CN101007899B - Resin composition for screen printing - Google Patents
Resin composition for screen printing Download PDFInfo
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- CN101007899B CN101007899B CN2007100044090A CN200710004409A CN101007899B CN 101007899 B CN101007899 B CN 101007899B CN 2007100044090 A CN2007100044090 A CN 2007100044090A CN 200710004409 A CN200710004409 A CN 200710004409A CN 101007899 B CN101007899 B CN 101007899B
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- 0 CCC(C)(C(C)*NC(*(C(NC(C)C)=O)C(O)=O)=O)NC(*(*)(C(*[Si](*)(O)OC(C)[Si](*)(O*)O*)=O)C(N*C(C)C)=O)=O Chemical compound CCC(C)(C(C)*NC(*(C(NC(C)C)=O)C(O)=O)=O)NC(*(*)(C(*[Si](*)(O)OC(C)[Si](*)(O*)O*)=O)C(N*C(C)C)=O)=O 0.000 description 1
Classifications
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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
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
Abstract
A resin combination for screen printing is characterized by the following necessary components: (A) 100wt. parts of a polyamic acid resin having alkoxysilyl group which is represented by the chemical formula (1) wherein X is 4-valent organic group, Y is 2-valent organic group, R<4> is alkyl group having 1 to 3 carbon atoms, R<5> is alkyl or alkoxy group having 1 to 3 carbon atoms, a is an integer of 0 to 4, p is an integer of 1 to 300, q is an integer of 1 to 300 and r is an integer of 1 to 100; (B) 5-350wt. parts of spherical metal oxide fine particles with average particle size of 0.05 to 10 microns; and (C) an effective amount of organic solvent for dissolving the component(A). The invention provides the screen printing resin composition which has good screen printability, does not cause mesh fill-in, bleeding and deterioration of the defoamability, can obtain a uniform film thickness, and excels in continuous moldability.
Description
Technical field
The present invention relates to resin composition for screen printing.
Background technology
Polyimide based resin is coated on semiconductor surface as the thermotolerance material; Play the effect of protection insulating film; As on these protective membranes, forming method of patterning, known with the method for carrying out patterning after the spin coating of varnish state, or adopt silk screen printing in coating, to carry out the method etc. of patterning.The former method can be enumerated: with varnish such as polyamic acid be spun on the wafer form protective membrane after; Range upon range of above that photo-resist; Adopt ultraviolet photoetching and video picture that sensitization part or non-sensitization are partly dissolved, also with the protective membrane dissolving of lower floor, form method of patterning simultaneously; Perhaps make polyimide based resin itself have the photoresist of ultraviolet sensing part, adopt ultraviolet photoetching and video picture to make sensitization part or the partly soluble method of non-sensitization etc.Owing under any situation, all comprise ultraviolet exposure, it is miscellaneous that operation becomes, therefore from shortening the operation aspect, the preferred latter's silk screen print method.But existing silk screen printing may not necessarily obtain satisfied result with varnish at aspects such as resolution, film flatness.As one of its reason, can enumerate in order to keep shape, in varnish, add inorganic filler and give the mesh that thixotropy produces residual, spread and sink in ooze, deaeration property deterioration etc.In addition, when particularly forming film, also exist the volatilization of solvent fast, lack the problem of continuously shaped property.
On the other hand; Generally carry out semiconductor elements such as transistor, diode, IC, LSI being encapsulated with resin materials such as epoxy resin; If but semiconductor element is encapsulated the water of invading through this resin material, the deterioration that ionic impurity often causes semiconductor element with these resin materials.Therefore the method that encapsulates with resin material, as its countermeasure, has been proposed with behind the excellent polyimide based resin lining protection semiconductor element of thermotolerance, electrical characteristic, mechanical characteristics.Particularly recently, pack miniaturized day by day, slimming, simultaneously the surface mounting mode becomes main flow aspect the method for substrate being installed to, and adopts existing composition epoxy resin can not keep enough safeties.In addition, because scolder unleaded in recent years, scolder flows (reflow) temperature again and has brought up to 260 ℃, if after the packing moisture absorption, weld, occur in packing go up produce the rimose problem and cracking do not produce before the lowered rough sledding of wet fastness.In these purposes, also hope the excellent in adhesion of exploitation and metal, plastic material, high heat-resisting and protective membrane that can silk screen printing.But the existing polyimide resin is not enough for the bonding force of Copper Foil, and if surpass the second-order transition temperature (Tg) of cured film, produce the problem that the thermotolerance of resin extremely descends.
Summary of the invention
The present invention In view of the foregoing proposes, and its purpose is to provide silk screen printing property good, can not cause that mesh is residual, spread and sink in ooze, the deterioration of deaeration property etc., obtain the thickness of homogeneous and the also excellent resin composition for screen printing of continuously shaped property.
In addition; Another object of the present invention is to provide excellent in adhesion with base material and plastic material; Eliminate chip cracks, the thermal destruction of the thermal stresses generation of package semiconductor effectively; Give the cured article of excellent heat resistance, the effective resin composition for screen printing of protective membrane material when semi-conductor being encapsulated as use semiconductor-sealing-purpose epoxy resin formed material.
The present inventor has carried out conscientiously research to achieve these goals; It is that spherical metal oxide microparticle, (C) organic solvent of 0.05～10 μ m serve as the resin composition for screen printing of necessary composition that the result finds with the polyamic acid resin that contains alkoxysilyl shown in (A) formula (1), (B) median size; The resin composition for screen printing that particularly contains the epoxy resin that has at least 2 epoxy group(ing) in (A), (B), (C) composition and (D) 1 molecule, (E) curing catalyst is effective, thereby has accomplished the present invention.
That is, the present invention provides following resin composition for screen printing.
[1] resin composition for screen printing is characterized in that with the following compositions being necessary composition:
(A) polyamic acid resin that contains alkoxysilyl shown in the formula (1): 100 mass parts,
(in the formula, X is the organic group of 4 valencys, and Y is the organic group of divalent, and Z is the group that following formula is represented,
R
4Be the alkyl of carbonatoms 1～3, R
5Be the alkyl or the alkoxyl group of carbonatoms 1～3, a is 0～4 integer, and p is 1～300 integer, and q is 1～300 integer, and r is 1～100 integer),
(B) median size is the spherical metal oxide microparticle of 0.05～10 μ m: 5～350 mass parts,
(C) organic solvent: the dissolving resin significant quantity of above-mentioned (A) composition.
[2] resin composition for screen printing is characterized in that containing:
(A) polyamic acid resin that contains alkoxysilyl shown in the above-mentioned general formula (1),
(B) median size be 0.05～10 μ m spherical metal oxide microparticle,
(C) organic solvent,
(D) have in 1 molecule at least 2 epoxy group(ing) epoxy resin,
(E) curing catalyst.
[3] above-mentioned [2] described resin composition for screen printing, the epoxy resin that it is characterized in that above-mentioned (D) composition is the epoxy resin shown in the formula (2),
(in the formula, G is a glycidyl, and R representes Wasserstoffatoms or monovalence alkyl, but all at least 1 among the R is the monovalence alkyl, and n is the integer more than 0 or 1).
[4] each described resin composition for screen printing in above-mentioned [1]～[3] is characterized in that the surface of the metal oxide microparticle of above-mentioned (B) composition is handled with silazane class and/or silane coupling agent.
[5] above-mentioned [4] described resin composition for screen printing is characterized in that above-mentioned silazane class is a hexamethyldisilazane.
[6] above-mentioned [4] described resin composition for screen printing is characterized in that above-mentioned silane coupling agent is more than a kind or 2 kinds of compound with the reactive group that is selected from amino, glycidyl, sulfydryl, urea groups, hydroxyl, alkoxyl group, sulfydryl.
[7] each described resin composition for screen printing in above-mentioned [1]～[6] is characterized in that above-mentioned (B) composition contains the spherical shape silicon-dioxide of median size 0.05～10 μ m of 60～100 quality %.
[8] each described resin composition for screen printing in above-mentioned [1]～[7] is characterized in that containing the organic solvent of boiling point more than 200 ℃ as above-mentioned (C) composition.
According to the present invention, can provide silk screen printing property good, can not cause that mesh is residual, spread and sink in ooze, the deterioration of deaeration property etc., obtain the thickness of homogeneous and the also excellent resin composition for screen printing of continuously shaped property.
In addition; Excellent in adhesion with base material and plastic material can be provided; Eliminate chip cracks, the thermal destruction of the thermal stresses generation of package semiconductor effectively; Give the cured article of excellent heat resistance, the effective resin composition for screen printing of protective membrane material when semi-conductor being encapsulated as use semiconductor-sealing-purpose epoxy resin formed material.
Embodiment
Below the present invention is carried out more detailed explanation.
(A) of the present invention composition is the polyamic acid resin that contains alkoxysilyl shown in the formula (1).
(in the formula, X is the organic group of 4 valencys, and Y is the organic group of divalent, and Z is the group that following formula is represented,
R
4Be the alkyl of carbonatoms 1～3, R
5Be the alkyl or the alkoxyl group of carbonatoms 1～3, a is 0～4 integer, and p is 1～300 integer, and q is 1～300 integer, and r is 1～100 integer).
This polyamic acid resin that contains alkoxysilyl makes through making polyamic acid resin and the alkoxysilane compound containing trialkylsilyl group in molecular structure reaction that contains epoxy group(ing).
The polyamic acid resin that uses among the present invention through according to ordinary method, with roughly wait the mole, the diamine reactant shown in tetracarboxylic dianhydride shown in the following structural formula (4) and the formula (5) is made.
(wherein, X representes the meaning same as described above).
H
2N-Y-NH
2 (5)
(wherein, Y representes the meaning same as described above).
Wherein, if the tetracarboxylic dianhydride shown in the concrete above-mentioned formula of illustration (4) for the compound shown in following formula (6)～(19) etc., but is not limited to these.Moreover, the tetracarboxylic dianhydride of above-mentioned formula (4) can use as required in the following compound more than a kind or 2 kinds.
As the diamines shown in the above-mentioned formula (5), can enumerate Ursol D, mphenylenediamine, 4,4 '-diaminodiphenyl-methane, 4; 4 '-diamino-diphenyl ether, 2,2 '-two (4-aminophenyl) propane, 4,4 '-diamino diphenyl sulfone, 4; 4 '-diamino-diphenyl thioether, 1, two (3-amino-benzene oxygen) benzene, 1 of 4-, two (4-amino-benzene oxygen) benzene, 1 of 4-; Two (p-aminophenyl alkylsulfonyl) benzene, 1 of 4-, two (the m-aminophenyl base alkylsulfonyl) benzene, 1 of 4-, two (p-aminophenyl thioether) benzene, 1 of 4-; Two (the m-aminophenyl base thioether) benzene, 2 of 4-, two [4-(4-amino-benzene oxygen) phenyl] propane, 2 of 2-, two [3-methyl-4-(4-amino-benzene oxygen) phenyl] propane, 2 of 2-; Two [3-chloro-4-(4-amino-benzene oxygen) phenyl] propane, 1 of 2-, two [4-(4-amino-benzene oxygen) phenyl] ethane, 1 of 1-, two [3-methyl-4-(4-amino-benzene oxygen) phenyl] ethane, 1 of 1-; Two [3-chloro-4-(4-amino-benzene oxygen) phenyl] ethane, 1 of 1-; Two [3,5-dimethyl--4-(4-amino-benzene oxygen) phenyl] ethane of 1-, two [4-(4-amino-benzene oxygen) phenyl] methane, two [3-methyl-4-(4-amino-benzene oxygen) phenyl] methane, two [3-chloro-4-(4-amino-benzene oxygen) phenyl] methane, two [3,5-dimethyl--4-(4-amino-benzene oxygen) phenyl] methane, two [4-(4-amino-benzene oxygen) phenyl] sulfone, 2; Two [4-(4-amino-benzene oxygen) phenyl] UN 2424s etc. of 2-contain the diamines of aromatic nucleus etc.; Preferred Ursol D, mphenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ether, 1; Two (3-amino-benzene oxygen) benzene, 1 of 4-; Two (4-amino-benzene oxygen) benzene, 2 of 4-, two [4-(4-amino-benzene oxygen) phenyl] propane, 2 of 2-, two [3-methyl-4-(4-amino-benzene oxygen) phenyl] propane of 2-etc.
In addition, in order to give cementability, flexibility, can use the siloxane diamine class as diamines to base material.
Specifically can enumerate the compound shown in following formula (20)～(28), be not limited to these certainly.In addition, these diamine compounds also can use a kind separately as required, also can combination more than 2 kinds be used.
If concrete example is enumerated in the formation reaction of polyamic acid resin, then under inert atmosphere, above-mentioned initial feed is dissolved in the solvent, reacting the synthesizing polyamides acid resin below 80 ℃, under preferred 0～40 ℃ usually.The organic solvent that uses in the above-mentioned reaction so long as be inert to the polyamic acid that makes, then can not dissolve above-mentioned initial feed also passable fully.Can enumerate for example THF, 1; 4-diox, ketopentamethylene, pimelinketone, gamma-butyrolactone, N-Methyl pyrrolidone, N; N-N,N-DIMETHYLACETAMIDE, N; Dinethylformamide and DMSO 99.8MIN., preferred aprotic polar solvent, preferred especially N-Methyl pyrrolidone, pimelinketone and gamma-butyrolactone.These solvents can use in 1 or combination use more than 2 kinds.
Moreover, in order to regulate the molecular weight of resin, also can add dicarboxylic anhydride and/or monoamines such as aniline, TERTIARY BUTYL AMINE such as maleic anhydride, Tetra hydro Phthalic anhydride.But the normally per 100 mass parts dicarboxylic acid dianhydride of the addition of dicarboxylic anhydride are 0～2 mass parts, and the normally per 100 mass parts diamines of the addition of monoamine are 0～2 mass parts.
The molecular weight of polyamic acid resin is as the weight-average molecular weight that adopts polystyrene conversion among the GPC, preferred about 3000～100000.If above-mentioned molecular weight less than 3000, the obdurability of cured film, flexibility descend, if surpass 100000, owing to be HV, therefore operability can descend sometimes.
Carboxyl through epoxy group(ing) that makes the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains epoxy group(ing) shown in the following formula (29) and the polyamic acid resin that obtains like this carries out addition reaction, can access the polyamic acid resin that contains alkoxysilyl shown in the following formula (1).
(in the formula, X is the organic group of 4 valencys, and Y is the organic group of divalent, and Z is the group that following formula is represented,
R
4Be the alkyl of carbonatoms 1～3, R
5Be the alkyl or the alkoxyl group of carbonatoms 1～3, a is 0～4 integer, and p is 1～300 integer, and q is 1～300 integer, and r is 1～100 integer).
Moreover, in above-mentioned formula, X, Y, Z and R
1, R
2, a, p, q, r as stated, p, q be 1～300 integer preferably independently of one another, special preferably 2～200 integer, r is 1～100 integer preferably, special preferably 2～80 integer, a preferably 0,1,2 or 3.
In addition, the reaction of above-mentioned carboxyl and epoxy group(ing) can be carried out according to ordinary method, and can make temperature of reaction is 30～130 ℃, and making the reaction times is about 1～10 hour, and the solvent in the time of can using polyamic acid resin synthetic as required carries out.Moreover; The usage quantity (molar ratio) of the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains epoxy group(ing) of above-mentioned formula; The reaction of the epoxy group(ing) in the silane compound of carboxyl in the raw material polyamic acid resin and formula (29) is quantitatively carried out under the prerequisite of (being feed rate ratio
modification ratio), is the amount of the compound that can form above-mentioned formula (1).
As the above-mentioned polyamic acid resin that contains alkoxysilyl, can use commercially available article, as commercially available article, can enumerate コ Application Port セ ラ Application H801D, H850D (waste river chemical industry (strain) system) etc.
Moreover, with above-mentioned polyamic acid resin and the usefulness that contains alkoxysilyl, can use the polyamic acid resin that does not contain alkoxysilyl.As this polyamic acid resin, with same, through according to ordinary method, roughly to wait mole, tetracarboxylic dianhydride and diamine reactant are made as the illustrative polyamic acid resin of the raw material of above-mentioned (A) composition institute.As tetracarboxylic dianhydride and diamines, can enumerate and above-mentioned (4) and (5) same concrete example.
(B) composition is that median size is the spherical metal oxide microparticle of 0.05～10 μ m.As this spherical metal oxide microparticle, preferably has 0.7～1.0 ワ one デ Le sphericity.
Wherein, So-called " ワ one デ Le sphericity " (with reference to chemical industry brief guide, the distribution of the kind Co., Ltd. of ball); Be meant the index of the sphericity of usefulness (circular diameter that equates with the shadow area of particle)/(the minimum circular diameter external) mensuration particle with the projection image of particle; This index is more near 1.0, then means it is more near the particle of spherosome.
Spherical metal oxide microparticle of the present invention, hope are more preferably 0.9～1.0, preferred especially 0.95～1.0 spherical shape of ワ one デ Le sphericity.If ワ one デ Le sphericity less than 0.7, then the thixotropy of compsn increases sometimes when the loading level of (B) composition increases.
From low thixotropy aspect,, preferably contain the spherical metal oxide microparticle of the spherical shape metal oxide microparticle of 60～100 quality %, preferred especially 80～100 quality % as (B) composition.Should explain that in this manual, so-called " spherical shape " is also to comprise the notion of sphericity at the ball of some distortion of 0.95～1 scope.
In addition, so-called " median size " is meant " volume average particle size ", for example, can make made laser diffraction and scattering formula particle size distribution device (trade(brand)name: LA910) and the mode of robotization is measured to adopt (strain) hole field.
Preferred 0.05～5 μ m of the median size of spherical metal oxide microparticle, more preferably 0.1～5 μ m.In addition, spherical metal oxide microparticle is preferably the spherical shape metal oxide microparticle.
Spherical metal oxide microparticle can be the particulate of a kind of MOX, also can be the particulate of the oxide compound (that is composite oxides) of metal more than 2 kinds.As the concrete example of a kind of MOX, can enumerate silicon-dioxide (SiO as the oxide compound of metals such as silicon, aluminium, magnesium, zirconium, titanium
2), aluminum oxide (Al
2O
3), titanium oxide (TiO
2), zirconium white (ZrO
2) etc.Concrete example as composite oxides; Can enumerate silica-alumina composite oxides, silicon-dioxide-titanium oxide composite oxides, silicon-dioxide-zirconia oxide compound, silica-magnesia composite oxides, aluminum oxide-binary system complex oxides such as Natural manganese dioxide composite oxides, three component system composite oxides such as silica-alumina-Natural manganese dioxide composite oxides, silica-alumina-titanium oxide composite oxides, silicon-dioxide-titanium oxide-Natural manganese dioxide composite oxides etc. as the composite oxides of above-mentioned metal.In the example of these spherical metal oxide microparticles, it is principal constituent (that is, containing 60～100 quality %) preferably with silicon dioxide microparticle spherical, particularly spherical shape.
Spherical metal oxide microparticle how to make can, preferably make metal burning and the metal oxide microparticle that obtains.This makes metal burning and the metal oxide microparticle that obtains, makes metal-powders such as silicon, aluminium, magnesium, zirconium, titanium; Reconcile into mullite and form (3Al
2O
32SiO
2～2Al
2O
3SiO
2) aluminium powder form and Si powder; Reconcile into spinel and form (MgAl
2O
4) magnesium dust and aluminium powder form; Reconcile into trichroite and form (2MgO2Al
2O
35SiO
2) aluminium powder form and metal powder mixtures such as magnesium dust and Si powder with carrier gas; In oxygen containing atmosphere, make its burning and form chemical flame, can in this chemistry flame, make the oxide compound of a kind of metal such as silicon-dioxide as target, aluminum oxide, titanium oxide, zirconium white or the particulate (particularly ultramicron) of composite oxides.Make metal burning at these and in the metal oxide microparticle that obtains, be the principal constituent particulate of (that is, containing 60～100 quality %) preferably with silicon dioxide microparticle spherical, particularly spherical shape.
Spherical metal oxide microparticle needs not to be and has carried out the spherical metal oxide microparticle of surface-treated, but preferably with silazane class and/or silane coupling agent the surface is handled.
Above-mentioned silazane class for example is silazane class or the combinations more than 2 kinds in them such as hexamethyldisilazane (HMDS), hexaphenyl disilazane.Wherein, from suppressing the aggegation of silicon-dioxide, make tart silicon-dioxide tend to alkalescence, raising is to organic affinity and improve homogeneity, and raising is set out to the aspects such as stability of the resin of (A) composition, preferred hexamethyldisilazane.
Above-mentioned silane coupling agent; For example be compound with at least a kind of reactive group (reactive organo-functional group) that is selected from amino, glycidyl, sulfydryl, urea groups, hydroxyl and alkoxyl group, or their combination (the for example combination of alkoxyl group and other reactive functional groups).Concrete example as silane coupling agent; Can enumerate γ-epoxypropoxy triethoxyl silane, β-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane etc. contains the organoalkoxysilane of epoxy functional group; Aminopropyl triethoxysilane, urea propyl-triethoxysilicane, N-phenylamino propyl trimethoxy silicane etc. contain the organoalkoxysilane of amino functional group; Alkoxy aryl silane such as phenyltrimethoxysila,e; Alkylalkoxy silanes such as methyltrimethoxy silane, octadecyl Trimethoxy silane, alkenyl alkoxy silanes such as vinyltrimethoxy silane, allyltrimethoxysilanis, γ-mercaptopropyl trimethoxysilane etc. contain the organoalkoxysilane of Mercaptofunctional property group etc.
Moreover, as treatment process, can adopt known method.
As spherical metal oxide microparticle,, can enumerate ア De マ Off ア イ Application SE series and the SC series of the ア of Co., Ltd. De マ テ Star Network ス etc. as commercially available article.
(B) composition can use a kind separately, also can be with more than 2 kinds and usefulness, and (B) use level of composition is 5～350 mass parts with respect to (A) composition 100 mass parts, preferred 5～300 mass parts, more preferably 10～200 mass parts.When this use level than 5 mass parts after a little while, can't obtain good silk screen printing property sometimes, and when surpassing 350 mass parts, suffer damage sometimes with cementability base material as (A) composition resin is original speciality.
Resin composition for screen printing of the present invention; Through using the spherical metal oxide microparticle of this composition; Even under above-mentioned use level, also can thixotropy be controlled at low-levelly, the pattern of formation can not cause that mesh is residual, spread and sink in ooze, the deterioration of deaeration property etc., obtain the thickness of homogeneous.
Moreover, as metal-oxide powder, in the scope of not damaging above-mentioned effect, can be with molten metal oxide powder, the broken thing of MOX, smog matter MOX non-spherical oxide powders such as (vapor phase process MOXs).Non-spherical metal-oxide powder and use ratio, with respect to spherical metal-oxide powder 100 mass parts of (B) composition, be preferably (0～25 mass parts) below 25 mass parts, be preferably 20 mass parts following (0～20 mass parts) especially.
In the organic solvent of (C) composition, can use the resin part or the consoluet organic solvent that can make (A) composition.
As the concrete example of (C) composition, can enumerate THF, 1,4-diox, ketopentamethylene, pimelinketone, gamma-butyrolactone, N-Methyl pyrrolidone, N-vinyl pyrrolidone, N; N-N,N-DIMETHYLACETAMIDE, N; Dinethylformamide, DMSO 99.8MIN., 1,3-dimethyl--2-imidazolone etc., preferred aprotic polar solvent; Preferred especially N-Methyl pyrrolidone, N-vinyl pyrrolidone, pimelinketone, gamma-butyrolactone and 1,3-dimethyl--2-imidazolone.
During film below the cured film that is formed by compsn of the present invention is 20 μ m, in order not damage the continuously shaped property that adopts silk screen printing, preferred especially and with the organic solvent of boiling point more than 200 ℃.As the organic solvent of boiling point more than 200 ℃, can enumerate for example gamma-butyrolactone, N-Methyl pyrrolidone, N-vinyl pyrrolidone, 1,3-dimethyl--2-imidazolone.
Moreover (C) composition can use a kind separately, also can be with also using more than 2 kinds.
(C) significant quantity of the use level of composition for dissolving above-mentioned (A) composition, preferably making the solids component amount usually is the amount of 10～80 quality %, especially preferably making the solids component amount is the amount of 20～70 quality %.
In resin composition for screen printing of the present invention, can also cooperate (D) epoxy resin, (E) curing catalyst.
The epoxy resin that has at least 2 epoxy group(ing) in 1 molecule of the present invention (D) composition does not have special restriction, as preferred example, can enumerate the epoxy resin shown in the formula (2).
(in the formula, G is a glycidyl, and R representes Wasserstoffatoms or monovalence alkyl, but all at least 1 among the R is the monovalence alkyl, and n is the integer more than 0 or 1).
Wherein, the monovalence alkyl of representing as R, non-replacement such as preferred carbonatoms 1～8, preferred especially 1～6 alkyl, aryl or replace the monovalence alkyl can be enumerated methyl, ethyl, propyl group, butyl, the tertiary butyl, phenyl etc. as representative groups.
In addition, in the epoxy resin of formula (2), n is the integer more than 0 or 1, preferred 0 or 1～20 integer, and preferred especially 0 or 1～10 integer, the epoxy resin of formula (2) can be the mixture with epoxy resin of different n values.In this case; In order to improve the second-order transition temperature of cured article as far as possible; The epoxy resin that preferably has following MWD: making n is that 0 epoxy resin is below the 70 quality %, is preferably below the 60 quality %, and the MV of the n of expression mean polymerisation degree is in 1～3 scope.Wherein, be 0 epoxy resin if contain the n of Duoing than 70 quality %, second-order transition temperature reduces sometimes.
As the epoxy resin of above-mentioned formula (2), the concrete following formula of illustration (30)～(32).
(in the formula, t-Bu representes the tertiary butyl, and OG representes following radicals, and n is (down together) as stated).
In the present invention; Epoxy resin except above-mentioned formula (2); Can also other epoxy resin of appropriate combination, the for example epoxy resin shown in bisphenol A type epoxy resin, phenolic resin varnish type epoxy resin, alicyclic epoxy resin, Racemic glycidol fundamental mode epoxy resin or following formula (33)～(35).
In addition, fire-retardant in order to make it, can use brominated epoxy resin.As brominated epoxy resin, can enumerate following formula (36), (37).
These epoxy resin can use separately or use mixing more than 2 kinds.In addition, the usage quantity of these epoxy resin is with respect to the polyamic acid resin that contains alkoxysilyl 100 mass parts, preferred 1～150 mass parts, more preferably 2～100 mass parts.If less than 1 mass parts can't obtain the bonding strength of cured article for base material, on the other hand,, the thermotolerance of cured article is reduced if surpass 150 mass parts.
In this case, the epoxy resin of above-mentioned formula (2) is preferably 1～100 quality % in the epoxy resin total amount, be preferably 5～100 quality % especially.
The curing catalyst of (E) of the present invention composition does not have special restriction, contains the polyamic acid resin of alkoxysilyl and the reactive height of epoxy resin from this, preferred amines catalyst.As amines catalyst, can cooperate glyoxal ethyline, 2-ethyl-4-methylimidazole, 1-1-cyanoethyl-2-methylimidazole, 2-phenyl-4, imdazole derivatives such as 5-dihydroxyl Methylimidazole etc. can use a kind or use more than 2 kinds from these.The preferred especially imidazolium compounds that uses following formula (38) through using the imidazolium compounds of this structure, can be given and solidify heat-resistingization of object height, high moisture-proofization and high adhesion.
(in the formula, Ph representes phenyl).
As other curing catalysts, also can specifically use the compound shown in triphenyl phosphine, triphenyl phosphonium triph-enylborate, tetraphenylphosphoniphenolate tetraphenyl borate salts, the following formula (39).
(in the formula, R
3～R
10Can enumerate halogen atoms such as Wasserstoffatoms, fluorine, bromine, iodine; The alkoxyl group of the alkynyl of the thiazolinyl of the alkyl of carbonatoms 1～8, carbonatoms 2～8, carbonatoms 2～8, carbonatoms 1～8, trifluoromethyl, phenyl etc., whole substituting groups can be the same or different).
The usage quantity of being somebody's turn to do the curing catalyst of (E) composition is measured 100 mass parts with respect to the total of polyamic acid resin that contains alkoxysilyl (A) and epoxy resin (D), preferred 0.001～20 mass parts, more preferably 0.01～10 mass parts.If less than 0.001 mass parts can not make its curing sometimes at short notice, if surpass 20 mass parts, compsn lacks storage stability sometimes.
In compsn of the present invention, except above-mentioned (A)～(E) composition, in the scope of not damaging effect of the present invention, can add for example tinting materials such as oxidation inhibitor, thermo-stabilizer, electroconductive stuffing, pigment, dyestuff etc. according to purpose.
Compsn of the present invention can adopt ordinary method with above-mentioned (A)～(C) composition, perhaps (A)～(E) composition and other compositions of containing sometimes mix and prepare.Particularly, can use the mixing roll that for example possesses whipping appts and heating unit, three rollers, ball mill, planetary-type mixer etc.In addition, can the appropriate combination more than 2 kinds of these mixing devices be used.
The lip-deep method (silk screen print method) that above-mentioned compsn is applied to matrixes such as silicon chip is carried out as follows: at first; Apparatus is the surface of the mask covering matrix of the peristome of desirable pattern to some extent; Compsn is dropped into scraping roller portion, scraping roller is moved, the limit adds flanging to compsn and on mask, moves; With filled compositions (filling work procedure) in the peristome of these mask parts, thereby then through mask being taken off the pattern that on the surface of above-mentioned matrix, forms compsn.The curing of the compsn that forms is like this carried out as follows: for example; Low temperature next stage ground (for example under 1 stage or the solidification value more than 2 stages) room temperature (20 ℃ ± 5 ℃)～200 ℃ is cured, and then carries out 200～350 ℃ hot setting (after fixing) as required.Moreover rear curing time is generally 0.1～20 hour.
Use resin combination of the present invention and adopt the resolution of the pattern that silk screen print method forms high, can not cause that mesh is residual, spread and sink in ooze, the deterioration of deaeration property etc., can access the thickness of homogeneous.In addition because continuously shaped property is also excellent; Therefore the alpha-ray shielding film of the splice protection film at the junction surface of the passive film of the semiconductor component surfaces on being fit to the formation wafer-level, protective membrane, diode, transistor etc., VLSI, interlayer dielectric, the ion implantation mask etc.; As the surface protection film of the protective membrane of the alignment films of the conformal coating that also be fit to form PC board, liquid crystal display device, spun glass, solar cell or cooperated the resin composition for screen printing of the conductive film etc. of electroconductibility weighting agent, can in wide scope, use.
When resin composition for screen printing of the present invention is used as the protective membrane of above-mentioned semiconductor element etc.; Adopt silk screen printing to be applied on semiconductor element and/or the lead frame; Through being heated curing, for example can forming, thickness is the tunicle about 0.1～100 μ m.After adopting above-mentioned condition of cure to form cured film,, can make semiconductor-sealing-purpose epoxy resin formed material and base material (for example Ni, Ag, Cu, Si, SiO through the semiconductor-sealing-purpose epoxy resin molding material is carried out moulding
2Deng inorganic substrate) cementability improve.Do not find during the scolder of the semiconductor device that obtains like this after moisture absorption flows again the semiconductor-sealing-purpose epoxy resin formed material cracking and with base material (for example Ni, Ag, Cu, Si, SiO
2Deng inorganic substrate) peel off, safety is high.
Embodiment
Below utilize embodiment and comparative example that the present invention is elaborated, but the present invention is not limited to these.
At first, be described below and prepare each composition of resin composition for screen printing.
The resin composition for screen printing composition
(A) base resin
Resin solution A:
It is 25% that the polyamic acid resin solution (コ Application Port セ ラ Application H801D: waste river chemical industry (strain) system) that will contain alkoxysilyl is modulated into resinous principle.
Resin solution B:
It is 25% that the polyamic acid resin solution (コ Application Port セ ラ Application H850D: waste river chemical industry (strain) system) that will contain alkoxysilyl is modulated into resinous principle.
Resin solution C (synthetic example):
In the flask that possesses whisking appliance, TM and nitrogen displacement apparatus, pack into as tetracarboxylic dianhydride's 3,3 '; 4,4 '-biphenyl tetracarboxylic dianhydride 32.22g (0.10mol) and N-N-methyl-2-2-pyrrolidone N-35g, the limit is regulated the temperature that makes reaction system and is no more than 50 ℃ of limits and slowly splashes into solution to it; This solution is with as 1 of diamines; Two (the 3-aminopropyls)-1,1,3 of 3-; 3-tetramethyl disiloxane 2.49g (0.01mol) and 4,4 '-diaminodiphenyl oxide 18.02g (0.09mol) is dissolved among the N-N-methyl-2-2-pyrrolidone N-20g and obtains.After splashing into end, at room temperature stirred again 12 hours, promote reaction to carry out, obtain the transparent polyamic acid resin solution of tawny.The viscosity of this solution is 250Pas, and the resin solid composition is 50.1 quality %.With it as resin solution C.
(B) epoxy resin
Softening temperature: 85 ℃, epoxy equivalent (weight): 214
(n=0:59 quality %, n=1:24 quality %, the n=2:8 quality, other: 9 quality %)
Softening temperature: 79 ℃, epoxy equivalent (weight): 165
(n=0:54 quality %, n=1:31 quality %, the n=2:9 quality, other: 6 quality %)
(3) bisphenol A-type (Epikotel001:JER society system)
Softening temperature: 64 ℃, epoxy equivalent (weight): 450
(C) curing catalyst
2-methyl-4,5-dihydroxyl Methylimidazole (2PHZ)
(D) weighting agent
(1) spherical shape silicon dioxide microparticle (ア De マ Off ア イ Application SC2500-SE: (strain) ア De マ テ Star Network ス system): median size 0.5 μ m
(2) fumed silica (AEROSIL R972: Japanese AEROSIL (strain) system, particle shape is amorphous)
(E) organic solvent
N-N-methyl-2-2-pyrrolidone N-(NMP)
1,3-dimethyl--2-imidazolone (DMI)
With above-mentioned (A)～(E) composition uniform mixing, obtain paste resin composition by the composition shown in the table 1 (unit is a mass parts).For the compsn that obtains, be described below and estimate.The result is shown in table 1.
Evaluation method
(A) viscosity
Use Digital Viscometer (BROOKFIELD system, trade(brand)name: the DV-II+) viscosity under measuring 23 ℃.
(B) silk screen printing property
(C.W.PRICE CO.INC. system, trade(brand)name: MODEL MC212) (325 orders, newborn thick: 15 μ m, silk screen are thick: 35 μ m) carry out with the silk screen mask to use screen process press.With the setting of mask, the filling of compsn and the taking off of mask of employing scraping roller, confirm to carry out the deterioration of the pattern form after continuously shaped 100 times as 1 molding procedure.With baking oven it was solidified 0.5 hour then, then expose 4 hours down it is solidified,, observe spreading and sinking in of mesh, foaming and pattern edge and ooze for the pattern that obtains at 250 ℃.
(C) cementability after the moisture absorption
Resin combination is applied on the various testing plate shown in the table 1, after the curing, at 175 ℃, 6865kPa (70kg/cm
2), under 90 seconds the condition of molding time with composition epoxy resin (KMC 3580CA: SHIN-ETSU HANTOTAI's chemical industry (strain) system) be shaped to floorage 10mm
2, high 3mm round shape, under 180 ℃, carry out 4 hours after fixing.Place it in the atmosphere of 85 ℃/85%RH 168 hours, after 260 ℃ of following IR flow, adopt the push-and-pull instrumentation to decide the peeling force of forming composition and various testing plate more again.
(D) resistance to cracking in the thermal cycling
Make the silicon and the 14PIN-IC frame (42 alloy) of 9.0mm * 4.5mm * 0.5mm size bonding; Then; Resin combination shown in the coating table 1 and it is solidified after, the above-mentioned composition epoxy resin of moulding above that under 175 ℃, 90 seconds is after carrying out 4 hours after fixing under 180 ℃; Carry out-50 ℃, 30 minutes～180 ℃, 30 minutes thermal cycling repeatedly, the resin cracks production rate after mensuration 1000 circulations.
Can confirm that from table 1 with respect to comparative example, the embodiment medium viscosity is suitably controlled, and printing is also excellent.In addition, can confirm that cementability and the resistance to cracking in the thermal cycling after the moisture absorption are also excellent.
Table 1
Claims (8)
1. resin composition for screen printing is characterized in that containing:
(A) polyamic acid resin that contains alkoxysilyl shown in the formula (1): 100 weight parts,
In the formula, X is the organic group from tetracarboxylic dianhydride's 4 valencys, and this tetracarboxylic dianhydride is selected from the tetracarboxylic dianhydride of following formula (6)～(19):
Y is the organic group from the divalent of diamines, and this diamines is selected from Ursol D, mphenylenediamine, 4,4 '-diaminodiphenyl-methane, 4; 4 '-diamino-diphenyl ether, 2,2 '-two (4-aminophenyl) propane, 4,4 '-diamino diphenyl sulfone, 4; 4 '-diamino-diphenyl thioether, 1, two (3-amino-benzene oxygen) benzene, 1 of 4-, two (4-amino-benzene oxygen) benzene, 1 of 4-; Two (p-aminophenyl alkylsulfonyl) benzene, 1 of 4-; Two (the m-aminophenyl base alkylsulfonyl) benzene, 1 of 4-, two (p-aminophenyl thioether) benzene, 1 of 4-, two (the m-aminophenyl base thioether) benzene, 2 of 4-; Two [4-(4-amino-benzene oxygen) phenyl] propane, 2 of 2-; Two [3-methyl-4-(4-amino-benzene oxygen) phenyl] propane, 2 of 2-, two [3-chloro-4-(4-amino-benzene oxygen) phenyl] propane, 1 of 2-, two [4-(4-amino-benzene oxygen) phenyl] ethane, 1 of 1-; Two [3-methyl-4-(4-amino-benzene oxygen) phenyl] ethane, 1 of 1-; Two [3-chloro-4-(4-amino-benzene oxygen) phenyl] ethane, 1 of 1-, two [3,5-dimethyl--4-(4-amino-benzene oxygen) phenyl] ethane of 1-, two [4-(4-amino-benzene oxygen) phenyl] methane, two [3-methyl-4-(4-amino-benzene oxygen) phenyl] methane, two [3-chloro-4-(4-amino-benzene oxygen) phenyl] methane, two [3; 5-dimethyl--4-(4-amino-benzene oxygen) phenyl] methane, two [4-(4-amino-benzene oxygen) phenyl] sulfone, 2, two [4-(4-amino-benzene oxygen) phenyl] UN 2424 and following formula (20)～(28) of 2-:
Z is the group that following formula is represented, R
4Be the alkyl of carbonatoms 1～3, R
5Be the alkyl or the alkoxyl group of carbonatoms 1～3, a is 0～4 integer, and p is 1～300 integer, and q is 1～300 integer, and r is 1～100 integer,
(B) median size be 0.05～10 μ m, ワ one デ Le sphericity is 0.95～1.0 spherical shape metal oxide microparticle: 5～350 weight parts; Above-mentioned MOX is to be selected from the oxide compound of a kind of metal in silicon, aluminium, magnesium, zirconium, the titanium or the composite oxides of metal more than 2 kinds; So-called " ワ one デ Le sphericity "; Be meant the index of the sphericity of usefulness (circular diameter that equates with the shadow area of particle)/(the minimum circular diameter external) mensuration particle with the projection image of particle
(C) organic solvent: the dissolving resin significant quantity of above-mentioned (A) composition, this organic solvent is for making the resin part or the consoluet aprotic polar solvent of above-mentioned (A) composition.
2. resin composition for screen printing is characterized in that containing:
(A) polyamic acid resin that contains alkoxysilyl shown in the formula (1),
In the formula, X is the organic group from tetracarboxylic dianhydride's 4 valencys, and this tetracarboxylic dianhydride is selected from the tetracarboxylic dianhydride of following formula (6)～(19):
Y is the organic group from the divalent of diamines, and this diamines is selected from Ursol D, mphenylenediamine, 4,4 '-diaminodiphenyl-methane, 4; 4 '-diamino-diphenyl ether, 2,2 '-two (4-aminophenyl) propane, 4,4 '-diamino diphenyl sulfone, 4; 4 '-diamino-diphenyl thioether, 1, two (3-amino-benzene oxygen) benzene, 1 of 4-, two (4-amino-benzene oxygen) benzene, 1 of 4-; Two (p-aminophenyl alkylsulfonyl) benzene, 1 of 4-; Two (the m-aminophenyl base alkylsulfonyl) benzene, 1 of 4-, two (p-aminophenyl thioether) benzene, 1 of 4-, two (the m-aminophenyl base thioether) benzene, 2 of 4-; Two [4-(4-amino-benzene oxygen) phenyl] propane, 2 of 2-; Two [3-methyl-4-(4-amino-benzene oxygen) phenyl] propane, 2 of 2-, two [3-chloro-4-(4-amino-benzene oxygen) phenyl] propane, 1 of 2-, two [4-(4-amino-benzene oxygen) phenyl] ethane, 1 of 1-; Two [3-methyl-4-(4-amino-benzene oxygen) phenyl] ethane, 1 of 1-; Two [3-chloro-4-(4-amino-benzene oxygen) phenyl] ethane, 1 of 1-, two [3,5-dimethyl--4-(4-amino-benzene oxygen) phenyl] ethane of 1-, two [4-(4-amino-benzene oxygen) phenyl] methane, two [3-methyl-4-(4-amino-benzene oxygen) phenyl] methane, two [3-chloro-4-(4-amino-benzene oxygen) phenyl] methane, two [3; 5-dimethyl--4-(4-amino-benzene oxygen) phenyl] methane, two [4-(4-amino-benzene oxygen) phenyl] sulfone, 2, two [4-(4-amino-benzene oxygen) phenyl] UN 2424 and following formula (20)～(28) of 2-:
Z is the group that following formula is represented, R
4Be the alkyl of carbonatoms 1～3, R
5Be the alkyl or the alkoxyl group of carbonatoms 1～3, a is 0～4 integer, and p is 1～300 integer, and q is 1～300 integer, and r is 1～100 integer,
(B) median size be 0.05～10 μ m, ワ one デ Le sphericity is 0.95～1.0 spherical shape metal oxide microparticle; Above-mentioned MOX is to be selected from the oxide compound of a kind of metal in silicon, aluminium, magnesium, zirconium, the titanium or the composite oxides of metal more than 2 kinds; So-called " ワ one デ Le sphericity "; Be meant the index of the sphericity of usefulness (circular diameter that equates with the shadow area of particle)/(the minimum circular diameter external) mensuration particle with the projection image of particle
(C) organic solvent, this organic solvent are the resin part or the consoluet aprotic polar solvent that can make above-mentioned (A) composition,
(D) epoxy resin that has at least 2 epoxy group(ing) in 1 molecule,
(E) curing catalyst.
3. the described resin composition for screen printing of claim 2, the epoxy resin that it is characterized in that above-mentioned (D) composition is the epoxy resin shown in the formula (2),
In the formula, G is a glycidyl, and R representes Wasserstoffatoms or monovalence alkyl, but all at least 1 among the R is the monovalence alkyl, and n is the integer more than 0 or 1.
4. claim 1 or 2 described resin composition for screen printing is characterized in that the surface of the metal oxide microparticle of above-mentioned (B) composition is handled with silazane class or silane coupling agent.
5. the described resin composition for screen printing of claim 4 is characterized in that above-mentioned silazane class is a hexamethyldisilazane.
6. the described resin composition for screen printing of claim 4 is characterized in that above-mentioned silane coupling agent is the compound with at least a kind of reactive group that is selected from amino, glycidyl, sulfydryl, urea groups, hydroxyl and alkoxyl group.
7. claim 1 or 2 described resin composition for screen printing is characterized in that above-mentioned (B) composition contains the spherical shape silicon-dioxide of median size 0.05～10 μ m of 60～100 weight %.
8. claim 1 or 2 described resin composition for screen printing is characterized in that containing the organic solvent of boiling point more than 200 ℃ as above-mentioned (C) composition.
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| JP2006015007A JP4771071B2 (en) | 2006-01-24 | 2006-01-24 | Resin composition for screen printing |
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| KR101064816B1 (en) | 2009-04-03 | 2011-09-14 | 주식회사 두산 | Polyamic acid solution, polyimide resin and flexible metal clad laminate using the same |
| JP5547456B2 (en) * | 2009-11-10 | 2014-07-16 | スリーエム イノベイティブ プロパティズ カンパニー | One-pack type epoxy resin composition and bonding method using the same |
| JP5338846B2 (en) * | 2011-04-25 | 2013-11-13 | 横浜ゴム株式会社 | Solar cell collecting electrode forming method, solar cell and solar cell module |
| JP6798510B2 (en) * | 2016-12-26 | 2020-12-09 | 東レ株式会社 | Photosensitive resin composition and photosensitive resin printing plate original plate containing it |
| CN110408206B (en) * | 2019-09-02 | 2022-05-17 | 无锡创彩光学材料有限公司 | Polyamic acid resin composition, method for preparing the same, and film formed from the same |
| CN110757972B (en) * | 2019-10-11 | 2021-07-20 | 扬州虹扬科技发展有限公司 | Retreatment process for electronic device with unqualified printed characters |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1173886A (en) * | 1995-10-20 | 1998-02-18 | 智索股份有限公司 | Polyamic acid, polyimide film and liquid crystal aligning film and liquid crystal display element |
| CN1673277A (en) * | 2004-03-25 | 2005-09-28 | 中国科学院化学研究所 | Polyimide film and its prepn process and use |
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| JP3539633B2 (en) * | 2001-01-24 | 2004-07-07 | 荒川化学工業株式会社 | Alkoxy-containing silane-modified polyamic acid resin composition and polyimide-silica hybrid cured product |
| JP2003020337A (en) * | 2001-07-06 | 2003-01-24 | Nippon Unicar Co Ltd | Bisnadimide-polysiloxane alternating copolymer or its derivative and epoxy resin composition for electronic material containing the same |
| JP2003113338A (en) * | 2001-10-03 | 2003-04-18 | Pi R & D Co Ltd | Heat-resistant block copolyimide composition for screen printing use and composition of ink using the polyimide and method of forming coating film |
| JP4599821B2 (en) * | 2002-10-09 | 2010-12-15 | 宇部興産株式会社 | Ink and printed matter that can print fine patterns |
| JP4276423B2 (en) * | 2002-11-13 | 2009-06-10 | トヨタ自動車株式会社 | Basic silica powder, method for producing the same, and resin composition |
| JP2005171208A (en) * | 2003-12-15 | 2005-06-30 | Toyota Motor Corp | Filler and resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1173886A (en) * | 1995-10-20 | 1998-02-18 | 智索股份有限公司 | Polyamic acid, polyimide film and liquid crystal aligning film and liquid crystal display element |
| CN1673277A (en) * | 2004-03-25 | 2005-09-28 | 中国科学院化学研究所 | Polyimide film and its prepn process and use |
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| JP特开2000-265056A 2000.09.26 |
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| JP2007197505A (en) | 2007-08-09 |
| TWI399407B (en) | 2013-06-21 |
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| KR101269820B1 (en) | 2013-05-30 |
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