JPS62220528A - Structural member - Google Patents

Abstract

PURPOSE:A member having good mechanical and thermal characteristics and extremely improved hot water resistance, comprising polyether imide bonded by an adhesive containing a specific epoxy resin, an aminobenzylamine and rubber. CONSTITUTION:A structural member comprising polyether imide bonded by an adhesive containing (A) an epoxy resin consisting of 100-30wt% epoxy resin containing >=three epoxy groups in one molecule and 0-70wt% epoxy resin containing <=two epoxy groups in one molecule, (B) an aminobenzylamine and (C) rubber, as a main component. The adhesive has a ratio of 0.5-1.5, preferably 0.8-1.2 hydrogen of amine group in the component B to one epoxy group in the component A, the amount of the component C is 5-40pts.wt., preferably 12-35pts.wt. based on 100pts.wt. component A, each component is blended and used.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a structural member containing polyetherimide as a main component.

(Conventional technology) In recent years, due to the development of highly functional resins and advances in composite materials, in addition to being lighter than metals, they have corrosion resistance, insulation properties, etc. that are not found in metal materials. In the past, metal materials have been commonly used in various structural components, such as frames and drive parts of electrical and electronic equipment, machinery, automobiles, and aircraft, as well as civil engineering and construction materials. Ta.

Various engineering plastics are used as high-performance resins, and among them, polyetherimide is an amorphous thermoplastic resin with excellent mechanical and thermal properties. Various types of structural members were being developed.

Structural components refer to items that are difficult to mold using normal molding methods, such as thick plates, large-volume components, and components with complex shapes. It is made up of. For example, when manufacturing a thick plate, a plate of a desired thickness is formed by a normal molding method such as injection molding or extrusion, and then laminated and bonded with an adhesive to form a plate of the desired thickness. It's like getting. By using parts and adhesives in this manner, members having arbitrary structures can be manufactured.

Conventionally, such structural members have been manufactured from polyetherimide by using components made of polyetherimide and using heat fusion, ultrasonic fusion, or solvents that partially dissolve the material on the surfaces to be bonded. There were methods such as joining via. It is not possible to join objects with complex shapes using heat fusion, and it is not possible to join thick objects using ultrasonic fusion.

Furthermore, bonding methods using solvents have had problems such as deterioration of the interface due to residual solvent, such as cracks, reduction in adhesive strength, and changes in appearance.

Furthermore, methods using epoxy adhesives have also been attempted. Epoxy adhesives come in various types, such as solvent-free, room-temperature-curing, and heat-curing types, making the bonding method easier and making it possible to join thick objects and objects with complex shapes.However, in this case However, the strength after bonding was insufficient, and there were problems with water resistance, hot water resistance, etc., and it had not been put to practical use.

(Problems to be Solved by the Invention) An object of the present invention is to provide a structural member whose main component is polyetherimide, which is bonded using a new epoxy adhesive.

(Means for Solving the Problems) In order to achieve the above object, the present inventors conducted various studies and as a result, completed the present invention.

That is, the structural member of the present invention includes (a) 100 to 30% by weight of an epoxy resin having three or more epoxy groups in one molecule, and 0 to 70% by weight of an epoxy resin having two or less epoxy groups in one molecule; % of epoxy resin, (b) aminobenzylamines, and (c) rubber.

The polyetherimide used in the present invention is a general term for polymers that have both ether bonds and imide bonds in their structure, and generally has the structure represented by formula (1). The product name Ultem manufactured by Electric Co., Ltd. is widely used, for example, JP-A-56-82
It can be easily produced by the method described in Publication No. 6.

This polymer is attracting attention as a non-grade thermoplastic engineering plastic with excellent heat resistance, chemical resistance, flame retardance, electrical properties, and moldability, and is used in fields such as electrical, electronic parts, automobile parts, and mechanical parts. It is expected that it will be widely applied.

The adhesive that can be used in the present invention is composed of an epoxy resin, aminobenzylamines, and rubber, and examples of the epoxy resin include the following.

(+) Amine-based epoxy resin, such as N, N, N', N'-tetraglycidyldiaminodiphenylmethane, meta-N, N-diglycidylaminophenylglycidyl ether, N, N, N'
.

It is synthesized from a compound having an amino group or an amide group, such as N°~tetraglycidyl terephthalamide, and shrimp halohydrin, such as epichlorohydrin, methylepichlorohydrin, and epibromhydrin.

Specific examples of compounds having an amino group include diaminodiphenylmethane, meta-xylylene diamine, para-xylylene diamine, meta-aminobenzylamine, para-aminobenzylamine, 1.3-bisaminomethylcyclohexane, 1.4-bisamino Methylcyclohexane, 1
．． 3-diaminocyclohexane, 1,4-diaminocyclohexane, para-phenylene diamine, para-phenylene diamine, benzylamine, diaminodiphenylsulfone, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl ketone, naphthalene diamine, aniline, toluidine, meta-aminophenol, para Examples include amine phenol and aminonaphthol.

Further, specific examples of compounds having an amide group include phthalamide, isophthalamide, terephthalamide, benzamide, toluamide/parahydroxybenzamide, and meta-hydroxybenzamide.

In these compounds having an amino group or an amide group, a hydro group other than an amino group or an amide group; a 1-syl group;
When it has a group that reacts with carboxyl epihalohydrin, part or all of these groups that react with epihalohydrin react with epihalohydrin and may be substituted with an epoxy convex.

(ii) Phenolic epoxy resin bisphenol A diglycidyl ether, EBOTO)
It can be synthesized from a phenolic compound and epihalohydrin, such as YDCN-220 (product of Tobu Kasei Co., Ltd.).

Specific examples of phenolic compounds include phenol, cresol, butylphenol, octylphenol, benzylphenol, cumylphenol, naphthol, hydroquinone, catechol, resorcinol, bisphenol A1 bisphenol F1 bisphenol sulfone, brominated bisphenol A, novolak resin, and sauce. Examples include sol novolank resin, tetraphenylethane, triphenylethane, and the like.

(iii) Alcohol-based epoxy resin, trimethylolpropane triglycidyl ether, neopentyl group. It can be synthesized from an alcohol compound and epihalohydrin, such as recall diglycidyl ether.

Specific examples of alcohol compounds include butyl alcohol, Nillifluoricol such as 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol,
Propylene glycol, dipropylene glycol, polypropylene glycol, 1.4-pucundiol, 1.
6-hexanediol, neopentyl glycol, trimethylolpropane, glycerin, pentaerythritol, polycaprolactone, polytetramethylene ether glycol, polybutadiene glycol, hydrogenated hisphenol A1 cyclohexane dimetatool, bisphenol A ethylene oxide adduct, Bisphenol A・
Examples include polyhydric alcohols such as propylene oxide adducts, and polyester polyols made from these lli alcohols and polyhydric carboxylic acids.

(1v) Epoxide of unsaturated compound cyclopenk diene dieboxide, epoxidized soybean oil,
Epoxidized polybutadiene, vinylcyclohexene dieboxide, styrene oxide, trade name of Union Carbide [! RL-4221, URL-4234, [
! Examples include epoxidized products of unsaturated compounds known such as RL-4299.

(v) Glycidyl ester-based epoxy resin Can be synthesized from carboxylic acid and epihalohydrin, such as benzoic acid glycidyl ester and tetrahydrophthalic acid diglycidyl ester.

Specific examples of carboxylic acids include monocarboxylic acids such as benzoic acid, paraoxybenzoic acid, butylbenzoic acid, adipic acid, sepacic acid, dodecanedicarboxylic acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, and tetrahydrophthalic acid. , methyltetrahydrophthalic acid, hexahydrofucric acid, het acid, nadic acid, maleic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, butanetetracarboxylic acid, benzophenonetetracarboxylic acid, 5-(2. Examples include polycarboxylic acids such as 5-dioxotetrahydrofuryl)-3-methyl-cyclohexene-1,2-dicarboxylic acid.

(vi) Urethane epoxy resin It can be synthesized from the above-mentioned polyhydric alcohol, diisocyanate, and glycidol.

Specific examples of diisocyanates include tolylene diisocyanate, cyphelmethane-4.4'-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and naphthalene diisocyanate.

(vi) Other epoxy resins include tris-evokibropylisocyanurate-1, glycidyl (meth)acrylate copolymers, and modified resins of the above-mentioned epoxy resins with diisocyanates, dicarboxylic acids, polyhydric phenols, etc. It will be done.

From the viewpoint of curing speed and heat resistance, epoxy resins having three or more epoxy groups are particularly preferred, and as types of epoxy resins, amine-based epoxy resins and phenolic epoxy resins Ml are particularly preferred.

In the present invention, epoxy resins can be used alone or in combination of two or more.

Specific examples of the epoxy resin used in the present invention have been listed above, but in the adhesive of the present invention, 1% of the total epoxy resin
00~30% by weight must be epoxy resin with 3 or more epoxy groups in the weight, if the amount of epoxy resin with 3 or more epoxy groups is less than 30% by weight. For example, not only the curing speed of the adhesive of the present invention becomes slow, but also the heat resistance of the cured product decreases.

As aminobenzylamines, para-aminobenzylamines, meta-aminobenzylamines, and seven combinations thereof are used. These adducts, which are products obtained by reacting a resin with an epoxy group under conditions such that the active hydrogen in the amino group is in excess, are included. Furthermore, this adduct may be a separate adduct, an endogenous adduct, or a mixture of both. Even if these benzylamines contain the ortho form that is usually produced as a by-product during the production of the para or meta form, as long as it does not impair the effects of the present invention, it may be used as is without purification as long as it is a small amount. do not have.

In the adhesive of the present invention, the ratio of each component used is that the hydrogen of the amino group in the aminobenzylamine is usually 0.5 to 1.5, preferably 0.8 to one epoxy group in the epoxy resin. It is used at a ratio of ~1.2 pieces.

Further, as for the ratio of the combined use of para-aminobenzylamines and meta-aminobenzylamines, the more the former is used, the lower the melting point of the mixture of the two can be. For example, the melting point of meta-aminobenzylamine is approximately 40°C, but when half of both are used, the melting point drops to approximately 15°C. Therefore, reactivity is improved, curing time is shortened, and heat resistance is also improved.

In the present invention, in order to improve adhesiveness with the base material,
Rubbers that are preferably mixed with rubber include, for example, acrylic ester, silicone, conjugated diene, olefin, polyester, and urethane, but especially acrylic ester, silicone, and conjugated diene Polymers are preferred. These may be used alone or in combination.

As the acrylic ester rubber, for example, JP-A-55
-16053, or as disclosed in JP-A-55-21432, thermosetting resins selected from the group consisting of formaldehyde condensation resins, carboxy group condensation resins, and polyaddition resins and acrylic ester polymers. A graft copolymer consisting of a polymer is used.

In this case, the acrylic ester polymer in the graft copolymer is used as the rubber component.

In addition, as silicone rubber, for example, Japanese Patent Application No. 1986-1
As disclosed in No. 8831, a crosslinked silicone rubber is used in which an incompatible silicone rubber is dispersed in a thermosetting resin and the silicone rubber is an addition type or a polyaddition type. In this case, silicone rubber present in the thermosetting resin is used as the rubber component.

Further, as the conjugated diene rubber, for example, l.

3-butadiene, 1,3-pentadiene, isoprene,
It is produced by polymerizing or copolymerizing monomers such as 1.3-hexadiene and chlorobrene, and commercially available products can be used.

The amount of rubber used is 5 to 40 parts by weight, preferably 12 to 35 parts by weight, per 100 fflft parts of epoxy resin.

When using an acrylic ester-based, silicone-based, or conjugated polymer alone, the amount of rubber used refers to the amount by weight, and the amount of rubber used is the amount dispersed in the graft polymer and thermosetting resin. When used in a state where the resin is used, the amount occupied in each resin is carefully calculated so that it falls within a predetermined usage amount range.

The rubber may be dissolved in an epoxy resin or
You can leave it alone. Alternatively, it may be dissolved in an epoxy resin and precipitated as particles upon curing. Alternatively, a graft copolymer with an epoxy resin may be used.

The adhesive of the present invention includes a curing agent and a curing accelerator.

Binding xylylene diamine, isophorone diamine, 1.
The effects of the present invention include aminos such as 3-bisaminomethylcyclohexane, diaminodiphenylmethane, polyamide resin, triethylamine, dimethylbenzylamine, imidazoles, trisdimethylaminomethylphenol, phenol, cresol, boron trifluoride amine salt, etc. Some of them can be used together as long as they do not impair the quality.

Also solvents, silane and titanium coupling agents, pigments, organic and inorganic fillers, plasticizers, liquid rubbers, probeability agents, leveling agents, antifoaming agents, coolants, non-reactive diluents, and low molecular weight polymers. , glass fiber, carbon fiber,
Metal fibers, ceramic fibers, etc. can also be added.

The adhesive thus obtained may be diluted and mixed with a solvent such as acetone, methyl ethyl ketone, tetrahydrofuran, xylene, toluene, etc., or a mixture thereof, if necessary.

The structural member according to the present invention is produced by manufacturing a component having an arbitrary shape from polyetherimide by a commonly known molding method such as compression molding, transfer molding, injection molding, extrusion molding, etc.
Two or more of these parts are assembled to form a desired structural member, and then bonded to each adhesive surface using an adhesive. The above-mentioned epoxy adhesive is applied to the surface of each part at a concentration of 10 to 1
Apply to a thickness of 00μ, then overlap the adhesive surfaces and apply at normal pressure preferably 1.0Kg/cJ or more to 100Kg/c
- Apply the following pressure and keep it in this state for at least 10 minutes at room temperature, in some cases for several days, or
It may be kept at a temperature of 0°C or higher and 200°C or lower; in this case, the bonding time will be significantly shorter than at room temperature.
If working time is an issue, heat treatment is recommended.

Parts made of polyetherimide do not need to be made of polyetherimide alone; in some cases, polyetherimide may be supplemented with commonly known fillers such as inorganic powders, glass fibers, etc.
It may contain carbon fiber, potassium titanate fiber, etc.

In addition, when manufacturing structural members, depending on the intended use, some parts containing polyetherimide as a main component may be mixed with other materials, such as polyarylate, polyethersulfone, polysulfone, etc., which have a glass transition temperature of 150°C. The above amorphous polymers, polyetheretherketone,
A component made of a crystalline polymer having a glass transition point of 50° C. or higher, such as polyphenylene sulfide, may be used in combination.

(Examples) The present invention will be described below with reference to production examples and examples of epoxy adhesives.

Incidentally, parts or percentages on each side are expressed on a weight M basis unless otherwise specified.

Lia of epoxy, dressing (8) The following rubber components were synthesized.

500 parts of phenolic epoxy resin made from phenol novolac resin and epichlorohydrin (trade name: Epicote 152, Yuka Shell Epoxy ■, main component has 2 epoxy groups in one molecule), 9 parts of acrylic acid, and 1 part of triethylamine. In addition, the temperature was raised to 110°C and the mixture was reacted for 8 hours, thereby producing 509 parts of an epoxy resin into which acrylic acid residues had been introduced.

Next, 370 parts of butyl acrylate, 1 part of azobisdimethylvaleronitrile, and 2 parts of azobisisobutyronitrile were added, and a polymerization reaction was carried out at 70°C for 3 hours and further at 90°C for 1 hour, resulting in an epoxy resin. A graft polymer of acrylic ester and acrylic ester was prepared. (It is referred to as AI.) This product contains 100 parts by weight of graft polymer and 4 parts by weight of rubber component.
It was 2 parts by weight.

Next, as an epoxy resin having three or more epoxy groups, an amine-based epoxy resin made from 4.4° diaminodiphenylmethane and epichlorohydrin (trade name Evoto-1-YH-434, manufactured by Tobu Kasei AM), Using vinyl cyclohexene dieboxide as an epoxy resin having 4 epoxy groups and 2 or less epoxy groups, adhesive (A) was prepared using the following blending ratio.
was manufactured.

Epototo Y) I-43443 part vinyl tsuku U hexene la epoxide
Part 5 A I
33-part aminohensylamine 16.
Part 2 (〇 2.8χ, m 48.3χ, p 48
．． 5χ) Epoxy system - The following was synthesized as a rubber component for production of (B).

Add 12 parts of acrylic acid and 1 part of triethylamine to 600 parts of diglycidyl ether of bisphenol F,
By raising the temperature to 0°C and reacting for 5 hours, 613 parts of an epoxy resin into which residual acrylic acid was introduced was produced.

Next, 15 parts of hydroxyethyl acrylate and 1 part of azobisisobutyronitrile were added to this, and a polymerization reaction was carried out at 70°C for 3 hours and further at 90°C for 1 hour.

Next, 70 parts of a silicone intermediate having a methoxy group in the molecule (Toray Silicone Co., Ltd., product DC-3037),
0.3 part of dibutyltin dilaurate was added and reacted at 150°C for 1 hour. The latter 30 minutes of the reaction was carried out under reduced pressure of 20 mm and 11 g in order to distill off the methanol produced.

In this way, a graft polymer of a modified epoxy resin and a silicone compound was made, and Shin-Etsu Chemical's Shin-Etsu Silicone B-12048 and E-12048 were used.
300 parts of silicone rubber consisting of a lil mixture was added and reacted for 2 hours with strong stirring to produce an epoxy resin in which silicone rubber was dispersed (referred to as Bl). The rubber component was 38 parts by weight.

Next, as an epoxy resin having three or more epoxy groups, an acin-based epoxy resin made from 4,4-diaminodiphenylmethane and epichlorohydrin (Tobu Kasei)
Product name Evo) -Yl+-434, 4 epoxy groups in one molecule) and vinyl cyclohexene diepoxide as an epoxy resin having 2 or less epoxy groups, and adhesive according to the blending ratio shown below. Agent (B) was produced.

Evototo Y11-434 43 parts vinylcyclohexene 11 parts
5th part B1
33 parts aminobenzylamine 16.2 parts (〇 2.8 χ, t 48.3 χ, p 48.5 χ) Epoxy resin (-(C) 11゛2 Epoxy resin having 3 or more epoxy groups As 4,
4゛ - Amine-based epoxy resin made from diaminodiphenylmethane and epichlorohydrin manufactured by Tobu Kasei (trade name: Epo)-YH-434 (4 epoxy groups in one molecule) and having 2 or less epoxy groups Adhesive (C) was produced using vinylcyclohexene dieboxide as the epoxy resin and at the blending ratio shown below.

Evototo Y11-434 43 parts vinyl cyclohexene di 11 x 1
5-part aminobenzylamine 1
Part 3 left LfLL Ho+) Knee Chill 4 MiF resin tlLTE? +100
0 (manufactured by G[! Co., Ltd.) with a molding cuff of 5 ton injection molding machine at a molding temperature of 380°C and 150 x 150 x
A 3-inch plate was produced.

Stack 10 of these flat plates, apply epoxy adhesive (^) or (B) to the stacked part to a thickness of 20μ, and adhere to lO at 100°C for 3 hours with a pressure of B/ctA'. Obtained dragon structural members. This structural member is 100
The samples were immersed in hot water at 10° C. for 10 days to observe changes in adhesion.

The results are shown in Table-1.

Using polyetherimide resin ULTEM2200 (manufactured by General Electric Co., containing 20X glass fiber), a molding temperature of 3.
150 x 150 x 3 fin plates were prepared at 80°C.

This flat plate was glued in the same manner as in Example-1 to a thickness of 3
Obtained structural members for 0 dragons. Changes in the situation after the hot water immersion test were observed in the same manner as in Example-1. The results are shown in Table-1.

Upper ring ■Upolyetherimide resin ULTI! Using M100O (manufactured by GE) and an injection molding machine with a mold clamping cuff of 5 tons,
A 150 x 150 x 3 - flat plate was manufactured at a molding temperature of 380°C.

Ten of these flat plates were stacked, and an epoxy adhesive (C) was applied to the stacked portion to a thickness of 20 μm, and the plates were bonded together under a pressure of 10 kg/cd.

This structural member was immersed in hot water at 100° C. for 10 days, and changes in the adhesion state were observed.

The results are shown in Table-1.

(Effect of the invention) In addition to mechanical properties and thermal properties, the structural member according to the invention has
It also has a remarkable effect on hot water resistance, and its industrial utility value is extremely large.

Table of contents

Claims (1)

Scope of Claims: (a) Consists of 100 to 30% by weight of an epoxy resin having three or more epoxy groups in one molecule, and 0 to 70% by weight of an epoxy resin having two or less epoxy groups in one molecule. A structural member mainly composed of polyetherimide bonded with an adhesive containing an epoxy resin, (b) aminobenzylamines, and (c) rubber.