A pet matt master batch and its preparation method and application

Abstract

The application discloses PET matte master batches, a preparation method and application thereof, and belongs to the field of functional material modification. Barium sulfate is used as an extinction agent, the volume density of the barium sulfate is large, the barium sulfate can be well mixed with resin, the problem of layered mixing is solved, the color of the barium sulfate itself is white, and the color of the master batch is not affected. Moreover, the barium sulfate is compounded with organic modified layered silicate to produce a synergistic effect, the light transmittance is effectively improved, a high light transmittance, high haze and high gloss film product is successfully prepared, and the film product can be applied to high-end industries.

Description

Technical Field

[0001] This invention belongs to the field of functional material modification technology, specifically relating to a PET matte masterbatch, its preparation method, and its application. Background Technology

[0002] Polyethylene terephthalate (PET) is a thermoplastic resin with advantages such as high strength, good dimensional stability, and excellent chemical and dielectric properties. It has been widely used in fiber, film, packaging, electronics, medical and health, construction, and automotive industries. Matte fibers and matte films represent one direction for the functionalization of PET and have wide applications in practical life and production, thus attracting extensive research.

[0003] Current research on matte masterbatches primarily uses silica as the matting agent, or silica is used in combination with matting resin. During mixing and feeding, silica and PET resin can separate, leading to uneven silica content in the masterbatch. Alternatively, additional additives can be added to bind the silica and resin together, but these additives may affect the color of the matte masterbatch. When using silica as a matting agent, its addition to the masterbatch is limited to a maximum of 25%, a relatively low content. Downstream applications require the addition of large amounts of matte masterbatch to achieve the desired effect, increasing downstream costs and resulting in more secondary melting of the masterbatch, which also affects the strength of the finished product. To increase the matting agent content in the matte masterbatch, silica is synergistically combined with modified matting resin. However, modified matting resin is expensive, and compatibility issues with PET need to be addressed. Furthermore, while matte products prepared using silica as a matting agent have good haze, their light transmittance and gloss are low, affecting the product's performance.

[0004] Barium sulfate has a refractive index similar to that of PET, therefore, matte products made using barium sulfate not only have good haze but also good light transmittance and haze. Currently, commercially available barium sulfate matte masterbatches suffer from problems such as small barium sulfate particle size and low concentration. Small barium sulfate particle size leads to agglomeration, and poor dispersion of barium sulfate in the masterbatch affects the matte effect. Low barium sulfate concentration requires large amounts to be added downstream, resulting in a large amount of masterbatch from secondary melting, which can affect the strength and other properties of downstream products. Summary of the Invention

[0005] The purpose of this section is to outline some aspects of embodiments of the present invention and to briefly describe some preferred embodiments. Simplifications or omissions may be made in this section, as well as in the abstract and title of this application, to avoid obscuring the purpose of these documents; however, such simplifications or omissions should not be construed as limiting the scope of the invention.

[0006] In view of the problems existing in the above and / or prior art, the present invention is proposed.

[0007] Therefore, the purpose of this invention is to overcome the shortcomings of the prior art and provide a matte PET masterbatch.

[0008] To solve the above-mentioned technical problems, the present invention provides the following technical solution: the masterbatch, by mass parts, comprises,

[0009] The mixture comprises 40-50 parts of polymeric resin, 40-60 parts of matting agent, 0-5 parts of dispersant, and 1-10 parts of organic modified lamellar silicate; wherein the matting agent is barium sulfate with a particle size of 2-10 μm.

[0010] As a preferred embodiment of the PET matte masterbatch of the present invention, wherein: the polymer resin is polyethylene terephthalate; and the dispersant includes one or more of montan wax, polyethylene wax, polyethylene oxide, polyvinylidene fluoride, polyimide, chitosan, polyethyleneimine, and polyvinyl alcohol.

[0011] As a preferred embodiment of the PET matte masterbatch of the present invention, wherein: the organic modified lamellar silicate is montmorillonite modified with a cationic surfactant, wherein the cationic surfactant includes one or more of hexadecyltrimethylammonium bromide, octadecyldimethylbenzylammonium chloride, octadecyltrimethylammonium chloride, and dodecyltrimethylammonium chloride, and the montmorillonite includes one or more of calcium-based montmorillonite, sodium-based montmorillonite, sodium-calcium-based montmorillonite, or magnesium-based montmorillonite.

[0012] As a preferred embodiment of the PET matte masterbatch of the present invention, the ratio of the matting agent to the organic modified lamellar silicate is 14 to 34:1.

[0013] The purpose of this invention is to overcome the shortcomings of the prior art and provide a method for preparing PET matte masterbatch.

[0014] To solve the above-mentioned technical problems, the present invention provides the following technical solution: including,

[0015] The dried polymer resin, matting agent, nano-sized organic modified lamellar silicate, and dispersant are fed into a vibrating mixer for mixing to obtain a pre-dispersed mixture. The pre-dispersed mixture is fed into the main feed port of an extruder for melt extrusion and pelletizing to obtain matte masterbatch.

[0016] In a preferred embodiment of the preparation method of the PET matte masterbatch of the present invention, the drying process includes a drying temperature of 105-120°C and a drying time of 3-5 hours.

[0017] In a preferred embodiment of the preparation method of the PET matte masterbatch of the present invention, the vibration frequency of the vibrating mixer is 20-50 Hz.

[0018] In a preferred embodiment of the method for preparing the matte PET masterbatch of the present invention, the feeding speed of the extruder is 12-18 kg / h, and the rotation speed of the main motor of the extruder is 250-350 r / min.

[0019] In a preferred embodiment of the method for preparing the matte PET masterbatch of the present invention, the process temperatures of each zone from the screw inlet to the extruder die are as follows: Zone 1: 260–280°C; Zone 2: 260–280°C; Zone 3: 260–280°C; Zone 4: 260–280°C; Zone 5: 200–240°C; Zone 6: 180–220°C; Zone 7: 180–220°C; Zone 8: 180–220°C; Zone 9: 180–220°C; Zone 10: 180–220°C; Zone 11: 200–240°C; and the die temperature is 240–265°C.

[0020] The purpose of this invention is to overcome the shortcomings of the prior art and provide an application of PET matte masterbatch in the preparation of matte fibers and matte films.

[0021] Beneficial effects of this invention:

[0022] (1) When barium sulfate is used as a matting agent, its bulk density is high and it can be mixed well with the resin, which solves the problem of material separation. The color of barium sulfate itself is white and will not affect the color of the masterbatch.

[0023] (2) Increase the concentration of barium sulfate in the masterbatch to solve the problem of large usage of matte masterbatch and reduce downstream usage costs.

[0024] (3) Barium sulfate and organic modified lamellar silicate are combined to produce a synergistic effect, which effectively improves the light transmittance and produces thin film products with high light transmittance, high haze and high gloss, which are applied in high-end industries. Attached Figure Description

[0025] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. Wherein:

[0026] Figure 1 This is a comparison image of the barium sulfate matte film prepared in Example 1 and the matte film prepared from commercially available barium sulfate matte masterbatch. Detailed Implementation

[0027] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the examples in the specification.

[0028] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0029] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that is mutually exclusive with other embodiments.

[0030] Unless otherwise specified, all raw materials used in this invention are commercially available.

[0031] The intrinsic viscosity of the PET chips used in this invention is 0.82 dL / g.

[0032] The method for testing the filtration performance of matte PET masterbatch is as follows:

[0033] Weigh out 1 part PET matte masterbatch and 1 part polyester chips, mix them manually until homogeneous, and then put them into a filtration performance testing machine to test the filtration pressure rise value. The temperature range is set to 280-290℃, the filter mesh size is 1400 mesh, and the total weight of the masterbatch is 3kg. During the test, if the filtration pressure rise value is greater than 4, the masterbatch sample is considered unqualified, and the filtration pressure rise value test is stopped.

[0034] The intrinsic viscosity of matte PET masterbatch was tested according to the capillary viscometer method in GB / T 14190-2017 "Test Method for Film Grade Polyester (PET) Chips" 5.1.1.

[0035] The testing methods for PET matte film are as follows:

[0036] Sampling was performed according to section 4.2 of GB / T 2410-2008 "Determination of transmittance and haze of transparent plastics", and the test was conducted using method B of the spectrophotometer in section 7.2. Gloss was measured using a 60° tester.

[0037] Example 1

[0038] (1) PET slices, D(50) 2.5μm barium sulfate, dried at 105℃ for 4h.

[0039] (2) Sodium-based montmorillonite was placed in distilled water to prepare a 10% suspension. A 2.5% aqueous solution of hexadecyltrimethylammonium bromide (CTAB) was slowly added to the montmorillonite dispersion system. The mixture was stirred continuously at 70°C for 5 hours. After the reaction was complete, the mixture was washed and dried to obtain CTAB-modified sodium-based montmorillonite, which is an organically modified lamellar silicate.

[0040] (3) Weigh 45 parts of PET chips, 50 parts of D(50)2.5μm barium sulfate, 2.5 parts of polyimide, and 2.5 parts of organic modified lamellar silicate. Mix them in a vibrating mixer with a vibration frequency of 35HZ to obtain a pre-dispersed mixture.

[0041] (4) The pre-dispersed mixture is fed into a co-rotating twin-screw extruder at a rate of 15 kg / h. The main motor of the screw extruder rotates at 300 r / min for melt extrusion. The process temperatures of each zone from the screw inlet to the extruder die are as follows: Zone 1: 270℃, Zone 2: 270℃, Zone 3: 270℃, Zone 4: 270℃, Zone 5: 220℃, Zone 6: 200℃, Zone 7: 200℃, Zone 8: 200℃, Zone 9: 200℃, Zone 10: 200℃, Zone 11: 220℃, and the die temperature is 255℃ to obtain matte masterbatch.

[0042] (5) 20 parts of matte masterbatch and 80 parts of PET chips were mixed evenly and then cast and biaxially stretched to obtain a film with a thickness of 50 μm.

[0043] Figure 1 The image shows a comparison between the barium sulfate matte film prepared in this embodiment and the matte film prepared from commercially available barium sulfate matte masterbatch. It can be seen that the barium sulfate matte film prepared in this embodiment has both good light transmittance and haze.

[0044] Example 2

[0045] The difference between this embodiment and Example 1 is that the D(50)2.5μm barium sulfate is adjusted to D(50)3.5μm barium sulfate, while the rest of the preparation process is the same as in Example 1, and barium sulfate matte masterbatch and film are obtained.

[0046] Example 3

[0047] The difference between this embodiment and Example 1 is that the barium sulfate with D(50)2.5μm is adjusted to barium sulfate with D(50)4.5μm. The rest of the preparation process is the same as in Example 1, and barium sulfate matte masterbatch and film are obtained.

[0048] Example 4

[0049] The difference between this embodiment and Example 1 is that the D(50)2.5μm barium sulfate is adjusted to D(50)5.5μm barium sulfate, while the rest of the preparation process is the same as in Example 1, and barium sulfate matte masterbatch and film are obtained.

[0050] Example 5

[0051] The difference between this embodiment and Example 1 is that the D(50)2.5μm barium sulfate is adjusted to D(50)7μm barium sulfate, while the rest of the preparation process is the same as in Example 1, and barium sulfate matte masterbatch and film are obtained.

[0052] Comparative Example 1

[0053] (1) PET slices, D(50) 2.5μm silica, dried at 105℃ for 4h.

[0054] (2) Weigh 78 PET chips, 20 D(50) 2.5μm silica and 2 polyimide, mix them in a vibrating mixer with a vibration frequency of 35HZ to obtain a pre-dispersed mixture.

[0055] (3) The pre-dispersed mixture is fed into a co-rotating twin-screw extruder at a speed of 15 kg / h. The main motor of the screw extruder rotates at 300 r / min for melt extrusion. The process temperatures of each zone from the screw inlet to the extruder die are as follows: Zone 1: 270℃, Zone 2: 270℃, Zone 3: 270℃, Zone 4: 270℃, Zone 5: 220℃, Zone 6: 200℃, Zone 7: 200℃, Zone 8: 200℃, Zone 9: 200℃, Zone 10: 200℃, Zone 11: 220℃, and the die temperature is 255℃ to obtain matte masterbatch.

[0056] (4) Mix 50 parts of matte masterbatch and 50 parts of PET chips evenly, and then cast and biaxially stretch to obtain a film with a thickness of 50 μm.

[0057] Comparative Example 2

[0058] The difference between this comparative example and Comparative Example 1 is that the D(50)2.5μm silicon dioxide was adjusted to D(50)3.5μm silicon dioxide. The rest of the preparation process is the same as that of Comparative Example 1, and matte masterbatch and film are obtained.

[0059] Comparative Example 3

[0060] The difference between this comparative example and Comparative Example 1 is that the D(50)2.5μm silicon dioxide was adjusted to D(50)4.5μm silicon dioxide. The rest of the preparation process is the same as that of Comparative Example 1, and matte masterbatch and film are obtained.

[0061] Comparative Example 4

[0062] The difference between this comparative example and comparative example 1 is that the D(50)2.5μm silicon dioxide was adjusted to D(50)5.5μm silicon dioxide. The rest of the preparation process is the same as that of comparative example 1, and matte masterbatch and film are obtained.

[0063] Comparative Example 5

[0064] The difference between this comparative example and comparative example 1 is that the D(50)2.5μm silicon dioxide was adjusted to D(50)7μm silicon dioxide, while the rest of the preparation process was the same as that of comparative example 1, and matte masterbatch and film were obtained.

[0065] The barium sulfate matte masterbatch prepared in the above examples and the silica masterbatch prepared in the comparative example were tested for filtration pressure and viscosity. The haze, transmittance and gloss of the prepared films were tested. The comparison results with Example 1 are shown in Table 1.

[0066] Table 1

[0067]

[0068] As shown in Table 1, the filtration pressure and intrinsic viscosity first decrease and then increase with the increase of barium sulfate particle size. This is because when the particle size is small, barium sulfate agglomerates, resulting in uneven dispersion. When the particle size is large, the filtration pressure increases. Comparing Examples 1-5 and Comparative Examples 1-5, it can be seen that the barium sulfate content in the masterbatch is 30% higher than that in silicon dioxide, but the filtration pressure of the barium sulfate masterbatch is superior to that of the silicon dioxide masterbatch. When barium sulfate and silicon dioxide have the same particle size and the same content in the film, their haze is similar, but in terms of transmittance and gloss, the film containing barium sulfate is significantly superior to the film containing silicon dioxide.

[0069] Example 6

[0070] The difference between this embodiment and Example 3 is that the content of barium sulfate is adjusted to 49 parts, the content of organic modified lamellar silicate is 3.5 parts, and the rest of the preparation process is the same as in Example 1, so as to obtain barium sulfate matte masterbatch and film.

[0071] Example 7

[0072] The difference between this embodiment and Example 3 is that the content of barium sulfate is adjusted to 51 parts, the content of organic modified lamellar silicate is 1.5 parts, and the rest of the preparation process is the same as in Example 1, so as to obtain barium sulfate matte masterbatch and film.

[0073] Comparative Example 6

[0074] The difference between this embodiment and Example 3 is that the content of barium sulfate is adjusted to 52.5 parts, and no organic modified lamellar silicate is added. The rest of the preparation process is the same as in Example 1, and barium sulfate matte masterbatch and film are obtained.

[0075] The barium sulfate matte masterbatch prepared in the above examples and comparative examples was tested for filtration pressure and viscosity. The haze, transmittance and gloss of the prepared film were tested. The comparison results with Example 3 are shown in Table 2.

[0076] Table 2

[0077]

[0078] As shown in the table above, adjusting the ratio of barium sulfate to organically modified lamellar silicate affects the performance of both the prepared barium sulfate matte masterbatch and the film. The lamellar structure of the organically modified lamellar silicate can work synergistically with barium sulfate to enhance light scattering; both excessively high and low ratios will lead to unsatisfactory scattering effects and affect product performance.

[0079] Example 8

[0080] The difference between this embodiment and Example 3 is that the modifier of sodium montmorillonite is changed to octadecyl dimethyl benzyl ammonium chloride, while the rest of the preparation process is the same as in Example 1, to obtain barium sulfate matte masterbatch and film.

[0081] Example 9

[0082] The difference between this embodiment and Example 3 is that the modifier of sodium montmorillonite is changed to dodecyltrimethylammonium chloride, while the rest of the preparation process is the same as in Example 1, to obtain barium sulfate matte masterbatch and film.

[0083] Comparative Example 7

[0084] The difference between this embodiment and Example 3 is that no modifier is added, but the rest of the preparation process is the same as in Example 1, and barium sulfate matte masterbatch and film are obtained.

[0085] The barium sulfate matte masterbatch prepared in the above examples and comparative examples was tested for filtration pressure and viscosity. The haze, transmittance and gloss of the prepared film were tested. The comparison results with Example 3 are shown in Table 3.

[0086] Table 3

[0087]

[0088] As shown in the table above, changing the type of modifier affects the properties of the prepared film. The type of modifier affects its effective dispersion in the polymer matrix, which may lead to filler aggregation or uneven local concentration, thereby increasing light scattering and refraction, reducing light transmittance, increasing haze, and reducing gloss.

[0089] This invention discloses a matte PET masterbatch, its preparation method, and its applications, belonging to the field of functional material modification. When using barium sulfate as a matting agent, its high bulk density allows for excellent mixing with the resin, solving the problem of material separation during mixing. Furthermore, barium sulfate itself is white and will not affect the color of the masterbatch. With a refractive index of 1.63 and PET's 1.65, the similar refractive indices improve light transmittance, successfully producing film products with high light transmittance, high haze, and high gloss, suitable for application in high-end industries.

[0090] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A PET matte masterbatch, characterized by: The master batch, in mass parts, comprises, 40-50 parts of high molecular polymer resin, 40-60 parts of matting agent, 0-5 parts of dispersant, and 1-10 parts of organic modified layered silicate; The matting agent is barium sulfate with a particle size of 2-10 microns. The organic modified layered silicate is montmorillonite modified by a cationic surfactant, wherein the cationic surfactant comprises one or more of cetyltrimethylammonium bromide, octadecyl dimethyl benzyl ammonium chloride, octadecyl trimethyl ammonium chloride, and dodecyl trimethyl ammonium chloride; and the montmorillonite comprises one or more of calcium-based montmorillonite, sodium-based montmorillonite, sodium-calcium-based montmorillonite, and magnesium-based montmorillonite. The ratio of the matting agent to the organic modified layered silicate is 14-34:

1.

2. The PET matte masterbatch of claim 1, wherein: The high molecular polymer resin is polyethylene terephthalate; and the dispersant comprises one or more of montan wax, polyethylene wax, polyethylene oxide, polyvinylidene fluoride, polyimide, chitosan, polyethylene imine, and polyvinyl alcohol.

3. The process for the preparation of PET matt masterbatch as claimed in claim 1 wherein: The method comprises, The high molecular polymer resin and the matting agent, the nanoscale organic modified layered silicate, and the dispersant are put into a vibration mixer to mix and obtain a pre-dispersed mixture; and the pre-dispersed mixture is put into a main feeding port of an extruder to be melt-extruded and pelletized to obtain the matte master batch.

4. The process for the preparation of PET matt masterbatch as claimed in claim 3 wherein: The drying is performed at a temperature of 105-120 degrees Celsius for 3-5 hours.

5. The process for the preparation of PET matt masterbatch as claimed in claim 3 wherein: The vibration frequency of the vibration mixer is 20-50 HZ.

6. The process for the preparation of PET matt masterbatch as claimed in claim 3 wherein: The feeding speed of the extruder is 12-18 kg / h, and the rotation speed of the main motor of the extruder is 250-350 r / min.

7. The process for the preparation of PET matt masterbatch as claimed in claim 3 wherein: The process temperature of each zone from the screw inlet to the die outlet of the extruder is as follows: the temperature of the first zone is 260-280 degrees Celsius, the temperature of the second zone is 260-280 degrees Celsius, the temperature of the third zone is 260-280 degrees Celsius, the temperature of the fourth zone is 260-280 degrees Celsius, the temperature of the fifth zone is 200-240 degrees Celsius, the temperature of the sixth zone is 180-220 degrees Celsius, the temperature of the seventh zone is 180-220 degrees Celsius, the temperature of the eighth zone is 180-220 degrees Celsius, the temperature of the ninth zone is 180-220 degrees Celsius, the temperature of the tenth zone is 180-220 degrees Celsius, the temperature of the eleventh zone is 200-240 degrees Celsius, and the temperature of the die is 240-265 degrees Celsius.

8. Use of the PET matte master batch of claim 1 in the preparation of matte fiber and matte film.

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