CN107619520A - For polyethylene or polyacrylic blue phase black agglomerate and preparation method thereof - Google Patents
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- CN107619520A CN107619520A CN201710785562.5A CN201710785562A CN107619520A CN 107619520 A CN107619520 A CN 107619520A CN 201710785562 A CN201710785562 A CN 201710785562A CN 107619520 A CN107619520 A CN 107619520A
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Abstract
The invention discloses one kind to be used for polyethylene or polyacrylic blue phase black agglomerate, and by mass percentage, it is made by following raw material：40 75%LLDPE resins, 25 40% carbon blacks, 0 5% dispersant, 0 2% lubricant and 0 12% inorganic filler.The present invention is less than 10 LLDPE resins, and the further colour carbon black of the iodine absorption value of appropriate mix particle diameter and oil factor from melt index, the glossiness and blackness of PE and PP products can be significantly improved in PE and PP injections, product can be made to show that blue phase is black；Manufacturing cost is low, and process is simple；Compared with import color masterbatch, in PE and PP injections, the black masterbatch of same aliquot is added, the black form and aspect that it is shown are more blue, have broad application prospects and the market competitiveness.
Description
Technical field
The present invention relates to technical field of polymer materials, and in particular to one kind is used for polyethylene or polyacrylic blue phase black
Master batch and preparation method thereof.
Background technology
The lustrous surface more brilliant black degree of black flexible glue based article is stronger, and the quality shown is higher, therefore, numerous
The producer, designer pursue high black plastic surface effect.In theory, carrying out coloring using high-carbon black pigment can be presented more preferably
Blackness, but high-carbon black pigment is more difficult scattered, and the form and aspect and the dispersiveness of carbon black that are showed in final product and
The quality of base-material, the factor such as the structure of screw rod, die surface luminosity, injection pressure have very big relation.
Matched colors on the market to reach the multi-purpose toner of high black effect now, color matching cost is higher, and production is set
Standby, production site pollutes, and the resting period is short, ageing very strong, and traditional color master-batch is in flexible glue systems such as injection PE, PP
It is more inferior relative to color matching positive effect in red phase, dispersion effect and quality during product.
Therefore, it is the problem that current techniques need to solve to produce a kind of color masterbatch granule product of high blackness.
The content of the invention
The present invention is not to remove the coloring problem that solves black by traditional thinking, but by studying the scattering of light and anti-
Principle is penetrated, so as to solve the diffusion of light and reflection problems using technological means.By using spy of the Masterbatch in plasthetics
Different dilution and dispersive property, so as to realize the more assimilation effects of visible ray, finally allow black to show blue phase, make plasthetics
With quality sense.
It is an object of the invention to provide a kind of manufacturing cost is low, process is simple, using effect it is good be used for polyethylene or
Polyacrylic blue phase black agglomerate.
The technical solution adopted by the present invention is：One kind is used for polyethylene or polyacrylic blue phase black agglomerate, by quality hundred
Divide than meter, be made by following raw material：
Preferably, the melt index of the LLDPE resins is less than 10, it is preferred that the melt index of LLDPE resins is 0.5-
6。
When from high melt index in 10 LLDPE resins, the black agglomerate being prepared does not have blue phase in injection
Effect, but aobvious reddish yellow phase.
Preferably, the iodine absorption value of the carbon black is more than 110g/Kg, and DBP absorption values are less than 105 × 10-5M3/kg.Preferably
The scope of the iodine absorption value of carbon black is 120-300g/Kg, and the scope of DBP absorption values is 50-105 × 10-5M3/kg.When the charcoal of selection
When black iodine absorption value is less than 110g/Kg, the black agglomerate that the is prepared blackness in injection is inadequate, is less than 105 from DBP absorption values
×10-5M3/ kg carbon black, the dosage of dispersant can be made to control in as far as possible small ratio, increase blue phase effect.
Preferably, the particle diameter of carbon black is 11-50nm.
Preferably, the dispersant is one kind in Tissuemat E (PE waxes), ethylene stearic amide (EBS) and EVA waxes
It is or several.
Preferably, the lubricant is the one or more in zinc stearate and calcium stearate.
Preferably, the particle diameter of the inorganic filler is 10-10000nm, inorganic filler be selected from calcium carbonate, barium sulfate,
Glass microballoon, kaolin, wollastonite, talcum powder, mica, montmorillonite, aluminium hydroxide, magnesium hydroxide, diatomite and silica
In one or more；The particle diameter of preferred inorganic filler is 50-3000nm.
The particle diameter of inorganic filler needs to control in rational scope, such as 10-10000nm, unfavorable if particle diameter is too small
In scattered, and particle diameter is too big, and product surface can be coarse.
Present invention also offers the preparation method for polyethylene or polyacrylic blue phase black agglomerate, including following step
Suddenly：
1) LLDPE resins, inorganic filler, carbon black, dispersant and lubricant are mixed in high-speed mixer by proportioning
8-12 minutes, obtain mixed material；
2) mixed material is put into banbury, banburying to plastic cement is all melted, and is crushed after pouring out cooling；
3) draw ratio 44 is used:1 double screw extruder extruding pelletization, with water ring pelletizing, obtain being used for polyethylene or poly-
The blue phase black agglomerate of propylene.
Preferably, below 180 DEG C, the extrusion temperature control in step 3) is the temperature control of banbury in step 2)
135-180℃。
In injection moulding process, it is only necessary to add minimal amount of blue phase black agglomerate of the invention, it becomes possible to make plasthetics
There is blue color in coloring, can give people the sensation for having blackness higher, improve the aesthetic feeling of product.
The chromophoric principle of the present invention is that (iodine absorption value is more than 110g/Kg, DBP absorptions using the carbon black for employing specified conditions
Value is less than 105 × 10-5M3/ kg) and the dispersant of special ratios be combined a kind of obtained special-effect, beyond defined model
Enclose, the form and aspect and blackness of the black agglomerate being prepared do not reach the high black effect of blue phase, the inorganic filler of appropriate particle size
(10nm-10000nm) can play Synergistic and promote scattered effect.
The beneficial effects of the invention are as follows：The present invention is less than 10 LLDPE resins from melt index, and further collocation is closed
The iodine absorption value of suitable particle diameter (11-50nm) and the colour carbon black of oil factor, PE and PP systems can be significantly improved in PE and PP injections
The glossiness and blackness of product, can make product show that blue phase is black；Manufacturing cost is low, and process is simple；Compared with import color masterbatch, in PE
And in PP injections, the blue phase black agglomerate of same aliquot is added, the black form and aspect that it is shown are more blue, before having wide application
Scape and the market competitiveness.
Embodiment
In order to preferably explain the present invention, this invention is described in detail with reference to specific implementation example.
Embodiment 1
By mass, by the LLDPE resins that 60% melt index is 8,12% average grain diameter is 200nm calcium carbonate,
25% carbon black is that iodine absorption value is 134g/Kg, and DBP absorption values are 95 × 10-5M3/ kg carbon black, 1% Tissuemat E (PE waxes), 2%
Zinc stearate, after being mixed 10 minutes in high-speed mixer, then banburying to plastic cement all melts (temperature control in banbury
At 170 DEG C), crushed after cooling fusing, then with draw ratio 44:1 double screw extruder extruding pelletization, extrusion temperature 135-
180 DEG C, with water ring pelletizing, it is made for polyethylene or polyacrylic blue phase black agglomerate.
Embodiment 2
By mass, by the LLDPE resins that 62% melt index is 5,5% average grain diameter is 500nm calcium carbonate,
30% carbon black is that iodine absorption value is 188g/Kg, and DBP absorption values are 68 × 10-5M3/ kg carbon black, 1.5% Tissuemat E (PE waxes),
1.5% calcium stearate, after being mixed 8 minutes in high-speed mixer, then banburying to plastic cement all melts (temperature in banbury
Control is at 170 DEG C), crushed after cooling fusing, then with draw ratio 44:1 double screw extruder extruding pelletization, extrusion temperature are
135-180 DEG C, with water ring pelletizing, it is made for polyethylene or polyacrylic blue phase black agglomerate.
Embodiment 3
By mass, by the LLDPE resins that 61.5% melt index is 3,35% carbon black is that iodine absorption value is 222g/Kg,
DBP absorption values are 55 × 10-5M3/ kg carbon black, 1.5% ethylene stearic amide (EBS), 2% zinc stearate, in mixed at high speed
After being mixed 10 minutes in machine, then banburying to plastic cement all fusings (temperature control is at 170 DEG C), is cooled down after melting in banbury
It is broken, then with draw ratio 44:1 double screw extruder extruding pelletization, extrusion temperature are 130-180 DEG C, with water ring pelletizing, are made
For polyethylene or polyacrylic blue phase black agglomerate.
Embodiment 4
By mass, by the LLDPE resins that 57% melt index is 2.2,40% carbon black is that iodine absorption value is 256g/Kg,
DBP absorption values are 52 × 10-5M3/ kg carbon black, 2% Tissuemat E (PE waxes), 1% zinc stearate, mixed in high-speed mixer
After closing 12 minutes, then banburying to plastic cement all fusings (temperature control is at 170 DEG C), cooling crushes after melting in banbury,
Draw ratio 44 is used again:1 double screw extruder extruding pelletization, extrusion temperature are 135-180 DEG C, with water ring pelletizing, are made and are used for
Polyethylene or polyacrylic blue phase black agglomerate.
Embodiment 5
By mass, by the LLDPE resins that 56% melt index is 1.3,40% carbon black is that iodine absorption value is 288g/Kg,
DBP absorption values are 50 × 10-5M3/ kg carbon black, 3% Tissuemat E (PE waxes), 1% zinc stearate, mixed in high-speed mixer
After closing 8 minutes, then banburying to plastic cement all fusings (temperature control is at 170 DEG C), crushes, most after cooling fusing in banbury
Draw ratio 44 is used afterwards:1 double screw extruder extruding pelletization, extrusion temperature are 135-180 DEG C, with water ring pelletizing, are made and are used for
Polyethylene or polyacrylic blue phase black agglomerate.
Embodiment 6
By mass, by the LLDPE resins that 48% melt index is 8,9% average grain diameter is 800nm glass microballoons,
40% carbon black is that iodine absorption value is 132g/Kg, and DBP absorption values are 98 × 10-5M3/ kg carbon black, 1% dispersant (0.6% polyethylene
Wax+0.4%EVA waxes), 2% lubricant (calcium stearate of 1% zinc stearate+1%), after being mixed 10 minutes in high-speed mixer,
Then banburying to plastic cement all fusings (temperature control is at 170 DEG C), crushes, then use draw ratio after cooling fusing in banbury
44:1 double screw extruder extruding pelletization, extrusion temperature are 135-180 DEG C, with water ring pelletizing, are made for polyethylene or poly-
The blue phase black agglomerate of propylene.
Embodiment 7
By mass, by the LLDPE resins that 60% melt index is 9,12% average grain diameter is 200nm talcum powder,
28% carbon black is that iodine absorption value is 188g/Kg, and DBP absorption values are 65 × 10-5M3/ kg carbon black, 8 points are mixed in high-speed mixer
Zhong Hou, then in banbury banburying to plastic cement all fusing (temperature control is at 170 DEG C), cooling fusing after crush, then with grow
Footpath is than 44:1 double screw extruder extruding pelletization, extrusion temperature are 135-180 DEG C, with water ring pelletizing, are made for polyethylene
Or polyacrylic blue phase black agglomerate.
Comparative example 1
By mass, by the LLDPE resins that 60% melt index is 20,12% average grain diameter is 200nm calcium carbonate,
25% carbon black is that iodine absorption value is 134g/Kg, and DBP absorption values are 95 × 10-5M3/ kg carbon black, 1% Tissuemat E (PE waxes), 2%
Zinc stearate, after being mixed 10 minutes in high-speed mixer, then banburying to plastic cement all melts (temperature control in banbury
At 170 DEG C), crushed after cooling fusing, then with draw ratio 44:1 double screw extruder extruding pelletization, extrusion temperature 135-
180 DEG C, with water ring pelletizing, it is made for polyethylene or polyacrylic black agglomerate.
Comparative example 2
By mass, by the LLDPE resins that 62% melt index is 5,5% average grain diameter is 15000nm calcium carbonate,
30% carbon black is that iodine absorption value is 188g/Kg, and DBP absorption values are 68 × 10-5M3/ kg carbon black, 1.5% Tissuemat E (PE waxes),
1.5% calcium stearate, after being mixed 8 minutes in high-speed mixer, then banburying to plastic cement all melts (temperature in banbury
Control is at 170 DEG C), crushed after cooling fusing, then with draw ratio 44:1 double screw extruder extruding pelletization, extrusion temperature are
135-180 DEG C, with water ring pelletizing, it is made for polyethylene or polyacrylic black agglomerate.
Comparative example 3
By mass, by the LLDPE resins that 61.5% melt index is 3,35% carbon black is that iodine absorption value is 85g/Kg,
DBP absorption values are 55 × 10-5M3/ kg carbon black, 1.5% ethylene stearic amide (EBS), 2% zinc stearate, in mixed at high speed
After being mixed 10 minutes in machine, then banburying to plastic cement all fusings (temperature control is at 150 DEG C), is cooled down after melting in banbury
It is broken, then with draw ratio 44:1 double screw extruder extruding pelletization, extrusion temperature are 160 DEG C, with water ring pelletizing, are made and are used for
Polyethylene or polypropylene black agglomerate.
Comparative example 4
By mass, by the LLDPE resins that 48% melt index is 8,9% average grain diameter is 800nm glass microballoons,
40% carbon black is that iodine absorption value is 132g/Kg, and DBP absorption values are 112 × 10-5M3/ kg carbon black, 1% dispersant (0.6% poly- second
Alkene wax+0.4%EVA waxes), 2% lubricant (calcium stearate of 1% zinc stearate+1%), mixed 10 minutes in high-speed mixer
Afterwards, then banburying to plastic cement all fusings (temperature control is at 170 DEG C), crushes, then use major diameter after cooling fusing in banbury
Than 44:1 double screw extruder extruding pelletization, extrusion temperature is 135-180 DEG C, with water ring pelletizing, be made for polyethylene or
Polyacrylic black agglomerate.
Comparative example 5
By mass, by the LLDPE resins that 49% melt index is 1.3,40% carbon black is that iodine absorption value is 288g/Kg,
DBP absorption values are 50 × 10-5M3/ kg carbon black, 10% Tissuemat E (PE waxes), 1% zinc stearate, mixed in high-speed mixer
After closing 8 minutes, then banburying to plastic cement all fusings (temperature control is at 170 DEG C), crushes, most after cooling fusing in banbury
Draw ratio 44 is used afterwards:1 double screw extruder extruding pelletization, extrusion temperature are 135-180 DEG C, with water ring pelletizing, are made and are used for
Polyethylene or polyacrylic black agglomerate.
By black agglomerate prepared by blue phase black agglomerate and comparative example 1-5 prepared by embodiment 1-7 make an addition to respectively PP and
In PE, wherein addition accounts for the 1% of PP mass or accounts for the 1% of PE mass respectively, and acquired results are as shown in Table 1 and Table 2.
The black agglomerate form and aspect test result (1% is added in PP) of table 1
The black agglomerate form and aspect of table 2 test (1% is added in PE)
| Project | L values | A values | B values |
| Embodiment 1 | 23.9 | -1.3 | -0.8 |
| Embodiment 2 | 23.7 | -0.9 | -2.1 |
| Embodiment 3 | 23.5 | -3.6 | -1.2 |
| Embodiment 4 | 23.1 | -1.77 | -0.9 |
| Embodiment 5 | 23.8 | -0.8 | -1.1 |
| Embodiment 6 | 24.2 | -0.8 | -2.2 |
| Embodiment 7 | 24.6 | -0.9 | -1.7 |
| Comparative example 1 | 26.1 | -0.2 | +2.5 |
| Comparative example 2 | 25.0 | +1.1 | +0.9 |
| Comparative example 3 | 26.8 | -0.2 | +1.8 |
| Comparative example 4 | 25.9 | +2.1 | +0.6 |
| Comparative example 5 | 27.0 | +1.28 | +1.1 |
From Tables 1 and 2, the blue phase black agglomerate of 1% embodiment 1-7 preparations is added in PP and PE, uses colour photometer
The result of test is that L values are respectively less than or smaller equal to 25, L values, and blackness is higher, and a values and b values are negative, represent the color of product
Skew is blue.Pass through naked-eye observation (30 standard Observers of no colour blindness and anomalous trichromatism age 18-40 year under d 65 illuminant simultaneously
In, there are 29 people to draw consistent blue phase conclusion).The brightness of the blue phase black agglomerate prepared from Tables 1 and 2, embodiment 1-7
It is higher, blue phase is showed, and black agglomerate prepared by comparative example 1-5 shows reddish yellow phase, does not have blue phase effect, filler fineness changes
The influence become to form and aspect is minimum.
Claims (8)
1. one kind is used for polyethylene or polyacrylic blue phase black agglomerate, it is characterised in that by mass percentage, by following original
Material is made：
2. according to claim 1 be used for polyethylene or polyacrylic blue phase black agglomerate, it is characterised in that described
The melt index of LLDPE resins is less than 10.
3. according to claim 1 be used for polyethylene or polyacrylic blue phase black agglomerate, it is characterised in that the carbon black
Iodine absorption value be more than 110g/Kg, DBP absorption values are less than 105 × 10-5M3/kg。
4. according to claim 1 be used for polyethylene or polyacrylic blue phase black agglomerate, it is characterised in that described scattered
Agent is the one or more in Tissuemat E, ethylene stearic amide and EVA waxes.
5. according to claim 1 be used for polyethylene or polyacrylic blue phase black agglomerate, it is characterised in that the lubrication
Agent is the one or more in zinc stearate and calcium stearate.
6. according to claim 1 be used for polyethylene or polyacrylic blue phase black agglomerate, it is characterised in that described inorganic
The particle diameter of filler is 10-10000nm, inorganic filler be selected from calcium carbonate, barium sulfate, glass microballoon, kaolin, wollastonite,
One or more in talcum powder, mica, montmorillonite, aluminium hydroxide, magnesium hydroxide, diatomite and silica.
7. the preparation method for being used for polyethylene or polyacrylic blue phase black agglomerate any one of claim 1-6, its
It is characterised by, comprises the following steps：
1) LLDPE resins, inorganic filler, carbon black, dispersant and lubricant are mixed into 8-12 in high-speed mixer by proportioning
Minute, obtain mixed material；
2) mixed material being put into banbury, banburying to plastic cement is all melted, and is crushed after pouring out cooling,
3) draw ratio 44 is used:1 double screw extruder extruding pelletization, with water ring pelletizing, obtain being used for polyethylene or polypropylene
Blue phase black agglomerate.
8. preparation method according to claim 7, it is characterised in that the temperature control of banbury is at 180 DEG C in step 2)
Hereinafter, the extrusion temperature control in step 3) is 135-180 DEG C.
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| CN113278303A (en) * | 2021-06-01 | 2021-08-20 | 诺垦(上海)新材料科技有限公司 | Black master batch and preparation method thereof |
| CN113583341A (en) * | 2021-07-28 | 2021-11-02 | 金发科技股份有限公司 | High-blue-phase high-heat-resistance polypropylene composition and preparation method and application thereof |
| CN114437378A (en) * | 2022-03-09 | 2022-05-06 | 佛山市高明彩盈福新材料有限公司 | PP material blue phase control method and PP material |
| CN115260626A (en) * | 2022-06-30 | 2022-11-01 | 广东九彩新材料有限公司 | Blue-biased high-content pigment carbon black coloring polyethylene master batch and preparation method thereof |
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