CN107501841A - The high-weatherability ABS fine-celled foams and preparation method of a kind of sandwich foam-injection - Google Patents

The high-weatherability ABS fine-celled foams and preparation method of a kind of sandwich foam-injection Download PDF

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Publication number
CN107501841A
CN107501841A CN201710695321.1A CN201710695321A CN107501841A CN 107501841 A CN107501841 A CN 107501841A CN 201710695321 A CN201710695321 A CN 201710695321A CN 107501841 A CN107501841 A CN 107501841A
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abs
injection
resin
die cavities
weatherability
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CN107501841B (en
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陈庆
曾军堂
昝航
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Dongguan Tengsheng Plastic Hardware Co., Ltd
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Chengdu New Keli Chemical Science Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/04—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles consisting of at least two parts of chemically or physically different materials, e.g. having different densities
    • B29C44/06—Making multilayered articles
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/16—Making multilayered or multicoloured articles
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/22—Expandable microspheres, e.g. Expancel®
    • 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
    • C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
    • C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

The present invention provides a kind of the high-weatherability ABS fine-celled foams and preparation method of sandwich foam-injection, and foam composition includes ABS resin, ASA resin, compatilizer, antioxidant, expandable microspheres.Using the bicomponent injection molding machine with two sets of injection moulding apparatus, first by wherein set of device injection ASA as cladding cortex, expandable microspheres and the ABS resin of other auxiliary agents are mixed with by the injection of same cast gate again, reinject a small amount of ASA melts envelope mould, prepared with this using ASA resin and be used as cladding cortex, ABS foamed composite of the ABS resin as the interlayer structure of sandwich layer, the present invention provides the above method and uses special Shooting Technique, the shortcomings that ABS weatherabilities are poor greatly compensate for using the strong ASA resin of a small amount of weatherability, overcome that ABS weatherabilities in the prior art are poor and technological deficiency that ABS composite material cost is higher, and then improve ABS resin material weatherability, reduce raw material use cost simultaneously, and process program is simple, it is suitable for mass producing.

Description

The high-weatherability ABS fine-celled foams and preparation method of a kind of sandwich foam-injection
Technical field
The present invention relates to polymer composite manufacture field, and in particular to a kind of high-weatherability of sandwich foam-injection ABS fine-celled foams and preparation method.
Background technology
ABS is the general thermoplastic engineering plastic to grow up 1940's, be a comprehensive mechanical property very Outstanding plastics variety, not only with good rigidity, hardness and processing fluidity, and there is high tenacity feature, can note Modeling, extrusion or thermoforming.Most of automobile component is processed with injection molding forming method, is anti-impact the advantages of ABS resin Property, sound-proofing, scratch-resistant, heat resistance is more preferable, more more attractive than PP, especially more strict in horizontal impact resilience and temperature in use Part.ABS resin is using being only second to polyurethane and polyacrylic the third-largest resin in automobile.ABS resin can be used for it is in-car and Car outer enclosure, the widget such as steering wheel, oil guide pipe and handle and button, car outside include preceding radiator grille and lampshade etc..
ABS resin is easily worked, and processing dimension stability and lustrous surface are good, easy application, coloring, can also be carried out The suitability for secondary processing such as spray metal, plating, welding and bonding, it can be widely applied to field of electronics, including various offices With consumer electronics/electrical equipment, office electrical equipment includes electronic data processing machine, office equipment.Nowadays in electronic apparatus market, ABS resin will keep its status, fire-retardant and high heat-proof ABS resin in fire-retardant and high heat-resisting electronic/electrical device market is required There is obvious advantage in the competition with the engineering plastic alloy such as ABS/PC.In machinery, automobile, building materials and electronics, electrical equipment work It is a kind of extremely wide thermoplastic engineering plastic of purposes in industry.
An ABS major defect is that weatherability is poor, and its basic reason is that the butadiene in component contains polymer molecule There is double bond structure, it is easy to it is oxidized, therefore ABS existing defects in weatherability.ASA resins be fine propylene, styrene, The terpolymer of acrylate, it is the alternative materials of ABS resins.Compared with ABS, due to introducing not double bond containing propylene Acid esters rubber instead of butadiene rubber, thus weatherability has the improvement of essence, and 10 times or so are higher by than ABS, other Mechanical property, processing characteristics, electrical insulating property, chemical-resistant are similar to ABS.In addition, ASA colorings are good, due to resin Itself has excellent weather resistance, and can dye various bright-coloreds without fugitive color.The product processed with ASA resin, applied without spray painting The surfacecti proteons such as dress, plating, directly can out of doors use, be exposed to the sun in the sunlight 9~15 months, impact strength and elongation are several Do not decline, color also has almost no change.
Chinese Patent Application No. 201510192462.2 discloses a kind of automobile-used weather-proof ASA materials and preparation method and application, ASA/AS/ABS is subjected to terblending modification according to specific ratio, and adds appropriate toughener, antioxidant, ultraviolet Absorbent, light stabilizer and dispersant prepare a kind of automobile-used weather-proof ASA materials by screw extruder, but with ASA materials Expect there is no ABS good for main body material price costliness and toughness.
Chinese Patent Application No. 201120016079.9 discloses a kind of ABS composite boards, compound in precision die mould An ASA material layers are compounded with ABS resin beds, a kind of good weatherability, shock resistance be strong, good toughness is suitable to open air so as to obtain The composite of application.But the ABS plane in composite board is still unavoidable from being in contact with natural environments such as ultraviolets, thus, The composite board use condition and service life of this kind of structure are by a definite limitation.
In summary, although ASA resin material and the mutually compound weatherability that can improve ABS of ABS resin material, Technical scheme disclosed in prior art still can not meet further to improve ABS resin weatherability under the premise of low cost is met Composite request.
The content of the invention
Have that ABS composite material cost is higher for prior art, the poor technological deficiency of weatherability, the present invention proposes one The high-weatherability ABS fine-celled foams and preparation method of kind sandwich foam-injection, top layer is obtained by using special Shooting Technique ASA ABS fine-celled foams are coated, and then improve ABS resin material weatherability, while reduce raw material use cost.
To solve the above problems, the present invention uses following technical scheme：
On the one hand a kind of high-weatherability ABS fine-celled foams of sandwich foam-injection are provided, the ABS fine-celled foams use following original Material is prepared：
ABS resin 69-71 parts
ASA resin 14-16 parts
Compatilizer 8-10 parts
Antioxidant 2-10 parts
Expandable microspheres 3-5 parts
Toner 0-3 parts
Wherein, the ABS resin be acrylonitrile-butadiene-styrene (ABS) terpolymer, described butadiene content be 30 ~ 50%, described acrylonitrile content is 20 ~ 30%；The ASA resin is acrylonitrile-styrene-acrylic ester copolymer, its rubber Phase acrylate content is 30 ~ 70%；The compatilizer be cyclic acid anhydride type, epoxy type, carboxylic acid type, it is isocyanate-based in one Kind；The antioxidant is to include at least one of antioxidant 1010 or irgasfos 168；The expandable microspheres are internal filling carbon The acrylonitrile copolymer of hydrogen compound, blowing temperature are 220-240 DEG C；The toner is pink group toner, yellow class toner, indigo plant At least one of color class toner, green class toner, white group toner and black class toner.
Preferably, the structure of the ABS fine-celled foams is ASA resin as cladding cortex, folder of the ABS resin as sandwich layer Core structure.
On the other hand, there is provided a kind of preparation method of the high-weatherability ABS fine-celled foams of sandwich foam-injection, using with The bicomponent injection molding machine of two sets of injection moulding apparatus is molded to the injection die cavities with movable post respectively, and preparation method is as follows：
（1）Movable post in injection die cavities is pressurizeed, the movable post is filled into the injection die cavities, the injection die cavities In filling, from cast gate injection 14-16 part melting ASA resins of the injection die cavities, be filled into the movable post with it is described On the inside of injection die cavities in the gap of cavity wall, as cladding cortex；
（2）After ASA resin solidification, the movable post is removed into the injection die cavities, the injection die cavities are in vacant state, lead to Cross same cast gate injection part containing 3-5 expandable microspheres, 8-10 parts compatilizer and 2-10 parts antioxidant, 69-71 parts ABS heating is melted Body, after the melt fills up the injection die cavities, heating devices heat reaches the blowing temperature of expandable microspheres, obtains core ABS resin foamed resin；
（3）ASA resin melt envelope mould is injected, obtains ASA resin as cladding cortex, interlayer structure of the ABS resin as sandwich layer Composite；
Wherein, the movable post is a cylinder, and the axis of the cylinder is identical with the injection die cavities, the radius of the movable post Less than the injection die cavities radius, the movable post can prolong melt flows direction relative to the injection die cavities and do piston movement.
Preferably, before cast gate injection 14-16 part melting ASA resins from the die cavity, methods described is also Including carrying out color matching processing to the ASA resin using 0-3 parts toner.
Preferably, the gap width of the movable post and the injection die cavities cavity wall is 0.3-10mm, the movable cylinder Length is more than or equal to the injection die cavities length.
Preferably, the movable column section is shaped as one kind in circular, ellipse, polygon.
Preferably, the solidification temperature of the ASA resin is 80-85 DEG C, hardening time 1-4h.
Preferably, the heating devices heat is reached for 220-240 DEG C, and expandable microspheres are foamed.
The present invention provide, compared with prior art, its protrude the characteristics of and excellent effect be：
1st, the present invention provides a kind of the high-weatherability ABS fine-celled foams and preparation method of sandwich foam-injection, with two sets of notes The bicomponent injection molding machine of molding apparatus, first by wherein set of device injection ASA as cladding cortex, then it is mixed by the injection of same cast gate There are expandable microspheres and the ABS resin of other auxiliary agents, finally inject ASA melts envelope mould, the ABS that top layer cladding ASA is obtained with this is micro- Hole foam.The present invention provide the above method use special Shooting Technique, overcome ABS weatherabilities in the prior art it is poor and The higher technological deficiency of ABS composite material cost, ABS weatherabilities greatly compensate for using the strong ASA resin of a small amount of weatherability The shortcomings that poor, reduce ABS composite material production cost.
2nd, the high-weatherability ABS fine-celled foam excellent in mechanical performance that scheme disclosed by the invention is prepared, uses mould knot Structure is simple, and injection preparation technology is simple, it is easy to accomplish scale industrial production.
3rd, scheme disclosed by the invention can carry out the bubble that the Exterior color of products that color matching is prepared enriches by toner to ASA Foam product, and then disclosure satisfy that the market demand.
Brief description of the drawings
Fig. 1 is to be molded ASA resin structural representation when injection die cavities are in filling in the embodiment of the present application；
Fig. 2 is to be molded ASA microcellular foam structure schematic diagrames when injection die cavities are in vacant state in the embodiment of the present application.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention Scope be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）0.5 part of toner is used to carry out color matching processing to rubber phase acrylate content for 30% ASA resin.In embodiment Toner is in pink group toner, yellow class toner, blue class toner, green class toner, white group toner and black class toner At least one, wherein, toner raw material type is as follows, pink group toner：Cadmium red, cadmium vermilion, iron oxide red, permanent bordeaux, lithol You are bright red, at least one of lithol your purplish red, lithol rubine；Yellow class toner：It is chrome yellow, Chinese husky of common dye, benzidine, forever solid At least one of yellow, fluorescein；Blue class toner：At least one of iron orchid, cobalt aluminate, phthalocyanine blue；Green class toner：Chromium At least one of green, Phthalocyanine Green G, fluorescence green GG；White group toner：In lithopone, zinc oxide ZnO, titanium dioxide extremely Few one kind；Black class toner：At least one of carbon black, biphenyl amido black, in the present embodiment with from the oxidation of pink group toner Illustrated exemplified by iron oxide red, those skilled in the art can select other one or more of cooperations as needed, in the application In be not specifically limited.
Movable post 02 in injection die cavities 01 is pressurizeed, movable post 02 is filled into injection die cavities 01, injection die cavities 01 In filling, as shown in figure 1, injecting 14-16 parts melting ASA resin from the cast gate 03 of injection die cavities 01, activity is filled into In the gap of post 02 and the inner side cavity wall of injection die cavities 01, as cladding cortex；Movable post 02 and the gap of the cavity wall of injection die cavities 01 Width is 5mm, and the movable length of post 02 is more than or equal to the length of injection die cavities 01.The movable cross sectional shape of post 02 is circular, oval, more One kind in the shape of side, in the present embodiment, movable column section are preferably circular.
（2）Prepare ABS melts.ABS melts contain 3 parts of expandable microspheres, and hydrocarbon is filled inside the expandable microspheres Acrylonitrile copolymer, foamed when temperature is 240 DEG C；8 parts of cyclic acid anhydride type compatilizers；10 parts of antioxidant 1010s；69 parts Butadiene content is 30%, the ABS resin heating melting that acrylonitrile content is 30%, obtains melt.
The solidification temperature of the ASA resin is 85 DEG C, hardening time 1h, and after ASA resin solidification, movable post 02 is moved Go out injection die cavities 01, injection die cavities are in vacant state, as shown in Fig. 2 injecting melt by cast gate 03, note is filled up in the melt After plastotype chamber 01, heating devices heat is reached for 220-240 DEG C, and expandable microspheres are foamed, and obtains core ABS resin foam tree Fat；
（3）ASA resin melt envelope mould is injected, obtains ASA resin as red cladding cortex, ABS resin is as the sandwich of sandwich layer Structural composite material.
A kind of high-weatherability ABS fine-celled foams of the sandwich foam-injection prepared in the present embodiment are tested by weatherability, It is as shown in table 1 to obtain data.
Embodiment 2
（1）Use rubber phase acrylate content to be melted for 370% ASA resin, the movable post 02 in injection die cavities 01 is added Pressure, movable post 02 is filled into injection die cavities 01, and injection die cavities 01 are in filling, as shown in figure 1, from injection die cavities 01 Cast gate 03 inject 14 parts of melting ASA resins, be filled into the gap of movable post 02 and the inner side cavity wall of injection die cavities 01, as bag Cover cortex；Movable post 02 and the gap width of the cavity wall of injection die cavities 01 are 0.3mm, and the movable length of post 02 is more than or equal to injection die cavities 01 length.The movable cross sectional shape of post 02 is one kind in circular, ellipse, polygon, and in the present embodiment, movable column section is excellent Elect circle as.
（2）Prepare ABS melts.ABS melts contain 5 parts of expandable microspheres, and hydrocarbon is filled inside the expandable microspheres Acrylonitrile copolymer, foamed when temperature is 220 DEG C；10 parts of epoxy type compatilizers；2 parts of irgasfos 168s；71 parts of fourths two Alkene content is 50%, the ABS resin heating melting that acrylonitrile content is 20%, obtains melt.
The solidification temperature of the ASA resin is 80 DEG C, hardening time 4h, and after ASA resin solidification, movable post 02 is moved Go out injection die cavities 01, injection die cavities are in vacant state, as shown in Fig. 2 injecting melt by cast gate 03, note is filled up in the melt After plastotype chamber 01, heating devices heat is reached for 220 DEG C, and expandable microspheres are foamed, and obtains core ABS resin foamed resin；
（3）ASA resin melt envelope mould is injected, obtains ASA resin as cladding cortex, interlayer structure of the ABS resin as sandwich layer Composite.
A kind of high-weatherability ABS fine-celled foams of the sandwich foam-injection prepared in the present embodiment are tested by weatherability, It is as shown in table 1 to obtain data.
Embodiment 3
（1）3 parts of toners are used to carry out color matching processing to rubber phase acrylate content for 50% ASA resin.Color in embodiment Powder is in pink group toner, yellow class toner, blue class toner, green class toner, white group toner and black class toner At least one, wherein, toner raw material type is as follows, pink group toner：Cadmium red, cadmium vermilion, iron oxide red, permanent bordeaux, lithol that At least one of your purplish red, lithol rubine of bright red, lithol；Yellow class toner：Chrome yellow, Chinese husky of common dye, benzidine, permanent yellow, At least one of fluorescein；Blue class toner：At least one of iron orchid, cobalt aluminate, phthalocyanine blue；Green class toner：Chrome green, At least one of Phthalocyanine Green G, fluorescence green GG；White group toner：At least one in lithopone, zinc oxide ZnO, titanium dioxide Kind；Black class toner：At least one of carbon black, biphenyl amido black, in the present embodiment by from exemplified by green class toner chrome green Illustrate, those skilled in the art can select other one or more of cooperations as needed, and those skilled in the art can To select one or more of cooperations as needed, it is not specifically limited in this application.
Movable post 02 in injection die cavities 01 is pressurizeed, movable post 02 is filled into injection die cavities 01, injection die cavities 01 In filling, as shown in figure 1, injecting 15 parts of melting ASA resins from the cast gate 03 of injection die cavities 01, movable post 02 is filled into With in the gap of the inner side cavity wall of injection die cavities 01, as cladding cortex；Movable post 02 and the gap width of the cavity wall of injection die cavities 01 For 1mm, the movable length of post 02 is more than or equal to the length of injection die cavities 01.The movable cross sectional shape of post 02 is circular, ellipse, polygon In one kind, in the present embodiment, movable column section be preferably ellipse.
（2）Prepare ABS melts.ABS melts contain 4 parts of expandable microspheres, and hydrocarbon is filled inside the expandable microspheres Acrylonitrile copolymer, foamed when temperature is 230 DEG C；9 parts of isocyanate-based compatilizers；4 parts of antioxidant 1010s；69 parts of fourths Diene content is 35%, the ABS resin heating melting that acrylonitrile content is 23%, obtains melt.
The solidification temperature of the ASA resin is 83 DEG C, hardening time 3.5h, after ASA resin solidification, by movable post 02 Injection die cavities 01 are removed, injection die cavities are in vacant state, as shown in Fig. 2 injecting melt by cast gate 03, are filled up in the melt After injection die cavities 01, heating devices heat is reached for 225 DEG C, and expandable microspheres are foamed, and obtains core ABS resin foam tree Fat；
（3）ASA resin melt envelope mould is injected, obtains ASA resin as green cladding cortex, ABS resin is as the sandwich of sandwich layer Structural composite material.
A kind of high-weatherability ABS fine-celled foams of the sandwich foam-injection prepared in the present embodiment are tested by weatherability, It is as shown in table 1 to obtain data.
Embodiment 4
（1）1 part of toner is used to carry out color matching processing to rubber phase acrylate content for 60% ASA resin.Color in embodiment Powder is in pink group toner, yellow class toner, blue class toner, green class toner, white group toner and black class toner At least one, wherein, toner raw material type is as follows, pink group toner：Cadmium red, cadmium vermilion, iron oxide red, permanent bordeaux, lithol that At least one of your purplish red, lithol rubine of bright red, lithol；Yellow class toner：Chrome yellow, Chinese husky of common dye, benzidine, permanent yellow, At least one of fluorescein；Blue class toner：At least one of iron orchid, cobalt aluminate, phthalocyanine blue；Green class toner：Chrome green, At least one of Phthalocyanine Green G, fluorescence green GG；White group toner：At least one in lithopone, zinc oxide ZnO, titanium dioxide Kind；Black class toner：At least one of carbon black, biphenyl amido black, in the present embodiment using from white group toner lithopone as Example illustrates, and those skilled in the art can select other one or more of cooperations, those skilled in the art as needed The cooperation of one or more can be selected as needed, be not specifically limited in this application.
Movable post 02 in injection die cavities 01 is pressurizeed, movable post 02 is filled into injection die cavities 01, injection die cavities 01 In filling, as shown in figure 1, injecting 16 parts of melting ASA resins from the cast gate 03 of injection die cavities 01, movable post 02 is filled into With in the gap of the inner side cavity wall of injection die cavities 01, as cladding cortex；Movable post 02 and the gap width of the cavity wall of injection die cavities 01 For 5mm, the movable length of post 02 is more than or equal to the length of injection die cavities 01.The movable cross sectional shape of post 02 is circular, ellipse, polygon In one kind, in the present embodiment, movable column section be preferably square.
（2）Prepare ABS melts.ABS melts contain 5 parts of expandable microspheres, and hydrocarbon is filled inside the expandable microspheres Acrylonitrile copolymer, foamed when temperature is 235 DEG C；8.5 parts of carboxylic acid type compatilizers；With 8 parts of irgasfos 168s；71 parts of fourths Diene content is 35%, the ABS resin heating melting that acrylonitrile content is 28%, obtains melt.
The solidification temperature of the ASA resin is 83 DEG C, hardening time 2h, and after ASA resin solidification, movable post 02 is moved Go out injection die cavities 01, injection die cavities are in vacant state, as shown in Fig. 2 injecting melt by cast gate 03, note is filled up in the melt After plastotype chamber 01, heating devices heat is reached for 240 DEG C, and expandable microspheres are foamed, and obtains core ABS resin foamed resin；
（3）ASA resin melt envelope mould is injected, obtains ASA resin as white cladding cortex, ABS resin is as the sandwich of sandwich layer Structural composite material.
A kind of high-weatherability ABS fine-celled foams of the sandwich foam-injection prepared in the present embodiment are tested by weatherability, It is as shown in table 1 to obtain data.
Embodiment 5
（1）3 parts of toners are used to carry out color matching processing to rubber phase acrylate content for 55% ASA resin.Color in embodiment Powder is in pink group toner, yellow class toner, blue class toner, green class toner, white group toner and black class toner At least one, wherein, toner raw material type is as follows, pink group toner：Cadmium red, cadmium vermilion, iron oxide red, permanent bordeaux, lithol that At least one of your purplish red, lithol rubine of bright red, lithol；Yellow class toner：Chrome yellow, Chinese husky of common dye, benzidine, permanent yellow, At least one of fluorescein；Blue class toner：At least one of iron orchid, cobalt aluminate, phthalocyanine blue；Green class toner：Chrome green, At least one of Phthalocyanine Green G, fluorescence green GG；White group toner：At least one in lithopone, zinc oxide ZnO, titanium dioxide Kind；Black class toner：At least one of carbon black, biphenyl amido black, in the present embodiment with from white group toner lithopone and Illustrated exemplified by black class toner biphenyl amido black, those skilled in the art can select other one or more as needed Coordinate, those skilled in the art can select the cooperation of one or more as needed, be not specifically limited in this application.
Movable post 02 in injection die cavities 01 is pressurizeed, movable post 02 is filled into injection die cavities 01, injection die cavities 01 In filling, as shown in figure 1, injecting 15 parts of melting ASA resins from the cast gate 03 of injection die cavities 01, movable post 02 is filled into With in the gap of the inner side cavity wall of injection die cavities 01, as cladding cortex；Movable post 02 and the gap width of the cavity wall of injection die cavities 01 For 6.5mm, the movable length of post 02 is more than or equal to the length of injection die cavities 01.The movable cross sectional shape of post 02 is circular, oval, polygon One kind in shape, in the present embodiment, movable column section are preferably circular.
（2）Prepare ABS melts.The ABS melts expandable microspheres of part containing 3-5, the expandable microspheres inside filling hydrocarbon Acrylonitrile copolymer, temperature be 225 DEG C when foamed；10 epoxy type compatilizers；9 parts of irgasfos 168s；69 parts of butadiene Content is 35%, the ABS resin heating melting that acrylonitrile content is 22%, obtains melt.
The solidification temperature of the ASA resin is 83 DEG C, hardening time 2.5h, after ASA resin solidification, by movable post 02 Injection die cavities 01 are removed, injection die cavities are in vacant state, as shown in Fig. 2 injecting melt by cast gate 03, are filled up in the melt After injection die cavities 01, heating devices heat is reached for 220-240 DEG C, and expandable microspheres are foamed, and obtains core ABS resin foam Resin；
（3）ASA resin melt envelope mould is injected, ASA resin is obtained and coats cortex as grey, ABS resin is as the sandwich of sandwich layer Structural composite material.
A kind of high-weatherability ABS fine-celled foams of the sandwich foam-injection prepared in the present embodiment are tested by weatherability, It is as shown in table 1 to obtain data.
Table one
Test performance Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Density g/cm3 0.621 0.712 0.739 0.698 0.769
Bending strength MPa 87 83 92 90 89
Tensile strength MPa 58 54 51 61 59
Shrinkage factor % 0.3 0.4 0.5 0.3 0.4
Heat-proof aging time h 9800 10200 11030 9950 10080

Claims (8)

  1. A kind of 1. high-weatherability ABS fine-celled foams of sandwich foam-injection, it is characterised in that the ABS fine-celled foams use with Lower raw material is prepared：
    ABS resin 69-71 parts
    ASA resin 14-16 parts
    Compatilizer 8-10 parts
    Antioxidant 2-10 parts
    Expandable microspheres 3-5 parts
    Toner 0-3 parts
    Wherein, the ABS resin be acrylonitrile-butadiene-styrene (ABS) terpolymer, described butadiene content be 30 ~ 50%, described acrylonitrile content is 20 ~ 30%；The ASA resin is acrylonitrile-styrene-acrylic ester copolymer, its rubber Phase acrylate content is 30 ~ 70%；The compatilizer be cyclic acid anhydride type, epoxy type, carboxylic acid type, it is isocyanate-based in one Kind；The antioxidant is to include at least one of antioxidant 1010 or irgasfos 168；The expandable microspheres are internal filling carbon The acrylonitrile copolymer of hydrogen compound, blowing temperature are 220-240 DEG C；The toner is pink group toner, yellow class toner, indigo plant At least one of color class toner, green class toner, white group toner and black class toner.
  2. A kind of 2. high-weatherability ABS fine-celled foams of sandwich foam-injection according to claim 1, it is characterised in that：It is described The structure of ABS fine-celled foams is ASA resin as cladding cortex, interlayer structure of the ABS resin as sandwich layer.
  3. 3. the preparation method of the high-weatherability ABS fine-celled foams of a kind of sandwich foam-injection, it is characterised in that using with two sets The bicomponent injection molding machine of injection moulding apparatus is molded to the injection die cavities with movable post respectively, and preparation method is as follows：
    （1）Movable post in injection die cavities is pressurizeed, the movable post is filled into the injection die cavities, the injection die cavities In filling, from cast gate injection 14-16 part melting ASA resins of the injection die cavities, be filled into the movable post with it is described On the inside of injection die cavities in the gap of cavity wall, as cladding cortex；
    （2）After ASA resin solidification, the movable post is removed into the injection die cavities, the injection die cavities are in vacant state, lead to Cross same cast gate injection part containing 3-5 expandable microspheres, 8-10 parts compatilizer and 2-10 parts antioxidant, 69-71 parts ABS heating is melted Body, after the melt fills up the injection die cavities, heating devices heat reaches the blowing temperature of expandable microspheres, obtains core ABS resin foamed resin；
    （3）ASA resin melt envelope mould is injected, obtains ASA resin as cladding cortex, interlayer structure of the ABS resin as sandwich layer Composite；
    Wherein, the movable post is a cylinder, and the axis of the cylinder is identical with the injection die cavities, the radius of the movable post Less than the injection die cavities radius, the movable post can prolong melt flows direction relative to the injection die cavities and do piston movement.
  4. 4. the preparation method of the high-weatherability ABS fine-celled foams of a kind of sandwich foam-injection according to claim 3, its feature It is, before cast gate injection 14-16 part melting ASA resins from the die cavity, methods described also includes using 0-3 Part toner carries out color matching processing to the ASA resin.
  5. 5. the preparation method of the high-weatherability ABS fine-celled foams of a kind of sandwich foam-injection according to claim 3, its feature It is, the movable post and the gap width of the injection die cavities cavity wall are 0.3-10mm, and the movable cylinder length is more than etc. In the injection die cavities length.
  6. 6. the preparation method of the high-weatherability ABS fine-celled foams of a kind of sandwich foam-injection according to claim 3, its feature It is, the movable column section is shaped as one kind in circular, ellipse, polygon.
  7. 7. the preparation method of the high-weatherability ABS fine-celled foams of a kind of sandwich foam-injection according to claim 3, its feature It is, the solidification temperature of the ASA resin is 80-85 DEG C, hardening time 1-4h.
  8. 8. the preparation method of the high-weatherability ABS fine-celled foams of a kind of sandwich foam-injection according to claim 3, its feature It is, the heating devices heat is reached for 220-240 DEG C, and expandable microspheres are foamed.
CN201710695321.1A 2017-08-15 2017-08-15 Sandwich injection foaming high-weather-resistance ABS (acrylonitrile butadiene styrene) microcellular foam and preparation method thereof Active CN107501841B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06287337A (en) * 1993-04-05 1994-10-11 Sekisui Chem Co Ltd Abs resin foam
CN1426323A (en) * 2000-04-28 2003-06-25 阿克佐诺贝尔公司 Chemical product and method
CN103602028A (en) * 2013-10-24 2014-02-26 合肥会通新材料有限公司 Injection-molding-grade foaming ABS material and preparation method thereof
CN106494042A (en) * 2016-11-15 2017-03-15 苏州亨达尔工业材料有限公司 A kind of ABS composite boards

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06287337A (en) * 1993-04-05 1994-10-11 Sekisui Chem Co Ltd Abs resin foam
CN1426323A (en) * 2000-04-28 2003-06-25 阿克佐诺贝尔公司 Chemical product and method
CN103602028A (en) * 2013-10-24 2014-02-26 合肥会通新材料有限公司 Injection-molding-grade foaming ABS material and preparation method thereof
CN106494042A (en) * 2016-11-15 2017-03-15 苏州亨达尔工业材料有限公司 A kind of ABS composite boards

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Title
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