High-saturation fluorescent orange polyester composition as well as preparation method and application thereof

Abstract

The invention discloses a high-saturation fluorescent orange polyester composition as well as a preparation method and application thereof, and relates to the technical field of high polymer materials. The fluorescent orange polyester composition comprises aromatic polyester resin and perylene black dye. Aromatic polyester resin is adopted as a matrix, a specific amount of perylene black dye is added, and the pi-pi stacking effect between perylene black dye molecules is destroyed by a benzene ring molecular chain structure of the aromatic polyester resin through the strong conjugation effect with dye small molecules at a high temperature, so that the perylene black molecules are uniformly dispersed between polyarylate resin molecular chains, and the perylene black dye is prepared. And self-assembling with a benzene ring molecular chain structure of aromatic polyester resin through pi-pi conjugation to obtain the orange polyester composition with high temperature resistance, strong fluorescence, strong covering power and high brightness.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and more specifically to a high-saturation fluorescent orange polyester composition, a preparation method and application thereof. Background Art

[0002] Polyester resins, such as PET, PBT and PC, have a very wide range of application markets, and are in great demand in the fields of plastic bottles, electronic appliances, auto parts, mechanical equipment, etc. The coloring of polyester plastic products has always been the key to enhancing the value and recognition of products, especially the bright fluorescent orange.

[0003] Due to the high molding temperature of polyester resin, most fluorescent orange dyes currently have poor high temperature resistance. For example, azo orange dyes have high saturation and high tinting power, but can only be used for low-temperature dyeing of fabrics and are not suitable for dyeing polyester resin. Orange dyes with good high temperature resistance generally have poor fluorescence properties and low brightness.

[0004] For example, patent CN103275515A discloses an orange naphthyl ketone dye and a preparation method thereof, which is a single-structure, high-purity orange dye that can be used for dyeing engineering plastics such as polystyrene, ABS, polycarbonate, and polyester, and can also be used for pre-spinning coloring of polyester fibers, and has the characteristics of bright color, high transparency, and excellent fastness. However, the orange resin dyed with the orange naphthyl ketone dye does not have fluorescence, has low brightness, and has low hiding power, and needs to be supplemented with a large amount of titanium dioxide to supplement the real color. Summary of the invention

[0005] The purpose of the present invention is to overcome the defects and shortcomings of the existing orange polyester resin and provide a fluorescent orange polyester composition with the characteristics of high saturation, high brightness, strong fluorescence and high hiding power.

[0006] Another object of the present invention is to provide a method for preparing the fluorescent orange polyester composition.

[0007] Another object of the present invention is to provide a fluorescent orange polyester composition for use in preparing an automobile interior door panel, an electric tool housing or a robot arm housing.

[0008] The above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0009] The present invention protects a fluorescent orange polyester composition, comprising the following components in parts by weight:

[0010] Aromatic polyester resin 97-99.9 parts, dye 0.01-0.3 parts, antioxidant 0-2 parts, dispersant 0-5 parts;

[0011] The dye is a perylene black dye, and the structural formula of the perylene black dye is shown in the following formula (I);

[0012]

[0013] In the fluorescent orange polyester composition provided by the present invention, an aromatic polyester resin is used as a matrix, a specific amount of perylene black dye is added, and at high temperature, the benzene ring molecular structure on the main molecular chain of the aromatic polyester resin utilizes a strong conjugation effect with small dye molecules to destroy the II-II stacking effect between perylene black dye molecules, so that the perylene black molecules are uniformly dispersed between the molecular chains of the polyarylate resin, and are self-assembled with the benzene ring molecular chain structure of the aromatic polyester resin through II-II conjugation, so that the originally black perylene black dye is dispersed in the aromatic polyester resin to present a bright orange color and has strong fluorescence, thereby obtaining an orange polyester composition with high temperature resistance, strong fluorescence, strong covering power and high brightness.

[0014] In some embodiments, the minimum mass fraction of the aromatic polyester resin in the high-saturation fluorescent orange polyester composition is 97%.

[0015] In some embodiments, the content of the aromatic polyester resin that can meet the purpose of the invention includes: 97 parts, 97.5 parts, 98 parts, 98.5 parts, 99 parts, 99.5 parts or 99.9 parts or above.

[0016] In some embodiments, the content of perylene black dye that can meet the purpose of the invention includes: 0.01 part, 0.02 part, 0.03 part, 0.04 part, 0.05 part, 0.06 part, 0.07 part, 0.08 part, 0.09 part, 0.10 part, 0.11 part, 0.12 part, 0.13 part, 0.14 part, 0.15 part, 0.16 part, 0.17 part, 0.18 part, 0.19 part, 0.20 part, 0.21 part, 0.22 part, 0.23 part, 0.24 part, 0.25 part, 0.26 part, 0.27 part, 0.28 part, 0.29 part or 0.3 part or the range between the above values.

[0017] The aromatic polyester resin described in the present invention refers to a polyester resin containing a benzene ring structure on the main molecular chain; in some embodiments, the aromatic polyester resin is one or more of bisphenol A polycarbonate (PC), polybutylene terephthalate (PBT) or polyethylene terephthalate (PET).

[0018] The present invention has no special requirements for bisphenol A polycarbonate (PC); preferably, the bisphenol A polycarbonate has a melt flow rate of 5-30 g / 10 min at 1.2 kg and 300° C., and the test standard is ISO1133.

[0019] The present invention has no special requirements for polyethylene terephthalate (PBT); preferably, the intrinsic viscosity of the polyethylene terephthalate is 0.6-1.2 dL / g; more preferably, 0.8-1 dL / g.

[0020] The present invention has no special requirements for polybutylene terephthalate (PET); preferably, the intrinsic viscosity of the polybutylene terephthalate is 0.6-1.2 dL / g; more preferably, it is 0.8-1 dL / g.

[0021] In some embodiments, the composition is composed of the following components in parts by weight:

[0022] 99.3-99.7 parts of aromatic polyester resin, 0.08-0.22 parts of perylene black dye, 0.1-2 parts of antioxidant, 0.1-2 parts of dispersant. In some embodiments, the dispersant is one or more of zinc stearate, calcium stearate, magnesium stearate, polyethylene wax or oxidized polyethylene wax.

[0023] In some embodiments, the antioxidant is a hindered phenol antioxidant and / or a phosphite antioxidant.

[0024] Preferably, the antioxidant is a hindered phenol antioxidant and / or a phosphite antioxidant in a mass ratio of 1:(0.5-2).

[0025] Preferably, the composition may also contain additives commonly used in the field of engineering plastics processing, including but not limited to: 3-10 parts of flame retardant and 2-3 parts of toughening agent.

[0026] The invention discloses a method for preparing a high-saturation fluorescent orange polyester composition, comprising the following steps: uniformly mixing the raw material components in the formula, performing melt blending and extrusion granulation to obtain the high-saturation fluorescent orange polyester composition.

[0027] In some embodiments, the raw material components are dispersed at a high speed of 300-500 rpm before melt blending.

[0028] In some embodiments, the melt blending temperature is 210-250°C.

[0029] In some embodiments, the rotation speed of the melt blending is 300-600 rpm.

[0030] In some embodiments, the melt blending is performed using a twin-screw extruder with a screw length-to-diameter ratio of 36 to 44:1.

[0031] The present invention protects the use of a fluorescent orange polyester composition in preparing an automobile interior door panel, an electric tool housing or a mechanical arm housing.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] The present invention provides a fluorescent orange polyester composition, which uses an aromatic polyester resin as a matrix, adds a specific amount of perylene black dye, and the benzene ring molecular chain structure of the aromatic polyester resin at high temperature utilizes a strong conjugation effect with a small dye molecule to destroy the Π-Π stacking effect between perylene black dye molecules, so that the perylene black molecules are uniformly dispersed between the polyarylate resin molecular chains, and self-assemble with the benzene ring molecular chain structure of the aromatic polyester resin through Π-Π conjugation, thereby obtaining a high temperature resistant, high fluorescence intensity and high brightness orange polyester composition. The composition has a strong covering power, can significantly reduce the light transmittance and improve the anti-aging performance when a small amount is added, and can effectively reduce the addition of auxiliary materials such as titanium dioxide when preparing products for application in the subsequent process. DETAILED DESCRIPTION

[0034] The present invention is further described below in conjunction with specific embodiments, but the embodiments do not limit the present invention in any form. Unless otherwise specified, the raw materials and reagents used in the embodiments of the present invention are conventionally purchased raw materials and reagents.

[0035] The raw materials used in the following examples and comparative examples are as follows:

[0036] Aromatic polyester resin:

[0037] Polycarbonate 1# (PC 1#): OFG CH8225, Cangzhou Dahua Co., Ltd.; 300°C, 1.2kg melt flow rate is 20.5g / 10min, test standard ISO1133.

[0038] Polycarbonate 2# (PC 2#): PC S1240, Wanhua Chemical (Yantai) Sales Co., Ltd.; 300°C, 1.2kg melt flow rate is 6g / 10min, test standard ISO1133.

[0039] Polyethylene terephthalate 1# (PET 1#): CR-8863, Dongguan Guoju Plastic Raw Materials Co., Ltd.; intrinsic viscosity 0.81 dL / g.

[0040] Polyethylene terephthalate 2# (PET 2#): PET BG85 brand, Sinopec Yizheng Chemical Fiber Co., Ltd.; intrinsic viscosity 0.86 dL / g.

[0041] Polybutylene terephthalate 1# (PBT 1#): PBT CH883, Zhejiang Changhong Biomaterial Co., Ltd.; intrinsic viscosity 1.00 dL / g.

[0042] Polybutylene terephthalate 2# (PBT 2#): KB718 HF, Zhuhai Jinfa Biomaterial Co., Ltd.; intrinsic viscosity 0.85 dL / g.

[0043] Aliphatic resins:

[0044] Polyamide: PA6 BL3240, Sinopec Hunan Petrochemical Co., Ltd.

[0045] Polypropylene: Moplen HP400H, ASELL ASIA PACIFIC LIMITED; 230°C, 2.16kg, melt flow rate: 2g / 10min, test standard: ISO1133.

[0046] Polyethylene: PE LL20200, SIBUR International Trading (Shanghai) Co., Ltd.; 190°C, 2.16kg, melt flow rate 2g / 10min, test standard ISO1133-1.

[0047] Polylactic acid (PLA): PLA FY804, Zhuhai Jinfa Biotechnology Co., Ltd.; 190°C, 2.16kg, melt flow rate 4g / 10min.

[0048] Polystyrene (HIPS): HIPS STL 888GH, Lianyungang Petrochemical Co., Ltd.; 200°C, 5kg, melt flow rate: 3.7g / 10min.

[0049] Antioxidant: Antioxidant 1010 and Antioxidant 168 mixed in a mass ratio of 1:1, commercially available.

[0050] Dispersant: PETS-AP, Shanghai Chengzaicheng Chemical Co., Ltd.

[0051] Perylene black dye 1#: Black L 0086, BASF, Germany.

[0052] Perylene black dye 2#: Lumogen K0088, from BASF, Germany.

[0053] Perylene orange fluorescent agent: Lumogen F-240, Beijing Guangwen Fine Chemical Research Institute.

[0054] Flame retardant: brominated epoxy resin, EP-25K, Xingsheng Chemical Company.

[0055] Toughening agent: GT-RE, Xingte Plastics Co., Ltd.

[0056] The preparation method of the high-saturation fluorescent orange polyester composition of the embodiment and the comparative example comprises the following steps: uniformly mixing the raw material components of the formula amount by a high-speed mixer, melt blending by a twin-screw extruder, and extruding and granulating to obtain the high-saturation fluorescent orange polyester composition. The twin-screw extruder has a screw length-to-diameter ratio of 40:1, a processing temperature of 210-250°C, and a rotation speed of 450rpm.

[0057] Examples 1 to 20

[0058] This embodiment provides a series of high-saturation fluorescent orange polyester compositions, and the raw material components thereof are shown in Tables 1-3 in parts by mass.

[0059] Table 1

[0060]

[0061] Table 2

[0062]

[0063] Table 3

[0064]

[0065] Comparative Examples 1 to 14

[0066] This comparative example provides a series of high-saturation fluorescent orange polyester compositions, and the raw material components thereof are shown in Tables 4-5 in parts by mass.

[0067] Table 4

[0068]

[0069] Table 5

[0070]

[0071]

[0072] Performance Testing

[0073] The high-saturation fluorescent orange polyester compositions of the above examples and comparative examples were subjected to color tests, real color tests, fluorescence intensity tests and anti-aging performance tests. The results are shown in Tables 6-7.

[0074] The test method is as follows:

[0075] Color test: The polyester composition and the aliphatic composition were injection molded into products of 12*10*2 cm. The color information of the polyester composition and the aliphatic composition was detected at 25°C using Datacolor, Spectro1050 equipment. The detection wavelength was 360nm~750nm. The detection items were: L*a*b* values ​​of the color plate.

[0076] Real color test (visible light transmittance test): The polyester composition and the aliphatic composition were injection molded into 12*10*2cm products. The transmittance of the polyester composition and the aliphatic composition was tested at 25°C using a Hangzhou Yuanfang HAM-300 haze meter. The detection wavelength was 380nm~780nm.

[0077] Fluorescence intensity comparison test: The polyester composition and the aliphatic composition were injection molded into a 12*10*2cm color plate. After being placed at room temperature for 12 hours, the color plate was placed under the UV light source of Changzhou Qianming Lighting Box to visually compare the fluorescence intensity of the polyester composition using perylene black dye and the ordinary orange color powder polyester composition, and visually compare the fluorescence intensity of the polyester composition using perylene black dye and the perylene black dye aliphatic polymer.

[0078] The fluorescence intensity is divided into four levels: strong, medium-strong, weak, and no fluorescence according to the strength of the visual fluorescence effect.

[0079] Anti-aging performance: Xenon lamp aging is carried out in accordance with ISO 4892-2:2013 test method, the test time is 200h, and the color difference △E of the color plate before and after aging is detected; △E≤2.0 is required.

[0080] Table 6

[0081]

[0082]

[0083] Table 7

[0084]

[0085]

[0086] It can be seen from the above table that in the high-saturation fluorescent orange polyester composition of the present invention, when the matrix is ​​PC resin, the La*b* value L* is above 51.4, a* is above 40.5, and b* is above 48.3, which has higher saturation and vividness; the light transmittance is below 80.2%, and the hiding power is high; the fluorescence intensity is above medium-strong, and the anti-aging performance △E≤1.6.

[0087] When the matrix is ​​PET resin, the La*b* value L* is above 60.5, a* is above 49.5, and b* is above 32.4, with high saturation and vividness; the transmittance is below 20.5%, with high hiding power; the fluorescence intensity is above medium strong, and the anti-aging performance △E≤1.5.

[0088] When the matrix is ​​PBT resin, the La*b* value L* is above 52.1, a* is above 40.8, and b* is above 35.3, with high saturation and vividness; the transmittance is below 21.8%, with high hiding power; the fluorescence intensity is above medium strong, and the anti-aging performance △E≤1.7.

[0089] When the substrate in Comparative Examples 1-3 is polyamide, polypropylene or polyethylene, it is black, has no fluorescent properties, and has a low La*b* value.

[0090] When perylene black dye 2 is used in Comparative Examples 4-6, it is black and has no fluorescent properties; when perylene orange fluorescent agents are used in Comparative Examples 7-9, compared with the high-saturation fluorescent orange polyester composition of the present invention, when the same amount of dye is added to the same matrix, its fluorescent properties are poor, the light transmittance is large, and the anti-aging performance is poor.

[0091] When the perylene black dye is used in excess in Comparative Examples 10-12, it is black and has no fluorescent properties. The reason is that the π-π stacking effect between molecules causes the dye to aggregate in the resin, which manifests as fluorescence quenching.

[0092] When the matrix in Comparative Examples 13-14 is made of PLA or HIPS, it is black and has no fluorescent properties.

[0093] The above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A fluorescent orange polyester composition, characterized in that: The composition comprises the following components in parts by weight: Aromatic polyester resin 97-99.9 parts, dye 0.01-0.3 parts, antioxidant 0-2 parts, dispersant 0-5 parts; The dye is a perylene black dye, and the structural formula of the perylene black dye is shown in the following formula (I); 2. The fluorescent orange polyester composition according to claim 1, characterized in that: The aromatic polyester resin is one or more of bisphenol A polycarbonate, polybutylene terephthalate or polyethylene terephthalate.

3. The fluorescent orange polyester composition according to claim 2, characterized in that: The bisphenol A polycarbonate has a melt flow rate of 5-30 g / 10 min at 1.2 kg and 300° C.

4. The fluorescent orange polyester composition according to claim 2, characterized in that: The intrinsic viscosity of the polyethylene terephthalate is 0.6-1.2 dL / g; and / or, The intrinsic viscosity of the polybutylene terephthalate is 0.6-1.2 dL / g.

5. The fluorescent orange polyester composition according to claim 1, characterized in that: It is composed of the following components in parts by weight: Aromatic polyester resin 99.3-99.7 parts, perylene black dye 0.08-0.22 parts, antioxidant 0.1-2 parts, dispersant 0.1-2 parts.

6. The fluorescent orange polyester composition according to claim 1 or 5, characterized in that: The dispersant is one or more of zinc stearate, calcium stearate, magnesium stearate, polyethylene wax or oxidized polyethylene wax.

7. The fluorescent orange polyester composition according to claim 1 or 5, characterized in that: The antioxidant is a hindered phenol antioxidant and / or a phosphite antioxidant.

8. A method for preparing the fluorescent orange polyester composition according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: uniformly mixing the raw material components in the formula amount, performing melt blending and extrusion granulation to obtain the fluorescent orange polyester composition.

9. The method for preparing the fluorescent orange polyester composition according to claim 7, characterized in that: The temperature of the melt blending is 210-250°C.

10. Use of the fluorescent orange polyester composition according to any one of claims 1 to 6 in the preparation of automobile interior door panels, power tool housings or robot arm housings.

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