated group and (c) resultant of reaction of polybasic acid anhydride by epoxy resin, (b) of following general formula (1) expression to this resultant of reaction
[changing 3]
[in the formula (1), R
1And R
2Represent the alkyl or the aryl of hydrogen atom, carbon number 1～8 independently of one another, n represents 0～50 integer.In addition, a plurality of R that exist in the formula (1)
1And R
2Can be identical, also can be different].
By making photosensitive polymer combination contain (A) epoxy resin that use has the compound formation of this spline structure of above-mentioned general formula (1), can take into account alkali-developable and anti-flammability simultaneously.
About constituting the concrete example that (b) that sour modification as (A) composition contains vinyl epoxy resin contains the monocarboxylic acid of unsaturated link, can enumerate for example acrylic acid, acrylic acid dipolymer, methacrylic acid, β-styrene acrylic, β-furfuryl group acrylic acid, crotonic acid, the alpha-cyano cinnamic acid, cinnamic acid, and as the half ester class of the reactant of (methyl) acrylate derivative that has 1 hydroxyl in saturated or unsaturated dicarboxylic acid anhydride and 1 molecule or as saturated or unsaturated dibasic acid and contain the half ester class etc. of reactant of single glycidyl compound of unsaturated group.
The half ester class for example is, with succinic anhydride, maleic anhydride, anhydride phthalic acid, the tetrahydro anhydride phthalic acid, the hexahydro anhydride phthalic acid, methyl hexahydro anhydride phthalic acid, the methyltetrahydro anhydride phthalic acid, itaconic anhydride, saturated or unsaturated dicarboxylic acid anhydride and (methyl) hydroxy-ethyl acrylates such as methyl endo-methylene group (メ チ Le エ Application De メ チ レ Application) tetrahydro anhydride phthalic acid, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid hydroxy butyl ester, polyethyleneglycol (methyl) acrylate, glycerine two (methyl) acrylate, trimethylolpropane two (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, (methyl) acrylate derivative class that has 1 hydroxyl in 1 molecule such as (methyl) acrylate of phenyl glycidyl ether with etc. mol ratio react and the half ester class that obtains, perhaps with saturated or unsaturated dibasic acid (succinic acid for example, maleic acid, hexane diacid, phthalandione, the tetrahydro phthalandione, the hexahydro phthalandione, itaconic acid, fumaric acid etc.) with the single glycidyl compound (for example (methyl) glycidyl acrylate etc.) that contains unsaturated group with etc. mol ratio react and the half ester that obtains etc.
These (b) monocarboxylic acids can use a kind or be used in combination more than 2 kinds separately.Particularly preferred (b) monocarboxylic acid is an acrylic acid.
About constituting the concrete example that contains (c) polybasic acid anhydride of vinyl epoxy resin as the sour modification of (A) composition, can enumerate for example maleic anhydride, succinic anhydride, anhydride phthalic acid, tetrahydro anhydride phthalic acid, hexahydro anhydride phthalic acid, methyltetrahydro anhydride phthalic acid etc.
(A) acid number of composition is preferably 60～150mgKOH/g, more preferably 80～120mgKOH/g.Acid number often is difficult to utilize dilute alkaline aqueous solution to develop during less than 60mgKOH/g; During greater than 150mgKOH/g, the insulating reliability of the cured film that obtains, reagent resistance and anti-plating tend to insufficient.
Here, (A) acid number of composition can be measured by following method.At first, accurately the about 1g of weighing adds 30g acetone, dissolving resin solution equably as behind the resin solution of (A) composition to this resin solution.Then, the phenolphthalein as indicator is added in this solution in right amount, use the KOH aqueous solution of 0.1N to carry out titration.Subsequently, calculate acid number by titration results by following formula.
[several 1]
A＝10×Vf×56.1/(Wp×I)
In the formula, A represents acid number (mgKOH/g), and Vf represents the titer (mL) of phenolphthalein, and Wp represents the quality (g) as the resin solution of (A) composition, and I represents the ratio (quality %) as the nonvolatile component of the resin solution of (A) composition.
(A) weight-average molecular weight of composition is not particularly limited, but considers from the angle of film forming and resolution, is preferably 1000～50000, and more preferably 2000～30000, be preferably 3000～15000 especially.
Contain vinyl epoxy resin as the phenolic varnish type acid modification with biphenyl backbone of (A) composition and also can be used as commodity and buy, for example also can use ZCR-1569H, ZCR-1596H, ZCR-1611H, ZCR-1610H (be Japanese chemical drug corporate system is made, trade name).
In addition, photosensitive polymer combination of the present invention can add and use to remove phenol phenolic varnish type acid modification and contain vinyl epoxy resin, cresols phenolic varnish type acid modification and contain vinyl epoxy resin, bisphenol A-type acid modification and contain vinyl epoxy resin, Bisphenol F type acid modification and contain the sour modification that the sour modification of phenolic varnish type that vinyl epoxy resin etc. has biphenyl backbone contains the vinyl epoxy resin and contain vinyl epoxy resin, acrylic resin, phenylethylene resin series, epoxy is a resin, acid amides is a resin, the acid amides epoxy is a resin, alkyd is resin, phenol resin.Wherein, consider, preferably use acryl resin from the angle of giving film forming.
Preferably constitute the resin that monomer comprises (methyl) acrylic acid and (methyl) acrylate as the aforesaid propylene acid resin, can comprise that the formation monomer of (methyl) acrylic acid and (methyl) acrylate carries out the incompatible manufacturing of radical polymerization by making.
Can enumerate the compound that is replaced by hydroxyl, epoxy radicals, halogen etc. by the alkyl of the compound of following general formula (3) expression and this compound as above-mentioned (methyl) acrylate.
[changing 4]
In the above-mentioned general formula (3), R
11Expression hydrogen atom or methyl, R
12The alkyl of expression carbon number 1～12, the ester ring type alkyl or the benzyl of carbon number 5～10.And, as by R
12The alkyl of expression for example can be enumerated methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl and their constitutional isomer.
The phenolic varnish type acid modification with biphenyl backbone at shared above-mentioned conduct (A) composition contains under the situation of vinyl epoxy resin and aforesaid propylene acid resin, consider from the angle that can improve film forming, the weight-average molecular weight of acryl resin is preferably 30,000～300, and 000, more preferably 40,000～200,000, be preferably 50 especially, 000～150,000.
＜(B) composition: phosphorus-containing compound 〉
Phosphorus-containing compound as (B) composition preferably includes the phosphinates of being represented by following general formula (2).
[changing 5]
In the formula (2), A and B represent the alkyl or the aryl of the carbon number 1～6 of a straight chain shape or a chain independently of one another, M represents to be selected from least a metal in the group that is made of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na and K, and m represents 1～4 integer.
At this, can enumerate for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, n-pentyl, phenyl etc. as the concrete example of A in the formula (2) and B.
In addition, the angle of the reliability when being used for photosensitive polymer combination and photosensitive element considers, preferably by 80 quality % of the phosphinates of above-mentioned general formula (2) expression above in, the granularity of phosphinates particle is below the 10 μ m, more preferably below the 5 μ m, be preferably especially below the 3 μ m.The granularity of this particle is during greater than 10 μ m, and the appearance of film of photosensitive polymer combination is often relatively poor, often is difficult to make high-resolution printed circuit board (PCB).
Above-mentioned phosphinates can use a kind or be used in combination more than 2 kinds separately.And above-mentioned phosphinates also can be used as commodity and buys, and for example also can use EXOLIT OP 930, EXOLIT OP 935, EXOLIT OP 940 (being the manufacturing of Clariant (Clariant) company, trade name).
Contain above-mentioned phosphinates as (B) composition by photosensitive polymer combination, solidify photosensitive polymer combination and the cured film that obtains can obtain anti-flammability more fully.And, be the structure that is difficult to hydrolysis by the phosphinates of above-mentioned general formula (2) expression, can prevent from effectively to produce the ionic impurity that reduces electrical insulating property, so cured film can have excellent insulating reliability.
In addition, the phosphorus-containing compound as (B) composition also preferably includes phosphate.Concrete example as phosphate for example can be enumerated, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate (diformazan phenyl ester), tolyl diphenyl phosphoester, xylyl diphenyl phosphoester, 1, the phenolic condensates, 2 of 3-dihydroxy benzenes phosphine tri chloride condensed polymer, the phenolic condensates of 2-two (p-hydroxybenzene) propane phosphine tri chloride oxide condensed polymer etc.It is obtained that these compounds can be used as commodity, can enumerate for example TPP, TCP, TXP, CDP, XDP, CR-733S, CR-741, CR-747 (being the manufacturing of big eight chemical companies, trade name), PFR, FP-600 and FP-700 (being the manufacturing of ADEKA company, trade name) etc.
Contain phosphate as (B) composition by photosensitive polymer combination, can further improve the anti-flammability of the cured film of solidifying photosensitive polymer combination and obtaining.And, because the effect of phosphate performance plastifier can further improve the flexible of cured film.
In addition, the phosphorus-containing compound as (B) composition also preferably includes phenoxy phosphazene compound.Concrete example as phenoxy phosphazene compound can be enumerated, by the compound with ring texture of following general formula (4) expression and/or the compound of being represented by following general formula (5) with chain structure.
[changing 6]
In the formula (4), r represents 1～20 integer.
[changing 7]
In the formula (5), s represents 1～20 integer.
Contain phenoxy phosphazene compound as (B) composition by photosensitive polymer combination, can further improve the anti-flammability of the cured film of solidifying photosensitive polymer combination and obtaining.And phenoxy phosphazene compound can make flexible and exudative (photosensitive polymer combination exudative) of cured film better.
Can use above-mentioned at least a by in phosphinates, above-mentioned phosphate and the phenoxy phosphazene compound of general formula (2) expression separately about (B) composition, preferably use above-mentioned phosphinates at least, especially preferably use above-mentioned phosphinates and above-mentioned phosphate or phenoxy phosphazene compound simultaneously by general formula (2) expression by general formula (2) expression.In addition, can also use in addition known phosphorus-containing compound about (B) composition.
＜(C) composition: compound〉with at least one alkene class unsaturated link
The concrete example that has the optical polymerism compound of at least one alkene class unsaturated group as (C) in molecule can be enumerated, for example bisphenol-A is (methyl) acrylate compounds, with α, beta-unsaturated carboxylic acid and polyol reaction and the compound that obtains, with α, the compound that beta-unsaturated carboxylic acid obtains with containing glycidyl compound reaction has the ammonia ester monomer or the ammonia ester oligomers such as (methyl) acrylate compounds of ammonia ester bond.In addition, all right illustration Nonylphenoxy polyoxyethylene acrylate, γ-chloro-beta-hydroxy propyl group-β '-(methyl) acryloxy ethyl phthalic ester, beta-hydroxy alkyl-β '-phthalandione based compounds such as (methyl) acryloxyalkyl phthalic ester, (methyl) alkyl acrylate, EO modification nonyl phenyl (methyl) acrylate etc.These compounds can use a kind or be used in combination more than 2 kinds separately.
As bisphenol-A system (methyl) acrylate compounds, for example can enumerate 2,2-two (4-((methyl) acryloxy polyethoxy) phenyl) propane, 2,2-two (4-((methyl) acryloxy gathers propoxyl group) phenyl) propane, 2,2-two (4-((methyl) acryloxy gathers butoxy) phenyl) propane and 2,2-two (4-((methyl) acryloxy polyethoxy gathers propoxyl group) phenyl) propane etc.
As 2,2-two (4-((methyl) acryloxy polyethoxy) phenyl) propane, for example can enumerate 2,2-two (4-((methyl) acryloxy diethoxy) phenyl) propane, 2,2-two (4-((methyl) acryloxy triethoxy) phenyl) propane, 2,2-two (4-((methyl) acryloxy tetraethoxy) phenyl) propane, 2,2-two (4-((methyl) acryloxy five ethoxys) phenyl) propane, 2,2-two (4-((methyl) acryloxy six ethoxys) phenyl) propane, 2,2-two (4-((methyl) acryloxy seven ethoxys) phenyl) propane, 2,2-two (4-((methyl) acryloxy eight ethoxys) phenyl) propane, 2,2-two (4-((methyl) acryloxy nine ethoxys) phenyl) propane, 2,2-two (4-((methyl) acryloxy ten ethoxys) phenyl) propane, 2,2-two (4-((methyl) acryloxy 11 ethoxys) phenyl) propane, 2,2-two (4-((methyl) acryloxy ten diethoxies) phenyl) propane, 2,2-two (4-((methyl) acryloxy ten triethoxies) phenyl) propane, 2,2-two (4-((methyl) acryloxy ten tetraethoxies) phenyl) propane, 2,2-two (4-((methyl) acryloxy 15 ethoxys) phenyl) propane and 2,2-two (4-((methyl) acryloxy 16 ethoxys) phenyl) propane etc.Wherein, 2,2-two (4-(methacryloxy five ethoxys) phenyl) propane can obtain with commodity BPE-500 (manufacturing of Xin Zhong village chemical industry, trade name) form, 2,2-two (4-(methacryloxy 15 ethoxys) phenyl) propane can obtain with commodity BPE-1300 (manufacturing of Xin Zhong village chemical industry, trade name) form.These compounds can use a kind or be used in combination more than 2 kinds separately.
As 2,2-two (4-((methyl) acryloxy gathers propoxyl group) phenyl) propane, for example can enumerate 2,2-two (4-((methyl) acryloxy dipropoxy) phenyl) propane, 2,2-two (4-((methyl) acryloxy tripropoxy) phenyl) propane, 2,2-two (4-((methyl) acryloxy four propoxyl group) phenyl) propane, 2,2-two (4-((methyl) acryloxy five propoxyl group) phenyl) propane, 2,2-two (4-((methyl) acryloxy six propoxyl group) phenyl) propane, 2,2-two (4-((methyl) acryloxy seven propoxyl group) phenyl) propane, 2,2-two (4-((methyl) acryloxy eight propoxyl group) phenyl) propane, 2,2-two (4-((methyl) acryloxy nine propoxyl group) phenyl) propane, 2,2-two (4-((methyl) acryloxy ten propoxyl group) phenyl) propane, 2,2-two (4-((methyl) acryloxy 11 propoxyl group) phenyl) propane, 2,2-two (4-((methyl) acryloxy ten dipropoxies) phenyl) propane, 2,2-two (4-((methyl) acryloxy ten tripropoxies) phenyl) propane, 2,2-two (4-((methyl) acryloxy 14 propoxyl group) phenyl) propane, 2,2-two (4-((methyl) acryloxy 15 propoxyl group) phenyl) propane and 2,2-two (4-((methyl) acryloxy 16 propoxyl group) phenyl) propane etc.These compounds can use a kind or be used in combination more than 2 kinds separately.
As 2,2-two (4-((methyl) acryloxy polyethoxy gathers propoxyl group) phenyl) propane can be enumerated, for example 2,2-two (4-((methyl) acryloxy diethoxy eight propoxyl group) phenyl) propane, 2,2-two (4-((methyl) acryloxy tetraethoxy four propoxyl group) phenyl) propane and 2,2-two (4-((methyl) acryloxy six ethoxys six propoxyl group) phenyl) propane etc.These compounds can use a kind or be used in combination more than 2 kinds separately.
As α, beta-unsaturated carboxylic acid and polyol reaction and the compound that obtains, can enumerate ethylidene number for example and be 2～14 polyglycol two (methyl) acrylate, the propylidene number is 2～14 polypropylene glycol two (methyl) acrylate, the ethylidene number is 2～14, the propylidene number is 2～14 polyglycol polypropylene glycol two (methyl) acrylate, trimethylolpropane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, EO modification trimethylolpropane tris (methyl) acrylate, PO modification trimethylolpropane tris (methyl) acrylate, EOPO modification trimethylolpropane tris (methyl) acrylate, tetramethylol methane three (methyl) acrylate, tetramethylol methane four (methyl) acrylate, dipentaerythritol five (methyl) acrylate and dipentaerythritol six (methyl) acrylate etc.These compounds can use a kind or be used in combination more than 2 kinds separately.
In addition, " EO " is meant " oxirane ", and " PO " is meant " epoxypropane ".And " EO modification " is meant to have ethylene oxide unit (CH
2CH
2O-) block structure, " PO modification " are meant to have propylene oxide units (CH
2CH
2CH
2O-) block structure.
As α, the compound that beta-unsaturated carboxylic acid obtains with containing the glycidyl compound reaction, can enumerate for example trihydroxymethylpropanyltri diglycidyl ether three (methyl) acrylate and 2,2-two (4-(methyl) acryloxy-2-hydroxypropyl oxygen) phenyl etc.As above-mentioned α, beta-unsaturated carboxylic acid can be enumerated (methyl) acrylic acid etc.These compounds can use a kind or be used in combination more than 2 kinds separately.
As ammonia ester monomer or ammonia ester oligomer; can enumerate (methyl) acryl monomer and the isophorone diisocyanate, 2 that for example have the OH base in the β position; 6-toluene diisocyanate, 2; 4-toluene diisocyanate, 1; the addition reaction of diisocyanate cpds such as 6-hexamethylene diisocyanate; three ((methyl) acryloxy tetraethylene glycol isocyanates) hexa-methylene chlorinated isocyanurates; EO modification ammonia ester two (methyl) acrylate; EO or PO modification ammonia ester two (methyl) acrylate contain carboxylated urethane (methyl) acrylate etc.These compounds can use a kind or be used in combination more than 2 kinds separately.
And then, as (methyl) alkyl acrylate, for example can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate and (methyl) acrylic acid-2-ethyl caproite etc.These compounds can use a kind or be used in combination more than 2 kinds separately.
Consider from the resolution of raising photosensitive polymer combination and the flexible angle of cured film, photosensitive polymer combination preferably comprises bisphenol-A system (methyl) acrylate compounds as (C) composition, and wherein more preferably comprising the bisphenol-A with alkylene oxide group is two (methyl) acrylate compounds.
＜(D) composition: Photoepolymerizationinitiater initiater 〉
About concrete example as the Photoepolymerizationinitiater initiater of (D) composition, can enumerate for example benzophenone, 4,4 '-two (dimethylamino) benzophenone (Mi Qile ketone), 4,4 '-two (diethylamino) benzophenone, 4-methoxyl-4 '-dimethylamino benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-1-butanone, the 2-EAQ, aromatic ketones such as phenanthrenequione, quinones such as alkyl-anthraquinone, benzoin methylether, benzoin ethyl ether, benzoin ether such as benzoin phenylate, the methylbenzene acyloin, benzoins such as ethylbenzene acyloin, benzil derivants such as benzil dimethyl ketal, the 9-phenylacridine, 1,7-two (9,9 '-acridinyl) acridine derivatives such as heptane, N-phenylglycine, the N-phenylglycine derivant, coumarin series compounds etc.These compounds can use a kind or be used in combination more than 2 kinds separately.
＜(E) composition: thermal curing agents 〉
About concrete example, for example can enumerate heat-curable compounds such as epoxy resin, phenol resin, carbamide resin, melamine resin etc. as the thermal curing agents of (E) composition.As epoxy resin, can enumerate for example three grades of fatty acid modified polyvalent alcohol epoxy resin of bisphenol A-type, 2-glycidyl ester classes such as phthalandione 2-glycidyl ester, tetrahydro phthalandione 2-glycidyl ester, diglycidyl amines such as diglycidylaniline, diglycidyl toluidine etc.These compounds can use a kind or be used in combination more than 2 kinds separately.
In addition, the thermal curing agents about as (E) composition also can use the block isocyanate compound as the potentiality thermal curing agents.As block isocyanate compound, can enumerate the polyisocyanate compound that for example passes through block agent blockizations such as alcoholic compound, phenolic compounds, 6-caprolactone, oxime compound, activity methene compound.Polyisocyanate compound as blockization, can enumerate 4,4-methyl diphenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, o-xylene diisocyanate, m xylene diisocyanate, 2, aromatic polyisocyanates such as 4-toluene dipolymer, hexamethylene diisocyanate, 4, aliphatic polyisocyantes such as 4-methylene two (cyclohexyl isocyanate), isophorone diisocyanate, ester ring type polyisocyanates such as bicycloheptane triisocyanate.Consider that from stable on heating angle the optimization aromatic polyisocyanates is considered preferred aliphat polyisocyanates or ester ring type polyisocyanates from preventing painted angle.
For photosensitive polymer combination has excellent flame-retardant performance, be benchmark with the solid constituent total amount of photosensitive polymer combination, the content of (A) composition in the photosensitive polymer combination is preferably 35～70 quality %, more preferably 40～65 quality %.When (A) content of composition was less than 35 quality %, the anti-flammability of cured film tended to reduce; During greater than 70 quality %, often be difficult to develop by dilute alkaline aqueous solution.
In addition, in order to obtain excellent flame-retardant performance, be benchmark with the solid constituent total amount of photosensitive polymer combination, the phosphorus content in the photosensitive polymer combination is preferably 1.5～5.0 quality %, more preferably 2.0～4.5 quality %.Phosphorus content is during less than 1.5 quality %, and the anti-flammability of cured film tends to reduce; During greater than 5.0 quality %, the folding resistance of cured film, insulating reliability etc. tend to reduce.
In addition, preferably be in above-mentioned scope and contain (B) composition with phosphorus content.And when using the phosphinates of being represented by above-mentioned general formula (2) as (B) composition, its content is benchmark with the solid constituent total amount of photosensitive polymer combination, is preferably 5～20 quality %.This content is during less than 5 quality %, and the anti-flammability of cured film tends to reduce; During greater than 20 quality %, flexible the tending to of cured film reduced.
In addition, when being used in combination phosphate and phosphinates as (B) composition, be benchmark with the solid constituent total amount of photosensitive polymer combination, the content of this phosphate is preferably 1～20 quality %, more preferably 3～10 quality %.This content is during greater than 20 quality %, and electrocorrosion and exudative (photosensitive polymer combination exudative) tend to variation.
In addition, when being used in combination phenoxy phosphazene compound and phosphinates as (B) composition, be benchmark with the solid constituent total amount of photosensitive polymer combination, the content of this phenoxy phosphazene compound is preferably 1～20 quality %, more preferably 3～15 quality %.This content is during greater than 20 quality %, and electrocorrosion and exudative (photosensitive polymer combination exudative) tend to variation.
Considering from the angle of resolution and anti-flammability, is benchmark with the solid constituent total amount of photosensitive polymer combination, and (C) content of composition is preferably 7～30 quality %, more preferably 10～25 quality %.When (C) content of composition was less than 7 quality %, resolution tended to variation; During greater than 30 quality %, the anti-flammability of cured film tends to reduce.
Considering from the angle of light sensitivity, is benchmark with the solid constituent total amount of photosensitive polymer combination, and (D) content of composition is preferably 0.1～10 quality %, more preferably 0.2～5 quality %.
When photosensitive polymer combination contains (E) composition, considering from the angle of anti-flammability and insulating reliability, is benchmark with the solid constituent total amount of photosensitive polymer combination, and its content is preferably 5～20 quality %, more preferably 8～15 quality %.
In addition, in the photosensitive polymer combination of the present invention, can contain malachite green and other dyes as required, light developers such as leuco crystal violet, the heat colour developing prevents plastifier such as agent or para toluene sulfonamide, inorganic pigments such as organic pigments such as phthalocyanines such as phthalocyanine blue system, azo system or titania, the filling agent that comprises inorganic pigments such as silicon dioxide, aluminium oxide, talcum, lime carbonate or barium sulphate, defoamer, stabilizing agent, adaptation imparting agent, levelling agent, antioxidant, spices or developer (imaging agent) etc.Solid constituent total amount with photosensitive polymer combination is a benchmark, and these compositions preferably contain 0.01～20 quality % scope separately.And mentioned component can use a kind or be used in combination more than 2 kinds separately.
And then, photosensitive polymer combination of the present invention can be dissolved into methyl alcohol, ethanol, acetone, butanone, methyl cellosolve, ethyl cellosolve, toluene, N as required, in dinethylformamide, propylene glycol monomethyl ether equal solvent or their mixed solvent, be that the solution of 30～70 quality % scopes is coated with solid constituent.
Aforesaid photosensitive polymer combination of the present invention; can be used as liquid resist-coating and after on the metal surfaces such as copper, copper series alloy, iron, iron-based alloy, carry out drying; then; the diaphragm that is covered as required uses, and perhaps can use by the form of photosensitive element described later.
In addition, the feature that forms the substrate of the cured film comprise photosensitive polymer combination of the present invention on flexible parent metals such as polyimide is to have excellent flame.Photosensitive polymer combination of the present invention makes the anti-flammability of cured film enough high owing to can not comprising halogen based compound and antimony based compound, thereby for example can reduce the carrying capacity of environment and the toxicity of printed circuit board (PCB).
In addition, photosensitive polymer combination of the present invention is owing to can form the cured film with abundant anti-flammability with high resolving power, and can form and have fully flexible cured film, thereby can be preferred for forming the permanent veil of printed circuit board (PCB), particularly flexible printed circuit board.
(photosensitive element)
Then, the photosensitive element at the photosensitive polymer combination that uses the invention described above describes.Fig. 1 is the schematic cross-section of a preferred embodiment of expression photosensitive element of the present invention.Photosensitive element 1 shown in Figure 1 is made of support 10 and the photosensitive polymer combination layer 14 that is arranged on the support 10.The layer that photosensitive polymer combination layer 14 constitutes for the photosensitive polymer combination by the invention described above.And photosensitive element 1 of the present invention also can be covered with diaphragm and be the face F1 of opposition side with support 10 on the photosensitive polymer combination layer 14.
Photosensitive polymer combination layer 14 is preferably as follows formation: after photosensitive polymer combination of the present invention is dissolved in above-mentioned solvent or the mixed solvent solution that forms solid constituent 30～70 quality % scopes, with such solution coat to support 10 and form.
The thickness of photosensitive polymer combination layer 14 is preferably 10～100 μ m but blow down the dried thickness that desolvates by heating and/or hot blast, more preferably 20～60 μ m according to purposes and difference.This thickness is during less than 10 μ m, industrially often is difficult to coating; During greater than 100 μ m, the above-mentioned effect that the present invention rose diminishes easily, and particularly flexible and resolution tends to reduce.
As the support 10 that photosensitive element 1 has, for example can enumerating, polyethylene terephthalate, polypropylene, tygon, polyester etc. have polymer film of thermotolerance and solvent resistance etc.
Support 10 thickness be preferably 5～100 μ m, 10～30 μ m more preferably.This thickness is during less than 5 μ m, and this support often breaks easily when peeling off support before development; During greater than 100 μ m, resolution and flexible tending to are reduced.
Aforesaidly comprise support 10 and photosensitive polymer combination layer 14 this photosensitive element of two layers 11 or comprise that this photosensitive element of three layers 1 of support 10, photosensitive polymer combination layer 14 and diaphragm for example can directly store, and perhaps can be clipped between the diaphragm and with the roller shape and be wound in spool and keeping.
Use the formation method of the resist pattern of photosensitive element of the present invention to comprise: the removal operation of removing diaphragm as required from above-mentioned photosensitive element; The sequential laminating of this photosensitive element according to photosensitive polymer combination layer, support formed with the lamination operation on the substrate at circuit; Make active ray pass through the established part that support shines the photosensitive polymer combination layer as required, make the photosensitive polymer combination layer form the exposure process of photocuring portion; Remove the developing procedure of photocuring portion photosensitive polymer combination layer in addition.In addition, circuit forms the substrate that is meant the conductor layer (comprising iron-based alloys such as copper, copper series alloy, nickel, chromium, iron, stainless steel, preferably copper, copper series alloy, iron-based alloy) that has insulation course and form with substrate on insulation course.
Remove the lamination method in the lamination operation after the removal operation of diaphragm as required, can enumerate and photosensitive polymer combination layer limit heating edge is crimped on circuit forms with the method for carrying out lamination on the substrate etc.Atmosphere gas during this lamination is not particularly limited, and considers from adaptation and tracing ability equal angles, preferably under reduced pressure carries out lamination.The surface of lamination is generally the face that circuit forms the conductor layer of using substrate, but also can be the face beyond this conductor layer.
The heating-up temperature of photosensitive polymer combination layer is preferably 70～130 ℃, and crimping pressure is preferably 0.1～1.0MPa scope, and more preferably Zhou Wei air pressure is below the 4000Pa, but these conditions are not particularly limited.In addition, if heat the photosensitive polymer combination layers at 70～130 ℃ as mentioned above, then do not need in advance circuit to be formed to carry out thermal pretreatment, but, can carry out the thermal pretreatment of circuit formation yet with substrate in order further to improve lamination with substrate.
After lamination finishes like this, in exposure process, to the established part irradiation active ray of photosensitive polymer combination layer and form photocuring portion.As the formation method of photocuring portion, can enumerate minus by being called former figure or eurymeric mask pattern method with image shape irradiation active ray.At this moment, under the support that exists on the photosensitive polymer combination layer is transparent situation, can the direct irradiation active ray; Under the opaque situation, after removing support, the photosensitive polymer combination layer is shone active ray.
About the light source of active ray, for example carbon arc lamp, mercury vapour arc lamp, ultrahigh pressure mercury lamp, high-pressure sodium lamp, xenon lamp etc. effectively radiate ultraviolet light source can to use known light source.And, can also use the effectively light source of radiation visible light such as photoflood lamp, daylight lamp.
Then, the exposure back exists on the photosensitive polymer combination layer under the situation of support, remove behind the support at developing procedure and utilize wet development, dry process development etc. to remove the photosensitive polymer combination layer beyond the photocuring portion and develop, form the resist pattern.
Under the situation of wet development, use developer solutions such as alkaline aqueous solution, by for example spray, shake dipping, scrub, known method such as scouring develops.Can adopt safety and stable, the good material of operability about developer solution, for example can adopt the lean solution (1～5 quality % aqueous solution) of 20～50 ℃ sodium carbonate etc.
Form under the situation of resist pattern that method obtains by above-mentioned as for example scolder resist of printed circuit board (PCB), after above-mentioned developing procedure finishes, for the scolding tin thermotolerance that improves the scolder resist, reagent resistance etc., preferably utilize high-pressure sodium lamp to carry out the ultraviolet ray irradiation or utilize baking oven to heat.
Under the situation of irradiation ultraviolet radiation, can adjust its exposure as required, for example also can be according to 0.2～10J/cm
2The exposure of scope is shone.And, under the situation about heating, preferably carried out 15～90 minutes 100～170 ℃ of scopes.And then, can implement ultraviolet ray irradiation and heating simultaneously, also can implement to implement another again after any one.
In addition, form the resist pattern that method obtains and be preferably used as the permanent veil that is formed on the printed circuit board (PCB) by above-mentioned.The cured film that is formed by photosensitive polymer combination of the present invention is owing to have excellent flame, therefore, and can be effectively as permanent veil to the printed circuit board (PCB) of double as distribution diaphragm after the substrate enforcement solder.
Embodiment
Be described more specifically the present invention based on embodiment and comparative example below, but the present invention is not limited to the following examples.
(embodiment 1～7, comparative example 1～4)
At first, according to each composition in match ratio (quality criteria) (but butanone is the quality criteria as the liquid) mixture table 1 of the solid constituent shown in the table 1, obtain the solution of photosensitive polymer combination.
In addition, (A-1) composition is biphenyl type epoxy acrylate (Japanese chemical drug corporate system is made, trade name " ZCR-1569H ", phenolic varnish type acid modification with biphenyl backbone contain vinyl epoxy resin, acid number=98, Mw=4500) in the table 1, (A-2) composition is bisphenol-a epoxy acrylate (Japanese chemical drug corporate system is made, trade name " ZAR-2001H ", acid number=103, Mw=13000), and (A-3) composition is Bisphenol F type epoxy acrylate (Japanese chemical drug corporate system is made, trade name " ZFR-1516 ", acid number=73, Mw=11000).
(B-1) composition is phosphinates (manufacturing of Clariant company, trade name " EXOLIT OP 935 ", a phosphorus content=23 quality %), (B-2) composition is phosphate (manufacturing of ADEKA company, trade name " A Dekasita goes on foot (ア デ カ ス Block) FP-600 ", a phosphorus content=8.9 quality %), and (B-3) composition is phenoxy phosphazene compound (manufacturing of big mound chemistry, trade name " SPB-100 ", a phosphorus content=13 quality %).
(C) composition is bisphenol A polyethenoxy dimethylacrylate (manufacturing of Xin Zhong village chemical industrial company, a trade name " BPE-10 ").
(D) composition is 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-1-butanone (manufacturing of CibaSpecialty Chemicals company, a trade name " I-369 ").
(E) composition is with the 75 quality % butanone solutions (firmly change Baeyer polyurethane company manufacturing, trade name " BL3175 ") of hexamethylene diisocyanate as the diacetylmonoxime block thing of the chlorinated isocyanurates of basic isocyanates.
In addition, in the table acryl resin for be copolymer composition with methacrylic acid/ethyl acrylate/methyl methacrylate/styrene, in toluene/methyl cellosolve (mass ratio=2/3) solution by the common method polymerization, acid number is that 80mgKOH/g, weight-average molecular weight are 100,000 multipolymer.
Table 1
Annotate: the value in the table 1 is the match ratio (except the butanone) of the solid constituent of each composition.And symbol "-" expression in the table does not contain this composition.
[making of photosensitive element]
The photosensitive polymer combination solution of embodiment 1～7 and comparative example 1～4 is uniformly coated on respectively as on the thick polyethylene terephthalate film of 16 μ m of support (manufacturing of Supreme Being people company, trade name " G2-16 "), form the photosensitive polymer combination layer, use hot air convection formula dryer to it 100 ℃ of dryings 10 minutes.The dried thickness of photosensitive polymer combination layer is 38 μ m.
Then, be sticking polyethylene film on the surface of opposition side (TAMAPOLY company makes, trade name " NF-13 ") in the side with contacting support of photosensitive polymer combination layer and, obtain photosensitive element as diaphragm.
[estimating making] with laminate
After with hydrochloric acid the flexible printed circuit board that forms at the thick Copper Foil of 18 μ m of lamination on the polyimide base material being carried out acid elution, washing with the copper surface of substrate (NIKKAN industrial group makes, trade name " F30VC1 "), carry out drying.
To above-mentioned flexible printed circuit board substrate, use continuous vacuum laminating machine (Hitachi changes into industrial group's manufacturing, trade name " HLM-V570 "), in 100 ℃ of temperature of shoe type well heater (ヒ one ト シ ユ one), laminate speed 0.5m/ minute, below the air pressure 4000Pa, under the condition of crimping pressure 0.3MPa, polyethylene film is peeled off to the photosensitive element that obtains in the limit, the limit obtains estimating and uses laminate at Copper Foil side lamination photosensitive polymer combination layer.
[evaluation of light sensitivity]
The above-mentioned evaluation that obtains with laminate on, driving fit has the minus exposure apparatus (photo tool) of Stouffer 21 rank exposure guide rules, and the residual lattice number after the HMW-201GX type exposure machine that uses OAK to make manufacturing develops with Stouffer21 rank exposure guide rule is that 8.0 energy exposes.
Then, left standstill 1 hour, peel off behind the PET film 30 ℃ 1 quality % aqueous sodium carbonate and developing in 40 seconds of spraying, 80 ℃ of heating (drying) 10 minutes at normal temperature.Above-mentioned energy when adopting exposure is as the numerical value of estimating light sensitivity.This numerical value is low more, shows that light sensitivity is high more.Its result is illustrated in the table 2.
[evaluation of resolution]
On estimating with laminate, driving fit has the exposure apparatus of Stouffer 21 rank exposure guide rules and has live width/spacing and is 30/30～200/200 (unit: the resolution evaluation of Wiring pattern μ m) is with the minus apparatus that exposes, and using residual lattice number after above-mentioned exposure machine develops with Stouffer 21 rank exposure guide rules is that 8.0 energy exposes.
Then, left standstill 1 hour, peel off behind the PET film 30 ℃ 1 quality % aqueous sodium carbonate and developing in 40 seconds of spraying, 80 ℃ of heating (drying) 10 minutes at normal temperature.At this, resolution is by the minimum value (unit: μ m) estimate of rectangle resist shape by the spacing between the resulting live width of development treatment.This value is more little, shows that resolution is excellent more.The result is illustrated in the table 2.
[estimating making] with FPC
The overlayer reliability evaluation that driving fit has the exposure apparatus of Stouffer 21 rank exposure guide rules and has a Wiring pattern on estimating with laminate is with the minus apparatus that exposes, and the residual lattice number after using above-mentioned exposure machine with Stouffer 21 rank exposure guide rules developments is that 8.0 energy exposes.
Then, peel off the polyethylene terephthalate on the laminate after normal temperature leaves standstill 1 hour, same developer solution and development conditions carried out spray development when estimating with light sensitivity, 80 ℃ of heating (drying) 10 minutes.Then, use OAK to make the ultraviolet lamp of manufacturing with 1J/cm
2Energy carry out ultraviolet ray irradiation, and then 160 ℃ of heat treated 60 minutes, thereby obtain being formed with tectal evaluation FPC.
[evaluation of flexible (folding resistance)]
By the lock seam machine, the evaluation that obtains is as mentioned above carried out 180 ° of bendings repeatedly with FPC, the overlayer of obtaining this moment is estimated according to following benchmark until the bending number of times that cracks.Here, confirm to have flawless to produce by microscope.Its result is illustrated in the table 2.
A: the situation of crackle is not found in bending yet at overlayer more than 5 times,
B: until the bending number of times that cracks is 3～4 times situation,
C: until the bending number of times that cracks is situation below 2 times.
[exudative evaluation]
Use 30t hand press (the smart mechanism of Japan is done institute's (strain) and made), utilize the condition of 160 ℃ of pressing machine temperature, press pressure 20kgf, the evaluation that obtains was as mentioned above pushed 30 minutes with FPC at thickness direction.Have or not the photosensitive polymer combination composition to ooze out at this moment by visualization, estimate according to following benchmark from overlayer.Promptly, do not have to find that the average evaluation that oozes out the photosensitive polymer combination composition from overlayer is " A ", some photosensitive polymer combination compositions are oozed out in discovery from overlayer average evaluation is " B ", and the significant average evaluation that oozes out of photosensitive polymer combination composition is " C ".Its result is illustrated in the table 2.
[evaluation of anti-flammability]
Remove the Copper Foil of copper-surfaced laminated board (manufacturing of chemical company of Nippon Steel, trade name " ESPANEX MB " series) by etching, obtain the PI film of thickness 25 μ m.Then, use continuous vacuum laminating machine (Hitachi changes into industrial group's manufacturing, trade name " HLM-V570 "), in 100 ℃ of shoe type heter temperatures, laminate speed 0.5m/ minute, below the air pressure 4000Pa, under the condition of crimping pressure 0.3MPa, the limit to above-mentioned photosensitive element peel off the polyethylene film limit to the two sides of above-mentioned PI film at PI film side lamination photosensitive polymer combination layer, obtain laminate.
Then, use OAK to make the HNW-201GX type exposure machine of manufacturing, to be 8.0 above-mentioned energy expose to the photosensitive polymer combination layer of above-mentioned photosensitive element the residual lattice number after developing with Stouffer 21 rank exposure guide rules.Then, left standstill 1 hour at normal temperature, peel off the polyethylene terephthalate film from laminate after, to laminate 30 ℃ the 1 quality % aqueous sodium carbonate and developing in 40 seconds of spraying, 80 ℃ of heating (drying) 10 minutes.
Then, to the photosensitive polymer combination layer of laminate, use the ultraviolet lamp of Oak making manufacturing, with 1J/cm
2Energy carry out ultraviolet ray irradiation, and then 160 ℃ of heat treated 60 minutes, thereby obtain being formed with tectal anti-flammability evaluation sample.
At this anti-flammability evaluation sample, carry out the thin material testing vertical flammability based on the UL94 standard.Evaluation is expressed as VTM-0, VTM-1 or VTM-2 based on the UL94 standard.The result is illustrated in the table 2.In addition, " NOT " is illustrated in anti-flammability evaluation sample perfect combustion in the burning test in the table 2, do not meet VTM-0, VTM-1 and VTM-2.
Table 2
From the result shown in the table 2 as can be known, according to the photosensitive polymer combination of embodiment 1～7, can confirm to obtain sufficient light sensitivity and resolution.And the laminated board with cured film that the photosensitive polymer combination by embodiment 1～7 forms is identified has sufficient anti-flammability.And then the cured film that is formed by the photosensitive polymer combination of embodiment 2,3 and 5～7 is identified has excellent flexible (folding resistance).
As mentioned above, can provide, can form the photosensitive polymer combination of the cured film of excellent in flame retardance when having excellent alkali-developable according to the present invention, and the photosensitive element that uses said composition.
Claims (8)
1. photosensitive polymer combination contains phenolic varnish type acid modification that (A) have biphenyl backbone and contains vinyl epoxy resin, (B) phosphorus-containing compound, (C) have the optical polymerism compound of at least one alkene class unsaturated group and (D) Photoepolymerizationinitiater initiater in molecule.
2. photosensitive polymer combination according to claim 1, described (A) epoxy resin comprises that the sour modification as following resultant of reaction contains vinyl epoxy resin, to be (a) contain the monocarboxylic acid of unsaturated group and (c) resultant of reaction of polybasic acid anhydride by epoxy resin, (b) of following general formula (1) expression to this resultant of reaction
In the formula (1), R
1And R
2Represent the alkyl or the aryl of hydrogen atom, carbon number 1～8 independently of one another, n represents 0～50 integer, and, a plurality of R that exist in the formula (1)
1And R
2Can be mutually the same, also can be different.
3. photosensitive polymer combination according to claim 1 and 2 further contains (E) thermal curing agents.
4. according to any described photosensitive polymer combination in the claim 1～3, described (B) phosphorus-containing compound comprises the phosphinates by following general formula (2) expression;
In the formula (2), A and B represent the alkyl or the aryl of the carbon number 1～6 of a straight chain shape or a chain independently of one another, M represents to be selected from least a metal in the group that is made of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na and K, and m represents 1～4 integer.
5. according to any described photosensitive polymer combination in the claim 1～4, described (B) phosphorus-containing compound comprises phosphate.
6. according to any described photosensitive polymer combination in the claim 1～5, described (B) phosphorus-containing compound comprises phenoxy phosphazene compound.
7. according to any described photosensitive polymer combination in the claim 1～6, it is the composition that is used for forming on flexible base, board as the cured film of permanent veil.
8. photosensitive element, the photosensitive polymer combination layer that comprises any described photosensitive polymer combination in the claim 1～7 that has support and on this support, form.
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| JP288720/2006 | 2006-10-24 | ||
| JP2006288720 | 2006-10-24 | ||
| JP082003/2007 | 2007-03-27 |
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| CNA2007800395894A Pending CN101529333A (en) | 2006-10-24 | 2007-10-17 | Photosensitive resin composition and photosensitive element using the same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102207681A (en) * | 2010-03-29 | 2011-10-05 | 新日铁化学株式会社 | Alkali-developable photosensitive resin composition, and partition suitable for display element and display element formed by employing same |
| CN102608867A (en) * | 2012-03-27 | 2012-07-25 | 惠州联大电子材料有限公司 | Photosensitive water developing corrosion-resistant composition and photosensitive water developing corrosion-resistant dry film |
| CN110083010A (en) * | 2011-08-10 | 2019-08-02 | 日立化成株式会社 | The manufacturing method of photosensitive polymer combination, photosensitive film, permanent resist and permanent resist |
| CN111919144A (en) * | 2018-03-27 | 2020-11-10 | 日立化成株式会社 | Wavelength conversion member, backlight unit, and image display device |
-
2007
- 2007-10-17 CN CNA2007800395894A patent/CN101529333A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102207681A (en) * | 2010-03-29 | 2011-10-05 | 新日铁化学株式会社 | Alkali-developable photosensitive resin composition, and partition suitable for display element and display element formed by employing same |
| CN102207681B (en) * | 2010-03-29 | 2015-10-14 | 新日铁住金化学株式会社 | Alkali-developable photosensitive resin composition and the partition of applicable display element using it and formed and display element |
| CN110083010A (en) * | 2011-08-10 | 2019-08-02 | 日立化成株式会社 | The manufacturing method of photosensitive polymer combination, photosensitive film, permanent resist and permanent resist |
| CN102608867A (en) * | 2012-03-27 | 2012-07-25 | 惠州联大电子材料有限公司 | Photosensitive water developing corrosion-resistant composition and photosensitive water developing corrosion-resistant dry film |
| CN102608867B (en) * | 2012-03-27 | 2014-04-02 | 惠州联大电子材料有限公司 | Photosensitive water developing corrosion-resistant composition and photosensitive water developing corrosion-resistant dry film |
| CN111919144A (en) * | 2018-03-27 | 2020-11-10 | 日立化成株式会社 | Wavelength conversion member, backlight unit, and image display device |
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Application publication date: 20090909 |