CN1196748C - Resin composition curable with actinic energy ray - Google Patents
Resin composition curable with actinic energy ray Download PDFInfo
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- CN1196748C CN1196748C CNB008176795A CN00817679A CN1196748C CN 1196748 C CN1196748 C CN 1196748C CN B008176795 A CNB008176795 A CN B008176795A CN 00817679 A CN00817679 A CN 00817679A CN 1196748 C CN1196748 C CN 1196748C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Abstract
A resin composition curable with actinic energy rays which comprises (A) at least one resin curable with actinic energy rays and (B) a free-radical photopolymerization initiator. In a first embodiment of the composition, at least 50 wt.% of the component (A) is accounted for by (A') a resin curable with actinic energy rays which has one radical-polymerizable ethylenically unsaturated bond, one or more hydroxyl groups, and one or more aromatic rings per molecule. In a second embodiment, the component (A) is (A'') a resin curable with actinic energy rays which has one ethylenically unsaturated bond per molecule, and the composition further contains (C) an epoxy resin. The first embodiment also preferably contains (C) an epoxy resin. In a preferred embodiment, the composition further contains at least one member selected from the group consisting of (D) a saturated polyester resin, (E) a vinyltriazine derivative, and (F) a silane coupling agent. Such resin composition is useful as an adhesive or coating material of the actinic-energy-ray-curing type for use in the protection of various electrodes.
Description
Technical field
The present invention relates to resin composition curable with actinic energy ray, and to be particularly related to various electrodes such as protection copper, silver electrodes be the composition of the actinic energy ray sclerotic type of purpose.
Background technology
Generally, the various electrodes of electronic component etc. are for the known resin combination that heat embrittlement class, UV cured class and room temperature vulcanizing class are arranged of protective material (supercoat) of outer gas (moisture).For example, the resin combination of heat embrittlement class is as the disclosed Resins, epoxy based resin composition of special fair 1-19834 communique that again, the resin combination of UV cured class is for to open the disclosed acrylic resin composition of clear 60-103343 communique as the spy.
Yet in these a little resin combinations, the resin combination of heat embrittlement class needs heating for a long time when hardening treatment, and it is poor to pretend the industry property, and worries to cause detrimentally affect for other materials.
Though it is fast that the resin combination of UV cured class has setting rate, but in the advantage of low-temperature stiffening, but because sclerosis shrink big, so hardening thing for the poor adhesion of base material, in the hardening thing residual strain and the crack takes place, has the shortcoming of poor water resistance.
The resin combination of room temperature vulcanizing class does not need hardening equipment, has advantages of being cheap, but that sclerosis needs is long-time, more necessaryly guarantees the hardened place, has the shortcoming of operation difference.
Relatively, can overcome the resin combination of above-mentioned various shortcomings, in the resin combination of UV cured class, also proposed to use especially low sclerosis to be punctured into the resin combination of the light cationic catalyst of its feature (reference special fair 2-30326 number, spy open flat 5-186755 communique) still, this based resin composition then takes place because the metal electrode that the light cationic catalyst is caused easily produces the corrosive new problem if use on metal electrode.
On the other hand, be that in the module of flat display board etc. today of carrying out the meticulous patternization of outer electrode of representative, its electrode are on glass substrate, stick with paste (paste) with photolithography with the calcining silver of narrow pitch patterning and made.Therefore, with this type of metal electrode, also can't obtain sufficient protective value to be protected as above-mentioned previous resin combination even desire with narrow pitch patterning.
Again; in order to make compactization of e-machine; also on the PET film, the silver paste is given silk screen printing recently; and form electrode (film liquid crystal, touch panel); but the protective membrane of this moment also requires the important characteristics such as low warpage, dimensional stability, adhesivity of film material except the so-called protection function.
Summary of the invention
Therefore, purpose of the present invention is to solve the problem points of prior art as the aforementioned, and provide and keep the advantage that UV cured based resin composition had, and water tolerance, adhesivity for base material is good, can bear the resin composition curable with actinic energy ray of the inter-electrode short-circuit that migration causes.
Can bear the performance of the inter-electrode short-circuit that migration causes, in be called " resistance to migration " to place an order herein.
In order to reach aforementioned purpose,, provide a kind of and contain (A) curable with actinic energy ray resin and (B) resin composition curable with actinic energy ray of optical free radical polymerization starter according to the present invention.In first embodiment, the 50 quality % of above-mentioned (A) composition are above to be had a free-radical polymerised ethylenic unsaturated double-bond, is its feature with the curable with actinic energy ray resin of an above hydroxyl and aromatic ring for (A ') intramolecularly, in second embodiment, above-mentioned (A) composition is for (A ") has the curable with actinic energy ray resin of an ethylenic unsaturated double-bond in an intramolecularly, and contains (C) Resins, epoxy for its feature.
In aforementioned second embodiment, must contain Resins, epoxy (C), but preferably make first embodiment also contain Resins, epoxy (C).Resins, epoxy (C) is more than 40 ℃ with softening temperature, at room temperature is that partly type or solid type state person are good admittedly.
In the embodiment of Yu Gengjia, resin composition curable with actinic energy ray of the present invention also contain from (D) saturated polyester resin, (E) vinyl pyrrolotriazine derivatives and (F) select among the silane coupling agent at least a.
Contain the resin composition curable with actinic energy ray of the present invention of composition as described above, operation than the resin combination of previous heat embrittlement class and room temperature vulcanizing class is good, and hydrophobicity prevents that for the adhesivity of various clung bodies, various electrodes migration effect is good.
Embodiment
Resin composition curable with actinic energy ray of the present invention is in first embodiment, curable with actinic energy ray resin (A) for have with an intramolecularly a free-radical polymerised ethylenic unsaturated double-bond, with the curable with actinic energy ray resin (A ') of above hydroxyl and aromatic ring as necessary constituent, and account for that the 50 quality % of (A) composition are above to be its feature.
This curable with actinic energy ray resin (A ') is defined as in 1 molecule 1 for functional group's (ethylenic unsaturated double-bond) number that will participate in photo-hardening and react, the influence that sclerosis when making the optical free radical polymerization is shunk suppresses to inferior limit, helps to prevent adhering reduction.In addition, the existence of hydroxyl goes far towards the adhesivity with base material, and having of aromatic ring helps water tolerance.
Above-mentioned curable with actinic energy ray resin (A ') can use the industrial monofunctional epoxy that can obtain easily (methyl) esters of acrylic acid, can be according to general method for making and the glycidyl of monofunctional epoxy resin is given (methyl) acroleic acid esterification.Concrete example can be enumerated (methyl) acroleic acid esterification thing of phenyl glycidyl ether, neighbour-xenyl glycidyl ether, naphthyl glycidyl ether etc.
Especially, the following general expression (1) of novel curable with actinic energy ray resin or (methyl) acrylic compound shown in (2), particularly (methyl) acroleic acid esterification thing of neighbour-xenyl glycidyl ether, naphthyl glycidyl ether etc. is good aspect hydrophobicity.
In the formula, X represents that hydrogen atom or methyl, Y represent-C (CH
3)
2-,-SO
2-,-CH
2-or direct key, R
1And R
2For the expression carbon number is the alkyl of 1～12 straight chain shape, ring-type or branch-like, m is the integer of expression 0～4, and n is the integer of expression 0～5.
Still, in first embodiment of resin composition curable with actinic energy ray of the present invention, can not cause in the dysgenic scope for the composition characteristic, promptly (A) composition all is discontented with in the scope of 50 quality %, can cooperate (A ) intramolecularly to have the curable with actinic energy ray resin of two above ethylenic unsaturated double-bonds, and/or not have other curable with actinic energy ray compounds beyond above-mentioned (A ') composition of curable with actinic energy ray resin etc. of hydroxyl and aromatic ring.
This type of curable with actinic energy ray resin (A ) if the compound that makes the ethylenic unsaturated double-bond carry out radical polymerization via actinic energy ray irradiation get final product, is not particularly limited, but serves as that the spy is good with (methyl) acrylic ester compound.Also can have acryl (methacryloyl) functional group in addition again.And, if simple function and have aromatic nucleus and cyclic rings in resin matrix then helps adhesivity, hydrophobicity aspect.
On the other hand, in second embodiment of resin composition curable with actinic energy ray of the present invention, the feature of curable with actinic energy ray resin (A) is, (A ") is as necessary constituent, and contains Resins, epoxy simultaneously to have the curable with actinic energy ray resin of an ethylenic unsaturated double-bond with an intramolecularly.
(A ") is defined in 1 molecule 1 for functional group's number that will participate in reaction to this curable with actinic energy ray resin, and the influence of the sclerosis contraction when making the optical free radical polymerization suppresses to inferior limit, helps to prevent adhering reduction.But, only with above-mentioned curable with actinic energy ray resin (A "), then resistance to migration and for the adhesivity of base material for abundant inadequately according to used purposes, so must and usefulness Resins, epoxy (C).Herein, Resins, epoxy (C) shrinks (improving adhesivity) for not participating in sclerosis so can effectively lower sclerosis.Again, Resins, epoxy (C) also effectively improves resistance to migration, though its reason is not bright.
(A "), the ethylenic unsaturated double-bond is that the compound that carries out radical polymerization get final product to aforementioned curable with actinic energy ray resin if make via actinic energy ray irradiation, is not particularly limited, but serves as that the spy is good with (methyl) acrylate based compound.Also can have acryl (methacryloyl) functional group in addition again.More and, if in resin matrix, have aromatic nucleus and cyclic rings, then help the hydrophobicity aspect.
(concrete example of A ") can be enumerated 4-(methyl) acryloxy three ring [5.2.1.O to this type of curable with actinic energy ray resin
26] decane, (methyl) vinylformic acid phenoxy ethyl, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) phenyl acrylate, (methyl) vinylformic acid phenoxy group glycol ether ester, (methyl) vinylformic acid phenoxy group macrogol ester, phenol EO modification (methyl) acrylate, to cumyl phenol EO modification (methyl) acrylate, nonylphenol EO modification (methyl) acrylate, nonylphenol PO modification (methyl) acrylate, vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid two cyclopentenes esters, (methyl) vinylformic acid two cyclopentenes 2-ethoxyethyl acetates, simple function (methyl) esters of acrylic acid of (methyl) vinylformic acid two ring pentyl esters etc. etc.
This a little simple functions (methyl) esters of acrylic acid also can give glycidyl (methyl) acroleic acid esterification.Particularly, can enumerate (methyl) acroleic acid esterification thing of neighbour-xenyl glycidyl ether, naphthyl glycidyl ether, phenyl glycidyl ether etc.
Still, can not cause in the dysgenic scope, promptly all be discontented with in the scope of 20 quality %, then can cooperate intramolecularly to have the curable with actinic energy ray resin of two above ethylenic unsaturated double-bonds at (A) composition in sclerosis contraction for composition.
Optical free radical polymerization starter (B) is not particularly limited if can get final product via the compound that actinic energy ray makes aforementioned curable with actinic energy ray resin (A) carry out radical polymerization.The concrete example of optical free radical polymerization starter (B) can enumerate 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2, the thioxanthene ketone of 4-di-isopropyl thioxanthone etc.; The anthraquinone class of 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 1-chloro anthraquinone etc.; 4,4 '-Benzophenones of two diethylin benzophenone etc.; The Alpha-hydroxy ketone of 1-hydroxyl-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone etc.; 2,4, (two) acylphosphine oxide class of 6-Three methyl Benzene formyl diphenyl phosphine oxide compound etc.; Plain body class such as the titanium of two (2,4-cyclopentadiene-1-yl) two (2,6-two fluoro-3-(1H-pyrroles-1-yl) phenyl) titanium etc.; 2-benzyl-2-dimethylin-1-(4-morpholinyl phenyl) butanone-1, the 2-methyl isophthalic acid-[4-(methylthio group) phenyl)-amido phenyl methyl ketone classes such as 2-morpholine propane-1 ketone; Benzyl, 4,4 '-α-diketone class of veratryl, camphorquinone etc. etc.
Again, above-mentioned optical free radical polymerization starter (B) also can be according to employed light source etc., and use several, it can enumerate for example the amido phenyl methyl ketone class of 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholine propane-1-ketone etc. and the combination of thioxanthene ketone or amido phenyl methyl ketone; The Alpha-hydroxy ketone and 2,4 of 1-hydroxyl-cyclohexyl-phenyl ketone etc., the combination of (two) acylphosphine oxide class of 6-Three methyl Benzene formyl diphenyl phosphine oxide compound etc. etc.More and can be in these a little known habitual optical free radical polymerization starters, the light-initiated auxiliary agent that adds the tertiary amine, dimethylin isoamyl benzoate, methacrylic acid, dimethylin ethyl ester etc. of trolamine etc.
In optical free radical polymerization starter (B) as the aforementioned; also with the phenyl ketone compounds, two (2 of 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-hydroxyl-cyclohexyl-phenyl ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholine propyl group-1-ketone, 2-benzyl-2-dimethylin-1-(4-morpholinyl phenyl) butanone-1-etc.; 4,6-trimethylbenzoyl) (two) the acylphosphine oxide class and the plain body compound of titanium of phosphniline oxide compound etc. are good.
The use level of these a little optical free radical polymerization starters (B) to serve as suitably more than 0.5 mass parts, below 20 mass parts, is preferably 0.5～5 mass parts with respect to aforementioned curable with actinic energy ray resin (A) 100 mass parts.The use level of optical free radical polymerization starter (B) is less than 0.5 mass parts, then can't fully carry out photo-hardening with actinic energy ray, in addition-aspect, even surpassing 20 mass parts cooperates in a large number, then, it is state of saturation so for uneconomic because of being hardened to, and probably remaining and make the characteristic of hardening thing reduce behind the photo-hardening of composition on the contrary.
In second embodiment of resin composition curable with actinic energy ray of the present invention, (C) Resins, epoxy is necessary composition, also to add Resins, epoxy, can reach the raising characteristic again in first embodiment.As described above, because Resins, epoxy (C) shrinks (improving adhesivity) for not participating in the photo-hardening reaction so can effectively lower sclerosis.
Resins, epoxy (C) is known habitual various Resins, epoxy; it can enumerate for example bisphenol A type epoxy resin; bisphenol f type epoxy resin; bisphenol-s epoxy resin; bromination phenol A type Resins, epoxy; bisphenol-A epoxy resin; bisphenol-type epoxy resin; di-toluene phenol-type epoxy resin; alicyclic epoxy resin; phenol novolak type epoxy resin; the cresylol phenolic resin varnish type epoxy resin; bromination phenol phenolic varnish type epoxy tree eyeball; the glycidyl ether compound of the phenolic resin varnish type epoxy resin of dihydroxyphenyl propane etc.; the terephthalic acid 2-glycidyl ester; six hydrogen phthalandione 2-glycidyl esters; the Racemic glycidol acyl compound of dimeracid 2-glycidyl ester etc.; triglycidyl isocyanurate; N; N; N '; N '-four glycidyl group m-xylene diamine; N; N; N '; N '-four glycidyl group diamine methylcyclohexane; N, the known habitual epoxy compounds of the Racemic glycidol amine compound of N-diglycidylaniline etc. etc.These a little Resins, epoxy can be used alone or in combination more than two kinds.
Resin composition curable with actinic energy ray of the present invention is in these a little Resins, epoxy, is more than 40 ℃ to use softening temperature especially, is that half Resins, epoxy of consolidating type or solid type state is good under the room temperature.By this, can improve surface hardening (touch dry), the water tolerance of resin combination.More and, the Resins, epoxy via selecting to have the hydrophobicity skeleton then can improve the hydrophobicity of resin combination, and effectively prevents migration.
People such as present inventor, in the various hydrophobic resins that contain Resins, epoxy, selected as above being set forth under the room temperature is half type or the Resins, epoxy of type state admittedly admittedly, as the resin that participates in resistance to migration, and heavily cover self-criticism again, the result learns in these a little Resins, epoxy, also give the epoxidised following constructor that has via peroxyacetic acid with allyl group, promptly, the epoxy compounds that in molecule, has the section construction shown in the following general expression (3), or have the alicyclic epoxy compound of arbitrary structure shown in following formula (4) or (5), for the derivative than Epicholorohydrin has better resistance to migration.Compare with the epichlorohydrin derived thing, the epoxy compounds with following structure is because the impurity ionic concn is low, so good electric performance.
In the formula, X is expression epoxy group(ing) and/or vinyl, and p is the integer of expression 1～100.But, in molecule, contain at least 1 epoxy group(ing).
Especially, the point of resistance to migration, in the epoxy compounds that has section construction shown in the following general expression (3) in the molecule, following formula (a) and (b) shown in the ratio (a)/(b) of functional group's number be average 1.0～4.0 to be good.
This based epoxy resin can be enumerated Ceroxide 3150, the Ceroxide 2085 etc. of Diacel chemical industry (strain) system.
Polyether-type epoxy resin with functional group shown in the above-mentioned general expression (3), can make the compound that has compound bearing active hydrogen and 4 vinyl cyclohexene 1-oxide compound or optionally have other epoxy group(ing), there is the vinyl of the polyether compound of reaction gained down in catalyzer, gives partially or completely epoxidation with the oxygenant of the peracid of peroxyacetic acid etc. and hydroperoxide kind etc. and then can obtain.At this moment, also can import a spot of ethanoyl etc.Having compound bearing active hydrogen is alcohols, can enumerate for example straight chain shape or branch's catenate fatty alcohol, is preferably the polyvalent alcohol of TriMethylolPropane(TMP) etc. and phenol, carboxylic-acid, amine, thio-alcohol.Have in the compound bearing active hydrogen in this, be not limited to only import the functional group shown in 1 aforementioned general expression (3), and can import several.But, in the situation that imports several, if aforementioned functional group heavily to cover the part number too much, then become the high compound of fusing point, so total number is being good below 100.In addition, also can use other polyether-type epoxy resins of special fair 7-25864 number record.About this type of polyether-type epoxy resin because of in above-mentioned communique, describing in detail, so it is in detail with reference to above-mentioned communique.
The use level of these a little Resins, epoxy (C), with respect to aforementioned curable with actinic energy ray resin (A) 100 mass parts, more than 5 mass parts, 60 mass parts are following to be suitably, is preferably 5～40 mass parts.The use level of Resins, epoxy (C) is less than 5 mass parts, and then difficulty obtains aforementioned effect, on the other hand, surpasses 60 mass parts and cooperates in a large number also because of the effect of being expected presents, and state of saturation so be uneconomic, again, probably hinders the photo-hardening of composition on the contrary.
Resin composition curable with actinic energy ray of the present invention is in above-mentioned each composition, adds to cooperate saturated polyester resin (D) for good.This saturated polyester resin (D) if it has the adhesivity effect person that can improve with clung body to get final product, is not particularly limited.The concrete example of saturated polyester resin (D) can be enumerated Japan and spin the Viron 200,220,240,245,270,280,290,296,300,500,530,550,560,600,630,650 of Viron series (Japan twist flax fibers and weave (strain) system), BX1001, GK110,130,140,150,180,190,250,330,590,640,680,780,810,880,890 etc.
More and, this type of saturated polyester film also has the restorative excellent characteristic that the behavior that makes hardening thing be peeled off by base material is carried out easily except improving adhering effect.
The use level of saturated polyester resin (D), with respect to aforementioned curable with actinic energy ray resin (A) 100 mass parts, more than 5 mass parts, 50 mass parts are following to be suitably, is preferably 5～30 mass parts.The use level of saturated polyester resin (D) is less than 5 mass parts, and then difficulty obtains aforementioned effect, on the other hand, even a large amount of the cooperation surpasses 50 mass parts, also because of the effect of being expected presents state of saturation, so be uneconomic, again, probably hinder the photo-hardening of composition on the contrary, make the characteristic of hardening thing reduce.
Resin composition curable with actinic energy ray of the present invention is in mentioned component, adds to cooperate vinyl pyrrolotriazine derivatives (E) for good.The purpose of using this vinyl pyrrolotriazine derivatives (E) is in order to effectively to prevent the migration of metal electrode.
The concrete example of vinyl pyrrolotriazine derivatives (E) can enumerate 2,4-two amidos-6-vinyl-5-triazine, 2,4-two amidos-6-methacryloxy-S-triazine and isocyanuric acid affixture thereof.These a little vinyl triaizine compounds or derivatives thereofs (E) are for use separately or with the mixture pattern more than two kinds.
The use level of these a little vinyl pyrrolotriazine derivatives (E), with respect to aforementioned curable with actinic energy ray resin (A) 100 weight parts, with 0.5～20 mass parts serves as suitable, be preferably 0.5～5 mass parts, the use level of vinyl pyrrolotriazine derivatives (E) is less than 0.5 mass parts, the anti-migration effect of then difficult fully raising, on the other hand, even a large amount of the cooperation surpasses 20 mass parts, also present state of saturation because of the effect of being expected, so for uneconomic, probably remaining behind the photo-hardening of composition on the contrary again, make the characteristic of hardening thing reduce.
Resin composition curable with actinic energy ray of the present invention is visual required, contains silane coupling agent (F).The purpose that adds silane coupling agent (F) is for improving and base material, the adhesivity of special and glass.Silane coupling agent (F) is not particularly limited if the adhesivity that can improve with base material gets final product.
The concrete example of silane coupling agent (F) can be enumerated TSL-8310, TSL-8311, TSL-8320, TSL-8395, TSL-8325, TSL-8331, TSL-8340, TSL-8345, TSL-8380, TSL-8350, TSL-8355, TSL-8370, and the TLS-8375 etc. of A-143, A-150, A-151, A-171, A-172, A-174, A-186, A-187, A-189, A-1100, A-1120 and A-1160, the Silicone of Toshiba (strain) system of Japanese Unica (strain) system.
In the resin composition curable with actinic energy ray of the present invention of as above explanation, can be in suitably cooperating additive beyond the composition as the aforementioned.For example, by the viewpoint of attenuating sclerosis shrinking percentage, attenuating coefficient of thermal expansion, raising dimensional stability, raising spring rate, adjustment viscosity, the thermal conductivity that improves, raising intensity, raising a piece of wood serving as a brake to halt a carriage etc., then can cooperate the weighting agent of organic or inorganic.This type of weighting agent can use polymkeric substance, pottery, metal, metal oxide, metal-salt etc., can be particle shape, fibrous etc. about shape, is not particularly limited.Still, when cooperating above-mentioned polymkeric substance, can be not for the weighting agent pattern be with polymer blend, polymer alloy pattern, dissolving in resin composition curable with actinic energy ray, half dissolving or differential loose and also can.
Again, resin composition curable with actinic energy ray of the present invention also can cooperate tinting material such as the pigment, dyestuff of organic or inorganic as additive, and in the purposes of coating, printing ink etc.
More and, resin composition curable with actinic energy ray of the present invention can suitably cooperate the additive as other such as flexibility imparting agent, softening agent, fire retardant, preserving stabilizer, antioxidant, UV light absorber, thixotroping imparting agent, dispersion stabilizer, mobility donor.
Resin composition curable with actinic energy ray of the present invention can be coated with on base material according to known customary way, and to formed coating irradiation actinic energy ray, and the compound that order has an ethylenic unsaturated link(age) carries out the optical free radical polymerization and hardens.
The irradiation light of actinic energy ray serves as suitable with Cooper-Hewitt lamp, middle medium pressure mercury lamp, high pressure mercury vapour lamp, extra-high-pressure mercury vapour lamp, gas lamp or metal halid lamp etc.Other, laser beam, electron rays etc. also can utilize as exposure activation evergy line.
Still, resin combination of the present invention can use aqueous, pasty state and the arbitrary kenel of film like.During with aqueous use,, can use the known viscosity modifier of suitable organic solvent etc. to be adjusted viscosity in order to adjust the viscosity of resin combination.
Below, embodiment is shown and comparative example specifies the present invention, but the present invention is defined in following embodiment.Still, following embodiment and the used activation evergy line hardening resin (A-1)～(A-3) of comparative example are to have following chemical constitution.
Embodiment 1～17
Each composition shown in table 1 and the table 2 with designated ratio, is mixed with whipping appts, modulate the resin composition curable with actinic energy ray that various one-tenth are grouped into.
Comparative example 1～6
Each composition shown in the table 3 with designated ratio, is mixed the curable with actinic energy ray resin composition that the various one-tenth of week system are grouped into whipping appts.
Table 1
| Form (mass parts) and characteristic | Embodiment | |||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | ||||
| A | A′ | A-1 | 100 | - | - | 95 | 50 | 60 | 100 | 100 | 100 | |
| A-2 | - | 100 | - | - | - | - | - | - | - | |||
| A-3 | - | - | 100 | - | - | - | - | - | - | |||
| A″ | PEA *1)L-4 *2) | - - | - - | - - | - - | 50 - | - 40 | - - | - - | - - | ||
| A | TMPTA *3) | - | - | - | 5 | - | - | - | - | - | ||
| B | IRUGACURE 184 *4) | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | ||
| C | YX-4000 *5) | - | - | - | - | - | - | 15 | - | - | ||
| EOCN 1020 *6) | - | - | - | - | - | - | - | 15 | - | |||
| Ceroxide 3150 *7) | - | - | - | - | - | - | - | - | 15 | |||
| D | Viron 200 *8) | - | - | - | - | - | - | - | - | - | ||
| F | A-174 *9) | - | - | - | - | - | - | - | - | - | ||
| Water-intake rate (%) | 0.31 | 0.30 | 0.28 | 0.25 | 0.23 | 0.22 | 0.33 | 0.29 | 0.27 | |||
| Resistance to migration (hr) | 1000 | 1000 | 1000 | 1000 | 1000 | 1000 | 1000 | 1000 | 1000 | |||
| Adhesivity | Glass PET | ○ ○ | ○ ○ | ○ ○ | ○ ○ | ○ ○ | ○ ○ | ○ ◎ | ○ ◎ | ○ ◎ | ||
| Warpage | ○ | ○ | ○ | ○ | ○ | ○ | ◎ | ◎ | ◎ | |||
| Restorative (branch) | 15 | 15 | 15 | 15 | 15 | 15 | 10 | 10 | 10 | |||
| Appendix | *1) vinylformic acid phenoxy ethyl *2) 2-phenylphenol TMOS affixture mono acrylic ester (Xin Zhong village chemistry (strain) system) *3) trimethyol propane triacrylate *4) Coba Specialty Chemicals (strain) system optical free radical polymerization starter: 1-hydroxyl-cyclohexyl-phenyl ketone *5) the solid type Resins, epoxy of oiling Shell Epoxy (strain) system xenol type *6) polyglycidyl ether of Japanese chemical drug (strain) system neighbour-cresylol phenolic varnish *7) Diacel chemical industry (strain) system 2,1 of 2-(methylol)-1-butanols, 2-epoxy-4 (2-oxane base) pimelinketone affixture *8) Japan twist flax fibers and weave (strain) system saturated polyester resin *9) Japanese Unica (strain) system silane coupling agent: γ-methacrylic oxygen propyl trimethoxy silicane is formed (mass parts) and characteristic | |||||||||||
Table 2
| Form (mass parts) and characteristic | Embodiment | |||||||||
| 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | |||
| A | A′ | A-1 A-2 A-3 | 100 - - | 100 - - | 100 - - | 100 - - | 100 - - | 100 - - | 100 - - | 100 - - |
| A″ | PEA *1)L-4 *2) | - - | - - | - - | - - | - - | - - | - - | - - | |
| A | TMPTA *3) | - | - | - | - | - | - | - | - | |
| B | IRUGACURE 184 *4) | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | |
| C | YX-4000 *5) | - | - | - | - | - | - | - | - | |
| EOCN 1020 *6) | - | - | 15 | - | - | 15 | 70 | - | ||
| Ceroxide 3150 *7) | - | - | - | 15 | - | - | - | - | ||
| D | Viron 200 *8) | 10 | - | 10 | - | 10 | 10 | - | 65 | |
| F | A-174 *9) | - | 1 | - | 1 | 1 | 1 | - | - | |
| Water-intake rate (%) | 0.30 | 0.32 | 0.28 | 0.26 | 0.30 | 0.2 | 0.36 | 0.38 | ||
| Resistance to migration (hr) | 1000 | 1000 | 1200 | 1500 | 1000 | 1200 | 800 | 800 | ||
| Adhesivity | Glass PET | ○ ◎ | ◎ ○ | ○ ◎ | ◎ ◎ | ◎ ◎ | ◎ ◎ | △ △ | △ △ | |
| Warpage | ◎ | ○ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | ||
| Restorative (branch) | 5 | 15 | 5 | 10 | 5 | 5 | 10 | 5 | ||
| Appendix | *1) vinylformic acid phenoxy ethyl *2) 2-phenylphenol TMOS affixture mono acrylic ester (Xin Zhong village chemistry (strain) system) *3) trimethyol propane triacrylate *4) Coba Specialty Chemicals (strain) system optical free radical polymerization starter: 1-hydroxyl-cyclohexyl-phenyl ketone *5) the solid type Resins, epoxy of oiling Shell Epoxy (strain) system xenol type *6) polyglycidyl ether of Japanese chemical drug (strain) system neighbour-cresylol phenolic varnish *7) Diacel chemical industry (strain) system 2,1 of 2-(methylol)-1-butanols, 2-epoxy-4 (2-oxane base) pimelinketone affixture *8) Japan twist flax fibers and weave (strain) system saturated polyester resin *9) Japanese Unica (strain) system silane coupling agent: γ-methacrylic oxygen propyl trimethoxy silicane | |||||||||
Table 3
| Form (mass parts) and characteristic | Comparative example | ||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | ||||
| A | A′ | A-1 A-2 A-3 | - - - | - - - | - - - | - 40 - | 40 - - | - - 40 | |
| A″ | PEA *1)L-4 *2) | - - | 10 - | - 100 | 60 - | - - | - 60 | ||
| A | TMPTA *3) | 100 | - | - | - | 60 | - | ||
| B | IRUGAGURE 184 *4) | 3 | 3 | 3 | 3 | 3 | 3 | ||
| C | YX-4000 *5) | - | - | - | - | - | - | ||
| EOCN 1020 *6) | - | - | - | - | - | - | |||
| Ceroxide 3150 *7) | - | - | - | - | - | - | |||
| D | Viron 200 *8) | - | - | - | - | - | - | ||
| F | A-174 *9) | - | - | - | - | - | - | ||
| Water-intake rate (%) | 0.21 | 0.32 | 0.26 | 0.27 | 0.26 | 0.28 | |||
| Resistance to migration (hr) | - | 800 | 500 | 800 | - | 600 | |||
| Adhesivity | Glass PET | × × | △ × | △ × | △ × | × × | △ × | ||
| Warpage | × | ○ | × | ○ | × | × | |||
| Restorative (branch) | - | 15 | 15 | 15 | - | 15 | |||
| Appendix | *)) the vinylformic acid phenoxy ethyl *2) 2-phenylphenol TMOS affixture mono acrylic ester (Xin Zhong village chemistry (strain) system) *3) trimethyol propane triacrylate *4) Coba Specialty Chemicals (strain) system optical free radical polymerization starter: 1-hydroxyl-cyclohexyl-phenyl ketone *5) the solid type Resins, epoxy of oiling Shell Epoxy (strain) system xenol type *6) polyglycidyl ether of Japanese chemical drug (strain) system neighbour-cresylol phenolic varnish *7) Diacel chemical industry (strain) system 2,1 of 2-(methylol)-1-butanols, 2-epoxy-4 (2-oxane base) pimelinketone affixture *8) Japan twist flax fibers and weave (strain) system saturated polyester resin *9) Japanese Unica (strain) system silane coupling agent: γ-methacrylic oxygen propyl trimethoxy silicane | ||||||||
For synthetic each resin combination like this, estimate water-intake rate, resistance to migration, adhesivity, warpage, reach reparation property.Evaluation method is as follows.Still, each resin combination is for using UV irradiation equipment (Oak makes institute's (strain) metal halid lamp), with irradiation dose 2000mJ/cm
2Hardened.
(1) water-intake rate:
With each resin combination test portion, flow into the figure teflon container made of diameter 150mm, degree of depth 2mm respectively after, sclerosis makes to measure and uses pellet.Measure this and measure with after the quality (a) of pellet, dipping is 24 hours in 20 ℃ ion exchanged water, measures the quality (b) after flooding.The water-intake rate of this moment is with { ((b)-(a))/(a) } * 100 values of being obtained (%).
(2) resistance to migration test:
In using on Corming 1737 sheet glass (thickness 0.7mm) of substrate, make comb-type electrode (L/S=100/100 μ m) for using with commercially available calcinated type silver paste as test.
This test is used on the comb-type electrode of substrate, after each resin combination is coated with thickness 2mm, places 1500 hours in the constant temperature and humidity cabinet of 85 ℃ of temperature, relative humidity 85%.The impressed voltage of the comb-type electrode of this moment is DC 100V, and measures the insulating resistance value in the constant temperature and humidity cabinet at any time.
Being evaluated as of resistance to migration shows 1.0 * 10 with the insulating resistance value in the aforementioned mensuration
5The moment of the following numerical value of Ω is considered as short circuit, and evaluation test begins the time till the short circuit.
(3) adhesiveness test (to glass substrate)
In above-mentioned resistance to migration test (2), with 85 ℃ of Visual Confirmation temperature, relative humidity 85%, the glass of DC 100V after following 1500 hours and the adhesivity of silver electrode and slurry.Be evaluated as follows.
◎:, also do not examine and see and float and peel off even more than 1500 hours.
On electrode, examine after zero: 1500 hour and see and somely float.
△: peeled off by on glass with interior in 1500 hours.
*: peel off immediately after the sclerosis.
(4) adhesiveness test (to the PET film)
, use to be coated with device and to paint thickness 35 μ m with each resin combination for the thick PET film of 100 μ m, after the sclerosis, the film that will cut out 2cm * 5cm is as test film.It is dropped into 40 ℃ of temperature, in the constant temperature and humidity cabinet of relative humidity 95%, estimate the state of peeling off.
◎:, also do not float and peel off even more than 1000 hours.
Zero: do not float till 1000 hours and peel off.
△: peeled off in 1000 hours.
*: peel off immediately after the sclerosis or when test film is made, peel off.
(5) warpage
Measure the amount of warpage of the test film of aforementioned adhesiveness test (4) made
The ◎ amount of warpage is below the 1mm, hardly warpage.
Zero: amount of warpage is below the 2mm.
*: amount of warpage is more than the 2mm.
(6) restorative:
Each resin combination is coated with on glass substrate and the hardened sample in right amount, in methyl ethyl ketone, floods, and measure time till beautiful peeling off.The result of aforementioned each test is shown in table 1～table 3 respectively.
As illustrated in the result shown in table 1 and table 2; if it is dead drunk through the simple function vinylformic acid that has hydroxyl and aromatic ring owing to use in the resin combination of optical free radical polymerizability according to the present invention; then the silver electrode for finer pitch also shows sufficient electrode protection effect, and can realize for glass and film substrate etc. adhesivity, and lower the warpage of base material.
Again, learn 1. via add Resins, epoxy then can obtain higher prevent migration effect, 2. via add Resins, epoxy, saturated polyester resin, silane coupling agent then can improve more adhesivity for clung body, 3. via add Resins, epoxy, saturated polyester resin then can be realized lowering more warpage, 4. then can improve restorative via adding saturated polyester resin.
Embodiment 18～24, comparative example 7,8
Each composition shown in the table 4 with designated ratio, is mixed the resin composition curable with actinic energy ray that the various one-tenth of adjustment are grouped into whipping appts.
For synthetic each resin combination of processing like this, the same method of former commentary valency method is estimated water-intake rate, resistance to migration, adhesivity (to glass substrate).Still, each resin combination is for using UV irradiation equipment (Oak makes institute's (strain) metal halid lamp), with irradiation dose 2000mJ/cm
2Harden.
The test-results merging is shown in table 4.
Table 4
| Form (mass parts) and characteristic | Embodiment | Comparative example | |||||||||
| 18 | 19 | 20 | 21 | 22 | 23 | 24 | 7 | 8 | |||
| A | A″ | PEA *1)EOA *2) | 100 - | 100 - | 100 - | - 100 | - 100 | 100 - | 100 - | - - | 100 - |
| A | TMPTA *3) | - | - | - | - | - | - | - | - | - | |
| B | IRUGACURE 184 *4) | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | - | |
| SP150 *5) | - | - | - | - | - | - | - | - | 2 | ||
| C | YX-4000 *6) | 30 | - | - | 30 | - | - | - | - | - | |
| EOCN 1020 *7) | - | 30 | - | - | - | - | - | - | - | ||
| Ceroxide 3150 *8) | - | - | 30 | - | 30 | 30 | 30 | 30 | 30 | ||
| D | Viron 200 *9) | - | - | - | - | - | 15 | - | - | - | |
| E | V.T *10) | - | - | - | 1 | 1 | 1 | 1 | - | - | |
| F | A-174 *11) | - | - | - | 2 | - | - | ||||
| Water-intake rate (%) | 0.30 | 0.27 | 0.28 | 0.30 | 0.27 | 0.29 | 0.29 | 0.29 | 0.27 | ||
| Resistance to migration (hr) | 1000 | 1000 | 1200 | 1200 | More than 1500 | More than 1500 | More than 1500 | n.m. | 150 | ||
| Adhesivity (glass) | ○ | ○ | ○ | ○ | ○ | ◎ | ◎ | × | ○ | ||
| Appendix | *1) vinylformic acid phenoxy ethyl *2) to cumyl phenol EO modification acrylate *3) trimethyol propane triacrylate *4) (strain) rising sun electrification system light cationic polymerisation catalyst *5) Coba Specialty Chemicals (strain) system optical free radical polymerization starter: 1-hydroxyl-cyclohexyl-phenyl ketone *6) the solid type Resins, epoxy of oiling Shell Epoxy (strain) system xenol type *7) polyglycidyl ether of Japanese chemical drug (strain) system neighbour-cresylol phenolic varnish *8) Diacel chemical industry (strain) system 2,1 of 2-(methylol)-1-butanols, 2-epoxy-4 (2-oxane base) pimelinketone affixture *9) Japan twist flax fibers and weave (strain) system saturated polyester resin *10) four countries change into (strain) system 2,4-two amidos-6-vinyl-s-triazine *11) Japanese Unica (strain) system silane coupling agent: γ-methacrylic oxygen propyl trimethoxy silicane n.m is because of adhering to bad can not the test | ||||||||||
Result as shown in table 4 is illustrated, if according to the present invention, adds Resins, epoxy as hydrophobic adhesive in the resin combination of optical free radical polymerizability, also can obtain sufficient electrode protection effect for the silver electrode of finer pitch.
Again, learning 1. also can be via using the few constructor of ion residue in the Resins, epoxy, obtain and higher prevent migration effect, 2. with the radical polymerization composition of crosslinked composition as sense radix 1, then can prevent adhesivity reduce, 3. via adding saturated polyester resin, then can improve adhesivity more for clung body.
Practicality on the industry
As mentioned above, if according to the present invention, then can keep the advantage that the resin combination of UV cured class has and solve its shortcoming, provide hydrophobicity and for also good resin composition curable with actinic energy ray of the adhesiveness of base material, resistance to migration.
Therefore, resin composition curable with actinic energy ray of the present invention, workability than the resin combination of previous thermmohardening class and room temperature vulcanizing class is good, and is extremely useful in as the adhesive and the coating agent that prevent the actinic energy ray constrictive type that migration effect is good for the adhesiveness of various clung bodies, various electrodes.
Claims (8)
1, a kind of resin composition curable with actinic energy ray, it contains (A) curable with actinic energy ray resin and reaches (B) optical free radical polymerization starter, it is characterized in that, the 50 quality % of above-mentioned (A) composition above for (A ') intramolecularly have a free-radical polymerised ethylenic unsaturated double-bond, with the curable with actinic energy ray resin of an above hydroxyl and aromatic ring.
2, composition as claimed in claim 1, wherein said curable with actinic energy ray resin (A ') are acrylic compound or the methacrylate compound shown in following general expression (1) or (2),
In the formula, X represents that hydrogen atom or methyl, Y represent-C (CH
3)
2-,-SO
2-,-CH
2-or direct key, R
1And R
2The expression carbon number is the alkyl of 1～12 straight chain shape, ring-type or branch-like, and m represents 0～4 integer, and n represents 0～5 integer.
3, composition as claimed in claim 1, it also contains (C) Resins, epoxy.
4, a kind of resin composition curable with actinic energy ray, it contains (A) curable with actinic energy ray resin and reaches (B) optical free radical polymerization starter, it is characterized in that, above-mentioned (A) composition is for having the curable with actinic energy ray resin (A "), and also contain (C) Resins, epoxy of an ethylenic unsaturated double-bond in an intramolecularly.
5, as each described composition of claim 1 to 4, it is characterized in that, also contain (D) saturated polyester resin, (E) vinyl pyrrolotriazine derivatives and (F) silane coupling agent form select in the group at least a.
6, as claim 3 or 4 described compositions, wherein said Resins, epoxy (C) is softening temperature more than 40 ℃, at room temperature is half type or solid type state admittedly.
7, composition as claimed in claim 6, the epoxy compounds of wherein said Resins, epoxy (C) in a molecule, having the section construction shown in the following general expression (3), or has an alicyclic epoxy compound of the arbitrary structure shown in following formula (4) or (5)
In the formula, X represents epoxy group(ing) and/or vinyl, and p represents 1～100 integer, but contains at least one epoxy group(ing) in the molecule.
8, composition as claimed in claim 5, wherein said vinyl pyrrolotriazine derivatives (E) is from 2,4-two amidos-6-vinyl-S-triazine, 2,4-two amidos-6-methacryloxy-S-triazine, and their isocyanuric acid affixture among select at least a.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP364277/1999 | 1999-12-22 | ||
| JP36427799A JP4497610B2 (en) | 1999-12-22 | 1999-12-22 | Photocurable resin composition |
| JP54077/2000 | 2000-02-29 | ||
| JP2000054077A JP4713704B2 (en) | 2000-02-29 | 2000-02-29 | Active energy ray-curable resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1413225A CN1413225A (en) | 2003-04-23 |
| CN1196748C true CN1196748C (en) | 2005-04-13 |
Family
ID=26581557
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB008176795A Expired - Fee Related CN1196748C (en) | 1999-12-22 | 2000-12-13 | Resin composition curable with actinic energy ray |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR100696412B1 (en) |
| CN (1) | CN1196748C (en) |
| TW (1) | TW530079B (en) |
| WO (1) | WO2001046288A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104918965A (en) * | 2013-01-15 | 2015-09-16 | 日产化学工业株式会社 | Cured-film-forming resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102205627B1 (en) * | 2016-08-30 | 2021-01-21 | 닛산 가가쿠 가부시키가이샤 | Photosensitive adhesive composition |
| CN109321145B (en) * | 2017-07-31 | 2022-01-04 | 东洋油墨Sc控股株式会社 | Active energy ray-polymerizable adhesive for optical use and optical laminate |
| DE102018121067A1 (en) | 2018-08-29 | 2020-03-05 | Delo Industrie Klebstoffe Gmbh & Co. Kgaa | Curable two-component compound |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6049024A (en) * | 1983-08-29 | 1985-03-18 | Shikoku Chem Corp | Curing of epoxy resin |
| JPS6084323A (en) * | 1983-10-13 | 1985-05-13 | Shikoku Chem Corp | Curing of epoxy resin |
| JPH05186755A (en) * | 1992-01-08 | 1993-07-27 | Yokohama Rubber Co Ltd:The | Photocurable adhesive composition |
| JP3190251B2 (en) | 1995-06-06 | 2001-07-23 | 太陽インキ製造株式会社 | Photocurable and thermosetting resin composition for alkali-developed flexible printed wiring boards |
| US5707780A (en) | 1995-06-07 | 1998-01-13 | E. I. Du Pont De Nemours And Company | Photohardenable epoxy composition |
-
2000
- 2000-12-13 WO PCT/JP2000/008812 patent/WO2001046288A1/en active Application Filing
- 2000-12-13 CN CNB008176795A patent/CN1196748C/en not_active Expired - Fee Related
- 2000-12-13 KR KR1020027008125A patent/KR100696412B1/en not_active IP Right Cessation
- 2000-12-19 TW TW089127271A patent/TW530079B/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104918965A (en) * | 2013-01-15 | 2015-09-16 | 日产化学工业株式会社 | Cured-film-forming resin composition |
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| Publication number | Publication date |
|---|---|
| KR20020064958A (en) | 2002-08-10 |
| TW530079B (en) | 2003-05-01 |
| KR100696412B1 (en) | 2007-03-20 |
| CN1413225A (en) | 2003-04-23 |
| WO2001046288A1 (en) | 2001-06-28 |
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