CN108148367B - PLA smart card base material and preparation method thereof - Google Patents
PLA smart card base material and preparation method thereof Download PDFInfo
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- CN108148367B CN108148367B CN201611107487.9A CN201611107487A CN108148367B CN 108148367 B CN108148367 B CN 108148367B CN 201611107487 A CN201611107487 A CN 201611107487A CN 108148367 B CN108148367 B CN 108148367B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention discloses a PLA smart card substrate and a preparation method thereof, the PLA sheet is prepared by a two-layer co-extrusion mode according to the following formula, wherein the PLA sheet comprises a layer A: 100 parts of PLA resin and TiO211-13 parts of antioxidant and 1-2 parts of antioxidant; layer B: 100 parts of polylactic acid copolymer resin and 1-2 parts of antioxidant. Uniformly mixing the raw materials of each layer according to the proportion, putting the mixture into a corresponding extruder, cooling and shaping the melt through a filter, a melt pump, a die and a three-roller calender to obtain the PLA sheet. According to the invention, polylactic acid copolymer resin is used as the co-extrusion layer, so that the problem that the PLA intelligent card INLAY layer is not firmly combined with the printing layer is solved.
Description
Technical Field
The invention belongs to the field of plastic processing, and particularly relates to a PLA intelligent card base material and a preparation method thereof.
Background
The development of smart cards such as bank cards, traffic cards, social security cards and the like promotes the improvement of social informatization level, and brings convenience to life of people. The main material of the cards is PVC resin, and the cards are difficult to recycle due to the metal contained in the cards and basically discarded, so that great pollution is caused, and the environmental problem caused by the smart cards is a difficult problem to solve urgently in the current industry.
Polylactic acid (PLA) is a new type of bio-based and biodegradable material made using starch feedstocks from renewable plant sources such as corn. The starch raw material is saccharified to obtain glucose, the glucose and certain strains are fermented to prepare high-purity lactic acid, and the polylactic acid with certain molecular weight is synthesized by a chemical synthesis method. The biodegradable plastic has good biodegradability, can be completely degraded by microorganisms in the nature under specific conditions after being used, finally generates carbon dioxide and water, does not pollute the environment, is very beneficial to environmental protection, and is a well-known environment-friendly material.
PLA is biodegradable and therefore a better alternative to PVC for making smart cards. Generally, card manufacturing is carried out in a step-by-step laminating mode, wherein an INLAY layer is manufactured and then laminated with a printing layer and an OVERLAY layer. Because PLA is a semi-crystalline material, in the manufacturing process of the INLAY layer, the crystallization degree is increased due to the heating of PLA, the structure is stable, and the PLA is difficult to be firmly combined with a printing layer in the next lamination.
The invention patent with the patent grant publication number of CN 103087483B provides a biaxial stretching polylactic acid sheet for a card base core layer and a preparation method thereof. The method solves the defects of small elongation at break, poor heat resistance, poor hydrolysis resistance and poor aging resistance of the PLA sheet through a special formula system and a biaxial stretching process. However, the heat resistance improved by the stretching process substantially increases the crystallinity of the PLA sheet, and the surface structure of the sheet is inert, which makes it more difficult to bond with the printed layer.
Disclosure of Invention
The invention aims to provide a PLA smart card substrate and a preparation method thereof, wherein a polylactic acid copolymer functional layer is formed on the surface of PLA by a co-extrusion process, so that an INLAY layer and a printing layer can be firmly laminated.
In order to achieve the purpose, the invention adopts the technical means as follows:
a PLA smart card substrate having an A/B structure prepared using the following formulation:
layer A:
100 parts of PLA resin
TiO211 to 13 portions of
1-2 parts of antioxidant
Wherein, the PLA resin is a stereocomplex formed by PDLA and PLLA, the melt index of the complex is 9-10g/10min, and the test condition is 190 ℃ and 2.16 KG.
The TiO is2Is rutile type, and has particle size of 30-60 nm.
The antioxidant is at least one of antioxidant 1010 and antioxidant 168.
Layer B:
polylactic acid copolymer resin 100 parts
1-2 parts of antioxidant
Wherein the polylactic acid copolymer resin is polylactic acid-glycolic acid copolymer, the proportion of glycolic acid monomer in the copolymer is 55-60%, the melt index of the copolymer is 11-13g/10min, and the test conditions are 190 ℃ and 2.16 KG.
The antioxidant is at least one of antioxidant 1010 and antioxidant 168.
The preparation method of the PLA smart card substrate comprises the following steps:
1) drying the PLA resin of the layer A for 5-6 hours at 60 ℃, and drying the polylactic acid copolymer resin of the layer B for 5-6 hours at 50 ℃;
2) and respectively uniformly mixing the raw materials of the layer A and the layer B according to the proportion, putting the mixture into a corresponding extruder, and cooling and shaping the melt through a filter, a melt pump, a die and a three-roll calender to obtain the PLA sheet.
The water content of the PLA resin and the polylactic acid copolymer resin after drying in the step 1) is less than 100 PPM.
Layer A in step 2): the extrusion temperature of the extruder is 140-200 ℃; the temperature of the melt pump is 190-195 ℃;
layer B: the extrusion temperature of the extruder is 190 ℃ plus 150 ℃, and the melt pump temperature is 190 ℃ plus 180 ℃;
the mold temperature was 195-.
And 2) 50-55 ℃ of the upper roll of the three-roll calender, 25-30 ℃ of the middle roll of the three-roll calender and 25-30 ℃ of the lower roll of the three-roll calender.
Has the advantages that:
glycolic acid is used as a comonomer, the molecular structure of polylactic acid can be disordered, the sheet does not further crystallize during hot pressing, the stability of the crystallinity is kept, and the lactic-glycolic acid copolymer is used as a B layer and used as a contact surface of an INLAY layer and a printing layer, so that the peeling strength is good after lamination.
Detailed Description
The present invention is further explained with reference to the following examples, which are not intended to limit the present invention in any way. For comparison, the sheet thicknesses were 260 μm, and the A, B layer thickness ratio was a/B = 15/85.
The PLA resin used in the following examples was a stereocomplex of PDLA and PLLA having a melt index of 9-10g/10min, and tested at 190 ℃ and 2.16KG, available from Natureworks, USA under the brand number 4043D.
The polylactic acid copolymer is polylactic-co-glycolic acid copolymer, the proportion of glycolic acid monomer in the copolymer is 55-60%, the melt index of the copolymer is 11-13g/10min, the test condition is 190 ℃ and 2.16KG, and the polylactic-co-glycolic acid copolymer is provided by Natureworks company of America and has the brand number of M700.
The TiO2 used in the following examples was in the rutile form, available from DuPont, USA, with a particle size of 40-50 nm.
The antioxidant used in the examples of the present invention was obtained from Ciba, Switzerland.
Example 1
A PLA smart card substrate having an A/B structure prepared using the following formulation:
layer A
100 parts of PLA resin
TiO211 portions of
10101 portions of antioxidant
Layer B
Polylactic acid copolymer resin 100 parts
10101 portions of antioxidant
The preparation method comprises the following steps:
1) drying the PLA resin of the layer A for 5-6 hours at 60 ℃, and drying the polylactic acid copolymer resin of the layer B for 5-6 hours at 50 ℃;
2) and respectively uniformly mixing the raw materials of the layer A and the layer B according to the proportion, putting the mixture into a corresponding extruder, and cooling and shaping the melt through a filter, a melt pump, a die and a three-roll calender to obtain the PLA sheet.
Layer A in step 2): the extrusion temperature of the extruder is 140-190 ℃; the melt pump temperature was 190 ℃;
layer B: the extrusion temperature of the extruder is 150-185 ℃, and the melt pump temperature is 180 ℃;
the mold temperature was 195 ℃.
And 2) 50 ℃ for the upper roll of the three-roll calender, 25 ℃ for the middle roll of the three-roll calender and 25 ℃ for the lower roll of the three-roll calender.
Example 2
A PLA smart card substrate having an A/B structure prepared using the following formulation:
layer A
100 parts of PLA resin
TiO213 portions of
1682 parts of antioxidant
Layer B
Polylactic acid copolymer resin 100 parts
1682 parts of antioxidant
A preparation method of a PLA smart card substrate comprises the following steps:
1) drying the PLA resin of the layer A for 5-6 hours at 60 ℃, and drying the polylactic acid copolymer resin of the layer B for 5-6 hours at 50 ℃;
2) and respectively uniformly mixing the raw materials of the layer A and the layer B according to the proportion, putting the mixture into a corresponding extruder, and cooling and shaping the melt through a filter, a melt pump, a die and a three-roll calender to obtain the PLA sheet.
Layer A in step 2): the extrusion temperature of the extruder is 150-200 ℃; the melt pump temperature was 195 ℃;
layer B: the extrusion temperature of the extruder is 155-190 ℃, and the melt pump temperature is 190 ℃;
the mold temperature was 200 ℃.
And 2) the upper roll of the three-roller calender is 55 ℃, the middle roll of the three-roller calender is 30 ℃ and the lower roll of the three-roller calender is 30 ℃.
Example 3
A PLA smart card substrate having an A/B structure prepared using the following formulation:
layer A
100 parts of PLA resin
TiO212 portions of
10101.5 parts of antioxidant
Layer B
Polylactic acid copolymer resin 100 parts
1681.5 parts of antioxidant
The preparation method of the PLA smart card substrate comprises the following steps:
1) drying the PLA resin of the layer A for 5-6 hours at 60 ℃, and drying the polylactic acid copolymer resin of the layer B for 5-6 hours at 50 ℃;
2) and respectively uniformly mixing the raw materials of the layer A and the layer B according to the proportion, putting the mixture into a corresponding extruder, and cooling and shaping the melt through a filter, a melt pump, a die and a three-roll calender to obtain the PLA sheet.
Layer A in step 2): the extrusion temperature of the extruder is 145-195 ℃; the melt pump temperature was 193 ℃;
layer B: the extrusion temperature of the extruder is 160-185 ℃, and the melt pump temperature is 182 ℃;
the mold temperature was 197 ℃.
And 2) the upper roll of the three-roller calender is 52 ℃, the middle roll of the three-roller calender is 26 ℃ and the lower roll of the three-roller calender is 26 ℃.
Comparative example 1
The method is implemented according to the technical scheme of the patent CN 103087483B, and the detection results are shown in the table 1.
TABLE 1 physical Properties of comparative and example samples
| Inspection item | Comparative experiment 1 | Example 1 | Example 2 | Example 3 | Test standard |
| Tensile Strength (MPa) | 38 | 42.5 | 44.2 | 43.1 | GB/T1040.3 |
| Elongation at Break (%) | 160 | 189 | 172 | 176 | GB/T1040.3 |
| Vicat softening temperature (. degree. C.) | 85 | 88.3 | 89.7 | 88.9 | GB/T1633 |
| Light transmittance (%) | 4.6 | 2.4 | 2.0 | 2.2 | GB/T2410 |
| Peel strength (N/cm) | 2.3 | Fracture of | Fracture of | Fracture of |
The detection result shows that the sheet obtained by the method has better tensile strength and elongation at break than those of a comparative example, the shading is good, and the embodiment of the invention breaks when the peel strength is tested after lamination, which shows that the lamination effect is good, and the method is suitable for manufacturing PLA intelligent cards.
Claims (5)
1. A PLA smart card substrate is characterized by being prepared by adopting the following formula:
layer A
100 parts of PLA resin
211-13 parts of TiO
1-2 parts of antioxidant
Layer B
Polylactic acid copolymer resin 100 parts
1-2 parts of an antioxidant;
the PLA intelligent card base material is characterized in that the A-layer PLA resin is a stereo composite formed by PDLA and PLLA, the melt index of the composite is 9-10g/10min, and the testing conditions are 190 ℃ and 2.16 KG;
the polylactic acid copolymer resin of the layer B is polylactic acid-glycolic acid copolymer, the proportion of glycolic acid monomer in the copolymer is 55-60%, the melt index of the copolymer is 11-13g/10min, and the test conditions are 190 ℃ and 2.16 KG.
2. The PLA smart card substrate of claim 1, wherein the TiO2 is rutile and has a particle size of 30-60 nm.
3. The PLA smart card substrate of claim 1 wherein the antioxidant is at least one of antioxidant 1010 and antioxidant 168.
4. A method of preparing a PLA smart card substrate as claimed in any one of claims 1 to 3, characterized in that: the method comprises the following steps:
1) drying the PLA resin of the layer A for 5-6 hours at 60 ℃, and drying the polylactic acid copolymer resin of the layer B for 5-6 hours at 50 ℃;
2) respectively and uniformly mixing the raw materials of the layer A and the layer B according to the proportion, then putting the mixture into a corresponding extruder, and cooling and shaping the melt through a filter, a melt pump, a die and a three-roll calender to prepare a PLA sheet;
layer A in step 2): the extrusion temperature of the extruder is 140-200 ℃; the temperature of the melt pump is 190-195 ℃; layer B: the extrusion temperature of the extruder is 190 ℃ plus 150 ℃, and the melt pump temperature is 190 ℃ plus 180 ℃; the temperature of the mould is 195-plus 200 ℃;
and 2) 50-55 ℃ of the upper roll of the three-roll calender, 25-30 ℃ of the middle roll of the three-roll calender and 25-30 ℃ of the lower roll of the three-roll calender.
5. A method of making the PLA smart card substrate of claim 4, wherein: the water content of the PLA resin and the polylactic acid copolymer resin after drying in the step 1) is less than 100 PPM.
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| CN201611107487.9A CN108148367B (en) | 2016-12-06 | 2016-12-06 | PLA smart card base material and preparation method thereof |
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| CN201611107487.9A CN108148367B (en) | 2016-12-06 | 2016-12-06 | PLA smart card base material and preparation method thereof |
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| CN108148367B true CN108148367B (en) | 2020-05-08 |
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Effective date of registration: 20230421 Address after: 221000 West side of the Pearl River Road, Zone B, Xinyi Economic and Technological Development Zone, Xuzhou, Jiangsu Province (No. 19, the Pearl River Road) Patentee after: Jiangsu Huaxin High-tech Materials Co.,Ltd. Address before: 221416 No.189 Daqiao East Road, Xinyi City, Xuzhou City, Jiangsu Province Patentee before: JIANGSU HUAXIN NEW MATERIAL Co.,Ltd. |