CN112552629B - High-blackness scratch-resistant PMMA/ASA alloy material and preparation method thereof - Google Patents

Abstract

The invention discloses a high-blackness scratch-resistant PMMA/ASA alloy material and a preparation method thereof. The modifier has better lubricity, the surface hardness of the material obtained by combining rubber, resin, processing aid and black filler is increased, meanwhile, the surface friction force is reduced, when external force is applied, a sharp contact is difficult to penetrate deeply and the surface of the material cannot be damaged, so that the color change of the surface after friction is smaller; the addition of the modifier improves the surface hardness of the PMMA/ASA alloy, reduces the surface friction coefficient and the like, has the refractive index similar to that of the base material, does not cause obvious birefringence phenomenon of light, is uniform in material coloring, and has good scratch resistance under the comprehensive action; the new alloy formula improves the scratch resistance of the product on the basis of obtaining high black and bright effect.

Description

A kind of high black bright anti-scratch PMMA/ASA alloy material and preparation method thereof

technical field

The invention belongs to composite material technology, and in particular relates to a preparation method of a high-black, bright and scratch-resistant PMMA/ASA alloy material.

Background technique

Styrene-acrylate-acrylonitrile terpolymer (hereinafter referred to as ASA) material is a material used outdoors to replace ABS. It has excellent weather resistance, excellent mechanical properties, convenient processing and molding, and recyclable scraps With the characteristics of reuse and low equipment investment, it is widely used in electronic appliances, automobile industry, outdoor products and other fields. However, ASA materials are currently used as outdoor products. Due to low gloss (less than 60glass) and low surface hardness (pencil hardness is usually 2B, lower than H), its decorative properties are somewhat less luster, and it cannot provide high gloss and high surface hardness. quality. PMMA material has excellent weather resistance and gloss, and is one of the directions for high-gloss extrusion products, but its use is limited due to its poor impact resistance.

The key technology for preparing ASA materials with high gloss and high surface hardness lies in the content and dispersion of rubber, resin, processing aids, etc. During melt blending, the modified acrylate rubber and processing aids are distributed in SAN under the action of strong shear force. In the continuous phase of the resin, the degree of dispersion and distribution has a great influence on the mechanical properties and surface gloss of the material. At present, the surface scratch resistance of high-black and bright PMMA/ASA alloy materials in China is difficult to meet the requirements of automobile factories. Therefore, how to improve the surface scratch resistance of such materials is the current difficulty.

Contents of the invention

The invention discloses a high-black, bright and scratch-resistant PMMA/ASA alloy material and a preparation method thereof. A new alloy formula is formed by adding modifiers, rubber, resin, processing aids, etc., and on the basis of obtaining high black and bright effects , Improve the scratch resistance of the product.

The present invention adopts following technical scheme:

A high-black, bright, scratch-resistant PMMA/ASA alloy material is prepared from ASA resin, PMMA resin, modifier, toughening agent, processing aid, and black filler; the modifier is long-chain ternary copolymerized nylon, benzene One or more of base silicone oil and fumed alumina.

The preparation method of the above-mentioned high-black, bright and scratch-resistant PMMA/ASA alloy material comprises the steps of extruding ASA resin, PMMA resin, modifier, toughening agent, processing aid, and black filler through a screw to obtain high-black, bright and scratch-resistant PMMA/ASA alloy material. ASA alloy material.

In the present invention, the modifying agent is composed of long-chain ternary copolymerized nylon, phenyl silicone oil, and fumed alumina. The three raw materials themselves are existing products. For example, the long-chain ternary copolymerized nylon is Shandong Guangyin TM126, and the phenyl silicone oil is Shin-Etsu KF-50-1000cs, fumed alumina is purchased from Guangzhou Jibisheng; preferably, in the modifier, by mass percentage, the long-chain ternary copolymer nylon is 10%-30%, and the phenyl silicone oil is 20%-40% %, fumed alumina is the balance. The modifier of the present invention has better lubricity, and at the same time, the refractive index in the PMMA+ASA system is close, the loss of light is small, the loss of light transmittance can be within 50%, and the increase of haze can be controlled within 40%. ; Modifiers combined with rubber, resin, processing aids, and black fillers increase the surface hardness of the material (reach 3H effect), while reducing surface friction. When external forces are applied, sharp contacts are difficult to penetrate and ensure that the surface of the material cannot be damaged , so that the color change after surface friction is small; the addition of modifiers improves the surface hardness of PMMA/ASA alloys, reduces the surface friction coefficient, etc., and the refractive index is similar to the substrate, which does not cause obvious birefringence of light. Uniform coloring, under the combined effect, PMMA/ASA alloy material has good scratch resistance.

In the present invention, the toughening agent is butyl acrylate, methyl methacrylate, acrylonitrile, and styrene copolymer, which has a core-shell structure, and the weight content of butyl acrylate is 40% to 70%.

In the present invention, processing aids are antioxidants, anti-ultraviolet agents, lubricants, etc., which are conventional aids.

In the present invention, the black filler is carbon black pre-dispersed masterbatch, wherein the weight concentration of carbon black is 30%-60%, the carrier is PETs, has excellent dispersibility, and the primary particle size of carbon black is 10-100nm.

In the present invention, the weight ratio of ASA resin, PMMA resin, modifier, toughening agent, processing aid and black filler is (15～35): (49.5～73.5): (1～15): (3～7 ): (1～2): (3～6), preferably (20～30): (55～65): (2.5～15): (4～6): (1～2): (3.5～5 ), more preferably (20-30):(55-65):(4.5-7.5):5:1.5:4.

ASA resin has low surface hardness and poor scratch resistance, PMMA resin has aging resistance, but is brittle and poor in impact resistance; ASA and PMMA have similar solubility parameters and good compatibility, but ASA/PMMA alloy There is a problem that the black and bright performance and the scratch resistance performance cannot be achieved at the same time. In the present invention, through the addition of a modifier, on the basis of the ASA/PMMA alloy, combined with the proportion of the toughening agent and the black filler, the obtained alloy material has a suitable melting index, is beneficial to processing, and has excellent scratch resistance, which exceeds the limit specified in the standard. 1.5, the scratch resistance grade is less than 2, and the impact performance is good, far greater than the standard 8kj/m ² , especially the blackness L value is low, and the appearance quality is good.

Description of drawings

Fig. 1 is the photo before and after five fingers scratching test of embodiment one ASA/PMMA alloy material;

Fig. 2 is the photo before and after the cross scratch test of embodiment one ASA/PMMA alloy material;

Fig. 3 is the grid photo that embodiment one ASA/PMMA alloy material prepares;

Fig. 4 is the rearview mirror photograph that embodiment one ASA/PMMA alloy material prepares;

Fig. 5 is the photo of the empennage prepared by the ASA/PMMA alloy material of the first embodiment.

Detailed ways

All raw materials of the present invention are commercially available products, such as in the present invention, the melt index of ASA resin is 3～30g/10min, notched impact strength 10kJ/m ^More than; The melt index of PMMA resin is 1～15g/10min. Under the technical scheme of the present invention, the selection of specific resins, additives, and grades of additives will not affect the realization of technical effects, as long as the raw materials meet the conventional requirements of auto parts. The inventiveness of the present invention lies in the addition of modifiers to the PMMA/ASA alloy, combined with rubber, resin, processing aids, etc., to form a new alloy formula, and to improve the scratch resistance of the product on the basis of obtaining a high black and bright effect .

The invention uses ASA resin, PMMA resin, modifier, toughening agent, conventional processing aid, and carbon black masterbatch as raw materials to prepare high-black, bright and scratch-resistant PMMA/ASA alloy material without adding other substances. After the raw materials are mixed, it can be Directly enter the twin-screw extrusion melt processing, or a single material can be added to the extruder through a loss-in-weight weighing scale, and the processing aid and carbon black masterbatch are mixed together and added through a single loss-in-weight weighing scale to ensure feeding The accuracy is within 0.5%; the diameter of the twin-screw equipment used can be 30-75mm, the speed can be 300-1200RPM, and the temperature can be processed at 190-240°C for molding and granulation. The specific preparation methods and testing methods of the present invention are conventional techniques in the art.

Material test method:

Melt index: According to ISO 1133, 220°C, 10kg;

Cross scratch method: according to GMW 14688 standard, method A, 10N load, scratch-resistant head diameter: 1mm, speed: 1000±50mm/min, evaluate the degree of whitening, and require ⊿L≤1.5;

Five-finger scraping method: According to FLTM_BN_108 standard, scraping head: steel ball type, diameter 1mm, scraping speed 100m/s, finger loading respectively 2N and 7N, evaluate scratches, damage and whitening level (refer to the table below), Requirements: Scratches/damages/whitening are grade 2 and below.

Gloss: At room temperature at 23+/-2°C, use a gloss meter to test the same mold injection sample. According to the standard GB/T 1743, the gloss at 20° angle is required to be ≥78 gloss;

Appearance color: at room temperature at 23+/-2°C, use a colorimeter to test the injection molding samples of the same mold, and require L value ≤ 24.6 (visual inspection to achieve the effect of high-gloss black spray paint);

Notched impact strength: at room temperature at 23+/-2°C, according to the standard ISO 179-1eA, the required value is ≥8kj/m ² .

Example

The formula is shown in Table 1. Among them, the melting index of ASA resin is 20g/10min; the melting index of PMMA resin is 10g/10min; the toughening agent is butyl acrylate, methyl methacrylate, acrylonitrile, and styrene copolymer, which is a core-shell structure, Japan Mitsubishi SX-006; in the modifier, by mass percentage, long-chain ternary copolymer nylon (source: TM126, Shandong Guangyin) is 20%, phenyl silicone oil (source: KF-50-1000cs, Shin-Etsu) is 30% , fumed alumina (source: Guangzhou Jibisheng) is 50%; carbon black pre-dispersed masterbatch, the weight concentration of carbon black is 55%, the carrier is PETs, which has excellent dispersibility, and the primary particle size of carbon black is 10 ~100nm; processing aids are antioxidant (1010), anti-ultraviolet agent (UV234), lubricant (Korean Shinwon Chemical EBS) at a weight ratio of 1:1:1. All raw materials are conventional commercially available products.

Table 1 embodiment, comparative example formula, numerical value is weight part

After the raw materials are mixed, they are directly put into twin-screw melting (190-240°C, 600rpm) extrusion process to obtain ASA/PMMA alloy material.

The above are the specific examples given by the present invention to facilitate the understanding of those skilled in the art, and do not limit the technical solution of the present invention. Under the technical solution of the present invention, the selection of specific raw materials, such as different grades, and the selection of specific preparation methods will not To affect the realization of the technical effect of the present invention, as long as the raw materials meet the requirements of automobile parts, and the preparation method can melt and mix all the raw materials evenly. The test was carried out according to the existing test method, and the results are shown in Table 2.

Fig. 1 is the photo before and after the five-finger scratch test of the ASA/PMMA alloy material of embodiment one; Fig. 2 is the photo before and after the cross scratch test of the ASA/PMMA alloy material of embodiment one.

Embodiment five

Replace the modifier in Example 1 with 50% long-chain ternary copolymerized nylon, 20% phenyl silicone oil, and 30% fumed alumina (by mass percentage), a total of 4.5 parts, and the rest remain unchanged to obtain an ASA/PMMA alloy , the cross scratch ⊿L is 1.28; the gloss (20° angle) is 79; the color blackness L value is 24.1.

Embodiment six

In Example 1, the weight parts of toughening agent, processing aid, and carbon black masterbatch were adjusted to 4:1.5:5 to obtain ASA/PMMA alloy, and the cross scratch ⊿L was 1.19; gloss (20° angle) is 79; the color blackness L value is 24.1.

Embodiment seven

Replace the modifier in Example 1 with 4.5 parts of fumed alumina, and keep the rest unchanged to obtain an ASA/PMMA alloy with a cross scratch ⊿L of 1.27; gloss (20° angle) of 75; color blackness L value is 24.8.

Embodiment Eight

In embodiment one, the parts by weight of ASA resin, PMMA resin, modifier, toughening agent, processing aid, carbon black master batch are adjusted to 30: 55: 4.5: 5: 1.5: 4, obtain ASA/PMMA alloy , the cross scratch ⊿L is 1.23; the gloss (20° angle) is 79; the color blackness L value is 24.2.

From the fifth to the eighth embodiment, the visual appearance quality meets the requirements. It can be seen that in the technical solution provided by the present invention, a modifier is added to the conventional main resin ASA/PMMA, combined with other components, on the basis of the high black and bright effect, the scratch resistance of the alloy is effectively improved, and the obtained ASA/PMMA PMMA alloy materials can be used to prepare automotive parts, such as grilles, rearview mirrors, and tail fins, according to conventional methods, see Figure 3, Figure 4, and Figure 5, respectively.

Claims (7)

1. The high-blackness scratch-resistant PMMA/ASA alloy material is characterized by being prepared from ASA resin, PMMA resin, a modifier, a toughening agent, a processing aid and a black filler; the modifier consists of long-chain ternary polymerization nylon, phenyl silicone oil and gas-phase alumina; in the modifier, the mass percentage of the long-chain ternary polymerization nylon is 10-30%, the phenyl silicone oil is 20-40%, and the gas phase alumina is the rest; the weight ratio of ASA resin to PMMA resin to modifier to toughening agent to processing aid to black filler is (15-35) to (49.5-73.5) to (1-15) to (3-7) to (1-2) to (3-6).

2. The Gao Heiliang scratch-resistant PMMA/ASA alloy material according to claim 1, wherein the toughening agent is butyl acrylate, methyl methacrylate, acrylonitrile and styrene copolymer, and the toughening agent is a core-shell structure, wherein the weight content of the butyl acrylate is 40-70%.

3. The Gao Heiliang scratch-resistant PMMA/ASA alloy material according to claim 1, wherein the weight ratio of ASA resin to PMMA resin to modifier to toughener to processing aid to black filler is (20-30) to (55-65) to (2.5-15) to (4-6) to (1-2) to (3.5-5).

4. The Gao Heiliang scratch-resistant PMMA/ASA alloy material of claim 1 wherein the black filler is a carbon black pre-dispersed masterbatch.

5. The method for preparing the Gao Heiliang scratch-resistant PMMA/ASA alloy material is characterized by comprising the following steps of extruding ASA resin, PMMA resin, a modifier, a toughening agent, a processing aid and a black filler through a screw to obtain the high-blackness scratch-resistant PMMA/ASA alloy material.

6. A method of preparing a Gao Heiliang scratch resistant PMMA/ASA alloy material according to claim 5 wherein the processing aid comprises an antioxidant, an anti-uv agent, a lubricant.

7. Use of the Gao Heiliang scratch-resistant PMMA/ASA alloy material of claim 1 for the preparation of a high black and bright scratch-resistant material.

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