CN108727797B - Polycarbonate substrate for in-mold decoration and preparation method thereof - Google Patents
Polycarbonate substrate for in-mold decoration and preparation method thereof Download PDFInfo
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- CN108727797B CN108727797B CN201710239357.9A CN201710239357A CN108727797B CN 108727797 B CN108727797 B CN 108727797B CN 201710239357 A CN201710239357 A CN 201710239357A CN 108727797 B CN108727797 B CN 108727797B
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—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
- 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
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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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
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
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- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The invention discloses a polycarbonate substrate for in-mold decoration and a preparation method thereof, wherein the substrate is prepared by an extrusion process according to the following formula, 100 parts of polycarbonate resin, 15-25 parts of copolyester and SiO21-3 parts of light stabilizer, 1-2 parts of antioxidant and 1-2 parts of antioxidant. The raw materials are uniformly mixed according to the proportion, the mixture is dried and then put into an extruder, and the melt is cooled and shaped through a filter, a melt pump, a die and a three-roller calender to prepare the polycarbonate sheet. The invention solves the problems of insufficient stretching deformation and easy breakage when the polycarbonate film is used for decoration in large deep cavities and special-shaped moulds by adopting the branched polycarbonate as a main raw material and modifying the polycarbonate film by copolyester.
Description
Technical Field
The invention belongs to the field of plastic processing, and particularly relates to a polycarbonate substrate for in-mold decoration and a preparation method thereof.
Background
In-mold Injection Molding (IMD), which is an In-molded decoration (In-mold decoration) technology, is a current international popular surface decoration technology, is mainly applied to surface decoration and functional panels of interior and exterior decorations and household electrical appliances In the automobile industry, is commonly used on panels, marks and other appearance parts In various fields such as mobile phone window lenses and shells, household electrical appliance control panels, automobile instrument panels, instruments and meters, medical equipment and the like, and has the characteristics of attractive decoration, long service life, friction resistance, corrosion resistance, dust prevention, moisture prevention, simple process, high production efficiency and low cost, thereby achieving greater development and wide application.
The IMD technology is developing towards the direction of environmental protection, electronization and functionalization, the application range is expanding towards large-scale and complex products, and the IMD technology is closely combined with other molding processes. However, the large film is easy to be locally broken or deformed in the deep cavity or special-shaped forming process, and the shape and position precision of the surface pattern or character is low, so that the large film is difficult to be applied to products such as large-sized, deep cavity and special-shaped parts, such as panels of notebook computers, interior trim parts of automobiles and the like.
The materials capable of being decorated in the mold are more, including PET, PMMA, PC (polycarbonate) and the like, wherein the PC has more purposes in the molding of special-shaped pieces due to good heat resistance and large stretching molding height. However, since the large deep cavity and the special-shaped part have larger stretching forming height, the existing PC film is difficult to satisfy the thermal stretching deformation amount and the puncture resistance strength, and therefore, a novel polycarbonate film for in-mold decoration is required to be provided. The current method for improving the amount of thermal tensile deformation and puncture strength of PC is mainly to increase the molecular weight distribution of PC resin, but the increase of molecular weight distribution will reduce the heat resistance of PC resin.
Disclosure of Invention
The invention aims to provide a polycarbonate substrate for in-mold decoration and a preparation method thereof, wherein the application of a polycarbonate film in large deep cavities and special-shaped parts is realized by blending branched polycarbonate and copolyester to improve the thermal stretching deformation amount and puncture resistance strength of the polycarbonate.
In order to achieve the purpose, the invention adopts the technical means as follows:
the polycarbonate substrate for in-mold decoration is prepared by adopting the following formula:
polycarbonate resin 100 parts
15-25 parts of copolyester
SiO21-3 parts of
1-2 parts of light stabilizer
1-2 parts of antioxidant
The polycarbonate resin is bisphenol A polycarbonate with a branched chain, the branching degree is 0.1-2%, the bisphenol A polycarbonate is preferably subjected to a branching reaction by using a branching agent with at least 2 hydroxyl groups or carboxyl groups, and the bisphenol A polycarbonate is more preferably subjected to a branching reaction by using one of 1,1, 1-tri (4-hydroxyphenyl) ethane and trimellitic acid.
The copolyester is butanediol copolymerization modified PET, the mass proportion of butanediol in dihydric alcohol is 14-21%, and the intrinsic viscosity is 0.65-0.87 dl/g.
The SiO2Surface-modified with a silane coupling agent having a particle diameter of 30 to 60nm, preferably a silane coupling agentIs one of KH550, KH560 and KH 570.
The light stabilizer is at least one of hindered amine and benzophenone, preferably at least one of UV-531, HS-770 and HS-944.
The antioxidant is at least one of antioxidant 1010 and antioxidant 168.
The preparation method of the polycarbonate substrate for in-mold decoration comprises the following steps:
1) uniformly mixing the components according to the proportion, and performing blast drying at the temperature of 120-125 ℃ for 4-6 hours to ensure that the water content is less than 200 PPM;
2) and (3) putting the dried raw materials into an extruder, and cooling and shaping the raw materials through a melt filter, a melt pump, a die and a three-roller calender to obtain the polycarbonate substrate.
The process temperatures in the step 2) are respectively 190 ℃ for the extruder, 275 ℃ for the filter 265, 280 ℃ for the melt pump 270, 285 ℃ for the mold, 135 ℃ for the upper roller of the three-roller calender, 155 ℃ for the middle roller of the three-roller calender and 155 ℃ for the lower roller of the three-roller calender.
Has the advantages that:
the branched bisphenol A polycarbonate is adopted as the main raw material, so that the strength of the base material in the thermal forming process can be improved, the puncture resistance is improved, and the problem of base material cracking in the forming process is solved; the carbon-carbon long chain structure in the butanediol has good flexibility, and the butanediol copolymerization modified PET is added, so that the activity space of benzene rings in a polycarbonate molecular chain can be increased, the rigidity of the polycarbonate is reduced, and the thermal stretching deformation quantity of the base material is increased.
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 thickness was 100 μm.
The polycarbonate resin used in examples 1 to 3 of the present invention was obtained from Saxat basic Innovative plastics, Inc., under the trade name Lexan154, and the resin was branched using 1,1, 1-tris (4-hydroxyphenyl) ethane as a branching agent, and the degree of branching was 1.2%.
The polycarbonate resin used in example 4 of the present invention was supplied by Dichen corporation under the trademark L-1250Y, and was a linear structure and did not contain a branched chain.
The copolyester used in the examples of the present invention was supplied by eastapak polymer 9921, usa.
SiO used in the examples of the present invention2KH550 is adopted for modification, the particle size is 40-50nm, and the product is provided by Beijing Serik science and technology Limited and is marked with SD-510.
The light stabilizer used in the examples of the present invention was HS-944, which was provided by Sumitopsilon Chemicals, Inc.
The antioxidant used in the examples of the present invention was I1010, manufactured by nubuck, switzerland.
Example 1
A polycarbonate substrate for in-mold decoration comprises the following components:
polycarbonate resin 100 parts
Copolyester 20 parts
SiO22 portions of
Light stabilizer HS-9441.5 parts
Antioxidant I10101.5 parts
A preparation method of a polycarbonate substrate for in-mold decoration comprises the following steps:
1) uniformly mixing the components according to the proportion, and carrying out forced air drying at 122-125 ℃ for 5 hours;
2) and (3) putting the dried raw materials into an extruder, and cooling and shaping the raw materials through a melt filter, a melt pump, a die and a three-roller calender to obtain the polycarbonate substrate.
The process temperatures in the step 2) are 195 ℃ of the extruder, 270 ℃ of the filter, 275 ℃ of the melt pump, 280 ℃ of the die, 130 ℃ of the upper roller of the three-roller calender, 150 ℃ of the middle roller of the three-roller calender and 150 ℃ of the lower roller of the three-roller calender respectively.
Example 2
A polycarbonate substrate for in-mold decoration comprises the following components:
polycarbonate resin 100 parts
Copolyester 15 parts
SiO21 part of
Light stabilizer HS-9441 parts
Antioxidant I10101 portion
A preparation method of a polycarbonate substrate for in-mold decoration comprises the following steps:
1) mixing the components uniformly according to the proportion, and carrying out forced air drying at 125 ℃ for 4 hours;
2) and (3) putting the dried raw materials into an extruder, and cooling and shaping the raw materials through a melt filter, a melt pump, a die and a three-roller calender to obtain the polycarbonate substrate.
The process temperatures in the step 2) are respectively 190 ℃ of the extruder, 275 ℃ of the filter, 280 ℃ of the melt pump, 285 ℃ of the die, 135 ℃ of the upper roller of the three-roller calender, 155 ℃ of the middle roller of the three-roller calender and 155 ℃ of the lower roller of the three-roller calender.
Example 3
A polycarbonate substrate for in-mold decoration comprises the following components:
polycarbonate resin 100 parts
Copolyester 25 parts
SiO23 portions of
Light stabilizer HS-9442 parts
Antioxidant I10102 parts
A preparation method of a polycarbonate substrate for in-mold decoration comprises the following steps:
1) uniformly mixing the components according to the proportion, and drying by blowing at 120 ℃ for 6 hours;
2) and (3) putting the dried raw materials into an extruder, and cooling and shaping the raw materials through a melt filter, a melt pump, a die and a three-roller calender to obtain the polycarbonate substrate.
The process temperatures in the step 2) are respectively 200 ℃ for the extruder, 280 ℃ for the filter 265 ℃, 270 ℃ for the melt pump, 265 ℃ for the die, 120 ℃ for the upper roller of the three-roller calender, 145 ℃ for the middle roller of the three-roller calender and 140 ℃ for the lower roller of the three-roller calender.
Example 4
A polycarbonate substrate for in-mold decoration comprises the following components:
polycarbonate resin 100 parts
Copolyester 25 parts
SiO 23 parts
Light stabilizer HS-9442 parts
Antioxidant I10102 parts
A preparation method of a polycarbonate substrate for in-mold decoration comprises the following steps:
1) uniformly mixing the components according to the proportion, and drying by blowing at 120 ℃ for 6 hours;
2) and (3) putting the dried raw materials into an extruder, and cooling and shaping the raw materials through a melt filter, a melt pump, a die and a three-roller calender to obtain the polycarbonate substrate.
The process temperatures in the step 2) are respectively 200 ℃ for the extruder, 280 ℃ for the filter 265 ℃, 270 ℃ for the melt pump, 265 ℃ for the die, 120 ℃ for the upper roller of the three-roller calender, 145 ℃ for the middle roller of the three-roller calender and 140 ℃ for the lower roller of the three-roller calender.
In-mold decorated PC film of the company sauter-based innovative plastics, having the designation LEXAN 8a35, was used as a comparison, and the physical properties of the samples of the examples were measured, and the results are shown in table 1.
TABLE 1 physical Properties of the comparative and example samples
| Inspection item | LEXAN*8A35 | Example 1 | Example 2 | Example 3 | Example 4 | Test standard |
| Puncture resistance (J) | 23 | 36 | 35 | 38 | 26 | GB/T10004 |
| Elongation deformation amount mm | 12.4 | 18.7 | 18.3 | 19.5 | 11.5 | - |
| Vicat softening temperature (. degree. C.) | 144.8 | 146.4 | 147.2 | 145.6 | 145.1 | GB/T1633 |
According to the detection result, the Vicat softening temperature of the base material obtained by the method is similar to that of the comparative example, and the puncture resistance and the tensile deformation are better than those of the comparative example.
Claims (6)
1. The polycarbonate substrate for in-mold decoration is characterized by being prepared by adopting the following formula:
the polycarbonate resin is bisphenol A polycarbonate which is subjected to a branching reaction by adopting one of 1,1, 1-tri (4-hydroxyphenyl) ethane and trimellitic acid, and the branching degree is 0.1-2%;
the copolyester is butanediol copolymerization modified PET, the mass proportion of butanediol in dihydric alcohol is 14-21%, and the intrinsic viscosity is 0.65-0.87 dl/g.
2. The polycarbonate substrate for in-mold decoration according to claim 1, wherein the SiO is2The surface is modified by a silane coupling agent, and the particle size is 30-60 nm.
3. The polycarbonate substrate for in-mold decoration according to claim 1, wherein the light stabilizer is at least one of hindered amine and benzophenone.
4. The polycarbonate substrate for in-mold decoration according to claim 1, wherein the antioxidant is at least one of antioxidant 1010 and antioxidant 168.
5. The polycarbonate substrate for in-mold decoration according to claim 2, wherein the silane coupling agent is one of KH550, KH560 and KH 570.
6. The method for preparing a polycarbonate substrate for in-mold decoration according to any one of claims 1 to 5, comprising the steps of:
1) uniformly mixing the components according to the proportion, and performing blast drying at the temperature of 120-125 ℃ for 4-6 hours to ensure that the water content is less than 200 PPM;
2) putting the dried raw materials into an extruder, and cooling and shaping the raw materials through a melt filter, a melt pump, a die and a three-roller calender to prepare a polycarbonate substrate;
the process temperature in the step 2) is respectively as follows: the extruder is 190-280 ℃, the filter is 265-275 ℃, the melt pump is 270-280 ℃, the die temperature is 265-285 ℃, the three-roller calender is 120-135 ℃, the middle roller of the three-roller calender is 145-155 ℃ and the lower roller of the three-roller calender is.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4874647A (en) * | 1986-12-04 | 1989-10-17 | Mitsui Petrochemical Industries, Inc. | Polyester composition, molded polyester laminate and use thereof |
| CN101619157A (en) * | 2009-07-28 | 2010-01-06 | 福建省石狮市通达电器有限公司 | Injection molding material for injection molding in mold and preparation method thereof |
| CN103951957A (en) * | 2014-05-12 | 2014-07-30 | 东莞市信诺橡塑工业有限公司 | Polycarbonate (PC) composition used for in-mold decoration (IMD) and preparation method thereof |
| CN104693769A (en) * | 2014-12-23 | 2015-06-10 | 深圳市科罗威材料科技有限公司 | PC/PET alloy material as well as preparation method and application of PC/PET alloy material |
-
2017
- 2017-04-13 CN CN201710239357.9A patent/CN108727797B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4874647A (en) * | 1986-12-04 | 1989-10-17 | Mitsui Petrochemical Industries, Inc. | Polyester composition, molded polyester laminate and use thereof |
| CN101619157A (en) * | 2009-07-28 | 2010-01-06 | 福建省石狮市通达电器有限公司 | Injection molding material for injection molding in mold and preparation method thereof |
| CN103951957A (en) * | 2014-05-12 | 2014-07-30 | 东莞市信诺橡塑工业有限公司 | Polycarbonate (PC) composition used for in-mold decoration (IMD) and preparation method thereof |
| CN104693769A (en) * | 2014-12-23 | 2015-06-10 | 深圳市科罗威材料科技有限公司 | PC/PET alloy material as well as preparation method and application of PC/PET alloy material |
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Effective date of registration: 20230407 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. |