CN102464847A - Resin composition and preparation method thereof - Google Patents
Resin composition and preparation method thereof Download PDFInfo
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- CN102464847A CN102464847A CN2010105443648A CN201010544364A CN102464847A CN 102464847 A CN102464847 A CN 102464847A CN 2010105443648 A CN2010105443648 A CN 2010105443648A CN 201010544364 A CN201010544364 A CN 201010544364A CN 102464847 A CN102464847 A CN 102464847A
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Abstract
The invention relates to a resin composition and a preparation method thereof. The resin composition comprises: by weight, 100 parts of resin, 0.2 to 3.0 parts of a bridge structure modifier, 0.3 to 4.0 parts of metal pigment, 0.3 to 2.0 parts of one or more lubricants, 0.1 to 1.0 part of one or more anti-oxidants and 0.1 to 0.3 parts of mineral oil. The preparation method comprises the following steps of mixing a part of the resin, the bridge structure modifier, the one or more lubricants and the one or more anti-oxidants according a certain ratio to obtain a mixture I, pre-mixing the rest of the resin and the mineral oil, adding the metal pigment into the mixture of the rest of the resin and the mineral oil to obtain a mixture II, adding the mixture I and the mixture II into a double screw extruder respectively from an upper feed inlet and a lower feed inlet, and carrying out melting extrusion, drawing, cooling and cutting to obtain the resin composition. The resin composition obtained by the preparation method has an excellent appearance, and solves the problem that when transparent or semitransparent resin is mixed with metal pigment having a certain length-diameter ratio, a streamline or a fusion line can be produced. The resin composition can be utilized for production of streamline-free resin compositions which are flashy or have metal luster.
Description
Technical field
The present invention relates to a kind of Polymer Resin And Its Preparation Method, especially relate to a kind of resin combination and preparation method thereof.
Background technology
In recent years, the consumer's goods have produced the intensive demand to the plastics with unique color and outward appearance.For example; The outward appearance product that has flicker effect and metal-like at present more and more receives human consumer's favor, compares with traditional single tone, and the outward appearance of this uniqueness can be brought great visual impact to the people; Make the human consumer can enjoy its aesthetic design, we call aesthstic resin to this material.
The traditional technical scheme of aesthstic resin is that moulding product is carried out aftertreatment, and using maximum is spraying coating process, can select pearlescent lacquer, metallic paint etc. according to product needed.But spraying coating process has many restrictions, and higher to the blank surface requirements like complex procedures, the result causes product cost to be multiplied; On the other hand, sprayed product can't reclaim, and environment has been caused great pressure.Therefore, developed novel metal pigment at present, can be directly and resin alloy obtain plastics with metalluster or flicker effect.In order to reach or, to give product true metal outward appearance or intensive flicker effect just often need metallic pigment to have certain length-to-diameter ratio near spraying effect.At present, aluminium powder is to use the metallic pigment that have certain length-to-diameter ratio the most widely, and aluminium powder pigment has " contrast effect ", and during promptly from its coating of different viewed, the color of coating can change along with the variation of angle.Usually during the top view coating, coating color is brighter, and during the viewed coating, it is dim relatively that its color then can seem.The ability of aluminium powder pigment reflection ray is more intense, but its coating reflect visible light not only, but also can emitted in ultraviolet light and infrared light, to the full spectral reflectance of visible light, thereby visually present silvery white, have extremely strong metal effect.
Through the selection of length-to-diameter ratio, can obtain the different appearance effect.As the fiber of high length-diameter ratio can be given the higher intensity of material, the length-to-diameter ratio of aluminium powder was big more, and metal-like that product showed and flicker effect are strong more, and this is often favored by the human consumer.But high aspect ratio additive tends to material is brought other negative impacts giving material in a certain respect outside the performance.For example, roving glass fiber can be given higher modulus of resin and intensity than short glass fiber, but the even more serious floating fine problem that the high length-diameter ratio glass brings lets the people be difficult to accept.Its shortcoming of goods that adds aluminium powder is that it has high length-diameter ratio; Often change orientation therefrom at bonding wire or other inhomogeneous mobile regional aluminium powders; Flow field in himself and the course of processing is consistent, thereby in end article, produces tangible streamline or bonding wire, in transparent or semitransparent goods, show as this zone aluminium powder disappearance; Form inaesthetic dark line, and this another one principal character of aluminium powder just: with corner effect.
The geometrical shape of granules of pigments often produces considerable influence to the optical effect of goods; Like sheet or silver dollar shape pigment often is polyhedron; The pigment of this type resistance to flow when running into thin-walled, screw hole or cavity improves in the moulding process; Cause these regional pigment to be piled up and other regional pigment disappearances, it is attractive in appearance to have influenced product greatly; In addition, near the cast gate and goods top layer is a high shear zone in the injection moulding, causes the lamellar pigment orientation easily, owing to reflectance varies causes unacceptable color.And particle spheric; Then isotropic on its rheodynamics; Thereby help reducing or eliminating of streamline or bonding wire; But because spherical pigment reflectivity is lower, metal-like that can't obtain to expect and flicker effect are so the resin combination that how to obtain not have streamline (bonding wire) and have the true metal outward appearance becomes the technical barrier that needs to be resolved hurrily.
Summary of the invention
The object of the invention is exactly a kind of macroscopic irregularity that has solved streamline or bonding wire is provided in order to overcome the defective that above-mentioned prior art exists, has resin combination of metal effect and excellent appearance and preparation method thereof.
The object of the invention can be realized through following technical scheme:
A kind of resin combination is characterized in that, this resin combination comprises following component and weight part content:
Transparent or semitransparent resin 100;
The properties-correcting agent 0.2～3.0 of bridge formation structure;
Metallic pigment 0.3～4.0;
Lubricant 0.3～2.0;
Oxidation inhibitor 0.1～1.0;
MO 0.1～0.3.
Described transparent or semitransparent resin is selected from one or more mixtures among commercially available PMMA, SAN, GPPS, PETG, PC, ABS or the MS.
The properties-correcting agent of described bridge formation structure is crosslinked Sipacril 2739OF or cross-linked styrene multipolymer, and microscopic pattern is spherical, and particle diameter is 1～300 μ m, preferred 2～200 μ m, more preferably 2～150 μ m.
The properties-correcting agent index difference of described resin and bridge formation structure is 0.01～0.15, and is preferred 0.04～0.1, and its rheology viscosity of the properties-correcting agent of bridge formation structure is far longer than the transparent or semitransparent resin of being selected for use.
Described metallic pigment are selected from one or more in aluminium, gold and silver, titanium, silver, MOX, mica, sheet glass or the tinting material, and the length-to-diameter ratio of metallic pigment is 1: 1～40: 1, preferred 1: 1～15: 1.
Described lubricant is one or more in silicone oil, white mineral oil, fatty acid amide, barium stearate, Magnesium Stearate, paraffin, polyethylene wax, ethylene bis stearic acid amide, Injecatable EVA Copolymer or the ethylene-acrylic acid copolymer.
Described oxidation inhibitor comprises refine one or more of Irganox 1010, Irganox 1076 or Irganox168 of company of CIBA.
This resin combination can also comprise one or more in tinting material, static inhibitor, fire retardant, photostabilizer or the anti-dripping agent, and the weight part content of above-mentioned auxiliary agent is 0.1～1.0.
A kind of preparation method of resin combination is characterized in that, this method may further comprise the steps:
(1) get the raw materials ready according to following component and weight part content:
Resin 100,
The properties-correcting agent 0.2～3.0 of bridge formation structure,
Metallic pigment 0.3～4.0,
Lubricant 0.3～2.0,
Oxidation inhibitor 0.1～1.0,
MO 0.1～0.3
(2) properties-correcting agent, lubricant and the oxidation inhibitor of the resin of said ratio 60～80wt%, bridge formation structure are pressed formula rate and are mixed after, place high-speed mixer premix 5～10min;
(3) remaining resin and MO are added metallic pigment continuation mixing 5min behind premix 3～5min in low speed mixer, metallic pigment are evenly distributed in the resin;
(4) mixture that step (1) is obtained adds from the upper reaches spout of twin screw extruder; The mixture that step (2) obtains adds from the downstream spout of twin screw extruder; Control reaction temperature is 180～230 ℃; Melt extrude, tie rod, cooling, pelletizing step, the resin combination that obtains having excellent appearance is product.
Compared with prior art, the present invention has the following advantages:
(1) properties-correcting agent through the bridge formation structure and " microcapsule " structure that metallic pigment form have solved the metallic pigment with certain length-to-diameter ratio owing to be orientated the streamline that causes or the macroscopic irregularity of bonding wire;
(2) true metal outward appearance is compared through selecting for use spherical metal pigment to reach the scheme that reduces streamline with existing, and the present invention has given full play to the true metal appearance of high length-diameter ratio metallic pigment, has higher market outlook.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated.
Following component is used for specific embodiment and Comparative Examples:
1, transparent resin:
PMMA/ABS: beautiful transparent resin HAM8541 of bright and beautiful lake day
2, the properties-correcting agent of bridge formation structure:
Properties-correcting agent-1: crosslinked polystyrene, particle diameter 120 μ m, specific refractory power 1.586;
Properties-correcting agent-2: crosslinked polystyrene, particle diameter 80 μ m, specific refractory power 1.584;
Properties-correcting agent-3: crosslinked PMMA, particle diameter 80 μ m, specific refractory power 1.516;
3, the metallic pigment that have certain length-to-diameter ratio:
Metallic pigment-1: length-to-diameter ratio 4: 1;
Metallic pigment-2: length-to-diameter ratio 20: 1;
Metallic pigment-3: length-to-diameter ratio 1: 1;
4, other components comprise:
Oxidation inhibitor 168, antioxidant 1010, vapour crust elite;
Lubricant: N, N-ethylidene-bis-stearamides EBS:HONEYWELL
Following preparation scheme is used for specific embodiment and Comparative Examples:
Implement 1～5
1) with part PMMA (80%) and other components except that metallic pigment and MO premix 5～10min in high-speed mixer by a certain percentage;
2) remaining PMMA (20%) is added metallic pigment mixing 5min by a certain percentage with MO behind premix 3～5min in low speed mixer, make metallic pigment can be evenly distributed in the resin;
3) through twin screw extruder, with 1) spout adds from the upper reaches, with 2) from downstream spout add melt extrude, tie rod, cooling, pelletizing step, the resin combination that obtains having excellent appearance.
Comparative Examples 1
All components added behind the premix 10min in the twin screw extruder in high-speed mixer by a certain percentage melt extrude, tie rod, cooling, pelletizing, the resin combination that obtains having excellent appearance.
Comparative Examples 2
1) with part PMMA (80%) and other components except that metallic pigment and MO premix 5～10min in high-speed mixer by a certain percentage;
2) remaining PMMA (20%) is added metallic pigment mixing 5min by a certain percentage with MO behind premix 3～5min in low speed mixer, make metallic pigment can be evenly distributed in the resin;
3) through twin screw extruder, with 1) spout adds from the upper reaches, with 2) from downstream spout add melt extrude, tie rod, cooling, pelletizing step, the resin combination that obtains having excellent appearance;
Comparative Examples 3
All components added behind the premix 10min in the twin screw extruder in high-speed mixer by a certain percentage melt extrude, tie rod, cooling, pelletizing, the resin combination that obtains having excellent appearance.
The every kind of component that is used for embodiment 1～5 and comparative example 1～3 is by setting shown in the table 1:
Table 1
Method of evaluating performance:
Sample to be tested mould: be of a size of 50cm*50cm*2mm, 2 in symmetric points cast gate
The sample of injection formed is through observation by light microscope welded bonds place's flicker effect and measure the welded bonds width;
Specific embodiment 1～5 is seen table 2 with Comparative Examples 1～3 test result
Table 2: embodiment 1～5 and contrast 1～3 compsn test result
Annotate: ★, and the flicker effect of representing is strong more;
★ is stronger than ☆ flicker effect;
Can find out that by table 2 embodiment that comprises component described in claims has good outward appearance, comprise the flicker effect that the weld bond degree that reduces and visual degree increase; Through embodiment 1 and Comparative Examples 2 contrast discoveries, the realization with resin combination of excellent appearance depends on preparation method of the present invention.
The product that obtains can be through injection moulding, extrude, blowing or other are by institute of the present invention limiting method moulding, is used for the outer case ring of LCD, air-conditioning panel etc.
Embodiment 6
A kind of preparation method of resin combination is characterized in that, this method may further comprise the steps:
(1) gets the raw materials ready according to following component and weight part content: the properties-correcting agent 0.2kg of transparent resin 100kg, bridge formation structure, metallic pigment 0.3kg, lubricant 0.3kg, oxidation inhibitor 0.1kg, MO 0.1kg; In addition, can also comprise the static inhibitor of 0.3kg, wherein; Transparent resin is that commercially available PMMA, the properties-correcting agent of bridge formation structure are crosslinked Sipacril 2739OF, and microscopic pattern is spherical, and particle diameter is 2 μ m; The properties-correcting agent index difference of transparent resin and bridge formation structure is 0.04, and its rheology viscosity of the properties-correcting agent of bridge formation structure is far longer than transparent resin, the metallic aluminium pigment of being selected for use, and length-to-diameter ratio is 1: 1; Lubricant is a silicone oil, and oxidation inhibitor is the refine Irganox 1010 of company of CIBA;
(2) properties-correcting agent, lubricant and the oxidation inhibitor of the transparent resin of said ratio 60wt%, bridge formation structure are pressed formula rate and are mixed after, place high-speed mixer premix 5min;
(3) remaining resin, MO and static inhibitor are added metallic pigment behind the premix 3min in low speed mixer and continue to mix 5min, metallic pigment are evenly distributed in the resin;
(4) mixture that step (1) is obtained adds from the upper reaches spout of twin screw extruder; The mixture that step (2) obtains adds from the downstream spout of twin screw extruder; Control reaction temperature is 180 ℃; Melt extrude, tie rod, cooling, pelletizing step, the resin combination that obtains having excellent appearance is product.
Embodiment 7
A kind of preparation method of resin combination, this method may further comprise the steps:
(1) gets the raw materials ready according to following component and weight part content: the properties-correcting agent 3kg of semi-transparent resin 100kg, bridge formation structure, metallic pigment 4kg, lubricant 2kg, oxidation inhibitor 1kg, MO 0.3kg; In addition, can also comprise the fire retardant of 0.1kg and the mixture of photostabilizer, wherein; Semi-transparent resin is that the properties-correcting agent of commercially available GPPS and PETG mixture, bridge formation structure is crosslinked cross-linked styrene multipolymer; Microscopic pattern is spherical, and particle diameter is 150 μ m, and the properties-correcting agent index difference of transparent resin and bridge formation structure is 0.1; Its rheology viscosity of the properties-correcting agent of bridge formation structure is far longer than semi-transparent resin, the burning titanium pigment of being selected for use; Length-to-diameter ratio is 15: 1, and lubricant is a silicone oil, and oxidation inhibitor is the refine Irganox 168 of company of CIBA;
(2) properties-correcting agent, lubricant and the oxidation inhibitor of the semi-transparent resin of said ratio 80wt%, bridge formation structure are pressed formula rate and are mixed after, place high-speed mixer premix 10min;
(3) remaining resin, MO, fire retardant and photostabilizer are added metallic pigment behind the premix 5min in low speed mixer and continue to mix 5min, metallic pigment are evenly distributed in the resin;
(4) mixture that step (1) is obtained adds from the upper reaches spout of twin screw extruder; The mixture that step (2) obtains adds from the downstream spout of twin screw extruder; Control reaction temperature is 230 ℃; Melt extrude, tie rod, cooling, pelletizing step, the resin combination that obtains having excellent appearance is product.
Claims (9)
1. a resin combination is characterized in that, this resin combination comprises following component and weight part content:
Resin 100;
The properties-correcting agent 0.2～3.0 of bridge formation structure;
Metallic pigment 0.3～4.0
Lubricant 0.3～2.0
Oxidation inhibitor 0.1～1.0;
MO 0.1～0.3.
2. a kind of resin combination according to claim 1 is characterized in that, described resin is selected from one or more mixtures among commercially available PMMA, SAN, GPPS, PETG, PC, ABS or the MS.
3. a kind of resin combination according to claim 1 is characterized in that, the properties-correcting agent of described bridge formation structure is crosslinked Sipacril 2739OF or cross-linked styrene multipolymer; Microscopic pattern is spherical; Particle diameter is 1～300 μ m, preferred 2～200 μ m, more preferably 2～150 μ m.
4. a kind of resin combination according to claim 1 is characterized in that, the properties-correcting agent index difference of described resin and bridge formation structure is 0.01～0.15, preferred 0.04～0.1.
5. a kind of resin combination according to claim 1; It is characterized in that; Described metallic pigment are selected from one or more in aluminium, gold and silver, titanium, silver, MOX, mica, sheet glass or the tinting material, and the length-to-diameter ratio of metallic pigment is 1: 1～40: 1, preferred 1: 1～15: 1.
6. a kind of resin combination according to claim 1; It is characterized in that described lubricant is one or more in silicone oil, white mineral oil, fatty acid amide, barium stearate, Magnesium Stearate, paraffin, polyethylene wax, ethylene bis stearic acid amide, Injecatable EVA Copolymer or the ethylene-acrylic acid copolymer.
7. a kind of resin combination according to claim 1 is characterized in that, described oxidation inhibitor comprises refine one or more of Irganox 1010, Irganox 1076 or Irganox 168 of company of CIBA.
8. a kind of resin combination according to claim 1; It is characterized in that; This resin combination can also comprise one or more in tinting material, static inhibitor, fire retardant, photostabilizer or the anti-dripping agent, and the weight part content of above-mentioned auxiliary agent is 0.1～1.0.
9. the preparation method of a resin combination as claimed in claim 1 is characterized in that, this method may further comprise the steps:
(1) get the raw materials ready according to following component and weight part content:
Resin 100,
The properties-correcting agent 0.2～3.0 of bridge formation structure,
Metallic pigment 0.3～4.0,
Lubricant 0.3～2.0,
Oxidation inhibitor 0.1～1.0,
MO 0.1～0.3;
(2) properties-correcting agent, lubricant and the oxidation inhibitor of the resin of said ratio 60～80wt%, bridge formation structure are pressed formula rate and are mixed after, place high-speed mixer premix 5～10min;
(3) remaining resin and MO are added metallic pigment continuation mixing 5min behind premix 3～5min in low speed mixer, metallic pigment are evenly distributed in the resin;
(4) mixture that step (1) is obtained adds from the upper reaches spout of twin screw extruder; The mixture that step (2) obtains adds from the downstream spout of twin screw extruder; Control reaction temperature is 180～230 ℃; Melt extrude, tie rod, cooling, pelletizing step, the resin combination that obtains having excellent appearance is product.
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| CN2010105443648A CN102464847A (en) | 2010-11-15 | 2010-11-15 | Resin composition and preparation method thereof |
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| CN2010105443648A CN102464847A (en) | 2010-11-15 | 2010-11-15 | Resin composition and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952362A (en) * | 2012-11-15 | 2013-03-06 | 合肥会通新材料有限公司 | Metallic super-toughened PMMA (polymethyl methacrylate) composite material and preparation method thereof |
| CN102993587A (en) * | 2012-12-14 | 2013-03-27 | 上海锦湖日丽塑料有限公司 | Resin composition containing effect pigments and preparation method of resin composition |
| CN103624915A (en) * | 2013-12-09 | 2014-03-12 | 四川长虹模塑科技有限公司 | Manufacturing method of air-conditioning panel |
| CN105612205A (en) * | 2013-10-14 | 2016-05-25 | 埃卡特有限公司 | Plastics composition comprising at least one metal pigment, method for production and use thereof |
| CN107629296A (en) * | 2017-10-18 | 2018-01-26 | 安徽天易金属新材料有限公司 | A kind of plastic cement low current mark aluminium pigment and preparation method thereof |
| CN109721922A (en) * | 2018-12-26 | 2019-05-07 | 金旸（厦门）新材料科技有限公司 | A kind of bathroom high glaze antibacterial flame-retardant AS/MS composite material and preparation method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952362A (en) * | 2012-11-15 | 2013-03-06 | 合肥会通新材料有限公司 | Metallic super-toughened PMMA (polymethyl methacrylate) composite material and preparation method thereof |
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| CN102993587A (en) * | 2012-12-14 | 2013-03-27 | 上海锦湖日丽塑料有限公司 | Resin composition containing effect pigments and preparation method of resin composition |
| CN102993587B (en) * | 2012-12-14 | 2014-12-17 | 上海锦湖日丽塑料有限公司 | Resin composition containing effect pigments and preparation method of resin composition |
| CN105612205A (en) * | 2013-10-14 | 2016-05-25 | 埃卡特有限公司 | Plastics composition comprising at least one metal pigment, method for production and use thereof |
| CN103624915A (en) * | 2013-12-09 | 2014-03-12 | 四川长虹模塑科技有限公司 | Manufacturing method of air-conditioning panel |
| CN107629296A (en) * | 2017-10-18 | 2018-01-26 | 安徽天易金属新材料有限公司 | A kind of plastic cement low current mark aluminium pigment and preparation method thereof |
| CN107629296B (en) * | 2017-10-18 | 2020-06-26 | 安徽天易金属新材料有限公司 | Low-flow-mark aluminum pigment for plastics and preparation method thereof |
| CN109721922A (en) * | 2018-12-26 | 2019-05-07 | 金旸（厦门）新材料科技有限公司 | A kind of bathroom high glaze antibacterial flame-retardant AS/MS composite material and preparation method |
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Application publication date: 20120523 |