A nylon composite material, its preparation method and application

Abstract

The present invention relates to a nylon composite material, a preparation method and an application thereof, belonging to the technical field of plastic coloring and color matching. The nylon composite material described in the present invention comprises the following components in parts by weight: 55-70 parts of nylon resin, 0.7-2 parts of white pigment, 0.1-0.7 parts of bis(p-chlorophenyl)-1,4-diketopyrrolo[3,4-c]pyrrole pigment, and 0.3-0.9 parts of perylene-based pigment. By compounding and adding perylene-based pigment and DPP pigment into nylon resin, the present invention can synergistically improve the color saturation of nylon material, and still enable the final product to have a low fluorescence intensity when the dosage of DPP is low. The nylon composite resin prepared by the present invention has a low fluorescence intensity, a redder hue, a higher chromaticity value, and the color difference after boiling in water at 100°C for 1 h is less than 1, which is of great significance for saving the coloring and color matching cost of nylon resin.

Description

Technical Field

[0001] The present invention belongs to the technical field of plastic coloring and color matching, and particularly relates to a nylon composite material, a preparation method thereof, and an application thereof. Background Art

[0002] With the increasing diversification of the color requirements of materials in different application fields, the demand for nylon products with high chroma, high saturation, and no fluorescence or less fluorescence effects is gradually increasing; however, the nylon material itself has the characteristics of high melting point, hygroscopicity, strong polarity, and easy crystallization, which will cause many pigments to be unable to be used in common with it. For example, bis(4-chlorophenyl)-1,4-diketopyrrolo[3,4-c]pyrrole (DPP) pigment has good weather resistance and high coloring degree, and is often used for coloring plastic products; when DPP is used in nylon, it will produce unstable fluorescence, resulting in unstable colors of the molded parts, which greatly limits the choice of colorants in nylon products.

[0003] CN109735102A discloses a non-fluorescent red nylon material and a preparation method thereof. This technology reduces the fluorescence effect of red nylon by increasing the dosage of DPP pigment; however, the dosage of DPP needs to be increased to more than 1.5 wt%, and too much DPP dosage will not only damage the performance of the final nylon material, but also cause a large amount of DPP pigment to be wasted.

[0004] CN116496619A discloses a red nylon composite material, a preparation method thereof, and an application thereof. This technology also selects DPP as the colorant of the nylon material, and can reduce the degradation of DPP pigment by selecting a nylon resin with a specific viscosity, while also improving the dispersibility of DPP. At the same time, by selecting a specific nucleating agent, the crystallization rate of nylon is accelerated; however, this technology still does not solve the problem that DPP used in nylon will cause nylon to produce fluorescence, and the generation of fluorescence will cause the color of the final product to be unstable, greatly affecting the use of the product.

[0005] In view of the problems existing in the above-mentioned colored nylon composite materials, studying a nylon composite material with high color saturation and low fluorescence effect is the current research focus. Summary of the Invention

[0006] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a nylon composite material with high red color saturation and low fluorescence effect.

[0007] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0008] In a first aspect, the present invention provides a nylon composite material, which comprises the following components in parts by weight: 55-70 parts of nylon resin, 0.7-2 parts of white pigment, 0.1-0.7 parts of bis(4-chlorophenyl)-1,4-diketopyrrolo[3,4-c]pyrrole pigment, and 0.3-0.9 parts of perylene pigment.

[0009] The bis(4-chlorophenyl)-1,4-diketopyrrolo[3,4-c]pyrrole pigment is abbreviated as DPP pigment.

[0010] Since the DPP pigment will produce unstable fluorescence when used in nylon, the color of the finally prepared parts is unstable. To solve this problem, the prior art reduces the fluorescence effect of red nylon by increasing the amount of DPP pigment to achieve the purpose of stabilizing its color; however, this method will waste too much DPP, and excessive DPP will also damage the performance of the final nylon material.

[0011] To address the above problems of DPP pigment in the application of nylon, the present invention uses perylene pigment as a specific pigment. On the one hand, the perylene pigment can play a covering role and weaken the fluorescence generated by DPP during application. On the other hand, the perylene pigment has an ultraviolet absorption effect and can block ultraviolet light from acting on the DPP pigment.

[0012] The inventors also found that the parts by weight of the perylene pigment in the present invention have a great influence on the fluorescence intensity, hue, and chromaticity of the final nylon composite material; if the parts by weight of the perylene pigment are too low, the hue of the final nylon composite material will be yellowish, the chromaticity value will be low, and the color saturation of the material will be poor; if the parts by weight of the perylene pigment are too high, the lightness value of the final product will be reduced, the chromaticity value will be decreased, and the color vividness will be reduced.

[0013] The present invention uses the perylene pigment and the DPP pigment together, and the two can synergistically improve the color saturation of the nylon material and make the finally prepared nylon composite material have a low fluorescence intensity and a high color vividness.

[0014] The inventors also found that by adopting the technical solution of using the perylene pigment and the DPP pigment together in the present invention, it is possible to obtain products with low fluorescence or even no fluorescence when the amount of DPP used is low.

[0015] At the same time, the inventors found in the experiment that adding white pigment to the above formula can also reduce the fluorescence intensity of the final product, and the addition of white pigment can also increase the lightness value and improve the vividness of the product.

[0016] As a preferred embodiment of the nylon composite material of the present invention, in the nylon composite material, the weight parts of the nylon resin are one of 55 parts, 60 parts, 65 parts, 70 parts or the range value of any two of them; the weight parts of the white pigment are one of 0.7 part, 1 part, 1.3 parts, 1.5 parts, 2 parts or the range value of any two of them; the weight parts of DPP are one of 0.1 part, 0.3 part, 0.5 part, 0.7 part or the range value of any two of them; the weight parts of the perylene-based pigment are one of 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or the range value of any two of them.

[0017] As a preferred embodiment of the nylon composite material of the present invention, the nylon composite material comprises the following components in parts by weight: 60 - 65 parts of nylon resin, 1.0 - 1.5 parts of white pigment, 0.3 - 0.5 part of bis(p-chlorophenyl)-1,4-diketopyrrolo[3,4-c]pyrrole pigment, and 0.4 - 0.8 part of perylene-based pigment.

[0018] As a preferred embodiment of the nylon composite material of the present invention, the perylene-based pigment comprises at least one of Paliogen Red K 3911, PV Fast Red B, Paliogen Red K3580, and Hostaperm Red P2GL.

[0019] As a preferred embodiment of the nylon composite material of the present invention, the white pigment comprises at least one of zinc sulfide, antimony white, and zinc oxide.

[0020] As a more preferred embodiment of the nylon composite material of the present invention, the weight parts of the perylene-based pigment are 0.5 - 0.7 parts.

[0021] The inventors of the present invention have found through research that when the weight parts of the perylene-based pigment in the present invention are within the above preferred range, the final nylon composite material can have a weak fluorescence intensity, a high color saturation, a redder hue, and a smaller color difference and more stable color after boiling in water at 100°C for 1 h.

[0022] As a preferred embodiment of the nylon composite material of the present invention, the mass ratio of the perylene-based pigment to the DPP pigment is DPP pigment:perylene-based pigment = 1:0.5 - 2; the inventors have found through a large number of experiments that within the above mass ratio range, the two cooperate to best improve the saturation of the nylon composite material and reduce the fluorescence intensity of the nylon composite material.

[0023] As a preferred embodiment of the nylon composite material of the present invention, the melting point of the nylon resin is 185 - 260°C.

[0024] As a more preferred embodiment of the nylon composite material of the present invention, the melting point of the nylon resin is 215-225°C.

[0025] The inventors found through a large number of experiments that in the present invention, when the melting point of the nylon resin is 215-220°C, the performance of the final nylon composite material will be improved more significantly. The reason may be that when the melting point is higher, the corresponding processing temperature is also higher, which will promote the reaction between DPP and the amide bond in nylon, resulting in enhanced yellow fluorescence, yellowing of the color, change in hue, and larger water-boiling color difference; when the melting point is lower, the intermolecular hydrogen bond force is weaker, and the change in the chemical environment in nylon will affect the coloring power of the color powder, resulting in a decrease in color vividness.

[0026] The melting point of the nylon resin described in the present invention is measured by differential scanning calorimetry.

[0027] As a preferred embodiment of the nylon composite material of the present invention, the nylon composite material further comprises the following components: 31-35 parts of glass fiber and 3-6 parts of toughening agent.

[0028] As a preferred embodiment of the nylon composite material of the present invention, the toughening agent is a copolymer of ethylene and an α-olefin containing 3-10 carbon atoms.

[0029] As a more preferred embodiment of the nylon composite material of the present invention, the toughening agent is maleic anhydride grafted ethylene-octene copolymer elastomer (POE-g-MAH); the melt flow rate of the toughening agent measured according to ASTM D1238 under the conditions of 190°C / 5 kg is 0.5-2 g / 10 min.

[0030] As a preferred embodiment of the nylon composite material of the present invention, the average diameter of the glass fiber is 8-12 um and the length is 2-5 mm.

[0031] As a preferred embodiment of the nylon composite material of the present invention, the nylon composite material further comprises 0.8-1.5 parts by weight of an auxiliary agent.

[0032] As a more preferred embodiment of the nylon composite material of the present invention, the auxiliary agent includes at least one of an antioxidant, a lubricant, and a light stabilizer.

[0033] As the most preferred embodiment of the nylon composite material of the present invention, the selected antioxidant preferably includes antioxidant 1098 and antioxidant 608; the lubricant includes an ester lubricant and a long-chain linear saturated carboxylate; the light stabilizer includes benzotriazole-based and hindered amine-based light stabilizers.

[0034] As a preferred embodiment of the nylon composite material of the present invention, the mass percentage content of the nylon resin in the nylon composite material is ≥54%.

[0035] In a second aspect, the present invention provides a method for preparing the above-mentioned nylon composite material, comprising the following steps:

[0036] S1. Weigh each component in the nylon composite material according to a proportion, mix them evenly to obtain a premix;

[0037] S2. Perform melt extrusion and pellet drying on the premix obtained in step S1 to obtain the nylon composite material.

[0038] As a preferred embodiment of the method for preparing the nylon composite material of the present invention, the nylon resin needs to be dried at a temperature of 110 - 120 °C for 2 - 4 h, and after being fully dried, it is mixed with other components.

[0039] In a third aspect, the present invention further provides the application of the above-mentioned nylon composite material in the preparation of the housing of power tools, especially in the preparation of railway electric wrenches.

[0040] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0041] By compounding perylene-based pigments and DPP pigments and adding them to nylon resin, the present invention can synergistically improve the color saturation of nylon materials, and still enable the final product to have a low fluorescence intensity when the dosage of DPP is low. The nylon composite resin prepared by the present invention has a low fluorescence intensity, a redder hue, a higher chromaticity value, and the color difference after boiling in water at 100 °C for 1 h is less than 1, which is of great significance for saving the coloring and color matching costs of nylon resin. Specific Embodiments

[0042] The following further illustrates the technical solutions of the present invention in conjunction with embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts fall within the scope of protection of the present invention; the methods or operations used in the embodiments, unless otherwise specified, are all conventional methods or conventional operations in the art.

[0043] In the embodiments, the materials, reagents, etc. used, unless otherwise specified, can be obtained from commercial channels.

[0044] In the embodiments and comparative examples of the present invention, the auxiliaries are compounded and used in a weight ratio of auxiliary 1: auxiliary 2: auxiliary 3: auxiliary 4 = 1:4:3:2.

[0045] The raw materials used in the embodiments and comparative examples are described as follows, but are not limited to these materials:

[0046] Nylon resin 1: Melting point 215 - 220 °C; HY - 2500A, Jiangsu Haiyang Technology Co., Ltd.

[0047] Nylon resin 2: Melting point 217 - 222 °C; PA6 J4001M, Hangzhou Juheshun New Materials Co., Ltd.

[0048] Nylon resin 3: Melting point 215 - 225 °C; PA6 BE3250, Jiangsu Hongsheng New Materials Co., Ltd.

[0049] Nylon resin 4: Melting point 185 °C; PA1012I1, Shandong Xianglong New Materials Co., Ltd.

[0050] Nylon resin 5: Melting point 260 °C; PA66 45A00, RADICI CHIMICA S.p.A (Radici Group).

[0051] Perylene - based pigment 1: Paliogen Red K 3911, BASF.

[0052] Perylene - based pigment 2: PV Fast Red B, Clariant Chemicals.

[0053] Perylene - based pigment 3: Paliogen Red K3580, BASF.

[0054] Perylene - based pigment 4: Hostaperm Red P2GL, Clariant Chemicals.

[0055] DPP pigment: Irgazin Red K 3840SQ, BASF.

[0056] White pigment 1: Cubic zinc sulfide, MX622, Guangdong Xinda New Materials Technology Co., Ltd.

[0057] White pigment 2: Antimony white, S - 05N, Changde Chenzhou Antimony Products Co., Ltd.

[0058] White pigment 3: Zinc oxide, BAO - 05, Zhuzhou Zexiang Industry Co., Ltd.

[0059] Glass fiber: Length 3 mm, diameter 10 μm, fiberglass ECS10 - 03 - 568H, Jushi Group Co., Ltd.

[0060] Toughening agent: Maleic anhydride - grafted ethylene - octene copolymer elastomer, melt flow rate under ASTM D1238 standard at 190 °C / 5 kg is 0.6 - 2.0 g / 10 min; PC - 28, Foshan Nanhai Baichen High - Molecular New Materials Co., Ltd.

[0061] Additive 1: Antioxidant 1098, RIANOX 1098, Tianjin Li'anlong New Materials Co., Ltd.

[0062] Additive 2: Antioxidant 608, Revonox 608, CBITEC.

[0063] Additive 3: ester lubricant, LOXIOL G 32, Emery Oleochemicals.

[0064] Additive 4: long-chain linear saturated carboxylic acid sodium salt lubricant, Licomont NAV101 PWD, Clariant.

[0065] Examples 1-17 and Comparative Examples 1-6

[0066] Examples 1-17 and Comparative Examples 1-6 are nylon composite materials of the present invention; the components and weight proportions of the nylon composite materials of Examples 1-17 and Comparative Examples 1-6 of the present invention are shown in Table 1-3.

[0067] The preparation method of the nylon composite material of Examples 1-17 and Comparative Examples 1-6 of the present invention comprises the following steps:

[0068] S1. Dry the nylon resin at 110-120° C. for 2-4 hours. After being fully dried, weigh the components in the nylon composite material in proportion, mix them evenly, and obtain a premix;

[0069] S2, melt-extrude, granulate and dry the premixed material in step S1 to obtain the nylon composite material; wherein the temperature of the melt-extrusion is 250-270°C.

[0070] Table 1

[0071]

[0072]

[0073]

[0074] Table 2

[0075]

[0076]

[0077] Table 3

[0078]

[0079] Effect example

[0080] The nylon composites described in Examples 1-17 and Comparative Examples 1-6 of the present invention were tested for relative fluorescence intensity, chromaticity, hue, and color difference:

[0081] (1) Relative fluorescence intensity: The fluorescence intensity was measured using a fluorescence spectrometer. Taking the fluorescence intensity of the sample in Comparative Example 6 as the reference value, the ratio of the fluorescence intensity of other samples to it was the relative fluorescence intensity value; the same test parameters were used for all samples.

[0082] (2) Hue (h): Hue h represents color information, that is, the position of the spectral color; this parameter is expressed in an angular measure, with a value range of 0° to 360°; if calculated counterclockwise starting from red, red is 0°, green is 120°, and blue is 240°. Their complementary colors are: yellow is 60°, cyan is 180°, and purple is 300°, and it was measured using a spectrophotometer.

[0083] (3) Chromaticity (c): Chromaticity c represents the purity of a color, also called saturation or chroma, usually in the range of 0-100%. The higher the chromaticity value, the more vivid the color, and it was measured using a spectrophotometer.

[0084] (4) Color difference ΔE: It refers to the difference in color perception between two samples, which includes differences in lightness, chroma, and hue. The larger the color difference value, the greater the color difference. It was calculated using the following formula, and the product was measured using a spectrophotometer after boiling in water at 100°C for 1 h.

[0085]

[0086] Among them, L represents the brightness of the color, a represents the red-green degree, and b represents the yellow-blue degree.

[0087] The test results are shown in Table 4.

[0088] Table 4

[0089]

[0090]

[0091] As can be seen from Table 4, when the technical solution of the present invention is adopted, the obtained nylon composite has a weak fluorescence intensity, a high color saturation, and a hue that is biased towards red; specifically, the relative fluorescence intensity of the nylon composite is less than 0.1, the chromaticity value is greater than 55, and the color difference after boiling in water at 100°C for 1 h is <1, and the color is stable.

[0092] Comparing Examples 1-5, it can be seen that the melting point of the nylon resin has a significant impact on the fluorescence intensity, hue, chromaticity, and color difference of the final nylon composite. When the melting point of the nylon resin used is in the range of 215-220 °C, the comprehensive performance of the final product is more excellent. Specifically, the relative fluorescence intensity is below 0.1, the hue is 28-30, the chromaticity > 57, and the color difference after boiling in water at 100 °C for 1 h is < 1.

[0093] Comparing Examples 1, 9-11 and Comparative Examples 1, 2, it can be seen that the weight fraction of the perylene-based pigment in the present invention has a very large impact on the fluorescence intensity, hue, chromaticity, and color difference of the final nylon composite. When the weight fraction of the perylene-based pigment is in the range of 0.5-0.7 parts, the obtained product can simultaneously have a weak fluorescence intensity and a high color saturation, and the hue is reddish. In Comparative Example 1, due to the too low weight fraction of the perylene-based pigment, the relative fluorescence intensity of the final product is strong, the hue of the product is yellowish, the chromaticity value is low, and the color difference of the product after boiling in water at 100 °C for 1 h > 1, and the color is unstable. In Comparative Example 2, due to the too high weight fraction of the perylene-based pigment, the hue of the final product is low, and the color saturation also differs greatly from that of the example.

[0094] Comparing Example 1 and Comparative Examples 3, 4, it can be seen that when the perylene-based pigment and the DPP pigment are used together in the present invention, the two can synergistically improve the saturation of the nylon material and make the finally prepared nylon composite have a low fluorescence intensity, and the lowest fluorescence intensity can be as low as 0.052. However, if the DPP pigment is used alone, it will cause a very high fluorescence intensity and a large color difference in the final product. If the perylene-based pigment is used alone, the hue cannot reach 28-30, and the color saturation of the product will also be greatly reduced.

[0095] Comparing Example 1 and Comparative Example 5, it can be seen that the white pigment in the present invention can also reduce the fluorescence intensity of the final product. At the same time, the addition of the white pigment can also improve the lightness of the product. In Comparative Example 5, since the white pigment is not added, the chromaticity of the final nylon composite is poor, and it also has different degrees of influence on the properties such as fluorescence intensity and chromaticity.

[0096] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention rather than to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A nylon composite material, characterized in that, The nylon composite material comprises the following components in parts by weight: 55 - 70 parts of nylon resin, 0.7 - 2 parts of white pigment, 0.1 - 0.7 parts of bis(p-chlorophenyl)-1,4-diketopyrrolo[3,4-c]pyrrole pigment, and 0.3 - 0.9 parts of perylene pigment; the perylene pigment is at least one of Paliogen Red K3911, PV Fast Red B, Paliogen Red K3580, and Hostaperm Red P2GL; the white pigment is at least one of zinc sulfide, antimony white, and zinc oxide; the mass ratio of the bis(p-chlorophenyl)-1,4-diketopyrrolo[3,4-c]pyrrole pigment to the perylene pigment is bis(p-chlorophenyl)-1,4-diketopyrrolo[3,4-c]pyrrole pigment:perylene pigment = 1:0.5 - 2.

2. The nylon composite material according to claim 1, characterized in that, The weight of the perylene pigment is 0.5 - 0.7 parts.

3. The nylon composite material according to claim 1, wherein The melting point of the nylon resin is 185 - 260 °C.

4. The nylon composite material according to claim 1, characterized in that, The melting point of the nylon resin is 215 - 225 °C.

5. The nylon composite material according to claim 1, wherein, The nylon composite material further comprises the following components: 31 - 35 parts of glass fiber and 3 - 6 parts of toughening agent.

6. The nylon composite material according to claim 5, wherein, The toughening agent is a copolymer of ethylene and an α-olefin containing 3 - 10 carbon atoms.

7. The nylon composite material according to claim 1, characterized in that, The nylon composite material further comprises 0.8 - 1.5 parts by weight of an auxiliary agent; the auxiliary agent includes at least one of antioxidant, lubricant, and light stabilizer.

8. The preparation method of the nylon composite material according to any one of claims 1-7, characterized in that, Comprising the following steps: S1. Weigh each component in the nylon composite material in proportion, mix evenly to obtain a premix. S2. Subject the premix obtained in step S1 to melt extrusion and granulation drying to obtain the nylon composite material.

9. Use of the nylon composite material according to any one of claims 1 - 7 in the preparation of an electric tool housing.

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