CN107603008B - Semi-dull material for BOPP semi-dull transfer base film and preparation method and application thereof - Google Patents

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

A kind of semi-matte material for BOPP semi-matte transfer base film and preparation method thereof application

technical field

The invention relates to a modified masterbatch and a preparation method thereof, in particular to a semi-matte material for BOPP semi-matte transfer base film, its preparation method and application.

Background technique

BOPP is a biaxially oriented polypropylene film. In addition to the packaging field, BOPP matte film can also be used in textile printing transfer, printing processing and other industrial fields. BOPP semi-matte transfer base film, also known as matte transfer base film, is a new type of film whose matte surface gloss is between 15% and 65%, mainly used for leather transfer and other purposes. Now, the transfer film with 5-layer structure is used to illustrate the use of BOPP semi-matte transfer base film. For example, the structure of a certain type of transfer film is as follows: substrate layer (such as semi-matte transfer base film) - release layer (silicone resin) ——Protection layer——Decorative layer——Transfer coating (PU resin system), after the transfer film and the bottom leather to be decorated are heated and pressurized by the laminating machine, the transfer coating and the bottom leather are firmly bonded Together, the substrate layer is peeled off, and the concave-convex topographic features on the surface of the substrate layer are replicated on the leather (see Figure 1). Therefore, the role of BOPP semi-matte transfer base film is to serve as a carrier substrate for subsequent coating processing, and to form soft and delicate diffuse reflection to enhance the decorative effect.

In the existing BOPP semi-matte transfer base film production technology, one is to add a certain amount of polypropylene and other small amounts of additives to the full-matte material, and to form a semi-matte layer after biaxial stretching by melt extrusion; All semi-matte materials and a small amount of other additives are used to form semi-matte layers after melt extrusion and biaxial stretching. The semi-matte transfer base film prepared by the first method, because the matting material is difficult to distribute evenly in the matting layer, the matting effect is not uniform, and it is in a cloudy shape with obvious uneven shades, and the decorative effect after the transfer does not meet the requirements. The semi-matte transfer base film prepared by the second method has greatly improved extinction uniformity, but there are still problems such as unstable extinction effect, poor uniformity and incomplete transfer.

SUMMARY OF THE INVENTION

The technical problem to be solved by the present invention is to provide a semi-matte material for BOPP semi-matte transfer base film and a preparation method and application thereof, so as to solve the problems of unstable extinction effect, poor uniformity, and transfer of the prior art semi-matte transfer base film. Incomplete and so on.

The present invention is achieved through the following technical solutions:

A semi-matte material for BOPP semi-matte transfer base film and a preparation method thereof, comprising the following components by weight:

PP resin: 66.7—86.9;

HDPE (high density polyethylene): 8—18;

Compatibilizer: 5—15;

Antioxidant: 0.1—0.3.

A further improvement scheme of the present invention is that the melt index of the PP resin is 3-15g/10min (test condition: 230°C, 2.16kg).

A further improvement scheme of the present invention is that the melt index of the PP resin is 6-12g/10min (test condition: 230°C, 2.16kg), which is more conducive to the uniform dispersion of HDPE in the melt.

A further improvement scheme of the present invention is that the PP resin is a binary polypropylene copolymer or a terpolymer, and preferably a binary polypropylene copolymer, compared with a terpolymer, a binary polypropylene copolymer The Vicat has a high softening point and a large elastic modulus, which can better meet the requirements of the transfer film substrate for better temperature resistance and small tensile deformation.

A further improvement scheme of the present invention is that the density of the HDPE is 0.920-0.961g/cm3; the melt index is 0.01-0.25g/10min (test conditions: 190°C, 2.16kg).

A further improvement scheme of the present invention is that the density of the HDPE is 0.935-0.955g/cm3; the melt index is 0.05-0.15g/10min (test conditions: 190°C, 2.16kg).

A further improvement scheme of the present invention is that the compatibilizer is LLDPE (linear low density polyethylene), and the LLDPE is a film grade LLDPE with a density of 0.918-0.935g/cm3 and a melt index of 1.5-4.0g/10min ( Test conditions: 190℃, 2.16kg).

Compatibilizers commonly used in the blending of PP and HDPE include EPDM (ethylene propylene rubber), POB (propylene-based elastomer), POE (ethylene-1-octene elastomer), etc., but due to EPDM, POB, The melting point of POE is about 90 ℃. In the film manufacturing process, it is easy to stick to the roller in the longitudinal drawing section, so it is not selected. The melting point of LLDPE is relatively high, which is suitable for the step-by-step biaxial stretching film making process, and its cost is also low. Therefore, film-grade LLDPE is used in the present invention, and its density is 0.918-0.935g/cm3, and the melt index is 1.5-4.0g/ 10min (test condition: 190℃, 2.16kg).

HDPE and PP resin are extremely incompatible two-phase blend systems. After adding the above-mentioned compatibilizer, in the process of melt extrusion, the aggregation of HDPE in the dispersed phase will be inhibited, and the size of the dispersed phase will be reduced and uniformly dispersed. , the stability and uniformity of the matting effect are improved. Because of the incompatibility between the dispersed phase (HDPE) and the continuous phase (PP resin), the bonding strength between the two phases is low, and cracks are prone to occur in the matte layer during the biaxial stretching process. When the release layer (0.3-0.8μm) is coated on the substrate, these cracks will produce capillary phenomenon, adsorb the surrounding release agent, resulting in the problem of unclean transfer and poor transfer effect. After adding the compatibilizer, the bonding strength between the two phases is improved, the cracks are reduced, and the depth of the cracks is shallower, so the transfer effect is also improved.

A further improvement scheme of the present invention is that the antioxidant is a compound antioxidant, containing a main antioxidant and an auxiliary antioxidant, wherein the mass ratio of the main antioxidant and the auxiliary antioxidant is 1:2, and the main antioxidant is The antioxidant is hindered phenolic antioxidant 1010 or hindered phenolic antioxidant 1076, and the auxiliary antioxidant is phosphite antioxidant 168 or phosphite antioxidant 626. The compound antioxidant is used in plastic material processing. , showing a synergistic effect, a good anti-thermal-oxidative aging effect can be achieved with a lower addition amount, and the processing can be carried out smoothly and its service life can be extended.

A preparation method of semi-matte material for BOPP semi-matte transfer base film, comprising the following steps: batching, mixing in a mixer for 8-10min, melting and extruding strips, and the strips are pelletized and dried to prepare The finished product is pelletized, and the extrusion temperature is 150-200°C.

The application of a semi-matte material for BOPP semi-matte transfer base film in BOPP semi-matte transfer base film, the semi-matte material is used as the upper surface layer material to produce the semi-matte transfer layer, and the polypropylene is used as the core layer and the bottom layer material, The upper surface layer material, the core layer material and the lower layer material are all formed by three-layer co-extrusion, casting, and biaxial stretching.

Compared with the prior art, the present invention has the following advantages:

The matte layer of the BOPP semi-matte transfer base film of the present invention has uniform surface roughness, uniform distribution of surface protrusions or depressions, stable matting effect, good transfer effect, and excellent decorative effect.

Description of drawings

Figure 1 shows the surface features of the substrate transferred to the leather.

2 is a schematic cross-sectional view of a BOPP semi-matte transfer base film with a three-layer structure.

Detailed ways

Example 1:

Binary copolymer polypropylene - Borouge Plastics (Shanghai) Co., Ltd. RD239CF (8.0±2g/10min): 86.8 copies;

High-density polyethylene - DGDA6098 of Sinopec Qilu Petrochemical Company (0.11g/10min, 0.948g/cm3): 8 copies;

Compatibilizer - Dow Chemical 2045G (1.0g/10min, 0.920g/cm3): 5 copies;

Antioxidant (mixture of 1010 and 168, the mass ratio of the two is 1:2): 0.2 part;

After the raw materials of the above formula are fully mixed with a high-speed mixer, the strips are melted and extruded through a twin-screw extruder, and the strips are cut into pellets and dried to make pellets to obtain BOPP semi-matte materials.

Example 2:

Binary copolymer polypropylene - Shanghai Petrochemical Co., Ltd. F800EDF (8.0±2g/10min): 78.8 copies;

High-density polyethylene - DGDA6098 of Sinopec Qilu Petrochemical Company (0.11g/10min, 0.948g/cm3): 12 copies;

Compatibilizer - Mitsui Chemicals SP1520H (2.0g/10min, 0.913g/cm3): 9 copies;

Antioxidant (mixture of 1010 and 168, the mass ratio of the two is 1:2): 0.2 part;

After the raw materials of the above formula are fully mixed with a high-speed mixer, the strips are melted and extruded through a twin-screw extruder, and the strips are cut into pellets and dried to make pellets to obtain BOPP semi-matte materials.

Example 3:

Binary copolymer polypropylene - Borouge Plastics (Shanghai) Co., Ltd. RD239CF (8.0±2g/10min: 72.8 parts;

High density polyethylene - Exxon Mobil Corporation HTA-001HD5 (0.07g/10min, 0.952g/cm3): 15 copies;

Compatibilizer - Shanghai SECCO Petrochemical Co., Ltd. LL0220AA (2.4g/10min, 0.921g/cm3): 12 copies;

Antioxidant (mixture of 1010 and 168, the mass ratio of the two is 1:2): 0.2 part;

After the raw materials of the above formula are fully mixed with a high-speed mixer, the strips are melted and extruded through a twin-screw extruder, and the strips are cut into pellets and dried to make pellets to obtain BOPP semi-matte materials.

Example 4:

Binary copolymer polypropylene - Shanghai Petrochemical Co., Ltd. F800EDF (8.0±2g/10min): 66.8 copies;

High density polyethylene - Exxon Mobil Corporation HTA-001HD5 (0.07g/10min, 0.952g/cm3): 18 copies;

Compatibilizer - Sinopec Zhenhai Refining and Chemical Company LL-ZF4533H (4.0g/10min, 0.932g/cm3): 15 parts;

Antioxidant (mixture of 1010 and 168, the mass ratio of the two is 1:2): 0.2 part;

After the raw materials of the above formula are fully mixed with a high-speed mixer, the strips are melted and extruded through a twin-screw extruder, and the strips are cut into pellets and dried to make pellets to obtain BOPP semi-matte materials.

Four kinds of matting materials and common commercially available matting materials HTX500 prepared in the above examples are used in the matting layer of the BOPP film according to the proportion of 100%, that is, the semi matting material is used as the upper surface material to produce the semi matting transfer layer, and polypropylene is used as the core layer. With the bottom layer material, the top layer material, the core layer material and the bottom layer material are all formed by three-layer co-extrusion, casting and biaxial stretching. A semi-matte transfer base film with a film thickness of 22 μm and a semi-matte layer thickness of 2.0 μm was prepared. The large roll of film is cut into small rolls of various specifications, and the small rolls of film at the same slitting position are taken to compare and observe the matting effect of the film surface, and detect the roughness and haze of the semi-matte surface.

Roughness detection: Take 8 samples of 10cm × 10cm along the length direction every 20cm in the middle of the small roll film, and use the MarSurf M300C roughness meter from Marr, Germany to test, and the measuring probe moves along the length direction (longitudinal direction), and the reference test standard It is GB/T13542.2-2009/8. The standard deviation of the test results can represent the uniformity of surface roughness, and the smaller the standard deviation, the more uniform the roughness is.

Haze detection: Take 8 samples of 10cm×10cm along the length direction every 20cm in the middle of the small roll film, and use the haze meter of BYK-Gardner company in Germany with the model BYK-4775 to detect, the reference test standard is GB/T2410 -2008. The standard deviation of the test results can directly reflect the extinction effect and the uniformity of the extinction film. The smaller the standard deviation, the better the extinction effect and the uniformity of the extinction.

The comparison test results are as follows:

From the results, it can be found that the surface roughness Ra and the standard deviation of the haze value of Examples 1-4 are smaller than that of the semi-matte transfer base film prepared from the common commercially available matting material HTX500, that is, the surface roughness Ra and The fluctuation of the haze value is smaller, which shows that the surface roughness of the matte films prepared in Examples 1-4 is more uniform, the haze distribution is more uniform, and the matting effect is more stable.

The haze of Examples 1-4 is different, and the visual effect of extinction is also different, and customers can choose according to their needs. Several transfer materials Co., Ltd. used the semi-matte transfer base film obtained in the above Example 2 for the production of leather transfer film. When the obtained product was used for leather transfer, the transfer was clean and complete. Compared with the transfer film made by HTX500, The transfer effect was significantly improved.

The above descriptions are only preferred embodiments of the present invention, and do not limit the present invention to any form of limitation. Any simple modifications made to the above embodiments according to the technical essence of the present invention, equivalent changes and modifications, are It belongs to the scope of the technical solution 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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