CN103257526A - UV curing transparent resin composition - Google Patents
UV curing transparent resin composition Download PDFInfo
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- CN103257526A CN103257526A CN2013100523245A CN201310052324A CN103257526A CN 103257526 A CN103257526 A CN 103257526A CN 2013100523245 A CN2013100523245 A CN 2013100523245A CN 201310052324 A CN201310052324 A CN 201310052324A CN 103257526 A CN103257526 A CN 103257526A
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Abstract
The invention aims to provide a UV curing transparent resin composition which can form undamaged condensate with various characteristics of folding resistance, distinguishability, and excellent transparency and flammability. The technical scheme of the present invention is the UV curing transparent resin composition which is characterized by comprising carboxyl-containing acrylic acid series resin (A), photo polymerization initiator (B), a thinner (C) and an epoxy resin (D). The carboxyl-containing acrylic acid series resin (A) is obtained according to the following processes that a part of carboxyl groups of copolymer obtained by reacting the (meth) acrylic acid and (meth) acrylate are added into compound having an ethylene oxide adduct ring and an ethylenic unsaturated bond, and then one part of the ethylenic unsaturated bond is added into a phosphorus compound having at least one aromatic ring.
Description
Technical field
The present invention relates to for example to be applicable to the ultra-violet solidified transparent resin composition of the anti-flammability of lining material, particularly be applicable to the ultra-violet solidified transparent resin composition for the anti-flammability of the lining material that is overlayed on the conductor circuit pattern that forms on the wiring substrate such as flexible wiring sheet.
Background technology
In the prior art, exist and use hardening resin composition as for example situation of the solder resist film of flexible wiring sheet.The mounting substrate that flexible wiring sheet waits as light-emitting diode (LED) sometimes at this moment, for the solder resist film that forms at installed surface, requires to make the function from the reflection of light rate raising of light source.And known reflectivity for the cured film that improves hardening resin composition cooperates inorganic Chinese whites such as titanium dioxide.
On the other hand, the solder resist film for forming at installed surface based on the purposes of flexible wiring sheet, not only requires bending property of folding mechanical properties such as (flexibilities) sometimes, also requires the transparency.In addition, for the touch panel of the front that is assembled in displays such as LCD electrode base board, because strong not hope reduces its visuality yet, require the material of the high electrode protective membrane of the transparency.Therefore, in patent documentation 1, proposed to provide have high transparent, reactive epoxy radicals carbonate and reactive polycarboxylate compound few and good solidfied material aspect the balance of obdurability, thermotolerance, moisture-proof to the light deterioration.
But the reactive epoxy radicals carbonate of patent documentation 1 and reactive polycarboxylate compound exist discoloration-resistant and transparent inadequate problem.
On the other hand, wiring substrate not only requires the transparency good in order to carry on electronic equipment, also requires anti-flammability.But when existing to fire retardants such as hardening resin composition interpolation phosphorus compounds, the impaired problem of property (flexibility) is bent in the transparency of the cured coating film of this hardening resin composition and folding.
The prior art document
Patent documentation
[patent documentation 1] WO2006/109572
Summary of the invention
Goal of the invention
In view of the foregoing, the purpose of this invention is to provide a kind of ultra-violet solidified transparent resin composition, it can form the transparency and the good solidfied material of anti-flammability under the situation of various characteristicses such as the curved property of harmless folding, resolution.And then, the purpose of this invention is to provide a kind of wiring substrate, it comprises the dielectric film with the curved property of folding, resolution, the transparency and anti-flammability by using described ultra-violet solidified transparent resin composition to obtain.
The means of dealing with problems
The solution of the present invention is a kind of ultra-violet solidified transparent resin composition, it is characterized in that: contain (A) carboxylic (methyl) acrylic resin, (B) Photoepolymerizationinitiater initiater, (C) thinning agent and (D) epoxy resin, described (A) carboxylic (methyl) acrylic resin obtains according to following process, after a part of addition to the carboxyl that makes the multipolymer that (methyl) acrylic acid and (methyl) acrylate reactions obtain has the compound of oxirane ring and ethene unsaturated link, and then, a part of addition of described ethene unsaturated link is contained the phosphorus compound of at least 1 aromatic rings.
In this scheme, for (A) carboxylic (methyl) acrylic resin, include the structural unit that comprises at least 1 aromatic rings and at least 1 P elements in the part of its side chain.This structural unit that comprises at least 1 aromatic rings and at least 1 P elements is given ultra-violet solidified transparent resin composition anti-flammability.Should illustrate that as long as mismatch the colorant (for example, Chinese white) that the transparency is lost, the present invention is exactly transparent resin combination, therefore, its solidfied material has the transparency.
The solution of the present invention is a kind of ultra-violet solidified transparent resin composition, it is characterized in that: the described phosphorus compound that contains at least 1 aromatic rings is general formula (i) or general formula compound (ii),
(in the formula, Z represents substituting group, and l is 0～5 integer, and m is 0～4 integer.)
The solution of the present invention is a kind of ultra-violet solidified transparent resin composition, it is characterized in that: described (A) carboxylic (methyl) acryl resin contains the P elements of 0.5～10 quality % in solid constituent.Described P elements is from the described phosphorus compound that contains at least 1 aromatic rings.
The solution of the present invention is a kind of ultra-violet solidified transparent resin composition, it is characterized in that: the acid number of the solid constituent of described (A) carboxylic (methyl) acryl resin is 30～140mgKOH/g.
The solution of the present invention is a kind of ultra-violet solidified transparent resin composition, it is characterized in that: two key equivalents of described (A) carboxylic (methyl) acryl resin are 400～2500g/mol.
The solution of the present invention is a kind of ultra-violet solidified transparent resin composition, it is characterized in that: also contain (E) (methyl) propylene acidifying epoxy resin.
The solution of the present invention is a kind of ultra-violet solidified transparent resin composition, it is characterized in that: also contain (F) (methyl) propylene acidifying urethane resin.
The solution of the present invention is a kind of wiring substrate, it is characterized in that: have the dielectric film that described ultra-violet solidified transparent resin composition is solidified and obtain.
The invention effect
In the solution of the present invention, (A) carboxylic (methyl) acryl resin is because have the structural unit that comprises at least one aromatic rings and at least one P elements at its a part of side chain, so carboxylic (methyl) acryl resin has good anti-flammability, and, harmless resolution.In addition, in the solution of the present invention, because need not add fire retardant in addition in order to give ultra-violet solidified transparent resin composition anti-flammability, so can prevent the rising of mist degree of solidfied material and the reduction of the curved property of folding, consequently, can under the situation of the curved property of harmless folding, obtain the good transparency.That is, contain mechanical property or the resolution such as the curved property of the harmless folding of solidfied material of the ultra-violet solidified transparent resin composition of carboxylic (methyl) acryl resin, have good anti-flammability and the transparency.
Embodiment
Then, ultra-violet solidified transparent resin composition of the present invention is described.Ultra-violet solidified transparent resin composition of the present invention is characterised in that, contain (A) carboxylic (methyl) acrylic resin, (B) Photoepolymerizationinitiater initiater, (C) thinning agent and (D) epoxy resin, described (A) carboxylic (methyl) acrylic resin obtains according to following process, after a part of addition to the carboxyl that makes the multipolymer that (methyl) acrylic acid and (methyl) acrylate reactions obtain has the compound of oxirane ring and ethene unsaturated link. and then, a part of addition of described ethene unsaturated link is contained the phosphorus compound of at least 1 aromatic rings.
(A)
Carboxylic (methyl) acrylic resin
Carboxylic (methyl) acrylic resin obtains according to following process, to making (a-1) (methyl) acrylic acid and (a-2) after a part of addition (a-3) of the carboxyl of the multipolymer that obtains of (methyl) acrylate reactions has the compound of oxirane ring and ethene unsaturated link, and then, a part of addition (a-4) of described ethene unsaturated link is contained the phosphorus compound of at least 1 aromatic rings.
Carboxylic (methyl) acrylic resin is because of contain the structural unit with at least one aromatic rings and at least one P elements that contains the phosphorus compound of at least 1 aromatic rings from (a-4) at side chain, even so do not cooperate fire retardant in addition, described carboxylic (methyl) acrylic resin also has anti-flammability.Consequently, ultra-violet solidified transparent resin composition of the present invention has anti-flammability and the transparency.
(a-1) (methyl) acrylic acid refers to any of acrylic acid and methacrylic acid.
(a-2) (methyl) acrylate is not particularly limited, for example can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) Hydroxyethyl Acrylate, (methyl) butyl acrylate, (methyl) acrylic acid hydroxyl butyl ester, (methyl) propyl acrylate. (methyl) acrylic acid hydroxy propyl ester, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate alcohol ester, (methyl) alkyl acrylates such as (methyl) cyclohexyl acrylate and (methyl) isobornyl acrylate, (methyl) acrylic acid phenoxy ethyl, aromatic series (methyl) acrylate such as (methyl) acrylic acid phenoxy group propyl ester, (methyl) acrylic acid dimethylamino ethyl ester, (methyl) propenoic acid dialkyl aminoalkyl esters such as (methyl) acrylic acid diethylamino ethyl ester, N-acryloxy ethyl hexahydrophthalic phthalimide etc.Wherein, from giving the viewpoint of the curved property of the good folding of ultra-violet solidified transparent resin composition, preferred (methyl) alkyl acrylate, (methyl) acrylic acid phenoxy ethyl.The independent use of these compounds is also passable, mixes to use more than 2 kinds also can.
Make (a-1) (methyl) acrylic acid and (a-2) in the multipolymer that (methyl) acrylate reactions obtains, be not particularly limited for the acrylic acid content of (a-1) (methyl) (input amount), but, from giving the viewpoint of the curved property of the good folding of ultra-violet solidified transparent resin composition, preferred 20～70 quality %, preferred especially 30～60 quality %.
The compound that has oxirane ring and ethene unsaturated link for (a-3) is not particularly limited, but, from reactive viewpoint, that preferably selects from comprise following general formula (iiia), (iiib) and compound group (iiic) is at least a.
(in the formula, R
1, R
3, R
4, R
7And R
8Represent hydrogen atom or methyl, R respectively independently
2, R
5, R
6And R
9Represent independently that respectively carbon number is 1～20 alkylidene.R
2, R
6And R
9Methylene preferably, R
5Preferably carbon number is 2～10 alkylidene, preferred especially butylidene.)
Though the content (input amount) for the compound with oxirane ring and ethene unsaturated link is not particularly limited, but from improving photosensitive viewpoint, its lower limit preferably, in carboxylic (methyl) acrylic resin, be 10 quality %, particularly preferably be 20 quality %.On the other hand, for its higher limit, preventing from adhering to the viewpoint on the film during from sensitization, preferably, in carboxylic (methyl) acrylic resin, is 50 quality %, particularly preferably is 40%.
As long as contain at least 1 aromatic rings and contain at least 1 P elements though (a-4) contain the phosphorus compound of at least 1 aromatic rings, be not particularly limited, but, carboxylic based on giving (methyl) acrylic resin is given anti-flammability and prevent that reliably the ultra-violet solidified transparent resin composition of brushing from adhering to the viewpoint on the film when exposure, the described phosphorus compound that preferably has a plurality of aromatic rings particularly preferably is the described phosphorus compound with 2 aromatic rings.As described phosphorus compound, for example, the phosphorus compound of (ii) being represented by following general formula (i), general formula preferably.
(in the formula, Z represents substituting group, and l is 0～5 integer, and m is 0～4 integer.)
As substituent Z, be not particularly limited, preferably the group of from alkyl, alkoxy, phenyl, halogen atom, selecting.Z exists under a plurality of situations, and they each other can be identical, also can be different.With the quantity of Z and kind irrespectively, described phosphorus compound with at least one aromatic rings adds to the side chain of carboxylic (methyl) acrylic resin, thereby can give carboxylic (methyl) acrylic resin anti-flammability, and can prevent from exposing that the ultra-violet solidified transparent resin composition of time brushing adheres on the film.
For the phosphorus compound that contains at least 1 aromatic rings, for example can enumerate 9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide (m=0 that is equivalent to general formula (i)), and diphenyl phosphine oxide (being equivalent to general formula l=0 (ii)) etc. has the phosphine oxide based compound of reactive hydrogen etc.Their independent uses are also passable, mix to use more than 2 kinds also can.
Though the content (input amount) for the phosphide that contains at least 1 aromatic rings is not particularly limited, but, for its lower limit, from giving the viewpoint of ultra-violet solidified transparent resin composition anti-flammability, in carboxylic (methyl) acrylic resin, 10 quality % preferably, from the viewpoint of further raising anti-flammability, 20 quality % are particularly preferred.On the other hand, for its higher limit, the viewpoint that reduces from the solidfied material physical strength that suppresses ultra-violet solidified transparent resin composition, in carboxylic (methyl) acrylic resin, 40 quality % preferably, from deliquescent viewpoint, 30 quality % are particularly preferred.
For the P elements containing ratio in the solid constituent of carboxylic (methyl) acrylic resin, select according to the service condition of ultra-violet solidified transparent resin composition.For example, for its lower limit, from giving the viewpoint of carboxylic (methyl) acrylic resin anti-flammability reliably, be 0.5 quality %, from guaranteeing that ultra-violet solidified transparent resin composition has the preferred 1.0 quality % of viewpoint of sufficient anti-flammability, from making ultra-violet solidified transparent resin composition positively satisfy the viewpoint of VTM-0 of the UL specification of anti-flammability, 2.0 quality % are particularly preferred.And, for its higher limit, for example, the viewpoint that reduces from the physical strength of the solidfied material that suppresses ultra-violet solidified transparent resin composition, be 10 quality %, from suppressing the viewpoint that physical strength reduces reliably, 5.0 quality % are preferred, from the viewpoint of the intermiscibility ultra-violet solidified transparent resin composition, 4.0 quality % are particularly preferred.
For the acid number of the solid constituent of carboxylic (methyl) acrylic resin, from finishing the viewpoint with the reaction of epoxy resin, 30～140mgKOH/g is preferred, and 60～130mgKOH/g is particularly preferred.For two key equivalents of carboxylic (methyl) acrylic resin, from ultra-violet solidified and viewpoint flexibility, 400～2500g/mol is preferred, and 500～1600g/mol is particularly preferred.
For the number-average molecular weight of carboxylic (methyl) acrylic resin, from the viewpoint of viscosity and brushability, 2000～50000th, preferred, 5000～20000th, particularly preferred.And, for weight-average molecular weight, 5000～100000th, preferred, 14000～50000th, particularly preferred.
(B) Photoepolymerizationinitiater initiater
Photoepolymerizationinitiater initiater is so long as normally used getting final product, be not particularly limited, can enumerate, for example, the oxime series initiators, benzoin, benzoin methyl ether, the benzoin ethylether, the benzoin isopropyl ether, benzoin-n-butyl ether, the benzoin isobutyl ether, acetophenone, the dimethylamino benzoylformaldoxime, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, the 1-hydroxy cyclohexyl phenylketone, 2-methyl isophthalic acid-[4-(methyl sulfenyl) phenyl]-2-morpholinyl-propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-2-(hydroxyl-2-propyl group) ketone, benzophenone, to phenyl benzophenone, 4,4 '-the diethylamino benzophenone, dichloro benzophenone, 2-methylanthraquinone, the 2-EAQ, 2-tert-butyl group anthraquinone, the 2-amino anthraquinones, 2-methyl thioxanthones, 2-ethyl thioxanthones, the 2-clopenthixal ketone, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, the benzil dimethyl ketal, the acetophenone dimethyl ketal, ESCAROL 507 ethyl ester etc.They can use separately, also can mix more than 2 kinds and use.
When ultra-violet solidified transparent resin composition of the present invention was shone in the ultraviolet ray of wavelength 300～400nm, described Photoepolymerizationinitiater initiater promoted the photocuring of ultra-violet solidified transparent resin composition.The use level of Photoepolymerizationinitiater initiater can suitably be selected, and for example, with respect to 100 mass parts carboxylic (methyl) acrylic resin, preferably 5～20 mass parts particularly preferably are 6～15 mass parts.
(C) thinning agent
Thinning agent for example is photopolymerization monomer, is the compound that per 1 molecule has the two keys of at least 2 above polymerisms.Be used for making the photocuring of carboxylic (methyl) acrylic resin of (A) composition fully to carry out, and obtain having acid resistance, the cured coating film of thermotolerance, alkali resistance etc.
Thinning agent so long as described compound get final product, be not particularly limited, for example, can enumerate 1,4-butylene glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, diglycol two (methyl) acrylate, NPGA neopentyl glycol adipate two (methyl) acrylate, hydroxy new pentane acid neopentyl glycol two (methyl) acrylate, two cyclopentyl two (methyl) acrylate, caprolactone modification dicyclopentenyl two (methyl) acrylate, oxirane modified phosphate two (methyl) acrylate, allylation cyclohexyl two (methyl) acrylate, isocyanuric acid ester two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, dipentaerythritol three (methyl) acrylate, dipentaerythritol three (methyl) acrylate, pentaerythrite three (methyl) acrylate, epoxy pronane modification trimethylolpropane tris (methyl) acrylate, three (acryloxy ethyl) isocyanuric acid ester, propionic acid modification dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate etc.They can use separately, also can mix more than 2 kinds and use.
The use level of thinning agent can suitably be selected according to service condition, for example, with respect to 100 mass parts carboxylic (methyl) acrylic resin, is 2～100 mass parts, preferably 10～90 mass parts.
(D) epoxy resin
Epoxy resin is used for improving the cross-linking density of solidfied material.As the epoxy resin of (D) composition, different with (methyl) propylene acidifying epoxy resin of (E) described later composition, refer to not by the epoxy resin of (methyl) propylene acidifying.As epoxy resin, can enumerate, bisphenol A type epoxy resin for example, bisphenol-A epoxy resin, novolac-type epoxy resin (phenol novolac-type epoxy resin, orthoresol novolac-type epoxy resin, p-t-butyl phenol novolac-type etc.), Bisphenol F type or bisphenol-s epoxy resin that the reaction of chloropropylene oxide and Bisphenol F or bisphenol S is obtained, and has a 7-oxa-bicyclo[4.1.0 base, epoxy tristane base, the alicyclic epoxy resin of cyclopentane epoxide base etc., three (2, the 3-epoxypropyl) isocyanuric acid ester, triglycidyl group three (2-hydroxyethyl) isocyanuric acid ester etc. has the triglycidyl group isocyanuric acid ester of triazine ring, dicyclopentadiene-type epoxy resin, diamantane type epoxy resin.
The use level of epoxy resin can suitably be selected according to service condition, for example, with respect to 100 mass parts carboxylic (methyl) acrylic resin, is 10～50 mass parts.
In ultra-violet solidified transparent resin composition of the present invention, except each composition of described (A)～(D), can also suitably cooperate (E) (methyl) propylene acidifying epoxy resin, (F) (methyl) propylene acidifying urethane resin.
(E) (methyl) propylene acidifying epoxy resin
(methyl) propylene acidifying epoxy resin is to instigate the epoxy resin that contains 2 above epoxy radicals in 1 molecule and (methyl) acrylic acid to carry out (methyl) acrylic acid epoxy ester of the partial esterification that esterification obtains.(methyl) propylene acidifying epoxy resin has and can shine (methyl) acryloyl group that carries out free radical polymerization by ultraviolet ray.So, when in ultra-violet solidified transparent resin composition of the present invention, cooperating (methyl) propylene acidifying epoxy resin, (methyl) propylene acidifying epoxy resin carries out cross-linking reaction each other because of the ultraviolet ray irradiation, the cross-linking density of solidfied material improves and curing property further improves, simultaneously, the flexibility of solidfied material improves and can give better folding curved property.
Though (methyl) propylene acidifying epoxy resin is not particularly limited, but preferably, making the epoxy resin that contains at least 2 above epoxy radicals in 1 molecule and epoxy radicals with respect to its epoxy resin is that (methyl) acrylic acid of 50～100% equivalents carries out (methyl) propylene acidifying epoxy resin that esterification obtains, particularly preferably be, carry out (methyl) propylene acidifying epoxy resin that esterification obtains with (methyl) acrylic acid of 80～100% equivalents.
Epoxy resin as the synthesis material of (methyl) propylene acidifying epoxy resin, for example can enumerate, bisphenol A type epoxy resin (bisphenol A-type liquid-state epoxy resin, bisphenol A-type modification flexible-epoxy, nuclear hydrogenation bisphenol A-type liquid-state epoxy resin etc.), novolac-type epoxy resin (phenol novolac-type epoxy resin, orthoresol novolac-type epoxy resin, p-t-butyl phenol novolac-type etc.), Bisphenol F type or bisphenol-s epoxy resin that the reaction of chloropropylene oxide and Bisphenol F or bisphenol S is obtained, and has a 7-oxa-bicyclo[4.1.0 base, epoxy tristane base, the alicyclic epoxy resin of cyclopentane epoxide base etc., three (2, the 3-epoxypropyl) isocyanuric acid ester, triglycidyl group three (2-hydroxyethyl) isocyanuric acid ester etc. has the triglycidyl group isocyanuric acid ester of triazine ring, dicyclopentadiene-type epoxy resin, diamantane type epoxy resin.In above-mentioned epoxy resin, from the viewpoint of the curved property of folding bisphenol A type epoxy resin preferably.These compounds can use separately, also can mix more than 2 kinds and use.
The use level of (methyl) propylene acidifying epoxy resin can suitably be selected according to service condition, with respect to 100 mass parts carboxylic (methyl) acrylic resin, from giving the viewpoint of the curved property of sufficient curing and folding, for example, 1～75 mass parts is preferred, and 3～50 mass parts are particularly preferred.
(F) (methyl) propylene acidifying urethane resin
For (F) (methyl) propylene acidifying urethane resin, so long as polyurethane (methyl) acrylate that (methyl) acrylic acid and urethane resin reaction are obtained gets final product, be not particularly limited.When in ultra-violet solidified transparent resin composition, comprising (methyl) propylene acidifying urethane resin, because can form extensibility and the curved good cured coating film of property of folding, so, effectively be applied to for example wiring substrate, particularly flexible wiring sheet.
Urethane resin is that the compound that contains 2 above isocyanate group in 1 molecule and the polyol compound that contains 2 above carboxyls in 1 molecule reaction are obtained.
For the compound that in 1 molecule, contains 2 above isocyanate group, be not particularly limited, for example, can enumerate hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), the di-2-ethylhexylphosphine oxide cyclohexyl isocyanate, trimethyl hexamethyl diisocyanate, hexamethylamine diisocyanate, the di-2-ethylhexylphosphine oxide cyclohexyl isocyanate, toluene diisocyanate, 1,2-diphenylethane diisocyanate, 1,3-diphenyl propane diisocyanate, methyl diphenylene diisocyanate, diisocyanate such as dicyclohexyl methyl diisocyanate.Use separately these compounds also can, mix to use more than 2 kinds and also can.
Polyol compound for containing 2 above carboxyls in 1 molecule is not particularly limited, can enumerate, for example, ethylene glycol, propylene glycol, trimethylene, 1,4-butylene glycol, 1,3-butylene glycol, 1, the 2-butylene glycol, 1,5-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 2,2-dimethyl-1, ammediol, neopentyl glycol, 1,6-hexanediol, 2,2-diethyl-1, ammediol, 3,3-dihydroxymethyl heptane, 2-ethyl-2-butyl-1, ammediol, 1,12-dodecanediol, C such as 1,18-octacosanol
2-C
22Alkanediol; The 2-butene-1,4-glycol, 2,6-dimethyl-1-octene-3, aliphatic diols such as alkenediols such as 8-glycol; 1,4-cyclohexane diol, alicyclic diols such as 1,4-cyclohexanedimethanol; Glycerine, 2-methyl-2-methylol-1, ammediol, 2,4-dihydroxy-3-methylol pentane, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, 2-methyl-2-methylol-1, ammediol, 2,4-dihydroxy-3-(methylol) pentane, aliphatics triols such as two (the methylol)-3-butanols of 2,2-; Tetramethylol methane (Tetramethylolmethane), pentaerythrite (Pentaerythritol), bipentaerythrite, xylitol etc. have the polyvalent alcohol of 4 above hydroxyls etc.Use separately these compounds also can, mix to use more than 2 kinds and also can.
For as (methyl) propylene acidifying urethane resin and commercially available situation, for example can enumerate " the purple light UV-1400B " of Japanese synthetic chemistry (strain), " purple light UV-1700B ", " purple light UV-6300B ", " purple light UV-7510B ", " purple light UV-7600B ", " purple light UV-7605B ", " purple light UV-7610B ", " purple light UV-7620EA ", " purple light UV-7630B " and " purple light UV-7640B ", on the root " the Art Resin UN-9000H " of industry (strain), " ArtResin UN-3320HA ", " Art Resin UN-3320HC ", " Art Resin UN-3320HS " and " Art Resin UN-901T ", " the NKOligo U-4HA " of Xin Zhong village chemical industry (strain), " NKOligo U-6HA ", " NKOligo U-6LPA ", " NKOligo U-15HA ", " NKOligo UA-32P ", " NKOligo U-324A " and " NKOligo U-6H ", Daicel cyanogen spy's (ダ ィ セ Le サ ィ テ ッ Network) (strain) " EBECRYL1204 ", " EBECRYL1205 ", " EBECRYL215 ", " EBECRYL230 ", " EBECRYL244 ", " EBECRYL245 ", " EBECRYL264 ", " EBECRYL265 ", " EBECRYL1280 ", " EBECRYL285 ", " EBECRYL8200 ", " EBECRYL8405 ", " EBECRYL8411 ", " EBECRYL8804 ", " EBECRYL9270 ", " KRM7735 ", " KRM8296 ", " EBECRYL1290 ", " EBECRYL1290K ", " EBECRYL5129 ", " EBECRYL210 ", " EBECRYL220 ", " EBECRYL284 ", " EBECRYL8210 ", " EBECRYL8402 " and " EBECRYL9260 ", " UX-2201 " of Japan's chemical drug (strain), " UX-2301 ", " UX-3204 ", " UX-3301 ", " UX-4101 ", " UX-0937 ", " UX-5000 ", " UX-5001 ", " UX-5002 ", " BEAMSET575 " of waste river chemical industry (strain), " M-313 " in East Asia synthetic (strain), " M-315 " and び " M-1200 ", " AH-600 " of common prosperity society chemistry (strain) etc.
Though the skeleton for (methyl) propylene acidifying urethane resin is not particularly limited, but because the possibility that the many situations of (methyl) acrylic-functional number exist cure shrinkage, extensibility to reduce, so (methyl) acrylic-functional number in preferred 1 molecule is 2～4.And, because, for weight-average molecular weight, its the value hour, the wiring diagram film adheres to substrate easily during exposure, is difficult to obtain the target cured coating film, so its lower limit is preferred 1500, because there is the tendency of the curved property reduction of folding when big in weight-average molecular weight, so its higher limit preferably 3000.
Use level for (methyl) propylene acidifying urethane resin, can suitably select according to service condition, for example, with respect to 100 mass parts carboxylic (methyl) acrylic resin, it is 1～40 mass parts, from the good viewpoint of balance of deep drawing quality and the curved property of folding, preferably 2～25 mass parts.Should illustrate, in order to obtain the curved good cured coating film of property of folding, also can cooperate described (methyl) propylene acidifying epoxy resin and (methyl) propylene acidifying urethane resin simultaneously.
Except each composition of above-mentioned (A)～(F), can also make ultra-violet solidified transparent resin composition of the present invention contain phosphorus compound, various adding ingredient as required, for example, various adjuvants, solvent etc.And, though impaired in order to prevent the transparency, ultra-violet solidified transparent resin composition of the present invention does not cooperate colorant,, be colored as under the situation of desired color, also can suitably cooperate colorants such as coloring pigment.
As mentioned above, give anti-flammability to ultra-violet solidified transparent resin composition of the present invention, but further improved anti-flammability in order to strengthen anti-flammability, also can in the scope of the use level that can't harm the curved property of the transparency and folding, add phosphorus compound.
Phosphorus compound for example can be enumerated: three (chloroethyl) phosphate, three (2,3-, two chloropropyls) phosphate, three (2-chloropropyl) phosphate, three (2,3-dibromopropyl) phosphate, three (bromine chloropropyl) phosphate, 2,3-dibromopropyl-2,3-dichloro propyl phosphate, three (tribromo phenyl) phosphate, three (dibromo phenyl) phosphate, Halogens such as three (tribromo neopentyl) phosphate are phosphate; Trimethyl phosphate, triethyl phosphate, the Tributyl phosphate ester, the trioctylphosphine phosphate, three butoxyethyl group phosphates, non-halogen such as triallyl phosphine are aliphatic phosphate ester; Triphenyl, the tolyl diphenyl phosphoester, two tolyl phenyl phosphate ester, the trimethylphenyl phosphate, three xylyl phosphates, the xylyl diphenyl phosphoester, three (isopropyl phenyl) phosphate, the isopropyl phenyl diphenyl phosphoester, diisopropyl phenyl phenyl phosphate ester, three (trimethylphenyl) phosphate, three (tert-butyl-phenyl) phosphate, the hydroxy phenyl diphenyl phosphoester, octyl group diphenyl phosphoester, 3-glycidyl oxygen base propylidene diphenyl phosphine oxide, 3-glycidyl oxygen base diphenyl phosphine oxide, the diphenylacetylene phosphine oxide, 2-(9,10-dihydro-9-oxy assorted-10-oxide-10-phospho hetero phenanthrene-10-yl) methylsuccinic acid is two-and (2-hydroxyethyl)-non-halogen such as ester polymer are aromatic phosphoric ester; Three diethyl phosphinic acids aluminium, trimethyl ethyl phosphinic acids aluminium, three diphenyl phosphonic acid aluminium, two diethyl phosphinic acids zinc, two Methylethyl phosphinic acids zinc, two diphenyl phosphonic acid zinc, two diethyl phosphinic acids oxygen titaniums, four diethyl phosphinic acids titaniums, two Methylethyl phosphinic acids oxygen titaniums, tetramethyl ethyl phosphinic acids titanium, two diphenyl phosphonic acid oxygen titaniums, the slaine of phosphinic acids such as four diphenyl phosphonic acid titaniums etc.
Using under the situation of phosphate as phosphorus compound, higher limit as the use level of phosphorus compound, with respect to 100 mass parts carboxylic (methyl) acrylic resin, from the viewpoint that prevents that the transparency is impaired, be 12 mass parts, from suppressing the viewpoint of the curved property reduction of the transparency and folding, preferably 10 mass parts reliably.On the other hand, use under the situation of slaine as phosphorus compound of phosphinic acids, the higher limit of its use level, carboxylic (methyl) acrylic resin with respect to 100 mass parts, viewpoint from the transparency that avoids damage, be 10 mass parts, from suppressing the viewpoint of the curved property reduction of the transparency and folding, preferably 8 mass parts reliably.
For various adjuvants, can enumerate the defoamer that acrylate copolymer is principal ingredient, be levelling agent of principal ingredient etc. with the potpourri of polyether-modified dimethyl silicone polymer and polyethers.
Solvent uses for viscosity or the drying property of regulating ultra-violet solidified transparent resin composition.As solvent, can enumerate for example ketone such as methyl ethyl ketone, cyclohexanone, toluene, dimethylbenzene etc. are aromatic hydrocarbon based, alcohols such as methyl alcohol, isopropyl alcohol, cyclohexanol, ester ring type such as cyclohexane, methylcyclohexane hydro carbons, oil such as sherwood oil, naphtha series solvent class, cellosolve such as cellosolve, butyl cellosolve class, carbitol such as carbitol, butyl carbitol class, acetate esters such as ethyl acetate, butyl acetate, cellosolve acetic acid esters, butyl cellosolve acetate, carbitol acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, acetate of butyl carbitol.Use level under the situation of using solvent is with respect to carboxylic (methyl) acrylic resin of 100 mass parts, preferably 1～500 mass parts.
For colorant, colorant so long as not devitrification gets final product, can be not particularly limited to use, under the situation that is colored as white, black, blueness, yellow etc., can be used white color agents, black colorant, blue colorant, yellow colorants etc. accordingly.
Manufacture method for described ultra-violet solidified transparent resin composition of the present invention, unqualified is specific method, can be, for example, with described composition (A)～(D) and after other compositions that add as required cooperate with predetermined ratio, at room temperature, undertaken mixing by stirring apparatuss such as kneading device such as three-roll mill, bowl mill, sand mill or super mixer, planetary-type mixers or mix and make.And, described mixing or mix before, also can carry out pre-mixing or premixed as required.
Then, the brushing method for described ultra-violet solidified transparent resin composition of the present invention describes.Herein, to form the method for film at flexible base, board brushing ultra-violet solidified transparent resin composition of the present invention, more specifically, describe as an example with the method that forms dielectric film at the flexible wiring sheet brushing ultra-violet solidified transparent resin composition of the present invention with the circuit pattern that forms by the etching Copper Foil.On the flexible wiring sheet with the circuit pattern that forms by the etching Copper Foil, the ultra-violet solidified transparent resin composition that uses methods such as silk screen print method, spraying process to make as mentioned above with the thickness coating of expectation.Then, when in ultra-violet solidified transparent resin composition, having cooperated solvent, in order to make solvent evaporates, carry out heating predrying about 15～60 minutes under the temperature about 60～80 ℃, solvent is volatilized from ultra-violet solidified transparent resin composition, and the surface of filming becomes the state of dry to touch.
Afterwards, on the ultra-violet solidified transparent resin composition that has been coated with, be close to that to have except the pad of described circuit pattern be the negative film of the pattern of light transmission, quadrature is penetrated ultraviolet ray from it.And, be coated with film development by being removed the territory, non-exposed area corresponding to described pad by dilute alkaline aqueous solution, making.As developing method, for example, can suitably use known method such as spray-on process, shower method.As the dilute alkaline aqueous solution that uses, for example can enumerate 0.5～5% aqueous sodium carbonate.After the development, carry out solidifying in 20～80 minutes (cure) by 130～170 ℃ heated air circulation type dryers etc., can form the target dielectric film at printed circuit board.
[embodiment]
Then, embodiments of the invention are described, but as long as the present invention is no more than its purport, just are not limited to these examples.
For (A) carboxylic (methyl) acrylic resin
The physical property measurement condition
1. the P elements containing ratio in the solid constituent is calculated by the theoretical value as the use level of each composition of raw material.The following calculating of solid constituent acid number, at first, by measure the solid constituent acid number of (A) carboxylic (methyl) acrylic resin based on the phenolphthalein variable color method of alkali acid-base titration, afterwards, multiply by the solid constituent ratio again and calculate, described solid constituent ratio be 150 ℃ with dry 2 hours of (A) carboxylic (methyl) acrylic resin, tried to achieve by the mass ratio before and after dry.For two key equivalents, the molal quantity (g/mol) of the solid constituent quality (g) by (A) carboxylic (methyl) acrylic resin/the have compound of oxirane ring and ethene unsaturated link is calculated.
2. weight-average molecular weight is measured in the following manner.
Use Dong Caoshe GPC device processed to measure.Condition determination is as described below.
Post: TSK gel (Dong Caoshe system, " SuperH4000 ", " SuperHZ2500 ")
Detecting device: differential refractometer
Launch solvent: tetrahydrofuran
Solute concentration: 10mg/ml
Standard substance: polystyrene standard (VARIAN society system, " EASICAL PS-2 " (single dispersed sample))
Flow velocity: 0.3ml/min
Temperature: 40 ℃
Synthesizing of the synthesis example (A-1)～(A-3) of use table 1 explanation (A) carboxylic (methyl) acrylic resin and the comparison synthesis example (A-4) of comparison resin.
Synthesis example 1
Possessing stirrer, thermometer, reflux condensing tube, tap funnel, 1 liter of nitrogen or air leading-in conduit is separated in the flask, drop into dipropylene glycol monomethyl ether (Sanyo changes into the DPM processed of product society) 550g, after under blanket of nitrogen, being warmed up to 100 ℃, dripped with 3 hours and to have mixed methacrylic acid (being equivalent to " a-1 " composition) 120g, methacrylic acid phenoxy ethyl (being equivalent to " a-2 " composition) 20g, methacrylic acid 2-carboxyl ethyl ester (being equivalent to " a-2 " composition) 30g, isobornyl methacrylate (being equivalent to " a-2 " composition) 30g and dimethyl 2,2 '-solution of two (2 Methylpropionic acid ester) (with the pure medicine of light V-601 processed of the society) 20g of azo, make slaking dripping under blanket of nitrogen, to continue in back 3 hours to react.Then, under air atmosphere, add 4-hydroxybutyl acrylate glycidyl ether (being equivalent to " a-3 " composition) (Japan changes into (strain) system (4HBAGE)) 150g, triphenylphosphine 1.0g, metoxyphenol 0.3g, make its reaction 8 hours at 110 ℃.And then, add 9,10-dihydro-9-oxy and mix-10-phospho hetero phenanthrene-10-oxide (being equivalent to " a-4 " composition) (three smooth society systems (HCA)) 100g, make its reaction 3 hours at 110 ℃.So, obtain the solution (A-1) of carboxylic (methyl) acrylic resin of solid constituent acid number 80.5mgKOH/g, two key equivalent 1567.7g/mol, P elements containing ratio 3.2 quality %, weight-average molecular weight 18000.
Synthesis example 2
Possessing stirrer, thermometer, reflux condensing tube, tap funnel, 1 liter of nitrogen or air leading-in conduit is separated in the flask, drop into dipropylene glycol monomethyl ether (Sanyo changes into the DPM processed of product society) 550g, after under blanket of nitrogen, being warmed up to 100 ℃, dripped with 3 hours and to have mixed acrylic acid (being equivalent to " a-1 " composition) 130g, methacrylic acid phenoxy ethyl (being equivalent to " a-2 " composition) 20g, acrylic acid 4-hydroxyl butyl ester (being equivalent to " a-2 " composition) 20g, isobornyl methacrylate (being equivalent to " a-2 " composition) 30g and dimethyl 2,2 '-solution of two (2 Methylpropionic acid ester) (with the pure medicine of light V-601 processed of the society) 20g of azo, make slaking dripping under blanket of nitrogen, to continue in back 3 hours to react.Then, under air atmosphere, add 4-hydroxybutyl acrylate glycidol ether (being equivalent to " a-3 " composition) (Japan changes into (strain) system (4HBAGE)) 150g, triphenylphosphine 1.0g, metoxyphenol 0.3g, make its reaction 8 hours at 110 ℃.And then, add diphenyl phosphine oxide (being equivalent to " a-4 " composition) (sheet mountain chemical industry (strain) system (OX-2)) 110g, make its reaction 3 hours at 110 ℃.So, obtain the solution (A-2) of carboxylic (methyl) acrylic resin of solid constituent acid number 131.6mgKOH/g, two key equivalent 2190.4g/mol, P elements containing ratio 3.7 quality %, weight-average molecular weight 14000.
Synthesis example 3
Comprising stirrer, thermometer, reflux condensing tube, tap funnel, 1 liter of nitrogen or air leading-in conduit is separated in the flask, drop into dipropylene glycol monomethyl ether (Sanyo changes into the DPM processed of product society) 550g, after under blanket of nitrogen, being warmed up to 100 ℃, dripped with 3 hours and to have mixed methacrylic acid (being equivalent to " a-1 " composition) 130g, methacrylic acid phenoxy ethyl (being equivalent to " a-2 " composition) 10g, methacrylic acid 2-carboxyl ethyl ester (being equivalent to " a-2 " composition) 20g, N-acryloxy ethyl hexahydrophthalic phthalimide (being equivalent to " a-2 " composition) (M-140 processed of (strain) society is synthesized in East Asia) 25g and dimethyl 2,2 '-solution of two (2 Methylpropionic acid ester) (with the pure medicine of light V-601 processed of the society) 20g of azo, make slaking dripping under blanket of nitrogen, to continue in back 3 hours to react.Then, under air atmosphere, add glycidyl methacrylate (being equivalent to " a-3 " composition) (day oil BLEMMER GH processed of (strain) society) 80g, 4-hydroxybutyl acrylate glycidol ether (being equivalent to " a-3 " composition) (Japan changes into society's system (4HBAGE)) 90g, triphenylphosphine 1.0g, metoxyphenol 0.3g, 110 ℃ of reactions 8 hours.And then, add 9,10-dihydro-9-oxy and mix-10-phospho hetero phenanthrene-10-oxide (being equivalent to " a-4 " composition) (the three smooth HCA of society) 95g, 110 ℃ of reactions 3 hours.So, obtain solid constituent acid number 62.1mgKOH/g, the solution (A-3) of carboxylic (methyl) acrylic resin of two key equivalent 784.6g/mol, P elements containing ratio 3.0 quality %, weight-average molecular weight 24000.
Compare synthesis example
Separate in the flask at 1 liter that possesses stirrer, thermometer, reflux condensing tube, tap funnel, nitrogen or air leading-in conduit, drop into dipropylene glycol monomethyl ether (Sanyo changes into product DPM processed) 550g, after under blanket of nitrogen, being warmed up to 100 ℃, dripped with 3 hours and to have mixed methacrylic acid 110g, butyl methacrylate 250g and dimethyl 2,2 '-solution of two (2 Methylpropionic acid ester) (with the pure medicine of light V-601 processed of the society) 20g of azo, make slaking dripping under blanket of nitrogen, to continue in back 3 hours to react.Then, under air atmosphere, add glycidyl methacrylate 90g, triphenylphosphine 1.0g, metoxyphenol 0.3g, under 110 ℃, make its reaction 8 hours.So, obtain the solution (A-4) of carboxylic (methyl) acrylic resin of solid constituent acid number 80.4mgKOH/g, two key equivalent 710.0g/mol, weight-average molecular weight 21000.
Table 1
Embodiment 1～23, comparative example 1～4
Cooperation ratio with following table 2 expression cooperates each composition shown in the following table 2, and uses three-roll mill at room temperature to mix dispersion, the ultra-violet solidified transparent resin composition that uses in modulation embodiment 1～23, the comparative example 1～4.Should illustrate that the use level of following table 2 expression is represented mass parts.
[table 2]
In the table 2, the carboxylic uv curing resin that does not have P elements that in comparative example, uses, as described below.
Cyclomer P-ACA-Z251: Daicel cyanogen spy (strain) makes, and contains the acryl resin of unsaturated group.
ZFR-1122: Japanese chemical drug (strain) system, the potpourri of acrylate oligomer (the anhydride modified product of acrylic acid epoxy ester), diethylene glycol monoethyl ether acetic acid esters, methyl hydroquinone.
Each composition in the table 2 beyond described, as described below.
(B) Photoepolymerizationinitiater initiater
IRGACURE184: Ciba (strain) system, 1-hydroxyl-cyclohexyl-phenyl-ketone.
IRGACURE1173: Ciba (strain) system, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone.
IRGACURE2529: Ciba (strain) system, 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone.
(C) thinning agent
LIGHT ESTER 2EG: common prosperity society chemistry (strain) system, diglycol two (methyl) acrylate.
M-306: East Asia synthetic (strain) system, pentaerythritol triacrylate.
DPHA: Japanese chemical drug (strain) system, dipentaerythritol and acrylic acid reaction product.
(D) epoxy resin
JER828: Mitsubishi Chemical's (strain) system, bisphenol A type epoxy resin.
JER837: Mitsubishi Chemical's (strain) system, bisphenol f type epoxy resin.
JER1003: Mitsubishi Chemical's (strain) system, bisphenol A-type solid epoxy resin.
(E) (methyl) propylene acidifying epoxy resin
EBECRYL3708: Daicel cyanogen spy (strain) system, the potpourri of acrylic acid epoxy ester and acrylic acid 2-hydroxy methacrylate.
Miramer PE110:MIWON system, acrylic acid phenyl epoxy-ester.
Miramer PE250:MIWON system, bisphenol A-type dimethacrylate epoxy-ester.
(F) (methyl) propylene acidifying urethane resin
EBECRYL8450: Daicel cyanogen spy (strain) system, urethane acrylate.
M-1200: East Asia synthetic (strain) system, urethane acrylate.
AH-600: common prosperity society chemistry (strain) system, phenylglycidyl ether acrylate hexamethylene diisocyanate polyurethane prepolymer.
Phosphorus compound (fire retardant)
Diphenylacetylene phosphine oxide: sheet mountain chemical industry (strain) system.
ME-P8: three light (strain) systems, 2-(9,10-dihydro-9-oxy assorted-10-oxide-10-phospho hetero phenanthrene-10-yl) methylsuccinic acid is two-(2-hydroxyethyl)-ester polymer.
EXOLIT OP935: Clariant Japan (strain) system, organic phosphate.
Adjuvant
UVX-189: this chemistry of nanmu (strain) system, vinyl based polymer.
POLYFLOW No.90: common prosperity society chemistry (strain) system, acrylate copolymer.
BYK-3610N: Bi Ke chemistry Japan (strain) system, acrylate copolymer.
BYK-307: Bi Ke chemistry Japan (strain) system, the potpourri of polyether-modified dimethyl silicone polymer and polyethers.
Colorant
Direct blue FG-7351: Toyo Ink (strain) system, phthalocyanine compound.
Gu U.S. saturating yellow AGR: Ciba (strain) system, anthraquinone compounds.
Solvent
Diethylene glycol monoethyl ether acetic acid esters: refreshing port organic chemistry industry (strain) system.
The test film production process
(Mitsubishi's gas chemistry (strain) is made to the clear polyimides film by isopropyl alcohol, thickness 30 μ m) after ungrease treatment is carried out on surface, the ultra-violet solidified transparent resin composition of modulating as mentioned above by the silk screen print method coating on the surface of having passed through ungrease treatment.After the coating, carry out the predrying of 20 minutes (in the BOX stove 25 minutes) at the BOX stove with 80 ℃.After predrying, have the photomask that makes beyond the predetermined pad to the pattern of light transmission filming to be close to, on (wavelength 300～450nm) is to 1000mJ/cm by exposure device (ORC corporate system HMW-680GW) exposure ultraviolet ray
2Afterwards, use 30 ℃ 1% sodium carbonate developer solution, develop with 0.1MPa, 60 seconds condition, afterwards, with 150 ℃ of back curing of carrying out 60 minutes (in the BOX stove 70 minutes), form the cured coating film of ultra-violet solidified transparent resin composition at the BOX stove at the PET film.The DRY thickness of cured coating film is 20～23 μ m.
Estimate
(1) Haze (mist degree) (%)
Replace the clear polyimides film, on the surface of quartz glass substrate (50mm * 50mm, thickness 1mm), form cured coating film by brushing with the same method of described test film production process, as test film.For this test film, be benchmark with JIS-K-7105, JIS-K-7136, use new and high technology society of Hitachi U-3310 spectrophotometric determination processed mist degree.
(2) resolution
Have the cured coating film that the photomask of the pattern of live width 30～150 μ m is produced as mentioned above for use, Visual Confirmation is also estimated the live width that is deposited in the minimum on the substrate as lines fully.
(3) the curved property of folding
For the test film of making at described test film production process, carry out repeatedly 180 ℃ of bendings repeatedly by crimping is folding, by visual and * 200 observation by light microscope this moment transparent cured coating film the crack produce situation, measure and do not produce the number of times in crack.
(4) anti-flammability
Replace the clear polyimides film, respectively on two surfaces of polyimide substrate (15mm * 25mm, thickness 5 μ m), by the method same with described test film production process, forming build is the cured coating film of 20 μ m, as test film.For this test film, carrying out with the UL94 specification is the testing vertical flammability of benchmark.Evaluation is based on the UL94 specification, by VTM-0～burning expression.
(5) insulation resistance (Ω)
Replace the PET film, at comb shape test pattern (live width 100 μ m, distance between centers of tracks 100 μ m), by brushing the formation cured coating film with the same method of described test film production process, as test film.This test film is applied direct current 50V in the groove of the atmosphere of 85 ℃ of temperature, humidity 85%, place after 1000 hours, this test film is fetched into groove measures insulating resistance value outward.
In table 3, represent evaluation result.
[table 3]
As described shown in the result of each embodiment of table 3 and each comparative example, during carboxylic (methyl) acrylic resin of having used addition and contain the phosphorus compound of at least 1 aromatic rings and having obtained, can access the curved property of harmless folding, resolution and insulativity and have the cured coating film with good transparency that anti-flammability, blur level have reduced.During the cooperation of embodiment 13～15 (methyl) propylene acidifying epoxy resin, during the cooperation of embodiment 16～18 (methyl) propylene acidifying urethane resin, further improve to the harmless transparency the curved property of folding respectively.And, by embodiment 1～9,13～23 as can be known, do not add the phosphorus compound as fire retardant, can prevent reliably that folding from bending the property reduction, balance has improved the curved property of folding and the transparency goodly.
On the other hand, by comparative example 2～4 as can be known, when use did not have the carboxylic uv curing resin of P elements and cooperate phosphorus compound as fire retardant, though have anti-flammability, mist degree rose and can not obtain the good transparency.In addition, by comparative example 1 as can be known, do not have the carboxylic uv curing resin of P elements in use, when mismatching the phosphorus compound as fire retardant, though can have the transparency and prevent that folding from bending the property reduction, can not obtain anti-flammability.
Industrial utilizability
Ultra-violet solidified transparent resin composition of the present invention is because can form the transparency and the good solidfied material of anti-flammability under the situation of each characteristics such as the curved property of harmless folding, resolution; so; for example, the field value height of using diaphragm at dielectric film or the touch panel of wiring substrate.
Claims (8)
1. a ultra-violet solidified transparent resin composition is characterized in that: contain
(A) carboxylic (methyl) acrylic resin, obtain according to following process, after a part of addition to the carboxyl that makes the multipolymer that (methyl) acrylic acid and (methyl) acrylate reactions obtain has the compound of oxirane ring and ethene unsaturated link, and then, a part of addition of described ethene unsaturated link is contained the phosphorus compound of at least 1 aromatic rings;
(B) Photoepolymerizationinitiater initiater;
(C) thinning agent;
(D) epoxy resin.
2. ultra-violet solidified transparent resin composition as claimed in claim 1, it is characterized in that: the described phosphorus compound that contains at least 1 aromatic rings is general formula (i) or general formula compound (ii),
In the formula, Z represents substituting group, and l is 0～5 integer, and m is 0～4 integer.
3. ultra-violet solidified transparent resin composition as claimed in claim 1 or 2, it is characterized in that: described (A) carboxylic (methyl) acrylic resin contains the P elements of 0.5～10 quality % in solid constituent.
4. as each described ultra-violet solidified transparent resin composition in the claim 1 to 3, it is characterized in that: the acid number of the solid constituent of described (A) carboxylic (methyl) acrylic resin is 30～140mgKOH/g.
5. as each described ultra-violet solidified transparent resin composition in the claim 1 to 4, it is characterized in that: two key equivalents of described (A) carboxylic (methyl) acrylic resin are 400～2500g/mol.
6. as each described ultra-violet solidified transparent resin composition in the claim 1 to 5, it is characterized in that: also contain (E) (methyl) propylene acidifying epoxy resin.
7. as each described ultra-violet solidified transparent resin composition in the claim 1 to 6, it is characterized in that: also contain (F) (methyl) propylene acidifying urethane resin.
8. wiring substrate is characterized in that: have to make as each described ultra-violet solidified transparent resin composition in the claim 1 to 7 and solidify and the dielectric film that obtains.
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| CN104977806A (en) * | 2014-04-11 | 2015-10-14 | 太阳油墨制造株式会社 | Photosensitive resin composition, dry film, cured product and printed circuit board |
| CN115725255A (en) * | 2021-08-30 | 2023-03-03 | 互应化学工业株式会社 | Adhesive agent |
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| JP5990291B2 (en) * | 2014-04-11 | 2016-09-14 | 太陽インキ製造株式会社 | Photosensitive resin composition, dry film, cured product, and printed wiring board |
| JP6503668B2 (en) * | 2014-09-19 | 2019-04-24 | Dic株式会社 | Curable resin composition, cured product thereof, and laminate |
| JP2017039857A (en) * | 2015-08-20 | 2017-02-23 | 昭和電工株式会社 | Composition for photoreactive transparent adhesive sheet, photoreactive transparent adhesive sheet, touch panel, image display device |
| JP6278933B2 (en) * | 2015-09-02 | 2018-02-14 | 株式会社タムラ製作所 | Insulating film forming method, electronic substrate manufacturing method, and photosensitive resin composition |
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| CN101151580A (en) * | 2005-03-31 | 2008-03-26 | 昭和电工株式会社 | Flame-retardant composition for solder resist and cured product thereof |
| JP2010224171A (en) * | 2009-03-23 | 2010-10-07 | Taiyo Ink Mfg Ltd | Curable resin composition, dry film using the same, and printed wiring board |
| CN102127115A (en) * | 2010-12-23 | 2011-07-20 | 山东旭锐化学有限公司 | Synthesis method of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104977806A (en) * | 2014-04-11 | 2015-10-14 | 太阳油墨制造株式会社 | Photosensitive resin composition, dry film, cured product and printed circuit board |
| CN104977806B (en) * | 2014-04-11 | 2019-11-08 | 太阳油墨制造株式会社 | Photosensitive polymer combination, dry film, solidfied material and printed circuit board |
| CN115725255A (en) * | 2021-08-30 | 2023-03-03 | 互应化学工业株式会社 | Adhesive agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013171135A (en) | 2013-09-02 |
| TW201343768A (en) | 2013-11-01 |
| TWI567126B (en) | 2017-01-21 |
| JP5964608B2 (en) | 2016-08-03 |
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