WO2019104570A1

WO2019104570A1 - Scented, mold-resistant thin film and preparation method therefor

Info

Publication number: WO2019104570A1
Application number: PCT/CN2017/113723
Authority: WO
Inventors: 李凯; 逯丽
Original assignee: 世界家庭用具制品厂有限公司
Priority date: 2017-11-30
Filing date: 2017-11-30
Publication date: 2019-06-06

Abstract

A novel thin film and a preparation method therefor. The present invention relates to the technical field of polyolefin thin films and, in order to provide a scented, mold-resistant thin film, uses a polyolefin supplemented by substances such as calcium carbonate, thus maintaining or even improving the performance of existing thin films while reducing the amount of polyolefin used. A technical solution of the present invention is as follows: a novel thin film, the thin film being prepared from substances of the following composition: a polyolefin, a polyethylene wax, an antioxidant, surface-modified calcium carbonate particles, a mold-resistant masterbatch, and a scented masterbatch. The beneficial effects of the present invention are such that, by adjusting the content of calcium carbonate of different particle sizes in the thin film, the amount of calcium carbonate added is increased while still ensuring the mechanical performance of the thin film, thus reducing costs for the thin film; and by adding mold-resistant particles and the scented masterbatch, user experience with the thin film is improved.

Description

\¥0 2019/104570 卩(:17 称17/113723

Smell-proof mold-proof film and preparation method thereof

Technical field

[0001] The present invention relates to the field of polyolefin film technology, and in particular to a high calcium carbonate filling amount with a fragrance, a polyethylene mildewproof film and a preparation method thereof. Background technique

[0002] Polyolefin films, especially polyethylene films, are widely used, and are widely used in shower curtains, tablecloths, garbage bags, packaging materials, and sanitary products. At the same time, with the progress of the production process, the performance of the film is continuously improved and expanded. It is expected that the amount of polyethylene film will continue to increase, but the polyethylene is mainly derived from non-renewable petrochemical resources. The international crude oil price remains high, so other can be reduced. The use of polyolefins is necessary to save non-renewable petrochemical resources.

technical problem

[0003] It is an object of the present invention to provide a mold-resistant mold-resistant film which is supplemented with a material such as calcium carbonate while using a polyolefin, and which can maintain or even improve the performance of the existing film while reducing the use of the polyolefin. Problem solution

Technical solution

[0004] The technical solution of the present invention is as follows:

[0005] A novel film prepared from the following components: polyolefin, polyethylene wax, antioxidant, surface-modified calcium carbonate particles, mold-resistant masterbatch, and flavor masterbatch;

[0006] wherein the polyethylene wax is added in an amount of 0.5% to 2.5% by weight of the polyolefin, preferably in an amount of 1.2% to 1.8% by weight of the polyolefin.

[0007] The antioxidant is added in an amount of 0.02% to 2.0% by weight of the polyolefin, preferably in an amount of 0.05% to 1.0% by weight of the polyolefin.

[0008] The weight ratio of the surface-modified calcium carbonate particles to the sum of other substances is about (0.6-1.25): 1 ; the surface modification is through stearic acid, titanate, silane coupling agent The surfactant is hydrophobically modified.

[0009] The amount of the mold-proof masterbatch added is preferably the weight of the polyolefin is 2 by weight of the polyolefin \¥0 2019/104570

%~4%.

_[0010] The flavoring masterbatch is added in an amount of 1% to 10% by weight of the polyolefin _; preferably, the amount is from 4% to 8% by weight of the polyolefin.

_[0011] The polyolefin includes: 〇 ^ _£ (high pressure polyethylene), LLDPE (linear low density polyethylene) and _£

0) _: (0~10) ;

_[0012] The calcium carbonate particles include large-diameter calcium carbonate particles and nano-calcium carbonate particles, and the large-diameter calcium carbonate particles have a particle diameter of 2000 to 15000 mesh, and a preferred particle size range is 5000 to 10000. Head.

_[0013] The nano calcium carbonate particles have a diameter of 1 to 10 〇 ₁₁₁₁₁ , and the weight ratio of the large particle diameter calcium carbonate to the nano calcium carbonate is (30 to 90) _: (10 to 50).

_[0014] The antioxidant is selected from four, pentaerythritol tetra [(3 - (3, 5 - di-4 - hydroxyphenyl) propionic acid] pentaerythritol, tris _{(2, 4 -} di-tert-butyl One or more of phenyl phosphite, stearyl propionate and alkylated polyphenols.

[0015] A novel film, the preparation method comprising the following steps:

[0016] (1) preparing each component substance;

The calcium particles and the nano calcium carbonate particles are added to an internal mixer, heated and mixed and stirred, and after being uniformly mixed, extruded, granulated and dried by a single rod extruder or a double rod extruder;

_[0018] The mixing temperature of the _internal mixer is 110~180 _° (: _;

_[0019] The extrusion temperature of a single rod extruder is 1 _70~200° (: ;

_[0020] (3) The mold-preventing masterbatch, the flavor masterbatch, and the particles obtained in the above step (2) are mixed and cast into a film by a casting machine, and the temperature of the casting machine is 1 _{70 to 230°} (:.

_{[0021] A} high temperature flavor can be added to the flavor masterbatch, and the fragrance can be floral, fruity, woody or other flavors.

_[0022] Calcium carbonate is the first choice of inorganic fillers with abundant yield, low price, white color and good comprehensive performance. It is also a widely used inorganic powder filler in the plastic processing industry, but in order to maintain the performance of the film itself. At present, the filling amount of calcium carbonate filled polyethylene film material is low, and the weight fraction generally does not exceed 30%. If the filling is too high, the polyethylene film after filling has mechanical properties. \¥0 2019/104570 Its toughness has dropped dramatically, and low calcium carbonate filling has been a bottleneck in the film manufacturing industry.

[0023] In order to meet the mechanical properties of the polyethylene film, the filling amount of calcium carbonate is increased as much as possible, and in order to reduce the production cost, reduce the environmental pollution, and improve the degradation performance of the polyethylene film, the case is made of filled calcium carbonate. Improvements have been made to use calcium carbonate of different particle sizes, and by adjusting the ratio of calcium carbonate of different particle sizes to improve the mechanical properties of the film, the filling amount of calcium carbonate can be increased.

[0024] The smaller the diameter of the calcium carbonate particles, the more the amount of filling in the polyethylene film, and the smaller the influence on the mechanical properties of the polyethylene film, so that the particle size is as small as nanometer-sized nano calcium carbonate or It is preferred to be a filler, however, due to the large specific surface area and high surface activity of the nano calcium carbonate particles, even after being surface-hydrophobically modified and blended with the non-polar polyethylene, it is highly agglomerated at a relatively high processing temperature, thereby Affecting the comprehensive performance of the polyethylene film, the present invention employs calcium carbonate particles having a particle diameter of 2000 to 15000 mesh and is mixed with a small amount of nano calcium carbonate particles. Large particle size calcium carbonate is dispersed as a main filler in the polymer matrix. The latter can be well filled in the tiny voids of the former. The mixed use of different sizes of calcium carbonate can not only increase the filling amount of calcium carbonate, but also reduce the pores inside the film. Defects, thereby improving the overall performance of the film

[0025] In addition, in the existing film production, calcium carbonate having a whiteness of not less than 90 can also partially replace the expensive titanium dioxide, which can reduce the whiteness of the polyethylene film while reducing the raw material cost, and has environmentally friendly characteristics. Therefore, in this case, it is also possible to replace titanium dioxide by selecting a portion of calcium carbonate having a whiteness of not less than 90.

[0026] At the same time, the addition of the anti-fungal agent and the flavor masterbatch enables the polyethylene film to have wider use properties and can increase the comfort of use of the final product.

Advantageous effects of the invention

Beneficial effect

[0027] The beneficial effects of the present invention are: by adjusting the content of calcium carbonate in the film of different particle diameters, the mechanical properties of the film are improved, the raw material cost is greatly reduced, and the film is improved by adding the anti-mold particles and the flavor masterbatch. The feeling of use. Invention embodiment

Embodiments of the invention

Embodiment 1

[0029] First, the temperature of the internal mixer chamber is preheated to 120° (:, and then according to the formulation of the embodiment 1 in Table 1, \¥0 2019/104570 will be 11 kg!^^ _£ , 33 kg

LLDPE, 1 kg of polyethylene wax, 45 kg of 2500 mesh calcium carbonate powder, 8 kg of nano calcium carbonate powder, 0.2 kg of antioxidant added to the internal mixer, stirred for 5 minutes to mix the materials thoroughly, and then heated to 150. After further mixing for 10 minutes, the volatile substances such as water molecules in the kneaded material were drained, and then mixed and dispersed for 15 minutes. Finally, the uniformly dispersed material is transferred to a twin-screw extruder at 1 _70~200 . (: melt extrusion, granulation, and drying in a temperature range to obtain cast particles (: -1.

_[0030] The casting particles obtained in the above step (: -1 is added to the casting machine at 1 _{70 to 230 °} (: casting, a highly filled polyethylene film ^1 can be obtained, and its mechanical properties are shown in the table). 2.

_[0031] Example 2

_{[0032] The} cast particles (: -2) were prepared according to the formulation of Example 2 in Table 1, and the process conditions were the same as in Example 1.

_{[0033] Casting} particles (: -2 and 3 kg of flavored masterbatch, 0.8 kg of mildew masterbatch into the casting machine, at 1 _{70 ~ 2} 30 ° (: casting, can be prepared with aroma, high The mechanical properties of the filled polyethylene mildew film ^2 are shown in Table 2.

Embodiment 3

_{[0035] The} cast particles (: -3) were prepared according to the formulation of Example 3 in Table 1, and the process conditions were the same as in Example 1.

_{[0036] The} cast particles (: -3 is added to the casting machine at 1 _{70 to 230 °} (: casting, high-filled polyethylene thin ^-3 can be obtained, and its mechanical properties are shown in Table 2.

Embodiment 4

[0038] The cast particles (: -4) were prepared in accordance with the formulation of Example 4 in Table 1, and the process conditions were the same as in Example 1.

_{[0039] Casting} particles (: -4 was added to the casting machine at 1 _{70 to 230 °} (: casting, a highly filled polyethylene film ₁ ^ 4 was obtained, and its mechanical properties are shown in Table 2.

Table 1. Preparation Formulation of High Calcium Carbonate Filled Polyolefin Granules in Examples 1-4 (Unit: kg)

_[0041] \¥0 2019/104570

[number]

[0042] Performance evaluation methods and implementation standards:

_[0043] According to the procedure of the present invention described above, after the scented high calcium carbonate-filled mold-resistant polyethylene film was prepared, the tensile properties were tested in accordance with _{ASTM 05034-95} . Stretch sample size: ₁₅₀ mm in length, ₁₀₀ mm in width, and ₃₀₀ mm per minute. The prepared film has a longitudinal tensile strength of not less than ₁₇ MPa and an elongation at break of not less than ₁ 〇〇 _% . The specific test results are as follows:

[0044] Related properties of cast film prepared in Table 2

[0045] \¥0 2019/104570 卩(:17€说17/113723

[number]

[0046]

Claims

\¥0 2019/104570 Claims

[Claim 1] A novel film characterized in that the film is prepared from the following components: polyolefin, polyethylene wax, antioxidant, and surface-modified calcium carbonate particles; wherein polyethylene wax The amount added is 0.5%~2.5% of the weight of the polyolefin;

The antioxidant is added in an amount of 0.02% to 2.0% by weight of the polyolefin _;

The weight ratio of the surface-modified calcium carbonate particles to the sum of other substances is about (0.6 to 1.25): 1;

The polyolefin includes

The weight ratio of eight is 1: (0.1-10): (0~10);

The calcium carbonate particles comprise large-diameter calcium carbonate particles and nano-calcium carbonate particles, wherein the large-diameter calcium carbonate particles have a particle diameter of 2000 to 15000 mesh, and the nano-calcium carbonate particles have a diameter of 1~ 10〇11111, the weight ratio of the large particle size calcium carbonate to the nano calcium carbonate is (

30-90) : (10~ 50).

[Claim 2] The novel film according to claim 1, wherein the polyethylene wax is added in an amount of 0.5 to 2.5% by weight, preferably 1.2% to 1.8% by weight based on the weight of the polyolefin.

[Claim 3] The novel film according to claim 1, wherein the large-diameter calcium carbonate particles have a particle diameter ranging from 2,000 to 15,000 mesh, preferably from 5,000 to 10,000 mesh.

[Claim 4] The novel film according to claim 1, wherein the antioxidant is selected from the group consisting of pentaerythritol ester, tetrakis [(3 - (3,5-di-tert-butyl-4-hydroxyphenyl) Propionic acid: One or more of pentaerythritol ester, phenyl tris(2,4-di-tert-butyl) phosphite, stearyl propionate and alkylated polyphenol.

[Claim 5] The novel film according to claim 1, wherein the antioxidant is added in an amount of 0.02% to 2% by weight based on the weight of the polyolefin, preferably 0.05% to 1.0% =:

[Claim 6] The novel film according to claim 1, wherein the substance further comprises an anti-mold masterbatch added in an amount of from 1% to 6% by weight based on the weight of the polyolefin.

[Claim 7] The novel film according to claim 6, wherein the mold-preventing masterbatch is added in an amount of 2% to 4% by weight based on the weight of the polyolefin.

[Claim 8] The novel film according to claim 1, wherein the substance further comprises a fragrance \¥0 2019/104570 Masterbatch, added in an amount of 1% to 10% by weight of the polyolefin.

[Claim 9] The novel film according to claim _8, wherein the flavor masterbatch is added in an amount of _{4% to 8% by} weight based on the weight of the polyolefin.

[Claim 10] A method for preparing a novel film, characterized in that the preparation method comprises the following steps:

( ₁₎ preparing a component of the novel film according to any one of claims ₁ to ₉ ;

The large-diameter calcium carbonate particles and the nano-calcium carbonate particles are added to an internal mixer, heated and mixed and stirred, and after being uniformly mixed, extruded, granulated and dried by an extruder;

The mixing temperature of the internal mixer is 110~180 _{° (} :;

The extrusion temperature of the extruder is 1 _{70~200° (} :;

( ₃₎ The mold-preventing masterbatch, the flavor masterbatch, and the particles obtained in the above step ( ₂₎ are mixed and cast into a film by a casting machine, and the temperature of the casting machine is 1 _{70 to 230 ° (} :.