CA1104734A - Unfilled thermoplastic molding compositions - Google Patents
Unfilled thermoplastic molding compositionsInfo
- Publication number
- CA1104734A CA1104734A CA314,471A CA314471A CA1104734A CA 1104734 A CA1104734 A CA 1104734A CA 314471 A CA314471 A CA 314471A CA 1104734 A CA1104734 A CA 1104734A
- Authority
- CA
- Canada
- Prior art keywords
- vinyl acetate
- ethylene
- weight
- copolymer
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
ABSTRACT OF THE DISCLOSURE
An unfilled thermoplastic molding composition having improved impact resistance is provided, the composition comprising a high molecular weight linear polyester and from about 0.1 to 4.5% by weight, based on the total composition, of a copolymer of ethylene and vinyl acetate.
An unfilled thermoplastic molding composition having improved impact resistance is provided, the composition comprising a high molecular weight linear polyester and from about 0.1 to 4.5% by weight, based on the total composition, of a copolymer of ethylene and vinyl acetate.
Description
3~
This invention relates to improved, unfilled thermoplastic molding compositions and, more particularly, to improved unfilled thermoplastic molding compositions.
High molecular weight linear polyesters and copolyesters of glycols and terephthalic or isophthalic acid have been available for a number of years. These are described inter alia in Whinfield et al, U.S. Patent No. 2,465,319 - dated March 22, 1949, and in U.S. Patent 3,047,539 - dated July 31, 1962. These patents disclose that the polyesters are particularly advantageous as film and fiber formers.
With the developement of molecular weight control, the use of nucleating agents and two-step molding cycles, poly-(ethylene terephthalate) has become an important constituent of injection-moldable compositions. Poly (1,4-butylene terephthalate), because of its very rapid crystallization from the melt, is uniquely usef~l as a component in such compositions. Workpieces molded from such polyester resins, in comparison with other thermoplastics, offer a high degree of surface hardness and abrasion resistance, high gloss, and lower surface friction.
Recently, block copolyesters, wherein the major portion of the repeating units are poly(l,4-butylene terephthalate) blocks, have been found to have enhanced impact resistance.
U.S. Patent No. 3,937,757 - dated February 10, 1976 - Seydl et al teaches that the tracking resistance of poly(l,4~butylene terephthalate) compositions can be improved by the addition of from 5 to 5Q% by weight of a polyolefin or ethylene copolymers, containing at least 50%
by weight ethylene units, thereto.
It has now been surprisingly discovered that if a small amount, i.e., less than 5% by weight, of a ~ 34 8CH-2670 copolymer of ethylene and viny' acetate is incorporated in unfilled thermoplastic molding compositions comprised of high molecular weight linear polyester such as those described hereinbefore, the compositions exhIbit vastly~
improved impact resistance. By the term "unfilled" herein, is meant that the compos~tions of this inYention do not contain fillers like talc and mica or xe-in~orcements, such as glass or conventional flame-~retardants.
According to this invention then, there are pro-vided unfilled thermoplastic compositions w~ich are use~ul for molding or extrusion, e.g~, injection moldingr injection blow molding, compression molding, transfex !
molding, profile extrusion, sheet extrusion, wire coating, extrusion blow molding and the like, the compositions have impro~ed impact resistance, said compositions comprising:
(a~ a high molecular weight linear polyester;
and (b) from about 0.1 to 4~5~, by weight, based on the weight of the total composition, of a copolymer of ethylene and yinyl acetate, ; 20 The high molecular weight linear polyesters used in the praçtice of the pxesent invention are polymeric glycol esters of terephthalic acid and isophthalic acids~
They are available commercially or can be prepared hy kno~n techniques, such as by the alcoholysis of esters of the phthalic acid with a ~lycol and subsequent polymerization, by~ heating ghycols with the free acids or ~ith halide deriyatives thereof, and similar processes.
These are descxibed in ~S. Patent No. 2,465,319 - dated March 22, 1949 - Whi~nfield et al and U,S. Patent No.
3~ 3,047,539 - dated July 31~ 1962 - Pengilly, and elsewhere.
Although the glycol portion of the polyester can contain from two to ten carbon atoms, it is preferred that it contain from two to four carbon at~ms in the form of 1~ 4 73'~ 8CH-2670 linear methylene chains.
Preferred polyesters will be of the family consisting of high molecular weight, polymeric glycol terephthalates or isophthalates having repeating units of the general formula:
This invention relates to improved, unfilled thermoplastic molding compositions and, more particularly, to improved unfilled thermoplastic molding compositions.
High molecular weight linear polyesters and copolyesters of glycols and terephthalic or isophthalic acid have been available for a number of years. These are described inter alia in Whinfield et al, U.S. Patent No. 2,465,319 - dated March 22, 1949, and in U.S. Patent 3,047,539 - dated July 31, 1962. These patents disclose that the polyesters are particularly advantageous as film and fiber formers.
With the developement of molecular weight control, the use of nucleating agents and two-step molding cycles, poly-(ethylene terephthalate) has become an important constituent of injection-moldable compositions. Poly (1,4-butylene terephthalate), because of its very rapid crystallization from the melt, is uniquely usef~l as a component in such compositions. Workpieces molded from such polyester resins, in comparison with other thermoplastics, offer a high degree of surface hardness and abrasion resistance, high gloss, and lower surface friction.
Recently, block copolyesters, wherein the major portion of the repeating units are poly(l,4-butylene terephthalate) blocks, have been found to have enhanced impact resistance.
U.S. Patent No. 3,937,757 - dated February 10, 1976 - Seydl et al teaches that the tracking resistance of poly(l,4~butylene terephthalate) compositions can be improved by the addition of from 5 to 5Q% by weight of a polyolefin or ethylene copolymers, containing at least 50%
by weight ethylene units, thereto.
It has now been surprisingly discovered that if a small amount, i.e., less than 5% by weight, of a ~ 34 8CH-2670 copolymer of ethylene and viny' acetate is incorporated in unfilled thermoplastic molding compositions comprised of high molecular weight linear polyester such as those described hereinbefore, the compositions exhIbit vastly~
improved impact resistance. By the term "unfilled" herein, is meant that the compos~tions of this inYention do not contain fillers like talc and mica or xe-in~orcements, such as glass or conventional flame-~retardants.
According to this invention then, there are pro-vided unfilled thermoplastic compositions w~ich are use~ul for molding or extrusion, e.g~, injection moldingr injection blow molding, compression molding, transfex !
molding, profile extrusion, sheet extrusion, wire coating, extrusion blow molding and the like, the compositions have impro~ed impact resistance, said compositions comprising:
(a~ a high molecular weight linear polyester;
and (b) from about 0.1 to 4~5~, by weight, based on the weight of the total composition, of a copolymer of ethylene and yinyl acetate, ; 20 The high molecular weight linear polyesters used in the praçtice of the pxesent invention are polymeric glycol esters of terephthalic acid and isophthalic acids~
They are available commercially or can be prepared hy kno~n techniques, such as by the alcoholysis of esters of the phthalic acid with a ~lycol and subsequent polymerization, by~ heating ghycols with the free acids or ~ith halide deriyatives thereof, and similar processes.
These are descxibed in ~S. Patent No. 2,465,319 - dated March 22, 1949 - Whi~nfield et al and U,S. Patent No.
3~ 3,047,539 - dated July 31~ 1962 - Pengilly, and elsewhere.
Although the glycol portion of the polyester can contain from two to ten carbon atoms, it is preferred that it contain from two to four carbon at~ms in the form of 1~ 4 73'~ 8CH-2670 linear methylene chains.
Preferred polyesters will be of the family consisting of high molecular weight, polymeric glycol terephthalates or isophthalates having repeating units of the general formula:
2)n - C - ~ ~
wherein n is a whole number of from two to four, and mixtures of such esters, including copolyesters of terephthalic and isophthalic acids of up to about 30 mole percent isophthalic units.
Especially preferred polyesters are poly(ethylene terephthalate) and poly(l,4-butylene terephthalate).
Special mention is made of the latter because it crystallizes at such a good rate that it may be used for injection molding without the need for nucleating agents or long cycles, as is sometimes necessary with poly (ethylene terephthalate).
Illustratively, high molecular weight polyesters will have an intrinsic viscosity of at least about 0.4 deciliters/gram and, preferably, at least 0.7 deciliters/
gram as measured in a 60:40 phenol tetrachloroethane mixture at 30 C. At intrinsic viscosities of at least about 1.1 deciliters/gram, there is a further enhancement in toughness of the present compositions.
The copolymers of ethylene and vinyl acetate which are used in accordance with the present invention are well known to those of ordinary skill in the art and for the most part are commercially available. For the purposes of the invention, i.e., providing improvement in impact 1~4734 8C~ 2670 resistance, it has been found that high or low vinyl - content copolymers can be employed. That is, ethylene-vinyl acetate copolymers containing less than, equal to, or greater than 50% vinyl content can be used herein.
Thus, illustrative copolymers of ethylene and vinyl acetate which are encompassed within the scope of this invention include ethylene-vinyl acetate copolymer having a vinyl TM
content of about 15~ by weight (Alathon 3152, sold by DuPont), ethylene-vinyl acetate copolymer containing 25~ by weight vinyl acetate (Alathon 3892, sold by DuPont), ethylene-vinyl acetate copolymer containing 28~ by weight vinyl acetate (Alathon 3180, DuPont), ethylene-vinyl acetate copolymer containing 45% by weight vinyl acetate TM
(Vynathene EY 903, sold by U.S.I. Chemicals, N.Y., N.Y.), and ethylene-vinyl acetate copolymer containing 52% by weight vinyl acetate (Vynathene EY 904, sold by U.S.I.
Chemicals).
In general, the ethylene-vinyl acetate copolymer additives are employed herein in amounts ranging from about 0.1% to 4.5~, by weight, of the total weight of the composition.
The compositions of the present invention are pre-pared in conventional ways. For example, in one way, the ethylene-vinyl acetate copolymer is put into an extrusion compounder with the polyester resin to produce molding pellets. The copolymer is dispersed in a matrix of the polyester resin in the process. In another procedure, the copolymer is mixed with the polyester resin by dry blending, then either fluxed on a mill and comminuted, or they are extruded and chopped. The ethylene-vinyl acetate copolymer can also be mixed with powdered or granular polyester resin and directly molded, e.g., by injection or ~' ~ 734 8CH-2670 transfer molding techniques. It is always important to thoroughly free the polyester resin from as much water as possible.
In addition, compounding should be carried out to ensure that the residence time in the machine is short;
the temperature is carefully controlled, the friction heat is utilized, and an intimate blend between the copolymer and the polyester resin is obtained.
Although it is not essential, best results are ob-tained if the ingredients are pre-compounded, pelletized, and then molded. Pre-compounding can be carried out in conventional equipment. For example, after carefully pre-drying the polyester resin, e.g., at 125C for 4 hours, a single screw extruder is fed with a dry blend of the polyester and the thylene-vinyl acetate copolymer, the screw employed having a long transition and metering section to ensure melting. On the other hand, a twin screw extrusion machine, e.g., a 28 mm Werner Pfleiderer machine can be fed with resin and additive at the feed port. In 2Q either case, a generally suitable machine temperature will be about 450 to 570F.
The pre-compounded composition can be extruded and cut up into molding compounds such as conventional granules, etc., by standard techniques.
The compositions of this invention can be molded in any equipment conventionally used for thermoplastic compositions. For example, with poly(l,4-butylene-terephthalate), good results will be obtained in an injection molding machine, e.g., of the Newbury type with conventional cylinder temperature, e.g., 450F and conventional mold temperatures, e.g., 1500F. On the other hand, with poly(ethylene terephthalate), because of the ----v ~ ~
lack of uniformity of crystallinization from interior to exterior of thick pieces, somewhat less conve;~tional but still well-known techniques can be used. For example, a nucleating agent such as graphite or a metal oxide, e.g., ZnO or MgO can be included and standard mold temperature of at least 230 F. will be used.
In order that those skilled in the art may better understand how to practice the present invention, the following examples are given by way of illustration and not by way of limitation.
Examples 1-6 The following formulations are mechanically blended, then extruded and molded into test pieces in a Van Dorn injection molding machine. The properties are also summarized in the table below.
Table 1 Example 1 2 -3 4 5 6 7 Inqreditents (parts by weight) TM a 99.8 95.3 95.398.897.395.3 97.3 Alathon 3180b 4.5 1.0 2.5 4.5 Vynathene EY903 4.5 Vynathene EY904d 2.5 Irganox 10930.150.15 0.15 0.15 0.15 0.15 0.05 Ferro 904f0.05 0.05 0.05 0.05 0.05 0.05 .S
Properties Notched Izod Impact ft.lb./in1.08 1.62 1.681.221.331.59 1.34 Unnotched Iæod48.039.5 41.645.145.349.3 43.2 Impact ft.lb./in Tensile strength psi 7991 6804 6920773673487236 7516 Elongation %303 396 289304351 316 329 Gardner Impact 9/10 10/10 10/10 10/10 10/10 10/10 5/10 @ 350 in.lbs.
Non Shatter~total tested A
.
1~47;~ 8CH- 2 6 7 0 Table 1 continued.......
* Control (a) poly(l,4-butylene ~erephthalate)about 0.9 intrinsic viscosity measured in a solution of phenol and tetrachloroethane (60:40) at 30c, available from G.E.
(b) ethylene vinyl acetate copolymer, 28% vinyl acetate (DuPont) (c) ethylene-vinyl acetate copolymer, 45O vinyl acetate (U.S.I. Chemicals) (d) ethylene-vinyl acetate copolymer, 52% vinyl acetate (U.S.I. Chemicals) (e) tetrakis (3,5-di-t-butyl-4 hydroxy phenylpropionyloxy methyl)methane ~f) diphenyl decylphosphite The above data show the improved notched IZOd impact resistance of the compositions within the scope of the invention herein in comparison to the control sample which does not employ the copolymer additive.
Obviously, other modifications and variations of the present invention are possible in light of the above teachings. For example, small amounts of materials such as dyes, pigments, stabilizers and plasticizers and the like can be added to the present compositions. It is to be understood, therefore, that changes may be in the particular embodiments of the invention described which are within the full intended scope of the invention as defined by the appended claims.
~ 7 ~
wherein n is a whole number of from two to four, and mixtures of such esters, including copolyesters of terephthalic and isophthalic acids of up to about 30 mole percent isophthalic units.
Especially preferred polyesters are poly(ethylene terephthalate) and poly(l,4-butylene terephthalate).
Special mention is made of the latter because it crystallizes at such a good rate that it may be used for injection molding without the need for nucleating agents or long cycles, as is sometimes necessary with poly (ethylene terephthalate).
Illustratively, high molecular weight polyesters will have an intrinsic viscosity of at least about 0.4 deciliters/gram and, preferably, at least 0.7 deciliters/
gram as measured in a 60:40 phenol tetrachloroethane mixture at 30 C. At intrinsic viscosities of at least about 1.1 deciliters/gram, there is a further enhancement in toughness of the present compositions.
The copolymers of ethylene and vinyl acetate which are used in accordance with the present invention are well known to those of ordinary skill in the art and for the most part are commercially available. For the purposes of the invention, i.e., providing improvement in impact 1~4734 8C~ 2670 resistance, it has been found that high or low vinyl - content copolymers can be employed. That is, ethylene-vinyl acetate copolymers containing less than, equal to, or greater than 50% vinyl content can be used herein.
Thus, illustrative copolymers of ethylene and vinyl acetate which are encompassed within the scope of this invention include ethylene-vinyl acetate copolymer having a vinyl TM
content of about 15~ by weight (Alathon 3152, sold by DuPont), ethylene-vinyl acetate copolymer containing 25~ by weight vinyl acetate (Alathon 3892, sold by DuPont), ethylene-vinyl acetate copolymer containing 28~ by weight vinyl acetate (Alathon 3180, DuPont), ethylene-vinyl acetate copolymer containing 45% by weight vinyl acetate TM
(Vynathene EY 903, sold by U.S.I. Chemicals, N.Y., N.Y.), and ethylene-vinyl acetate copolymer containing 52% by weight vinyl acetate (Vynathene EY 904, sold by U.S.I.
Chemicals).
In general, the ethylene-vinyl acetate copolymer additives are employed herein in amounts ranging from about 0.1% to 4.5~, by weight, of the total weight of the composition.
The compositions of the present invention are pre-pared in conventional ways. For example, in one way, the ethylene-vinyl acetate copolymer is put into an extrusion compounder with the polyester resin to produce molding pellets. The copolymer is dispersed in a matrix of the polyester resin in the process. In another procedure, the copolymer is mixed with the polyester resin by dry blending, then either fluxed on a mill and comminuted, or they are extruded and chopped. The ethylene-vinyl acetate copolymer can also be mixed with powdered or granular polyester resin and directly molded, e.g., by injection or ~' ~ 734 8CH-2670 transfer molding techniques. It is always important to thoroughly free the polyester resin from as much water as possible.
In addition, compounding should be carried out to ensure that the residence time in the machine is short;
the temperature is carefully controlled, the friction heat is utilized, and an intimate blend between the copolymer and the polyester resin is obtained.
Although it is not essential, best results are ob-tained if the ingredients are pre-compounded, pelletized, and then molded. Pre-compounding can be carried out in conventional equipment. For example, after carefully pre-drying the polyester resin, e.g., at 125C for 4 hours, a single screw extruder is fed with a dry blend of the polyester and the thylene-vinyl acetate copolymer, the screw employed having a long transition and metering section to ensure melting. On the other hand, a twin screw extrusion machine, e.g., a 28 mm Werner Pfleiderer machine can be fed with resin and additive at the feed port. In 2Q either case, a generally suitable machine temperature will be about 450 to 570F.
The pre-compounded composition can be extruded and cut up into molding compounds such as conventional granules, etc., by standard techniques.
The compositions of this invention can be molded in any equipment conventionally used for thermoplastic compositions. For example, with poly(l,4-butylene-terephthalate), good results will be obtained in an injection molding machine, e.g., of the Newbury type with conventional cylinder temperature, e.g., 450F and conventional mold temperatures, e.g., 1500F. On the other hand, with poly(ethylene terephthalate), because of the ----v ~ ~
lack of uniformity of crystallinization from interior to exterior of thick pieces, somewhat less conve;~tional but still well-known techniques can be used. For example, a nucleating agent such as graphite or a metal oxide, e.g., ZnO or MgO can be included and standard mold temperature of at least 230 F. will be used.
In order that those skilled in the art may better understand how to practice the present invention, the following examples are given by way of illustration and not by way of limitation.
Examples 1-6 The following formulations are mechanically blended, then extruded and molded into test pieces in a Van Dorn injection molding machine. The properties are also summarized in the table below.
Table 1 Example 1 2 -3 4 5 6 7 Inqreditents (parts by weight) TM a 99.8 95.3 95.398.897.395.3 97.3 Alathon 3180b 4.5 1.0 2.5 4.5 Vynathene EY903 4.5 Vynathene EY904d 2.5 Irganox 10930.150.15 0.15 0.15 0.15 0.15 0.05 Ferro 904f0.05 0.05 0.05 0.05 0.05 0.05 .S
Properties Notched Izod Impact ft.lb./in1.08 1.62 1.681.221.331.59 1.34 Unnotched Iæod48.039.5 41.645.145.349.3 43.2 Impact ft.lb./in Tensile strength psi 7991 6804 6920773673487236 7516 Elongation %303 396 289304351 316 329 Gardner Impact 9/10 10/10 10/10 10/10 10/10 10/10 5/10 @ 350 in.lbs.
Non Shatter~total tested A
.
1~47;~ 8CH- 2 6 7 0 Table 1 continued.......
* Control (a) poly(l,4-butylene ~erephthalate)about 0.9 intrinsic viscosity measured in a solution of phenol and tetrachloroethane (60:40) at 30c, available from G.E.
(b) ethylene vinyl acetate copolymer, 28% vinyl acetate (DuPont) (c) ethylene-vinyl acetate copolymer, 45O vinyl acetate (U.S.I. Chemicals) (d) ethylene-vinyl acetate copolymer, 52% vinyl acetate (U.S.I. Chemicals) (e) tetrakis (3,5-di-t-butyl-4 hydroxy phenylpropionyloxy methyl)methane ~f) diphenyl decylphosphite The above data show the improved notched IZOd impact resistance of the compositions within the scope of the invention herein in comparison to the control sample which does not employ the copolymer additive.
Obviously, other modifications and variations of the present invention are possible in light of the above teachings. For example, small amounts of materials such as dyes, pigments, stabilizers and plasticizers and the like can be added to the present compositions. It is to be understood, therefore, that changes may be in the particular embodiments of the invention described which are within the full intended scope of the invention as defined by the appended claims.
~ 7 ~
Claims (7)
1. An unfilled thermoplastic molding composition having improved impact resistance, the composition comprising:
(a) a poly(1,4-butylene terephthalate) resin, and (b) from about 0.1 to 4.5% by weight, based on the total weight of the composition, of an impact resistance improving additive, said additive consisting of a copolymer of ethylene and vinyl acetate.
(a) a poly(1,4-butylene terephthalate) resin, and (b) from about 0.1 to 4.5% by weight, based on the total weight of the composition, of an impact resistance improving additive, said additive consisting of a copolymer of ethylene and vinyl acetate.
2. A composition as defined in claim 1 wherein component (a) has an intrinsic viscosity of at least about 0.4 deciliters per gram when measured in a solution in 60:40 mixture of phenol and tetrachloroethane at 30°C.
3. A composition as defined in claim 1 wherein said copolymer of ethylene and vinyl acetate contains more than 50%
by weight vinyl acetate.
by weight vinyl acetate.
4. A composition as defined in claim 1 wherein said copolymer of ethylene and vinyl acetate contains 50% or less, by weight, vinyl acetate.
5. A process for improving the impact resistance of a poly(1,4-butylene terephthalate) resin, said process comprising intimately admixing with said poly(1,4-butylene terephthalate) resin from about 0.1% to 4.5%, by weight, of the total composi-tion, of an impact resistance improving additive, said additive consisting of a copolymer of ethylene and vinyl acetate.
6. A process as defined in claim 5 wherein said copolymer of ethylene and vinyl acetate contains 50% or less, by weight, vinyl acetate.
7. A process as defined in claim 5 wherein said copolymer of ethylene and vinyl acetate contains more than 50%, by weight, vinyl acetate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US86605977A | 1977-12-30 | 1977-12-30 | |
| US866,059 | 1977-12-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1104734A true CA1104734A (en) | 1981-07-07 |
Family
ID=25346842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA314,471A Expired CA1104734A (en) | 1977-12-30 | 1978-10-27 | Unfilled thermoplastic molding compositions |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS54100451A (en) |
| AU (1) | AU527661B2 (en) |
| CA (1) | CA1104734A (en) |
| DE (1) | DE2855512A1 (en) |
| FR (1) | FR2413433B1 (en) |
| GB (1) | GB2011443B (en) |
| NL (1) | NL7812414A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4185047A (en) * | 1977-12-30 | 1980-01-22 | General Electric Company | Thermoplastic molding compositions |
| US4322333A (en) * | 1979-11-05 | 1982-03-30 | General Electric Company | Reinforced PBT-copolyaromatic/aliphatic block copolyesters |
| US4369280A (en) * | 1981-08-04 | 1983-01-18 | General Electric Company | Polybutylene terephthalate molding compositions and articles molded therefrom |
| US4564658A (en) * | 1982-11-24 | 1986-01-14 | General Electric Company | Thermoplastic polyester-linear low density polyethylene molding compositions |
| DK480086A (en) * | 1985-10-09 | 1987-04-10 | Kuraray Co | SPRAJTE-STRAEKBLAEST TANK |
| US5196482A (en) * | 1990-07-31 | 1993-03-23 | General Electric Company | Thermoplastic molding compositions |
| WO1993004123A1 (en) * | 1991-08-27 | 1993-03-04 | General Electric Company | Thermoplastic molding compositions |
| WO1993018526A1 (en) * | 1992-03-06 | 1993-09-16 | Raychem Corporation | Dual wall insulation and jacketing |
| DE4314042A1 (en) * | 1993-04-29 | 1994-11-03 | Bayer Ag | Thermoplastic molding compounds based on polyalkylene terephthalate and ethylene-vinyl acetate polymers |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD82565A (en) * | ||||
| DE1694168A1 (en) * | 1967-07-18 | 1971-06-09 | Hoechst Ag | Thermoplastic polyester molding compounds |
| JPS517827B2 (en) * | 1971-09-25 | 1976-03-11 | ||
| JPS554156B2 (en) * | 1972-08-15 | 1980-01-29 | ||
| JPS5644892B2 (en) * | 1973-03-30 | 1981-10-22 | ||
| JPS5072950A (en) * | 1973-09-04 | 1975-06-16 | ||
| JPS5120231A (en) * | 1974-07-31 | 1976-02-18 | Toray Industries | KINZOKUHIFUKUYOJUSHI SEIBUTSU |
| US4172859A (en) * | 1975-05-23 | 1979-10-30 | E. I. Du Pont De Nemours And Company | Tough thermoplastic polyester compositions |
-
1978
- 1978-10-27 CA CA314,471A patent/CA1104734A/en not_active Expired
- 1978-12-13 GB GB7848352A patent/GB2011443B/en not_active Expired
- 1978-12-14 AU AU42543/78A patent/AU527661B2/en not_active Expired
- 1978-12-21 NL NL7812414A patent/NL7812414A/en not_active Application Discontinuation
- 1978-12-22 DE DE19782855512 patent/DE2855512A1/en not_active Withdrawn
- 1978-12-27 JP JP16463278A patent/JPS54100451A/en active Pending
- 1978-12-29 FR FR7836879A patent/FR2413433B1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2413433B1 (en) | 1985-12-20 |
| GB2011443A (en) | 1979-07-11 |
| AU4254378A (en) | 1979-07-05 |
| JPS54100451A (en) | 1979-08-08 |
| GB2011443B (en) | 1982-10-13 |
| DE2855512A1 (en) | 1979-07-05 |
| AU527661B2 (en) | 1983-03-17 |
| NL7812414A (en) | 1979-07-03 |
| FR2413433A1 (en) | 1979-07-27 |
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