CN105385094A - Low-gloss ABS resin composition and preparation method thereof - Google Patents
Low-gloss ABS resin composition and preparation method thereof Download PDFInfo
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- CN105385094A CN105385094A CN201510969094.8A CN201510969094A CN105385094A CN 105385094 A CN105385094 A CN 105385094A CN 201510969094 A CN201510969094 A CN 201510969094A CN 105385094 A CN105385094 A CN 105385094A
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
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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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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Abstract
The invention discloses a low-gloss ABS resin composition and a preparation method thereof. The composition is prepared from 100 parts of ABS resin, 0.5-10 parts of polymer micro-powder, 0.5-5 parts of compatilizer, 0.05-1 part of an antioxidant and 0.1-2 parts of a lubricant. Semicrystalline polyethylene glycol terephthalate micro-powder is adopted as the polymer micro-powder, the intrinsic viscosity of the micro-powder is 0.9-1.4 dL/g, the melting point of the micro-powder is 245 DEG C-270 DEG C, the glass-transition temperature of the micro-powder is 70 DEG C-85 DEG C, and the particle size of the micro-powder is 1-50 micrometers. All the components are premixed in a high-speed mixer for 3-10 minutes, extrusion pelletizing is performed on premix through a double-screw extruder, and then the low-gloss ABS resin composition is obtained. Compared with the prior art, the ABS resin composition with the excellent matte finish effect is directly prepared through a one-step method, the preparation method is simple in technological process, the glossiness is ultra-low, and the problems of uneven glossiness distribution, physical and mechanical performance deterioration and a complex technology are solved.
Description
Technical field
The present invention relates to polymeric material field, be specifically related to a kind of low gloss ABS resin composition and method of making the same.
Background technology
Acrylonitrile-butadiene-styrene terpolymer (ABS) is a kind of high glossiness, the engineering plastics of the high comprehensive performances such as resistance to chemical attack, high heat-resisting, easy processing, superior dimensional stability, have a wide range of applications in the field such as electric, automobile, household electrical appliance, office.When ABS resin is applied on a lot of electronic apparatuss and automotive interior part, as computer casing, keyboard, mouse, the dashboard in automotive trim, sun visor, navigating instrument frame etc., often need the surface realizing extinction effect.Especially in automotive trim field, produce vision for avoiding solar radiation reflection to officer disturb and alleviate the eye strain of officer, thus reach the driving object of safety and comfort, generally all carry out delustring or matte management, reduce the surface luster of inside gadget as much as possible.
Usually, the method reducing ABS article surface glossiness mainly contains following several.
One, die surface dermatoglyph process.Namely by the surface treatment of mould, make the surface of Injection moulded part have rough texture structure, thus effectively reduce gloss.But reach fall only by changing the texture structure on interior trim surface, the method of low-luster, still can not meet the requirement of glossiness in some cases well, itself there is resin and the alloy thereof of high gloss characteristics as PC, and certain restriction is also brought to interior trim surface design degree of freedom.In addition, once the loss of the inside gadget dermatoglyph structure brought due to resin scrape resistant problem, the significant difference of glossiness will be there is immediately, cause visual color, cause losing efficacy.So the low gloss of thermoplastic resin is very important, the dependence of to interior die surface can be alleviated to a certain extent, thus widen the range of application of resin, extend its work-ing life.
Two, the rubber size of ABS resin is improved.The glossiness of ABS resin is mainly determined by the particle diameter of divinyl rubber, and rubber size is larger, and glossiness is lower.The rubber size of letex polymerization ABS resin is usually within 0.5 μm, so its surface gloss is higher, and the rubber size of bulk polymerization of ABS resin is greater than 0.6 μm usually, so its surface gloss is lower.Such as US Patent No. 4677162 and US4526926 pass through use mass polymerization, and the ABS resin containing larger rubber grain reaches the object reducing ABS material gloss.But adopt the mechanical property that can affect ABS resin in this way for the size of the reduction limited efficiency rubber size of gloss, especially particularly remarkable on the impact of rigidity.Rubber size increases, and significantly can reduce tensile strength and the tensile modulus of ABS resin.In addition, rubber size is larger, and its deformability is also larger, so also more easily produce White Patches, current mark, the defects such as weld bond when injection moulding is processed and be painted.In order to balance other performances, the gloss being reduced ABS by increase rubber size is very limited.
Three, incompatible polymers or filler is added.The gloss of ABS all can be reduced as added the incompatible polymers such as SEBS, nitrile rubber (CN1128776A), the SAN (CN102108176, US5580924) of gelation, (methyl) alkyl acrylate (CN101724129) of three-dimensional net structure in ABS system.Add the mineral fillers such as silicate, aluminate, silicon-dioxide and also can reduce resin surface gloss.But add the physical and mechanical properties severe exacerbation that these material Incompatible Substances can cause final material, the occasion that mechanical property requirements is high can not be met.The resin of gelation is when using as matting agent, and because it is partial cross-linked, so product surface exists too coarse, and the problem that glossiness is uneven, especially when the dermatoglyph structure of product surface be fine and smooth design, this problem exposes particularly evident.
Four, reaction resin is added.There is the resin of reactive behavior, by the carboxyl in epoxide group wherein and system, hydroxyl isoreactivity group generation crosslinking reaction thus reach the object of delustring as added PS-g-GMA, SAN-g-GMA etc.Patent CN101851430, CN101787192, US4902743, US4596851, US4742104 disclose the resin added containing glycidyl methacrylate (GMA) functional group in PC and alloy thereof can reduce its glossiness.Patent US6395828 discloses a kind of method being reduced ASA resinous luster degree by epoxy-functional and amidine functional group cross-linking reaction.CN104403061A discloses one superoxide as initiator, complete in extruding pelletization process between linking agent and ABS molecular chain in ABS resin and macromolecular radical crosslinking reaction occurs, achieve single stage method and directly prepare the ABS resin group with matte effect.Adopt such scheme, be cross-linked by realization response the effect reaching dumb light.Crosslinking reaction often makes the melt bar at extruding dies place that obvious melt occurs to swell phenomenon, and then makes follow-up pelletizing and the dispersion in resin become difficulty.And the stability of crosslinking reaction is often difficult to control, very easily cause the fluctuation of product matte degree between product surface degree of roughness uneven and different batches large.CN104559033A discloses a kind of use and extrudes through twin screw extruder the dumb light that obtained dumb light master batch realizes ABS resin containing the Resin A of maleic anhydride functional groups, the resin B containing glycidyl methacrylate functional group, polyolefine-alkyl alkylacrylate multipolymer C, aerosil, hydration zinc borate and processing aid, can prepare material surface evenly, dumb light sense is soft, glossiness is low ABS material.But this legal system, for process need two step, is unfavorable for High-efficient Production; Reaction system is complicated, can face the problem that matte degree that crosslinking reaction stability causes batch is not inconsistent equally.
Summary of the invention
For the defect that above-mentioned prior art exists, the invention provides a kind of low gloss ABS resin composition and method of making the same, to solve in prior art the problems such as the mechanical property existed when preparing low gloss ABS resin worsens, glossiness is low not, skewness, surface irregularity, low gloss heat-proof ABS resin composition of the present invention is that a kind of surface is soft, glossiness is ultralow, good mechanical performance ABS resin.
For achieving the above object, the technical scheme that the present invention takes is:
First aspect, the present invention relates to a kind of low gloss ABS resin composition, described composition comprises each component of following parts by weight: ABS resin 100 parts, polymkeric substance micro mist 0.5 ~ 10 part, compatilizer 0.5 ~ 5 part, 0.05 ~ 1 part, oxidation inhibitor, lubricant 0.1 ~ 2 part; Described polymkeric substance micro mist is hemicrystalline polyethylene terephthalate micro mist.
Preferably, the limiting viscosity of described hemicrystalline polyethylene terephthalate micro mist is 0.9 ~ 1.4dL/g, and fusing point is 245 ~ 270 DEG C, and second-order transition temperature is 70 ~ 85 DEG C, and particle diameter is 1 ~ 50 μm.
Preferably, the average weight-molecular mass of described ABS resin is 80000 ~ 200000, and in described ABS resin, rubber content is 10 ~ 20wt%, and the number average bead diameter of rubber is 0.2 ~ 3.0 μm.
Preferably, described compatilizer comprises one or more in styrene-maleic anhydride copolymer (SMA), acrylonitrile-styrene-maleic acid (AS-g-MAA), acrylonitrile-styrene-copolymer-maleic anhydride (AS-g-MAH), acrylonitrile-styrene-methacrylic dehydrated glyceride multipolymer (AS-g-GMA).
Preferably, described oxidation inhibitor is selected from one or more in aromatic amine oxidation inhibitor, Hinered phenols antioxidant, phosphite ester kind antioxidant, monothioester kind antioxidant, aromatic phosphate acid ester, pentaerythritol ester, auxiliary antioxidant.
Preferably, described lubricant is selected from one or more in silicone oil, white mineral oil, fatty acid amide, barium stearate, Magnesium Stearate, paraffin, polyethylene wax, ethylene bis stearic acid amide, ethylene-vinyl acetate copolymer, pentaerythritol stearate, ethylene-acrylic acid copolymer, aromatic phosphate acid ester.
Second aspect, the invention still further relates to a kind of preparation method of low gloss ABS resin composition, described method comprises the steps:
S1, by described ABS resin, polymkeric substance micro mist, compatilizer, oxidation inhibitor premix 3 ~ 10 minutes in high-speed mixer;
S2, Preblend, through twin screw extruder extruding pelletization, namely obtain described low gloss ABS resin composition.
Preferably, the extrusion temperature of described twin screw extruder is 190 ~ 240 DEG C, and screw slenderness ratio is 32 ~ 45, and screw speed is 200 ~ 600 revs/min.
Cardinal principle of the present invention is interval in the processing temperature of ABS, and half hitch moral character polyethylene terephthalate micro mist keeps original microparticle state to realize the dumb light of ABS resin.Can be regulated the matte effect of material by the addition and particle size range controlling micro mist, matte degree uniform and smooth, lot stability is high.Dystectic hemicrystalline ethylene glycol terephthalate micro mist contains a large amount of non-crystalline regions, in extrusion, the non-crystalline region polyethylene terephthalate molecular chain melting solution of micro mist periphery twines reacts with the active function groups of reactive compatibilizers the consistency improving polyethylene terephthalate micro mist and body material, thus improves the mechanical property of material.In the course of processing, the crystalline region melt temperature of polyethylene terephthalate micro mist is higher than processing temperature, only melting is softened in non-crystalline region, micro mist still keeps particle form, and compatilizer addition is limited, micro mist will cause melt extrusion to grow up with compatilizer overreaction, material property declines, article surface gloss uneven.
Compared with prior art, the present invention has following beneficial effect:
1. the present invention uses dystectic polyethylene terephthalate micro mist to realize the matte degree of ABS resin, matte degree uniform and smooth.Can be regulated the matte effect of material by the addition and particle size range controlling micro mist, matte effect does not rely on complicated chemical reaction, and lot stability is high.
2. use of the present invention and the fabulous reactive compatibilizers of ABS resin consistency improve the consistency of polyethylene terephthalate micro mist and body material, and the mechanical property of material is improved obviously than additive method.
3. preparation technology of the present invention is very simple, is conducive to a large amount of production.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make certain adjustments and improvements.These subordinates are in protection scope of the present invention.
embodiment 1 ~ 7 and comparative example 1 ~ 7
Each component in embodiment 1 ~ 7 and comparative example 1 ~ 7 in low gloss ABS resin composition and content as shown in table 1, get the raw materials ready according to the component of embodiment each in table 1 and comparative example and content respectively.First the material got ready is fully stirred premix 3 ~ 10 minutes in high-speed mixer, again twin screw extruder is passed through in Preblend, at 190 ~ 240 DEG C of extrusion temperatures, screw speed is melt extrude under 200 ~ 600 revs/min of conditions, cooling granulation, obtains the ABS resin composition with matte effect.
Component is related to and characteristic is as follows in above embodiment and comparative example:
ABS1: butadiene rubber content 20%, number average bead diameter is 0.2 μm, weight-average molecular weight 80,000;
ABS2: butadiene rubber content 16%, number average bead diameter is 1.4 μm, weight-average molecular weight 100,000;
ABS3: butadiene rubber content 10%, number average bead diameter is 3 μm, weight-average molecular weight 200,000;
ABS4: butadiene rubber content 13%, number average bead diameter is 0.9 μm, weight-average molecular weight 150,000;
ABS5: butadiene rubber content 10%, number average bead diameter is 4 μm, weight-average molecular weight 200,000.
PET1:Tm270 DEG C, Tg85 DEG C, limiting viscosity 1.4dL/g, particle diameter 1 ~ 10 μm;
PET2:Tm260 DEG C, Tg80 DEG C, limiting viscosity 1.1dL/g, particle diameter 10 ~ 30 μm;
PET3:Tm245 DEG C, Tg70 (DEG C, limiting viscosity 0.9dL/g, particle diameter 20 ~ 40 μm;
PET4:Tm255 DEG C, Tg75 DEG C, limiting viscosity 1.1dL/g, particle diameter 10 ~ 25 μm.
Silicon-dioxide: particle diameter 10 ~ 25 μm, prepared by chemical precipitation method.
Compatilizer 1: styrene-maleic anhydride copolymer (SMA), maleic anhydride content 18wt%, weight-average molecular weight 10W;
Compatilizer 2: acrylonitrile-styrene-copolymer-maleic anhydride (AS-g-MAH), maleic anhydride content 5wt%, weight-average molecular weight 8W;
Compatilizer 3: acrylonitrile-styrene-maleic acid (AS-g-MAA), MAA content 6wt%, weight-average molecular weight 12W;
Compatilizer 4: acrylonitrile-styrene-methacrylic dehydrated glyceride multipolymer (AS-g-GMA), GMA content 2wt%, weight-average molecular weight 11W.
Gelation (being cross-linked) SAN:BMAT; St content 30wt%, weight-average molecular weight 15 ~ 20W in SEBS; Oxidation inhibitor: 1076; Lubricate EBS.
Table 1 component and containing scale
Quantitative measurement method:
Tensile strength (50mm/min) ASTMD638;
Flexural strength (3mm/min) ASTMD790;
Modulus in flexure (3mm/min) ASTMD790;
IZOD notched Izod impact strength (3.2mm) ASTMD256;
Vicat(5kg，50℃/h)ASTMD1525；
Glossiness: according to the method for ASTMD2457, use Konica Minolta Multigloss268 vancometer, injection moulding colour table test angle is 60 °
Table 2 embodiment and comparative example physicals
Known by the Comparative result of table 1 and table 2, the invention has the advantages that: 1. use dystectic ethylene glycol terephthalate micro mist to realize the matte degree of ABS resin, the matte effect of material can be regulated by the addition and particle size range controlling micro mist, matte degree uniform and smooth, and use the SAN of gelation, material surface exists too coarse, and glossiness is uneven; 2. use of the present invention and the fabulous reactive compatibilizers of ABS resin consistency improve the consistency of ethylene glycol terephthalate micro mist and body material, the mechanical property of material is improved obviously than additive method, add silica flatting agent and can impact degradation, improve ABS rubber phase particle diameter and add the degradation that incompatible body SEBS can cause rigidity.The present invention uses single stage method to realize dumb light in addition, and matte effect does not rely on crosslinking reaction, and preparation technology is very simple, and stability is high, is conducive to a large amount of production.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (8)
1. a low gloss ABS resin composition, is characterized in that, described composition comprises each component of following parts by weight: ABS resin 100 parts, polymkeric substance micro mist 0.5 ~ 10 part, compatilizer 0.5 ~ 5 part, 0.05 ~ 1 part, oxidation inhibitor, lubricant 0.1 ~ 2 part; Described polymkeric substance micro mist is hemicrystalline polyethylene terephthalate micro mist.
2. low gloss ABS resin composition according to claim 1, it is characterized in that, the limiting viscosity of described hemicrystalline polyethylene terephthalate micro mist is 0.9 ~ 1.4dL/g, and fusing point is 245 ~ 270 DEG C, second-order transition temperature is 70 ~ 85 DEG C, and particle diameter is 1 ~ 50 μm.
3. low gloss ABS resin composition according to claim 1, it is characterized in that, the average weight-molecular mass of described ABS resin is 80000 ~ 200000, and in described ABS resin, rubber content is 10 ~ 20wt%, and the number average bead diameter of rubber is 0.2 ~ 3.0 μm.
4. low gloss ABS resin composition according to claim 1, it is characterized in that, described compatilizer comprises one or more in styrene-maleic anhydride copolymer, acrylonitrile-styrene-maleic acid, acrylonitrile-styrene-copolymer-maleic anhydride, acrylonitrile-styrene-methacrylic dehydrated glyceride multipolymer.
5. low gloss ABS resin composition according to claim 1, it is characterized in that, described oxidation inhibitor is selected from one or more in aromatic amine oxidation inhibitor, Hinered phenols antioxidant, phosphite ester kind antioxidant, monothioester kind antioxidant, aromatic phosphate acid ester, pentaerythritol ester, auxiliary antioxidant.
6. low gloss ABS resin composition according to claim 1, it is characterized in that, described lubricant is selected from one or more in silicone oil, white mineral oil, fatty acid amide, barium stearate, Magnesium Stearate, paraffin, polyethylene wax, ethylene bis stearic acid amide, ethylene-vinyl acetate copolymer, pentaerythritol stearate, ethylene-acrylic acid copolymer, aromatic phosphate acid ester.
7. a preparation method for the low gloss ABS resin composition according to any one of claim 1 ~ 6, it is characterized in that, described method comprises the steps:
S1, by described ABS resin, polymkeric substance micro mist, compatilizer, oxidation inhibitor premix in high-speed mixer;
S2, Preblend, through twin screw extruder extruding pelletization, namely obtain described low gloss ABS resin composition.
8. the preparation method of low gloss ABS resin composition according to claim 7, is characterized in that, the extrusion temperature of described twin screw extruder is 190 ~ 240 DEG C, and screw slenderness ratio is 32 ~ 45, and screw speed is 200 ~ 600 revs/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107298827A (en) * | 2017-06-29 | 2017-10-27 | 上海金山锦湖日丽塑料有限公司 | Low gloss heat-resisting ABS resin and preparation method thereof |
| CN108456392A (en) * | 2018-03-16 | 2018-08-28 | 常州丰盛光电科技股份有限公司 | A kind of extinction material and its preparation method and application for thermoforming |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107298827A (en) * | 2017-06-29 | 2017-10-27 | 上海金山锦湖日丽塑料有限公司 | Low gloss heat-resisting ABS resin and preparation method thereof |
| CN108456392A (en) * | 2018-03-16 | 2018-08-28 | 常州丰盛光电科技股份有限公司 | A kind of extinction material and its preparation method and application for thermoforming |
| CN108456392B (en) * | 2018-03-16 | 2021-04-09 | 常州丰盛光电科技股份有限公司 | Extinction material for thermal forming and preparation method and application thereof |
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| CN105385094B (en) | 2018-11-13 |
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