JPS60221427A - Manufacture of composite material - Google Patents

Abstract

PURPOSE:To provide a composite giving a printed circuit board having excellent heat resistance and curl resistance, and silicon wafer or ceramic base free from warpage, by integrating an inorganic material with a polyimide made from a specific diamine. CONSTITUTION:An inorganic material is integrated with a polyimide prepared by the polymerization of (A) a diamine component composed of the diamine of formula (X is halogen, alky, fluoroalkyl, OCH3 or OH) and another diamine (at a molar ratio of 50:50-95:5) and (B) a tetracarboxylic acid dianhydride component containing >=50mol% pyromellitic dianhydride. The adhesivity can be improved by adding a siloxane-containing diamine in an amount of <=5mol% based on the whole amine component.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention is directed to a method for manufacturing IIFI thermally coated double-layered moldings.

[Prior art]

Published π 7■ノ弗-1/7'Ruinbachi 11 West 1 Drama hook...(/J
Polyimide film and gold JI on each tobi! ! It is manufactured by attaching a layer of foil and a t-adhesive agent.

Therefore, the heat resistance of the adhesive is not sufficient, so the heat resistance of the polyimide film is sufficient for VC, and the early heat resistance of the substrate is about 260°C.

In addition, in Publication No. 39-348 of 1988, aromatic polyamides prepared from aromatic cyamines such as pyromellitic acid and 4,4'-diaminodine enyl ether were reported. An example of how to apply it and use it as a shield was described. C Kiei has a curl problem, if the silicon wafer or ceramic substrate used in the production of beef thinner has a boria band τ cordon, and if it is heated to imidize it, the thickness of the polyimide section is thin. There is no problem at all, but if the film thickness becomes too thick, warping will occur similar to silicon wafers or ceramics, which will cause problems. These gold birds, silicone.

This is based on the mismatch between the swelling field coefficients of inorganic materials such as ceramics and polyimide. [Purpose of Issue 8A] Non-inventive 0 Polyamide varnish used with special diamine.
It has excellent heat resistance when used.

A 2-lexiple printed circuit board substrate that does not curl.

Silicon wafer without warpage coated with polyamide τ or ceramic base/r! The purpose is to provide the first-class Tawaradai offering.

[Brother BAc/) Sengeki]

Haloken, alkyl group, 2-fluoroalkyl group.

OC)1. , OH) and other aromatic diamine in a molar ratio of 50:50 to 95:5, and a diamine component and a tetracarboxylic anhydride enriched with 50 mol% or more of pyromellito dianhydride ? Imidization is carried out by assembling the polyamic acid varnish obtained by reacting the 21 components with the inorganic material in an aprotic polar bath medium.
I am interested in the manufacturing method of the composite material called Karune.

Aromatic diamine remolar ratio U50:50 to 95:5 is preferable, and IL is good for the buttocks (U65: less than 35 to 900%; curls and warps will occur when the ai is maintained.7C
More than 95 mol% (7i:/) ta as a component of tetracarboxylic dianhydride other than pyromellitic dianhydride used in the invention.6. s
, '4.4'-benzo2enonetetraanhydride, 3. s; 4.4'-cyenyl ethertetate dianhydride s 2.3. s; 4'~Binko Nil Tetra Sword Rubon Keijien Suimono, 6.6; 4.4'
- Bifu20tetracarpon dianhydride, 2,3,6.
7-Naphthalene dianhydride, 1,2,5
゜6-su2talintetracarboxylic anhydride, 1゜4,
5.8-S2talintetracarboxylic anhydride@.

Perylenetetracarboxylic anhydride Th, 3.3.4.4
'-Diphenylpropane tetracarboxylic acid is a dianhydride, 3
．． s; 4.4'-dinenylhe V-bunfluorofurobane tetracarboxylic dianhydride, s, b; 4
．． 4'-72 enyl sulfone tetra sword rubon kijimu 7X
thing.

Butanetetracarboxylic anhydride, cyclopentanetetracarboxylic anhydride, ethylene bistrimelitate tetracarboxylic anhydride vA, etc. It is preferable to use these components in an amount of 50 mol % or less.

A member of the diamine represented by the above formula used in the present invention is O3,3'-dichlorobenzidine, 6,6'-dimethylbenzidine, 3. ．． 5'-di(trinluo mef)
k) henzidine, 3,3'-diethylbenzidine, 3,6'-dimethoxybenzidine, 3,5'-dihydroxybenzidine s 3,3'-synluoropenzidine, -2,3,5,6,2ζ3r5: These include 6'-octanefluorobenzidine and 3,3'-dibromobenzidine.

In combination with the above diamines, as other aromatic diamines, σ
4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane% 4,4'-diaminodienyl sulfone, 5,5'-diaminodienyl sulfone, 4,4'-diaminotonenylgOHane, 44' -Diaminodiphenyl hexafluoropropuff 1 m-2 enylene diamine % p -2 enylene diamine, 4,4"
-Diaminoter-2-Dynyl, 4,4''-Diaminoquataphenyl, 2゜4-Diaminotoluene, 2,6-Diaminotoluene, 2,4-Cyaminobenzotrialolide, 2,5-Cyaminobenzotrial Oride, 1,4
-bis<p-aminoneenoxy)benzene, 1゜6-bis(p-aminoneenoxy)benzene, 4,4'-di(
m-aminoneenoxy)dinylsulfone, 4.4'
-di(p-aminoneenoxy)dinenylsulfone, 4
．． Examples include 4'-di(r-aminoenoxy)dinylsulfone and 4,4'-bis(p-amino2enoxy)biphenyl. Furthermore, if the total amine component is less than 5 mol%, the siloxane-poor diamine can also be used as a nitrate DT because it has good properties and is non-grotonic. , ON-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylformamide, N,N-diethylformamide, simetersulfoxide, sulfolane, methylsulfolane, tetramenal urine, hexamenal as a solvent. Preferred examples include phosphoramide and butyl lactone. These may be used in combination. List of these and xylene, toluene,
Phenol, acetone, methyl sulfolane, diacetone alcohol, selonlube, selonlube acetate.

Calpitols, methyl isobutyl ketone, sol, xylenol, dioxane, cyclohexanone, hexa2
Solvents such as fluorinated globanol can be used as long as the polyamide does not precipitate. The molar ratio of all diamine components to all tetracarboxylic dianhydride components is a, etc. It's nice, but either - is it a component of force? 5
There is no problem even if the amount is too much or too little within mol%.

Polyamide sales bath aQ) Sandness a between 6 and 25 degrees and 1% is good in terms of viscosity and iron resistance.
Once it becomes viscous, the polyamide varnish and inorganic material obtained in this way are mixed together and the heart is melted (t). As vvj
Hereafter Ct) Monokameゐdyolwachi.

1. FP4 substrate coated on copper, iron, aluminum, and stainless steel. 2. Coated on silicon, potassium, and clay. Use trap ψ skin arrangement LS
I 3, coated on the LSI chip, passivation film and α
Used as a rock membrane, the device is 4,000 yen, aluminum, stainless steel, and nickel.

4270 I, Amber Temple c/) The Reiyu board and the Yashira P3 connection (/, 4 Ritako ゐKapen Mototsune 5,
Apply on glass plate and remove as d & self 1iiJ tear 41
Usage 4) Kinsho display device 6, magnetic tape made by applying magnetic sτ dull varnish to solid, medium-sized clay, magnetic disk 2 alumina,
Polyimide tP3 is coated onto a substrate made of silicon carbide, zircon, beryllia, sapphire, etc. using a coater or die.

Heated VC! l1m medium T: Ring closure is performed with the removal of the six-centered core, and imidization is performed. Imidization CI) It is preferable to carry out the process in an inert gas to prevent ash and Kanahashi oil conversion.

When coating silicon wafers and ceramic substrates, it is best to use a spinner.

Meiha example 1゜Thermometer, stirrer, and calcium chloride tube YC51
6,6'-dimethoxybenzidine 20
7.4g, 4.4'-diaminodiphenyl ether 30
g, N-1f rubirolidone 20'Cl0g, N, N-
Add 2000 g of dimethylacetamide, stir the contents, and make the flask water-tight. Pyromellitic dianhydride 21
8gk gradually eroded and reacted at 10°C for 9 hours. 1.856i per i degree
/g (solvent N-methylpyrrolidone, Isogi 0.1 g/
I'm a friend. Stiffness bath number τ
It was applied to a rolled copper amount of 65 μm and heated for 100 minutes in a room atmosphere.
Heat at 71111C for 50 minutes, then set the crucian carp temperature to 0.
゛10 minutes, heat treated at 400℃ for 10 minutes, tilted thickness 25μ
m(1)Nregular printing grid #C/) Similarity τ and π
0 stiff board V co first M, etching Hou did not sword - 7ζ 0 gode Tsuyoshi county sleepy Shaomi 350 C but red fL (
1) There was a large number of outbreaks.

215.05 g of 6,6'-dichlorobenzidine, 30 g of 4,4'-diaminodine-dyl ether, and 20 L of N-methyl-2-hyrolidone were added directly to Example 1 and Example 18.
Charge with 2000 g of lOg, N, N-dimethylacetamide, stir the contents and cool with water in the flask. Next, 218 g of pyromellitic anhydride, 珀≧Katana Rolle, reacted with ff1J at 9 o'clock at 10°C, and hid in a polyamide acid bath aτ Samurai π0 2. + 56A/g 0 This seedling trap was fabricated using standard cloth and fabricated on 65 μm copper foil in the same manner as in Example 1. Not curled on stiff board・7to
Kato yc, swollen even after taking an early bath at 350 degrees C1,)
Occurrence &;ni'iZl for 1ζ Qo and 1 seagull? Is the polyamide bath number (61 to 20 pos) with the same composition as Rigoni Tensoku ψsu1? I-Silicone cube was repeatedly spin-coded, heat-treated to a thickness of 20 μm.
Etch and create a line τ with a convergence of 100 μm (1).
In addition, there is polyamide on the top. ll-coated to form a 20 μm thick polyimide layer, coated with photoresist τ, etched with h1 polyimide, removed with photoresist, and then aluminum? I layered it one point, etched it, t'L? In particular, a trap was prepared using a polyimide thick 200μIn remote base.
Compared to the conventional polyamides [(made from 4,4'-diaminodiphenyl ether and pyromellitic dianhydride)], the warpage is reduced and there is less warpage.[Inventive effect] Due to non-invention 1II11 #I fall behind and prevent it from curling.

A ridged body with less warpage was granted. 〇Procedural amendment document Showa 5 Provisional October 17th 1. Display of the case 1982 Patent Application No. 77062 2. Name complex of invention (new name) 3. Amendment Patent applicant name (445) Hitachi Chemical Co., Ltd. 4, agent 6) "Relating to a method for producing a composite" in the fourth line from the bottom of page 1 of the specification to "relating to a composite" and correct it.

4) "That is, etc." from page 8, line 2 of the specification sheet to line 5, page 9 of the specification sheet is corrected as follows.

“In other words.

1. Apply to copper, iron, aluminum, stainless steel, etc. 7.
VC is deposited on chips such as tFPC substrates, amorphous solar cell substrates 2, silicon 5 gallium arsenide, etc., and multilayer wiring LSI A LSI chips are used as multilayer distribution interlayer insulating films.
Semiconductor device used as Fuchijahei film 4, M, iron, aluminum, stainless steel, nickel.

4270, gold such as amber)'A Metal base number 5 used as an insulating film to insulate between wires and wiring, liquid display device & alumina used as a liquid crystal coordination film by coating on glass substrate, Multilayer board B, which is coated as a polyimide insulating film on a substrate made of silicon carbide, zircon, beryllia, sapphire, etc. Enameled wire a, which is used as an insulating material for conductive wires such as copper wire A, which is formed by vapor deposition or sputtering on a polyimide film Magnetic recording medium or EL display device 9 having a thin film such as a magnetic tape or a magnetic disk formed by applying varnish containing magnetic powder onto a polyimide film. 5) Insert the following sentence after Example 3.

[Example 4] The polyamic acid varnish of Example 1 was cast-coated onto a stainless steel belt, and heat treated at 100°C for 10 minutes and at 400°C for 10 minutes to obtain a polyimide film. This film was attached to a sputtering device and a thin stainless steel film was applied to the film to a thickness of 5,000 mm. Next, after sequentially forming "+' pP type amorphous silicon thin films by CVD method, an indium oxide film was applied to a thickness of about 700^ by sputtering. Then, a comb-shaped [silver was evaporated to obtain an amorphous solar cell] A diamine component consisting of the diamine shown in Attachment 2 above (indicating the scope of claims) and other aromatic diamine in a molar ratio of 50:50 to 95:5. and a tetracarboxylic dianhydride component containing pyromellitic dianhydride in an amount of 50 mol% or more.

Claims (1)

[Claims] Since the molar ratio of the diamine represented by A method of making a straw bag in which the anhydride component is reacted in an aprotic cyan bath medium and the inorganic material is combined with the polyamide sheet to imidize it.