JPH0326751A - Polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having remarkably improved moldability and epoxy resin adhesivity while keeping the characteristic mechanical properties and electrical properties of the base resin by compounding a polyester resin with a specific graft copolymer, a sulfonamide, a reinforcing material, etc. CONSTITUTION:The objective composition is produced by compounding (A) 100 pts.wt. of an aromatic polyester resin with (B) 1-80 pts.wt. of a graft copolymer produced by reacting an ethylene-glycidyl methacrylate copolymer with a monomer selected from styrene, acrylonitrile and methyl methacrylate, (C) 1-30 pts.wt. of a sulfonamide of formula (R<1> is H or 1-5C alkyl; R<2> and R<3> are H or 2-30C alkyl provided that both R<2> and R<3> are not H at the same time; n is 0-5) and (D) 0-150 pts.wt. of a fibrous reinforcing material and/or an inorganic filler. The component C is e.g. benzenesulfone butylamide.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polyester resin composition that is particularly useful as a case for electrical or electronic parts.

(Prior art) Aromatic polyester usually has excellent mechanical properties and electrical insulation properties, so it is suitable as a case material for electrical parts and electronic parts.
Because they are often sealed with epoxy resin or potted for protection, their S contact strength is low and problems such as peeling occur during use. In addition, aromatic polyester molding materials, especially polyethylene terephthalate molding materials, are compounded with mold release agents in order to improve mold release properties and increase productivity, and this negative effect is added to the problem of adhesion with sealants. The properties were even lower, making it unsuitable for this purpose.

Therefore, a polybutylene terephthalate molding material that has both mold releasability and adhesive properties was used as a compromise in combination with modified epoxy resin, but this adhesive property was also unsatisfactory in practical terms, and improvements were needed.

(Problems to be Solved by the Invention) The present invention provides excellent mechanical properties of aromatic polyester,
The objective is to obtain an aromatic polyester compound that maintains heat resistance, electrical properties, and chemical resistance, and has good formability and adhesion to epoxy resin.

(Means for Solving the Problems) Therefore, the present inventors conducted intensive studies in order to obtain a polyester resin composition with good adhesion to epoxy resin and good formability, and as a result, they finally completed the present invention. It was. That is, the present invention has the following features:A. 100 parts by weight of aromatic polyester resin, B. Ethylene-glycidyl methacrylate copolymer, styrene,
1 to 80 parts by weight of a graft copolymer obtained by reacting one or more monomers selected from acrylontolyl and methyl methacrylate; C. Sulfonates 1 to 3 represented by the following general formula (T)
0 parts by weight and D. Fibrous reinforcement and/or inorganic filler 0-150
This is a polyester resin combination product characterized by containing parts by weight. In the present invention, the aromatic polyester, which is the A precept, is a polyester resin containing one or more types of acid component selected from terephthalic acid, isophthalic acid, naphthalene 1,4- or 2,5-dicarboxylic acid, and in addition to these, Aliphatic acids such as adipic acid and sebacic acid can also be used as copolymerization components. Preferably, 85 mol% or more of terephthalic acid,
More preferably, it is an aromatic polyester with an acid content of 95 mol% or more. Examples of the glycol component include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexanedimethanol, 2,2-bis(4-hydroxyphenyl)propane, and the like. Furthermore, a trifunctional moiety may be copolymerized in a small amount so as not to impair moldability. It is preferable that the aromatic polyester resin has an intrinsic viscosity of 0.4 or more as measured at 30° C. using a phenol/tetrachloroethane mixed solvent (674 weight ratio) solution.

Next, the graft copolymer, component B, is composed of ethylene-glycidyl methacrylate or a small amount of a monomer, preferably containing 2 to 20% by weight of glycidyl methacrylate, for example, styrene, acrylonitrile, styrene, etc.・It is a graft copolymer obtained by reacting 15 to 70% by weight of acrylonitrile, methyl methacrylate, styrene methyl methacrylate, acrylonitrile methyl methacrylate, and styrene acrylonitrile methyl methacrylate as main monomers, and from 0.01 to 70% by weight. It has a dispersion structure of 2μ. Note that even if the ethylene-glycidyl meccrylate copolymer and polystyrene, polymethyl methacrylate, or styrene-acrylonitrile copolymer are mechanically kneaded using an extruder or the like, the compatibility is poor and a dispersed structure exceeding 2μ is obtained, so it is preferable. do not have. In addition, the graft copolymerization used in the present invention is
Because they are chemically bonded, they do not separate in the aromatic polyester composition and exist mainly as a graft copolymer. Due to the graft portion having good compatibility with the aromatic polyester, this copolymer is uniformly dispersed in the &Ilt2 product, and therefore,
This is presumably because the glycidyl groups, which are thought to comb with the epoxy resin, are uniformly and effectively distributed, making it difficult for adhesion defects to occur. Note that the effect is small if the graft fraction is less than 15 wt% or more than 70-t%.

If the amount of the graft copolymer is less than 1 part by weight, the effect of improving adhesion will be small, and if it is added in more than 80 M parts, heat resistance and chemical resistance will decrease, which is actually undesirable.

Further, the sulfonamide as the C component used in the present invention consists of one or more types of N-substituted benzenesulfonamide derivatives or N-substituted toluenesulfonamide derivatives represented by formula (I).

-i In formula 1), R1 is a hydrogen atom, a methyl group, an alkyl group having 1 to 5 carbon atoms such as an ethyl group, and l? 2 and R3 are a hydrogen atom or a linear, branched or alicyclic alkyl group having 2 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and are not hydrogen atoms, and n is an integer of 0 to 5.

Specifically, benzenesulfone butyl acetate, o-, p-toluenesulfone butylate, N-cyclhexyl-p-toluenesulfonate, N-ethyl o-. p-
Examples include 1-toluenesulfonamide and tallow p-toluenesulfonamide.

The polyester composite of the present invention containing sulfonamide maintains high adhesion to epoxy resin, has high heat resistance, and has improved mold releasability. This indicates that the crystallinity of the aromatic polyester at low temperatures is enhanced. The effects of the present invention are surprising in view of the fact that it has conventionally been the case that adhesion deteriorates considerably when crystallinity is increased. If this sulfonate is blended in an amount exceeding 30M parts per 100 parts by weight of the aromatic polyester, it is not preferable because it will bleed onto the surface of the shaped product and the appearance will be impaired.

In addition, examples of the fibrous reinforcing material and inorganic filler which are the D precepts used as necessary in the present invention include glass fiber, carbon fiber, potassium titanate, boron fiber, gypsum fiber,
Examples include one type or a combination of two or more types selected from acicular mineral fibers, talc, mineral fibers, glass flakes, wollastonite, clay, calcium carbonate, glass beads, titanium oxide, and the like. These reinforcing materials and inorganic fillers
When the composition of the present invention is blended in an amount of 10 to 150 parts by weight based on 100 parts by weight of polyester, the adhesive strength after heat cycle and thermal shock tests is significantly improved, and the composition becomes even more effective. This is because this composition has high stiffness at high temperatures;
This is thought to be due to the small dimensional change. If the total amount of the fibrous reinforcing material and the inorganic filler exceeds 150 parts by weight based on 100 parts by weight of the aromatic polyester, the moldability will decrease, making it unfavorable for tight molding for electrical and electronic parts.

The composition of the present invention may contain additives such as stabilizers, antioxidants, ultraviolet absorbers, plasticizers, lubricants, flame retardants, antistatic agents, mold release agents, colorants, etc., depending on the purpose and use. It is preferable.

Further, the method for producing the polyester Mi product of the present invention is not particularly limited, and any method may be used. For example, a method of premixing all the ingredients and then kneading them in an extruder or seconder, or a method of premixing an arbitrary number of ingredients in an extruder or seconder, and then adding other ingredients to the pellet obtained. Examples include a method of melting and mixing.

The kumikaimono of the present invention does not require special shaping methods or shaping conditions, and can be molded under certain shaping conditions of ordinary crystalline thermoplastic resin, and has excellent heat-resistant dimensional accuracy and mechanical properties. give something. Therefore, it is used in various prestige items as well as tubular objects, containers, and plate shapes.

(Function) The present invention provides aromatic polyester resin with a specific amount of a specific graft copolymer that has affinity for both aromatic polyester and epoxy resin, and depending on the purpose, a specific sulfonate ξ
By blending specific amounts of resin, fibrous reinforcing materials, and inorganic fillers, the adhesion with epoxy resin is significantly improved, and this molded product can be sealed with epoxy resin or botted for the purpose of protection from the environment. This improves the durability of electrical and electronic components.

(Example) The present invention will be explained below with reference to Examples. Note that parts and percentages in the examples are based on weight. In addition, the characteristics of the test pieces in the examples were evaluated by the following test method.

(I) A test piece with adhesive strength of 100 x 30 x 3 m is annealed at 130'C for 3 hours. On this test piece, in its center 10 x IQ. 30 x 20 x cut out
0.6am (7) Place cardboard as a spacer. Two liquids of addition-type two-component epoxy resin containing acid anhydride as a curing agent are mixed at a ratio of 100:27 into the cut-out portion, and the mixture is degassed under reduced pressure at room temperature and injected. After injection, test beads of the same shape were stacked on the spacer, and Lion Clip No. 11
Set 12 pieces. This was heated at 100'C for 2 hours and then for 1 hour.
Cure at 50°C for 2 hours. After leaving it at 23°C 50% IIH for 24 hours, remove the clip and test it for 5 m using a universal tensile tester Tensilon UTMr model.
The tensile shear strength of the adhesive surface was measured at a deformation rate of /sin and is expressed as adhesive strength.

(2) Heat distortion temperature According to ASTM 0648, high load (I8.6kg/c
Measured under the stress of j).

Examples 1 to 21, Comparative Examples 1 to 17 Polyethylene terephthalate (intrinsic viscosity number 0.62),
Talc (average particle size 4μ), glass fiber (I0μ diameter, 3 square length), various graft copolymers shown in Table 1, and other components were premixed in the proportions shown in Table 2, and then subjected to twin-screw extrusion. PCM30 machine hopper, cylinder temperature 2
Compound chips were obtained by melt-kneading at 70''C.

After drying this compound chip at 130°C for 4 hours, it was placed in an injection molding machine (Nissei Plastic Industries FS) with cylinder temperature adjusted to 26°C to 265°C to 275°C and mold temperature adjusted to 90°C.
Test beads were molded using the following method. The physical properties of the obtained precepts were evaluated and the results are shown in Table 2. Margin table 3 below

Claims (1)

[Claims] A, 100 parts by weight of aromatic polyester resin, B, ethylene-glycidyl methacrylate copolymer,
1 to 80 parts by weight of a graft copolymer obtained by reacting one or more monomers selected from styrene, acrylontrile, and methyl methacrylate, C, 1 to 80 parts by weight of a sulfonamide represented by the following general formula (I);
30 parts by weight and D, fibrous reinforcement and/or inorganic filler 0-150
A polyester resin composition characterized in that it contains parts by weight. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) However, R^1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R^2 and R^3 are a hydrogen atom or an alkyl group having 2 to 30 carbon atoms. R^2 and R^3 are not hydrogen atoms at the same time. Note that n is an integer of 0 to 5.