CN109575417A - Novel color masterbatch mixed thing and preparation method thereof - Google Patents
Novel color masterbatch mixed thing and preparation method thereof Download PDFInfo
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- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
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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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of novel color masterbatch mixed things and preparation method thereof, the novel color masterbatch mixed thing is made of polyolefin resin, toner, polyethylene wax and organic pigment, specific method is first to process organic pigment and polyolefin resin and polyethylene wax to obtain high concentration monochrome masterbatch, it is diluted again to obtain low concentration monochrome masterbatch with polyolefin resin, finally processes to obtain novel color masterbatch mixed thing with polyolefin resin, toner and polyethylene wax again.Method of the invention can finally be made that tinctorial strength is higher, the preferable color masterbatch mixed thing of dispersion degree, and excellent color permeability can be generated by applying it in plastic products coloring, be suitable for the coloring processing of medium-to-high grade polyolefin plastic products.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of novel color masterbatch mixed thing and its preparation side
Method.
Background technique
Pearly-lustre color masterbatch because its excellent special texture make its in plastic processing using very extensive.However, existing
Pearly-lustre color masterbatch still have larger deficiency in terms of organic pigment dispersibility and pearly-lustre texture.
Organic pigment dispersion effect is poor to not only result in that pearly-lustre color masterbatch dispersion degree is poor, and tinctorial strength is not high, and
Plastic products can also be made, and there are irregular color dots.
Existing pearly-lustre color masterbatch is substantially using high-speed mixer mixing, mixed at high speed to pearly-lustre Powder Particle Size destroy compared with
Greatly, pearly-lustre texture is influenced, the color permeability of institute's colored plastic articles is bad.
Although also there is document report (referring to Chinese patent literature CN101392077A and CN104312109A) first high
Speed mixes other materials, adds pearl powder and carries out mixed on low speed, but the technological means is limited to the improvement of pearly-lustre texture, and
It is little to the dispersibility effect of organic pigment.
Summary of the invention
The purpose of the present invention is to solve the above problem, provide a kind of tinctorial strength is higher, dispersion degree preferably, pearly-lustre texture
Relatively strong, the preferably novel color masterbatch mixed thing of color permeability of institute's colored plastic articles and preparation method thereof.
Realizing the technical solution of the object of the invention is: a kind of novel color masterbatch mixed thing, by the group of following weight percentage
Divide and be made: polyolefin resin 20~45%；Pearl powder 20~30%；Polyethylene wax 5~10%；Low concentration monochrome masterbatch 30~40%.
The low concentration monochrome masterbatch is made of the component of following weight percentage: polyolefin resin 75~85%；High concentration
Monochromatic masterbatch 15~25%.
The high concentration monochrome masterbatch is made of the component of following weight percentage: polyolefin resin 57~65%；Organic face
Material 30~40%；Polyethylene wax 3~5%.
The polyolefin resin is one of LLDPE, LDPE, EVA, POE, PP or two or more (containing two kinds)；It is excellent
Select LLDPE and/or LDPE.
The powdered granule that the preferred average grain diameter of the LLDPE and/or LDPE is 50~300 μm.
When the polyolefin resin is using two or more (containing two kinds), it can be added, can also successively be added simultaneously.
The organic pigment is the organic pigment of the high grade of transparency；It is preferred that one of following pigment or two or more (containing
Two kinds): C.I.Pigment Yellow 17, C.I.Pigment Yellow 83, C.I.Pigment Yellow 180,
C.I.Pigment Orange 64, C.I.Pigment Orange 71,48 ︰ 2 of C.I.Pigment Red, C.I.Pigment
48 ︰ 3 of Red, 57 ︰ 1 of C.I.Pigment Red, C.I.Pigment Red 122, C.I.Pigment Violet 19,
C.I.Pigment Violet 23,15 ︰ 1 of C.I.Pigment Blue, 15 ︰ 3 of C.I.Pigment Blue, C.I.Pigment
Green 7、C.I.Pigment Green 36。
The preparation method of above-mentioned novel color masterbatch mixed thing, has follow steps:
1. processing organic pigment and polyolefin resin and polyethylene wax to obtain high concentration monochrome masterbatch according to above-mentioned formula；
2. by step, 1. high concentration monochrome masterbatch dilution obtained obtains low concentration monochrome masterbatch；
3. by step 2. obtained low concentration monochrome masterbatch and polyolefin resin, pearl powder and polyethylene wax according to above-mentioned formula
Processing obtains novel color masterbatch mixed thing [also referred to as pearly-lustre color masterbatch].
Above-mentioned steps 1. described in processing using continuous mixing technique.
The temperature of the continuous mixing technique is 170~200 DEG C.
The time of the continuous mixing technique is 1~15min, preferably 3~5min.
The concentration of organic pigment is preferably 5~10wt% in 2. low concentration monochrome masterbatch that above-mentioned steps dilute.
Above-mentioned steps 2. described in dilution be by high concentration monochrome masterbatch and polyolefin resin according to 15~25% ︰ 75~85%
Weight percent mixing after, process to obtain using single screw extrusion machine.
Each area's temperature of the single screw extrusion machine and die head temperature are 145~155 DEG C.
The single screw extrusion machine screw speed is 80~120rpm.
Above-mentioned steps 3. described in processing be first mixed with helical-ribbon type horizontal mixer, then with single screw extrusion machine into
Row processing.
The ribbon revolving speed of the helical-ribbon type horizontal mixer is 50~100rpm.
The time that is stirred of the helical-ribbon type horizontal mixer is 1~15min, preferably 3~5min.
The single screw extrusion machine is preferably provided with the single screw extrusion machine of vacuum degasser.
Each area's temperature of single screw extrusion machine are as follows: 95~105 DEG C of an area, two 115~125 DEG C of areas, three areas 135~145
DEG C, four 145~155 DEG C of areas, five 145~155 DEG C of areas, six 135~145 DEG C of areas, seven 125~135 DEG C of areas, 130 ± 5 DEG C of die head.
The single screw extrusion machine screw speed is 80~120rpm.
The good effect that the present invention has:
(1) method of the invention uses the polyolefin resin and organic pigment of a small amount of (being no more than 2 times of dosages of organic pigment) in advance
High concentration monochrome masterbatch is made, is then mixed and made into low concentration monochrome masterbatch, this processing method with part polyolefin resin again
It can be obviously improved the dispersibility of organic pigment, improve the tinctorial strength of pearly-lustre color masterbatch, improve dispersion degree.
(2) method of the invention by being made low concentration monochrome masterbatch in advance, then again by itself and pearl powder and part
Pearly-lustre color masterbatch is made in polyolefin resin, compared with the prior art only mixes subsequent be added in mixture of pearl powder in high speed
The processing method that mixed on low speed is carried out in conjunction machine can preferably improve pearly-lustre texture.
(3) at present in the mixing processing of pearly-lustre color masterbatch almost without using continuous internal mixer and helical-ribbon type is horizontal stirs
Machine is mixed, although the former mixing efficiency is higher, its high shear force can bring greater loss to pearl powder, although and the latter has
There is lower shearing force, but mixing efficiency is lower；And method of the invention can exactly play the advantages of the two, and avoid
The shortcomings that the two.
(4) method of the invention can finally be made tinctorial strength is higher, dispersion degree preferably, the stronger pearly-lustre of pearly-lustre texture
Color masterbatch, excellent pearl effect can be generated by applying it in plastic products coloring, and color permeability is preferable, is suitable for
The coloring of high-grade polyolefin plastic products is processed.
Specific embodiment
(embodiment 1)
The preparation method of the novel color masterbatch mixed thing of the present embodiment is specific as follows:
1. preparing high concentration monochrome masterbatch.
The LLDPE resin, the organic pigment of 2.52kg and the polyethylene wax of 0.28kg of 4.2kg are added to continuous mixing
In machine (deriving from Farrel Corp., the U.S.), 7kg is obtained in 185 ± 2 DEG C of at a temperature of 3~5min of continuous mixing, then through being granulated
High concentration monochrome masterbatch.
The concentration of organic pigment is 36wt% in the high concentration monochrome masterbatch.
The organic pigment that the present embodiment uses is C.I.Pigment Yellow 17.
2. preparing low concentration monochrome masterbatch.
After 1. 7kg high concentration monochrome masterbatch obtained mix with the LLDPE resin of 28kg, it is crowded to be added to single screw rod for step
Out in machine, through squeezing out mixing, tie rod water cooling, pelletizing, 35kg low concentration monochrome masterbatch is obtained.
The concentration of organic pigment is 7.2wt% in the low concentration monochrome masterbatch.
Each area's temperature of the single screw extrusion machine and die head temperature are 150 ± 5 DEG C, screw speed 100rpm.
3. preparing novel color masterbatch mixed thing.
By step 2. the LLDPE resin of obtained 35kg low concentration monochrome masterbatch and 33kg, the polyethylene wax of 7kg and
The pearl powder of 25kg is added to helical-ribbon type horizontal mixer and is mixed, and then adds mixture to and fills equipped with vacuum outgas again
In the single screw extrusion machine set, is squeezed out and be kneaded, vacuumize degassing, tie rod water cooling, pelletizing, obtain novel color masterbatch mixed thing.
The ribbon revolving speed of helical-ribbon type horizontal mixer is 75rpm, and being stirred the time is 3~5min.
Each area's temperature of the single screw extrusion machine are as follows: 100 DEG C of an area, two 120 DEG C of areas, three 140 DEG C of areas, four 150 DEG C of areas, 5th area
150 DEG C, six 140 DEG C of areas, seven 130 DEG C of areas, 130 DEG C of die head, screw speed 100rpm.
The present embodiment step 1.~step 3. in the LLDPE resin that uses be average grain diameter for 150~200 μm of powdery
Particle.
For the molecular weight for the polyethylene wax that the present embodiment uses for 3000~4500, fusing point is 103~107 DEG C.
The pearl powder that the present embodiment uses is white pearlescent powder and 15kg average grain diameter of the 10kg average grain diameter for 5~25 μm
For 10~60 μm of golden pearl powder.
(2~embodiment of embodiment 3)
The preparation method of each embodiment is substantially the same manner as Example 1, and difference is shown in Table 1.
Table 1
(4~embodiment of embodiment 6)
The preparation method of each embodiment is substantially the same manner as Example 1, and difference is shown in Table 2.
Table 2
| Embodiment 1 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Step 1. in be added resin | The LLDPE resin of 4.2kg | The LLDPE resin of 4.2kg | The LDPE resin of 4.2kg | The LLDPE resin of the LDPE resin+2.1kg of 2.1kg |
| Step 2. in be added resin | The LLDPE resin of 28kg | The LLDPE resin of 28kg | The EVA resin of 28kg | The LLDPE resin of the LDPE resin+14kg of 14kg |
| Step 3. in be added resin | The LLDPE resin of 33kg | The EVA resin of 33kg | The LLDPE resin of 33kg | The LLDPE resin of the LLDPE resin+17kg of 16kg |
(comparative example 1)
The preparation method of the color masterbatch of this comparative example is specific as follows:
1. by 65.2kg average grain diameter be 150~200 μm powdered granule LLDPE resin, 10kg average grain diameter be 5~25 μm
White pearlescent powder, the white pearlescent powder that 15kg average grain diameter is 10~60 μm, 7.28kg polyethylene wax [molecular weight is 3000~
4500, fusing point be 103~107 DEG C] and 2.52kg organic pigment C.I.Pigment Yellow 17 be added to together high speed
In mixing machine, 3~5min of mixed at high speed under the revolving speed of 800rpm obtains uniformly mixed material.
2. 1. material that step is obtained is then added in the single screw extrusion machine equipped with vacuum degasser, mixed through squeezing out
It refines, vacuumize degassing, tie rod water cooling, pelletizing, obtain color masterbatch.
(comparative example 2)
The preparation method of the color masterbatch of this comparative example is specific as follows:
1. being 150~200 μm of powdered granule LLDPE resin by 65.2kg average grain diameter, the polyethylene wax [molecular weight of 7.28kg
Be 3000~4500, fusing point be 103~107 DEG C] and the organic pigment C.I.Pigment Yellow 17 of 2.52kg be first added
Into high-speed mixer, 3~5min of mixed at high speed under the revolving speed of 800rpm obtains uniformly mixed material.
2. it is average for 5~25 μm of white pearlescent powder and 15kg that 10kg average grain diameter is then added into high-speed mixer
The white pearlescent powder that partial size is 10~60 μm, 3~5min of mixed on low speed under the revolving speed of 100rpm obtain uniformly mixed object
Material.
3. 2. material that step is obtained is then added in the single screw extrusion machine equipped with vacuum degasser, mixed through squeezing out
It refines, vacuumize degassing, tie rod water cooling, pelletizing, obtain color masterbatch.
(test case)
Respectively to color made from novel color masterbatch mixed thing made from embodiment 1 and embodiment 6 and comparative example 1 and comparative example 2
Masterbatch carries out correlated performance test, the results are shown in Table 3.
Table 3
| Embodiment 1 | Embodiment 6 | Comparative example 1 | Comparative example 2 | |
| Tinctorial strength (%) | 104 | 101 | 92 | 95 |
| Dispersion degree (a/100mm × 100mm) | 1 | 2 | 10 | 8 |
| Pearly-lustre texture | By force | By force | It is weak | In |
(application examples)
Respectively by color made from novel color masterbatch mixed thing made from embodiment 1 and embodiment 6 and comparative example 1 and comparative example 2
Masterbatch is applied in plastic products coloring processing (additive amount is 10wt%) using conventional method, is tested correlated performance, is as a result seen
Table 4.
Table 4
| Embodiment 1 | Embodiment 6 | Comparative example 1 | Comparative example 2 | |
| Color dot (a/m of > 1.0mm2) | Nothing | Nothing | 2 | 1 |
| Color dot (a/m of 0.6~1.0mm of >2) | Nothing | Nothing | 10 | 4 |
| Color dot (a/m of 0.3~0.6mm2) | 1 | 2 | It is more | 8 |
| Current mark | Nothing | Nothing | It is more | It is less |
| Color permeability | It is good | It is good | Difference | In |
Note: the tinctorial strength and dispersion degree in table 3 and the test method of the color dot in table 4 are referring to professional standard " QB/
T1648-1992 polyethylene color masterbatch ".
Claims (10)
1. a kind of novel color masterbatch mixed thing, it is characterised in that be made of the component of following weight percentage: polyolefin resin 20
~45%；Pearl powder 20~30%；Polyethylene wax 5~10%；Low concentration monochrome masterbatch 30~40%；
The low concentration monochrome masterbatch is made of the component of following weight percentage: polyolefin resin 75~85%；High concentration is monochromatic
Masterbatch 15~25%；
The high concentration monochrome masterbatch is made of the component of following weight percentage: polyolefin resin 57~65%；Organic pigment 30
~40%；Polyethylene wax 3~5%.
2. novel color masterbatch mixed thing according to claim 1, it is characterised in that: the polyolefin resin be LLDPE,
One of LDPE, EVA, POE, PP are two or more.
3. novel color masterbatch mixed thing according to claim 1, it is characterised in that: the organic pigment is in following pigment
One or two kinds of above (containing two kinds): C.I.Pigment Yellow 17, C.I.Pigment Yellow 83,
C.I.Pigment Yellow 180、C.I.Pigment Orange 64、C.I.Pigment Orange 71、
48 ︰ 2 of C.I.Pigment Red, 48 ︰ 3 of C.I.Pigment Red, 57 ︰ 1 of C.I.Pigment Red, C.I.Pigment
Red 122, C.I.Pigment Violet 19, C.I.Pigment Violet 23,15 ︰ 1 of C.I.Pigment Blue,
15 ︰ 3 of C.I.Pigment Blue, C.I.Pigment Green 7, C.I.Pigment Green 36.
4. the preparation method of novel color masterbatch mixed thing described in one of claims 1 to 3, has follow steps:
1. organic pigment and polyolefin resin and polyethylene wax are obtained high concentration monochrome masterbatch according to formula processing；
2. by step, 1. high concentration monochrome masterbatch dilution obtained obtains low concentration monochrome masterbatch；
3. by step 2. obtained low concentration monochrome masterbatch and polyolefin resin, pearl powder and polyethylene wax according to above-mentioned formula
Processing obtains novel color masterbatch mixed thing.
5. the preparation method of novel color masterbatch mixed thing according to claim 4, it is characterised in that: above-mentioned steps 1. in institute
Processing is stated using continuous mixing technique.
6. the preparation method of novel color masterbatch mixed thing according to claim 5, it is characterised in that: the continuous mixing work
The temperature of skill is 170~200 DEG C, and the time is 1~15min.
7. the preparation method of novel color masterbatch mixed thing according to claim 4, it is characterised in that: 2. above-mentioned steps dilute
The concentration of organic pigment is 5~10wt% in obtained low concentration monochrome masterbatch.
8. the preparation method of novel color masterbatch mixed thing according to claim 4, it is characterised in that: above-mentioned steps 3. in institute
Stating processing is first to be mixed with helical-ribbon type horizontal mixer, then processed with single screw extrusion machine.
9. the preparation method of novel color masterbatch mixed thing according to claim 8, it is characterised in that: the helical-ribbon type is horizontal
The ribbon revolving speed of blender is 50~100rpm, and being stirred the time is 1~15min.
10. the preparation method of novel color masterbatch mixed thing according to claim 8, it is characterised in that: the single screw rod is squeezed
Machine is the single screw extrusion machine equipped with vacuum degasser out.
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