WO2019101037A1

WO2019101037A1 - Composite board, preparation method therefor, refrigeration device inner container and refrigeration device

Info

Publication number: WO2019101037A1
Application number: PCT/CN2018/116189
Authority: WO
Inventors: 黄玲; 沈剑; 谢玉虎
Original assignee: 合肥华凌股份有限公司; 合肥美的电冰箱有限公司; 美的集团股份有限公司
Priority date: 2017-11-27
Filing date: 2018-11-19
Publication date: 2019-05-31
Also published as: CN107914447A

Abstract

A composite board, a preparation method therefor, a refrigeration device inner container and a refrigeration device. The composite board comprises a surface bright layer (100), the material forming the surface bright layer (100) comprising methyl methacrylate-acrylonitrile-butadiene-styrene copolymer; an intermediate layer (200) provided on the lower surface of the surface bright layer (100); and a corrosion resistant layer (300) provided on the lower surface of the intermediate layer (200). The composite board has good corrosion resistance, is less susceptible to cracking, and has high surface gloss, being particularly suitable for use in refrigeration device inner containers.

Description

Composite sheet and preparation method thereof, refrigeration equipment liner and refrigeration equipment

Cross-reference to related applications

This application claims the priority of the Chinese patent application filed on November 27, 2017, the Chinese Patent Office, the application number is 201711205622.8, and the application name is "composite sheet and its preparation method, refrigeration equipment liner and refrigeration equipment". This is incorporated herein by reference.

Technical field

The present application relates to the field of material technology, and in particular, to a composite sheet and a preparation method thereof, a refrigeration equipment liner and a refrigeration device.

Background technique

At present, HIPS (high-impact polystyrene) is used as the material of the composite sheet used in the cooling equipment liner. The surface-level HIPS surface is matte rough, and the gloss can be improved by surface co-extrusion, but the high-light HIPS resistance obtained is high. Corrosion performance is poor, easy to crack, there is a quality risk, in order to reduce the risk of cracking, the thickness of the high-light HIPS layer is limited, so the surface gloss of the prepared composite sheet is still low, it is difficult to meet the aesthetic needs of users.

Therefore, the related technology of the existing refrigeration equipment liner still needs to be improved.

Summary of the invention

The present application aims to solve at least one of the technical problems in the related art to some extent. To this end, an object of the present application is to provide a composite sheet which is excellent in corrosion resistance, is not easily cracked, has a high surface gloss, or is particularly suitable for use in a liner of a refrigeration apparatus.

In one aspect of the application, the application provides a composite panel. According to an embodiment of the present application, the composite sheet material comprises: a surface bright layer, the material forming the surface bright layer comprises a methyl methacrylate-acrylonitrile-butadiene-styrene copolymer; an intermediate layer disposed in the a lower surface of the surface bright layer; and a corrosion resistant layer disposed on a lower surface of the intermediate layer. The inventors have found that the composite sheet has good corrosion resistance, is not easy to crack, has high surface gloss, and is particularly suitable for use in a refrigeration equipment liner.

According to an embodiment of the present application, the material forming the intermediate layer comprises high impact polystyrene.

According to an embodiment of the present application, the material forming the intermediate layer further includes at least one of a return material and a masterbatch.

According to an embodiment of the present application, the mass ratio of the high impact polystyrene, the recycled material and the masterbatch is (65 to 95): (0 to 30): (0 to 95).

According to an embodiment of the present application, the return material includes waste material generated during processing of the composite sheet material.

According to an embodiment of the present application, the material forming the corrosion resistant layer includes a PE/PS alloy material.

According to an embodiment of the present application, the mass ratio of the material forming the surface bright layer, the intermediate layer, and the corrosion-resistant layer is (1 to 15): (75 to 98): (1 to 10).

In another aspect of the present application, the present application provides a method of making a composite sheet as described above. According to an embodiment of the present application, the method includes subjecting a material forming the surface bright layer, the intermediate layer, and the corrosion resistant layer to a multi-layer coextrusion treatment to obtain the composite sheet. The inventors have found that the method is simple, convenient, easy to implement, and easy to industrialize. The prepared composite sheet has good corrosion resistance, is not easy to crack, has high surface gloss, and is particularly suitable for use in a refrigeration equipment liner.

According to an embodiment of the present application, the multilayer coextrusion process is carried out using a single screw extruder.

In yet another aspect of the present application, the present application provides a refrigeration equipment bladder. According to an embodiment of the present application, at least a portion of the refrigeration equipment bladder is formed using the composite sheet material previously described. The inventor has found that the refrigeration equipment has good corrosion resistance, is not easy to crack, has good quality, high surface gloss, meets the aesthetic requirements of users, and has all the features and advantages of the composite sheet described above, and is no longer excessive here. Narration.

In still another aspect of the present application, the present application provides a refrigeration apparatus. According to an embodiment of the present application, the refrigeration apparatus includes the refrigeration unit liner previously described. The inventors have found that the refrigeration apparatus has all of the features and advantages of the composite sheet and the refrigeration unit liner described above, and will not be described again.

DRAWINGS

Fig. 1 is a schematic view showing the structure of a composite sheet according to an embodiment of the present application.

Reference mark:

100: surface bright layer 200: intermediate layer 300: corrosion resistant layer

Detailed ways

Embodiments of the present application are described in detail below. The embodiments described below are illustrative and are merely illustrative of the present application and are not to be construed as limiting. Where specific techniques or conditions are not indicated in the examples, they are carried out according to the techniques or conditions described in the literature in the art or in accordance with the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are conventional products that can be obtained commercially.

In one aspect of the application, the application provides a composite panel. According to an embodiment of the present application, referring to FIG. 1, the composite sheet material comprises: a surface bright layer 100, and the material forming the surface bright layer 100 comprises a methyl methacrylate-acrylonitrile-butadiene-styrene copolymer; A layer 200 disposed on a lower surface of the surface light-emitting layer 100; and a corrosion-resistant layer 300 disposed on a lower surface of the intermediate layer 200. The inventors have found that the composite sheet has good corrosion resistance, is not easy to crack, has high surface gloss, and is particularly suitable for use in a refrigeration equipment liner.

According to the embodiment of the present application, in order to obtain better corrosion resistance and higher surface gloss, the inventors have thoroughly investigated and verified the specific material types of the surface bright layer 100 forming the composite sheet, The inventors have found that the material forming the surface bright layer 100 can make the composite sheet of the present application have good corrosion resistance, cracking and surface gloss as long as it comprises a methyl methacrylate-acrylonitrile-butadiene-styrene copolymer. The degree is high, and the materials are widely available, easy to obtain, and low in cost.

According to an embodiment of the present application, the material of the material forming the surface bright layer 100 of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer is not particularly limited, as long as the requirements are met, those skilled in the art can Need to make flexible choices. In some embodiments of the present application, the methyl methacrylate-acrylonitrile-butadiene-styrene copolymer may be selected from MABS-TR557 produced by LG Chemical Co., Ltd. of Korea, and MABS-920 produced by Toray Chemical of Japan. Brand. Thereby, the quality of the composite sheet product described in the present application can be made high.

According to the embodiment of the present application, the thickness of the surface bright layer 100 is not particularly limited, and a person skilled in the art can flexibly select as needed as long as the requirements are met. In some embodiments of the present application, the surface bright layer 100 may have a thickness of 0.01 mm to 0.3 mm. In some preferred embodiments of the present application, the surface bright layer 100 may have a thickness of 0.01 mm, 0.05 mm, 0.1 mm, 0.15 mm, 0.2 mm, 0.25 mm, and 0.3 mm. Thereby, the composite sheet material described in the present application can further have good corrosion resistance and is not easy to crack, and the surface thereof still has high gloss.

According to the embodiment of the present application, the specific material type of the intermediate layer 200 is not particularly limited, and a person skilled in the art can flexibly select as needed as long as the requirements are met. In some embodiments of the present application, the material forming the intermediate layer 200 includes HIPS (High Impact Polystyrene). Thereby, the composite sheet material described in the present application can have excellent corrosion resistance and high gloss while having excellent impact resistance.

According to an embodiment of the present application, the material forming the intermediate layer 200 may further include a return material, and the return material includes a waste material generated during the processing of the composite sheet material, for example, may be generated when the composite sheet material is co-extruded. The waste edge or the crushed material produced when the composite sheet is prepared by vacuum forming to prepare the inner tank of the refrigeration equipment. The amount of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer added to form the surface bright layer 100 of the present application is small, and methyl methacrylate-acrylonitrile-butadiene-benzene The ethylene copolymer itself has a certain compatibility with the HIPS, so the recycled material can be directly used after being crushed. Thereby, the materials are recycled to reduce environmental pollution and reduce production costs.

According to an embodiment of the present application, the material forming the intermediate layer 200 may further include a masterbatch including a pigment, a carrier and a dispersing agent, the carrier being a high impact polystyrene, the dispersing agent It is a polyethylene wax and has good compatibility with the methyl methacrylate-acrylonitrile-butadiene-styrene copolymer described herein. Thereby, the composite sheet material described in the present application can have a specific color while having a higher gloss to meet the aesthetic standards of different people.

According to the embodiment of the present application, the mass ratio of the high impact polystyrene, the return material, and the masterbatch is not particularly limited, and those skilled in the art can flexibly select as needed as long as the requirements are met. In some embodiments of the present application, the mass ratio of the high impact polystyrene, the recycled material, and the masterbatch may be (65-95): (0-30): (0-95) . Thereby, the composite sheet according to the present application can be made to meet the aesthetic standards of different people, and the material can be recycled to the greatest extent while having better impact resistance, thereby reducing environmental pollution and reducing production cost. .

According to the embodiment of the present application, the thickness of the intermediate layer 200 is not particularly limited, and a person skilled in the art can flexibly select as needed as long as the requirements are met. In some embodiments of the present application, the intermediate layer 200 may have a thickness of 0.01 mm to 0.3 mm. In some preferred embodiments of the present application, the surface bright layer 100 may have a thickness of 0.01 mm, 0.05 mm, 0.1 mm, 0.15 mm, 0.2 mm, 0.25 mm, and 0.3 mm. Thereby, the composite sheet material described in the present application can be prevented from being inferior in impact resistance due to the excessively thin intermediate layer, and also does not affect the corrosion resistance and surface gloss of the composite sheet due to the excessive thickness of the intermediate layer.

According to the embodiment of the present application, the specific material for forming the corrosion-resistant layer 300 is not particularly limited, and those skilled in the art can flexibly select as needed as long as the requirements are met. In some embodiments of the present application, the specific material forming the corrosion resistant layer 300 may include a PE/PS (polyethylene/polystyrene) alloy material. Therefore, the composite sheet material described in the present application can further have good toughness, good corrosion resistance, environmental stress crack resistance, and no multiple silver streaks and softening and foaming when contacting the foaming agent. phenomenon.

According to the embodiment of the present application, the thickness of the corrosion-resistant layer 300 is not particularly limited, and a person skilled in the art can flexibly select as needed as long as the requirements are met. In some embodiments of the present application, the corrosion-resistant layer 300 may have a thickness of 0.01 mm to 0.3 mm. In some preferred embodiments of the present application, the surface bright layer 100 may have a thickness of 0.01 mm, 0.05 mm, 0.1 mm, 0.15 mm, 0.2 mm, 0.25 mm, and 0.3 mm. Thereby, the composite sheet according to the present application can be prevented from affecting the surface gloss of the composite sheet due to the excessive thickness of the corrosion resistant layer.

According to the embodiment of the present application, in order to obtain a composite sheet having more excellent performance in various aspects, the inventors have carefully performed the mass ratio of the materials forming the surface bright layer 100, the intermediate layer 200, and the corrosion-resistant layer 300. Investigation and experimental verification, the inventors found that when the quality ratio of the material forming the surface bright layer 100, the intermediate layer 200 and the corrosion-resistant layer 300 is (1 to 15): (75 to 98): ( 1 to 10), for example, specifically 3:92:5 or the like, which can make the composite sheet described in the present application have superior corrosion resistance, environmental stress crack resistance and higher surface gloss, and at the same time High impact resistance.

In another aspect of the present application, the present application provides a method of making a composite sheet as described above. According to an embodiment of the present application, the method includes subjecting a material forming the surface light-emitting layer 100, the intermediate layer 200, and the corrosion-resistant layer 300 to a multi-layer coextrusion process to obtain the composite sheet. The inventors have found that the method is simple, convenient, easy to implement, and easy to industrialize. The prepared composite sheet has good corrosion resistance, is not easy to crack, has high surface gloss, and is particularly suitable for use in a refrigeration equipment liner.

According to an embodiment of the present application, specific process conditions of the multi-layer coextrusion treatment, such as temperature, pressure, and the like, are not particularly limited, and those skilled in the art can flexibly select as needed, as long as the requirements are met.

According to an embodiment of the present application, the multilayer coextrusion process is carried out using a single screw extruder. The specific model, technical parameters and the like of the single-screw extruder are not particularly limited, and those skilled in the art can flexibly select according to requirements as long as the requirements are met.

According to the embodiment of the present application, the specific position where the refrigerating device liner is formed by using the above composite plate material is not particularly limited, and those skilled in the art can flexibly select according to needs. In some embodiments of the present application, the refrigeration unit liner is integrally formed from the composite sheet material previously described. As a result, the entire refrigeration equipment has good corrosion resistance, is not easy to crack, has good quality, and has high surface gloss, which meets the aesthetic needs of users.

According to an embodiment of the present application, the refrigerating device liner is formed by vacuum forming using the composite sheet as described above. The specific process conditions of the vacuum forming, such as the heating mode, the temperature, the heating time, the degree of vacuum, and the like, are not particularly limited, and those skilled in the art can flexibly select as needed as long as the requirements are met.

According to an embodiment of the present application, the surface gloss test of the cooling device liner is performed by using a surface gloss tester, the test condition is: D65 light source, the test angle is 60°, and the surface gloss of the cooling device liner is measured to be 80. %~100%.

According to the embodiment of the present application, the type of the refrigerating apparatus is not particularly limited, and those skilled in the art can flexibly select as needed as long as the usage requirements are met. In some embodiments of the present application, the refrigeration device may be a refrigerator, a freezer, a fresh cabinet, or the like.

According to the embodiment of the present application, the shape, configuration, and manufacturing process of the refrigerating apparatus are not particularly limited, and those skilled in the art can flexibly select according to needs as long as the usage requirements are met. It can be understood by those skilled in the art that the refrigeration device has the structure of a conventional refrigeration device, and details are not described herein again.

Embodiments of the present application are described in detail below.

Example 1

From 3 parts by weight of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer as surface bright layer, 60 parts by weight of high impact polystyrene, 26 parts by weight of recycled material, and 4 parts by weight of masterbatch as intermediate Layer, 5 parts by weight of PE/PS alloy as a corrosion-resistant layer, the above materials are subjected to multi-layer co-extrusion treatment, and the extruder is heated at a temperature of 200 ° C to 240 ° C to obtain a composite sheet.

Experimental methods and results:

(1) Corrosion resistance:

Test method: the composite sheet is placed in a fixture for bending treatment, the surface of the composite sheet is covered with medical gauze (one layer) and coated with a blending oil for 8 hours, and the blending oil on the composite sheet is wiped clean and left for 24 hours, according to GB. /T 1040 was subjected to a tensile test in which the stretching speed was (10 ± 5) mm/min (no load).

Test result: The spline does not break.

(2) Surface gloss: The surface gloss was tested by a surface gloss tester. The test conditions were: D65 light source, the test angle was 60°, and the surface gloss of the plate was measured to be 90%.

Comparative example 1

High gloss HIPS is prepared by co-extrusion of commonly used sheet grade HIPS.

3 parts by weight of high gloss HIPS as a surface bright layer, 60 parts by weight of high impact polystyrene, 26 parts by weight of recycled material, 4 parts by weight of masterbatch as an intermediate layer, and 5 parts by weight of PE/PS alloy as a corrosion resistant layer, The above materials are subjected to multi-layer co-extrusion treatment, and the extruder is heated at a temperature of 200 ° C to 240 ° C to obtain a composite sheet.

Experimental methods and results:

(1) Corrosion resistance: The test method is as described above, and the test result is that the spline is broken.

(2) Surface gloss: The test method was as described above, and the surface gloss of the sheet was measured to be 60%.

In the description of the present application, it is to be understood that the terms "center", "longitudinal", "transverse", "length", "width", "thickness", "upper", "lower", "front", " After, "Left", "Right", "Vertical", "Horizontal", "Top", "Bottom", "Inside", "Outside", "Clockwise", "Counterclockwise", "Axial", The orientation or positional relationship of the indications of "radial", "circumferential", etc., is based on the orientation or positional relationship shown in the drawings, and is merely for convenience of description of the present application and simplified description, and does not indicate or imply the indicated device or component. It must be constructed and operated in a particular orientation, and is therefore not to be construed as limiting.

In the present application, the first feature "on" or "below" the second feature may be the direct contact of the first and second features, or the first and second features are indirectly through the intermediate medium, unless otherwise explicitly stated and defined. contact. Moreover, the first feature "above", "above" and "above" the second feature may be that the first feature is directly above or above the second feature, or merely that the first feature level is higher than the second feature. The first feature "below", "below" and "below" the second feature may be that the first feature is directly below or obliquely below the second feature, or merely that the first feature level is less than the second feature.

In the description of the present specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" and the like means a specific feature described in connection with the embodiment or example. A structure, material or feature is included in at least one embodiment or example of the application. In the present specification, the schematic representation of the above terms is not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in a suitable manner in any one or more embodiments or examples. In addition, various embodiments or examples described in the specification, as well as features of various embodiments or examples, may be combined and combined.

While the embodiments of the present application have been shown and described above, it is understood that the above-described embodiments are illustrative and are not to be construed as limiting the scope of the present application. The embodiments are subject to variations, modifications, substitutions and variations.

Claims

A composite board characterized by comprising:

a surface bright layer, the material forming the surface bright layer comprises a methyl methacrylate-acrylonitrile-butadiene-styrene copolymer;

An intermediate layer disposed on a lower surface of the surface bright layer;

A corrosion resistant layer is disposed on a lower surface of the intermediate layer.
The composite sheet according to claim 1, wherein the material forming the intermediate layer comprises high impact polystyrene.
The composite panel according to claim 2, wherein the material forming the intermediate layer further comprises at least one of a regrind and a masterbatch.
The composite sheet according to claim 3, wherein the mass ratio of the high impact polystyrene, the recycled material and the masterbatch is (65 to 95): (0 to 30): ( 0 to 95).
A composite sheet according to claim 3 or 4, wherein said return material comprises waste material produced during processing of said composite sheet material.
The composite sheet according to any one of claims 1 to 5, wherein the material forming the corrosion-resistant layer comprises a PE/PS alloy material.
The composite sheet according to any one of claims 1 to 6, wherein a mass ratio of a material forming the surface bright layer, the intermediate layer and the corrosion-resistant layer is (1 to 15): 75 to 98): (1 to 10).
The method for preparing a composite board according to any one of claims 1 to 7, which comprises:

The material forming the surface bright layer, the intermediate layer and the corrosion resistant layer is subjected to multilayer coextrusion treatment to obtain the composite sheet.
The preparation method according to claim 8, wherein the multilayer coextrusion treatment is carried out using a single screw extruder.
A refrigerating device liner characterized in that at least a part of the refrigerating device inner liner is formed by using the composite sheet material according to any one of claims 1 to 7.
A refrigerating apparatus comprising the refrigerating apparatus inner liner according to claim 10.