CN110684279A - Pearlescent master batch for biaxially oriented film and preparation method and application thereof - Google Patents
Pearlescent master batch for biaxially oriented film and preparation method and application thereof Download PDFInfo
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- CN110684279A CN110684279A CN201910962538.3A CN201910962538A CN110684279A CN 110684279 A CN110684279 A CN 110684279A CN 201910962538 A CN201910962538 A CN 201910962538A CN 110684279 A CN110684279 A CN 110684279A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Abstract
The invention provides a pearlescent master batch for a biaxially oriented film, and a preparation method and application thereof. The pearlescent master batch for the biaxially oriented film comprises the following components in percentage by weight: 24.4 to 39.4 percent of polypropylene resin; 60-75% of calcium carbonate powder; 0.2 to 5 percent of additive A; 0.2 to 5 percent of lubricant; 0.2 to 1 percent of antioxidant master batch; wherein the additive A is a compatilizer, a coupling agent or a dispersant. The preparation method comprises the following steps: s1: mixing and conveying raw materials; s2: melt extrusion; s3: granulation and post-treatment. The BOPP film is prepared by co-extruding and biaxially stretching first surface layer resin, middle layer resin and second surface layer resin, and the pearlescent master batch is applied to the middle layer of the film and accounts for 2-40% of the total weight of the resin. The pearly-luster master batch for the biaxially oriented film disclosed by the invention has the advantages that the pressure on a filter screen is lower in the production of the BOPP film, the blockage of the filter screen can be effectively avoided, the pearly-luster effect and the shading performance of the film are more excellent, and the production cost is lower.
Description
Technical Field
The invention belongs to the technical field of auxiliary agents for plastic films, and particularly relates to a pearlescent master batch for a biaxially oriented film, and a preparation method and application thereof.
Background
White opaque films have a satin-like texture, a soft and pleasant pearl gloss, low density, excellent flatness, and gas barrier properties, and for example, BOPP films having the above characteristics are widely used for products such as foods, gift packages, face films, and paper-like films. The excellent effect of the BOPP film is from the pearl master batch added in the BOPP film, the pearl master batch and the polypropylene main material are extruded and cast into a film after being mixed in an extruder, and the BOPP film can be obtained after the thick sheet of the film is stretched in two directions. Because the calcium carbonate contained in the pearlescent master batch has low adhesive force to polypropylene, countless uniform cavities can be formed through biaxial stretching, and the process belongs to mechanical foaming; when light enters the cavity, multilayer interference light is generated due to the interference of the light, and a pearly-lustre effect is formed; meanwhile, the addition of the calcium carbonate improves the light-shielding property of the film, reduces the density of the BOPP film, and greatly reduces the production cost compared with the expensive and non-renewable polypropylene raw material.
With the increase of the addition proportion of the pearly-luster master batch in the BOPP film, the content of calcium carbonate is increased, the pearly-luster effect and the light-shading performance of the BOPP film become more excellent, and the cost is lower. Meanwhile, with the increase of the addition ratio of the pearlescent master batch, the dispersion difficulty of calcium carbonate in a polypropylene matrix is increased, the agglomeration is serious, and the problems of excessive reduction of the density of the BOPP film, reduction of the tensile strength and easy embrittlement are caused.
Disclosure of Invention
Accordingly, an object of the present invention is to provide a pearlescent masterbatch for biaxially oriented films, which is used in an intermediate layer of a multilayer co-extruded biaxially oriented film, can increase the proportion of the pearlescent masterbatch to be used, can provide more excellent pearlescent effect and light-shielding property, can reduce the cost of film production, and can ensure the quality of the product by making calcium carbonate have good dispersibility in the main resin of the film product.
The technical scheme adopted by the invention is as follows:
the pearlescent master batch for the biaxially oriented film is characterized by comprising the following components in percentage by weight:
the additive A is a compatilizer, a coupling agent or a dispersing agent, and the compatilizer is a maleic anhydride grafting compatilizer.
The pearlescent master batch for the biaxially oriented film is simple in formula, is prepared from polypropylene resin and additives such as calcium carbonate powder, an additive A, a lubricant, an antioxidant master batch and the like, and can improve the interface performance of the calcium carbonate powder and polypropylene, reduce the agglomeration of calcium carbonate and improve the dispersibility of the calcium carbonate in the polypropylene under the action of the additive A.
Further, the polypropylene resin is one of isotactic polypropylene, syndiotactic polypropylene and atactic polypropylene, and the melt index is 2-25g/10 min. The polypropylene resin within the melt index range is selected to be film-grade polypropylene, and the prepared pearlescent master batch can ensure that the film thickness is uniform, the film breakage is reduced and the smooth production is ensured when the pearlescent master batch is used for the subsequent film production.
Further, the average particle size of the calcium carbonate powder is 1.0-2.5 μm. The calcium carbonate powder with the particle size range is selected, so that the use ratio of the pearlescent master batch in film production can be effectively improved, and the uniformity and the thickness smoothness of film foaming are improved. Preferably, the whiteness of the calcium carbonate powder is greater than 90%, so that the final film product can show better appearance effect.
Preferably, the calcium carbonate powder is wet modified activated calcium carbonate. The activation is carried out by a wet modification method, so that the hydrophobicity of the calcium carbonate can be improved, and the agglomeration of the calcium carbonate is further avoided.
Further, the compatilizer comprises one or more of PP-g-MAH, PE-g-MAH, EVA-g-MAH and POE-g-MAH; the coupling agent is one or more of titanate, silane and aluminate compounds; the dispersant is a polyester type hyper-dispersant. The coupling agent is a substance with two functional groups with different properties, the molecule of the coupling agent contains two groups with different chemical properties, one group is an inorganophilic group, and the coupling agent is easy to chemically react with the surface of an inorganic substance; the other is an organophilic group capable of chemically reacting with synthetic resins or other polymers; therefore, the coupling agent (additive A) of the present invention can be used as a "molecular bridge" to improve the interface between the inorganic substance (calcium carbonate) and the organic substance (polypropylene). Similarly, a compatibilizer may also be considered a macromolecular coupling agent.
Further, the lubricant is compounded by one or more of stearic acid, calcium stearate, magnesium stearate, zinc stearate, paraffin, polyethylene wax and oxidized polyethylene wax. The addition of the lubricant can improve the lubricity of the master batch, reduce the adhesion of the master batch in extrusion equipment during the use process, improve the processability of the master batch, and also play a certain auxiliary role in improving the dispersion of calcium carbonate in polypropylene, thereby being further beneficial to the dispersion of the calcium carbonate.
Further, the antioxidant master batch comprises an antioxidant and polypropylene, wherein the antioxidant accounts for 10-15 wt%. The antioxidant in the pearlescent master batch is added in an antioxidant master batch mode, so that the problem of uneven mixing caused by direct addition of the antioxidant is avoided, and the antioxidant master batch is granular material and can be better blended with polypropylene (in a granular material mode), so that the pearlescent master batch is more convenient to process, and the product quality is more uniform and stable. The addition of the antioxidant master batch can improve the processing resistance of the pearlescent master batch, and the addition of the antioxidant master batch can ensure that the master batch is not degraded in a specific retention time in extrusion equipment.
The invention also provides a preparation method of the pearlescent master batch for the biaxially oriented film, which is characterized by comprising the following steps:
s1: raw material mixing and conveying: mixing the polypropylene resin, the additive A, the lubricant and the antioxidant master batch in a high-speed mixer according to a formula, and then conveying the materials into a feeder in a material suction manner through a spiral feeding machine; meanwhile, conveying calcium carbonate powder into a feeding machine in a material suction mode;
s2: melt extrusion: conveying the materials in the feeding machine to an extruder, and outputting an extrudate after uniform melting and mixing;
s3: granulation and post-treatment: and (3) bracing the extrudate, cooling, air-drying, granulating, screening, drying, homogenizing in a finished product bin, and finally packaging to obtain a finished product.
The selection and the preparation method of the pearlescent master batch for the biaxially oriented film have the advantages of simple process and convenient operation, can realize continuous production of the pearlescent master batch, and can realize uniform mixing of materials, and the finally obtained pearlescent master batch has stable product quality and more uniform distribution of calcium carbonate in the pearlescent master batch.
Further, in the S1, mixing the polypropylene resin, the additive A, the lubricant and the antioxidant master batch in a high-speed mixer for 5-10 minutes at the rotating speed of 300 rpm; the total flow of material conveying in the S2 is controlled at 250kg/h in 150-; the cooling temperature in S3 was 25 ℃.
The invention also provides a BOPP film, which is characterized in that: the pearlescent composite film comprises a first surface layer, a middle layer and a second surface layer, and is prepared by co-extruding and biaxial stretching first surface layer resin, middle layer resin and second surface layer resin, wherein the first surface layer resin and the second surface layer resin are both resins taking polypropylene as a main body, the middle layer resin comprises polypropylene resin and the pearlescent master batch, and the pearlescent master batch accounts for 2-40% of the total weight of the middle layer resin. The BOPP film prepared from the pearlescent master batch for the biaxially oriented film has more excellent pearlescent effect and uniform and stable thickness distribution.
The invention has the beneficial effects that:
(1) the pearlescent master batch for the biaxially oriented film is simple in formula, less in volatile matter and less in smoke, can improve the interface performance of calcium carbonate powder and polypropylene, reduces the agglomeration of calcium carbonate, and improves the dispersibility of calcium carbonate in polypropylene; meanwhile, the use proportion of the pearlescent master batch in the film main body resin can be improved, so that the pearlescent effect and the shading performance are more excellent, and the film production cost is lower;
(2) the preparation method of the pearlescent master batch for the biaxially oriented film has the advantages of simple process and convenient operation, can realize continuous production of the pearlescent master batch, and the finally obtained pearlescent master batch has stable product quality and more uniform distribution of calcium carbonate in the pearlescent master batch;
(3) the pearlescent master batch for the biaxially oriented film is applied to the preparation of film products, and the dosage of the pearlescent master batch can be adjusted as required to obtain different film products; the pearly-lustre effect cannot be influenced even if the using amount is increased, so that the pearly-lustre effect of the film is more excellent, and the thickness distribution is uniform and stable; for the BOPP film, the additive amount of 40 percent (weight percentage) can be realized at most, and the cost can be obviously reduced on the premise of meeting the requirements of the density, the thickness and the tensile strength of the BOPP film;
(4) the BOPP film produced by using the pearlescent master batch has good light-shielding property, has good barrier property to water vapor and oxygen, and can be applied to products such as food, gift packaging, facial masks, paper-like films and the like.
Detailed Description
For a better understanding and practice, the invention is described in detail below with reference to specific embodiments.
The pearlescent master batch for the biaxially oriented film comprises the following components in percentage by weight:
wherein the additive A is a compatilizer, a coupling agent or a dispersant.
The technical indexes of the pearlescent master batch for the biaxially oriented film are as follows:
melt index: 2-15g/10min (test standard GB/T3682, test temperature 230 ℃, test pressure 2.16 kg);
moisture content: 0.01-0.2% (test standard GB/T6284);
density: 1.2-1.7g/cm3 (test standard GB/T1033);
the number of particles per gram: 30-60 parts of;
oxidative induction period (180 ℃): ≧ 10 min.
Specific examples of pearlescent concentrates for biaxially oriented films are shown in table 1:
TABLE 1 pearlescent masterbatch for biaxially oriented films of examples 1 to 4 (unit: weight percentage)
Example 5
The preparation method of the pearlescent masterbatch for the biaxially oriented film of the embodiment comprises the following steps:
s1: raw material mixing and conveying: mixing polypropylene resin, an additive A, a lubricant and an antioxidant master batch in a high-speed mixer according to the pearlescent master batch formula for the biaxially oriented film in the embodiment 1-4, and conveying the materials to a feeder in a material suction manner through a spiral feeding machine; meanwhile, conveying calcium carbonate powder into a feeding machine in a material suction mode;
s2: melt extrusion: conveying the materials in the feeding machine to an extruder, and outputting an extrudate after uniform melting and mixing;
s3: granulation and post-treatment: and (3) bracing the extrudate, cooling, air-drying, granulating, screening, drying, homogenizing in a finished product bin, and finally packaging to obtain a finished product.
Preferably, the mixing time of the polypropylene resin, the additive A, the lubricant and the antioxidant master batch in the S1 in a high mixing machine is 5-10 minutes, and the rotating speed is 300 rpm; the total flow of material conveying in the S2 is controlled at 250kg/h in 150-; the cooling temperature in the S3 is 25 ℃, for example, the cooling can be carried out in a water tank; the material cutting mode in the S3 can be strand cutting and underwater cutting.
Example 6
The pearlescent masterbatch products of examples 1 to 4 were tested, and the technical indexes are shown in table 2:
TABLE 2 technical indexes of the pearlescent masterbatch for biaxially oriented films of examples 1 to 4
In addition, when the pearlescent master batch product is used in the production of the BOPP film, the pressure on the filter screen is found to be low, the blockage of the filter screen can be avoided, the time interval for replacing the filter screen is prolonged, and the produced BOPP film has uniform thickness and less broken film. This indicates that the calcium carbonate has good dispersibility in the pearlescent masterbatch.
Example 7
The BOPP film comprises a first surface layer, a middle layer and a second surface layer, and is prepared by co-extruding and biaxially stretching first surface layer resin, middle layer resin and second surface layer resin, wherein the first surface layer resin and the second surface layer resin are both resins taking polypropylene as a main body, the middle layer resin comprises polypropylene resin and the pearlescent master batch for the biaxially stretched film, and the pearlescent master batch accounts for 2-40% of the total weight of the middle layer resin.
In other embodiments, the pearlescent master batch of the present invention can also be applied to other biaxially oriented films, as long as it adopts the biaxially oriented preparation process, the calcium carbonate powder therein can form cavities in the polypropylene resin after biaxially oriented to form the pearlescent effect of the final product film.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. The pearlescent master batch for the biaxially oriented film is characterized by comprising the following components in percentage by weight:
the additive A is a compatilizer, a coupling agent or a dispersing agent, and the compatilizer is a maleic anhydride grafting compatilizer.
2. The pearlescent masterbatch for biaxially oriented film according to claim 1, characterized in that: the polypropylene resin is one of isotactic polypropylene, syndiotactic polypropylene and atactic polypropylene, and has a melt index of 2-25g/10 min.
3. The pearlescent masterbatch for biaxially oriented film according to claim 1, characterized in that: the average grain diameter of the calcium carbonate powder is 1.0-2.5 mu m.
4. The pearlescent masterbatch for biaxially oriented film according to claim 3, characterized in that: the calcium carbonate powder is activated calcium carbonate modified by a wet method.
5. The pearlescent masterbatch for biaxially oriented film according to claim 1, characterized in that: the compatilizer comprises one or more of PP-g-MAH, PE-g-MAH, EVA-g-MAH and POE-g-MAH; the coupling agent is one or more of titanate, silane and aluminate compounds; the dispersant is a polyester type hyper-dispersant.
6. The pearlescent masterbatch for biaxially oriented film according to claim 1, characterized in that: the lubricant is prepared by compounding one or more of stearic acid, calcium stearate, magnesium stearate, zinc stearate, paraffin, polyethylene wax and oxidized polyethylene wax.
7. The pearlescent masterbatch for biaxially oriented film according to claim 1, characterized in that: the antioxidant master batch comprises an antioxidant and polypropylene, wherein the antioxidant accounts for 10-15 wt%.
8. The method for preparing a pearlescent masterbatch for biaxially oriented film according to any one of claims 1 to 7, characterized by comprising the steps of:
s1: raw material mixing and conveying: mixing the polypropylene resin, the additive A, the lubricant and the antioxidant master batch in a high-speed mixer according to a formula, and then conveying the materials into a feeder in a material suction manner through a spiral feeding machine; meanwhile, conveying calcium carbonate powder into a feeding machine in a material suction mode;
s2: melt extrusion: conveying the materials in the feeding machine to an extruder, and outputting an extrudate after uniform melting and mixing;
s3: granulation and post-treatment: and (3) bracing the extrudate, cooling, air-drying, granulating, screening, drying, homogenizing in a finished product bin, and finally packaging to obtain a finished product.
9. The method for producing a pearlescent masterbatch for biaxially oriented film according to claim 1, characterized in that: mixing the polypropylene resin, the additive A, the lubricant and the antioxidant master batch in the S1 in a high-speed mixer for 5-10 minutes at the rotating speed of 300 rpm; the total flow of material conveying in the S2 is controlled at 250kg/h in 150-; the cooling temperature in S3 was 25 ℃.
10. A BOPP film is characterized in that: the pearlescent masterbatch comprises a first surface layer, a middle layer and a second surface layer, wherein the pearlescent masterbatch is prepared by co-extruding and biaxial stretching first surface layer resin, middle layer resin and second surface layer resin, the first surface layer resin and the second surface layer resin are both polypropylene-based resins, the middle layer resin comprises polypropylene resin and the pearlescent masterbatch according to any one of claims 1 to 7, and the pearlescent masterbatch accounts for 2 to 40 percent of the total weight of the middle layer resin.
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Cited By (4)
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| CN111472091A (en) * | 2020-05-07 | 2020-07-31 | 江苏伟创力新材料有限公司 | Three-dimensional facial mask non-woven fabric and manufacturing method thereof |
| CN111925595A (en) * | 2020-08-18 | 2020-11-13 | 广东竣富新材料科技有限公司 | Pearlescent master batch for biaxially oriented polypropylene film |
| CN112046106A (en) * | 2020-07-02 | 2020-12-08 | 佛山市高明海能科技有限公司 | BOPP film and production equipment thereof |
| CN114181463A (en) * | 2021-12-25 | 2022-03-15 | 昆山禾振瑞新复合材料有限公司 | Superfine nano calcium carbonate master batch, pearlized film and preparation method thereof |
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| CN111472091A (en) * | 2020-05-07 | 2020-07-31 | 江苏伟创力新材料有限公司 | Three-dimensional facial mask non-woven fabric and manufacturing method thereof |
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| CN114181463A (en) * | 2021-12-25 | 2022-03-15 | 昆山禾振瑞新复合材料有限公司 | Superfine nano calcium carbonate master batch, pearlized film and preparation method thereof |
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