CN112280275B

CN112280275B - Thermoplastic resin for enhancing UV vacuum coating and preparation method thereof

Info

Publication number: CN112280275B
Application number: CN202011229038.8A
Authority: CN
Inventors: 董相茂; 黄河生; 张永; 田征宇; 艾军伟; 岑茵; 佟伟
Original assignee: Shanghai Kingfa Science and Technology Co Ltd; Jiangsu Kingfa New Material Co Ltd
Current assignee: Shanghai Kingfa Science and Technology Co Ltd; Jiangsu Kingfa New Material Co Ltd
Priority date: 2020-11-06
Filing date: 2020-11-06
Publication date: 2023-04-14
Anticipated expiration: 2040-11-06
Also published as: CN112280275A

Abstract

The invention relates to a thermoplastic resin for enhancing UV vacuum coating and a preparation method thereof. The invention solves the problem of poor paint adhesion effect on the surface of PC from the resin direction, omits the process of roughening the surface of the material, greatly saves the processing cost, avoids the pollution to the environment and expands the engineering application of the thermoplastic resin.

Description

Thermoplastic resin for enhancing UV vacuum coating and preparation method thereof

Technical Field

The invention belongs to the field of vacuum coating, and particularly relates to a thermoplastic resin for enhancing UV vacuum coating and a preparation method thereof.

Background

Compared with the traditional electroplating, the vacuum coating has the advantages of good decorative effect, strong metal feeling, low cost, small pollution, easy operation and the like, and particularly has incomparable advantages compared with the traditional electroplating in the application of non-metal objects. The principle of vacuum coating is that metal is heated and vaporized under high vacuum state, and then deposited on the surface of a base material in molecular or atomic form, so that a layer of metal film is formed on the surface of a plated part. Before vacuum coating, the surface of the substrate is coated with coating paint which plays a role in fixing the substrate and the metal film, and the UV light aging curing paint is generally used. Polycarbonate has good hardness, heat resistance and mechanical properties, is applied to various plastic products at present, but the adhesion effect of common coatings to PC or PC/ABS substrates is generally poor, and the UV paint is easy to shrink, so that the leveling and continuity of a vacuum plating layer are further poor, and the attractiveness is influenced.

At present, in order to improve the bonding force between PC and a coating, the surface of PC is activated before a coating is prepared on the surface of PC, and the method comprises a plasma method, an ultraviolet ozone method, a chemical oxidation method or a coupling method and the like. The technology in recent years focuses on surface treatment technologies such as plasma (Zhang Guanli, wu Jianhua, zhang Zhen, et al. Impact of low energy ion beam surface modification on Polycarbonate (PC) bonding performance [ J ] material engineering, 2009,28 (012): 42-44.), chromic acid (Zhang Xuan, zhong Yanli, yan Yue. Polycarbonate surface chromic acid pretreatment impacts on coating adhesion performance [ J ] material science and technology, 2019.) and surface laser (Wang Suhuan. Impact of laser surface modification on bisphenol a type polycarbonate material surface performance [ D ].2014 ]). In addition, there have been many developments in paints (Zhang Songyun. A UV-curable coating composition for vacuum coating; amitt S.Coalcani, tomas Du Ermi, jeffery angstroms Xie Naoer. Polycarbonate blends with improved adhesion to electroplate; lin Xiaojun, lai Mingzheng, yang Lijun, et al. The effect of adhesion promoters on the application of plastic coatings to polycarbonate substrates [ J ]. Chinese coatings, 2012,27 (002): 57-59.). However, the above-mentioned techniques have the disadvantages of high processing cost, influence on production efficiency, serious environmental pollution, etc.

In the aspect of substrate resin, the improvement of adhesion between the substrate resin and paint by changing the resin component is not reported at present, and the substrate resin is particularly applied to vacuum coating.

Disclosure of Invention

The invention aims to solve the technical problem of providing the thermoplastic resin for enhancing the UV vacuum coating and the preparation method thereof, which solve the problem of poor paint adhesion effect on the surface of PC from the resin direction, omit the process of roughening the surface of a material, greatly save the processing cost, avoid the pollution to the environment and expand the engineering application of the thermoplastic resin.

The invention provides a thermoplastic resin for enhancing UV vacuum coating, which comprises the following components in parts by weight:

the PC resin is at least one of aromatic polycarbonates with viscosity average molecular weight of 10000-40000.

The styrene-acrylonitrile copolymer is at least one of a styrene-acrylonitrile binary copolymer and a styrene-acrylonitrile and butadiene or acrylate terpolymer, wherein the styrene-acrylonitrile binary copolymer is preferred.

The reactive copolymer is at least one of ethylene-acrylate-glycidyl methacrylate terpolymer, maleic anhydride functionalized ethylene-vinyl acetate copolymer, ethylene-octene-glycidyl methacrylate terpolymer, ethylene-acrylate-glycidyl methacrylate terpolymer and styrene-N-phenylmaleimide-maleic anhydride, wherein the preferred is styrene-N-phenylmaleimide-maleic anhydride.

The surface modifier is an organic phosphate comprising at least one of bisphenol a bis (diphenyl phosphate) (BDP), resorcinol bis (diphenyl phosphate) (RDP), triphenyl phosphate (TPP), and hydroquinone bis (diphenyl phosphate) (PX-220), with hydroquinone bis (diphenyl phosphate) (PX-220) being preferred.

The toughening agent is at least one of methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, acrylic toughening agent, acrylonitrile-styrene-acrylate copolymer and organic silicon rubber graft toughening agent. More preferably, the toughening agent is a methyl methacrylate-butadiene-styrene copolymer toughening agent.

The antioxidant is a propionate antioxidant such as octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, other suitable antioxidants include, but are not limited to, organophosphites such as tris (nonylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite; alkylated monophenols or polyphenols; the alkylated reaction products of polyphenols with dienes, such as tetrakis [ methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) ] methane; butylated reaction products of p-cresol or dicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenyl ether; an alkylidene bisphenol; a benzyl compound; esters of beta- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with mono-or polyhydric alcohols; esters of beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with mono-or polyhydric alcohols; esters of thioalkyl or thioaryl compounds, such as distearylthiopropionate, dilaurylthiopropionate, tricosylthiodipropionate, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl 4-hydroxyphenyl) propionate; an amide of β - (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid, or a combination of the foregoing antioxidants.

The invention also provides a preparation method of the thermoplastic resin for enhancing the UV vacuum coating, which comprises the following steps:

according to the proportion, the raw materials are sequentially put into a mixer and blended until the mixture is uniform, so as to obtain a premix; then putting the premix into a double-screw extruder for melt mixing and extrusion granulation to prepare the thermoplastic resin for enhancing the UV vacuum coating; wherein, the length-diameter ratio of the screw of the double-screw extruder is 40, the temperature of the screw cylinder is 240-260 ℃, and the rotating speed of the screw is 400-500 rpm.

The invention also provides application of the thermoplastic resin for enhancing the UV vacuum coating. The method is particularly suitable for occasions with higher requirements on use environments, in particular to the fields of household appliances, industrial machines and the like which require the ball pressure temperature to be above 125 ℃ and need vacuum coating.

Advantageous effects

According to the invention, the styrene-acrylonitrile copolymer is added into the PC resin, so that the fluidity of the PC material is improved, and the reactive copolymer is added, so that the fluidity and the surface energy of the material are improved while the heat-resistant temperature is kept; by adding the adhesion promoter and the surface conditioning agent, the adhesion force of the resin base material and the UV paint is greatly improved, the surface property of the base material is thoroughly changed, the UV paint can be coated on the base material without roughening and other treatments, and the paint film is uniformly coated without shrinkage. The invention solves the problem of poor paint adhesion effect on the surface of PC from the direction of resin, omits the process of roughening the surface of the material, greatly saves the processing cost, avoids the pollution to the environment and enlarges the engineering application of the thermoplastic resin.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

The types and sources of raw materials used in the examples and comparative examples:

PC resin is PC S-2000F (Mitsubishi, japan) with viscosity average molecular weight of 22000; the styrene-acrylonitrile copolymer is NF2200 (Taiwan, styrene-acrylonitrile binary copolymer), and the other styrene-acrylonitrile copolymer is PA-757 (Qimei, styrene-acrylonitrile-butadiene terpolymer); the reactive copolymer is MS-L2A (Japanese electric, styrene-N-phenyl maleimide-maleic anhydride), and the other reactive copolymer is PTW (DuPont, ethylene-acrylate-glycidyl methacrylate terpolymer); KF-027 (Shaoxingjiahua) is selected as the adhesion promoter; the surface modifier is PX-220 in Wansheng Zhejiang, and the other surface modifiers are FP-600 (Ai Dike); the toughening agent is M-701 of clock source chemistry; the antioxidant is Chinox 1076, namely beta- (3,5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate (CAS NO.: 2082-79-3), and is commercially available.

The thermoplastic resins prepared in examples and comparative examples were tested for notched izod impact strength, heat resistance, and UV paint uniformity, respectively, and the extrusion process was recorded, with reference to the standards or methods described below.

(1) Method for measuring Izod impact Strength (Normal temperature): notched izod impact strength was measured using a molded notched izod impact bar 3.2mm thick. Notched Izod impact strength was measured according to ASTM D256, the results being reported in J/m and the testing being carried out at room temperature (23 ℃).

(2) Method for measuring Melt Flow Rate (MFR). The plastic pellets were allowed to melt into plastic fluid for a period of time (10 minutes) at a temperature and pressure (different for each material standard) and the number of grams of fluid that flowed through a 2.1mm diameter round tube was measured. The larger the outflow gram value is, the better the processing flowability of the plastic material is, otherwise, the poorer the processing flowability is; the test standard used herein is ISO 1133, unit: g/10min. The test conditions were: melt Flow Rate (MFR) at 260 ℃ under a 5kg load.

(3) Heat resistance: using a 125 ℃ ball pressure test, the assay method: and (3) injection molding to obtain a square plate with the thickness of 4mm multiplied by 60mm, testing the ball indentation at 125 ℃ according to IEC695-10-2, judging that the ball indentation at the test temperature is passed if the ball indentation is less than 2mm, and otherwise, judging that the ball indentation does not pass. (4) UV paint application uniformity: and (3) injection molding to obtain a square plate with the thickness of 4mm multiplied by 60mm, spraying UV (ultraviolet) photocuring paint on the surface of the square plate, baking at the temperature of 80 ℃ for 5-10min, and then passing through an ultraviolet UV curing device. After one day at room temperature, visual inspection was performed and judged by the size and area of the exposed substrate of the UV paint, the more marked indicates the less exposed substrate, the better the uniformity of the paint film application, wherein marked indicates no exposed substrate at all.

TABLE 1 amount (parts by weight) of raw materials and test results for examples and comparative examples

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As can be seen from Table 1, comparative examples 1 and 2, to which no styrene-acrylonitrile copolymer and no reactive copolymer were added, even no adhesion promoter and surface conditioner were added, resulted in thermoplastic resins having poor flowability and UV paint coating uniformity. Comparative example 3 the addition of other styrene-acrylonitrile copolymers, although the flowability is improved, the uniformity of the UV lacquer application is still unsatisfactory. As can be seen from comparative examples 4 and 5, the adhesion promoter and the surface conditioner need to be added simultaneously to achieve the desired coating uniformity of the UV paint. As can be seen from comparative example 6, the use of other surface modifiers, although the coating uniformity of the UV paint was improved, the effect was not ideal. As can be seen from comparative example 7, with the use of large amounts of the styrene-acrylonitrile copolymer and the reactive copolymer, the thermoplastic resin was very good in flowability, but the ball pressure test could not be passed. As can be seen from comparative example 8, with the use of other reactive copolymers, the thermoplastic resin could not be improved not only in fluidity but also in ball pressure test. As can be seen from comparative example 9, the coating uniformity of the UV paint was poor without the addition of the reactive copolymer. As can be seen from comparative example 10, the resin flowability was poor without adding the styrene-acrylonitrile copolymer, and further, the reactive copolymer failed to exert its effect in the absence of the styrene-acrylonitrile copolymer, and the coating uniformity of the UV paint was also poor.

Claims

1. A thermoplastic resin for enhancing UV vacuum coating is characterized in that: the coating comprises the following components in parts by weight:

70-80 parts of PC resin;

2-10 parts of styrene-acrylonitrile copolymer;

5-15 parts of a reactive copolymer;

1-5 parts of an adhesion promoter;

1-3 parts of a surface conditioning agent;

1-5 parts of a toughening agent;

0.1-1 part of antioxidant;

wherein the styrene-acrylonitrile copolymer is at least one of styrene-acrylonitrile binary copolymer and styrene-acrylonitrile and acrylate ternary copolymer; the reactive copolymer is at least one of maleic anhydride functionalized ethylene-vinyl acetate copolymer, ethylene-octene-glycidyl methacrylate terpolymer and styrene-N-phenylmaleimide-maleic anhydride; the surface regulator is hydroquinone bis (diphenyl phosphate); the adhesion promoter is high carbon chain ethoxy amide wax; the toughening agent is at least one of methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, acrylonitrile-styrene-acrylate copolymer and organic silicon rubber graft toughening agent.

2. The thermoplastic resin according to claim 1, characterized in that: the PC resin is at least one of aromatic polycarbonates with viscosity average molecular weight of 10000-40000.

3. The thermoplastic resin according to claim 1, characterized in that: the antioxidant is at least one of propionate antioxidant, phosphite antioxidant, alkylated monophenol or polyphenol, alkylated reaction product of polyphenol and diene, butylated reaction product of p-cresol or dicyclopentadiene, hydroxylated thiodiphenyl ether, alkylidene bisphenol, benzyl compound, ester of beta- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid and monohydric or polyhydric alcohol, ester of beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid and monohydric or polyhydric alcohol, and ester of thioalkyl or thioaryl compound.

4. A method for preparing the UV vacuum deposition enhancing thermoplastic resin of claim 1, comprising:

according to the proportion, the raw materials are sequentially put into a mixer and blended until the mixture is uniform, so as to obtain a premix; then putting the premix into a double-screw extruder for melt mixing and extruding granulation to prepare the thermoplastic resin for enhancing the UV vacuum coating; wherein the length-diameter ratio of a screw of the double-screw extruder is 40, the temperature of a screw cylinder is 240-260 ℃, and the rotating speed of the screw is 400-500rpm.

5. Use of the UV vacuum coating enhanced thermoplastic resin according to claim 1 in UV paint.