CN107603008B - Semi-dull material for BOPP semi-dull transfer base film and preparation method and application thereof - Google Patents
Semi-dull material for BOPP semi-dull transfer base film and preparation method and application thereof Download PDFInfo
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- CN107603008B CN107603008B CN201710739060.9A CN201710739060A CN107603008B CN 107603008 B CN107603008 B CN 107603008B CN 201710739060 A CN201710739060 A CN 201710739060A CN 107603008 B CN107603008 B CN 107603008B
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Abstract
The invention discloses a semi-extinction material for a BOPP semi-extinction transfer base film, which comprises the following components in parts by weight: PP resin: 66.7 to 86.9; HDPE: 8 to 18; compatibilizer: 5-15; antioxidant: 0.1-0.3. The invention also discloses a preparation method of the semi-extinction material for the BOPP semi-extinction transfer base film, which comprises the following steps: mixing, mixing in a mixer for 8-10min, melt-extruding into strips, granulating, and drying to obtain granule. The invention also discloses an application of the semi-extinction material for the BOPP semi-extinction transfer base film in the BOPP semi-extinction transfer base film. The matte layer of the BOPP semi-matte transfer base film has uniform surface roughness, uniform distribution of surface bulges or depressions, stable matte effect and good transfer effect, and can obtain excellent decorative effect.
Description
Technical Field
The invention relates to a modified master batch and a preparation method thereof, in particular to a semi-dull material for a BOPP semi-dull transfer base film, and a preparation method and application thereof.
Background
The BOPP is a biaxially oriented polypropylene film. The BOPP extinction film can be used in the field of packaging, and also can be used in the industrial fields of textile printing transfer, printing processing and the like. The BOPP semi-dull transfer base film is also called a matte transfer base film, is a novel film with a dull surface gloss of 15-65% and is mainly used for leather transfer and other purposes. The application of BOPP semi-matt transfer base film will now be described with a transfer film having a 5-layer structure, for example, a certain type of transfer film structure comprises: the transfer film is heated and pressurized by a laminating machine, the transfer coating is firmly adhered to the ground leather, and then the base material layer is peeled off, so that the concave-convex morphological characteristics on the surface of the base material layer are copied to the leather (see attached figure 1). Thus, the BOPP semi-matt transfer base film functions as: the coating is used as a bearing substrate for subsequent coating processing, and soft and exquisite diffuse reflection is formed, so that the decorative effect is enhanced.
In the existing BOPP semi-dull transfer base film production technology, one is to add a certain amount of polypropylene and other small amount of additives into a full dull material, and the mixture is subjected to melt extrusion and biaxial stretching to form a semi-dull layer; and secondly, the semi-matt layer is formed by completely adopting semi-matt materials and other small amount of additives through melt extrusion and biaxial stretching. The semi-extinction transfer base film prepared by the first method has uneven extinction effect due to the fact that the extinction material is difficult to be uniformly distributed in the extinction layer, the extinction layer is in a cloud shape with obvious uneven shade, and the decoration effect after transfer cannot meet the requirement; the semi-dull transfer base film prepared by the second method has greatly improved extinction uniformity, but still has the problems of unstable extinction effect, poor uniformity, incomplete transfer and the like.
Disclosure of Invention
The invention aims to solve the technical problems of providing a semi-dull material for a BOPP semi-dull transfer base film, a preparation method and application thereof, and solving the problems of unstable dull effect, poor uniformity, incomplete transfer and the like of the semi-dull transfer base film in the prior art.
The invention is realized by the following technical scheme:
a semi-dull material for BOPP semi-dull transfer basal membrane and a preparation method thereof comprise the following components in parts by weight:
PP resin: 66.7 to 86.9;
HDPE (high density polyethylene): 8 to 18;
compatibilizer: 5-15;
antioxidant: 0.1-0.3.
In a further development of the invention, the PP resin has a melt index of 3 to 15g/10min (test conditions: 230 ℃ C., 2.16 kg).
In a further improvement of the invention, the PP resin has a melt index of 6-12g/10min (test conditions: 230 ℃ and 2.16 kg), and is more beneficial to uniform dispersion of HDPE in the melt.
The invention has the further improvement scheme that the PP resin is a binary polypropylene copolymer or a ternary polypropylene copolymer, and the binary polypropylene copolymer is preferably selected, compared with the ternary polypropylene copolymer, the binary polypropylene copolymer has high Vicat softening point and large elastic modulus, and can better meet the requirements of the transfer film substrate on better temperature resistance, small tensile deformation and the like.
In a further development of the invention, the HDPE has a density of from 0.920 to 0.961g/cm 3; the melt index was 0.01 to 0.25g/10min (test conditions: 190 ℃ C., 2.16 kg).
In a further improvement of the invention, the HDPE has a density of 0.935 to 0.955g/cm 3; the melt index was 0.05 to 0.15g/10min (test conditions: 190 ℃ C., 2.16 kg).
In a further development of the invention, the compatibilizer is LLDPE (linear low density polyethylene), the LLDPE is a film-grade LLDPE with a density of 0.918 to 0.935g/cm3 and a melt index of 1.5 to 4.0g/10min (test conditions: 190 ℃ C., 2.16 kg).
The commonly used compatibilizer for blending PP and HDPE also comprises EPDM (ethylene propylene diene monomer), POB (propylene-based elastomer), POE (ethylene-1-octene elastomer) and the like, but the melting points of EPDM, POB and POE are about 90 ℃, so that rollers are easy to stick at a longitudinal drawing section in the film manufacturing process, and the compatibilizer is not selected. The LLDPE has higher melting point, is suitable for a gradual biaxial stretching film-making process, and has lower cost, so the invention uses the film-grade LLDPE with the density of 0.918-0.935g/cm3 and the melt index of 1.5-4.0g/10min (the test condition is 190 ℃ and 2.16 kg).
HDPE and PP resin are extremely incompatible two-phase blending system, and after the compatibilizer is added, the aggregation of HDPE of a disperse phase can be inhibited in the melt extrusion process, so that the size of the disperse phase is reduced and the disperse phase is uniformly dispersed, and therefore, the stability and uniformity of the extinction effect are improved. Since the dispersed phase (HDPE) and the continuous phase (PP resin) are incompatible, the bonding strength between the two phases is low, and the matte layer is easily cracked during biaxial stretching. When a release layer (0.3-0.8 μm) is coated on a substrate, the cracks generate a capillary phenomenon, and adsorb surrounding release agents, so that the problems of incomplete transfer and poor transfer effect are caused. After the compatibilizer is added, the bonding strength between two phases is improved, cracks are reduced, the depth of the cracks becomes shallow, and therefore the transfer effect is also improved.
The invention further improves the scheme that the antioxidant is a compound antioxidant and comprises a main antioxidant and an auxiliary antioxidant, wherein the mass ratio of the main antioxidant to the auxiliary antioxidant is 1:2, the main antioxidant is a hindered phenol antioxidant 1010 or a hindered phenol antioxidant 1076, the auxiliary antioxidant is a phosphite antioxidant 168 or a phosphite antioxidant 626, the compound antioxidant shows a synergistic effect in the processing of plastic materials, a good thermal oxidation aging resistant effect can be achieved with a low addition amount, and the processing can be smoothly carried out and the service life of the compound antioxidant can be prolonged.
A preparation method of a semi-dull material for a BOPP semi-dull transfer base film comprises the following steps: mixing materials, mixing for 8-10min in a mixer, melting and extruding strips, granulating and drying the strips to obtain finished granules, wherein the extrusion temperature is 150-200 ℃.
The application of a semi-dull material for a BOPP semi-dull transfer base film in the BOPP semi-dull transfer base film is characterized in that the semi-dull material is used as an upper surface material to produce a semi-dull transfer layer, polypropylene is used as a core layer and a lower surface material, and the upper surface material, the core layer material and the lower surface material are subjected to three-layer co-extrusion, sheet casting and two-way stretching and then are subjected to one-step forming.
Compared with the prior art, the invention has the following advantages:
the matte layer of the BOPP semi-matte transfer base film has uniform surface roughness, uniform distribution of surface bulges or depressions, stable matte effect and good transfer effect, and can obtain excellent decorative effect.
Drawings
FIG. 1 is a representation of the topography of the substrate surface transferred onto leather.
Fig. 2 is a schematic cross-sectional view of a BOPP semi-dull transfer base film having a three-layer structure.
Detailed Description
Example 1:
86.8 parts of binary copolymer polypropylene, namely 86.8 parts of polypropylene, namely RD239CF (8.0 +/-2 g/10 min) from Bolu plastics (Shanghai);
8 portions of high-density polyethylene, namely DGDA6098 (0.11 g/10min,0.948g/cm 3) of China petrochemical Qilu petrochemical company;
5 portions of compatibilizer-Dow chemical 2045G (1.0G/10 min,0.920G/cm 3);
0.2 part of antioxidant (a mixture of 1010 and 168, with the mass ratio of 1: 2);
and (3) fully mixing the raw materials in the formula by using a high-stirring machine, melting and extruding strips by using a double-screw extruder, and granulating and drying the strips to obtain a finished particle product so as to obtain the BOPP semi-extinction material.
Example 2:
binary copolymer polypropylene, Shanghai Shimai GmbH F800EDF (8.0 + -2 g/10 min) 78.8 parts;
12 portions of high-density polyethylene, namely DGDA6098 (0.11 g/10min,0.948g/cm 3) of China petrochemical Qilu petrochemical company;
compatibilizer-Sanjing Chemicals SP1520H (2.0 g/10min,0.913g/cm 3): 9 parts;
0.2 part of antioxidant (a mixture of 1010 and 168, with the mass ratio of 1: 2);
and (3) fully mixing the raw materials in the formula by using a high-stirring machine, melting and extruding strips by using a double-screw extruder, and granulating and drying the strips to obtain a finished particle product so as to obtain the BOPP semi-extinction material.
Example 3:
binary copolymer polypropylene-Bolu plastics (Shanghai) Co., Ltd. RD239CF (8.0 + -2 g/10min:72.8 parts;
15 parts of high-density polyethylene, namely Exxon Mobil HTA-001HD5 (0.07 g/10min,0.952g/cm 3);
12 parts of compatibilizer-Shanghai Seikeke petrochemical engineering Limited liability company LL0220AA (2.4 g/10min,0.921g/cm 3);
0.2 part of antioxidant (a mixture of 1010 and 168, with the mass ratio of 1: 2);
and (3) fully mixing the raw materials in the formula by using a high-stirring machine, melting and extruding strips by using a double-screw extruder, and granulating and drying the strips to obtain a finished particle product so as to obtain the BOPP semi-extinction material.
Example 4:
binary copolymer polypropylene, Shanghai Shimai GmbH F800EDF (8.0 + -2 g/10 min) 66.8 parts;
18 parts of high-density polyethylene, namely 18 parts of Exxon Mobil HTA-001HD5 (0.07 g/10min,0.952g/cm 3);
15 portions of compatibilizer-LL-ZF 4533H (4.0 g/10min,0.932g/cm 3) from China petrochemical and Zhehai refining company;
0.2 part of antioxidant (a mixture of 1010 and 168, with the mass ratio of 1: 2);
and (3) fully mixing the raw materials in the formula by using a high-stirring machine, melting and extruding strips by using a double-screw extruder, and granulating and drying the strips to obtain a finished particle product so as to obtain the BOPP semi-extinction material.
The four extinction materials prepared in the above example and the ordinary commercial extinction material HTX500 are used in the extinction layer of the BOPP film according to the proportion of 100%, namely, the semi-extinction material is used as the upper layer material to produce the semi-extinction transfer layer, the polypropylene is used as the core layer and the lower layer material, and the upper layer material, the core layer material and the lower layer material are all subjected to three-layer co-extrusion, sheet casting and biaxial tension and then are formed at one step. A semi-matt transfer base film having a film thickness of 22 μm and a semi-matt layer thickness of 2.0 μm was produced. The large roll film is cut into small rolls with various specifications, the small roll film at the same cutting position is taken, the extinction effect of the film surface is observed in a contrast mode, and the roughness and the haze of the semi-extinction surface are detected.
And (3) roughness detection: 8 samples of 10cm x 10cm are taken every 20cm in the middle of the film roll along the length direction and detected by a MarSurf M300C coarseness tester manufactured by German Mark company, and the measuring probe moves along the length direction (longitudinal direction) according to the test standard GB/T13542.2-2009/8. The standard deviation of the test results may indicate the uniformity of the surface roughness, with smaller standard deviations indicating more uniform roughness.
Haze detection: 8 10cm x 10cm samples were taken every 20cm lengthwise in the middle of the film coil and tested using a BYK-4775 model haze meter, BYK-Gardner, Germany, with reference to GB/T2410-2008. The standard deviation of the test result can directly reflect the extinction effect and the extinction uniformity of the extinction film, and the smaller the standard deviation is, the better the extinction effect and the extinction uniformity are.
The comparative test results are given in the following table:
from the results, it can be found that the surface roughness Ra and the standard deviation of the haze value thereof are smaller in examples 1 to 4, i.e., the fluctuation of the surface roughness Ra and the haze value thereof is smaller, compared to the semi-dull transfer base film prepared by the general commercially available matting material HTX500, which indicates that the surface roughness, the haze distribution and the matting effect of the matting films prepared in examples 1 to 4 are more uniform.
The haze and matte visual effect of examples 1-4 were different and were selected by the customer as desired. Several transfer material companies apply the semi-dull transfer base film obtained in example 2 to the production of a leather transfer film, and when the obtained product is applied to leather transfer, the transfer is clean and complete, and compared with the transfer film prepared by HTX500, the transfer effect is obviously improved.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiments according to the technical spirit of the present invention are included in the scope of the present invention.
Claims (7)
1. A semi-extinction material for a BOPP semi-extinction transfer base film is characterized by comprising the following components in parts by weight:
PP resin: 66.7 to 86.9;
HDPE：8—18；
compatibilizer: 5-15;
antioxidant: 0.1 to 0.3;
the compatibilizer is LLDPE, the LLDPE is film-grade LLDPE, the density of the LLDPE is 0.918-0.935g/cm3, and the melt index of the LLDPE is 1.5-4.0g/10 min;
the antioxidant is a compound antioxidant and comprises a main antioxidant and an auxiliary antioxidant, wherein the mass ratio of the main antioxidant to the auxiliary antioxidant is 1:2, the main antioxidant is a hindered phenol antioxidant 1010 or a hindered phenol antioxidant 1076, and the auxiliary antioxidant is a phosphite antioxidant 168 or a phosphite antioxidant 626;
the PP resin is a binary polypropylene copolymer or a ternary polypropylene copolymer;
the HDPE has a melt index of 0.01-0.25g/10 min.
2. The semi-dull material for BOPP semi-dull transfer base film according to claim 1, wherein: the melt index of the PP resin is 3-15g/10 min.
3. The semi-dull material for BOPP semi-dull transfer base film according to claim 2, wherein: the melt index of the PP resin is 6-12g/10 min.
4. The semi-dull material for BOPP semi-dull transfer base film according to claim 1, wherein: the density of the HDPE is 0.920-0.961g/cm3。
5. The semi-dull material for BOPP semi-dull transfer base film according to claim 4, wherein: the density of the HDPE is 0.935-0.955g/cm3(ii) a The melt index is 0.05-0.15g/10 min.
6. A process for the preparation of a semimatt transfer film as claimed in any one of claims 1 to 5 for BOPP, wherein: the method comprises the following steps: the components in the weight portion of claim 1 are mixed in a mixer for 8-10min, and then the mixture is melted and extruded into strips, and the strips are granulated and dried to prepare a finished granular product, wherein the extrusion temperature is 150 ℃ and 200 ℃.
7. Use of a semi-matt compound as defined in any one of claims 1 to 5 for a BOPP semi-matt transfer base film in a BOPP semi-matt transfer base film.
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| CN112644121A (en) * | 2020-12-16 | 2021-04-13 | 安徽金田高新材料股份有限公司 | BOPP semi-dull transfer film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010101582A1 (en) * | 2009-03-03 | 2010-09-10 | E. I. Du Pont De Nemours And Company | Laminated polymer film and solar module made thereof |
| CN102197085A (en) * | 2008-10-31 | 2011-09-21 | 巴斯夫欧洲公司 | Method of modifying gloss with modified polymers and related products and uses |
| CN105980458A (en) * | 2013-12-30 | 2016-09-28 | 艾利丹尼森公司 | Films for printing |
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| US9139728B2 (en) * | 2008-06-30 | 2015-09-22 | Fina Technology, Inc. | Single pellet polymeric compositions |
| CN103497422A (en) * | 2013-09-16 | 2014-01-08 | 苏州康斯坦普工程塑料有限公司 | Matting master batch for biaxially oriented polypropylene film and production process of matting master batch |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102197085A (en) * | 2008-10-31 | 2011-09-21 | 巴斯夫欧洲公司 | Method of modifying gloss with modified polymers and related products and uses |
| WO2010101582A1 (en) * | 2009-03-03 | 2010-09-10 | E. I. Du Pont De Nemours And Company | Laminated polymer film and solar module made thereof |
| CN105980458A (en) * | 2013-12-30 | 2016-09-28 | 艾利丹尼森公司 | Films for printing |
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