WO2013104081A1 - Composition d'élastomère de polyéther-ester thermoplastique et film préparé à partir de celle-ci - Google Patents

Composition d'élastomère de polyéther-ester thermoplastique et film préparé à partir de celle-ci Download PDF

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Publication number
WO2013104081A1
WO2013104081A1 PCT/CN2012/000025 CN2012000025W WO2013104081A1 WO 2013104081 A1 WO2013104081 A1 WO 2013104081A1 CN 2012000025 W CN2012000025 W CN 2012000025W WO 2013104081 A1 WO2013104081 A1 WO 2013104081A1
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Prior art keywords
film
thermoplastic elastomer
derivatives
group
composition
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PCT/CN2012/000025
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English (en)
Chinese (zh)
Inventor
林裕卫
蔡朝辉
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佛山佛塑科技集团股份有限公司
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Priority to KR1020147021577A priority Critical patent/KR101795669B1/ko
Priority to PCT/CN2012/000025 priority patent/WO2013104081A1/fr
Publication of WO2013104081A1 publication Critical patent/WO2013104081A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59

Definitions

  • the present invention relates to a polydecyl ester thermoplastic elastomer composition and a film produced therefrom; more particularly, the present invention relates to a polyetherester thermoplastic elastomer composition having high gas permeability and a film produced therefrom.
  • Polydecyl ester thermoplastic elastomer materials are the focus of research at home and abroad in recent years. From the synthesis of various raw material resins to various modification methods, the synthesis mainly focuses on the molecular structure design and basic performance design; the modification is based on Formulation changes are made by processing conditions, use, and various performance requirements. The current modification mainly focuses on the formulation of photothermal stability and the improvement of moisture permeability.
  • CN101358020 discloses a modified formulation of a modified polyetherester film material which enhances the thermal stability of the product by the addition of organic functional materials.
  • CN1032220C discloses a water vapor permeable thermoplastic film comprising polyetheresteramine as a main component, which improves the moisture permeability and mechanical strength of the product.
  • CN1303408 discloses a polydecyl ester copolymer composition having greatly improved UV stability, which is particularly suitable for use as a film.
  • CN1278839 discloses the preparation of polyetheresteramides and articles thereof.
  • CN101346228 discloses a waterproof, water vapor permeable multilayer film having at least one first layer and
  • a thermoplastic polymer selected from the group consisting of polydecyl esters, polyphthalamides or polyether urethanes, and are bonded to each other.
  • US 6,380,290 discloses the addition of organic materials to polydecyl ester elastomers to improve thermal stability.
  • US 7,422,795 B2 discloses an elastomeric film having an organic soft segment and an organic hard segment. No. 4,562,232 discloses the use of dimers to improve the hot melt behavior and crystallization of polyetherester starting materials to increase the pressure resistance.
  • US 6,749,923 discloses a highly permeable film formed on a substrate.
  • US 6,261,674 discloses a two layer breathable polymer film which has a second spread which is lower than the first moisture permeability.
  • US 6,1 14,024 discloses a 5-spread breathable film in which a core layer and an adhesive layer are coextruded and stretched into a film.
  • No. 5,998,505 discloses the composition of a microporous organic thermoplastic elastomer and a film forming method which is formed by solution or extrusion. Summary of the invention
  • An object of the present invention is to provide an improved polystyrene ester thermoplastic elastomer composition and a film prepared therefrom, wherein the film produced has excellent moisture permeability, a small wet resistance value and excellent mechanical properties.
  • the present invention provides a composition of a polydecyl ester thermoplastic elastomer, wherein the composition comprises, by mass percentage, the composition comprises:
  • dispersant is a group having an affinity with the chewable ester thermoplastic elastomer Machine material.
  • the polyether ester thermoplastic elastomer resin material may be a copolymer and a blend of a dicarboxylic acid and a diol, an epoxy compound, and an auxiliary agent; or a bisamide and Copolymers and blends of diols, and epoxy compounds and auxiliaries. Copolymers and blends of dicarboxylic acids and diols, epoxides and auxiliaries are preferred.
  • the blend may also include a secondary recovery of a polyetherester thermoplastic elastomer or a thermoplastic film recyclate of the present invention.
  • the inorganic powder material may be compounded with various inorganic powders or various inorganic powders, and the compounding ratio may be any, preferably titanium dioxide, silicon dioxide, montmorillonite, various inorganic pigments, carbonic acid. Calcium, barium sulfate white, ceramic powder, etc., wherein the inorganic pigment can also be used alone or in combination with a plurality of inorganic pigments, and the compounding ratio is arbitrary, wherein the ceramic powder can be aluminum oxide, can reflect infrared rays, and emit negative ions.
  • the nanometer powder; wherein the powder particle diameter is preferably from 0.1 to 30 ⁇ , more preferably from 0.1 to 20 ⁇ , still more preferably within 5 ⁇ .
  • the amount of the inorganic powder added is preferably 5 to 75%, more preferably 10 to 59%.
  • the molecular weight of the organic low molecular material is preferably less than 2,000, more preferably less than 1,000, which may be one or more photothermal stabilizers and one or more selected from a group of substances: antioxidants, dyes, chain extenders, and perfumes; wherein the photothermal stabilizers include: benzophenones, benzoxazinone, benzoxazoles, and benzotriazoles
  • the antioxidant is one or more substances selected from the group consisting of pentaerythritol diphosphite antioxidants, triazines, esters, hindered benzoates, hindered amines.
  • the inorganic material and the organic low molecular material may be compounded or used alone, preferably compounded, and the compounding ratio is arbitrary, preferably 10: 1-1 : 1.
  • the dispersing agent is preferably a paraffin wax, a fatty acid, an aliphatic amide, an ester, a saponin, and/or a low molecular wax. More preferred are fatty acids, aliphatic amides, esters, and/or low molecular waxes.
  • the proportion of the dispersant is preferably from 0.1% to 4%, more preferably from 0.4% to 3%.
  • the polyether ester thermoplastic elastomer composition of the present invention may comprise: 22% to 92% of a polyether ester thermoplastic elastomer resin material, 5 to 75% of an inorganic powder material, and/or Organic low molecular materials, and 0.1-4% dispersant.
  • the poly-K ester thermoplastic elastomer composition of the present invention may comprise: 42% to 88% of a polyetherester thermoplastic elastomer resin material, 10-59% of an inorganic powder material and/or Or organic low molecular materials, and 0.4-3% dispersant.
  • the present invention provides a polyetherester thermoplastic elastomer film prepared from the above composition, which film has a thickness of from 1 to 250 ⁇ m, preferably from 2 to 100 ⁇ m, more preferably 2-50 ⁇ , of which 2-30 ⁇ is better, 2-1 5 ⁇ is optimal.
  • the moisture permeability of the film of the invention should be above 100g/m 2 *24h, preferably at 1000g/m 2 *24h, 5000g/m 2 *24h or more, wherein ultra-high moisture permeability
  • the moisture permeability is more preferably 7000 g/m 2 * 24 h or more.
  • the wet resistance value of the film of the present invention is preferably less than 20 m2Pa/w (ISO11092), wherein 15 m2Pa/w or less is preferable, 2 m2Pa/w or less is more preferable, and 1.5 m2Pa/w or less is optimal.
  • the moisture permeability is related to the formulation, appearance, processing technique, thickness, and the like of the film.
  • the above composition may be mechanically mixed by a twin screw or a single screw, and then subjected to premixed fusion granulation or directly extruded into a film, which is preferably carried out according to different formulations.
  • a twin screw or a single screw it is preferred to directly extrude into a film, and if it contains an inorganic powder formulation, it is preferably premixed and melt granulated to form a film.
  • a multi-extrusion co-extrusion or single-layer extrusion apparatus may be employed, and when the layers are co-extruded, the materials of the respective layers are uniform. It is preferably a single screw multi-extrusion co-extrusion or a single-layer extrusion, more preferably 1-3 layers of extrusion.
  • the melt processing temperature may be 160-300 degrees Celsius, preferably 160-270 degrees Celsius, and may be adjusted according to the formulation, such as an inorganic powder formulation, and the temperature is preferably 190-260 degrees Celsius, such as pure organic low molecular weight. Formulation, the temperature is again preferably 180-240 degrees Celsius.
  • the various processing steps may be intermediate special processes, trimming, splitting, slitting into rolls, etc., preferably any of the processes are combined or separately performed, wherein the intermediate special processes may be surface treatment, solvent cleaning, printing, Online curing, coating or gluing, etc., preferably surface treatment, printing, sizing, and in-line aging.
  • the surface treatment method is on-line or off-line, preferably on-line, and the method includes imprinting pigment, pattern, and matte molding; sizing is mainly a coating process of coating, glue, etc. according to requirements; performing various online curing methods, preferably For online mode matching production line speed, as described in CN101767465A.
  • the intermediate special process changes the properties of the product, particularly in terms of moisture permeability, appearance, strength, hand feeling, toughness and the like.
  • the film product of the present invention may be matt, bright, transparent, transparent, translucent, or matt.
  • the light transmittance ASTM D 1003-2007
  • the transparent film is preferably 80% -100%
  • the opaque color film is 20%-100%
  • the matte film is used. It is preferably 30% to 100%.
  • the film of the present invention is tested at a temperature lower than 50 ° C above the melting point of the above polyetherester film formulation, and the heat shrinkage ratio in the longitudinal and transverse directions is maintained within 5%, preferably within 3%.
  • the above method for testing the heat shrinkage rate is to take a square sample and mark the mark of 0, 90, 45 and 135 degrees of A 10 mm - 1000 mm on the sample with a ruler at 25 ° C and 50% humidity.
  • the test is carried out in an oven at a temperature lower than the melting point of the above polyether ester film formulation by 50 degrees Celsius or more, and taken out after 10s-300s, and then the test length B is tested with each ruler.
  • the change of the heat shrinkage size of the film has a certain relationship with the process means in the process of film preparation.
  • the elongation at break ( ASTM D828 ) of the film of the invention is greater than 120%, preferably more than 200%, and the value is the toughness performance of the film.
  • the tensile elastic recovery rate of the film of the invention is more than 35%, 40% or more is superior, and 60% or more is more preferable. This value is closely related to the formulation and is also affected by the internal microstructure of the polyester material.
  • This test method simulates the FZ00007 fixed length elastic recovery test design, using a tension machine, pay attention to the film material below 20ym, the upper and lower fixtures of the tension machine are preferably coated with soft materials.
  • the film is cut into a strip film sample of 15 mm width and 15 cm length, the sample is clamped to the upper clamp, and the lower clamp is also clamped to the lower end of the sample to ensure that the effective length of the sample on the tensile machine is 10 cm (L0).
  • the upper clamp is stretched to a film length L1 at a temperature of from 100 mm/min to 1000 mm/min, preferably from 100 mm/min to 500 mm/min, and the length may be from 1 to 45 cm, preferably from 15 to 30 cm, and then
  • the upper jig returns to L0 at the same speed, and the number of times is repeated 2 to 12 times, preferably 2 to 10 times, and more preferably 3 to 9 times.
  • the present invention also provides lamination of a thermoplastic resin film. And wherein the laminate comprises:
  • At least one layer of thermoplastic resin products At least one layer of thermoplastic resin products
  • thermoplastic resin product layer is a thermoplastic resin film or a thermoplastic resin fiber product
  • thermoplastic resin fiber product is a textile fiber and/or a non-woven fabric (non-spunbond nonwoven fabric or a material containing a spunbonded nonwoven fabric structure).
  • the textile fiber may be a fiber material selected from the group consisting of polyether esters and Derivative fiber, polyester and its derivative fiber, nylon and its derivative fiber, spandex and its derivative fiber, and polypropylene and its derivative fiber;
  • the non-woven fabric may be a non-woven fabric selected from the group consisting of: Non-woven fabrics of olefins and their derivatives, non-woven fabrics of polyester and its derivatives, non-woven fabrics of nylon and its derivatives, non-woven fabrics of spunlace and its derivatives, and non-woven fabrics of degradable plant fibers and their derivatives
  • Preferred are polypropylene nonwoven fabrics, polyester nonwoven fabrics, and nonwoven fabrics of degradable vegetable fibers and derivatives thereof.
  • the adhesive layer is a discontinuous layer, more preferably a discontinuous layered layer, a striped strip layer or a grid-like layer to increase the breathability and moisture permeability of the laminate.
  • the films and exhibits prepared by using the polyacrylate thermoplastic elastomer composition of the present invention have excellent performance in terms of gas permeability, moisture permeability, wet resistance value, and mechanical properties.
  • the invention is further described in the following with reference to the accompanying drawings and specific embodiments.
  • Example one to ten As shown in Table 1, the sample-measured mixture of Examples 1 to 10 was measured by the thermal analysis instrument DSC to directly measure the melting point of the mixture, and directly into the co-extrusion melt-molding thin (see Fig. 2)!] Working temperature 160 °C - 290 ° C, through the surface treatment process, trimming, winding, and finally prepared into a 20 ⁇ ⁇ matte film finished film, film speed of 30m / min.
  • Formulation 7 is a 20 ⁇ matte white film finished product, and the formulas of five, six, eight, and ten are 20 ⁇ fragrance matte white film products, and the specific performance test is shown in Table 2.
  • Example 1 show that the appropriate photothermal stabilizer has an effect on the improvement of thermal temperature and toughness. Comparing Example 3 with Example 4, the moisture permeability of the example 4 was significantly improved, but the elongation at break decreased and the elastic weight recovery rate decreased. The appearance of Example 6 was significantly better than that of Example 5, and the elongation at break was improved, but it was still much lower than the other examples, the thermal stability was better, and the elastic recovery rate was lowered.
  • Example 7 The elongation at break of Example 7 is close to the normal level, the thermal stability is kept close to that of Example 6, the moisture permeability is higher than other examples, and the elastic recovery rate is slightly decreased.
  • Examples 8 to 10 are aroma films, and the addition of the fragrance does not affect the moisture permeability of the product, but the modulus of elasticity slightly increases.
  • the moisture permeability was slightly improved in the examples 8 and 9, the elongation at break was increased, the elastic modulus was slightly increased, and the thermal stability was improved.
  • Example 12 Input single-layer extrusion melt-molded film processing temperature 190 °C -230 °C, after surface treatment processing, trimming, winding, and finally prepared into 20 ⁇ matte film finished , film making speed of 35m / min. . Then the specific performance test was carried out as shown in Table 3, and compared with Example 7. Compared with Example 11 and Example 12, the elongation at break decreased and the elastic recovery rate also decreased. The drop indicates that the inorganic powder is well dispersed after granulation.
  • Example 14 Example of elastic recovery rate Fourteen> Example thirteen> Example fifteen.
  • Example 10 As shown in Table 1, the mixture measured by the formulation of Example 10 was used to determine the melting point of the mixture by thermal analysis instrument DSC, first granulation, and then into a double-layer extrusion melt-molded film (see Fig. 1), Example 10 Six processing temperature 160 ° C -290 ° C, the example seventeen processing temperature 200 ° C -250 ° C, through the surface treatment process, trimming, winding, Example 16 made of 5 ⁇ white matte film, film The speed was 40 m/min; Example 7 was made into an 8 ⁇ white matte film at a film forming speed of 40 m/min. The specific performance test described above was then carried out as shown in Table 3. In comparison with Example 15, the elongation at break and the elastic recovery ability were decreased. In the seventeenth example, the thickness is significantly increased, the elongation at break is increased, and the moisture permeability is decreased.
  • Example 1 As shown in Table 1, the metered mixture of Example 1 was measured by thermal analysis instrument DSC to determine the melting point of the mixture, first granulation, and then Example 18 was put into two layers of extruded melt-molded film (Fig. 2). The film speed was 35m/min, and the example 19 was put into three extrusion extrusion melt-formed films (Fig. 2). 40m / min, the rest of the processing temperature is 160 ° C -290 ° C, through the surface treatment process, trimming, winding, made 20 ⁇ ⁇ colorless matte film. The results of the test with Example 1 are shown in Table 3.
  • Example 18 It shows that the elongation at break of the formulation of Example 1 is slightly decreased after granulation, but the film forming speed of Example 18 and Example 19 also needs to be increased to obtain For the film of the same thickness, the film forming speed of Example 18 was lower than that of Example 19.
  • Example 21 surface treatment processing, 130 ° C high temperature curing process, trimming, winding, made 20 ⁇ matte, high toughness, high moisture permeability, high resilience film, film speed 30m / Example 21
  • the test results of Example 1 are shown in Table 4.
  • Example 20 and Example 22 are significantly better than the example one, the moisture permeability is improved, and the elastic recovery and toughness are enhanced a lot.
  • the performance of Example 22 is slightly lower than that of Example 20, indicating that the speed has an effect on the performance of the intermediate special process of the film.
  • Example 21 and Example 23 are adhesive films, the moisture permeability is obviously decreased, and the hand feels hard, especially in the case of Example 21, which almost loses the moisture permeability.
  • the inorganic powders of Examples 5 to 10 are: white titanium dioxide powder; the fragrance of Example 9 is jasmine; the fragrance of Example 10 is rose; the dispersant of Examples 5 to 10 is low molecular wax dispersion of olefins.
  • the photothermal stabilizers of Examples 1 to 10 are selected from the group consisting of benzotriazole ultraviolet absorbers, hindered phenol antioxidants, hindered benzoic acids, and phosphates. Table 1 Example 1 to Example 10 Recipe Table
  • Example 28 is a polyol chain extender
  • Example 29 is an extended chain extender with a functional group having a reactive epoxy group
  • Formulation 30 and Example 31 are trifunctional bands.
  • the active ring-based chain extender polyether ester masterbatch the polyether ester is a substrate.
  • the inorganic powder of Example 34 is indigo blue.
  • the dispersant of Example 32 to Example 33 is a long chain fatty acid ester mixture E PTS.
  • the photothermal stabilizers of Examples 20 to 34 are all two benzotriazole compounds, and the antioxidants are pentaerythritol diphosphite antioxidants, triazine stabilizers, and ester antioxidants. The only system of ingredients.
  • the film produced in Example 24 to Example 26 is a polyether ester color film which can be made into a thickness.
  • the specific process is the same as in the first example. Only the extruder is a single extruder, and the ageing resistance increases with the increase of the addition amount, wherein the heat aging resistance is 130 ° C, respectively, 3.5 h, 3 h, 1 h; Aging: 60 degrees Celsius, 102 minutes UV-A and UVB simultaneous irradiation (light intensity about 0.9 W / cm 2 ), 18 min tap water, 32h, 27h, 16h, film fracture.
  • Example 27 to 31 the product is a matte film with a thickness of 20 ⁇ .
  • the specific process is the same as the example of the twenty-fourth.
  • the melt index Ml changes, 230 degrees Celsius, 2.16KG, and the melting index is 23g/10min, 14 g/10min, 5 g/10min, 13 g/ 10min, 13 g/10min.
  • Example thirty-two the product is a white matte film, the thickness is 20 ⁇ , the specific process is the same as the example twenty-four. According to ASTM D1003, the light transmittance is 30% and the haze is 90%. The basic properties of the film are the same as in Example 6.
  • Example thirty-three to the thirty-ninth example by melt-extrusion granulation by a twin-screw at 160-290 degrees Celsius, the products are all masterbatch, wherein the example thirty-three is a white pigment masterbatch, and the example thirty-four is Blue pigment masterbatch, example thirty-five is a purple pigment masterbatch.
  • Example 40 to Example 42 the specific process conditions are the same as the example 24, the product color is blue film, 5 ⁇ , according to ASTM D1003, light transmittance 76%, haze 37%, moisture permeability simulation ASTM ⁇ 96 -2000 steamed water pouring cup method, temperature 23 degrees Celsius, humidity 50%, wind speed 1 m / s, Toyo Seiki equipment, the average value of test results are about 10300 g / square meter * 24h, elastic modulus, elastic recovery Rate Near Example 8, the elongation at break is close to seventeen (because the 5 ⁇ film is stretched too much in the longitudinal direction), and the slightly different dispersion dose has little effect on the performance;
  • Example forty-three is the parent particle of example thirty-three, 25%, the example thirty-four and the example thirty-five masterbatch are respectively 4%, after mixing, the specific process conditions are the same as the example twenty-four, making the same example forty
  • the blue film of the same color was 5 ⁇ , which was tested by the moisture permeability test method of the same example, and the result was 10142 g/m 2 * 24 h; the other properties were the same as those of the example forty. It shows that the effect of pigments and dyes on performance is not obvious.
  • the addition of masterbatch has an effect on the moisture permeability of the product.
  • the forty-fifth example is the formulation of the example eight, the process is the same as the example twenty-five, the moisture permeability rate is 1 1200 g / square meter * 24h, the other performance is the same as the example forty.
  • the addition of masterbatch has an effect on the moisture permeability of the product.
  • Example 40 to Example 43 The moisture permeability of Example 40 to Example 43 is lower than that of Example 45 because the addition of titanium dioxide is reduced, and the moisture permeability of pigments and dyes is not as good as that of titanium dioxide.
  • the inorganic powder of Example 35 is a purple pigment
  • the dispersing agent of Example 36 to Example 39 is a high melting point solid stone baking lubricant
  • the inorganic powder of Example 40 to Example 41 is a white pigment
  • the dye is a combination of a blue dye and a purple dye, the dispersant is the same as the example thirty-three; the example is a blue dye, the rest is the same as the forty; the light stabilizer of the example thirty-fifth to the fourth is the same as the third fourteen.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition d'élastomère de polyéther-ester thermoplastique, et un film et un laminé (textiles non-tissés non-filés-liés ou un laminé contenant une structure non-tissée filée-liée) préparés à partir de celle-ci. La composition élastomère de polyéther-ester thermoplastique de la présente invention comprend : de 10 % à 99 % d'un matériau de résine d'élastomère de polyéther-ester thermoplastique, de 0,01 à 90 % d'un matériau en poudre inorganique ayant une taille de particule de moins de 100 μm et/ou un matériau organique de faible poids moléculaire ayant un poids moléculaire inférieur à 20000 daltons, et de 0 à 5 % d'un agent dispersant, l'agent dispersant étant un matériau organique avec un groupe ayant une affinité avec l'élastomère de polyéther-ester thermoplastique. Le film et le laminé (les textiles non-tissés non-filés-liés ou le laminé contenant la structure non-tissée filée-liée) préparés à partir de la composition de la présente invention ont une perméabilité à l'air et à la vapeur, un indice de résistance à la vapeur, et des propriétés mécaniques souhaitables.
PCT/CN2012/000025 2012-01-09 2012-01-09 Composition d'élastomère de polyéther-ester thermoplastique et film préparé à partir de celle-ci WO2013104081A1 (fr)

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KR1020147021577A KR101795669B1 (ko) 2012-01-09 2012-01-09 폴리에테르 에스테르 열가소성 탄성체 조성물 및 이로부터 제조된 박막
PCT/CN2012/000025 WO2013104081A1 (fr) 2012-01-09 2012-01-09 Composition d'élastomère de polyéther-ester thermoplastique et film préparé à partir de celle-ci

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Citations (8)

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Publication number Priority date Publication date Assignee Title
CN1212972A (zh) * 1998-08-21 1999-04-07 南亚塑胶工业股份有限公司 改良了耐光性的热塑性嵌段式共聚醚酯
CN1303407A (zh) * 1998-05-29 2001-07-11 Dsm有限公司 耐热的嵌段聚醚酯共聚物组合物
CN1329110A (zh) * 2000-06-13 2002-01-02 沃尔夫瓦尔斯罗德有限公司 具有改进加工性的热塑性弹性体模塑组合物
CN1454230A (zh) * 2000-10-04 2003-11-05 旭化成株式会社 阻燃增强聚酰胺树脂组合物
CN1480477A (zh) * 2002-09-04 2004-03-10 中纺投资发展股份有限公司 低硬度高熔点的高性能热塑性聚醚酯弹性体
US20040259996A1 (en) * 2002-08-27 2004-12-23 Georg Stoppelmann High-viscous moulding materials with nano-scale fillers
CN101155865A (zh) * 2005-02-03 2008-04-02 纳幕尔杜邦公司 光稳定的共聚醚酯组合物
CN101611094A (zh) * 2007-02-12 2009-12-23 帝斯曼知识产权资产管理有限公司 聚合物组合物及由其制成的塑料管

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1303407A (zh) * 1998-05-29 2001-07-11 Dsm有限公司 耐热的嵌段聚醚酯共聚物组合物
CN1212972A (zh) * 1998-08-21 1999-04-07 南亚塑胶工业股份有限公司 改良了耐光性的热塑性嵌段式共聚醚酯
CN1329110A (zh) * 2000-06-13 2002-01-02 沃尔夫瓦尔斯罗德有限公司 具有改进加工性的热塑性弹性体模塑组合物
CN1454230A (zh) * 2000-10-04 2003-11-05 旭化成株式会社 阻燃增强聚酰胺树脂组合物
US20040259996A1 (en) * 2002-08-27 2004-12-23 Georg Stoppelmann High-viscous moulding materials with nano-scale fillers
CN1480477A (zh) * 2002-09-04 2004-03-10 中纺投资发展股份有限公司 低硬度高熔点的高性能热塑性聚醚酯弹性体
CN101155865A (zh) * 2005-02-03 2008-04-02 纳幕尔杜邦公司 光稳定的共聚醚酯组合物
CN101611094A (zh) * 2007-02-12 2009-12-23 帝斯曼知识产权资产管理有限公司 聚合物组合物及由其制成的塑料管

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