JPS63326A - Novel structural member comprising polyether sulfone - Google Patents

Abstract

PURPOSE:To obtain the title member having excellent mechanical and thermal characteristics and hot water resistance, by joining parts of polyether sulfone with an adhesive comprising a polyester resin and a polyisocyanate. CONSTITUTION:An adhesive is obtd, by blending 100pts.wt. polyester resin (a) whose MW is 3,000-20,000 with 5-25pts.wt. polyisocyanate (B) (e.g., diphenylmethane-4,4'-diisocyanate) and, if necessary, an additive (c) such as a silane coupling agent, a surface active agent, a defoaming agent etc., a flame retardant (d) such as Sb2O3, etc. Then, two or more of parts with arbitrary shapes obtd. by molding polyether sulfone represented by the formula wherein phiis a p-phenylene residue) etc., are assembled together to make a required structural member and each surface to be adhered is coated with the above adhesive in a thickness of 10-100mu and joined together under a pressure of atmospheric-100kg/cm<2> and at room temp. for 10min or more and, if necessary, under heating.

Description

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

(Conventional technology) In recent years, the use of metal materials has become commonplace because high-performance resins are lighter than metals and have corrosion resistance and insulation properties that are not found in metal materials. It has come to be frequently used in various structural members, such as frames and driving parts of electrical and electronic equipment, machinery, automobiles, and aircraft, as well as civil engineering and construction materials.

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

Structural components are things that are difficult to mold using normal molding methods, such as thick plates, large-capacity components, etc. J [Indicates a roughly shaped member, etc., which is generally constructed by assembling various parts with an adhesive layer interposed between them.

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 something.

By using parts and adhesives in this manner, members having arbitrary structures can be manufactured.

Traditionally, such structural members have been manufactured from polyethersulfone by heat fusing, ultrasonic fusing, or using a solvent that partially dissolves the material on the surfaces to be bonded. There were methods such as joining via. What is the shape of heat fusion? It was impossible to join 9t materials, and thick materials could not be joined by ultrasonic welding. Furthermore, bonding methods that use solvents have had problems such as deterioration of the interface due to residual solvent, such as cranking, reduction in adhesive strength, and changes in appearance.

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

(Problems to be Solved by the Invention) An object of the present invention is to provide a new structural member whose main component is polyether sulfone, which is bonded using a new polyester 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 is made of polyether sulfone bonded by an adhesive containing (i) 1041 parts of a polyester resin having a number average molecular weight of 3000 to 20000 and (ii) 5 to 25 parts by weight of polyisocyanate. This is a new structural member whose main components are:

The polyether sulfone referred to in the present invention is a type obtained by, for example, a condensation reaction between an alkali ferulate group and an aromatic halogen group activated with an electron-withdrawing sulfone group in an aprotic polar solvent. It is a linear polymer with three essential bonding units: arylene bonds (aromatic bonds), ether bonds, and sulfone bonds.

For example, a very typical example has the following structure.

[11(-0-φ-so,-φ-]1 f21(-0-φ-SO,-φ-0-φ-0-φ-),
CI(l (41(-0-φ-so,-φ-0-φ-φ-)1+5
1(-0-φ-SO,-φ-φ-SO,-φ-0-φ-
]F61(-0-φ-so,-φ-0-φ-ct+,-
φ-k (-φ- in the above formula represents p-phenylene group) These polyether sulfones are
No. 0067, Special Publication No. 1977-7799 and Special Publication No. 1977
It can be easily produced by the method described in, for example, No.-617.

In the present invention, from the viewpoint of heat resistance, those represented by the above-mentioned formula (1) are particularly preferable.

The polyester resin referred to in the present invention is a resin having a number average molecular weight of 3,000 to 20,000 obtained by a condensation reaction using an aromatic polycarboxylic acid or its lower alkyl ester, an aliphatic polycarboxylic acid, and a polyhydric alcohol as raw materials. It is.

In the present invention, the number average molecular weight refers to the result of measurement using gel permeation chromatography as a polystyrene equivalent value.When the number average molecular weight is less than 3,000, the flexibility of the adhesive is poor, or when the number average molecular weight is less than 20,000. When it is larger, the viscosity of the resin to be handled is high and the coating workability is poor, so that it cannot be used as the adhesive of the present invention.

The aromatic polycarboxylic acid or its lower alkyl ester may be a known one commonly used in conventional polyester resins, such as terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, naphthalene dicarboxylic acid, trimellitic anhydride. Examples include acids or compounds esterified with lower alcohols such as methanol and ethanol, and one or more of these may be used in combination. Examples of the aliphatic polycarboxylic acids include compounds such as succinic acid, adipic acid, azelaic acid, and cepatic acid. Examples of polyhydric alcohols include Eva, ethylene glycol, propylene glycol, butanediol, bentanediol, hexanediol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, and the like. is,
One or more of these may be used in combination.

A polyester obtained by copolymerizing the above acid component and a polyhydric alcohol can be used, but preferably acetone,
Ketone solvents such as methyl ethyl ketone and cyclohexanone, aromatic solvents such as toluene and quidylole, cellosolve solvents such as cellosolve acetate, ethyl cellosolve and butyl cellosolve, and commonly used organic solvents such as trichlorethylene and carbon tetrachloride, either alone or in combination. Polyester resins that are soluble in solvents are preferred.

To give a more specific example, isophthalic acid 20 to 40 mol χ,
Terephthalic acid 20-40 mol χ, adipic acid 20-60
A polyester resin consisting of an acid component containing molar χ and a glycol component consisting of one or more of ethylene glycol, neopentyl glycol, hexanediol, trimethylolpropane, etc., or terephthalic acid 30~
A polyester resin consisting of an acid component containing 40 to 70 moles χ of succinic acid, adipic acid or cepatic acid, and a glycol component consisting of one or more types of ethylene glycol, neopentyl glycol, trimethylolpropane, etc. etc.

The polyisocyanates referred to in the present invention include various isocyanates, such as 2°6-tolylene diisocyanate, 2,4-tolylene diisocyanate, diphenylmethane-4,4°-diisocyanate, and polymethylene polyphenyl polyisocyanate, either alone or in active form. hydrogen compound 2
A prepolymer reacted with is used. Especially workability,
From the viewpoint of heat resistance and the like, diphenylmethane-4,4'-diisocyanate and polymethylene polyphenyl polyisocyanate are preferred.

The adhesive in the present invention has heat resistance, adhesive properties,
Although it has excellent flexibility, it also contains silane cuff-bringing agents that are normally used in adhesives, additives for surfactant and antifoaming sides, flame-retardant inorganic fillers such as antimony dioxide and aluminum hydroxide, and silica. Fillers such as , alumina, etc. can be mixed and used within a range that does not impede the effects of the present invention.

The novel structural member according to the present invention is produced by manufacturing a part having an arbitrary shape using polyether sulfone by a commonly known molding method, such as compression molding, transfer molding, injection molding, extrusion molding, etc., and then assembling two or more of these parts. After forming the desired structural member, each bonding surface is bonded using an adhesive. The adhesive mentioned above is applied to the surface of each part at a concentration of 10 to 100%.
Coat with a thickness of μ, then overlap the adhesive surfaces, under normal pressure preferably 1.0 Kg/co1 or more 100 Kg/cd
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
The temperature may be maintained at a temperature of .degree. C. or higher and 200.degree. C. or lower. In this case, the bonding time is significantly shorter than that at room temperature, so if working time is a problem, heat treatment is recommended.

Parts made of polyether sulfone do not need to be composed of polyether sulfone alone; in some cases, polyether sulfone may contain commonly known fillers such as inorganic powder, glass fiber, carbon fiber, potassium titanate fiber, etc. good.

In addition, when manufacturing new structural members, depending on the intended use, some parts containing polyethersulfone as a main component may be mixed with other materials, such as polyarylate, polyetherimide, polysulfone, etc., which have a glass transition temperature of 150°C.
Parts made of the above-mentioned hycrystalline polymers or crystalline polymers having a glass transition point of 50° C. or higher, such as polyether ether ketone and polyphenylene sulfide, may be used in combination.

〔Example〕

The present invention will be explained in more detail with reference to Examples below. In Examples and Comparative Examples, "parts" and "%" mean parts by weight and % by weight, respectively, unless otherwise specified.

Manufacturing example This example is an example of manufacturing polyester.

In a reactor equipped with a stirrer, condenser and thermometer, add 0.5 mol part of dimethyl terephthalate, 0.5 mol part of isophthalic acid, 0.3 mol part of adipic acid, and 0 mol of neopentyl glycol.
．． 5 mole parts, 0.3 mole parts of 1.6-hexanediol,
0.4 mole part of ethylene glycol, 0.1 mole part of trimethylolpropane, and 0.1 part of dibutyltin oxide were added to 100 parts of the above raw materials, and first 160 parts of
℃, then gradually raise the temperature to 160℃ to 260℃ to perform demethanol reaction and dehydration reaction to promote condensation. When the amount of dehydration becomes small, further condensation is performed under vacuum, and the number average A polyester resin 1 having a molecule of zsooo was obtained. This polyester was dissolved in a mixed solvent consisting of toluene/cyclohexanone/cellosolve acetate-70/20/10 and used.

Polyester was obtained using the resin composition shown in Table 1 in the same manner as Resin 1.

Examples-1 to 4 Polyether sulfone resin PES 4100G (ICr
150 x 150 x 3 m at a molding temperature of 360°C using a 5 ton injection molding machine with a mold clamping cuff.
m flat plates were manufactured.

The adhesive was prepared by mixing each raw material at room temperature according to the formulation in Table 2, and the thickness after drying was 15 mm on the stacked surface of the flat plate.
It was coated to a thickness of ~20μ and dried for 5 minutes in an oven at 80°C.Then, 10 flat plates were stacked together and 1
Bonded at 00℃ for 3 hours at a pressure of 10Kg/ci to a thickness of 3
0III11 structural members were obtained. This structural member is 100
The samples were immersed in hot water at ℃ for 10 days and changes in adhesion were observed.

The results are shown in Table 3.

Example-5 Polyether sulfone resin PES 3601GL20 (
1 (manufactured by: 1 company, containing 20x glass fiber) at a molding temperature of 360°C using a 5 ton injection molding machine with a mold clamping cuff.
A flat plate of 50 x 150 x 3 mm was manufactured.

This flat plate was glued in the same manner as in Example-1 to a thickness of 3
A structural member of 0IIfi was obtained. 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 3.

Comparative Examples 1 to 3 Using polyether sulfone resin PE54100G (manufactured by ICI), using an injection molding machine with a mold clamping cuff of 5 tons,
A 150×15Q×3@@ flat plate was manufactured at a molding temperature of 360°C.

The adhesive was prepared by mixing each raw material at room temperature according to the formulation in Table 2, and the thickness after drying was 15 mm on the stacked surface of the flat plate.
Coated to a thickness of ~20μ and dried in an oven at 80°C for 5 minutes, then 10 flat plates were glued together.
Bonded at 00℃ for 3 hours at a pressure of 10Kg/cd to a thickness of 3
(A structural member of 1w+* was obtained. This structural member was heated to 100°C.
The samples were immersed in hot water for 10 days to observe changes in adhesion.

The results are shown in Table 3.

(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 2 Q group *Displayed as solid content* 3lJE I7:,? (!a lc! fEI
JcO! =: m ~ 31.5 Polymethylene polyphenyl polyisocyanate system...Mitsui Toatsu Kagaku Q product name Reactant of tolylene diisocyanate and trimethylolpropane Effective ℃ α = 11 ~ 1 ℃, non-volatile content 75 χ Procedure master book 1
(issued) March a, 1986

Claims (1)

Scope of Claims: Mainly polyether sulfone bonded by an adhesive comprising (i) 100 parts by weight of a polyester resin having a number average molecular weight of 3,000 to 20,000 and (ii) 5 to 25 parts by weight of polyisocyanate. New structural members as components.