CN109161151A - Transparent ABS frosted resin and preparation method thereof - Google Patents
Transparent ABS frosted resin and preparation method thereof Download PDFInfo
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- CN109161151A CN109161151A CN201810655908.4A CN201810655908A CN109161151A CN 109161151 A CN109161151 A CN 109161151A CN 201810655908 A CN201810655908 A CN 201810655908A CN 109161151 A CN109161151 A CN 109161151A
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
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Abstract
The present invention relates to frosted resins, more specifically, it relates to transparent ABS frosted resin and preparation method thereof.Aim to solve the problem that ground glass with respect to frosted resin than heavier, breakable problem.Its key points of the technical solution are that: including following components and weight percent: ABS resin 80-97%, 3-20% parts of organosilicon microballoon.By using the above proportion, the refractive index of ABS resin is increased to 1.6-1.7, and light transmittance declines 5-15%, and the light for issuing LED light is softer, and intensity is high, and good toughness, formula is simple, easily prepared, at low cost, more meets consumer demand.
Description
Technical field
The present invention relates to frosted resins, more specifically, it relates to transparent ABS frosted resin and preparation method thereof.
Background technique
In general, frosted is exactly that the smooth object in script surface is become rough, is formed on its surface light irradiation
One procedure of diffusing reflection shape, resulting product become frosted product.
Lamps and lanterns usually all select ground glass or resin to achieve the effect that light is soft, but are machined into method
Produce ground glass or resin, such as blasting craft, not only large labor intensity, and also effect is not ideal enough.
In view of the above-mentioned problems, currently, the Chinese patent of Publication No. CN103342952A discloses a kind of polyurethane resin
Frosted coating and preparation method thereof, its key points of the technical solution are that: a kind of multi-component polyurethane frosted coating is first produced, then again
Polyurethane frosted coating is sprayed on the glass by cleaning up, imitative frosted finish effect is obtained after baking.
Although above scheme improves the frosted finish effect of glass, but ground glass made from foregoing invention is with respect to frosted tree
Rouge is easily broken than heavier.
Summary of the invention
In view of the deficienciess of the prior art, the purpose of the present invention one is to provide transparent ABS frosted resin, resin itself
Just there is frosted finish effect, light-weight, good toughness, and LED light light obtained is softer.
Above-mentioned technical purpose one of the invention has the technical scheme that transparent ABS frosted resin, packet
Include following components and weight percent:
ABS resin 80-97%
Organosilicon microballoon 3-20%.
By using above-mentioned technical proposal, ABS resin, full name is acrylonitrile-butadiene-styrene copolymer, is a kind of
Intensity height, good toughness, thermoplastics type's Polymer Materials ' Structure easily processed into type.ABS resin be acrylonitrile, 1,3-butadiene,
The terpolymer of styrene can act normally in the environment of -25 DEG C ~ 60 DEG C, and have good mouldability, process
Product surface it is bright and clean, easy to dye and plating, and can be with various kinds of resin with blending together blend.
The present invention by wherein addition rule and the higher organosilicon microballoon of surface gloss so that entire ABS tree
Rouge carries the effect of frosted after the extrusion, have it is preferable stop effect of light, while reducing surface light and vertically reflect and instead
Rate is penetrated, light loss is preferably reduced, when being used as lampshade, without manufacturing the effect of frosted on its surface by reprocessing；
And organosilicon microballoon is a kind of multifunctional special organic siliconresin microballoon, for snowy white it is regular flow freely it is spherical subtle
Powder has three-dimensional cross-linked netted molecular structure, shows outstanding heat resistance, dispersion performance, while entering ABS resin
When middle, it is uniformly dispersed in matrix with a kind of subtle transparent glass sphere, passes through the difference of the refractive index in ABS, light source
Penetration reflect, and changes the travelling route of light, to achieve the effect that frosted.
By using the above proportion, the 1.6-1.7 that the refractive index of ABS resin is mentioned, light transmittance declines 5-15%, makes to be made
The light that issues of LED light it is softer, and intensity is high, and good toughness, formula is simple, at low cost, more meets consumer demand.
The present invention is further arranged to: the transparent ABS frosted resin further includes coupling agent.
By using above-mentioned technical proposal, coupling agent can reduce in plastic processes as a kind of surface modifier
The viscosity of molten synthetic resin improves the dispersion degree of filler to improve processing performance, obtains product applied to the present invention good
Good surface quality and machinery, heat and electrical property, so that the ABS resin produced is with the same of preferable frosted finish effect
When there are also preferable mechanical strength, thermal stability and electric durability energy.
The present invention is further arranged to: the coupling agent includes zirconium class coupling agent, titanate coupling agent and silane coupling agent
One or more of combination.
By using above-mentioned technical proposal, zirconium class coupling agent is the inorganic polymer of the low molecular weight containing zirconium aluminate.It is not
The bonding between ABS resin and organosilicon microballoon can only be promoted, and the performance of composite system can be improved, especially
Rheological property；
Titanate coupling agent can promote the better bonding between ABS resin and organosilicon microballoon, there is good coupling effect；
The general formula of silane coupling agent is RSiX3, R represents amino, sulfydryl, vinyl, epoxy group, cyano and methacryl in formula
The groups such as oxygroup, these groups and different matrix resins all have stronger respond, can promote ABS resin and organic
Bonding between silicon microballoon.
The present invention is further arranged to: the transparent ABS frosted resin further includes lubricant.
By using above-mentioned technical proposal, lubricant and ABS resin and organosilicon microballoon have good compatibility, play drop
The effect of low ABS resin and organosilicon microballoon intermolecular cohesion, so as to improve the internal frictional heat generation and melt of plastic melt
Mobility.In-lubricant and ABS resin and the intermolecular combination of organosilicon microballoon are not strong, it is possible to create are similar to the axis of rolling
The effect held, therefore its own can be arranged on melt flows direction, can be with so that internal friction reduces to slide over each other
It is effective to reduce time and energy required for ABS resin and organosilicon microballoon completion mixed process.
The present invention is further arranged to: the lubricant is polyethylene lubricant, polytetrafluoroethylene (PTFE) lubricant and polypropylene
The combination of one or more of lubricant.
By using above-mentioned technical proposal, polyethylene lubricant, polytetrafluoroethylene (PTFE) lubricant and polypropylene lubricant and ABS
Resin and organosilicon microballoon have good compatibility, keep the uniform mixing of ABS resin and organosilicon microballoon easier.
The present invention is further arranged to: the transparent ABS frosted resin further includes antioxidant.
By using above-mentioned technical proposal, antioxidant can prevent the adverse effect of oxygen, prevent or delay ABS resin
With the oxidation of organosilicon microballoon, the stability of ABS resin and organosilicon microballoon is improved, is prolonged the service life.
The present invention is further arranged to: the antioxidant was four [3- (3,5- di-t-butyl -4- hydroxyphenyl) propionic acid] seasons
One or more of the double lauryls of Doutrate, three [2,4- di-tert-butyl-phenyl] phosphite esters and thio-2 acid
Combination.
By using above-mentioned technical proposal, four [3- (3,5- di-t-butyl -4- hydroxyphenyl) propionic acid] pentaerythritol esters are white
Color crystalline powder, chemical property are stablized；Volatility is small, and resistance to extractable is good, thermal stability is high, lasting effect is long, not colored, not dirty
It contaminates, is nontoxic；It is a kind of hindered phenol antioxygen of high molecular weight, volatility is very low, and not easy to migrate, resistance to extraction；It can be effectively
Thermal oxidative degradation of ABS resin during long-term ageing is prevented, while being also a kind of efficient processing stabilizers, can be improved poly-
Close discoloration-resistant of object material under the conditions of high temperature process；
Three [2,4- di-tert-butyl-phenyl] phosphite esters and ABS resin compatibility are good, alleviate ABS resin during long-term ageing
Thermal oxidative degradation, have it is efficient, non-discolouring, do not pollute, the excellent properties such as odorless；
The double lauryls of thio-2 acid, abbreviation DLTP alleviate thermal oxidative degradation of ABS resin during long-term ageing, and
It is nontoxic, it is environmentally protective；
Four [3- (3,5- di-t-butyl -4- hydroxyphenyl) propionic acid] pentaerythritol esters and DLTP and three [2,4- di-tert-butyl-phenyls] are sub-
Phosphate has good synergistic effect, can improve the thermal stability of ABS resin hot procedure.
The purpose of the present invention two is to provide the preparation method of transparent ABS frosted resin, be formulated simply, preparation manipulation is simple
It is single, it is at low cost.
Above-mentioned technical purpose two of the invention has the technical scheme that transparent ABS frosted resin
Preparation method includes the following steps:
S1: corresponding each component is weighed respectively according to the proportion；
S2: each material is poured into high-speed mixer and is stirred 10~20 minutes；
S3: the material mixed is put into screw extruder and carries out extrusion molding.
By using above-mentioned technical proposal, each component ingredient is mixed, so that it is whole more uniform, then put
Enter screw extruder to be squeezed out, facilitate the formation of ABS resin frosted finish effect, while making the overall distribution in extrusion process
More uniform frosted finish effect.
The present invention is further arranged to: the screw extruder during extrusion molding, extruder temperature 190~
240℃。
By using above-mentioned technical proposal, since screw rod drives moving ahead for material, in order to enable material melts and occurs anti-
It answers, needs screw rod to control suitable temperature, it is excessively high to the case where carbonization, melanism occur that temperature occurs in reduction, and temperature is too low
Then material is made not enter into molten condition, so that the case where squeezing out failure occurs.
The present invention is further arranged to: the screw extruder includes feed zone, melting zone, is kneaded area, die head area and mould
Has head outlet, the feed zone temperature is 185-193 DEG C, and the melting zone temperature is 195-205 DEG C, and mixing area temperature is
215-222 DEG C, die head area temperature is 228-235 DEG C, and the mould head outlet temperature is 205-215 DEG C.
By using above-mentioned technical proposal, each section of temperature control is all different, and the temperature close to feed zone is with respect to it
Remaining part point is lower, prevents feeding inlet material melts from causing to block, also can not be too low, if charge temperature is too low, makes Solid Conveying and Melting
Area extends, and reduces the length of plasticizing zone and melt delivery area, can cause to be plasticized bad, influences product quality, and for melting
Area and be kneaded for area, come the vacuum degree for controlling this section be an important technic index by control temperature, if vacuum degree compared with
It is low, it will affect exhaust effect, lead to there is bubble in tubing, seriously reduce the mechanical property of tubing.In order to make inside material
Gas be easy evolution, should control material this section of gelation degree cannot be excessively high, while also often to clear up gas exhaust piping in order to avoid
Block barrel, and should improve screw speed in die head area, reduce head resistance and improve thermometer pressure in plasticizing zone has
Conducive to the raising of delivery rate, and mould head outlet is the molding important component of extruded product, its effect is that generation is higher
Melt pressure and the shape for keeping melt forming required are allowed to form certain shape no longer to be melting by proper temperature reduction
State.
In conclusion the invention has the following advantages:
1. the ABS resin prepared can be made to show preferable frosted finish effect by above-mentioned formula and preparation method, together
When it is integrally more dispersed, production effect is preferable, have good shading performance and preferable light reflectivity, the lamp for LED light
Lacquer finish line is softer, and at low cost, more meets consumer demand.
The height of product intensity made from 2., good toughness, long service life.
3. preparation method is simple, the final product quality of preparation is high, easy to spread.
Specific embodiment
Below with reference to table and embodiment, the present invention will be described in detail.
Lubricant does not have special category requirement, can select polyethylene lubricant, polytetrafluoroethylene (PTFE) lubricant and polypropylene
Two or more combination in one of lubricant or polyethylene lubricant, polytetrafluoroethylene (PTFE) lubricant and polypropylene lubricant.
Coupling agent does not have special category requirement, can select in zirconium class coupling agent, titanate coupling agent and silane coupling agent
One kind or zirconium class coupling agent, titanate coupling agent and silane coupling agent in two or more combination.
Antioxidant does not have special category requirement, can select for four [3- (3,5- di-t-butyl -4- hydroxyphenyl) propionic acid] seasons
One of Doutrate, the double lauryls (abbreviation DLTP) of three [2,4- di-tert-butyl-phenyl] phosphite esters and thio-2 acid or
Two or more combinations.
Organosilicon microballoon is bought by the treasured plastic material Co., Ltd that Shenzhen gathers, other raw materials are bought by market.
ABS resin, full name are acrylonitrile-butadiene-styrene copolymer.
Embodiment one
Transparent ABS frosted resin, including following components and weight percent:
80 parts of ABS resin
20 parts of organosilicon microballoon
0.002 part of polyethylene lubricant
0.002 part of zirconium class coupling agent
Four 0.001 part of pentaerythritol ester of [3- (3,5- di-t-butyl -4- hydroxyphenyl) propionic acid]
Three 0.001 part of phosphite ester of [2,4- di-tert-butyl-phenyl]
Wherein the partial size of organosilicon microballoon is 30 microns.
Embodiment two
Transparent ABS frosted resin, embodiment two and embodiment one are the difference is that by the weight of ABS resin and organosilicon microballoon
Amount adjusts separately as 85 parts and 15 parts.
Embodiment three
Transparent ABS frosted resin, embodiment three and embodiment one are the difference is that by the weight of ABS resin and organosilicon microballoon
Amount adjusts separately as 90 parts and 10 parts.
Example IV
Transparent ABS frosted resin, example IV and embodiment one are the difference is that by the weight of ABS resin and organosilicon microballoon
Amount adjusts separately as 95 parts and 5 parts.
Embodiment five
Transparent ABS frosted resin, embodiment five and embodiment one are the difference is that by the weight of ABS resin and organosilicon microballoon
Amount adjusts separately as 97 parts and 3 parts.
Embodiment six
Transparent ABS frosted resin, embodiment six and embodiment five be not the difference is that add polyethylene lubricant, zirconium class
Coupling agent, four [3- (3,5- di-t-butyl -4- hydroxyphenyl) propionic acid] pentaerythritol esters and three [2,4- di-tert-butyl-phenyl] phosphorous
Acid esters.
Embodiment seven
Transparent ABS frosted resin, embodiment seven and embodiment one are the difference is that the partial size of organosilicon microballoon is 40 microns.
Embodiment eight
Transparent ABS frosted resin, embodiment eight is with embodiment one the difference is that the partial size of organosilicon microballoon is 60 micro-
Rice.
Embodiment nine
Transparent ABS frosted resin, embodiment nine and embodiment one are the difference is that the partial size of organosilicon microballoon is 80 microns.
Comparative example 1
ABS resin is formulated to be only added to 100 parts of ABS resins.
1 embodiment and comparative example data component of table and proportion summarize
The embodiment of organosilicon microballoon of the table 2 containing different-grain diameter summarizes
The performance evaluation of 3 embodiment and comparative example of table
Table 1 is to summarize to above embodiments and comparative example data component and proportion, and table 2 is to organic containing different-grain diameter above
Silicon microballoon embodiment summarizes, the more intuitive difference for showing each embodiment and comparative example addO-on therapy and proportion, with
And the difference containing organosilicon microspherulite diameter.
Performance evaluation is carried out to embodiment each in Tables 1 and 2 and obtains table 3, it can be with by the analysis to all data in table 3
It was found that, with the increase of organosilicon microballoon proportion, the refractive index of ABS resin is gradually in the case where other conditions are constant
Increase, light transmittance gradually decreases；Mist degree gradually increases, and surface roughness also gradually increases.Furthermore it is discovered by experiment that with having
The increase of machine silicon microballoon proportion obtains ABS resin concave-convex surface density also with increase；Organosilicon microspherulite diameter is bigger,
It is bigger to obtain ABS resin concave-convex surface degree.The addition due to organosilicon microballoon can be evident that from experimental result, very
The good frosted finish effect for improving ABS resin surface, light diffuser plate or light-diffusing films as LED can make light more soft
With.
Although polyethylene lubricant, zirconium class coupling agent, four [3- (the tertiary fourths of 3,5- bis- cannot directly be embodied from the data of table 3
Base -4- hydroxyphenyl) propionic acid] pentaerythritol ester, three [2,4- di-tert-butyl-phenyl] phosphite esters addition after to transparent ABS frosted tree
The influence of rouge, but time and preparation in these four compounds affects transparent ABS frosted resin interferences preparation process
The quality of transparent ABS frosted resin out, all plays the role of very important.
Embodiment 10
The preparation method of transparent ABS frosted resin, the preparation step for preparing transparent ABS frosted resin in embodiment 1 are as follows:
S1 weighs corresponding each component respectively according to the proportion；
Each material is poured into high-speed mixer and is stirred 10~20 minutes by S2；
The material mixed is put into screw extruder and carries out extrusion molding by S3；
The screw extruder includes feed zone, melting zone, is kneaded area, die head area and mould head outlet, the feed zone temperature
It is 190 DEG C, the melting zone temperature is 200 DEG C, and mixing area's temperature is 220 DEG C, and die head area temperature is 230 DEG C, institute
Stating mould head outlet temperature is 210 DEG C.
For the quality of finished product, the temperature setting in each area of screw extruder will be controlled, wherein the feed zone temperature
It is 185-193 DEG C, the melting zone temperature is 195-205 DEG C, and mixing area's temperature is 215-222 DEG C, die head area temperature
Degree is 228-235 DEG C, and the mould head outlet temperature is 205-215 DEG C, and final product quality obtained all compares in the above range
It is good.
Embodiment 11-19
The preparation method of transparent ABS frosted resin, embodiment 11-19 are respectively the preparation step for preparing embodiment 2-9 and comparative example 1
It suddenly, is only the difference of weighed component or weight with the difference of embodiment 10.
In addition, the present invention has also done traditional performance test to finished product made from embodiment 1 and embodiment 7, specifically see the table below:
Heat resistance in embodiment is measured using the vicat softening temperature standard of Deutsche industry norm (DIN) DIN 53460, is had
Body is temperature when the certain pressure head of measurement is vertically pierced into sample 1mm depth under some force；According to test philosophy,
Vicat temperature is higher, then the heat resistance of material is better, conversely, then heat resistance is poorer.Ageing-resistant performance uses national standard GB-
T16422 xenon lamp accelerated aging tests are measured, and specially carry out Mechanics Performance Testing batten according to the standard of GB29344
Xenon lamp accelerated aging tests test the discoloration degree before xenon lamp aging and after 1000h respectively with colour photometer, and obtain value of chromatism Δ E；
According to test philosophy, Δ E value is bigger, then the ageing-resistant performance of material is poorer, conversely, then ageing-resistant performance is better.
As can be seen from the above table, finished product tensile strength, notch impact strength, bending made from embodiment 1 and embodiment 7
Intensity is improved to some extent, and mechanical strength is relatively good；Vicat temperature is also obviously improved, therefore heat resistance is more preferable；It is resistance to
Ageing properties are remarkably improved.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example, all technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It should be pointed out that for the art
Those of ordinary skill for, several improvements and modifications without departing from the principles of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. transparent ABS frosted resin, it is characterised in that: including following components and weight percent:
ABS resin 80-97%
Organosilicon microballoon 3-20%.
2. transparent ABS frosted resin according to claim 1, it is characterised in that: the transparent ABS frosted resin further includes
Coupling agent.
3. according to claim 2, it is characterised in that: the coupling agent includes zirconium class coupling agent, titanate coupling agent and silane
The combination of one or more of coupling agent.
4. transparent ABS frosted resin according to claim 1, it is characterised in that: the transparent ABS frosted resin further includes
Lubricant.
5. transparent ABS frosted resin according to claim 4, it is characterised in that: the lubricant be polyethylene lubricant,
The combination of one or more of polytetrafluoroethylene (PTFE) lubricant and polypropylene lubricant.
6. transparent ABS frosted resin according to claim 1, it is characterised in that: the transparent ABS frosted resin further includes
Antioxidant.
7. transparent ABS frosted resin according to claim 6, it is characterised in that: the antioxidant is four [3- (3,5-
Di-t-butyl -4- hydroxyphenyl) propionic acid] pentaerythritol ester, three [2,4- di-tert-butyl-phenyl] phosphite esters and thio-2 acid pair
The combination of one or more of lauryl.
8. the preparation method of transparent ABS frosted resin, characterized by the following steps:
S1: corresponding each component is weighed respectively according to the proportion of ABS frosted resin described in any one of claim 1-7；
S2: each material is poured into high-speed mixer and is stirred 10~20 minutes；
S3: the material mixed is put into screw extruder and carries out extrusion molding.
9. the preparation method of transparent ABS frosted resin according to claim 8, it is characterised in that: the screw extruder
During extrusion molding, extruder temperature is at 190~240 DEG C.
10. the preparation method of transparent ABS frosted resin according to claim 8, it is characterised in that: the screw extruder
Including feed zone, melting zone, it is kneaded area, die head area and mould head outlet, the feed zone temperature is 185-193 DEG C, described molten
Tabetisol temperature is 195-205 DEG C, and mixing area's temperature is 215-222 DEG C, and die head area temperature is 228-235 DEG C, described
Mould head outlet temperature is 205-215 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02263852A (en) * | 1989-04-04 | 1990-10-26 | Toray Ind Inc | Low lustrous thermoplastic resin composition |
| CN102329490A (en) * | 2011-05-31 | 2012-01-25 | 深圳市科聚新材料有限公司 | Semitransparent light diffusion modified PC (Polycarbonate) and preparation method thereof |
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| CN109161151B (en) | 2021-07-23 |
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