CN105385094B - low gloss ABS resin composition and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of low gloss ABS resin compositions and preparation method thereof；The composition includes：100 parts of ABS resin, 0.5~10 part of polymer micro mist, 0.5~5 part of compatilizer, 0.05~1 part of antioxidant, 0.1~2 part of lubricant.The polymer micro mist is hemicrystalline polyethylene terephthalate micro mist, 0.9~1.4dL/g of inherent viscosity, 245~270 DEG C of fusing point, 70~85 DEG C of glass transition temperature, 1~50 μm of grain size.Said components are premixed 3~10 minutes in high-speed mixer, then premix obtains low gloss ABS resin composition through double screw extruder extruding pelletization.Compared with prior art, the problem of one-step method of the present invention directly prepares the ABS resin composition with excellent matte effect, and preparation method technical process is simple, and glossiness is ultralow, solves glossiness and is unevenly distributed, physical mechanical property deterioration, complex process.

Description

Low gloss ABS resin composition and preparation method thereof

Technical field

The present invention relates to polymeric material fields, and in particular to a kind of low gloss ABS resin composition and preparation method thereof.

Background technology

Acrylonitrile-butadiene-styrene terpolymer (ABS) is a kind of high gloss, it is resistant to chemical etching, high it is heat-resisting, The engineering plastics of the high comprehensive performances such as easy processing, superior dimensional stability, in electric, automobile, household electrical appliance, office etc. Field has a wide range of applications.ABS resin on many electronic apparatus and automotive interior part in application, as computer casing, Keyboard, mouse, instrument board, sunshading board, navigator frame etc. in automotive trim generally require to realize the surface for having extinction effect. Especially in automotive trim field, regarded to avoid sunlight reflection from generating vision interference to driver and mitigate driver Feel fatigue, to reach the driving purpose of safety and comfort, generally all carries out delustring or matte management, reduce inside gadget as much as possible Lustrous surface.

In general, the method for reducing ABS article surface glossiness is mainly the following.

One, die surface dermatoglyphization is handled.I.e. by the surface treatment of mold, make the surface of Injection moulded part that there are bumps not Flat texture structure, to effectively reduce gloss.However reach drop only by the texture structure for changing interior trim surface, it is low The method of glossiness cannot still meet the requirement of glossiness well in some cases, itself has high glaze as PC The resin and its alloy of characteristic, and certain limitation is also brought to interior trim surface design freedom.In addition, once due to tree The loss for the inside gadget dermatoglyph construction that fat scratch-resistant problem is brought, the significant difference of glossiness will occurs, cause vision immediately Aberration causes to fail.So the low gloss of thermoplastic resin is very important, can mitigate to a certain extent internally The dependence of gadget die surface extends its service life to widen the application range of resin.

Two, the rubber size of ABS resin is improved.The glossiness of ABS resin is mainly determined by the grain size of butadiene rubber Fixed, rubber size is bigger, and glossiness is lower.The rubber size of emulsion polymerization ABS resin usually within 0.5 μm, so its Surface gloss is higher, and the rubber size of bulk polymerization of ABS resin is typically larger than 0.6 μm, so its surface gloss is relatively low. Such as United States Patent (USP) US4677162 and US4526926 be by using bulk polymerization, the ABS resin containing larger rubber grain To achieve the purpose that reduce ABS material gloss.It is limited for the reducing effect of gloss but rubber size in this way Size can influence the mechanical property of ABS resin, and the especially influence to rigidity is especially pronounced.Rubber size increases, can significantly Reduce the tensile strength and stretch modulus of ABS resin.In addition to this, rubber size is bigger, deformability also bigger, so Injection molding is processed and when coloring is also easier to generate White Patches, the defects of current mark, weld bond.In order to balance other performances, It is very limited come the gloss for reducing ABS by increasing rubber size.

Three, incompatible polymers or filler are added.SEBS, nitrile rubber (CN are added such as in ABS systems 1128776A), (methyl) acrylic acid alkyl of the SAN (CN 102108176, US 5580924), three-dimensional net structure of gelation The incompatible polymers such as ester (CN 101724129) can reduce the gloss of ABS.Add silicate, aluminate, silica Equal inorganic fillers can also reduce resin surface gloss.But the physics of final material can be led to by adding these substance Incompatible Substances Mechanical performance severe exacerbation cannot meet the high occasion of mechanical property requirements.The resin of gelation as delustering agent in use, Since it is partial cross-linked, so product surface presence is excessively coarse, and the non-uniform problem of glossiness, especially when product table When the dermatoglyph structure in face is fine and smooth design, the problem is particularly evidently exposed.

Four, reaction resin is added.Such as adding PS-g-GMA, SAN-g-GMA has the resin of reactivity, passes through it In epoxy group crosslinked with carboxyl, the hydroxyl isoreactivity group in system and react to achieve the purpose that delustring.Patent CN 101851430, CN 101787192, US 4902743, US 4596851, US 4742104 are disclosed in PC and its alloy Middle resin of the addition containing glycidyl methacrylate (GMA) functional group can reduce its glossiness.Patent US 6395828 Disclose a kind of method that ASA resin glossiness is reduced by epoxy-functional and amidine functional group cross-linking reaction.CN 104403061 A disclose it is a kind of use peroxide as initiator, complete crosslinking agent during ABS resin is in extruding pelletization Macromolecular radical cross-linking reaction occurs with ABS molecule interchains, realizes one-step method and directly prepares the ABS trees with matte effect Fat group.Using the above scheme, by realizing cross-linking reaction to achieve the effect that dumb light.Cross-linking reaction often makes extruding dies The melt item at place occurs apparent melt and swells phenomenon, and then subsequent pelletizing and the dispersion in resin is made to become difficult. And the stability of cross-linking reaction is difficult often control, is produced between easily causing product surface degree of roughness uneven and different batches The fluctuation of product matte degree is big.104559033 A of CN disclose a kind of Resin A with containing maleic anhydride functional groups, contain metering system The resin B of acid glycidyl ester functional group, polyolefin-alkyl alkylacrylate copolymer C, aerosil, hydration boron Sour zinc and processing aid squeeze out dumb light master batch obtained to realize the dumb light of ABS resin through double screw extruder, can prepare material Expect the ABS material that surface is uniform, dumb light sense is soft, glossiness is low.But the method preparation process needs two steps, is unfavorable for efficient life Production；Reaction system is complicated, the problem that equally can be faced cross-linking reaction stability not enough and cause the matte degree of batch inconsistent.

Invention content

In view of the above-mentioned drawbacks of the prior art, a kind of low gloss ABS resin composition of present invention offer and its preparation Method, existing mechanical property deteriorates when to solve to prepare low gloss ABS resin in the prior art, glossiness is not low enough, divides The problems such as cloth is uneven, rough surface, low gloss heat-proof ABS resin composition of the present invention is that a kind of surface is soft, light Damp degree is ultralow, good mechanical performance ABS resin.

To achieve the above object, the technical solution adopted by the present invention is that：

In a first aspect, the present invention relates to a kind of low gloss ABS resin composition, the composition includes following parts by weight Each component：100 parts of ABS resin, 0.5~10 part of polymer micro mist, 0.5~5 part of compatilizer, 0.05~1 part of antioxidant, lubrication 0.1~2 part of agent；The polymer micro mist is hemicrystalline polyethylene terephthalate micro mist.

Preferably, the inherent viscosity of the hemicrystalline polyethylene terephthalate micro mist is 0.9~1.4dL/g, Fusing point is 245~270 DEG C, and glass transition temperature is 70~85 DEG C, and grain size is 1~50 μm.

Preferably, the average weight-molecular mass of the ABS resin is 80000~200000, rubber in the ABS resin Content is 10~20wt%, and the number average bead diameter of rubber is 0.2~3.0 μm.

Preferably, the compatilizer includes styrene-maleic anhydride copolymer (SMA), acrylonitrile-styrene-maleic acid Copolymer (AS-g-MAA), acrylonitrile-styrene-copolymer-maleic anhydride (AS-g-MAH), acrylonitrile-styrene-methyl-prop One or more of olefin(e) acid dehydrated glyceride copolymer (AS-g-GMA).

Preferably, the antioxidant be selected from aromatic amine antioxidant, Hinered phenols antioxidant, phosphite ester kind antioxidant, One or more of thioester antioxidant, aromatic phosphate acid ester, pentaerythritol ester, auxiliary antioxidant.

Preferably, the lubricant is selected from silicone oil, White Mineral Oil, fatty acid amide, barium stearate, magnesium stearate, paraffin, gathers Ethylene waxes, ethylene bis stearic acid amide, ethylene-vinyl acetate copolymer, pentaerythritol stearate, ethylene-acrylic acid copolymer One or more of object, aromatic phosphate acid ester.

Second aspect, the invention further relates to a kind of preparation methods of low gloss ABS resin composition, and the method includes such as Lower step：

S1, the ABS resin, polymer micro mist, compatilizer, antioxidant are premixed 3~10 minutes in high-speed mixer；

S2, premix are through double screw extruder extruding pelletization to get to the low gloss ABS resin composition.

Preferably, the extrusion temperature of the double screw extruder is 190~240 DEG C, and screw slenderness ratio is 32~45, screw rod Rotating speed is 200~600 revs/min.

The cardinal principle of the present invention is in the processing temperature section of ABS, half hitch moral character polyethylene terephthalate micro mist Original microparticle state is kept to realize the dumb light of ABS resin.It can be adjusted by the additive amount and particle size range that control micro mist Save the matte effect of material, matte degree uniform and smooth, lot stability height.Dystectic hemicrystalline terephthalate Ester micro mist contains a large amount of amorphous area, in extrusion, the amorphous area polyethylene terephthalate molecule of micro mist periphery Chain melting solution, which twines to react with the active function groups of reactive compatibilizers, improves polyethylene terephthalate micro mist and matrix material The compatibility of material, so as to improve the mechanical property of material.The crystalline region of polyethylene terephthalate micro mist is molten in process Melting temperature and is higher than processing temperature, only amorphous area softening melting, micro mist still maintains particle shape, and compatilizer additive amount is limited, Micro mist will not cause melt extrusion to grow up with compatilizer overreaction, material property declines, article surface gloss uneven.

Compared with prior art, the present invention has the advantages that：

1. the present invention realizes the matte degree of ABS resin using dystectic polyethylene terephthalate micro mist, mute Luminosity uniform and smooth.The matte effect of material can be adjusted by the additive amount and particle size range that control micro mist, matte effect is not Dependent on complicated chemical reaction, lot stability is high.

2. the present invention improves polyethylene terephthalate using with the fabulous reactive compatibilizers of ABS resin compatibility The mechanical property of the compatibility of micro mist and basis material, material improves obviously than other methods.

3. the preparation process of the present invention is very simple, be conducive to mass production.

Specific implementation mode

The following describes the present invention in detail with reference to examples.Following embodiment will be helpful to those skilled in the art The present invention is further understood, but the invention is not limited in any way.It should be pointed out that those skilled in the art For, without departing from the inventive concept of the premise, it can also make certain adjustments and improvements.These subordinates are in the guarantor of the present invention Protect range.

Examples 1 to 7 and comparative example 1~7

Each component and its content such as 1 institute of table in Examples 1 to 7 and comparative example 1~7 in low gloss ABS resin composition Show, stocks up respectively according to the component and content of each embodiment and comparative example in table 1.First by the material got ready in high-speed mixer It inside carries out being sufficiently stirred premix 3~10 minutes, then by premix by double screw extruder, in 190~240 DEG C of extrusion temperatures, Screw speed carries out melting extrusion under the conditions of being 200~600 revs/min, and cooling granulation obtains the ABS trees with matte effect Oil/fat composition.

Component and characteristic are as follows involved in above example and comparative example：

ABS1：Butadiene rubber content 20%, number average bead diameter are 0.2 μm, weight average molecular weight 80,000；

ABS2：Butadiene rubber content 16%, number average bead diameter are 1.4 μm, weight average molecular weight 100,000；

ABS3：Butadiene rubber content 10%, number average bead diameter are 3 μm, weight average molecular weight 200,000；

ABS4：Butadiene rubber content 13%, number average bead diameter are 0.9 μm, weight average molecular weight 150,000；

ABS5：Butadiene rubber content 10%, number average bead diameter are 4 μm, weight average molecular weight 200,000.

PET1：85 DEG C, inherent viscosity 1.4dL/g of 270 DEG C of Tm, Tg, 1~10 μm of grain size；

PET 2：80 DEG C, inherent viscosity 1.1dL/g of 260 DEG C of Tm, Tg, 10~30 μm of grain size；

PET 3：245 DEG C of Tm, Tg 70 (DEG C, inherent viscosity 0.9dL/g, 20~40 μm of grain size；

PET 4：75 DEG C, inherent viscosity 1.1dL/g of 255 DEG C of Tm, Tg, 10~25 μm of grain size.

Silica：It is prepared by 10~25 μm of grain size, 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 are equal 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 copolymer (AS-g-GMA), GMA contents 2wt%, weight average molecular weight 11W.

Gelation (crosslinking) SAN：BMAT；St contents 30wt% in SEBS, 15~20W of weight average molecular weight；Antioxidant： 1076；Lubricate EBS.

1 component of table and content table

Quantitative measurement method：

Tensile strength (50mm/min) ASTM D638；

Bending strength (3mm/min) ASTM D790；

Bending modulus (3mm/min) ASTM D790；

IZOD notch impact strengths (3.2mm) ASTM D256；

Vicat (5kg, 50 DEG C/h) ASTM D1525；

Glossiness：According to the method for ASTM D2457,268 vancometers of Konica Minolta Multigloss, note are used It is 60 ° to mould colour table test angle

2 embodiment and comparative example physical property of table

By the Comparative result of Tables 1 and 2 it is found that the invention has the advantages that：1. using dystectic terephthalic acid (TPA) second Diol ester micro mist realizes the matte degree of ABS resin, and material can be adjusted by the additive amount and particle size range that control micro mist Matte effect, matte degree uniform and smooth, and the SAN of gelation is used, material surface presence is excessively coarse, and glossiness is uneven It is even；2. the present invention using with the fabulous reactive compatibilizers of ABS resin compatibility improve ethylene glycol terephthalate micro mist and The mechanical property of the compatibility of basis material, material improves obviously than other methods, and addition silica dioxide delustring agent can cause to rush Degradation is hit, rigid degradation can be caused by improving ABS rubber phases grain size and adding incompatible body SEBS.In addition this hair Bright to realize dumb light using one-step method, for matte effect independent of cross-linking reaction, preparation process is very simple, and stability is high, favorably In mass production.

Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited in above-mentioned Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow Ring the substantive content of the present invention.

Claims (6)

1. a kind of low gloss ABS resin composition, which is characterized in that the composition includes each component of following parts by weight： 100 parts of ABS resin, 0.5~10 part of polymer micro mist, 0.5~5 part of compatilizer, 0.05~1 part of antioxidant, lubricant 0.1~2 Part；The polymer micro mist is hemicrystalline polyethylene terephthalate micro mist；

The inherent viscosity of the hemicrystalline polyethylene terephthalate micro mist be 0.9~1.4dL/g, fusing point be 245~ 270 DEG C, glass transition temperature is 70~85 DEG C, and grain size is 1~50 μm；

The compatilizer is acrylonitrile-styrene-maleic acid, acrylonitrile-styrene-copolymer-maleic anhydride, propylene One or more of nitrile-styrene-t dehydrated glyceride copolymer；

In the processing temperature section of ABS, hemicrystalline polyethylene terephthalate micro mist keeps original microparticle state To realize the dumb light of ABS resin.

2. low gloss ABS resin composition according to claim 1, which is characterized in that the weight of the ABS resin is opposite Molecular mass is 80000~200000, and rubber content is 10~20wt% in the ABS resin, and the number average bead diameter of rubber is 0.2 ~3.0 μm.

3. low gloss ABS resin composition according to claim 1, which is characterized in that the antioxidant is selected from aromatic amine One or more of kind antioxidant, Hinered phenols antioxidant, auxiliary antioxidant.

4. low gloss ABS resin composition according to claim 1, which is characterized in that the lubricant is selected from silicone oil, white Dormant oil, fatty acid amide, barium stearate, magnesium stearate, paraffin, polyethylene wax, ethylene bis stearic acid amide, ethyl vinyl acetate second One or more of alkene copolymer, pentaerythritol stearate, ethylene-acrylic acid copolymer.

5. a kind of preparation method of low gloss ABS resin composition according to any one of claims 1 to 4, feature It is, described method includes following steps：

S1, the ABS resin, polymer micro mist, compatilizer, antioxidant, lubricant are premixed in high-speed mixer；

S2, premix are through double screw extruder extruding pelletization to get to the low gloss ABS resin composition.

6. the preparation method of low gloss ABS resin composition according to claim 5, which is characterized in that the twin-screw The extrusion temperature of extruder is 190~240 DEG C, and screw slenderness ratio is 32~45, and screw speed is 200~600 revs/min.