WO2013104081A1

WO2013104081A1 - Thermoplastic polyether ester elastomer composition and film prepared from same

Info

Publication number: WO2013104081A1
Application number: PCT/CN2012/000025
Authority: WO
Inventors: 林裕卫; 蔡朝辉
Original assignee: 佛山佛塑科技集团股份有限公司
Priority date: 2012-01-09
Filing date: 2012-01-09
Publication date: 2013-07-18
Also published as: KR101795669B1; KR20140109469A

Abstract

The present invention provides a thermoplastic polyether ester elastomer composition, and a film and a laminate (non-spunbonded non-woven fabrics or a laminate containing a spunbonded non-woven structure) prepared from the same. The thermoplastic polyether ester elastomer composition of the present invention comprises: 10%-99% of a thermoplastic polyether ester elastomer resin material, 0.01-90% of an inorganic powder material with a particle size within 100 μm and/or an organic low-molecular material with a molecular weight lower than 20000 daltons, and 0-5% of a dispersing agent, the dispersing agent being an organic material with a group having affinity with the thermoplastic polyether ester elastomer. The film and laminate (the non-spunbonded non-woven fabrics or the laminate containing the spunbonded non-woven structure) prepared from the composition of the present invention have desirable air and vapor permeability, vapor resistance value, and mechanical property.

Description

Polydecyl ester thermoplastic elastomer composition and film prepared therefrom

Technical field

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. Background technique

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. However, the design of various functions is only modified from formula modification, or only modified to improve a certain performance, and The influence of the processing technology on various performance characteristics is not considered, and the pre-processing of the film later is not used as one of the film forming processes, so that various technical obstacles for post-processing into finished products are formed between production and end use, which hinders The correct assessment of the product by the consumer.

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

1

Confirmation A second layer in which all of the layers are composed of 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

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.

In one aspect, in order to achieve the above object of the present invention, the present invention provides a composition of a polydecyl ester thermoplastic elastomer, wherein the composition comprises, by mass percentage, the composition comprises:

10%-99% of polyetherester thermoplastic elastomer resin material,

0.01-90% of an inorganic powder material having a particle diameter of 100 μΓΠ and/or an organic low molecular material having a molecular weight of 20,000 Daltons, and

0-5% dispersant, wherein the dispersant is a group having an affinity with the chewable ester thermoplastic elastomer Machine material.

In the composition of the present invention, 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.

In the composition 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 μΓΠ, more preferably from 0.1 to 20 μΓΠ, still more preferably within 5 μηη. The amount of the inorganic powder added is preferably 5 to 75%, more preferably 10 to 59%.

In the composition of the present invention, 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 compound; the antioxidant is one or more substances selected from the group consisting of pentaerythritol diphosphite antioxidants, triazines, esters, hindered benzoates, hindered amines. , hindered Β & class, triketones, phosphites, thioesters and derivatives thereof; chain extenders one or more substances selected from the group consisting of polyols and derivatives thereof, and A polyfunctional organic low molecular material having a reactive epoxy group and a derivative thereof, wherein the number of functional groups is 2 to 10. The amount of the organic low molecular material added is preferably from 5 to 75%, more preferably from 10 to 59%. In the present invention, 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.

In the composition of the present invention, 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%.

As a specific embodiment of the present invention, 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.

As another specific embodiment of the present invention, 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. On the other hand, in order to achieve the object of the present invention, the present invention provides a polyetherester thermoplastic elastomer film prepared from the above composition, which film has a thickness of from 1 to 250 μm, preferably from 2 to 100 μm, more preferably 2-50μπι, of which 2-30μιη is better, 2-1 5μΓΠ is optimal. According to the ASTM Ε96-2000 BW method, 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.

In the present invention, the moisture permeability is related to the formulation, appearance, processing technique, thickness, and the like of the film. The more transparent the appearance, the lower the moisture permeability, and the more the inorganic powder is added, the smaller the wet resistance value. The thinner the thickness, the moisture permeability and The lower the wet impedance value.

In the present invention, 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. In the case of an organic low molecular type formulation, 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.

In the present invention, 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.

In the present invention, 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.

In the present invention, 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.

In the present invention, 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 ) may be 0.01-100%, preferably according to the appearance and thickness of the film, the transparent film is preferably 80% -100%, the opaque color film is 20%-100%, and 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. Calculate according to the following formula:

Heat shrinkage rate = ( A-B ) /Α 100%

(Note: If it is a negative number, the film size becomes larger)

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 higher the proportion of the inorganic powder, the lower the elongation at break; the more uniform the dispersion of the dispersant The higher the elongation at break; the higher the proportion of the polyacrylate material in the formulation, the greater the toughness and the higher the elongation at break; the chain extender can increase the distribution of the 'square material' within a certain range. In combination, the toughness is improved, but beyond this range, the film will have a decrease in toughness.

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. After stopping, take out the sample and immediately test the length L2 of the effective length of the film. After standing for 60s-180s (preferably 60s400s), test the effective length L3 of the film again, let stand for 1 h-120h (preferably 24h-120h), and measure the effective length again. L4. The tensile elastic recovery ability at various times after stretching was then calculated by the following formula.

Formula for immediate elastic recovery rate: ( L1-L2 ) / ( L1-L0 ) χ 100%

Formula for elastic recovery after standing for 60s-180s: ( L1-L3 ) / ( L1-L0 ) χ 100%

Formula for elastic recovery after standing for 1 h to 120 h: ( L1 - L4 ) / ( L1 - L0 ) χ 100% On the other hand, in order to achieve the object of the present invention, the present invention also provides lamination of a thermoplastic resin film. And wherein the laminate comprises:

At least one of the polyacrylate thermoplastic elastomer films as described above;

At least one layer of thermoplastic resin products;

And an adhesive bond formed by the glue between the polyether ester thermoplastic elastomer film layer and the thermoplastic resin product layer;

Wherein the thermoplastic resin product layer is a thermoplastic resin film or a thermoplastic resin fiber product, and the 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). In the exhibit of the present invention, 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.

Preferably, in the laminate of the present invention, 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. BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a schematic view of a single extrusion process in accordance with an embodiment of the present invention; and FIG. 2 is a schematic view of a two-layer or multi-extrusion extrusion process in accordance with another embodiment of the present invention. detailed description

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 20μ ΓΠ matte film finished film, film speed of 30m / min. Formulation 7 is a 20μηι matte white film finished product, and the formulas of five, six, eight, and ten are 20μίτι fragrance matte white film products, and the specific performance test is shown in Table 2. Each example exhibited a different melting point, with Examples I through Example 4 having lower melting points than the other formulations, and Examples 5 through 7 were higher than Examples 8 through 10. Examples 1 and 2 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. 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. In the tenth example, due to the addition of the chain extender, 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 11~12:

As shown in Table 1, the mixture of the sample of Example 7 was measured, and the melting point of the mixture was measured by a thermal analysis instrument DSC. The processing temperature was first 160 ° C - 290 ° C granulation, and then the example 11 was put into two layers of coextrusion. The melt-forming thin warfare is shown in Fig. 2) 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 20μΓη 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 13 ~ Example 15

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 all were put into a single extrusion melt-molded film (Fig. 1), processing temperature 160 ° C -290 ° C, through the surface treatment process, trimming, winding, the final example of the thirteenth preparation into a 20μ ΓΤΐ colorless matte film finished product, Example fourteen made of glossy white 20μπι film, example fifteen It became a 5 μm matte film with a film forming speed of 30 m/min. Then the specific performance test described above is shown in Table 3. After comparison, the moisture permeability is shown in Example 14 <Example 13 <Example 15 and the elongation at break Example 14> Example 13> Example 15 Example of elastic recovery rate Fourteen> Example thirteen> Example fifteen.

Example 16 ~ Example 17

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 5μηι white matte film, film The speed was 40 m/min; Example 7 was made into an 8 μπ 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 18 ~ Example 19

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 20μ ΓΤΐ colorless matte film. The results of the test with Example 1 are shown in Table 3. 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 twenty to twenty three

As shown in Table 1, the sample after metering of the sample of Example 1, the melting point of the mixture was measured by thermal analysis instrument DSC, and both were directly put into two layers of extruded melt-molded film (Fig. 2), and the processing temperature was 160 °C- 290 ° C, Example 20 by surface treatment processing, 130 ° C high temperature curing process, trimming, winding, made 20μπι matte, high toughness, high moisture permeability, high resilience film, film speed 30m / Example 21 Example 21 surface treatment process, adhesive process, 130 ° C high temperature curing process, trimming, winding, made of 20 μ ΓΠ matte, solvent glue full gelatinous adhesive, high toughness adhesive film, The film forming speed was 30 m/min. Example Twenty-two film forming process and formula pass example 20, but the film forming speed is 40 m / min. Example Twenty-three with the same example 21, only the adhesive process is a solvent glue point adhesive. 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.

Note: 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. Agent. 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

Table 2 Example 1 to Example 10 Performance Table

Table 3 Example 10 to Example 19 Performance Table

Reduction rate 45 degrees % 1.2 1.2 1.1 1.1 2.3 2.5 2.3 1.2 1.2

(Upper 90 degrees% 1.8 1.8 1.3 1.3 3.0 5.0 4.5 2 2) 135 degrees% 1.5 1.5 1.1 1.1 2.0 3.0 3.0 1.5 1.5 Moisture permeability ASTM g/m2*24h 8800 8800 8900 7500 9500 9500 9400 7500 750 E96-2000 BW

Wet resistance value m2Pa/w 1.0 1.0 0.9 2.0 0.3 0.3 0.5 4 4 ISO11092

Elongation at break % 710/720 690/705 550/580 700/750 250/400 230/380 250/420 525/570 540/590 ASTM D828

Elastic modulus MPa 70/75 72/75 75/78 100/120 75/80 80/85 85/90 78/82 74/78

ASTM D828

Stretch back immediately % 67 67 67 68 65 64 64 67 67 elastic complex rate,

Table 4 Example Twenty to Example Twenty-three Performance Table

Performance comparison Unit Example 20 Example twenty-one Example twenty-two Example twenty-three appearance White matte Matte white, full adhesive film Matte white Glossy white Thickness Mm 20 20 20 20

Point ( DSC ) °C 185 185 185 185

Table 5 formula table

Dispersant 0.5 0.4 Note: 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.

Example twenty-four - example twenty-six

The film produced in Example 24 to Example 26 is a polyether ester color film which can be made into a thickness.

15μΓτι. 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 - Example 31

Example 27 to 31, the product is a matte film with a thickness of 20 μΓΠ. The specific process is the same as the example of the twenty-fourth. With the addition of the chain extender, 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

Example thirty-two, the product is a white matte film, the thickness is 20μηι, 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 Ξ-example forty-five

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, 5μΓΠ, according to ASTM D1003, light transmittance 76%, haze 37%, moisture permeability simulation ASTM Ε96 -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 5μΓτι 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 μΓΠ, 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.

Example forty-four identical example and twenty-five formula and process method to prepare a 5 μΓΠ natural matte film, using the same example of the 40 moisture permeability test method, the moisture permeability rate is 9300 g / square meter '24h, other properties In the same example, for example, 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. The reason is that the masterbatch is subjected to secondary processing during the granulation process, and there is a certain degradation, the moisture-permeable functional group is increased, and the added dispersion is added. Agents and inorganic powders, especially titanium dioxide, carry a large number of hydrophilic functional groups which increase moisture permeability. 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.

Table 6 formula table

Note: 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.

Claims

Rights request

A composition of a polyetherester thermoplastic elastomer, wherein the composition comprises, by mass percentage, the:

10%-99% of polyetherester thermoplastic elastomer resin material,

0.01-90% of an inorganic powder material having a particle diameter of ΙΟΟμηη and/or an organic low molecular material having a molecular weight of 20,000 or more, and

0-5% dispersant, wherein the dispersant is an organic material having a group which is affinity with the polyetherester thermoplastic elastomer.

2. The composition of claim 1 wherein said polyetherester thermoplastic elastomer resin material is: a copolymer or blend of a dicarboxylic acid and a glycol, an epoxy compound, and/or

A copolymer or blend of a diamide and a glycol, an epoxy compound.

3. The composition according to claim 1, wherein the inorganic powder material is one or more inorganic powders selected from the group consisting of titanium dioxide, silicon dioxide, montmorillonite, Various inorganic pigments, calcium carbonate, barium sulfate, and ceramic powders.

4. The composition of claim 1 wherein said organic low molecular material is one or more photothermal stabilizers and one or more materials selected from the group consisting of: Antioxidants, dyes, chain extenders, and fragrances; Wherein, the photothermal stabilizer comprises: a benzophenone, a benzoxazinone, a benzoxazole, and a benzotriazole compound;

The antioxidant is one or more substances selected from the group consisting of pentaerythritol diphosphite antioxidants, triazines, esters, hindered benzoates, hindered amines, Hindered phenols, tri-turns, phosphites, thioesters and their derivatives;

The chain extender is one or more selected from the group consisting of polyhydric alcohols and derivatives thereof, and polyfunctional organic low molecular materials having active epoxy groups and derivatives thereof, wherein The number of functional groups is 2-10.

The composition according to claim 1, wherein the dispersing agent is one or more organic materials selected from the group consisting of stone culture, fatty acids, aliphatic amides, and esters. , Jin Li soap, and low molecular waxes.

6. The composition according to claim 1, wherein the composition comprises: 22% to 92% by weight of the polysulfonated thermoplastic elastomer resin material, 5 to 75% of the inorganic powder material and/or Or organic low molecular materials, and 0.1-4% dispersant.

7. The composition according to claim 6, wherein the composition comprises, by mass percentage, 42% to 88% of a polyetherase thermoplastic elastomer resin material, 10-59% of an inorganic powder material, and/or Or organic low molecular materials, and 0.4-3% dispersant.

The composition according to claim 1, wherein the inorganic powder material has a particle diameter of 0.1 to 20 μm.

A polyetherester thermoplastic elastomer film prepared from the composition according to any one of claims 1-8, wherein the film has a thickness of from 1 to 250 μm, preferably from 2 to 100 μm; wherein The film has a moisture permeability of 1000g/m2*24h or more (ASTM E96-2000 BW method) 6

The polyetherester thermoplastic elastomer film according to claim 9, wherein said film has a wet resistance value of less than 20 m2Pa/w (ISO1 1092).

The polyetherester thermoplastic elastomer film according to claim 9 or 10, wherein the film has an elongation at break of greater than 120%, an elastic modulus of less than 300 MPa, and a tensile elasticity of more than 35%. Response rate.

The polydecylester thermoplastic elastomer film according to claim 11, wherein the film has a multi-fold structure formed by co-extrusion.

13. A composite of a thermoplastic resin film, wherein the exhibit comprises:

At least one layer of a polyetherester thermoplastic elastomer film according to any one of claims 9-12; at least one layer of a thermoplastic resin article;

And an adhesive layer formed of glue between the polyether ester thermoplastic elastomer film layer and the thermoplastic resin product; Wherein, the thermoplastic resin product is a thermoplastic resin film or a thermoplastic resin fiber product, and the thermoplastic resin fiber product is a textile fiber, a non-spunbond nonwoven fabric and/or a material containing a spunbonded nonwoven fabric structure.

14. The exhibit of claim 13 wherein said textile fibers are one or more of a group of fibrous materials selected from the group consisting of polyetheresters and derivatives thereof, polyesters and Its derivative fiber, nylon and its derivative fiber, spandex and its derivative fiber, and polypropylene and its derivative fiber, and a mixture of any of the above resins.

The spread composition according to claim 13 wherein the nonwoven fabric is one or more of a nonwoven fabric selected from the group consisting of polyolefins and derivatives thereof, and nonwoven fabrics. Nonwoven fabric of polyester and its derivatives, non-woven fabric of nylon and its derivatives, non-woven fabric of spunlace and its derivatives, and non-woven fabric of degradable plant fiber and its derivatives, etc., preferably polypropylene non-woven fabric, A polyester nonwoven fabric, and a nonwoven fabric of degradable plant fibers and derivatives thereof, and a mixture of any of the foregoing resins.

16. The stent of claim 13 wherein said adhesive layer is a discontinuous stretch, preferably a discontinuous dot-like exhibit, a spaced strip-like layer or a grid a layered layer.