JPS58117269A - Method for manufacturing thermosetting adhesive sheet - Google Patents

Abstract

PURPOSE:To produce the titled sheet having excellent sealing performance, by impregnating a fiber substrate with a thermosetting resin compsn., curing the impregnated substrate, impregnating the cured substrate with a thermosetting resin, and semi-curing the impregnated material. CONSTITUTION:A hardener (in such an amount as to give a ratio by equivalent of epoxy group to functional group of 0.5-1.5) such as phthalic anhydride, 0.1- 10wt% radical polymn. initiator such as benzoyl peroxide, a solvent, a filler, a flame retarder, etc. are blended with a thermosetting resin such as a polybutadiene-modified epoxy resin to obtain a thermosetting resin compsn. A substrate composed of an inorg. fiber and/or an org. fiber is impregnated with 10-500wt% said thermosetting resin comspn. and heated at room temp. to 150 deg.C to cure the resin compsn. Then the substrate is impregnated with a thermosetting resin compsn. and heated at room temp. to 150 deg.C to bring into the B-stage.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a thermosetting adhesive sheet, and more specifically, to a method for manufacturing a thermosetting adhesive sheet with improved sealing performance. Traditionally, adhesive sheets for sealing i+ cages have been used to protect semiconductor integrated circuit elements from the effects of outside air, especially water and humidity, and are made of woven fabrics made of inorganic fibers such as glass or organic fibers such as polyester. A semi-cured M (B stage) fabric with a thickness of approximately 0.1-0.5 mm obtained by impregnating a non-woven fabric with a thermosetting resin such as epoxy resin, a curing agent, etc. and heating it at an appropriate temperature. ! There is a redareg sheet. In addition, this Yuzu epoxy Grigreg sheet does not have adhesiveness at room temperature, but exhibits fluidity when cured by heating, and has the ability to cure and adhere after wetting the surface to which it is applied, but it has poor sealing performance (sealability). ) but not necessarily in good condition.

The present inventors have conducted intensive research to obtain a round part curable adhesive sheet with improved sealing performance, and have found that inorganic fibers and/or
Alternatively, a base material made of organic fibers is impregnated with a thermosetting resin composition (hereinafter referred to as lower value resin) and then cured, and further impregnated with a thermosetting resin composition (hereinafter referred to as top coat resin). It was discovered that a semi-cured adhesive sheet has extremely good sealing performance (sealability), and the present invention was completed.

Thermosetting resins used in the present invention include phenolic resins, urea resins, melamine resins, epoxy resins, alkyd resins, unsaturated polyester resins, diallyl phthalate resins, silicone resins, and polyurethane resins, which may be used alone or in combination. Preferably, phenolic resins, area resins, I-urethane resins, and epoxy resins are used, and more preferably, polyurethane resins are used. The above-mentioned undercoat resin and topcoat resin may have the same composition or different compositions, but a combination with good adhesion and compatibility between the undercoat resin and topcoat resin is desirable, and the topcoat resin has a composition of Nixy resin. particularly preferred.

As the epoxy resin used in the present invention, those having at least two or more I-oxy groups in one molecule can be used, and can be used alone or in a mixed system. For example, bisphenol epoxy resin, Nogelac type resin, alicyclic type resin, glycidyl ester type resin, etc.
epoxy resins, hydrogenated bisphenol mglycidyl ether type epoxy resins, glycidylamine epoxy resins, heterocyclic epoxy resins, polybutadiene-modified epoxy resins, and the like.

This polybutadiene-modified epoxy resin is an anti-resin in which an epoxy resin (b) is added to a butadiene homoprimer and/or colimer (a) in which Cal has a xyl group,
It is (a) and (i) where Cal is 1 xyl group 11i
It is produced by heating and reacting a suitable amount of (b) with 1.8 to 30 equivalents of epoxy groups per 1 epoxy group.

The butadiene homoprimer and/or copolymer having a carzaxyl group in the molecule used in the present invention is, for example, Nippon Soda MNtsao PB, C! −
1000, 0-2000, Gutdrich Co., Ltd. Hyca
r-OTB, 0TBX, 0TBN, -k''Nera/(Te10gIn-OTB manufactured by Yasha, Butarez-OTL manufactured by Philips, HTPB, etc.).

Mata, Japan's No.1 moxibustion for butanoene homo4rimer and copolymer with terminal hydroxyl group "@"' PB, G
100012000 s 3000 s ARe O company g POly-BD, Filinno company But town rez-
Resins obtained by half-esterifying HT, Hycar-HTB manufactured by Gutdrich, Telogsn-HT manufactured by General Tire Co., etc. with an acid anhydride such as maleic anhydride by a conventional method also have a xyl group at the terminal. It can be used as a diene homo-4-rimer and co-4-rimer.

Furthermore, it is also possible to use a modified resin which does not have a terminal functional group and is obtained by adding maleic anhydride to a butadiene homopolymer or copolymer and then halfestering the anhydride ring with a hydroxyl group-containing compound to form a ring. Furthermore, the 21 bonds of the primer may be partially or completely saturated by hydrogenation.

Furthermore, for the purpose of further improving the flexibility, monocarboxylic acids such as oleic acid, and polyfunctional carnoic acids such as dimer acid may be mixed with the butadiene homopolymer or copolymer.

When these epoxy resins are used as undercoat resins, there is no need to consider tackiness in the B-stage state because they are used after curing, but when used as topcoat resins, epoxy resins that are in a solid layer near room temperature are most preferable. For example, (IL) Product name of Bisphenolum Type I Resin Shell Chemical ■ Epiny) 1001, 1004, 1007: Product name of Dow Chemical ■ DIR661J 1 Do66
4J, 667 J: Dainippon Ink Chemical Industry Mari's trade name Epicloy 1010, 4 3010; Product name Epicron N-740: Product name of Chipagayi hook KPM 1138 (O)
Is Talezorno a rack mold maker? ECI4 1280 (trade name of xylene resin Cipa Geigy); trade name of Epic ay N-673, ECI4 N-680 of Dainippon Ink & Chemicals (■).

N-695 Japan Hojo■ Product name RooN-102, KOON -
103, gOclJ -104(d) Product name of alicyclic epoxy resin fine polymers ■ Phi/Shitsukus 31
3; Product name of Chisso ■ Chisson Knox 313, 090.
091, 092, 301 (・) Brominated bisphenol molding I xy resin ° Shell Chemical - trade name Epicor) DI -245, 1045 - B- (fund); Chipagay ■ trade name Aralmate 8011, Same 8
047: Dainippon Ink &Chemicals' trade name Evicron 152, 1120: Dainippon Ink Chemical Co., Ltd.'s trade name DIIIR517, 54
Examples include polybutadiene-modified polybutadiene resins of (a) to (.) and mixtures of polybutadiene-modified resins (a) to (e) and modified polybutadiene resins.

The thermosetting resin composition in the present invention is, for example, a resin mixed solution of an epoxy resin, an epoxy resin curing agent or a radical polymerization initiator, and appropriate amounts of solvent, filler, flame retardant, and other additives depending on the required KE. shows. That is, the thermosetting resin composition refers to a resin mixed solution containing a thermosetting resin, a curing agent for the resin, and, if necessary, a suitable solvent and other additives.

Epoxy resin curing agents include diethylenetriamine,
metaphenylenediamine, diaminodiphenylmethane,
Amines such as diaminodiphenylsulfone, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, ethylene glycol bistrimelitate, glycerol tristrimelitate, dodecynylsuccinic anhydride, hexahydrophthalic anhydride , tetrahydrophthalic anhydride, methylnadic anhydride, chlorendic anhydride, I-lyaselic polyanhydride, nochlorosuccinic anhydride, carboxylic acid anhydride such as dodecenyl anhydride, monoethylamine complex of Bll'3 and B
P.

BF, system complex compounds such as pyridine complexes, or complex compounds such as triethanolamine, dicyandiamide, diazide hydrazide, titanium alkoxide, 18H group, -MCO group, -N0 day group, -C0
Examples include compounds having one or more NH groups in the molecule. The amount of these curing agents used is an amount equivalent to the ratio of the functional group equivalent to the functional group equivalent of the epoxy resin from 0.5 to 1.5.

As the radical polymerization initiator, diacyl peroxides such as di(benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, octanoyl oxide, lauroyl/4-oxide), dialkyl peroxides such as di-tertiary zotyl oxide, etc. Mother oxide, dicumyl oxide, etc., peroxy esters such as tert-butyl benzoate, tert-butyl/mother-acetate, di-tert-butyl/4-7 tallate, 2,5-dimethyl-2,5 -Ketones/oxides, such as di(pe/diyl/4'-oxy)hexane, such as methyl ethyl ketone peroxide, cyclohexanone peroxide, /Sidrono!-oxides, such as tertiary butylhydrono-oxide, cumene Preferably, hydrono-oxide, α-7 alethyl hydrofluoro-4-oxide, cyclohexenylhydro-4-oxide, etc., and mixtures thereof, are excessive and non-foaming, and the amount used is based on the total resin content. 0.1~t
o 1 lid, preferably 0.5 to 5 weight.

Examples of solvents include hydrocarbon solvents such as benzene and toluene, chlorinated hydrocarbon solvents such as carbon tetrachloride and monochlorobenzene, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate and butyl acetate, Methyltetrahydrofuran and dimethylformamide.

As the filler, calcium carbonate, talc, clay, silica, quartz, mica, lithium silicate, zirconium silicate, kaolin, alumina, fluminilum hydroxide, glass powder, etc. are used.

Aluminum hydroxide (
Organic halodane compounds include chlorinated rhaffin, benzene tetrachloride, benzene hexachloride, chlorinated diphenyl, chlorinated diphenyl,
chlorine ylyzx, 3,3.3-)chloroa f
a-pyrene oxide/rif-, chloropentacyclotecan; commercially available products include dechlorane glass and dechlorane from Fukka 1; brominated products include, for example, tetrabromobutane, tetrabromobutane, and tetrabromobutane; Acetylene, hexabromobenzene, tribromotoluene, dipromoglobyl ether of hexaprimotodecatribromophenol, tetrapromopisphenol, bisallyl ether of tetrapromopisphenol, bisdibromoglobyl ether of tetrabromobisphenol A, penta Bromodiphenyl ether, octabromobiphenol, HB manufactured by Teijin Kasei Co., Ltd., Pirocard 8R-100 manufactured by Dai-Kogyo Seiyaku Co., Ltd. Examples of chlorobrominated compounds include dichlorotetrabromoethane, dibromotetrachloroethane, 1,2-dibromo-3-chloro f El
Examples of the halodane-containing phosphates include tris(-monochloroethyl) phosphate, tris(
Chloropropyl) phosphate, tris(cycloglovir) phosphate, tris(2-bromoethyl) phosphate, tris(2,3-dipromoglovir) phosphate, tris(dipromozotyl) phosphate, tris(promochloroglovir) phosphate, tris(2-bromoglovir) phosphate
-chloroethyl) phosphate, tris(2-bromo-2-chloroisopropyl) phosphate, tris(1-
7" lomo-3-chloroisopropyl) phosphate, and as acrylic ester and methacrylic ester flame retardants, tribromophenyl methacrylate, tribromo-7
xyl acrylate, pentabromophenyl methacrylate, pentabromophenyl acrylate, trichloro7enyl methacrylate, trichlorophenyl acrylate, pentachlorophenyl methacrylate,
Pentachlorophenylacrylate, antimony trioxide, and the like may be used alone or in combination of two or more.

Examples of the base material used in the present invention include glass, silica, inorganic fibers such as asbestos, or ? Riester, 4s 7. Woven fabrics, non-woven fabrics, mats, paper made of organic synthetic fibers such as
A combination of these base materials can be used, but it is important to consider the impregnability of the resin mixed solution into the base material, defoaming performance, solvent dissipation during drying, and the moisture resistance, heat resistance, and dimensional stability of the cured sheet. Accordingly, glass fiber substrates are most preferred.

The thermosetting adhesive sheet in the present invention includes inorganic fibers and/or
Alternatively, the thermosetting resin composition is applied to a base material entwined with organic fibers in an amount of 10 to 500% by weight, preferably 20 to 30% by weight based on the weight of the base material.
After impregnation with 0% by weight, the solvent is removed and cured at room temperature to 180°C, preferably 50 to 150°C, and further impregnated with a thermosetting resin composition, and then room temperature to 150°C, preferably 50°C.
It is manufactured by removing the solvent and B-staging it at 0 to 130°C.

The thermosetting adhesive sheet obtained in this way is punched out or cut according to the shape of the target object to be adhered, and then inserted between the objects to be adhered without pressure or without any pressure. 80~2 with constant pressure applied.
Curing is carried out by heating at 00°C, preferably 100 to 160°C.

The % characteristic of the present invention is an adhesive obtained by impregnating and curing a thermosetting resin composition into a fiber base material, further impregnating it with a thermosetting resin composition that has good layerability and compatibility with the cured resin, and then converting it into a B stage. Compared to a imaginary sheet in which a conventional fiber base material is impregnated with a B-stage thermosetting resin composition by -1-,
The sealing performance, especially the initial sealing performance (sealability), is improved. In conventional adhesive sheets, the surface of the fiber base material is not impregnated with B-stage thermosetting resin composition E7, so this sheet is interposed between the objects to be adhered and then heated and cured under compression. When the thermosetting resin composition in the B stage state exhibits fluidity (7. When the adhered surface is wetted, it hardens and adheres, so the fluidity can be improved by subtle changes in conditions such as heating temperature and degree of compression). When the resin did not flow and flowed too much, in the worst case, there was direct contact between the base fiber and the adhered object, resulting in a decrease in sealing performance.However, the thermosetting adhesive sheet of the present invention In this case, a part of the thermosetting resin layer that is in direct contact with the base material has already been cured, and the thermosetting resin composition is in a B-stage state with good adhesion and compatibility with the cured resin layer. Since the material layer covers the surface, even if there is a slight change in conditions during heat curing and compression, the lower cured resin layer will prevent the B-stage resin from flowing too much and reduce excessive compression. It exhibits a stable sealing property.The effect is particularly great when the fiber base material used is an inorganic fiber base material.

EXAMPLES Next, the present invention will be specifically explained using Examples, but the present invention is not limited thereto. In the following Examples and Comparative Examples, parts represent parts by weight.

[l] Synthesis of thermosetting resin composition (1) Ii fat composition mubisphenol muciglycidyl ether (Shell Chemical @
Made by Epicor) 1004, Epoxy 1i 890)
A thermosetting resin composition A was obtained by uniformly stirring and mixing 100 parts of methylnadic anhydride (hereinafter abbreviated as MW), 1 part of trimethylbenzolamine, and 100 parts of methyl ethyl ketone.

(2) Resin composition B Calculate at the end of the molecule? Butadiene low polymer with xyl group (Nl580-PBC-1000 manufactured by Nippon Soda ■, number average molecular weight = 1590, acid value = 58.5) ioos, bisphenol musi glycysol ether (Epicoat 1001° manufactured by Shell Chemical @ Epoxy Roane 450 ) 200 parts, 1 part of tetra-n-butylammonium bromide, and 300 s of methyl ethyl ketone, while stirring.
The reaction was carried out at 0° C. for 8 hours to obtain a pale yellow transparent resin liquid B-1 with an acid value of 0.1 or less.

Thermosetting resin composition B was obtained by uniformly mixing and stirring 8.5 parts of 1-gum into 1100 parts of resin liquid B.

(3) Resin composition C Cresol no black-based engineering 4-oxy resin (manufactured by Nippon Kayaku ■ 1ooN-103, engineering I-oxygen equivalent 225
) Add and mix Supplementary Resin Liquid B-1,900 parts to a solution of 50 parts of methyl ethyl ketone sekibu with stirring,
A thermosetting resin composition C was obtained by uniformly mixing and stirring 0 to 1,100 parts of the resin liquid and 14 parts of the aluminum.

(4) Resin composition D nxsso -pBc -2000 (number average molecular weight 23
50.

Acid value 33.6) 100 m, bisphenol siglycidyl ether (Epicor manufactured by Shell Chemical Co., Ltd.) 100
4. 180 parts of engineering f-oxygen (890 parts), 3 parts of tetra-n-butylammonium bromide, and 300 parts of methyl isobutyl ketone were reacted at 110 to 115°C for 8 hours with stirring to produce a pale yellow transparent product with an acid value of 0.1 or less. A resin liquid was obtained. Next, 6 parts of hexahydrophthalic anhydride and dicumyl/arm oxide lfA were added to 200 parts of the cough resin liquid, and the mixture was uniformly stirred and mixed to obtain a thermosetting resin composition.

(5) Resin composition E 2 equipped with a thermometer, stirrer, dropping funnel, and cooler
Weigh the 2,4-tolylene diisocyanate part and the methyl ethyl ketone part into a four-bottle flask, and adjust the internal temperature to 70°C.
It was stirred as This was combined with a butadiene low polymer having a hydroxyl group at the molecular end (Nl8SO-P manufactured by Nippon Soda).
BG-IQQQ, number average molecular weight 1450, OHV 6
5.8) 171 fik to methyl ethyl ketone 17
One part of the solution was gradually dropped from the dropping funnel.
After completion of the dropwise addition, the reaction was carried out at 70° C. for 3 hours, and the incyanate group content was determined by a conventional method and was found to be 2.01% by weight, indicating that the reaction was complete.

Next, bisphenol A-,) glycidyl ether (manufactured by Shell Chemical ■, Epicor) 1001 Nixi Todo 450
) was dissolved in 360 parts of methyl ethyl ketone, the resulting solution was added, and the reaction was carried out at 70° C. for 5 hours. After 9 hours, the incyanate group had almost completely disappeared. Further, the epoxy equivalent of the resin component was determined to be 700 by a conventional method.

Thermosetting resin composition E was obtained by adding 11 parts of tetrahydrophthalic anhydride to 100 seconds of the obtained resin solution and uniformly stirring and mixing.

[Rei] Sealing test method First, the equipment used in the sealing test will be explained with reference to FIGS. 1 to 3.

In this test method, as shown in Figure 1, first, a capacitance of 1
A 1L Mylar film capacitor (6) of 000 PF was connected to its lead terminal (7) and external lead terminal (5) with a copper wire (8) to form a conductive path. The case is
As shown in its plane in FIG. 1 and its cross section in FIG. 2, the lid abutting portion has approximately the same shape as the peripheral edge of the aluminum lid (4) and has a predetermined width. (2) and further the contact part (
The outer pressure of 2) includes a lid guide step (to) that contacts the @ surface of the lid (4).

As shown in FIG. 3, the sheet adhesive (9) is punched out in advance to have approximately the same shape as the still-contacting part (2) of the case, and this sheet adhesive (9) is attached to the lid (4). and the case contact area (
2) to complete the sealing test device as shown in Figure 2.

Lid of iA for sealing test obtained in this way (4)
and the case (1) with clips and put it into the heating furnace.
The thermosetting sheet adhesive (9) was cured and sealed by heat treatment at 130° C. for 3 hours, and then cooled to room temperature and the clips were removed. The sealability was tested using this sealed test device, and the test conditions were as follows: (a) A boiling test with tap water containing a small amount of liquid detergent was performed for 2 minutes, followed by immersion in tap water at room temperature for 10 minutes. Boiling test - The immersion operation was performed three times and the presence or absence of leakage caused by this was investigated. This is called the initial sealability test.

(1)) For the products that passed the initial sealability test, after an aging test at 130°C for 100 hours, a sealability test (IL) was conducted once to investigate the presence or absence of leakage. This is called a sealability test after heat aging.

(C) For products that passed the sealability test after heat aging, at 130°C
×1 hour ~ -40. After repeating one cycle of C, x 1 hour 5 times, a (-) sealing test was conducted once to investigate the presence or absence of leakage.

This is called a sealing test after heat cycle.

Examples 1 to 3 Glass fiber woven fabric (WIC18K 104 B manufactured by Nittobo
Z-2, thickness 180/Jm) K thermosetting resin composition,
Impregnated with B and C respectively and dried at 12°C for 10 minutes.
It was heated and cured at 0°C. Further impregnated with thermosetting resin compositions A1, B and 0 of the same type, respectively,
They were dried for 10 minutes at ℃ and B-staged to obtain thermosetting adhesive sheets 1, 1 and 1, respectively.

The obtained pressure-adhesive sheet was punched out in the shape shown in FIG. 3 to obtain adhesive sheet pieces for sealing tests.

A sealability test was conducted using each adhesive sheet. The results are shown in Table 1. Note that additional samples for the sealability test were made for each sheet, and the test results were expressed in terms of the number of leaks.

Examples 4-7 The same substrates and operations were used as in Examples 1-3.

However, the undercoat resin was kept constant as thermosetting resin composition B, and the topcoat resins were changed to M, 0, D, and E, respectively. The results of the sealability test are shown in Table 1.

Example 8 Polyester fiber non-woven fabric (Japan Piry y@
A thermosetting sheet (2) was prepared using the same thermosetting resin composition and operation as in Example 5, except that H-8010 (thickness: 220/Jm) was used, and a sealing test was conducted in the same manner as in Example 5. The results are shown in Table 1.

Comparative Examples 1 and 2 Glass fiber woven fabric (Nittobo Co., Ltd. WJ8K 104 BZ-
2. After impregnating thermosetting resin composition B into a sheet (180 μm thick), drying the thermosetting sheet) K for 10 minutes at (180 μm) and further impregnating it with the same resin composition B (180 μm) and drying at (180 μm) C for 10 minutes. A dry B-staged thermosetting sheet x was obtained. A sealability test was conducted using these sheets, and the results are shown in Table 1.

Examples 9-11, Comparative Examples 3-. 5゜The thermosetting adhesive sheet U made in Example 2 and the thermosetting adhesive sheet Shown in the table.

[Brief explanation of the drawing]

Figures 1 to 3 are drawings showing the equipment and sheet adhesive used in the bandability test. Figure 1 is a plan view (however,
Lid (4) and punched sheet adhesive (9)
) is excluded. ). FIG. 2 is a cross-sectional view thereof, and FIG. 14 is a plan view of the punched sheet adhesive (9). 1: Case 2: Lid contact portion 4゛: Lid body 5: External lead terminal 6: Capacitor 9 = Sheet-like adhesive lO: Lid guide stepped portion Patent applicant Nippon 1Tatsu Co., Ltd. Agent Ito Haruno Do Yokoyama Yoshimi No. 1 @ 2rIA Figure 3 Procedural Amendments April 1980 ^ Japan Patent Office Commissioner Shima 1) Haruki Tono 1, Indication of Case Patent Order No. 210453 of 1982 2, Invention Name of Thermosetting Adhesive Sheet Manufacturing Method 3゜Relationship with the Amended Person Case Patent Applicant 2-2-1 Otemachi, Chiyoda-ku, Tokyo (yjtp) Nippon Soda Co., Ltd. Representative Yoshio Morisawa 4, Attorney Yu 100 Nippon Soda Co., Ltd., 2-2-1 Otemachi, Chiyoda-ku, Tokyo Telephone (245) 6234 5-t 9B5 wmy, C Cursed Son's Affair 6, Contents of Amendment (11 Specification, page 15, line 15) and insert the following sentence between line 16.
I・Transistor・Diode・Hybrid IC・
Used for sealing electronic components such as capacitors, resistors, coils, watch module boards, and magnetic bubble memories. Furthermore, the thermosetting adhesive sheet of the present invention can be used for bonding composite boards such as aluminum and plastic, aluminum and veneer, aluminum and slate, iron and stainless steel, melamine and plywood, PVC and aluminum and PVC, and bonding laminated glass. For bonding glass,
For adhesion of automobile interior parts such as PVC sheets and foamed urethane, for adhesion of ferrite cores, for fixing rotating machine wire coils, slot liners, and coils, for securing lead wires, and for coils (
It can also be applied to exterior insulation (mold transformers), vibrating linings, adhesives for composite films, etc. ”

Claims (1)

[Claims] A method for manufacturing an adhesive sheet, which comprises impregnating a base material made of inorganic fibers and/or organic fibers with a thermosetting resin composition and then curing it, and further impregnating the thermosetting resin composition and curing it in the second half.