KR810001802B1 - Poly ethylene terephthalate resin composition - Google Patents

Abstract

Poly(ethylene terephthalate) resin (I), having an improved gloss of resulting moldings, comprised Na salt or K salt selected from carboxyl group-contg. org. polymers and low mol wt. org. ester. Thus, the resin composition was consisted of A) I having > 0.4 specific viscosity B) 10-60wt.% reinforcing materials or filler C) Na salt or K salt of carboxyl group-contg. org. polymer for increasing the crystn. rate of I. D) C1-20 alip. hydrocarbon contg. 1-3 carboxylic acid and org. ester compd. prepd. from HO-(R"O)y-R"' [R" = C2-15 hydrocarbon; R"' = H or C2-20 hydrocarbon (if R"' is H, y is integer between 2-15; if R"' is hydrocarbon, y is integer between 1-15).

Description

Terephthalic Acid Polyethylene Resin Composition

The present invention relates to useful terephthalic acid polyethylene resins that can be used for driving. Specifically, it relates to terephthalic polyethylene containing inorganic enhancers and fillers. It is desirable to increase the strength of a material made of terephthalic acid polyethylene resin made from a reinforcing agent and a coupling agent such as glass fiber, quartz fiber or other mineral fiber in the resin. It is sometimes sufficient to change only a small amount of the resin using a low proportion of beads or mineral fillers. Until now, however, a high mold temperature of 130 ° C. or higher was required to obtain a reinforced or filled resin having a glossy surface and a soft touch surface. If the temperature is not high enough, the molded object will be rough and not shiny. It is considered that the surface of the molded article is not good because the crystallization rate of terephthalate polyethylene is too late at a temperature of 130 ° C. or lower.

On the other hand, in good condition, the mold temperature must be 130 ° C or higher, but such a mold temperature is not practical in the mold field. Because most molds are heated with water, they can only rise to 85-110 ° C.

Molding devices have been devised to raise the temperature above 85-110 ° C by using oils such as oil, but these are generally inconvenient to use and have uneven surfaces due to unacceptable or inadequate molds. Due to this heat-related problem, tools for casting high temperature filled or filled terephthalate polyethylene resins have not been universally used. Preferred is a method of making reinforced or filled terephthalate polyethylene resins that are molded at temperatures below 110 ° C., yet have a smooth and glossy surface. The reinforced or filled terephthalic acid polyethylene resin according to the present invention comprises the following. 1) Sodium or potassium salts selected from organic polymers containing carboxyl groups. 2) Low molecular weight organic esters selected.

In particular, the resin of the present invention is a composition comprising the following.

A. Terephthalate polyethylene having an intrinsic viscosity of at least 0.4.

B. Enhancers or fillers with a weight ratio of 10 to 60%.

H_H/

H_C비율이 0.25보다 낮게 하기에 충분한 양의 카복실기를 함유하는 유기 중합체의 나트륨염이나 칼륨염.C. Mixture of ABC Components

H _H /

Sodium or potassium salts of organic polymers containing carboxyl groups in an amount sufficient to bring the H _C ratio below 0.25.

D. The next compound in an amount sufficient to ensure that TPK is at least 4 ° C. lower than the A B C component mixture.

Aliphatic carboxylic acid having 1 to 20 carbon atoms containing 1 to 3 carboxyl groups and the structural formula HO- (R ＂O) _y -R '', where R 'is 2 to 15 carbon atoms, preferably 2 to 8 hydrocarbon groups, R '' is -H or 2 to 20 carbon atoms, preferably 2 to 12, and when the phosphorus hydrocarbon group R '' is -H, y is 2 to 15, preferably 2 to 8, and R '' is Selected organic esters produced from alcohols in which y is 1 to 15, preferably an integer between 2 and 8, in the case of a hydrocarbon group, the terephthalic acid polyepylene used herein is at least 0.4 intrinsic viscosity. It is desirable that the intrinsic viscosity be at most about 1.2 or less. Intrinsic viscosity is measured at 30 ° C using methylene chloride and trifluoroacetic acid in a 3: 1 ratio (capacity ratio). The concentration of polyethylene terephthalate (PET) used to determine the intrinsic viscosity is 0.5 g in 100 cc of liquid.

Terephthalic acid polyethylene may contain minor amounts of monomers such as diethylene glycol and glutamic acid.

As the reinforcing agent or filler used herein, glass fibers, glass beads, aluminum silicate, quartz, mica, or mixtures thereof may be used, such as a mixture of mica and glass fibers.

H_H/

H_C비율을 0.25이하로 하기위한 본 발명 조성물의 물질(성분)로서는 올레핀과 아크릴산 혹은 메트아크릴 공중합체나 방향족 올레핀과 무수말레인산 공중합체와 같은 카복실기를 함유하는 유기 중합체의 나트륨이나 칼륨염을 포함한다.

H _H /

And the substance (component) of the invention composition for the H _C ratio of 0.25 or less include sodium or potassium salt of an organic polymer containing carboxyl groups, such as olefins and acrylate or methacrylate copolymers and aromatic olefins and maleic anhydride copolymer .

Preferred as such substances are sodium or potassium salts / methacrylic acid copolymers of ethyle (either totally or partially neutralized, eg at least 30% neutralized) and sodium salts / maleic anhydride copolymers of styrene (fully or partially). Neutralized, for example at least 30% neutralized), the olefin or aromatic olefin portion of the copolymers listed above generally accounts for 50-98% of the weight of the copolymer, preferably 80-98%. Copolymers are made by conventional pneumatic polymerization techniques.

Preferred as organic esters of the above-mentioned D-components are aliphatic hydrocarbons having 1-3 carboxyl groups (preferably 1 or 2) in aliphatic carboxylic acids and alcohols having 4-10 carbon atoms. In other words, the R group in the alcohol is an alkyl or alkylene group according to a particular R group.

When the carboxylic acid contains two or more carboxyl groups, it is preferable that both the carboxyl groups form ester (COO) bonds so that the free carboxyl group does not exist in the ester. Moreover, it is preferable that all the hydroxyl groups in alcohol give ester (COO) bond, and the free hydroxyl group does not exist in ester.

Compounds meeting these conditions are listed below. (The numbers in parentheses are the lower fractions of TPK when 1% compound is added to the weight of reinforced or filled terephthalic acid polyethylene.); Butyl carbiate adipate (2.9), triethylene glycol capric acid-capric acid salt (2.7).

In the present invention, (C) and (D) component increases the crystallization rate of the terephthalic acid polyethylene when casting at a temperature of 110 ℃ or less to help to obtain a glossy surface of the mold. The component (C) is believed to primarily increase the rate of crystallization and the component (D) is believed to increase the fluidity of the terephthalic acid polyethylene in the supercooled state by lowering the viscosity of the supercooled mixture. Both components are necessary to obtain a glossy mold.

H_H/

H_C의 비를 0.25보다 낮출수 있는 양이다.

H_H

H_C비를 얻으려면, 테레프탈산 폴리에틸렌을 1/16인치 두께의 판에서 70℃의 온도로 성형한다. 판을 가열하고 95℃와 120℃사이의 온도에서 열을 듀퐁 900차동 열분서기(DTA)에 장치된 차동 스케닝 칼로메타 (DSC)쎌에 기록한다.(

H_H)In the composition of the present invention, the amount of component (C)

H _H /

The amount of H _C can be lowered to 0.25.

H _H

To obtain the H _C ratio, terephthalic polyethylene is molded at a temperature of 70 ° C. on a 1/16 inch thick plate. Heat the plate and record heat at a temperature between 95 ° C and 120 ° C in a differential scanning calometa (DSC) device fitted with a DuPont 900 Differential Thermal Spectrometer (DTA).

H _H )

H_C)온도에서 시료의 응고로 부터 열이 기록된다.

H_H/

H_C의 비율이 결정하의 정도를 측정하는 간편한 방법이라는 것이 밝혀졌다.The plate is brought to 290 ° (temperature near melting point) and the fused sample is cooled to 10 ° C./min. 200-220 ° C

Heat is recorded from the solidification of the sample at H _C ).

H _H /

It has been found that the proportion of H _C is a simple way of measuring the degree of determination.

In the configuration of the present invention, TPK is the temperature at which heat is released most during the aforementioned thermal cycle.

As described above, in the present invention, the amount of component (D) is an amount that lowers at least TPK by at least 4 ° C. from the original composition containing no component (D).

The maximum of the usage-amount of a component (C) and (D) is not prescribed. However, physical properties will be worse as the amount increases. Usually the maximum for any component is 12% by weight of terephthalate polyethylene and the minimum is about 1%. The maximum amount of the salt / methacrylic acid copolymer of ethylene which is a preferred component (C) is about 12% (weight ratio) and the minimum is about 0.5.

However, preferably a range of 2-7% is used.

In addition to the above components, the composition of the present invention may contain such as coloring / manufacturing agent, antioxidant, UV stabilizer, heat inhibitor, and the like, which are usually used in polymer resins.

Additives may be used to improve physical properties such as tensile and extension forces.

As such additives, 0.1-1.5% of epoxy compounds (eg, epoxy compounds made from bisphenol-A and epichlorohydrin) are used in the weight ratio of the composition.

The composition of the present invention is made by mixing the components together by any convenient method. There are no demanding conditions for temperature or pressure. For example, terephthalate polyethylene is mixed and melt-extruded with dry ingredients B, C and D in a suitable mixer or vessel. The extrudate is cut and mixed with the enhancer and the mixture is melt extruded. More conveniently, all ingredients are mixed dry in any suitable mixer or bowl and melt extruded.

H_H/

H_C비율과 TPK는 위에서 설명한 방법에 의해 측정하였다. 주형된 시료의 광택은 실시예에서 정한 도수에 따라 가드너 광택도수기(GG9095)으로 측정하였다.The following examples show the best embodiment of the invention.

H _H /

H _C ratio and TPK were measured by the method described above. Gloss of the molded sample was measured by a Gardner gloss meter (GG9095) according to the frequency determined in the Examples.

EXAMPLE

H_H/

H_C는 0.16이고 D성분의 T_pk는 다른 성분 혼합물의 T_pk보다 낮은 15.4이다.Dry terephthalic acid polyethylene (PET) having an intrinsic viscosity of about 0.6, 277B glass fiber, ethylene / methacrylic acid copolymer (85/15 weight ratio) neutralized by 25% of total OCF and 60% by sodium, 5.7% of PET weight, triethylene Glycol caprylic acid-caprylate is mixed by hand with 5.7% PET by weight, bisphenol A and epichlorohydrin products by 0.6% by weight, and phenolic antioxidants by 0.3% by weight. C component

H _H /

H _C is 0.16 and the D component of the T _pk is lower than 15.4 T _pk of the other components the mixture.

The resulting mixture is extruded at 285 ° C. in a two stage two inch single screw extruder and extruded to 28 inches in vacuum. The extrudate is cut and the resulting resin plate is dried at 110 ° C. for 16 hours in a vacuum oven. The resin plate is 9.2cm high, 7.5cm top diameter, 5.5cm bottom diameter, and 0.19cm thick. The melting point of the casting machine is 295 ℃ but the surface temperature of the casting is 85 ℃ and the circulation time is 10/20.

Gloss is measured several times on the same sample using a Gardner gloss meter (GG-9095 type) at 60 ° C. Gloss is measured at the third point above the perimeter of the vessel. The highest was 64 and the lowest was 50.

In the control experiments, the original subdivision was used except for triethylene glycol caprylic acid-caprylate. The highest gloss was 20 and the lowest was 15. Molding time also increased by 10-30 seconds for casting. Therefore, it was demonstrated that the D component is necessary to obtain substantially high glossiness.

Claims (1)

A. terephthalate polyethylene having an intrinsic viscosity of at least about 0.4, B. Enhancers or fillers in a weight ratio of about 10 to 60%, C.

H _H /

Sodium or calirium salts of organic polymers containing carboxyl groups in an amount sufficient for the proportion of H _{C to} be lower than 0.25 compared to the mixtures of A, B and C, and D. In an amount sufficient to ensure that T _pk is at least 4 ° C. lower than the mixture of ABC components, C1-C20 aliphatic hydrocarbon containing 1-3 carboxylic acids and the structural formula HC- (R '' wherein R 'is a hydrocarbon group having 2-15 carbon atoms, R' 'is -H or A hydrocarbon group wherein y is an integer between 2 and 15 when R 'is H and y is an integer between 1 and 15 when R' is a hydrocarbon group. .