JPS60217256A - Polyester composition - Google Patents

Abstract

PURPOSE:The titled composition, obtained by incorporating a specific ionic copolymer, phosphonite compound or phosphite compound, polyfunctional epoxy compound and fibrous reinforcing material with a polyester, having good moldability and improved heat discoloration resistance and heat resistant strength. CONSTITUTION:A polyester composition obtained by incorporating 100pts.wt. thermoplastic polyester, e.g. PET or PBT, with (A) 0.1-15pts.wt., preferably 1- 10pts.wt. ionic copolymer, consisting of an alpha-olefin and salt of an alpha,beta-unsaturated carboxylic acid, and containing mono- - trivalent metal ions, (B) 0.005-2pts. wt., preferably 0.01-1pt.wt. at least one of phosphonite compound or phosphite compound, (C) 0.01-3pts.wt., preferably 0.1-2pts.wt. polyfunctional epoxy compound, e.g. bis-beta,gamma- epoxypropyl ether, and (D) 0-150pts.wt. fibrous reinforcing material, e.g. glass fibers.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyester composition that has good moldability and provides a molded article with excellent heat discoloration resistance and heat resistant strength. More specifically, the present invention relates to a polyester composition that has a high crystallization rate, provides an excellent molded product even at a mold temperature of about 120° C. or less during injection molding, and has excellent heat resistance stability.

Polyethylene terephthalate has excellent mechanical properties, electrical properties, heat resistance, chemical resistance, etc., and is used in many industrial products as fibers and films.

In this way, when used as fiber or film, 9
Normally, stretched products are used, but for example, when used as injection molded products for plastic purposes,
It is known that since the above-mentioned stretching treatment is not performed, various problems occur in terms of molding and physical properties. In other words, since the crystallization rate at low temperatures is low, the crystallization rate is insufficient at the mold temperature of about 120°C or lower, which is normally used when injection molding other plastics, so the resulting molded product has a Differences in crystallinity occur within the interior, resulting in mechanical properties 1 dimensional stability.

The shape stability becomes non-uniform, and it is extremely difficult to obtain a molded product that can withstand practical use. Many methods have been proposed to solve these problems, such as using a high-temperature mold and adding a crystal nucleating agent or a crystallization promoter.

For example, Japanese Patent Publication No. 45-26225 discloses that when an ionic copolymer (hereinafter abbreviated as ionomer salt) described as component (a) in the claims is added to a thermoplastic polyester, the crystallization rate increases. It is shown. However, a molded article whose basic composition is a thermoplastic polyester and an ionomer salt has a major drawback in that it turns brown when heated at high temperatures for a long period of time, for example at 150 DEG C. or higher for several days.

As a method to prevent heat-resistant discoloration of conventional polymers.

Various phosphorus compounds have been added, but when phosphorus compounds are added to thermoplastic polyester.

It is known that even if heat-resistant discoloration can be prevented, a new problem arises in that the heat-resistant strength is significantly reduced by the addition of a phosphorus compound.

The present inventors conducted extensive research to improve the above-mentioned drawbacks of a composition that has excellent moldability (fast crystallization rate) and has a basic composition of thermoplastic polyester and ionomer salt. It has been found that when a polyfunctional epoxy compound is simultaneously blended with at least one of bosphite or bosphite compounds, the relationship between heat discoloration resistance and heat resistance strength is improved, and when a fibrous reinforcing phase is blended as necessary, mechanical properties and properties are further improved. The present invention was achieved by discovering that a composition with excellent heat resistance can be obtained.

That is, the present invention uses (a) an ionic copolymer consisting of an α-olefin and a salt of an α, β-unsaturated carboxylic acid and containing mono- to trivalent metal ions, based on 100 parts by weight of the thermoplastic polyester. In this case, α, β-unsaturated carboxylic acid or carboxylic acid ester may also be a component of the copolymer depending on the case) 0.1 to 15 parts by weight, (b) at least one of phosphonite compounds or phosphite compounds (0) .005-2 parts by weight, Q\) Polyfunctional epoxy compound 0
．． The present invention relates to a polyester composition containing 0 to 3 parts by weight, and 0 to 150 parts by weight of a fibrous reinforcing material. .

Examples of the thermoplastic polyester used in the present invention include polyethylene terephthalate.

Examples include polyalkylene terephthalates such as polybutylene terephthalate, or copolyesters containing ethylene terephthalate or butylene terephthalate units as main components.

Various acid components and glycol components can be used as copolymerization components. For example, acid components include isophthalic acid, naphthalene dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylmethane dicarboxylic acid, diphenylsulfone dicarboxylic acid, I'-(2-hydroxyethoxy)benzoic acid, 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, Sebacic acid, decane
1,10-dicarboxylic acid, dodecane-1112-dicarboxylic acid, tetradecane-1,14-dicarboxylic acid, heptadecane-1115-dicarboxylic acid, hexadecane-1
, 16-dicarboxylic acid, octadecane-1,18-dicarboxylic acid, icosane-1,20-dicarboxylic acid, decane-1,6-dicarboxylic acid, 6-nitylhexadecane-I+16-dicarboxylic 5-acid, 6-nitylide Examples include decane-1,12-dicarboxylic acid.

Examples of glycol components include propylene glycol, diethylene glycol, pentyl glycol, neopentyl glycol, hexamethylene glycol, polyethylene glycol, and polytetramethylene glycol.

Ionomer salts that can be used as component (a) of the present invention include copolymers of olefins such as ethylene, propylene, and butene-1 and (meth)acrylic acid, and copolymers of olefins and maleic anhydride.

Specific examples include metal salts such as copolymers of styrene and (meth)acrylic acid and copolymers of styrene and maleic anhydride.2 Usually, olefin and (meth)acrylic acid or styrene and (meth)acrylic acid are used. Copolymer metal salts of acids are used. And as a metal that forms a salt with a carboxyl group.

Alkali metals, alkaline earths, A6. Metals of group 1 of the periodic table such as B are used, but alkali metals are excellent in increasing the crystallization rate, and thorium and potassium are also used.

Examples of the phosphonite compound or phosphite compound used as a component in the present invention include tetrakis(2,4-di-tert,-butylphenyl)4,4'-phenylphosphonite, tetrakis(
2,4-di-tert, ~butylphenyl) 4.4
'-diphenylphosphonite, tetrakis(2,4-
Specific examples include di-tert, -butylphenyl)4,4'-diphenyl ether phosphonite, tris(nonylphenyl)phosphite, bis-stearyl-pentaerythritol-diphosphite, and the like. Various epoxy compounds can be used as the polyfunctional epoxy compound used as component (iii), such as bis-β.

γ-epoxypropyl ether, ethylene glycol,
Propylene glycol, butylene glycol, pentyl glycol, neopentyl glycol, hexamethylene glycol, diethylene glycol diglycidyl ethers of bisphenol A, diglycidyl ethers and triglycidyl ethers of glycerol, diglycidyl ethers and triglycidyl ethers of trimethylolpropane, polyglycidyl ethers of diglycidyl, polyglycidyl ethers of zalbitol, and even phthals. acid, isophthalic acid, diglycidyl ester of terephthalic acid, polyglycidyl ester of trimellitic acid,
Specific examples include tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, and 1-epoxyethyl-3,4-epoxycyclohexane.

Examples of fibrous reinforcing materials that may be used in the present invention as needed include glass fibers and carbon fibers.

Specific examples include aromatic polyamide fibers and titanate fibers.

Regarding the blending amount of each component in the polyester composition of the present invention, if the blending amount of component (a), that is, the ionomer salt, is less than 0.1 part by weight based on 100 parts by weight of the thermoplastic polyester, the crystallization rate will be reduced. It does not have the effect of increasing the crystallization rate, and even if more than 15 parts by weight is added, the effect of increasing the crystallization rate does not increase in proportion to the amount added, and on the contrary, it decreases the heat resistance etc. of the polyester, which is not preferable. .

Therefore, the blending amount of component (a) is 0.1 to 15 parts by weight per 100 parts by weight of thermoplastic polyester.

Preferably it is 1 to 10 parts by weight. In addition, if the amount of the component (i.e., at least one of the phosphonite compounds and phosphites 1 to 1) is less than 0.005 parts by weight per 100 parts by weight of the thermoplastic polyester, the heat-resistant discoloration prevention effect will not be sufficient. On the other hand, even if more than 2 parts by weight is added, the discoloration prevention effect is not much different than when 2 parts by weight is added, but on the contrary, discoloration may become significant and the strength decreases significantly, which is not preferable. Therefore, the amount of component (b) is 0.005 to 2 parts by weight, preferably 0.01 to 1 part by weight, per 100 parts by weight of the thermoplastic polyester. Regarding the blending amount, if the blending amount is less than 0.01 parts by weight based on 100 parts by weight of thermo9-plastic polyester, the effect of increasing heat resistance strength will not be sufficient, and on the other hand, if it is blended in more than 3 parts by weight, This is not preferable because the composition may gel.

Therefore, the blending amount of the polyfunctional epoxy compound is 0.01 to 3 parts by weight per 100 parts by weight of thermoplastic polyester.
Preferably it is 0.1 to 2 parts by weight.

Furthermore, regarding the amount of fibrous reinforcing material that may be blended as needed in the present invention, if it is blended in an amount exceeding 150 parts by weight based on 100 parts by weight of the thermoplastic polyester, it will be difficult to mix, disperse, and disperse the material uniformly. It is usually 150 parts by weight or less, preferably 5 to 150 parts by weight.

The composition of the present invention may optionally contain other antioxidants, stabilizers such as ultraviolet absorbers, plasticizers, gate agents, flame retardants, antistatic agents, 9 colorants, mold release agents, fillers, etc. Various inorganic or organic compounds can be blended.

For example, when a hindered phenol type antioxidant is used in combination as an antioxidant, an even more remarkable heat resistance 10- discoloration prevention effect may be exhibited, and in order to further increase the crystallization rate of polyester, a plasticizer compatible with polyester may be used. It is also a useful method to blend the like as a crystallization accelerator.

The polyester composition of the present invention can be mixed and produced by various methods, and the production method is not particularly limited, and it can be produced in various forms and for various uses.

For example, various molded products, films, sheets), fJ! i Fibrous material.

Coating agents, coating agents, which can be formed into tubular objects, etc.
It can also be used as an adhesive and a modifier for other resins.

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Note that "parts" shown in Examples and Comparative Examples indicate "parts by weight."

Example 1. Comparative Examples 1 and 2 Intrinsic viscosity (measured in phenol/tetrachloroethane-6/4, ?a degree 0.5%, temperature 20°C) 0.68 (1
) Surlyn 1555 (manufactured by DuPont, sodium salt of ethylene-acrylic acid copolymer) was added to 100 parts of a pellet of polyethylene telescrate (hereinafter abbreviated as PIET).
3 parts, tetrakis(214-di-tert,-butylphenyl>4.4'-diphenylphosphonite 0.
5 parts, diglycidyl ether of neopentyl glycol [manufactured by Nagase Kasei Kogyo 0 Kiku, trade name Denacol EX, 21
110.5 parts of glass fiber [Asahi Fiber Glass 0-suke manufactured product number 429.3 mm long chopped strand] was blended at 15% by weight based on the total composition, and fed to an extruder to produce 260~ A pellet was made by extrusion at 270°C.

Similarly, for comparison, pellets were prepared from a composition containing neither bosphite nor a polyfunctional epoxy compound (Comparative Example 1) and a composition containing no polyfunctional epoxy compound (Comparative Example 2). The obtained pellet was dried under reduced pressure at 130°C for 8 hours, and the cylinder temperature was 240-270-280°C.
, mold temperature 115℃, injection holding time 10 seconds, cooling time 1
A bending test piece measuring 2 inches x 1/4 inch x 2.5 inches was injection molded for 5 seconds at an injection pressure of 300 to 600 kg/cm'. This test piece was placed in a hot air constant temperature bath at 150°C for 2
Thermal discoloration and oral changes in bending strength after heat treatment for 0 days were investigated. A composition consisting of PET and Surlyn 1555 becomes noticeably discolored when heat treated, and adding phosphonite to it can prevent heat discoloration, but the strength is greatly reduced.Furthermore, blending phosphonite and a polyfunctional epoxy compound at the same time may result in poor heat discoloration and heat resistance strength. I saw my partner improve. The results are shown in Table 1.

13-14- Example 2 770 parts of PIE with intrinsic viscosity of 0.68 1 molecule = 2. ooooo
Surlyn 15552 was added to 1.30 parts of polyethylene terephthalate copolymerized with 10% by weight of polyethylene glycol.
Department.

Phosphite compound represented by the following structural formula (1) 0.3
part, hindered phenolic antioxidant, Irganox 1010 (manufactured by Ciba Geigi Co., Ltd.) 0.2 parts, 3 parts of a polyfunctional epoxy compound represented by the following structural formula (If), 0.3 parts of glass fiber, based on the total composition. 15% by weight, pelletized according to the method shown in Example 1, and molded at a temperature of 10%.
Bending test pieces were molded at 0°C. Bending strength before heat treatment is 1
Even after heat treatment at 150°C for 20 days at 490h/cm2, almost no coloring was observed and the 1 bending strength was 1095K.
g/cmt (retention rate 73.5%).

It showed excellent strength retention.

PI with intrinsic viscosity 0.68! T 60 parts, octadecane
40 parts of polyethylene terephthalate copolymerized with 15% by weight of 1,18-dicarboxylic acid, 4 parts of Surlyn 1601C manufactured by DuPont, ethylene-acrylic acid copolymer sodium salt], and a bosphite compound represented by the following structural formula (■). 0.8 parts of tetrahydrophthalic acid diglycidyl ester and 0.6 parts of glass fibers were mixed to make a total amount of 30% by weight based on the total composition, and the mixture was pelletized by the method shown in Example 1, and the mold temperature was 80°C. A bending test piece was formed using the following steps. The bending strength before heat treatment is 1940Kg/cm2.

Even after heat treatment at 150°C for 20 days, almost no coloring was observed, and the bending strength was 1520 Kg/ctn'' (retention rate 78.4%), showing excellent strength retention.

Patent applicant: Unitika Co., Ltd.

Claims (1)

[Claims] 1. Based on 100 parts by weight of thermoplastic polyester. (a) An ionic copolymer consisting of an α-olefin and a salt of an α, β-unsaturated carboxylic acid and containing mono- to trivalent metal ions (in this case, depending on the case, an α-, β-unsaturated carboxylic acid or Carposi acid ester may also be a component of the copolymer) 0.1 to 15 parts by weight. (b) 0.005 to 2 parts by weight of at least one of phosphonite compounds or bosphite compounds; (c)
0.01 to 3 parts by weight of polyfunctional epoxy compound, +=+1
A polyester composition containing 0 to 150 parts by weight of JIi fibrous reinforcement.