CN112646361A - Highlight black spraying-free PA/ASA composition and preparation method thereof - Google Patents

Abstract

The invention relates to a highlight black spraying-free PA/ASA composition and a preparation method thereof. The composition comprises the following components in percentage by weight: 53.5-86% of PA resin, 10-40% of ASA resin, 1-5% of compatibility promoter, 2-4% of carbon black and 1-1.5% of processing aid. The composition has excellent gloss, blackness and weatherability.

Description

Highlight black spraying-free PA/ASA composition and preparation method thereof

Technical Field

The invention belongs to the field of resin compositions and preparation thereof, and particularly relates to a highlight black spraying-free PA/ASA composition and a preparation method thereof.

Background

The spraying-free product can achieve the 'beautiful' appearance effect required by spray painting without spraying and direct one-time injection molding, has the characteristics of good surface gloss, rich colors, scratch resistance, corrosion resistance, more environmental protection, capability of recycling 100 percent, lower comprehensive cost and the like, can meet diversified aesthetic requirements, and is mature in the fields of home appliances and automobiles. The existing spraying-free materials in the market mainly comprise ABS, PC/ABS, ASA/PMMA, PBT, PA and other materials, although the spraying-free materials are widely applied, the application and popularization of the existing spraying-free materials still have many problems to be solved.

The PA/ASA resin is more and more concerned by the material field due to the excellent scratch resistance and light aging resistance, and Chinese patent CN108034235A discloses a PA/ASA alloy material and a preparation method thereof, wherein the PA/ASA alloy material has good spraying-free matte effect and wear resistance comparable to that of a spray paint product is prepared by adding a wear-resistant filler and a compatibilization toughening agent. Chinese patent CN108047700B discloses a PA/ASA alloy and a preparation method and application thereof, wherein the scratch resistance of the PA/ASA alloy is improved by adding modified porous silica into the PA/ASA alloy. Although the PA/ASA resin has good effects of scratch resistance, spraying-free matte and the like, the glossiness and the blackness of the PA/ASA resin cannot meet the use requirements of spraying-free materials.

Disclosure of Invention

The invention aims to solve the technical problem of providing a highlight black spray-free PA/ASA composition and a preparation method thereof, so as to overcome the defects of poor glossiness and blackness of PA/ASA resin in the prior art.

The invention provides a highlight black spraying-free PA/ASA composition, which comprises the following components in percentage by weight: 53.5-86% of PA (polyamide) resin, 10-40% of ASA (acrylonitrile-styrene-acrylate) resin, 1-5% of a compatibility promoter, 2-4% of carbon black and 1-1.5% of a processing aid, wherein the light transmittance of the PA resin at 400-750 nm is more than 85%, and the particle size of the acrylate rubber of the ASA resin is 10-150 nm.

The ASA resin has a core-shell structure with SAN as a shell and organosilicon/acrylate as a core.

The compatibility promoter is styrene-acrylonitrile-glycidyl methacrylate terpolymer SAN-g-GMA.

The carbon black is inorganic carbon black.

The processing aid comprises one or more of an antioxidant, a light stabilizer and a lubricant.

The antioxidant is at least one of hindered phenol antioxidant and phosphite antioxidant.

The light stabilizer is a mixture of benzotriazole UV absorbers and hindered amine.

The lubricant is pentaerythritol stearate.

The invention also provides a preparation method of the highlight black spraying-free PA/ASA composition, which comprises the following steps:

the components are mixed according to the weight percentage, then the mixture is added into a double-screw extruder for extrusion, and the mixture is cooled and granulated to obtain the highlight black spraying-free PA/ASA composition.

The invention also provides application of the highlight black spray-free PA/ASA composition in outer columns, triangles, grids or automobile interior parts (such as panels).

Advantageous effects

The PA resin, the ASA resin and the compatibility promoter have a synergistic effect, so that the glossiness of the PA/ASA composition can be obviously improved, the blackness of the PA/ASA composition can be improved by adding the carbon black, the PA/ASA composition has a high-gloss black spraying-free effect, the PA/ASA composition has excellent weather resistance, and the PA/ASA composition has excellent comprehensive properties such as tensile strength, flexural modulus, notch impact strength and the like.

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 examples and comparative examples relate to the following starting materials, but are not limited to the following:

PA resin 1, with a transmittance of 91% at 400-750 nm, was purchased from Tolli;

PA resin 2 with transmittance of 55% at 400-750 nm, purchased from marine chemical fiber;

ASA resin 1: the grain size of the olefine acid ester rubber is 50-70 nm, and the olefine acid ester rubber has a core-shell structure with SAN as a shell and organic silicon/acrylic acid ester as a core and is purchased from UMG.

ASA resin 2: the grain size of the olefine acid ester rubber is 120-200 nm, and the olefine acid ester rubber has a core-shell structure with SAN as a shell and organic silicon/acrylic acid ester as a core and is purchased from entropy energy.

A compatibility promoter, styrene-acrylonitrile-glycidyl methacrylate terpolymer (SAN-g-GMA), RAS-302, available from Waals.

Carbon black, CB5093, available from ECOS, korea.

The antioxidant is hindered phenol and phosphite ester, and the antioxidant Y-001 and the antioxidant Y-002 are purchased from Ciba company with the mass ratio of 1: 1.

The light stabilizer is a combination of a benzotriazole UV absorber and a high molecular weight hindered amine in a mass ratio of 1:1, TINUVIN234CHIMASSORB 944FDL, available from BASF corporation.

Lubricant, pentaerythritol stearate, available from LOZA corporation.

The formulation components of the PA/ASA compositions in the examples and comparative examples are shown in Table 1 in weight percent.

The PA/ASA compositions of the examples and comparative examples were prepared by:

PA resin, ASA resin, a compatibility promoter, carbon black, an antioxidant, a light stabilizer and a lubricant are mixed according to the weight percentage in the table 1, and then the mixture is added into a main cylinder of a double-screw extruder (the diameter of a screw is 35mm, and the length-diameter ratio L/D is 48). The temperature of each section of the main machine cylinder (from a feed inlet to a machine head outlet) is controlled to be 200 ℃, 210 ℃, 220 ℃ and 220 ℃, the rotating speed of the twin-screw is 350 r/min, and extruded strips are cut into granules after being cooled by a water tank to obtain the highlight black spraying-free PA/ASA composition.

The PA/ASA composition in the examples and the comparative examples is dried for 4 hours at 80 ℃, injection molding is carried out by an injection molding machine (the injection molding process is a conventional process in the field), the injection molding temperature is 220-240 ℃, and the prepared sample plate and sample strip are subjected to conventional mechanical property test, glossiness test and L AB value test, wherein the specific test method is as follows:

(1) tensile strength: the tensile rate is 50mm/min, according to ISO 527 standard.

(2) Flexural modulus: with reference to ISO 178 standard, the bending rate is 2 mm/min.

(3) Notched impact strength: reference is made to the ISO 179 standard, 23 ℃.

(4) Gloss test (20 ° angle): the test was carried out according to ISO 2813. (gloss tester test)

(5) Color L value: the test was carried out according to ISO 12647. (color tester test)

(6) Light aging resistance: xenon lamp agingThe reaction was carried out according to SAE J2527 standard for 1900 h. Color values L1, A1, B1 were recorded before photoaging, color values L2, A2, B2 after photoaging, { (L2-L1)²+(A2-A1)²+(B2-B1)²}^1/2。

TABLE 1

TABLE 2

As can be seen from Table 2, the gloss of the PA/ASA compositions of comparative example 1 and comparative example 2 was significantly lower than that of example 1, using conventional ASA resin and conventional PA resin for comparative example 2. Comparative example 3 without the addition of a compatibilizing promoter, the gloss of the PA/ASA composition was significantly lower than that of example 1. The PA/ASA compositions of examples 1 to 5 had better gloss, jetness and light-fastness. Therefore, the special ASA resin and PA resin in the invention have synergistic action with the compatibility promoter, so that the glossiness of the PA/ASA composition can be obviously improved, and the PA/ASA composition has excellent weather resistance and blackness.

Claims (8)

1. The highlight black spray-free PA/ASA composition is characterized by comprising the following components in percentage by weight: 53.5-86% of PA resin, 10-40% of ASA resin, 1-5% of a compatibility promoter, 2-4% of carbon black and 1-1.5% of a processing aid, wherein the light transmittance of the PA resin at 400-750 nm is more than 85%, and the particle size of acrylate rubber of the ASA resin is 10-150 nm.

2. Composition according to claim 1, characterized in that the ASA resin has a core-shell structure with SAN as shell and silicone/acrylate as core.

3. The composition of claim 1, wherein the compatibility promoter is styrene-acrylonitrile-glycidyl methacrylate terpolymer SAN-g-GMA.

4. The composition of claim 1, wherein the carbon black is an inorganic carbon black.

5. The composition of claim 1, wherein the processing aid comprises one or more of an antioxidant, a light stabilizer, and a lubricant.

6. The composition of claim 5, wherein the antioxidant is at least one of a hindered phenolic antioxidant and a phosphite antioxidant; the light stabilizer is a mixture of benzotriazole UV absorbers and hindered amine; the lubricant is pentaerythritol stearate.

7. A method of preparing the composition of claim 1, comprising:

the components are mixed according to the weight percentage, then the mixture is added into a double-screw extruder for extrusion, and the mixture is cooled and granulated to obtain the highlight black spraying-free PA/ASA composition.

8. Use of the composition of claim 1 in an outer pillar, a triangle, a grille or an automotive interior part.