JPH03185050A - Resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition good in moldability, capable of giving molded products of high heat resistance with high mechanical strength retained even after long-term thermal aging, comprising polyethylene terephthalate, a fibrous reinforcing material, a specific compound and polycaprolactone. CONSTITUTION:The objective composition comprising (A) 100 pts.wt. of polyethylene terephthalate, (B) a fibrous reinforcing material, (C) 0.1-1 pt.wt. of a hindered phenolic compound of the formula (R1 and R2 are each methyl or t-butyl; R3 is n-valent alcoholic ester residue or n-valent amine-based amide residue; n is 1-4) {e.g. triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate]} and (D) 3-20 pts.wt. of polycaprolactone >=30000 in number-average molecular weight.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a polyester resin composition that has good moldability, excellent heat resistance, and provides molding distortion. More specifically, the present invention relates to a polyester resin composition that provides mold strain while retaining excellent strength during long-term heat aging.

[Conventional technology]

Polyethylene terephthalate has excellent mechanical properties, electrical properties, heat resistance, chemical resistance, etc., and is used in industrial products such as films. In particular, those reinforced with fibrous reinforcing materials such as glass fibers have excellent performance as engineering plastics due to their excellent rigidity and thermal properties.

Engineering plastics are used as metal substitutes in electrical products, automobile parts, etc.
It is necessary to have the ability to withstand harsh conditions such as being used at high temperatures for long periods of time, and in particular, excellent heat aging resistance is required.

Conventionally, in order to solve such problems, methods of adding various antioxidants such as phosphorus-based antioxidants have been used.

[Problem that the invention seeks to solve]

However, when a phosphorus-based antioxidant or the like is added, the heat aging resistance is slightly improved, but the result is not fully satisfactory.

The object of the present invention is to provide a resin composition that provides a molded article useful as an engineering plastic having excellent heat aging resistance that could not be achieved using conventional techniques.

Means for Solving Problems] As a result of intensive studies to solve these problems, the present inventors discovered that a specific hindered phenol compound and a polyamide with a number average molecular weight of 130,000 or more. The present invention was achieved by discovering that excellent heat aging resistance can be achieved by using caprolactone in combination.

That is, the present invention provides: (1) <A) polyethylene terephthalate 100
Shigesatobe, ([+>Fibrous reinforcing material 0 to 200 parts by weight, ■
0.1 to 1 part by weight of a compound represented by the following general formula (1),
R9 Hz 0 However, R1 and R2 are methyl group or t-butyl group R1 is n-valent alcohol ester residue or n-valent amine amide residue, n is an integer from 1 to 4, (b) number average molecular weight 30,000 or more polycaprolactone 3-20
parts by weight.

The polyethylene terephthalate resin used in the present invention is mainly a polyethylene terephthalate resin obtained by using terephthalic acid or its ester-forming derivative as the acid component and ethylene glycol or its ester-forming derivative as the glycol component. A part of the terephthalic acid component and/or ethylene glycol component may be replaced with a copolymer component.

Such copolymerization components include, for example, isophthalic acid and phthalic acid; halogen-substituted phthalic acids such as tetrabromophthalic acid and tetrabromoterephthalic acid; alkyl-substituted phthalic acids such as methyl terephthalic acid and methyl isophthalic acid; 2,6 - naphthalene dicarboxylic acid 1 such as naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1.5-naphthalene dicarboxylic acid, etc.; diphenyl dicarboxylic acid 1 such as 4,4'-diphenyl dicarboxylic acid, 3,4'-diphenyl dicarboxylic acid, etc. Acids; 4,4'-
Aromatic dicarboxylic acids such as diphenoxyethane dicarboxylic acid; aliphatic or alicyclic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, decadicarboxylic acid, cyclohexane dicarboxylic acid, etc.; trimethylene glycol, tetramethylene glycol , hexamethylene glycol, neopentyl glycol, 1.4-
Aliphatic or alicyclic diols such as cyclohexane dimetatool etc.; dihydroxybenzene I such as hydroquinone, resorcinol etc.; 2゜2-bis(hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)-sulfone Bisphenols such as: aromatic diols such as ether diols obtained from bisphenols and glycols such as ethylene glycol;
Examples include polyoxyalkylene glycols such as holoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, etc.; and oxycarboxylic acids such as ε-oxycaproic acid, hydroxybenzoic acid, hydroxyethoxybenzoic acid, etc.

One or more of these copolymerization components can be used, and the proportion thereof is 20% per total dicarboxylic acid (for oxycarboxylic acid, half the amount is calculated as carboxylic acid).
It is preferably at most mol %, particularly at most 10 mol %.

Furthermore, the above-mentioned polyethylene terephthalate resin may contain a branching component, for example, an acid capable of forming a trifunctional or tetrafunctional ester such as tricarballylic acid, trimellisic acid, trimellitic acid, etc., or tetrafunctional ester such as pyromellitic acid, or glycerin, trimethylolpropane, Copolymerized with 1.0 mol% or less, preferably 0.5 mol% or less, more preferably 0.3 mol% or less of an alcohol capable of forming a trifunctional or tetrafunctional ester such as pentaerythritol. It may be.

The intrinsic viscosity of the polyethylene terephthalate resin mentioned above is
When measured at 35°C using orthochlorophenol solvent, it is 0.35 or more, more 0.45 or more, especially 0.
It is preferably 50 or more.

Such a polyethylene terephthalate resin can be produced by a conventional production method, such as a melt polymerization reaction or a method combining this with a solid phase polymerization reaction.

Specific examples of the fibrous reinforcing material used in the present invention include glass fibers, carbon fibers, aromatic polyamide fibers, silicon carbide fibers, and titanate fibers, but glass fibers are usually often used. Ru. There are no particular restrictions on the diameter and length of the various fibers; however, if the fiber length is not long, it will be difficult to mix and disperse uniformly with polyester and other ingredients; If it is too long, the effect as a reinforcing material will be insufficient, so a fiber length of 0.1 to 10 m is usually used. In particular, when the fibrous reinforcing material is glass fiber, the fiber length is 0.1 m to 10 m. 1 to 7 is preferable, more preferably 0.
3 to 4 ms is desirable. In addition, the fibrous reinforcing material can be treated with various compounds as necessary in order to improve the interfacial adhesion with polyester and increase the reinforcing effect. When using various surface treatment agents, such as vinyltriethoxysilane, T-methacryloxypropylmethoxysilane, β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, T-glycidoxypropyl Those treated with silane-based processing agents such as trimethoxysilane, γ-aminopropyltriethoxysilane, T-chloropropylmethoxysilane, and T-mercaptopropyltrimethoxysilane, and chromium-based processing agents such as methacrylate chromic chloride are used. .

In the present invention, the amount of component (B) added is 0 to 200 parts by weight per 100 parts by weight of thermoplastic polyester. If the amount added exceeds 200 parts by weight, the melt flowability of the composition will deteriorate, making it impossible to obtain a molded product with a good appearance, and the expected effect of the addition as a filler will also be saturated. Unfavorable to reach.

The hindered phenol compound (O component) used in the present invention is a compound represented by the general formula (1). However, R9 and R2 are a methyl group or t-butyl group, and R1 is an n-valent alcohol ester. residue or n
amine-based amide residue, n is an integer of 1-4.

-a Examples of the n-valent alcohol serving as the n-valent alcohol ester residue in formula (1) include n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-nonyl alcohol, lauryl alcohol, and myristyl alcohol. , monohydric alcohols such as octadecyl alcohol, such as ethylene glycol, propylene glycol, 4-butanediol, 1,5-bentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, Examples include glycols such as 2-thiodiethylene glycol, trihydric alcohols such as glycerin and trimethylolpropane, and tetrahydric alcohols such as erythritol and pentaerythritol.

Examples of n-valent amines that become n-valent amine-based amide residues include tetramethylene cyanide, hexamethylene cyanide, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, .2.4-. 2,4.4-trimethylhexylhexamethylene diamine and the like.

Specific examples of hindered phenol compounds include triethylene glycol-bis[3(3-t-phthyl-5-methyl-4-hydroxyphenyl)propione-)Ll, 6-hexanediolbis(3-( 3,5
-di-t-butyl-4-hydroxyphenyl)propionate], pentaerythrityl-tetrakis (3-(3
,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis(3-
(3,5-di-t-butyl-4-hydroxyphenyl)
propionate], octadecyl-3-(3゜5-di-
Examples include t-butyl-4-hydroxyphenyl)propiomonamide, N,N'-hexamethylenebis(3,5-diE-butyl-4-hydroxy-hydrocinnamamide), and the like.

In the present invention, the amount of component 0 added is 0.1 to 1 part by weight per 100 parts by weight of polyethylene terephthalate as component (A). If the amount is less than 0.1 part by weight, excellent aging performance cannot be achieved, and if the amount exceeds 1 part by weight, the effect reaches saturation, which is not preferable.

The polycaprolactone component (■) used in the present invention is usually ε catalyzed by a cationic or anionic initiator.
- Obtained by ring-opening polymerization of caprolactone. Its number average molecular weight is more than 30,000, and 30,000
If it is less than that, excellent heat aging performance will not be exhibited, which is not preferable.

In the present invention, the amount of component (■) added is determined by the amount of component (A) added.
3 to 20 per 100 parts by weight of terephthalate
The amount is preferably 5 to 10 parts by weight, and if it is less than 3 parts by weight, excellent heat aging performance will not be exhibited, and if it exceeds 20 parts by weight, heat resistance (HDT) will decrease, which is not preferable.

Furthermore, the composition of the present invention includes talc, mica, kaolin,
It is preferable to use a crystal nucleating agent such as silica in combination to further promote crystallization.

Further, it is preferable to use a phosphorus type or a sulfur type in combination with the hindered phenol type (Component (2)) because the heat aging resistance is further improved.

In addition, if necessary, ultraviolet absorbers, flame retardants, flame retardant aids,
Colorants, fillers, etc. can be added.

The method for producing the composition of the present invention is not particularly limited, and the composition can be molded into various shapes, such as various molded sheets, fibrous materials, and tubular materials.

〔Example〕

Next, the present invention will be specifically explained using Examples and Comparative Examples.

Examples 1 to 5 and Comparative Examples 1 to 6 Intrinsic viscosity (Fugo, Nor/Tetrachloroethane-6/4
To 100 parts by weight of polyethylene terephthalate (PET) with a concentration of 0.5% and a temperature of 20°C (measured at a temperature of 20°C), 50 parts of glass fiber (Asahi Fiberglass ■3 Chopped Strand No. 429) was added. Parts by weight, 3 parts of tar (Nippon Talc Micro Ace -1), polycaprolactone of various molecular weights (Daicel Chemical Plaxel), and various hindered phenol compounds (Ciba Geigy, Irganox) are shown in Table 1. The mixture was heated to a cylinder temperature of 260°C using a co-directional twin-screw extruder (Ikegai Tetsujir, ■PCl4-45).
"C, the slurry was kneaded and extruded under the conditions of 1 revolution of the slurry and 200 rpm, and then cut with a pelletizer to obtain pellets.

After drying this pellet under reduced pressure until the moisture content is 0.02% or less, the cylinder temperature is 260''C5 injection pressure cuff 00
kg/c4, cooling time 20 seconds and full cycle 35
A test piece of 1/8 inch x 1/2 inch x 5 inch was molded under the molding conditions of 1/2 inch, and the breakage strength was measured according to ASTM D-790, and it was 18.56 k according to ASTM D-648.
The heat distortion temperature under g/d load was measured. In addition, the same molded product was subjected to aging treatment at 150°C for 1000 hours, and the strength retention rate thereafter was evaluated.

Table of results Shown in 1.

Plaxel 4 Molecular weight: 10,000 4 to 67,000 to 100,000 Irganox 010 Irganox Irganox-tsu [Effects of the invention] According to the present invention, a specific hindered phenol compound and polycaprolactone having a molecular weight of 130,000 or more are combined. When used together, it maintains the original performance of polyethylene terephthalate while achieving advanced levels that cannot be achieved by using it alone.
-It has become possible to provide molded products with good anti-aging performance.

Claims (1)

[Claims] (1), (A) 100 parts by weight of polyethylene terephthalate, (B) 0 to 200 parts by weight of fibrous reinforcing material, (C) 0.1 to 1 part by weight of a compound represented by the following general formula (I), ▲
There are mathematical formulas, chemical formulas, tables, etc.▼(I) However, R_1 and R_2 are methyl groups or t-butyl groups, R_3 is an n-valent alcohol ester residue or an n-valent amine amide residue, and n is 1 to 1. An integer of 4, (D
) A resin composition comprising 3 to 20 parts by weight of polycaprolactone having a number average molecular weight of 30,000 or more.