WO2024125252A1 - High-performance color masterbatch and polypropylene composition prepared therefrom - Google Patents

Abstract

The present invention relates to the technical field of polymer materials. Disclosed are a high-performance color masterbatch and a polypropylene composition prepared therefrom. By using an ethylene/methacrylic acid copolymer partially neutralized by specific metal ions as a carrier resin, in conjunction with an azo pigment, the high-performance color masterbatch product of the present invention can be used directly in a polypropylene composition product for color matching, thereby meeting the requirements in the existing market for higher product saturation and colorful appearance effects. Moreover, after use, the product maintains a remarkable scratch-resistant effect and a remarkable light stability effect, and the stability of the external color scheme of the product can be maintained for a long time.

Description

A high-performance color masterbatch and polypropylene composition prepared therefrom Technical Field

The invention relates to the technical field of polymer materials, and in particular to a high-performance color masterbatch and a polypropylene composition prepared therefrom.

Background technique

Currently, plastic products are required to have a more saturated and colorful appearance. However, this high-saturation, colorful appearance is inseparable from the use of organic pigments or dyes. During service, these materials will have serious discoloration problems, especially under light conditions. Among the existing organic pigments, azo pigments have the highest usage rate, but there is currently no effective modification method for this pigment.

Polypropylene is a thermoplastic synthetic resin with excellent performance, which is widely used in the automotive, power tools, electronic and electrical industries. However, there are unstable tertiary carbon atoms in the polypropylene chain, which are easy to form active and easily degradable tertiary carbon free radicals in the presence of heat, light or oxygen, causing polypropylene to age. However, after the introduction of brightly colored organic pigments into polypropylene, the interaction between the two makes the problem of material aging and discoloration more serious.

The conventional approach to improving the light aging problem of colored polypropylene materials is to increase the dosage of antioxidants, but not only is the effect minimal, but there is also a risk of precipitation due to excessive dosage.

CN201710617918.4 discloses a weather-resistant colored polypropylene composite material, which is prepared by adding a specific compounding weight ratio and a specific type of composite colorant to a polypropylene matrix resin, but the product requires a pigment of a specific color system and cannot match a high-saturation color appearance effect; at the same time, the light stabilizer content introduced is as high as 2%, which not only has little effect, increases production costs, but also causes the risk of precipitation. CN202111682717.5 discloses a method for preparing a polypropylene material with high weather resistance, heat resistance and heat retention of red plastic parts using DPP red (bis (p-chlorophenyl) 1.4 diketopyrrolopyrrole) and cerium sulfide, but it is only for red products and is not suitable for other color materials; in addition, the inorganic pigment cerium sulfide used may accelerate the aging and discoloration of the polypropylene material due to the residual free transition metal elements during the light aging process, and it is necessary to add additional light stabilizers or metal passivators to overcome this shortcoming, which increases production costs.

Summary of the invention

Based on the defects of the prior art, the purpose of the present invention is to provide a high-performance color masterbatch, which uses a specific metal ion partially neutralized ethylene/methacrylic acid copolymer as a carrier resin and an azo pigment, and can be directly used in polypropylene composition products for color matching, meeting the current market requirements for products with higher saturation and various colors. At the same time, the product has significant scratch resistance and light stability after use, and can maintain the stability of the product appearance color for a long time.

In order to achieve the above object, the technical solution adopted by the present invention is:

A high-performance color masterbatch, comprising the following components in parts by weight:

60-80 parts of carrier resin and 10-20 parts of organic pigment;

The carrier resin is an ethylene/methacrylic acid copolymer partially neutralized with metal ions; and the organic pigment is an azo pigment.

Azo pigments have rich color systems, especially some high-saturation color effects that cannot be replaced by inorganic pigments, but their own fastness is low and easily affected by external factors. In order to obtain high-saturation appearance color effects, existing polypropylene products often add azo pigments to the products, but based on the properties of the azo pigments themselves and the activity of the polypropylene resin, the scratch resistance and appearance stability of the products are poor, and more additives are often required for compounding, which not only increases the cost, but also has poor improvement effects. In the technical solution of the present invention, the inventor uses ethylene/methacrylic acid copolymers in which methacrylic acid groups are partially neutralized by metal ions as carrier resins for compounding azo pigments to prepare color masterbatches. This color masterbatch can be directly used in polypropylene products to achieve coloring. At the same time, the inventor found that due to the specificity of the group, the carrier resin can not only react with the azo group and amide group in the azo pigment, but also realize the hydrogen bonding between molecules, so that the color fastness of the color masterbatch after use is significantly improved, and the aggregation morphology of the azo pigment in the masterbatch has changed, and the effect tends to be partially agglomerated rather than traditionally dispersed. At the same time, based on the loading of the carrier resin, a highly stable protective film is formed on the surface of the azo pigment, which prevents the polypropylene resin or external factors (light, heat) from corroding the azo pigment and thus ensures the color stability of the product. In addition, after the introduction of polypropylene products, the product does not need to introduce additional amounts of scratch resistance agents or weather resistance agents (light stabilizers) in the original formula, which has high economic benefits.

Preferably, the ethylene/methacrylic acid copolymer has a density of 0.95 to 0.97 g/cm ³ and a melting point of 70 to 88°C.

Preferably, the metal ion is at least one of zinc ion and sodium ion.

More preferably, the metal ion is a sodium ion.

When the metal ion remaining after partial neutralization in the ethylene/methacrylic acid copolymer is sodium, the effect of compounding it with the azo pigment is better, and the obtained color masterbatch has better scratch resistance and color stability during use.

Preferably, the high-performance color masterbatch also includes 10 to 20 parts of solid glass microspheres.

The inventors found in experiments that when solid glass microspheres replace part of the carrier resin or organic pigment in high-performance color masterbatch, the color stability of the product can be further enhanced. However, when the amount of solid glass microspheres introduced is too much, the interface contact area brought by the solid glass microspheres increases, making the probability of external oxygen entering the product for oxidation also increase. Therefore, the comprehensive performance of the product is best when the above ratio is maintained.

Preferably, the particle size D ₅₀ of the solid glass microspheres is ≤30 μm.

More preferably, the particle size D ₅₀ of the solid glass microspheres is 2 to 30 μm.

The color masterbatch products prepared using solid glass microbeads within the above-mentioned particle size range have better performance.

Another object of the present invention is to provide a method for preparing the high-performance color masterbatch, comprising the following steps:

The components are mixed and dispersed evenly by adding a dispersant, and then transferred into a twin-screw extruder for melt extrusion and vacuum granulation to obtain the high-performance color masterbatch.

Preferably, the dispersing speed is 500-1000 rpm.

Preferably, the dispersant is white oil, and the temperature of each screw zone of the twin-screw extruder is 80-100°C.

Using white oil as a dispersant can make the azo pigments, solid glass beads and other components more dispersed. At the same time, the white oil can be volatilized and separated during the processing, so it will not remain in the product.

The preparation method of the high-performance color masterbatch of the present invention has simple operation steps and can realize industrial large-scale production.

Another object of the present invention is to provide a polypropylene composition, the components of which include the high-performance color masterbatch of the present invention.

The carrier resin used in the high-performance color masterbatch of the present invention has high compatibility with the polypropylene resin and can be used as a binding layer and a protective layer for the azo pigment, so that the fastness and color stability of the azo pigment used to color the polypropylene resin are higher than those of products prepared with ordinary pigments or products prepared by directly adding the azo pigment to the polypropylene resin.

Preferably, the polypropylene composition comprises the following components in parts by weight: 40 to 98 parts of polypropylene resin, 0 to 30 parts of toughening agent, 0 to 30 parts of filler, 3 to 8 parts of the high-performance color masterbatch of the present invention, and 0.2 to 1 part of industrial auxiliary agent.

Preferably, the polypropylene tree has a melt mass flow rate of 1 to 150 g/10 min at 230°C and 2.16 kg load according to ASTM D1238-2021.

Preferably, the toughening agent is at least one of a polyolefin elastomer and a styrene-hydrogenated butadiene block copolymer.

The processing aid is at least one of an antioxidant, a lubricant, and a light stabilizer.

Preferably, the antioxidant is a compound of a hindered phenol antioxidant and a phosphite antioxidant.

Preferably, the method for preparing the polypropylene composition comprises the following steps:

After the components are uniformly mixed, they are transferred to a twin-screw extruder for melt extrusion and vacuum granulation to obtain the polypropylene composition.

More preferably, the mixing speed is 1000-2000 rpm and the mixing time is 1-3 min.

More preferably, the temperature of each screw zone of the twin-screw extruder is 190-230°C.

Another object of the present invention is to provide the use of the high-performance color masterbatch and/or polypropylene composition of the present invention in the preparation of automotive parts and household appliances.

The high-performance color masterbatch of the present invention has a good high-saturation appearance, good color stability, and good scratch resistance. It can be directly used to prepare some automotive parts and household appliances that have high requirements for appearance effects. At the same time, it can also be further prepared into a polypropylene composition product according to actual needs for processing and application.

The beneficial effect of the present invention is that the present invention provides a high-performance color masterbatch, which uses a specific metal ion partially neutralized ethylene/methacrylic acid copolymer as a carrier resin and an azo pigment, and can be directly used in polypropylene composition products for color matching, meeting the current market requirements for products with higher saturation and various colors. At the same time, the product has significant scratch resistance and light stability after use, and can maintain the stability of the product appearance color for a long time.

Detailed ways

In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments and comparative examples, the purpose of which is to understand the content of the present invention in detail, rather than to limit the present invention. All other embodiments obtained by those of ordinary skill in the art without making creative work premise belong to the protection scope of the present invention. The experimental reagents and instruments involved in the implementation of the present invention, unless otherwise specified, are all commonly used common reagents and instruments.

Examples 1 to 12

The embodiments of the high-performance color masterbatch and the preparation method thereof of the present invention, the components of the high-performance color masterbatch are shown in Table 1.

The method for preparing the high-performance color masterbatch comprises the following steps:

The components are mixed and 0.1% of the total weight of commercially available white oil is added to disperse in a high-speed mixer at a speed of 800 rpm for 3 minutes until uniform, and then transferred to a twin-screw extruder for melt extrusion and vacuum granulation to obtain the high-performance color masterbatch; the temperature of each screw zone of the twin-screw extruder is 80-100°C.

Comparative Examples 1 to 5

The difference between the comparative examples and the embodiments is only in the types and proportions of components, as shown in Table 1.

Among the components described in each embodiment and comparative example,

Carrier resin 1 is an ethylene/methacrylic acid copolymer, in which the methacrylic acid groups are partially neutralized by sodium ions, with a melting point of 88°C and a density of 0.95 g/cm ³ , Surlyn 8920 produced by Dow Chemical, USA;

Carrier resin 2 is ethylene/methacrylic acid copolymer, in which the methacrylic acid groups are partially neutralized by sodium ions, with a melting point of 87° C. and a density of 0.96 g/cm ³ , Surlyn 8140 produced by Dow Chemical, USA;

Carrier resin 3 is an ethylene/methacrylic acid copolymer, in which the methacrylic acid groups are partially neutralized by zinc ions, with a melting point of 70°C and a density of 0.96 g/cm ³ , Surlyn 9320 produced by Dow Chemical, USA;

Carrier resin 4 is polypropylene resin, EP548R produced by CNOOC and Shell;

Carrier resin 5 is ethylene-vinyl acetate copolymer, Elvax 250 produced by Dow Chemical of the United States;

Solid glass microspheres 1: 050-20-223 produced by SOVITEC, particle size _D50 is 15-30 μm;

Solid glass microspheres 2: NP3-P0 produced by SOVITEC, with a particle size D ₅₀ of 2 to 4 μm;

Solid glass microspheres 3: 050-40-223 produced by SOVITEC, particle size _D50 is 30-45 μm;

Hollow glass microspheres: iM60K produced by 3M; particle size _D50 is 22 μm;

Glass fiber: Jushi Fiberglass production ECS13-04-508A;

Azo pigment 1 is commercially available yellow pigment P.Y.180;

Azo pigment 2 is a commercially available orange pigment P.O.64;

Azo pigment 3 is commercially available red pigment P.R.214;

Organic pigment 1 is a commercially available yellow pigment P.R.138, a non-azo pigment.

Table 1

In order to verify the performance of each high-performance color masterbatch of the present invention, the products of each embodiment and comparative example are further processed into a polypropylene composition, as follows:

Examples A to T

The embodiments of the polypropylene composition of the present invention include components of the polypropylene composition as shown in Table 2.

The method for preparing the polypropylene composition comprises the following steps:

After the components are evenly mixed, they are transferred to a twin-screw extruder for melt extrusion and vacuum granulation to obtain the The polypropylene composition; the mixing rate is 2000rpm, and the time is 3min; the temperature of each zone of the screw of the twin-screw extruder is 190-230℃.

Examples A to M respectively use the high-performance color masterbatches prepared in the above-mentioned Examples 1 to 13, and Examples N to T use the high-performance color masterbatches prepared in Example 3. The products are prepared in each example according to the composition ratio in Table 3.

Comparative Examples a to e

The difference between Comparative Examples a to e and Examples A to T is only that the color masterbatches prepared in Comparative Examples 1 to 5 are used in the components.

Comparative Examples f to g

The preparation method of the polypropylene composition described in this comparative example is the same as that of the embodiments, and the composition is shown in Table 2.

Comparative Example

The preparation method of the polypropylene composition described in this comparative example is:

The product was prepared according to the components and preparation method of the polypropylene composition described in Example 3, wherein the high-performance masterbatch was replaced by the various preparation raw materials of the high-performance color masterbatch described in Example 3, that is, the product components of Example 3 were not mixed or prepared as masterbatches, but directly replaced the high-performance color masterbatch for preparing the polypropylene composition.

Among the components described in each embodiment and comparative example,

Polypropylene resin 1 is BX3900 produced by SK Chemical of South Korea, and the melt mass flow rate is 60 g/10 min at 230°C and 2.16 kg load;

Polypropylene resin 2 is MX7900 produced by LG Chemical of South Korea, with a melt mass flow rate of 150 g/10 min at 230°C and a load of 2.16 kg;

Polypropylene resin 3 is EPS30R produced by China Dushanzi Petrochemical, with a melt mass flow rate of 1 g/10 min at 230 °C and a load of 2.16 kg;

Toughener 1 is polyolefin elastomer Engage8842 produced by Dow Chemical;

Toughener 2 is styrene-hydrogenated butadiene block copolymer SEBS1657 produced by China Kraton Chemical;

The filler is commercially available talc;

The processing aid is a mixture of a commercial hindered phenol antioxidant, a commercial phosphite antioxidant, a commercial lubricant calcium stearate and a commercial light stabilizer in a ratio of 2:2:2:3.

Unless otherwise specified, the components and raw materials used in the embodiments and comparative examples of the present invention are all commercially available raw materials. The components and raw materials used in each parallel experiment were of the same type.

Table 2

The polypropylene composition products prepared in Examples A to T and Comparative Examples a to h were subjected to the following performance tests, and the specific steps are as follows:

(1) Weathering performance test (color stability test): Each product was injection molded into a 55*85*2mm sample, and then tested according to ISO 4892-2-2013: the sample was placed under a xenon lamp for 1000h irradiation treatment, and a daylight filter was used for 102min illumination + 18min spray treatment; the irradiance was (0.51±0.02)W/(m·nm)@340nm, the black mark temperature was (65±3)℃, the sample treatment temperature was (38±3)℃, and the relative humidity was (50±10)%. The changes in the L, a, and b values of the sample before and after treatment were tested using a colorimeter, and dE was calculated. The smaller the dE of the product, the better the weathering performance of the material;

(2) Scratch resistance test: Each product was injection molded into a sample of 100*100*3 mm and tested with a load of 10 N according to PV3952. The change in L value of the sample before and after treatment was tested using a colorimeter and △L was calculated. The smaller the △L of the product, the better the scratch resistance of the material.

The test results are shown in Tables 3 and 4.

table 3

Table 4

It can be seen from Tables 3 and 4 that the high-performance color masterbatch prepared in each embodiment has good color stability and scratch resistance after being used to prepare polypropylene composition products, wherein the dE after testing is not higher than 7 and the ΔL is not higher than 3.5. Among them, according to the use performance of the high-performance color masterbatch prepared in Example A, Example B and Example I, when the carrier resin uses ethylene/methacrylic acid copolymer partially neutralized with sodium ions, the effect is better than that of ethylene/methacrylic acid copolymer partially neutralized with other metal ions. According to the performance comparison of the products prepared in Examples B to E, when a part of solid glass microspheres is introduced into the product, the solid glass microspheres will synergize with the ethylene/methacrylic acid copolymer, and the high-performance color masterbatch prepared has better appearance color stability, but if the amount of solid glass microspheres added is too much, the performance of the product will decrease, as shown in the product of Example 5. According to the use performance of the products prepared in Examples 3 and Examples J to M, when the product contains solid glass microspheres, the particle size cannot be too large, otherwise the probability of the product being invaded by external oxygen will increase and the performance of the product will decrease. However, in the high-performance color masterbatch of the present invention, adding any filler material can not further enhance the color stability of the product. For example, hollow glass microspheres will not significantly improve the product performance after being added to the product. At the same time, according to Examples N to T, the high-performance color masterbatch of the present invention is suitable for polypropylene compositions prepared under various formulas, and the polypropylene compositions can achieve good appearance color stability and scratch resistance, and will not cause the product to fade due to external scratches. In contrast, the products prepared in Comparative Examples a and b use inappropriate carrier resins, which cannot anchor and protect azo pigments well; Comparative Example c uses non-azo pigments, although it can also achieve a high-saturation appearance color, it cannot be effectively connected with the carrier resin, and the product cannot achieve the expected scratch resistance and color stability; in the products of Comparative Examples d and e, the amount of azo pigment added is too much, or the content of the carrier resin is too little, which is also difficult to achieve the expected effect. At the same time, according to Comparative Examples f to h, when preparing a polypropylene composition product, if azo pigments are directly introduced, the product cannot guarantee good color stability, and discoloration will occur after being scratched. Even if a certain amount of solid glass beads are introduced, the above problems cannot be effectively suppressed. At the same time, as shown in Comparative Example 8, even if the same raw materials of the color masterbatch of the present invention are added during the preparation of the polypropylene composition, the carrier resin and the azo pigment in the product cannot be connected and hydrogen-bonded in time, and the dispersion uniformity of the azo pigment in the polypropylene resin is too high. In the absence of local aggregation in the form of the color masterbatch of the present invention, the azo pigment is too highly affected by the activity of the polypropylene resin, and it is also difficult to maintain effective scratch resistance and weather resistance, and the appearance color is unstable.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention and are not intended to Limitation of the protection scope of the invention: Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that the technical solution of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims (10)

1. A high-performance color masterbatch, characterized by comprising the following components in parts by weight:

   60-80 parts of carrier resin and 10-20 parts of organic pigment;

   The carrier resin is an ethylene/methacrylic acid copolymer partially neutralized with metal ions; and the organic pigment is an azo pigment.
2. The high-performance color masterbatch according to claim 1, characterized in that the metal ion is at least one of zinc ion and sodium ion; preferably, the metal ion is sodium ion.
3. The high-performance color masterbatch according to claim 1 is characterized in that the components of the high-performance color masterbatch also include 10 to 20 parts of solid glass microspheres.
4. The high-performance color masterbatch as described in claim 3 is characterized in that the particle size D50 of the solid glass microspheres is ≤30 μm; preferably, the particle size D50 of the solid glass microspheres is 2 to 30 μm.
5. The method for preparing the high-performance color masterbatch according to any one of claims 1 to 4, characterized in that it comprises the following steps:

   The components are mixed and dispersed evenly by adding a dispersant, and then transferred into a twin-screw extruder for melt extrusion and vacuum granulation to obtain the high-performance color masterbatch; preferably, the dispersant is white oil.
6. A polypropylene composition, characterized in that the components include the high-performance color masterbatch according to any one of claims 1 to 4.
7. The polypropylene composition according to claim 6, characterized in that it comprises the following components in parts by weight: 40 to 98 parts of polypropylene resin, 0 to 30 parts of toughening agent, 0 to 30 parts of filler, 3 to 8 parts of the high-performance color masterbatch according to any one of claims 1 to 4, and 0.2 to 1 part of processing aid.
8. The polypropylene composition according to claim 7, characterized in that it comprises at least one of the following (1) to (3):

   (1) The melt mass flow rate of the polypropylene resin at 230° C. and 2.16 kg load is 1 to 150 g/10 min;

   (2) The toughening agent is at least one of a polyolefin elastomer and a styrene-hydrogenated butadiene block copolymer;

   (3) The processing aid is at least one of an antioxidant, a lubricant, and a light stabilizer.
9. The polypropylene composition according to claim 6, characterized in that the method for preparing the polypropylene composition comprises the following steps:

   After the components are uniformly mixed, they are transferred to a twin-screw extruder for melt extrusion and vacuum granulation to obtain the polypropylene composition; the mixing rate is 1000-2000 rpm and the time is 1-3 minutes; the temperature of each screw zone of the twin-screw extruder is 190-230°C.
10. Use of the high-performance color masterbatch according to any one of claims 1 to 4 or the polypropylene composition according to any one of claims 6 to 9 in the preparation of automotive parts and household appliances.