Spraying-free polypropylene material with dot color flow line effect and preparation method thereof

Abstract

The invention discloses a polypropylene material with a spraying-free dot-color flow line effect and a preparation method thereof. The polypropylene material comprises dot-color flow line color master batches and a polypropylene plastic material in a mass ratio of (1-20): 100. The preparation process comprises the following steps: S1, preparing the color master batch with the dot color flow line effect, wherein the materials comprise PP resin 1 #, rubber powder, a compatibilizer 1 #, an antioxidant 1 #, an antioxidant 2 #, a lubricant and toner 1 #; s2, preparing a polypropylene plastic material, wherein the materials comprise PP resin 2 #, a compatibilizer 2 #, an antioxidant 1 #, an antioxidant 2 #, a lubricant, a weather-proof agent and toner 2 #; and S3, adding one or more color master batches with the dot color flow line effect prepared in the step S1 into the polypropylene plastic material prepared in the step S2, and uniformly mixing to obtain the product. The polypropylene plastic material disclosed by the invention can be prepared into a plastic product with a spraying-free flow line effect, which has mechanical properties and aesthetic property, after injection molding.

Description

Technical Field

[0001] The present invention belongs to the field of spray-free technology, and relates to a polypropylene material with a spray-free stippled flow pattern effect and a preparation method thereof. Background Art

[0002] Plastic products are widely used in daily necessities. In order to meet consumers' requirements for aesthetics, plastic products are given rich appearances through post-processing such as painting, electroplating, printing, etc., so as to meet consumers' aesthetic needs and enrich consumers' visual experience. Spray-free plastics are plastic products with aesthetics that are formed by one-time injection molding without spraying, and have the advantages of environmental protection, one-time molding, short production cycle, and low cost. With the development of spray-free materials, various differentiated appearance effects have been continuously developed to meet the personalized needs of different application scenarios.

[0003] Pointillism is a painting technique, and the stippled flow pattern effect is an appearance effect that simulates pointillism. Compared with the traditional spray-free flow pattern effect, the stippled flow pattern removes the filamentous flow lines and flow states, but presents a dot-like flow state.

[0004] For spray-free flow pattern effect plastic products, during the injection molding process, they naturally flow and distribute on the surface of the product, simulating the natural flow state, with filamentous flow lines. Combined with different colors, they have a changeable and unique texture appearance, and can simulate the effects of marble patterns, wood grains, jade, etc. Chinese Patent CN12745665A discloses a masterbatch for injection molding flow pattern effect and a preparation method thereof for polypropylene materials, and Chinese Patent CN116904010A discloses a spray-free flow pattern effect polycarbonate plastic material and a preparation method thereof. However, the plastic materials prepared by the above patents are all traditional spray-free flow pattern effects and cannot present the stippled flow pattern effect. Therefore, the present invention develops a polypropylene material with a spray-free stippled flow pattern effect, endowing the polypropylene plastic material with a new spray-free effect. Summary of the Invention

[0005] The purpose of the present invention is to overcome the deficiencies of the prior art. Compared with the spray-free flow pattern effect, the present invention provides a polypropylene material with a spray-free stippled flow pattern effect and a preparation method thereof.

[0006] The purpose of the present invention can be achieved through the following solutions:

[0007] <First Aspect>

[0008] The present invention provides a polypropylene material with a spray-free stippled flow pattern effect, and the polypropylene material comprises a stippled flow pattern color masterbatch and a polypropylene plastic material with a mass ratio of 1 - 20:100; wherein, the stippled flow pattern color masterbatch comprises the following raw materials in parts by weight:

[0009]

[0010]

[0011] The polypropylene plastic material comprises raw material components in the following parts by weight:

[0012]

[0013] As an embodiment, the PP resin 1# is homopolymerized PP, and the melt index thereof under the conditions of 230°C * 2.16 kg is 0.5 to 8 g / 10 min.

[0014] As an embodiment, the PP resin 2# is homopolymerized PP, and the melt index thereof under the conditions of 230°C * 2.16 kg is 10 to 100 g / 10 min.

[0015] As an embodiment of the present invention, the rubber powder includes one or more of SBS, SBR, SEBS, NBR, and ABS high rubber powder; the styrene content in the rubber powder is 28-32%, and the viscosity measured in a 10 wt% toluene solution at 25°C is 2400 to 5000 cps.

[0016] As an embodiment of the present invention, the compatibilizer 1# includes one or more of rubber powder grafted maleic anhydride and rubber powder grafted glycidyl methacrylate.

[0017] As an embodiment of the present invention, the compatibilizer 2# includes one or more of PP resin powder grafted maleic anhydride and PP resin powder grafted glycidyl methacrylate.

[0018] As an embodiment of the present invention, the antioxidant 1# is one or more of antioxidant 1010 and antioxidant 1076.

[0019] As an embodiment of the present invention, the antioxidant 2# is one or more of antioxidant 168 and antioxidant 300.

[0020] As an embodiment of the present invention, the lubricant includes one or more of stearate, polypropylene wax, ethylene bisstearamide, and silicone.

[0021] As an embodiment of the present invention, the weathering agent is a compound of benzotriazoles and hindered amines, wherein the mass ratio of benzotriazoles to hindered amines is 0.2 to 1:1. In some embodiments, the benzotriazoles include UVP, and the hindered amines include light stabilizer UV-770.

[0022] As an embodiment of the present invention, the toner 1# is a conventional pigment, including one or more of titanium dioxide, carbon black, titanium yellow, iron red, phthalocyanine blue, and phthalocyanine green.

[0023] As an embodiment of the present invention, the toner 2# is a conventional pigment, including one or more of titanium dioxide, carbon black, titanium yellow, iron red, phthalocyanine blue, and phthalocyanine green.

[0024] <Second aspect>

[0025] The present invention also provides a method for preparing a spray-free stippled flow pattern polypropylene material, comprising the following steps:

[0026] S1. Prepare the stippled flow pattern masterbatch;

[0027] Mix PP resin 1#, rubber powder, compatibilizer 1#, antioxidant 1#, antioxidant 2#, lubricant, and toner 1# evenly, then add them to a twin-screw extruder, and obtain the stippled flow pattern masterbatch through melt extrusion and pelletization.

[0028] S2. Prepare the polypropylene plastic material;

[0029] Mix PP resin 2#, compatibilizer 2#, antioxidant 1#, antioxidant 2#, lubricant, weathering agent, and toner 2# evenly, then add them to a twin-screw extruder, and obtain the polypropylene plastic material through melt extrusion and pelletization.

[0030] S3. Prepare the spray-free stippled flow pattern polypropylene material;

[0031] Add the stippled flow pattern masterbatch to the polypropylene plastic material and mix them mechanically to obtain the product.

[0032] As an embodiment, in step S1, the temperatures of the first to fifth zones of the twin-screw extruder are 170 - 180 °C, 180 - 190 °C, 190 - 200 °C, 200 - 210 °C, and 210 - 220 °C in sequence, and the rotational speed of the twin-screw is 400 - 600 r / min.

[0033] As an embodiment, in step S2, the temperatures of the first to fifth zones of the twin-screw extruder are 160 - 170 °C, 170 - 180 °C, 180 - 190 °C, 190 - 200 °C, and 200 - 210 °C in sequence, and the rotational speed of the twin-screw is 400 - 600 r / min.

[0034] In step S3 of the present invention, one or more stippled flow pattern masterbatches can be added to the polypropylene plastic material according to a certain ratio according to the appearance effect.

[0035] <Third aspect>

[0036] The present invention also provides a plastic part prepared using the polypropylene material, which is prepared by the following method: injecting the polypropylene material, and setting the injection temperature of the injection molding machine to be 150 - 160 °C, 160 - 170 °C, 170 - 180 °C, 190 - 200 °C, and then obtaining it after injection molding.

[0037] The formation of the traditional spray-free flow pattern effect is achieved by adding a flow pattern masterbatch with a processing temperature higher than that of the base material to the base material. During the injection molding process, the base material melts while the flow pattern masterbatch is in a semi-melted state. The spray-free stippled flow pattern effect provided by the present invention is achieved by adding a high proportion of rubber powder and a low-fluidity PP resin to the masterbatch; and in terms of the effect, the spray-free stippled flow pattern effect removes the continuous filamentous flow lines and flow states, presenting a fine non-continuous flow state in the form of dots. This appearance effect is similar to the painting stippling technique and is a new type of spray-free effect.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] By adding a high proportion of rubber powder and a low-fluidity PP resin to the masterbatch, the high proportion of rubber powder and low-fluidity PP have lower fluidity than the base material during the injection molding process, making it difficult for them to spread. At the same time, the high proportion of rubber has the characteristics of rubber and cannot form continuous filamentous flow lines, enabling the prepared polypropylene material to have a spray-free stippled flow pattern effect, that is, removing the continuous filamentous flow lines and flow states and presenting a fine non-continuous flow state in the form of dots. Compared with the traditional spray-free flow pattern effect showing a long and continuous flow state, the polypropylene material of the present invention provides a new type of spray-free effect. After injection molding, it can be made into a spray-free flow pattern effect plastic product that takes into account both mechanical properties and aesthetics, and can meet the personalized needs of more application scenarios. Description of the Drawings

[0040] By reading the detailed description of the non-restrictive embodiments with reference to the following drawings, other features, objectives, and advantages of the present invention will become more apparent:

[0041] Figure 1 It is the stippled flow pattern effect diagram of the polypropylene material prepared in Example 5;

[0042] Figure 2 It is the flow pattern effect diagram of the polypropylene materials prepared in Comparative Examples 1 - 4; among them, A - D are respectively the flow pattern effect diagrams of the polypropylene materials in Comparative Examples 1 - 4. Detailed Embodiments

[0043] The present invention will be described in detail below in conjunction with the accompanying drawings and specific embodiments. The following examples are implemented on the premise of the technical solution of the present invention, providing detailed implementation manners and specific operation processes, which will help those skilled in the art to further understand the present invention. It should be noted that the protection scope of the present invention is not limited to the following embodiments. Several adjustments and improvements made under the premise of the concept of the present invention all belong to the protection scope of the present invention.

[0044] The following describes a polypropylene material with a spray-free dot-color flow pattern effect and its preparation method in an embodiment, both of which are carried out according to the following steps:

[0045] S1. Prepare the dot-color flow pattern masterbatch. Mix PP resin #1, rubber powder, compatibilizer #1, antioxidant #1, antioxidant #2, lubricant, and color powder #1, and then add them to a twin-screw extruder. The temperatures of the first to fifth zones of the twin-screw extruder are 180°C, 190°C, 200°C, 210°C, and 220°C in sequence. The rotation speed of the twin-screw is 500 r / min. After melting and extrusion granulation, the dot-color flow pattern masterbatch is obtained. Prepare one or more dot-color flow pattern masterbatches in the same way.

[0046] S2. Prepare the polypropylene plastic material. Mix PP resin #2, compatibilizer #2, antioxidant #1, antioxidant #2, lubricant, weathering agent, and color powder #2, and then add them to a twin-screw extruder. The temperatures of the first to fifth zones of the twin-screw extruder are 160°C, 170°C, 180°C, 190°C, and 200°C in sequence. The rotation speed of the twin-screw is 500 r / min. After melting and extrusion granulation, the polypropylene plastic material is obtained.

[0047] S3. Prepare a polypropylene material with a spray-free dot-color flow pattern effect. Add one or more dot-color flow pattern masterbatches to the polypropylene plastic material prepared in S2, and the addition ratio is 5% of the mass fraction of the polypropylene plastic material, then a polypropylene material with a spray-free dot-color flow pattern effect is obtained.

[0048] Inject the polypropylene material with a spray-free dot-color flow pattern effect. The set temperatures of the injection molding machine are 160°C, 170°C, 180°C, and 200°C. After injection molding, a part made of the polypropylene material with a spray-free dot-color flow pattern effect can be obtained.

[0049] For the polypropylene material with a spray-free dot-color flow pattern effect and its preparation method in the embodiment, the compositions of the dot-color flow pattern masterbatch and the polypropylene plastic material are shown in Table 1 and Table 2.

[0050] Table 1 Dot-color flow pattern masterbatch ratio

[0051]

[0052] Table 2 Polypropylene plastic material ratio

[0053]

[0054]

[0055] In Table 1, PP resin 1# is homopolymer PP, and its melt index is 0.5 g / 10 min under the conditions of 230 °C * 2.16 kg;

[0056] The rubber powder is SBS, the styrene content of SBS is 28%, and the viscosity measured in a 10 wt% toluene solution at 25 °C is 2400 cps;

[0057] The compatibilizer 1# is SBS grafted maleic anhydride (SBS-g-MAH);

[0058] The antioxidant 1# is antioxidant 1010, and the antioxidant 2# is antioxidant 168;

[0059] The lubricant is zinc stearate;

[0060] The color powder 1# is phthalocyanine blue.

[0061] In Table 2, PP resin 2# is homopolymer PP, and its melt index is 10 g / 10 min under the conditions of 230 °C * 2.16 kg;

[0062] The compatibilizer 2# is PP grafted maleic anhydride (PP-g-MAH);

[0063] The antioxidant 1# is antioxidant 1010, and the antioxidant 2# is antioxidant 168;

[0064] The lubricant is zinc stearate;

[0065] The weathering agent is a compound of UVP and light stabilizer UV-770, and their mass ratio is 0.2;

[0066] The color powder 2# is titanium dioxide.

[0067] Examples 1-16

[0068] A polypropylene material with a spray-free dot-color streaky effect and its preparation method, and the composition parts are shown in Table 3.

[0069] Table 3 Material components of a polypropylene material with a spray-free dot-color streaky effect

[0070]

[0071]

[0072] Example 17

[0073] The difference from Example 5 is that PP resin #1 is homopolymer PP and has a melt index of 5 g / 10 min under the conditions of 230 °C * 2.16 kg.

[0074] Example 18

[0075] The difference from Example 5 is that PP resin #1 is homopolymer PP and has a melt index of 8 g / 10 min under the conditions of 230 °C * 2.16 kg.

[0076] Example 19

[0077] The difference from Example 5 is that the rubber powder is SEBS, the styrene content of SEBS is 32%, and the viscosity measured in a 10 wt% toluene solution at 25 °C is 2800 - 5000 cps; compatibilizer #1 is SEBS grafted maleic anhydride (SEBS-g-MAH).

[0078] Example 20

[0079] The difference from Example 5 is that the rubber powder is SEBS, the styrene content of SEBS is 32%, and the viscosity measured in a 10 wt% toluene solution at 25 °C is 2800 - 5000 cps; compatibilizer #1 is SEBS grafted glycidyl methacrylate (SEBS-g-GMA).

[0080] Example 21

[0081] The difference from Example 5 is that the rubber powder is NBR; compatibilizer #1 is NBR grafted maleic anhydride (NBR-g-MAH, Kraton C1010GT from the United States).

[0082] Example 22

[0083] The difference from Example 5 is that the rubber powder is high rubber content ABS; compatibilizer #1 is SAN grafted maleic anhydride (SAN-g-MAH).

[0084] Example 23

[0085] The difference from Example 5 is that the rubber powder is SBS and SEBS, the styrene content of SBS is 28%, and the viscosity measured in a 10 wt% toluene solution at 25 °C is 2400 - 3600 cps; the styrene content of SEBS is 32%, and the viscosity measured in a 10 wt% toluene solution at 25 °C is 2800 - 5000 cps, and the mass ratio is 1:1. Compatibilizer #1 is SEBS grafted maleic anhydride (SEBS-g-MAH).

[0086] Example 24

[0087] The difference from Example 5 is that antioxidant 1# is antioxidant 1070 and antioxidant 2# is antioxidant 300.

[0088] Example 25

[0089] The difference from Example 5 is that the lubricant is polypropylene wax.

[0090] Example 26

[0091] The difference from Example 5 is that the lubricant is ethylene bisstearamide.

[0092] Example 27

[0093] The difference from Example 5 is that the lubricant is silicone.

[0094] Example 28

[0095] The difference from Example 5 is that PP resin 2# is homopolymerized PP and has a melt index of 30 g / 10 min under the conditions of 230 °C * 2.16 kg.

[0096] Example 29

[0097] The difference from Example 5 is that compatibilizer 2# is PP grafted glycidyl methacrylate (PP-g-GMA).

[0098] Example 30

[0099] The difference from Example 5 is that the stipple flow pattern masterbatch is prepared by the same method, and color powder 1# is phthalocyanine green.

[0100] Example 31

[0101] The difference from Example 5 is that the stipple flow pattern masterbatch prepared in Example 5 and the stipple flow pattern masterbatch prepared in Example 30 are mixed as the stipple flow pattern masterbatch, and the mass ratio is 1:1.

[0102] Performance test:

[0103] The mechanical properties of the spray-free stipple flow pattern polypropylene materials prepared in Examples 1 - 31 were tested.

[0104] Test method:

[0105] Table 4 Test conditions and test standards

[0106]

[0107]

[0108] Table 5 Test results of various properties of the spray-free stipple flow pattern polypropylene materials prepared in Examples 1 - 31

[0109]

[0110]

[0111] Comparative Example 1

[0112] The difference from Example 5 is that in the components of the stippled flow pattern masterbatch, the dosage of PP resin 1# is 70, and the dosage of rubber powder is 30.

[0113] Comparative Example 2

[0114] The difference from Example 5 is that in the components of the stippled flow pattern masterbatch, PP resin 1# is homopolymerized PP, and the melt index is 15 g / 10 min under the conditions of 230°C * 2.16 kg.

[0115] Comparative Example 3

[0116] The difference from Example 5 is that in the components of the stippled flow pattern masterbatch, PP resin 1# is polyhexamethylene adipamide (PA66).

[0117] Comparative Example 4

[0118] The difference from Example 5 is that in the components of the stippled flow pattern masterbatch, PP resin 1# is polyethylene terephthalate resin (PET).

[0119] The stippled flow pattern effect of Example 5 is as Figure 1 shown, and the flow pattern effects of Comparative Examples 1-4 are as Figure 2 shown. Therefore, from Example 5 and Comparative Examples 1-2, it can be seen that only by adding a high proportion of rubber powder and low-flow PP resin to the masterbatch can the spray-free stippled flow pattern effect be produced. If the proportion of rubber powder is reduced or high-flow PP resin is used, the stippled effect cannot be achieved. From Example 5 and Comparative Examples 3-4, it can be seen that using other conventional resins cannot produce the stippled effect.

[0120] The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art can make various deformations or modifications within the scope of the claims, which does not affect the essence of the present invention.

Claims

1. A polypropylene material with spray-free stippling effect, characterized in that: The polypropylene material includes a pointillism flow color masterbatch and a polypropylene plastic material in a mass ratio of 1-20:100; wherein the pointillism flow color masterbatch includes the following raw material components in parts by weight: The polypropylene plastic material comprises the following raw materials in parts by weight:

2. The polypropylene material with spray-free stippling effect according to claim 1, characterized in that: The PP resin 1# is homopolymer PP, and its melt index at 230°C*2.16kg is 0.5-8g / 10min; the PP resin 2# is homopolymer PP, and its melt index at 230°C*2.16kg is 10-100g / 10min.

3. The polypropylene material with spray-free stippling effect according to claim 1, characterized in that: The rubber powder includes one or more of SBS, SBR, SEBS, NBR and ABS high rubber powder.

4. The polypropylene material with spray-free stippling effect according to claim 1, characterized in that: The compatibilizer 1# includes one or more of rubber powder grafted with maleic anhydride and rubber powder grafted with glycidyl methacrylate; the compatibilizer 2# includes one or more of PP resin powder grafted with maleic anhydride and PP resin powder grafted with glycidyl methacrylate.

5. The polypropylene material with spray-free stippling effect according to claim 1, characterized in that: The antioxidant #1 is one or more of antioxidant 1010 and antioxidant 1076; the antioxidant #2 is one or more of antioxidant 168 and antioxidant 300.

6. The polypropylene material with spray-free stippling effect according to claim 1, characterized in that: The lubricant includes one or more of stearate, polypropylene wax, ethylene bis stearamide, and silicone; the weathering agent is a compound of benzotriazoles and hindered amines, wherein the mass ratio of benzotriazoles to hindered amines is 0.2 to 1:

1.

7. The polypropylene material with spray-free stippling effect according to claim 1, characterized in that: The toner 1# includes one or more of titanium dioxide, carbon black, titanium yellow, iron oxide red, phthalocyanine blue, and phthalocyanine green; the toner 2# includes one or more of titanium dioxide, carbon black, titanium yellow, iron oxide red, phthalocyanine blue, and phthalocyanine green.

8. A method for preparing a polypropylene material with spray-free stippling effect as claimed in any one of claims 1 to 7, characterized in that: The following steps are involved: S1, preparing pointillism color masterbatch; PP resin 1#, rubber powder, compatibilizer 1#, antioxidant 1#, antioxidant 2#, lubricant, and color powder 1# are mixed and added into a twin-screw extruder, and granulated by melt extrusion to obtain a pointillism color masterbatch; S2, preparing polypropylene plastic material; PP resin 2#, compatibilizer 2#, antioxidant 1#, antioxidant 2#, lubricant, weathering agent, and color powder 2# are mixed and added into a twin-screw extruder, and granulated by melt extrusion to obtain a polypropylene plastic material; S3, preparing a polypropylene material with a spray-free pointillism effect; The pointillism flow masterbatch is added into the polypropylene plastic material and mixed evenly to obtain the product.

9. The preparation method according to claim 8, characterized in that: In step S1, the temperatures of zones 1 to 5 of the twin-screw extruder are 170-180°C, 180-190°C, 190-200°C, 200-210°C, 210-220°C, and the twin-screw speed is 400-600r / min; In step S2, the temperatures of zones 1 to 5 of the twin-screw extruder are 160-170°C, 170-180°C, 180-190°C, 190-200°C, and 200-210°C, respectively, and the twin-screw speed is 400-600r / min.

10. A plastic part with spray-free stippling effect, characterized in that: The plastic part is obtained by injection molding the polypropylene material as described in any one of claims 1 to 7 or the polypropylene material obtained by the preparation method as described in any one of claims 8 to 9; the injection molding temperature of the injection molding machine is set to 150-160°C, 160-170°C, 170-180°C, 190-200°C.

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