JP2002156758A - Method for producing high-density flexible board using photosensitive polyimide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a high density flexible board, in which a photosensitive polyimide can be developed using a aqueous weak alkali solution and can serve as high-density flexible board, as it is. SOLUTION: In the method for producing a high-density flexible board, a photosensitive ink, containing a photosensitive imidosiloxane component which is a reaction product obtained by reacting a (1R,1'S,3R,3'S,4R,4'S)- dicyclohexyl-3,3',4,4'-tetracarboxylic acid dianhydride having an aromatic diamine with a reactive functional group on its benzene ring and a diaminopolysiloxane, carrying out imidation and causing the resulting imidosiloxane oligomer or polyimidosiloxane to react with a compound having a photosensitive group, is applied to a metal wiring obtained by patterning metal foil, preferably a laminate of a polyimide resin layer and a metal layer stacked directly and the ink is patternwise exposed, developed with an aqueous alkali solution and then post-baked to form a low elasticity insulation film on the metal wiring.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a high-density flexible substrate, and more particularly to a method for forming a pattern from a metal foil, preferably a laminate in which a polyimide resin layer and a metal layer such as copper are directly laminated. The present invention relates to a method for manufacturing a high-density flexible substrate in which a polyimide-based photosensitive ink is laminated on a metal wiring formed, developed with an alkaline aqueous solution, and then cured to form an insulating film. The present invention relates to a chip-on-flexible substrate, TA
B and so on.

[0002]

2. Description of the Related Art A photosensitive material is desired to be applied to a chip-on-flexible substrate, a TAB, etc. due to requirements for heat resistance, high density, high integration, and the like. Conventionally, a method of applying a polyimide resin to an element substrate, partially protecting the surface with a photoresist, and etching the polyimide resin film with hydrazine or the like is known, but the process is complicated and highly toxic. It is necessary to use a strong alkaline aqueous solution of hydrazine.

[0003] Japanese Patent Publication No. 55-30207, Japanese Patent Publication No. 5
JP-A-5-341422 discloses a resin in which a photopolymerizable acryloyl group is introduced into polyamic acid as a precursor of a polyimide resin, and JP-B-59-52822 discloses a resin in which an acryloyl group is introduced as a salt into amic acid. A method for etching is described. Also, JP-A-6-2
Japanese Patent No. 58835 discloses a photosensitive positive type polyimide having naphthoquinonediazide introduced into a carboxyl group of a polyamic acid, and Japanese Patent Application Laid-Open No. 10-95848 further discloses a carboxyl group introduced into a side chain of a polyamic acid having an acryloyl group introduced therein. A photosensitive negative-working polyimide is described. In order to form a protective film using such a photosensitive polyimide resin, it is necessary to heat the postbaking at a high temperature of 350 ° C. or more, which causes a defect in dimensional stability of the substrate.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a high-density flexible substrate which is photosensitive and can be developed with a weak alkaline aqueous solution and which can be used as it is as a high-density flexible substrate.

[0005]

According to the present invention, a metal foil, preferably a metal wiring formed by patterning a laminate in which a polyimide resin layer and a metal layer are directly laminated, has the following general formula (1):

[0006]

Embedded image (1R, 1'S, 3R, 3'S, 4R,
4'S) -dicyclohexyl-3,3'4,4'-tetracarboxylic dianhydride and the following formula (2)

[0007]

Embedded image

(Where Y is O, CH2, SO2 or a direct bond, Z is OH, COOH or SH) and an aromatic diamine represented by the following general formula (3): H ₂ NR [Si (R ') ₂ -O] _n -Si (R') ₂ -R-NH ₂ (3)

(Where R is an alkyl group or phenyl group having 1 to 4 carbon atoms, R 'is an alkyl group or phenyl group having 1 to 3 carbon atoms, and n is an integer of 3 to 50). A pattern of a photosensitive ink containing a photosensitive imidosiloxane component which is a reaction product of an imidosiloxane polymer obtained by reacting a polysiloxane and imidizing with a compound having a photosensitive group is exposed to light, The present invention relates to a method for producing a high-density flexible substrate which is developed by an aqueous solution and then post-baked to form an insulating and low-elasticity film.

[0010]

Embodiments of the present invention will be described below. (1) The photosensitive ink comprises (1) 100 parts by weight of a photosensitive ink siloxane component, (2) 0.01 to 30 parts by weight of a photopolymerization initiator, and (3) an imide-based photosensitive resin composition of an organic solvent. Manufacturing method of high-density flexible substrate. 2) A method for producing a high-density flexible substrate as described above, wherein the photosensitive ink is further applied to a chip-on-flexible substrate, TAB or the like containing (4) a photocrosslinking agent and / or (5) an inorganic filler.

3) A photosensitive imide siloxane component represented by the formula (1): (1R, 1'S, 3R, 3'S, 4R, 4'S) -dicyclohexyl-3,3'4,4'- A total of 80 to 100 mol% of the diamine of 100 mol% of tetracarboxylic dianhydride, 10 to 50 mol% of the aromatic diamine compound represented by the formula (2), and 10 to 70 mol% of the diaminopolysiloxane represented by the formula (3) % Of the above-mentioned high-density flexible substrate obtained by using an imide siloxane polymer obtained by reacting at a ratio of 0.1%.

The present invention will be described by taking COF to which a high-density flexible substrate is applied and bent TAB to which a high-density flexible substrate is applied, as examples. In a high-density flexible substrate for COF, an insulating and low-elastic coating formed of a photosensitive ink is provided on metal wiring such as copper directly laminated on a polyimide film substrate. On one side of the metal wiring, a chip component connected to an IC driver and the metal wiring via a solder ball is arranged. A TFT array substrate is disposed on the other side of the metal wiring via an anisotropic conductive film and an aluminum electrode. A deflection plate is disposed on one side of the TFT array substrate.
A filter and a deflection plate are connected.

In another example, a high-density flexible substrate for a bent TAB is provided by providing an insulating and low-elastic film formed of a photosensitive ink on metal wiring such as copper directly laminated on a polyimide film substrate. I have. And
One side of the metal wiring is connected to an IC driver, which is sealed with a sealant. On the other hand, a printed circuit board is connected to the metal wiring, and a deflection plate and a TFT array substrate are disposed on the metal wiring. Is connected to a color filter and a deflecting plate with a liquid crystal interposed therebetween. Organic EL instead of the above liquid crystal
(Electroluminescence) may be used.

In the present invention, as a method of forming a pattern from a laminate in which a polyimide resin layer and a metal layer such as copper are directly laminated, an etching method known per se can be used. For example, an etching resist is printed in a circuit pattern (wiring pattern) on the surface of the metal layer of the laminate, and the wiring of the etching resist protects the surface of the metal layer where the wiring pattern is formed. After the pattern is formed, the portion where the wiring is not formed is removed by etching using an etching solution by a method known per se, and the etching resist is finally removed. The wiring pattern thus formed has a width as the wiring pattern of 0.01.
The pitch as a wiring pattern is about 0.02 to 2.0 mm.

A laminate in which the above-mentioned polyimide resin layer and a metal layer such as copper are directly laminated is, for example, a biphenyltetracarboxylic dianhydride or a benzophenonetetracarboxylic dianhydride and paraphenylenediamine as essential components. On at least one side of the heat-resistant polyimide film,
If necessary, after performing a discharge treatment such as a plasma discharge treatment or a corona discharge treatment, 1,3-bis (3-aminophenoxybenzene) and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride are added. And polyimides obtained from bis (3,4-dicarboxyphenyl) ether dianhydride and pyromellitic dianhydride and 1,3-bis (3-aminophenoxybenzene) After the adhesive is provided by a method such as application of a precursor solution, heat drying and imidization, the polyimide adhesive and a metal layer such as a copper foil are superposed, and then heat-pressing is performed.

Alternatively, a laminate in which the polyimide resin layer and the metal layer are directly laminated is obtained by applying a thermocompression-bondable polyimide precursor solution to a metal foil, heating and drying, and then applying a highly heat-resistant aromatic polyimide precursor solution. A method of forming a polyimide layer on a metal foil by coating and heating and drying, and a method of thinly applying a flexible polyimide precursor solution to a self-supporting film of a highly heat-resistant aromatic polyimide precursor solution and the flexibility of a multilayer polyimide film heated and dried. If necessary, the conductive polyimide layer can be manufactured by a method in which a metal is deposited after a discharge treatment such as a plasma discharge treatment and then a plating treatment is performed to form a metal layer.

In the present invention, trans-tetracarboxylic dianhydride (1R, 1'S, 3R, 3 ') is used as the tetracarboxylic dianhydride of the photosensitive resin component.
S, 4R, 4'S) -Dicyclohexyl-3,3'4
4'-tetracarboxylic dianhydride (trans-DCD
Abbreviated as A-1. ) Is, for example, (1R, 1'S, 3
R, 3 ′S, 4R, 4 ′S) -Dicyclohexyl-3,
Hydrolysis of tetramethyl 3′4,4′-tetracarboxylate gives (1R, 1 ′S, 3R, 3 ′S, 4R, 4 ′S)
-Dicyclohexyl-3,3'4,4'-tetracarboxylic acid, which can be obtained by dehydration.

The starting material (1R, 1 ')
A method for producing and confirming tetramethyl S, 3R, 3 ′S, 4R, 4 ′S) -dicyclohexyl-3,3′4,4′-tetracarboxylate (abbreviated as trans-DCTM-1) has already been disclosed in a patent application. A patent application has been filed as 2000-191051.

That is, biphenyl-3,3'4,4 '
-Tetramethyl tetracarboxylate (abbreviated as BPTM,
For example, it can be easily synthesized by a method described in JP-B-60-33379, in which dimethyl phthalate is coupled in the presence of oxygen, a palladium salt and 1,10-phenanthroline or bipyridyl to produce a biphenyl compound. ) In an organic solvent such as methanol as a catalyst and 0.1 to 10% by weight of supported Ru / C (car).
Bon), Rh / C, Pd / C, or an alumina carrier, a silica carrier, etc.
Atmospheric pressure, preferably 10 to 50 atm, 50 to 250 ° C., preferably 100 to 200 ° C., for 1 to 10 hours for hydrogenation reduction reaction, after removing the catalyst from the reaction solution by an operation such as filtration,
The solvent is removed, and the product mixture which is a viscous solid is recrystallized with a common organic solvent such as methanol, ethanol, butanol, ethyl acetate, tetrahydrofuran, and the like.
s-Dicyclohexyl-3,3'4,4'-tetramethyl tetracarboxylate (cis-DCTM) is preferentially precipitated.

The cis-DCTM (purified product) is isomerized by heating in methanol in the presence of an alkali metal alcoholate catalyst in methanol to obtain an isomer having a trans structure. In addition, cis-DCTM (purified product) is separated from a reaction solution containing a product (crude product) obtained by hydrogen reduction of tetramethyl biphenyl-3,3′4,4′-tetracarboxylate without being obtained. The isomerization can be carried out, and the isomer having a trans structure can be separated and obtained directly from the reaction solution.

In the present invention, a pattern can be formed from a laminate in which a resin layer and a copper foil are directly laminated by an etching method. The formed wiring pattern has a width of about 0.01 to 1.0 mm and a pitch of 0.02 to 2.0 mm.
mm. The laminate can be manufactured by applying a polyimide precursor to a copper foil and drying by heating. After applying the photosensitive ink to the metal wiring, it is pre-baked to form a thin film, exposed,
After the alkali development, post-baking is performed at 250 ° C. or less to form an insulating film.

The reaction between the tetracarboxylic dianhydride and the diamine can be prepared by a usual synthesis method in a solvent. However, at the time of imidization, if the reaction temperature is too high, the trans configuration of the formula (1) may change and may be changed to another isomer. Therefore, chemical imidization is better.

The diamine requires the second aromatic diamine in addition to the diaminopolysiloxane. For example, 3,3'-diamino-4,4'-dihydroxydiphenylmethane, 4,4'-diamino-diamine 3,3'-dihydroxydiphenylmethane, 4,4'-diamino-2,
2′-dihydroxydiphenylmethane, 2,2-bis [3-amino-4-hydroxyphenyl] propane,
2,2-bis [4-amino-3-hydroxyphenyl]
Propane, 4,4'-diamino-2,2 ', 5,5'-
Tetrahydroxydiphenylmethane, 3,3′-diamino-4,4′-dihydroxydiphenylether, 4,
4'-diamino-3,3'-dihydroxydiphenyl ether, 4,4'-diamino-2,2'-dihydroxydiphenyl ether, 4,4'-diamino-2,2 ',
5,5′-tetrahydroxydiphenyl ether, 2,
2-bis [4- (4-amino-3-hydroxyphenyl) phenyl] propane, 4,4'bis (4-amino-
Two O, such as 3-hydroxyphenoxy) biphenyl
Aromatic diamines having an H group are mentioned.

Further, as the second aromatic diamine, for example, 3,3'-diamino-4,4'-dicarboxybiphenyl, 4,4'-diamino-3,3'-dicarboxybiphenyl, , 4'-Diamino-2,2'-
Dicarboxybiphenyl, 4,4'-diamino-2,
2 ', 5,5'-tetracarboxybiphenyl, 3,
3'-diamino-4,4'-dicarboxydiphenylmethane, 4,4'-diamino-3,3'-dicarboxydiphenylmethane, 4,4'-diamino-2,2'-dicarboxydiphenylmethane, 2,2- Bis [3-amino-4-carboxyphenyl] propane, 2,2-bis [4-amino-3-carboxyphenyl] propane,
4,4'-diamino-2,2 ', 5,5'-tetrahydroxybiphenylpropane, 2,2-bis [4- (4-
Amino-3-carboxyphenoxy) phenyl] propane, 3,3'-diamino-4,4'-dicarboxydiphenyl ether, 4,4'-diamino-3,3'-dicarboxydiphenyl ether, , 4'-diamino-
2,2'-dicarboxydiphenyl ether, 4,4 '
-Diamino-2,2 ', 5,5'-tetracarboxydiphenyl ether, 4,4'-bis (4-amino-3-
Two Cs, such as carboxyphenoxy) biphenyl
An aromatic diamine having an OOH group can be given.

As the diaminopolysiloxane,
α, ω-bis (2-aminoethyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (4-aminophenyl) polydimethylsiloxane, α, ω-bis (4-amino-3
-Methylphenyl) polydimethylsiloxane, α, ω-
Bis (3-aminopropyl) polydiphenylsiloxane, α, ω-bis (4-aminobutyl) polydimethylsiloxane and the like can be mentioned.

Examples of the reaction solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, Examples include caprolactam, N-methylcaprolactam, diethylene glycol dimethyl ether (diglyme), and triethylene glycol dimethyl ether (triglyme).

The above components are reacted and imidized, and an imide siloxane polymer and a compound having a photosensitive group, for example, a photosensitive epoxy compound are mixed and uniformly mixed at room temperature. React the parts,
A composition containing a photosensitive imidosiloxane component as a reactant is obtained. The polymer and the compound having a photosensitive group may react at the time of mixing at room temperature, or may react in a subsequent step by heating during drying.

Examples of the photosensitive epoxy compound include glycidyl methacrylate, glycidyl acrylate, glycidyl polysiloxane methacrylate, and half epoxy (meth) acrylate. For example, about 5 out of about 10 epoxy groups are acrylate or methacrylate groups. It is a substituted compound. Specific examples include trade name: Lipokin 630X-501, a carboxy-containing half epoxy acrylate (ENC manufactured by Kagawa Chemicals), manufactured by Showa Kogyo KK

The ratio of the imide siloxane polymer to the photosensitive epoxy compound depends on the amount of the reactive functional group (COOH,
Or OH), the amount of the epoxy group is preferably equivalent to 3 to 3 times, for example, 1 to 80 parts by weight based on 100 parts by weight of the imidosiloxane polymer.

As a photopolymerization initiator, Michler's ketone,
4,4′-bis (diethylamino) benzophenone, acetophenone, benzoin, 2-methylbenzoin, benzoinmethyl ether, benzoinethyl ether,
Benzoin isopropyl ether, benzoin isobutyl ether, 2-t-butylanthraquinone, 1,2-
Benzo-9,10-anthraquinone, methylanthraquinone, thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl- [4-
(Methylthio) phenyl] -2-morpholino-propanone-1,2-benzyl-2-dimethylamino-1- (4
-Morpholinophenyl) -butanone-1, diacetylbenzyl, benzyldimethylketal, benzyldiethylketal, 2- (2'-furylethylidene) -4,6-
Bis (trichloromethyl) -S-triazine, 2-
[2 ′-(5 ″ -methylfuryl) ethylidene] -4,6
-Bis (trichloromethyl) -S-triazine, 2-
(P-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,6-di (p-azidobenzal) -4-methylcyclohexane, 4,4′-diazidochalcone, di (tetraalkyl Ammonium)
4,4'-diazidostilbene-2,2'-disulfonate, N-phenylglycine, 3-phenyl-5-isoxazolone, 1-phenyl-1,2-butanedione-2
-(O-methoxycarbonyl) oxime and the like.

The amount of the photopolymerization initiator to be used depends on the amount of the photosensitive imide siloxane component 10 such as a photosensitive imide siloxane polymer.
The amount is 0.01 to 30 parts by weight, preferably 1 to 20 parts by weight based on 0 parts by weight. Outside this range, insufficient exposure or performance degradation may occur.

As an auxiliary (sensitizer) for the photopolymerization initiator, 4
-Ethyl dimethylaminobenzoate, ethyl 4-diethylaminobenzoate, methyl dimethylaminoanthranilate, benzophenone, 2,6-bis (4-diethylaminobenzal) -4-methylcyclohexanone and the like can be used.

Examples of the organic solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylmethoxyacetamide, dimethylsulfoxide,
γ-butyrolactone, N-methyl-2-pyrrolidone,
Examples thereof include 1,3-dimethyl-2-imidazolidinone, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), and propylene glycol diethyl ether. Some of these are converted to methyl ethyl ketone, methyl isobutyl ketone, methyl n, or the like by using ethyl cellosolve, butyl cellosolve, propylene glycol monobutyl ether, or the like.
-Methyl acetate, such as amyl ketone, cyclohexanone,
Ethyl acetate, butyl acetate, ethyl lactate, diethyl oxalate,
Diethyl malonate, methyl 3-methoxypropione
, Ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate and the like. The amount used is 50 to 300 parts by weight based on 100 parts by weight of a photosensitive imide siloxane component such as a photosensitive imide siloxane oligomer.

Photocrosslinking agents, for example, carboxy-containing half epoxy acrylate (ENC manufactured by Kagawa Chemicals), 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, ethylene glycol, methoxy tetra Mono- or diacrylates such as ethylene glycol, polyethylene glycol, propylene glycol, N, N-dimethylacrylamide, N-methylolacrylamide,
Polyhydric acrylates of adducts of ethylene oxide, propylene oxide, or ε-caprolactone such as N, N-dimethylaminoethyl acrylate, trimethylolpropane, pentaerythritol, and dipentaerythritol; Phenoxyacrylate, phenoxyethyl acrylate, or acrylate of ethylene oxide or propylene oxide adduct thereof, acrylate of melamine such as trimethylolpropane triglycidyl ether, or methacrylate, phosphoric acid Acryloyl, methacryloyl phosphate, polyvalent (meth) acrylic acid derivative (tris (2-acryloyloxyethyl) isocyanurate, etc.) or an adduct thereof with diaminosiloxane, polysiloxanediol and (meth) acrylic acid Esterification [Shin Chemical Industry Co., Ltd., X-22-1
64B] may be added. The amount of the photocrosslinking agent to be used is 0 to 100 parts by weight, preferably 1 to 50 parts by weight, per 100 parts by weight of the photosensitive imide siloxane oligomer.

Inorganic fillers such as Aerosil, talc,
Mica, barium sulfate and the like may be added. The average particle size is 0.001 to 15 μm, particularly 0.005 to 1 μm.
0 μm is good. These fillers are used in an amount of 1 to 1 with respect to 100 parts by weight of the photosensitive imide siloxane oligomer.
00 parts by weight, preferably 5 to 75 parts.

These imide-based photosensitive resin compositions can be applied by spin coating using a spinner, printing, roll coating, or the like.
Etc. can be used. This coated thin film is 150 ° C or less,
Preferably, the thin film is formed by prebaking by heating at 80 to 120 ° C for 10 to 60 minutes. Thereafter, ultraviolet rays are irradiated to a desired pattern to expose the pattern. The wavelength of this light is 30
0 to 500 nm is good.

The unirradiated portion is developed to obtain a pattern. As the developer, an aqueous alkaline solution, preferably a weakly alkaline aqueous solution is used. This aqueous alkali solution is a hydroxide of an alkali metal, alkaline earth metal, or ammonium ion,
Carbonates, hydrogen carbonates, amine compounds, etc., for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, ammonium hydrogen carbonate, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide , Tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, N-methyldiethanolamine, N-ethyldiethanolamine,
N, N-dimethylethanolamine, triethanolamine, triisopropanolamine, triisopropylamine and the like can be mentioned. Particularly, sodium carbonate can be preferably used. This concentration is 0.1-20% by weight, preferably 1-3%.

Alkali development includes spray, paddle, immersion,
Methods such as ultrasonic waves can be used. After the development, the pattern is rinsed and sprayed with water, an acidic aqueous solution or the like. Then, the photocured film is post-baked by heating and crosslinked to obtain a final pattern. This condition is below 250 ° C., preferably 1
Perform at 50 to 200 ° C. for 30 to 120 minutes.

[0039]

EXAMPLES Hereinafter, embodiments of the present invention will be described in detail with reference to examples. The 5% weight loss temperature (Td ⁵ ) was measured by SSC5200 TG manufactured by Seiko Instruments Inc.
/ DTA320 in nitrogen at a heating rate of 10 ° C./min. The mechanical strength was measured using a 4 mm wide sample, TENSILON AR600 manufactured by Orientec.
The measurement was performed using a 0 series, a universal tensile tester UTM-II-20, and a flat type automatic equilibrium recorder R-840 under the conditions of a chuck distance of 30 mm and a tensile speed of 2 mm / min.

Example 1 A stirrer and a reflux condenser were attached to a 100-mL three-necked flask, and 2.144 g (7 mM) of the formula (1) represented by the formula (1) was added thereto (1R, 1'S, 3R, 3'S, 4R). , 4'S)
-Dicyclohexyl-3,3 ', 4,4'-tetracarboxylic dianhydride was converted to N-methyl-2-pyrrolidone 17.3.
Dissolved in 5 g, 4.738 g (5.25 mM) of α,
ω-Bis (3-aminopropyl) polydimethylsiloxane and 0.501 g (1.75 mM) of 4,4′-diamino-3,3′-dicarboxydiphenylmethane were added, and the mixture was stirred at room temperature for 8.5 hours. . Next, 8 mL of acetic anhydride and 4 mL of pyridine were added, and the mixture was heated at 60 ° C. for 8 hours. After standing at room temperature overnight, the mixture was poured into 400 mL of water, pulverized by a cooking mixer, filtered, washed with water, and dried at 100 ° C. Yield 6.45 g. 6.00 g of this powder was combined with 4.00 g of triglyme and 3.0 g of N-methyl-2-pyrrolidone.
Dissolved in 100 g and filtered. 11.50 g of solution (solid content 46.2%) was added to an antifoaming agent (Dow Chemical DB-10).
0) 0.27 g, 1.90 g of a photopolymerization initiator (Ciba-Geigy-Irgacure 651), half epoxy acrylate (Ripoxy 630X-50, Showa Polymer Co., Ltd.)
1) 2.13 g, carboxy-containing half epoxy acrylate as a photo-crosslinking agent (Kagawa Chemicals ENC) 1.26
g and polyethylene glycol dimethacrylate (NK9G, Shin-Nakamura Chemical Co., Ltd.) and 0.66 g of methacryloyl phosphate (Nippon Kayaku Co., Ltd., PM2), a photocrosslinking agent for promoting adhesion, were added and stirred. . Next, 1.62 g of barium sulfate, 0.54 g of talc, and 0.95 of Aerosil (No. 200 of Nippon Aerosil Co., Ltd.)
g was added, stirred uniformly, and left overnight. This mixture was kneaded using three rolls. The viscosity of the obtained ink was 250 poise, and the solid content was 53.4%.

This dope was cast on an electrolytic copper foil (3EC-VLP, Mitsui Mining & Smelting Co., Ltd.) and uniformly coated with a bar coater. The solvent was removed by prebaking at 120 ° C for 30 minutes. The pre-baked film was cut for 500 m using a vacuum contact type ultra-high pressure mercury apparatus (HMW-6N, manufactured by Oak Manufacturing Co., Ltd.).
J exposure was performed. Using a 1% aqueous solution of sodium carbonate in a spray type developing device at 30 ° C. and a discharge pressure of 1.0 kgf / c.
m ² , development for ² to 3 minutes. Rinsing was performed at a water pressure of 11.5 kgf / cm ^{2 for} 1 minute to form a pattern having a thickness of 10 μm and a line / space of 75 μm. Mechanical properties (heat treatment conditions: 200 ° C., 1 hour) Tensile strength 1 kgf / mm ² , elongation 5%, initial elastic modulus 60 kgf / mm ² Thermal properties (heat treatment conditions: 200 ° C., 1 hour) 5% Weight loss temperature 358 ° C.

[0042]

According to the present invention, the following effects can be achieved. The present invention can provide a high-density flexible substrate that can be developed with a weak alkaline aqueous solution and has good dimensional stability without requiring high-temperature treatment.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA04 AA10 AA13 AA20 AB15 AB17 AB20 AC01 AD01 BC13 BC42 BC69 BC78 BC83 CA00 CB25 CB33 CC08 DA19 DA30 FA17 FA29 2H096 AA26 AA27 BA06 EA02 GA09 HA01 4J043 PA04 PA08 QB QSAB UA061 UA081 UA132 UB011 UB121 UB301 UB351 YB29 ZB22 5E314 AA27 AA36 BB02 BB11 DD06 DD07 FF06 FF19

Claims (4)

[Claims] 1. A metal foil, preferably a metal wiring formed by patterning a laminated body in which a polyimide resin layer and a metal layer are directly laminated, is applied to a metal wiring represented by the following general formula (1). (1R, 1'S, 3R, 3'S, 4R,
4'S) -dicyclohexyl-3,3'4,4'-tetracarboxylic dianhydride and the following formula (2) (Where Y is O, CH2, SO2 or a direct bond, Z
Is OH, COOH or SH. ) And the following general formula (3): H ₂ N—R [Si (R ′) ₂ —O] _n —Si (R ′) ₂ —R—NH ₂ (3) (where R is An alkyl group or a phenyl group having 1 to 4 carbon atoms, R 'is an alkyl group or a phenyl group having 1 to 3 carbon atoms, and n is an integer of 3 to 50). Exposure to a pattern of a photosensitive ink containing a photosensitive imide siloxane component which is a reaction product of an imide siloxane oligomer or polyimide siloxane obtained with the compound having a photosensitive group, and development with an aqueous alkali solution, A method of manufacturing a high-density flexible substrate which is post-baked to form an insulating and low-elastic film. 2. A photosensitive ink comprising (1) 100 parts by weight of a photosensitive ink siloxane component, and (2) a photopolymerization initiator of 0.01 to 0.01 parts by weight.
2. The method for producing a high-density flexible substrate according to claim 1, comprising 30 parts by weight and (3) an imide-based photosensitive resin composition of an organic solvent. 3. The method for producing a high-density flexible substrate according to claim 1, wherein the photosensitive ink is further applied to a chip-on-flexible substrate, TAB or the like containing (4) a photocrosslinking agent and / or (5) an inorganic filler. . 4. A photosensitive imide siloxane component represented by the formula (1) (1R, 1'S, 3R, 3'S, 4R, 4 '
S) -Dicyclohexyl-3,3'4,4'-tetracarboxylic dianhydride 100 mol%, aromatic diamine compound represented by formula (2) 10 to 50 mol%, diaminopoly represented by formula (3) The method for producing a high-density flexible substrate according to claim 1, wherein the siloxane is obtained by using an imidosiloxane polymer obtained by reacting a total of diamines of 10 to 70 mol% of siloxane at a ratio of 80 to 100 mol%.