JPS61136565A - Adhesive composition - Google Patents

Abstract

PURPOSE:To provide an adhesive compsn. consisting of (a) reaction product of polyamide-imide resin with epoxy resin, (b) polyaminobismaleimide resin and (c) specified reactive rubber and exhibiting excellent heat resistance and high tensile shear bond strength. CONSTITUTION:An aromatic polycarboxylic acid (A) having at least three carboxyl groups (carboxyl group-forming groups) which are on aromatic nucleus in the molecule and at least two of which are vicinal, a polyamide-imide resin (B) having at least one aromatic imide bond which is obtained from an aromatic diamine having at least two aromatic nuclei in the molecule and an epoxy resin (C) are made to interact in almost equivalent amounts at 100-180 deg.C for 0.5-2hr in an inert solvent, followed by cooling. 0.01-10pts. polyaminobismaleimide resin obtained from a bismaleimide and an aromatic diamine is added to the above reaction soln. and 100pts.wt. resulting adhesive is mixed with 0.5-100pts.wt. reactive rubber having functional groups capable of reacting with an amino or vinyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Applications] The present invention relates to adhesive compositions. More specifically, the present invention relates to an adhesive composition with improved heat resistance and tensile shear adhesive strength.

[Conventional technology]

1! Along with the demand for smaller machines and electronic parts, more complex automobile parts, and lighter weight, the level of demand for adhesives is increasing. One of these requirements is good heat resistance. Condensation-type polyimide resins, which have been developed as structural adhesives such as those used to bond aircraft honeycomb fur to face materials, have extremely high bonding temperatures and are difficult to remove condensed water generated during curing. 9) It cannot be immediately applied as an adhesive for consumer devices due to problems such as these. Furthermore, heat-resistant epoxy resins are inferior to polyimide resins in terms of heat aging resistance.

[Problem that the invention seeks to solve]

Addition-type polyamino bismaleimide resin is actually used as a matrix resin for high-density multilayer wiring boards and as a sliding member for OA equipment, taking advantage of its properties of high heat resistance and processability. However, this resin has the characteristic of being hard compared to thermosetting resins, and it is known that its adhesiveness is low because it has few functional groups that have an affinity for metals and the like.

A mixture of such polyamino bismaleimide resin and polyamideimide resin has been used as an adhesive for attaching metal foil to a film on a printed circuit board or for metal plating. Although adhesives can achieve their adhesion purpose, they have the drawback of causing blistering and peeling when high temperatures are applied to the metal surfaces for soldering.

The applicant has previously considered the cause of such defects, and found that it is probably due to functional groups such as carboxyl groups and amine groups remaining in the polyamideimide resin reacting with the polybismaleimide resin to generate water. By reacting with epoxy resin to eliminate these unreacted functional groups, and then blending with polybismaleimide Jugetsu Hyaku, the blistering and peeling observed on the metal surface were eliminated. Solve the problem of
1, No. 799).

Although such an adhesive composition exhibits good heat resistance from each of these components, it has been newly discovered that when a reactive rubber is further blended therein, the tensile shear adhesive strength increases.

[Means for Solving the Problems] and [Operation] Accordingly, the present invention relates to an adhesive composition having improved heat resistance and tensile shear adhesive strength, and this adhesive composition comprises a polyamide-imide resin and an epoxy resin. polyamino bismaleimide resin and a reactive rubber having functional groups that react with amino or vinyl groups.

The polyamide-imide resin used is an aromatic polyester having a structure in which the molecule has three or more carboxyl groups, the first being a radical-opening group, on the aromatic nucleus, and at least two of these groups are adjacent to each other. Derived from a carboxylic acid and an aromatic diamine having two or more aromatic nuclei in the molecule, and having at least one aromatic imide bond mal to an integer of 4, for example, trimellitic acid, pyromellitic acid, hemimellitic acid, naphthalene-2,3,6-tricarboxylic acid, diphenylmethane-3,3',4-tricarboxylic acid, diphenyl ether-a,a',4'-tricarboxylic acid, diphenyl sulfide-3,3',4-tricarboxylic acid,
diphenylsulfone-3,3',4-tricarboxylic acid, diphenylpropane-3,3',4-) IJ carboxylic acid, biphenyl-3,3',4-tricarboxylic acid or their derivatives, acid halides, acids Amides, acid imides, acid anhydrides, etc. (aromatic diamines, preferably those of the following formula [■]) Z
2OH2,0,+9. ,SO'! or so2 lower acyl group Examples: Eva, 4,4'-diaminodiphenylsulfone, 3.
3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, m-7 22-diamine, p-7 22-diamine, 2,2-bis(4-amino 7-ether) 2) propane,
Benzidine, 4,4'-diaminodiphenylsulfide, bis(4-aminophenyl)methylphosphine oxide, bis(4-aminophenyl)phenylphosphine oxide, bis(4-amino7,000nyl)methylamine, 1
．． 5-diaminonaphthalene, 1.1-bis(p-aminophenyl)phthalane, 4.4'-diaminobenzophenone, 4.4'-diaminoazobenzene, bis(4-amino7enyl)phenylmethane, 1.1 -bis(4-amino/phenyl)cyclohexane, 1,1-bis(4-amino-3-methylphenyl)cyclohexane, 2゜5-bis(m-aminophenyl)-1,3,4-oxadiazole, 2,5-bis(p-ami/phenyl)-1,3
, 4-oxadiazole, 2,5-bis(m〒aminophenyl)thiazolo(4,5-a)thiazole, 5.5'
-di(m-aminophenyl) -2,2'-bis(1,
3,4-oxadiazolyl), 4,4'-bis(p-
aminophenyl)-2,2'-dithiazole, m-bis(4-p-aminophenyl-2-thiazolyl)benzene, 2,2'-bis(m-aminophenyl)-5,5'-
Dibenzimidazole, 4,4'-diaminopenthanilito, 4,4'-diaminophenylbenzoate, N,
H'-bis(4-aminobenzyl)-p-phenylenediamine, 3,5-bis(m-aminophenyl)-4-phenyl-1,2,4-triazole, and inorganic acid salts thereof, etc. Examples of the aromatic polyamide-imide resin obtained by reacting an aromatic polycarboxylic acid and an aromatic diamine include Toluron CI, a commercially available product of Amoco.

Epoxy resins to be reacted with such polyamideimide resins include, for example, ethylene glyfur, diethylene glycol, triethylene glycol, polyethylene glycol, propane-1,2-diol, propane-1
, 3-diol, polypropylene gelicol, butane-
1,4-diol, polyethylene glycol, penkune-1,5-diol, hexane-1,6-diol, hexane-2゜4.6-1liol, glycerin, 1,1
．． 1- Polyglycidyl ethers of acyclic alcohols such as trimethylolpropane, pentaerythritol, poly(epichlorohydrin); resorcinol, quinitol, bis(4-hydroxycyclohexyl)methane,
Polyglycidyl ether of alicyclic alcohol such as 2,2-bis(4-hydroxycyclohexyl)cropane, 1,1-bis(hydroxymethyl)cyclohexene-3 *N, M-bis(2-hydroxyethyl)aniline, 4
．． Polyglycidyl ethers of alcohols having an aromatic nucleus such as 4'-bis(2-and-droxyethylamino)diphenylmethane; resorcinol, hydroquinone, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)sulfone, 1. 1.2.2-tetrakis(4-hydroxyphenyl)ethane, 2,2-bis(4
-hydroxyphenyl)furopane [bisphenol A]
, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane and other polyglycidyl ethers of single g''t7'ch polynuclear phenols; aldehydes such as formaldehyde, acetaldehyde, chloral, and flumethylaldehyde, and phenols. , polyglycidyl ether of novolak obtained from phenols such as 4-chlorophenol, 2-methylphenol, 4-tert-butylphenol; epichlorohydrin and aniline, n-
Reaction products with amines such as butylamine, bis(4-aminophenyl)methane, bis(4-methylaminophenyl)methane; triglycidyl isocyanurate; ethylene urine! , diglycidyl derivatives of cyclic ureas such as 1.3-7' robylene urea or hydantoins such as 5,5-dimethylhydantoin; dithiols such as ethane-1,2-dithiol and bis(4-mercaptoethylphenyl) ether diglycidyl derivative; oxalic acid,
Acetic acid, glutaric acid, adipic acid, pinellinic acid, speric acid, azelaic acid, sebacic acid, dimerized linoleic acid, 3
fL linoleic acid, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid, 4-methylhexahydrophthalic acid, heptalic acid, isophthalic acid,
Reaction products of polycarboxylic acids such as terephthalic acid and epichlorohydrin or glycerine dichlorohydrin; N, H, Q-)liglycidyl derivatives of p-aminophenol; salicylic acid friends include glycidyl ether-glycidyl ester of phenolphthalein, etc. or allyl glycidyl ether,
Compounds having a monoepoxy group such as phenylglycidyl ether, epichlorohydrin, and styrene oxide are used.

These polyamideimide S resins and epoxy resins are generally used in an inert solvent, preferably N-methyl-7-butyrolactam (N-methyl-2-pyrrolidone), N-ethyl-
N-alkyl substituted lactams such as r-butyrolactam, N-isopropyl-1-caprolactam or N,N
- Reaction in an N-alkyl substituted acid amide such as dimethylformamide, N,N-dimethylacetamide.

In the reaction, both are used in approximately equivalent amounts; generally, they are reacted at around 150°C for about an hour, then cooled, and the reaction product solution is added with polyamino bismaleimide and a heat-resistant rubber as described below. An adhesive composition is prepared by sequentially adding K.

In preparing this adhesive composition, polyamino bismaleimide is used in a ratio of about 0.01 to 10 to the reaction product of polyamideimide resin and epoxy resin, and the resulting composition For example, if the reaction is carried out at about 50° C. for about one hour, an extremely durable adhesive bond can be obtained.

The polyamino bismaleimide resin mixed into the reaction product of the polyamideimide resin and the epoxy resin is a mixture of bismaleimide represented by the following general formula [■] and aromatic diamine represented by the above general formula [...]. Obtained as a reaction product.

Family basic example, t! f, N, N'-m-y enylene dimaleimide, N, N' p-phenylene dimaleimide, N, N'-oxy(j-p-phenylene) simaleimide\N, N'-methylene (j-p-7 di N,N'-ethylene (di-p-phenylene) simaleimide, N,N'-sulfo(di-p-7enylene) simaleimide, N,N'-m-7enylene bis(
p-oxyphenylene) simaleimide, N, N'-ethylene dimaleimide), N, N'-hexamethylene dimaleimide, H, M/-decamethylene dimaleimide, M, M
'-oxydipropylene dimaleimide, ethylenedioxybis(N-7'robylmaleimide), N,N'-
Methylene (di-1,4-cyclohexylene) simaleimide, N,N'-isopropylidene (di-1,4-cyclohexylene) simaleimide, 2,6-xylylene simaleimide, 2. S-Oxadiazolylene cymaleimide, N
, H' p-phenylene (dimethylene) simaleimide, H, H'-2-methyl-P-) ylene dimaleimide, M, H'-thio (sifthenylene) dicitrafunimide, M, N'-methylene ( jeep-722lene)bis(
chlormaleimide), N,N'-hexamethylenebis(cyanomethylmaleimide), etc. Also, examples of reactive rubbers having a functional group that reacts with an amino group or a vinyl group include amino group-terminated nitrile rubber, vinyl group-terminated rubber, etc. (Nitrile rubber) Epoxy-modified carboxyl group-terminated nitrile rubber, epoxidized terminal-terminated polybutadiene rubber, polybutadiene glycol diglycidyl ether, and other polyimides that can be condensed with amino groups, vinyl groups, or glycidyl groups (
However, since combinations of amine 7 groups or vinyl groups do not react with each other, rubbers having the following are naturally excluded.

These reactive rubbers are used in an amount of about 0.00 parts per 100 animal parts (based on solid content) of the total amount of the reaction product of the polyamideimide resin and the epoxy resin and the polyamino bismaleimide resin.
It is used in a proportion of 5 to 100 parts by weight.

The preparation of the adhesive composition is as described above, in which polyamide-imide resin and epoxy resin are dissolved in a solvent and reacted at a temperature of about 100 to 180°C for about 2 to 2 hours. After cooling to ℃, polyamino bismaleimide resin was added thereto, and after stirring for about 1 hour, reactive rubber was added while being cooled with ice water, and stirred with an Ihomo mixer.
It is done by mixing.

Adhesion using the adhesive composition prepared in this way is carried out by sandblasting the surface of the adherend, degreasing it with trichlene, etc., and then using conventional application methods such as spray painting, brush painting, and dipping. After drying at 120℃ for 15 minutes to 170℃ for 2 minutes, fix with a pinch cock etc. with the contact surfaces facing each other, and leave it open at 160 to 180℃. After that, the fixing jig is preferably removed and the material is heated and cured for about 1 hour at 200° C. for 6 hours to 250° C. for 2 hours in an open environment.

〔Effect of the invention〕

The adhesive composition according to the present invention is produced by further blending a reactive rubber with a reaction product of a polyamideimide resin and an epoxy resin and a polyamino bismaleimide resin.
It not only improves heat resistance but also significantly improves tensile shear adhesive strength.

Such a significant improvement effect is seen both at room temperature (21℃) and high temperature (200℃), and while their absolute values are large, the residual adhesion between metal plates at high temperature compared to room temperature is significant. The ratio is also high.

First, the adhesive composition can also be laminated or adhered to a metal plate as a sheet adhesive, such as a glass fiber impregnation; such a laminate can be used, for example, as a core of a honeycomb structure of an aircraft wing or flap. It can also be applied to adhesion between aluminum and aluminum surface materials.

〔Example〕

Next, the present invention will be explained with reference to examples.

Examples 1 to 2 In a 3-ton flask equipped with a stirrer, a thermometer, and a condenser, bisphenol A type epoxy resin (Mitsui Petrochemical epoxy product Evomic R-140; epoxy equivalent: 190) and polyamide-imide resin were added. (Toluron manufactured by Mitsubishi Chemical Industries, Ltd.) 34.17 was charged and dissolved in N-methylpyrrolidone solvent 34a2. This solution was reacted at 150°C for 1 hour, then cooled to room temperature,
Next, polyamino bismaleimide resin (loin,
Boulan product Kelimide 601) 187.5
q was added and completely dissolved at 50°C to prepare a solution with a solid content concentration of about 40%.

To 100 ml of the nine solutions prepared in this way, terminal epoxidized polybutadiene rubber (Nippon Soda product Evo Shin 12
B: Epoxy equivalent: 525) 5 g of 2-te was added, and the mixture was stirred and mixed using a homomixer while cooling with ice water to prepare an adhesive composition.

Using this adhesive composition, mild steel plates or aluminum plates are bonded together, and the resulting laminate has an interlayer gap of 1
Tensile shear adhesive strength was measured. i.e. 25 x 100
A metal plate with a size of
The adhesive composition was applied to an area of % inch L, dried for about 5 minutes in an open air at 160° C., and then the coated surfaces were overlapped and fixed with metal fittings. This was cured at 180°C for 1 hour, further heated at 200°C for 6 hours to perform post-curing, and then 21
℃ and 200℃, and the ratio (200T near/21 t: )
is expressed as the adhesive residual rate at high temperature.

Examples 3-4 In Examples 1-2, terminal epoxidized polybutadiene rubber with an epoxy equivalent of 340 was used.

Examples 5-8 In Example 1, other reactive rubbers were used.

(Example 5) Nitrile rubber containing a terminal amine group (Hiker ATBN 1300 X 16, manufactured by Ube Industries) (Example 6) Nitrile rubber containing a terminal amine group (Hiker 0TEN 1300 X 1:3, a product of Ube Industries) (Example 7) Vinyl group-containing nitrile rubber (product of the company) 1 Squid-V
xBM 1300 Kosan Products Hiker oTyni 1300 x 16) 40! ;l
, bisphenol A type epoxy W&f (Evomic R
-140) 45 g o! vivi xy enol h159 2
A rubber-modified epoxy resin was prepared by reacting at 180° C. for 4 hours in the presence of a 11,000 pp GO triphenylphosphine catalyst.

Solution XOa prepared in Example 1 and having a solid content concentration of about 40%
Then, this rubber-modified epoxy resin #11 (l) was added as a reactive rubber, and an adhesive composition was prepared in the same manner.

The measurement results for each of the above Examples and Comparative Examples are shown in the following table.

Table Example 1 2 209 162 78
144 76 53 Example 2 5 2
30 128 56 128 69 5
4 Example 3 2 218 158 72
139 78 56 Example 4 5
253 142 56 150 80
53 Example 5 - C 175 125 7
1 125 112 90 Example 6 #
186 120 65 150 11
0 73 Example 7 # 164 1
15 70 132 95 72 Example 8
/f190 181 95 142
75 53 Comparative example 1 - 84 73
87 70 49 70 Example 9
10 168 126 75 130
91 70 Example 10 The adhesive composition prepared in Example 1 was applied to aminosilane-treated glass cloth (Kanebo Glass Fiber Products KS 77).
FH) After K impregnation, dry at 160°C for 5 minutes in air open, and dry this on a mild steel plate at 180°C for 4 hours.
1 hour -200℃4~. The interlaminar tensile shear strength of the i&laminate obtained by laminating under conditions of 6 hours was measured in the same manner as in Example 1, and the following values were obtained.

21°C 175~200°C 145~ Adhesive residual rate 83% Comparative example 2 Polyamino bismaleimide resin (Kelimide 601) t
-Dissolved in N-methylpyrrolidone, solid content concentration 40
% adhesive solution was prepared, and using this solution, lamination and interlayer tensile shear strength were measured in the same manner as in Example 10, and the following values were obtained.

21℃　　　48Made 200℃　　　　45~ Adhesive residual rate: 94%

Claims (1)

[Scope of Claims] 1. An adhesive composition comprising a reaction product of a polyamideimide resin and an epoxy resin, a polyamino bismaleimide resin, and a reactive rubber having a functional group that reacts with an amino group or a vinyl group. 2. Claim 1, in which the reaction product of polyamideimide resin and epoxy resin is prepared as a solvent solution.
The adhesive composition described in .