CN112480589A - Soft-touch HIPS composition and preparation method thereof - Google Patents
Soft-touch HIPS composition and preparation method thereof Download PDFInfo
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- CN112480589A CN112480589A CN202011433457.3A CN202011433457A CN112480589A CN 112480589 A CN112480589 A CN 112480589A CN 202011433457 A CN202011433457 A CN 202011433457A CN 112480589 A CN112480589 A CN 112480589A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to a soft-touch HIPS composition and a preparation method thereof, wherein the composition comprises the following components in parts by weight: 50-90 parts of HIPS resin, 10-50 parts of combined master batch and 0.5-2 parts of other auxiliary agents, wherein the combined master batch comprises 40-80 parts of TPU, 10-50 parts of ethylene-vinyl acetate copolymer 1(EVA-1), 1-10 parts of ethylene-vinyl acetate copolymer 2(EVA-2) and other auxiliary agents: 0.1 to 1 portion. Compared with the prior art, the preparation method has the advantages that through the preparation of the master batch with excellent touch feeling, the frictional resistance of the surface of the HIPS is greatly reduced, the surface hardness of the material is reduced to a certain degree, and the surface presents lubrication and special soft touch feeling, so that the preparation method can be applied to various appearance pieces and handle pieces and has wide market application prospect.
Description
Technical Field
The invention relates to the field of high polymer materials, and in particular relates to a soft-touch HIPS composition and a preparation method thereof.
Background
High Impact Polystyrene (HIPS) is a widely used thermoplastic polymer, a two-phase system consisting of a rubber phase and a continuous polystyrene phase, and has a wide range of impact and processability properties, making it widely used in applications such as automobiles, instruments, appliances, toys, disposables, and the like. HIPS not only has easy processability, good performance and relatively stable size, but also has lower price. Currently, with the improvement of living standard of people, consumer electronics products are also continuously upgraded, consumers pay more and more attention to good touch feeling of surfaces of workpieces such as automobiles, household appliances, stationery and the like, and soft touch feeling gradually becomes one of important trends in consumer product markets. However, the conventional HIPS has a poor surface touch, and the conventional HIPS part with a glossy surface touched by hands has an obvious astringent texture.
The traditional method for improving the surface touch of the material is generally to encapsulate the material by the elastomer, but the method is high in processing cost, and the surface of the elastomer is easy to have dirt and viscosity precipitation along with the prolonging of the service time, even the elastomer is degummed, so that the method is not beneficial to maintaining the long-term soft touch effect of the material.
Disclosure of Invention
The invention aims to solve the problem that the surface touch of the modified HIPS material is poor, and provides a soft touch HIPS composition and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
a soft-touch HIPS composition comprising the following components in parts by weight:
HIPS resin: 50-90 parts;
combining master batches: 10-50 parts;
other auxiliary agents: 0.5-2 parts;
wherein the combined master batch comprises the following components in parts by weight:
thermoplastic Polyurethane (TPU): 40-80 parts;
ethylene-vinyl acetate copolymer 1 (EVA-1): 10-50 parts;
ethylene-vinyl acetate copolymer 2 (EVA-2): 1-10 parts;
other auxiliary agents: 0.1 to 1 portion.
Preferably, the weight average molecular weight of the HIPS resin is 15-30 ten thousand, the rubber particle size is 1-5 um, the rubber content is 5-15%, and the melt index (200 ℃, 5kg) is 1-15 g/10 min.
Preferably, the TPU in the combined master batch is polyester polyurethane, the Shore A hardness is 70-100, and the melt index (200 ℃, 5kg) is 10-40 g/10 min.
Preferably, the EVA-1 in the combined master batch has a VA content of 20-45 wt%, a Shore A hardness of 50-90, and a melt index (200 ℃, 5kg) of 50-600 g/10 min.
Preferably, the EVA-2 in the combined master batch has a VA content of 55-85 wt%, a Shore A hardness of 30-45, and a melt index (200 ℃, 5kg) of 20-50 g/10 min.
Further preferably, the EVA is an ELVAX series product manufactured by dupont, and the numbers are 3128, 3129, 3130, 3135, 3165A, 3165SB, and preferably 3165SB, and the combined masterbatch is prepared by a one-step extrusion method, which includes the following steps:
(1) preparing materials according to a formula, fully and uniformly stirring TPU, EVA-1, EVA-2 and an antioxidant, and mixing in a stirrer for 10-30 min to obtain a mixture;
(2) and feeding the obtained mixture from the side feed or the main feed of a double-screw extruder, performing melt reaction on the mixture and the main-fed nylon, extruding, cooling, drying and granulating to obtain the combined master batch.
Preferably, the other auxiliary agents comprise one or more of a lubricant, a heat stabilizer, a mold release agent, an ultraviolet light absorber and a flame retardant.
A method of making a soft-touch HIPS composition comprising the steps of:
(1) preparing the combined master batch:
a1, weighing the components according to the weight parts of the combined master batch;
b1, fully and uniformly stirring the components in the A1, and mixing in a stirrer for 20-40 min to obtain a mixture;
c1, feeding the mixture obtained in the step B1 from a main feed of a double-screw extruder, performing melt extrusion, cooling, drying and granulating to obtain a combined master batch;
preferably, the method of making the soft-touch HIPS composition:
a2, weighing the components according to the parts by weight of the soft-touch HIPS composition;
b2, mixing the components weighed in the step A2 in a high-speed mixer for 5-25 min to obtain a mixture;
and C2, feeding the mixture obtained in the step B2 from a main feed of a double-screw extruder, and carrying out melt extrusion, cooling, drying and cutting into granules to obtain the soft-touch HIPS composition.
Preferably, in the steps C1 and C2, the twin-screw extruder is a co-rotating twin-screw extruder, the length-diameter ratio of the screws is 25-40, and the barrel of the screw is provided with a vacuum pumping device and a temperature control device.
Preferably, the temperature of a feeding section of the double-screw extruder is 170-210 ℃, the temperature of a plasticizing section of the double-screw extruder is 180-210 ℃, and the temperature of a homogenizing section of the double-screw extruder is 190-220 ℃; the rotation speed of the screw is 200-700 rpm.
Compared with the prior art, the invention has the following beneficial effects:
the content of Vinyl Acetate (VA) in EVA varies from 18 to 85 wt.%, thus presenting a significant difference in flexibility, and the high or low content of VA significantly changes its solubility parameter, thereby achieving different compatibility with HIPS. According to the invention, by adjusting the content of two VA, the excellent touch master batch is prepared, the frictional resistance of the HIPS surface is greatly reduced, the surface hardness of the material is reduced to a certain extent, the surface presents lubrication and special soft touch, the impact strength of the material is improved while the strength and the modulus of the material are ensured, the surface of the material has dry and silky touch, the added value of the HIPS product is obviously improved, and the HIPS master batch can be applied to various appearance pieces and handle pieces and has wide market application prospect.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The following examples and comparative examples used the following starting materials:
the HIPS resin is Korean Jinhu HI425TVL, the melt index (200 ℃, 5kg) is 13g/10min, the rubber content is 8%, the particle size is 1.5-3 um, and the weight average molecular weight is 18.4 ten thousand;
the TPU is selected from Tuntanhua polyester 85A thermoplastic polyurethane with the density of 1.2g/cm3；
EVA-1 is from Taiwan polymerization chemistry, the VA content is 33% wt, and the Shore hardness is 70A;
EVA-2 is from Acoma, Evatane 42-60, VA content 50% wt, Shore hardness 40A;
the antioxidant is B900 (gasoline refining), and the lubricant is barium stearate;
example 1
The embodiment is a preparation method of touch modified master batch, the raw material ratio of which is detailed in table 1, and the specific preparation method comprises the following steps:
a1, weighing the raw material components according to the parts by weight in the table 1;
b1, fully and uniformly stirring the components in the A1, and mixing in a stirrer for 20-40 min to obtain a mixture;
c1, feeding the mixture obtained in the step B1 from a main feed of a double-screw extruder, performing melt extrusion, cooling, drying and granulating to obtain a combined master batch;
the device comprises a double-screw extruder, a vacuum pump, a temperature control device, a screw rod and a screw rod, wherein the double-screw extruder is a co-rotating double-screw extruder, the length-diameter ratio of the screw rod is 35, and a cylinder of the screw rod is provided with the vacuum pump and the temperature control device; the temperature of a feeding section of the double-screw extruder is 200 ℃, the temperature of a plasticizing section is 190 ℃, and the temperature of a homogenizing section is 200 ℃; the screw speed was 350 rpm.
The combined master batches 1 to 8 are respectively prepared by the method, wherein the combined master batches 1 to 4 are prepared according to the formula of the invention, and the combined master batches 5 to 8 are not prepared according to the formula of the invention and are used as a comparison example.
Table 1 water-absorbing modified master batch raw material component ratio (in table, the numerical values are in parts by weight)
The following is a method for preparing a tactile HIPS composition, and the raw material ratios are detailed in Table 2.
Example 2
The embodiment provides a soft-touch HIPS composition and a preparation method thereof, and the preparation method comprises the following specific steps:
(1) weighing the components according to the weight ratio in the table 2, wherein the auxiliary agent is an antioxidant and a lubricant in the weight ratio of 1: 1;
(2) mixing the weighed components in a high-speed mixer for 20min to obtain a mixture;
feeding the mixed mixture from a main feed of a double-screw extruder, and performing melt extrusion, cooling, drying and grain cutting to obtain a sample; the double-screw extruder is a co-rotating double-screw extruder, the length-diameter ratio of a screw is 40, and a barrel of the screw is provided with a vacuum pumping device and a temperature control device; the temperature of a feeding section of the double-screw extruder is 200 ℃, the temperature of a plasticizing section is 190 ℃, and the temperature of a homogenizing section is 200 ℃; the screw speed was 500 rpm.
Example 3
This example provides a soft-touch HIPS composition and method of making, the raw materials weight ratios are shown in Table 2, the method of making is the same as example 1.
Example 4
This example provides a soft-touch HIPS composition and method of making, the raw materials weight ratios are shown in Table 2, the method of making is the same as example 1.
Example 5
This example provides a soft-touch HIPS composition and method of making, the raw materials weight ratios are shown in Table 2, the method of making is the same as example 1.
Example 6
This example provides a soft-touch HIPS composition and method of making same, with substantially the same weight ratios of the raw materials as in example 5, except that the amount of the combination masterbatch 4 is reduced.
Comparative example 1
This comparative example provides a soft-touch HIPS composition and method of preparation, the raw materials weight ratios are shown in Table 2, and the method of preparation is the same as example 1 without the addition of the combination masterbatch.
Comparative example 2
The comparative example provides a soft-touch HIPS composition and a method of making the same, the raw materials are in weight proportions as shown in Table 2, and the combined masterbatch 5 is added in the same manner as in example 1.
Comparative example 3
The comparative example provides a soft-touch HIPS composition and a method of making the same, the raw materials are in weight proportions as shown in Table 2, and the combined masterbatch 6 is added in the same manner as in example 1.
Comparative example 4
The comparative example provides a soft-touch HIPS composition and a method of making the same, the raw materials are in weight proportions as shown in Table 2, and the combined masterbatch 7 is added in the same manner as in example 1.
Comparative example 5
The comparative example provides a soft-touch HIPS composition and a method of making the same, the raw materials are in weight proportions as shown in Table 2, and the combined masterbatch 8 is added in the same manner as in example 1.
TABLE 2 Soft touch HIPS composition raw material component ratios (in the tables, the numerical values are in parts by weight)
And (3) performance testing:
HIPS resins prepared in examples 2 to 6 and comparative examples 1 to 5 were dried at 80 ℃ for 5 hours, and then injection-molded into sample bars of standard physical properties under the same injection molding conditions according to ASTM standards, and the heat resistance, physical properties and surface touch of each resin composition were measured, and the specific test standards and conditions are shown in Table 3.
TABLE 3 HIPS resin Performance test standards
| Physical Properties | Test conditions | Test standard |
| Izod notched impact Strength (1/8) (J/m) | 23℃ | ASTM D256-10 |
| Tensile Strength (MPa) | 50mm/min | ASTM D638-10 |
| Flexural Strength (MPa) | 3mm/min | ASTM D790-10 |
| Flexural modulus (MPa) | 3mm/min | ASTM D790-10 |
| Surface touch feeling | Hand touch | - |
The physical properties and surface results of the HIPS compositions of examples 2 to 6 and comparative examples 1 to 3 are shown in Table 4 below.
TABLE 4 HIPS resin Performance test results
Note: surface tactile impression in the surface: excellent, good, normal Δ, poor x.
The test results of the examples and the comparative examples in Table 4 show that the touch lubricity of the material is obviously improved by introducing the TPU and the EVA master batch into the HIPS while ensuring the strength of the material.
As can be seen from comparative example 1, various properties of the product were the worst without adding the combination master batch; it is understood from comparative examples 2 to 5 that the touch feeling is common when the combination mother particle 5 and the combination mother particle 8 are used, respectively, and one kind of EVA is not added or is added.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A soft-touch HIPS composition is characterized by comprising the following components in parts by weight:
HIPS resin: 50-90 parts;
combining master batches: 10-50 parts;
other auxiliary agents: 0.5-2 parts;
wherein the combined master batch comprises the following components in parts by weight:
thermoplastic Polyurethane (TPU): 40-80 parts;
ethylene-vinyl acetate copolymer 1 (EVA-1): 10-50 parts;
ethylene-vinyl acetate copolymer 2 (EVA-2): 1-10 parts;
other auxiliary agents: 0.1 to 1 portion.
2. The soft-touch HIPS composition according to claim 1, wherein the HIPS resin has a weight average molecular weight of 15 to 30 ten thousand, a rubber particle diameter of 1 to 5um, a rubber content of 5 to 15%, and a melt index (200 ℃, 5kg) of 1 to 15g/10 min.
3. The soft-touch HIPS composition of claim 1, wherein the TPU in the combined masterbatch is a polyester polyurethane, the Shore A hardness is 70-100, and the melt index (200 ℃, 5kg) is 10-40 g/10 min.
4. The soft-touch HIPS composition of claim 1, wherein the EVA-1 in the combined masterbatch has a VA content of 20-45 wt%, a Shore A hardness of 50-90, and a melt index (200 ℃, 5kg) of 50-600 g/10 min.
5. The soft-touch HIPS composition of claim 1, wherein the EVA-2 in the combined masterbatch has a VA content of 55-85 wt%, a Shore A hardness of 30-45, and a melt index (200 ℃, 5kg) of 20-50 g/10 min.
6. The soft-touch HIPS composition of claim 1, wherein the combination masterbatch is prepared by a one-step extrusion method, comprising the following steps:
(1) preparing materials according to a formula, fully and uniformly stirring TPU, EVA-1, EVA-2 and an antioxidant, and mixing in a stirrer for 10-30 min to obtain a mixture;
(2) and feeding the obtained mixture from the side feed or the main feed of a double-screw extruder, performing melt reaction on the mixture and the main-fed nylon, extruding, cooling, drying and granulating to obtain the combined master batch.
7. The soft-touch HIPS composition of claim 1, wherein the other additives include one or more of lubricants, heat stabilizers, mold release agents, ultraviolet light absorbers, and flame retardants.
8. A method of making a soft-touch HIPS composition of claim 1, comprising the steps of:
s1, preparing a combined master batch, which is prepared by a one-step extrusion method;
s2, preparing the soft-touch HIPS composition, namely batching according to components, mixing the raw materials of each component in a high-speed mixer for 5-25 min to obtain a mixture, feeding the obtained mixture from a main feed of a double-screw extruder, and carrying out melt extrusion, cooling, drying and grain cutting to obtain the soft-touch HIPS composition.
9. The method for preparing a soft touch HIPS composition according to claim 8, wherein the twin-screw extruder is a co-rotating twin-screw extruder, the length-diameter ratio of the screws is 25 to 40, and the barrels of the screws are provided with a vacuum pumping device and a temperature control device.
10. The method for preparing a soft touch HIPS composition according to claim 8, wherein the temperature of the feeding section of the twin-screw extruder is 170 to 210 ℃, the temperature of the plasticizing section is 180 to 210 ℃, and the temperature of the homogenizing section is 190 to 220 ℃; the rotation speed of the screw is 200-700 rpm.
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