CN101003653A - Method for fabricating products of rigid polyvinyl chloride with high glossiness - Google Patents
Method for fabricating products of rigid polyvinyl chloride with high glossiness Download PDFInfo
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- CN101003653A CN101003653A CN 200610132320 CN200610132320A CN101003653A CN 101003653 A CN101003653 A CN 101003653A CN 200610132320 CN200610132320 CN 200610132320 CN 200610132320 A CN200610132320 A CN 200610132320A CN 101003653 A CN101003653 A CN 101003653A
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Abstract
This invention discloses a method for producing high-luster hard poly (vinyl chloride) product. The formula comprises: poly (vinyl chloride) 100 parts, organic tin stabilizer 1.6-2.2 parts, internal lubricant 0.6-1.0 part, external lubricant 0.2-0.5 part, and impact modifier 6-14 parts. The method comprises: measuring, mixing in a high-speed mixer, mixing in a low-speed mixer, extruding by a planetary extruder, extruding by a single-screw extruder, calendaring by a calender, cooling to below 80 deg.C in a liquid (deionized water) cooling tank, annealing at 105-110 deg.C by an annealing tackle, cooling by a cooling tackle, and coiling. The obtained hard poly (vinyl chloride) product has such advantages as high crystallinity, small grain sizes, large grain number, good luster, and good scraping performance.
Description
Technical field:
The present invention relates to a kind of making method of polrvinyl chloride product.
Background technology:
The finishing material of high gloss is had relatively high expectations to glossiness and scratch resistance performance.The rigid polyvinyl chloride sheets of high gloss generally adopts calendering formation technology to make the base material work in-process, then MULTILAYER COMPOSITE finished product as requested.The glossiness of finished product and scratch resistance performance directly depend on the performance of surface material.
1, the whether transparent relation of glossiness and surface material:
Surface material can be divided into transparent and opaque two classes.Opaque surface material generally contains a large amount of non-strong absorption opaque pigments, and non-strong absorption opaque pigment has following feature: a. particle diameter is not less than the half-wavelength of visible light wave.The refractive index of b refractive index and polyvinyl chloride is inconsistent.Non-strong absorption opaque pigment is to adopt strong scattering and reach.Therefore, opaque pigment must cause material surface scattering (diffuse-reflectance also is a low-luster).And transparent material, specific refractory power basically identical in the system, the then less substantially diffuse-reflectance in surface.So no matter in theory still practice proves that all the glossiness of transparent material is higher than opaque material.
2, the relation of glossiness and surface material crystalline condition
The crystallization of polymkeric substance is different with low molecular crystal, be difficult to form perfect monocrystalline, crystal imperfection, and exist crystallize to unformed various gradual change forms and deposit, do not have complete crystalline polymkeric substance and complete unformed polymkeric substance substantially.Under the polymer processing condition of routine, generally be to form incomplete crystallite (wafer) earlier, reassociate (growth) becomes spherocrystal, fibrous crystalline substance, shish-kebab etc., wherein generally is that spherocrystal accounts for main body, and fibrous crystalline substance, shish-kebab are less relatively.Because spherocrystal is to be formed by crystallite bunchy and bending, unidirectional refraction can not appear, show as scattering, and its size can reach several microns even several millimeters, can influence visible region fully, therefore, what of spherocrystal directly influence glossiness with size.The material glossiness height few with spherocrystal quantity, that yardstick (particle diameter) is little.
3, crystallization and scratch resistance property relationship
The scratch resistance performance is a kind of index that relates to surface hardness.The molecular chain of crystallizing field is fine and close in order, hardness is greater than unformed area, the scratch resistance performance of the sample that degree of crystallinity is big is better than the little sample of degree of crystallinity, and the crystalline size also influences the scratch resistance performance, this be because, under the condition of same degree of crystallinity, because small particle size crystalline crystal number is more, cause more substantial stress stress point, better disperse, homogenizing are played in the corresponding field of force, significantly reduce stress concentration, thereby reduce the development of stress rupture and stress rupture, so small particle size crystalline product scratch resistance performance is better than big particle diameter crystal.As seen with regard to the scratch resistance performance, big with degree of crystallinity, the little product of crystallization particle diameter is for well.
4, complete processing and prescription influence crystalline
A) the polymer crystallization temperature influences crystalline
From crystallization rate and Tc relation curve, usually Tc is divided into shown in several intervals (as Fig. 1).Crystallization rate in these intervals is subjected to the influence of nucleation rate and crystal growth rate two aspects.Tm is a crystalline melting point, and Tg is the second-order transition temperature point, and Tmax is a crystallization rate maximum temperature point.And can estimate by Tmax=0.63Tm+0.37Tg-18.5.
In the I district (below the fusing point 10～30 ℃), be that melt was cooled to cold metastable zone by high-temp liquid.Nucleation rate is minimum, so crystallization rate is almost equal to zero.
In the II district, along with temperature reduces, crystallization rate increases rapidly.In this interval, crystalline growth speed is than faster, but because high-polymer molecular and sub-chain motion fierceness, from thermodynamics, the nucleus instability of generation, the check figure order few, nucleation process crystallization control speed.
In the III district, the speed of nucleation and the stability of nucleus are all higher, and simultaneously, crystalline growth speed is also than higher, and both actings in conjunction make crystallization rate reach maximum value.This zone is the crystalline main region.
In the IV district, crystallization velocity mainly is to be subjected to the grain growing rate-controlling, because on kinetics, the crystalline growth process is that macromolecular chain and segment spread and the regular process that enters lattice to nucleus, temperature drops to the closer to Tg, the ability of sub-chain motion is also low more, and the speed of grain growing and the total speed of corresponding crystallization are also just slow more.Temperature is lower than Tg, and sub-chain motion is frozen, and crystallization rate also just goes to zero.
B) speed of cooling and crystalline relation
The i.II district, this district's crystal growth rate is bigger.If slowly cooling, the crystal that can obtain big scale (particle diameter) reaches bigger percent crystallization in massecuite, while nucleus instability, and the crystal number increases few, if quick cooling, percent crystallization in massecuite decline, crystal particle diameter sharply descends, and the crystal reduced number is few.
The ii.III district, this distinguishes crystal growth rate, nucleation rate is all more stable.If slowly cooling can obtain bigger percent crystallization in massecuite, crystal particle diameter and number.Quick cooling is then opposite.
The iii.IV district, nucleation rate is bigger, and crystal growth rate is very low.If slowly cooling can obtain more crystallization number, but the crystal particle diameter increase is very little, and percent crystallization in massecuite increases few.If quick cooling, then the crystallization number is less, and crystal particle diameter, percent crystallization in massecuite increase are littler.
C) softening agent and crystalline relation
A large amount of softening agent has intercepted between the molecular chain and has acted on, and has reduced crystallization, but a spot of softening agent, and the effect that intercepts between the molecular chain is not obvious, provides bigger free volume on the contrary, helps that degree of crystallinity improves and crystal particle diameter becomes greatly.
5, the crystalline condition of polyvinyl chloride
It is generally acknowledged that polyvinyl chloride is an amorphous polymer, but still have small amount of crystalline that be estimated as 5～10%, the PVC crystalline density is 1.53g/cm
3(common PVC density is 1.40g/cm
3), fusing point is 175 ℃, and the Tm of polyvinyl chloride is 175 ℃, and Tg is 78 ℃, and Tmax is 122 ℃.Crystallization has only the fibrous crystalline substance and the shish-kebab of minute quantity based on spherocrystal.
6, the making method of the hard polrvinyl chloride product of conventional high glossiness is as follows:
Prescription:
PVC 100
Organotin stabilizer 1.8
Internal lubricant 0.8
External lubricant 0.3
Pigment is an amount of
Impact modifier 8
These prescription characteristics are to add a spot of softening agent, the influence of softening agent as described above, the result causes the crystallization crystal particle diameter to become big, degree of crystallinity improves.
The technological process of production:
Metering → high-speed mixer → low speed mixer → planetary forcing machine → single screw rod extruding filter → calendering main frame → draw and get wheels → cooling wheels → reeling machine.
Material enters to draw gets wheels, draw that to get the wheels routine be 7～12, about 5～6 seconds of residence time of material, material is through first cooling wheel, temperature is quickly cooled to 170 ℃ from 205 ℃, after this temperature drops to 110 ℃ gradually from 170 ℃, and this temperature range just is the interval of crystalline growth speed and crystallization rate maximum, and the result is crystal and the big percent crystallization in massecuite that generates very big particle diameter.After this enter the cooling wheels, from 110 ℃ of quick cooling to 60 ℃, this post crystallization stops substantially at cooling wheels first cooling wheel temperature of charge.The characteristics of common process are that percent crystallization in massecuite is bigger, and the crystallization crystal particle diameter is very big, and crystallization crystal number is less, and consequently the glossiness of product surface is low, and scratch resistance is poor.
Goal of the invention:
Goal of the invention of the present invention is to provide the making method of the hard polrvinyl chloride product of a kind of percent crystallization in massecuite height, the xln particle diameter is little, the xln number is many high glossiness.
The present invention realizes like this
The goods prescription is as follows:
PVC 100
Organotin stabilizer (1.6-2.2)
Internal lubricant (0.6-1.0)
External lubricant (0.2-0.5)
Pigment is an amount of
Impact modifier (6-14)
These prescription characteristics are not add any plasticizer in the prescription, have avoided the influence of softening agent, reduce and finish brilliant crystalline particle diameter.
The technological process of production of the present invention is as follows:
Metering → high-speed mixer → low speed mixer → planetary forcing machine → single screw rod extruding filter → calendering main frame → liquid (deionized water) cooling tank → annealing insulation wheels → cooling wheels → reeling machine.
The high temperature polrvinyl chloride product that comes out from the calendering main frame enters liquid (deionized water) cooling tank, goods and liquid (deionized water) is contact cooling directly, the cooling tank temperature is controlled at 50～60 ℃, owing to there is the very big temperature difference, more because huge heat is taken away in liquid (deionized water) gasification, goods about the utmost point in the short period of time (in 0.2～0.3 second) reduce to below 100 ℃, (in 1.5 seconds) are reduced under 80 ℃ then at short notice, goods are in the tank time very short (about 2～5 second time), in this operation, the products temperature most of the time is in the big and extremely low situation of crystalline growth speed of crystallization generating rate, and the result is that to generate the crystal number a lot of and crystal particle diameter is very little.Temperature was about 70 ℃ when goods left the liquid cooling groove.
Goods enter annealing insulation wheels after leaving the liquid cooling groove, goods are about 13～15 seconds in the time of annealing insulation wheels, preceding half regional temperature of annealing wheels is set at 120～140 ℃, and later half regional temperature is set at 105～125 ℃, and temperature of charge remains on 105～110 ℃ scope substantially.In this operation, temperature of charge very the most of the time be the big and low situation of crystalline growth speed of crystallization generating rate, the result is that the crystal number further rolls up, and the crystal median size is still very little.Annealing insulation operation and the residing temperature range of liquid cooling operation material are roughly at same crystal region, promptly mainly in III, IV district, temperature of charge decline process that different is in the liquid cooling groove operation is mainly in the IV district, and annealing insulation operation, material is to be in the process that temperature rises and keeps, and this process mainly reaches the III district part adjacent with the IV district in the IV district.
After this material enters the cooling wheels, the reeling machine operation, and temperature of charge is reduced to 60 ℃ gradually.Crystallization stops substantially.
The present invention compared with the prior art, to cool off back and then anneal fast from the high temperature polrvinyl chloride product that the calendering main frame comes out owing to adopt, therefore, prepared hard polrvinyl chloride product has the percent crystallization in massecuite height, the xln particle diameter is little, the xln number is many, the advantage that glossiness is good, the scratch resistance performance is high of surface material.
In addition, surface material and primer are combined into the process of finishing material and the processing temperature interval of the high-temperature vacuum plastics sucking moulding technology that finishing material adopts by reprocessing the time is generally 130～170 ℃, this temperature range just is in crystalline II district, be the big interval of crystalline growth rate, and process period is all longer, the result causes degree of crystallinity to strengthen, and, just may cause glossiness to descend, but by products obtained therefrom of the present invention to increase the crystallization particle diameter, because the crystallization number is big, particle diameter is little, compare common process, under similarity condition, the amplitude that particle diameter increases is relatively little a lot, therefore, glossiness descends very slight.
Description of drawings:
Fig. 1 is the relation curve of superpolymer crystal speed to temperature.
Embodiment:
Now in conjunction with the embodiments the present invention is described in further detail:
The present invention realizes like this
The goods prescription is as follows:
100 parts of PVC
Organotin stabilizer 1.6-2.2 part, preferably 1.7-1.9 part
Internal lubricant 0.6-1.0 part, preferably 0.7-0.9 part
External lubricant 0.2-0.5 part, preferably 0.2-0.4 part
Pigment an amount of (consumption is according to the requirement to color)
Impact modifier 6-14 part, preferably 7-9 part
The technological process of production of the present invention is as follows:
Metering → high-speed mixer → low speed mixer → planetary forcing machine → single screw rod extruding filter → calendering main frame → liquid (deionized water) cooling tank → annealing insulation wheels → cooling wheels → reeling machine,
The high temperature polrvinyl chloride product that comes out from the calendering main frame enters liquid (deionized water) cooling tank, goods and liquid (deionized water) is contact cooling directly, and the cooling tank temperature is controlled at 50～60 ℃, and goods are very short in the tank time to be 2～5 seconds, temperature was about 70 ℃ when goods left the liquid cooling groove
Goods enter annealing insulation wheels after leaving the liquid cooling groove, goods are about 13～15 seconds in the time of annealing insulation wheels, and preceding half regional temperature of annealing wheels is set at 120～140 ℃, and later half regional temperature is set at 105～125 ℃, temperature of charge remains on 105～110 ℃ scope substantially
After this material enters the cooling wheels, the reeling machine operation, and temperature of charge is reduced to 60 ℃ gradually.
Claims (5)
1, a kind of making method of hard polrvinyl chloride product of high glossiness is characterized in that
The goods prescription is as follows:
100 parts of PVC
Organotin stabilizer 1.6-2.2 part
Internal lubricant 0.6-1.0 part
External lubricant 0.2-0.5 part
Pigment is an amount of
Impact modifier 6-14 part
The technological process of production is as follows:
Metering → high-speed mixer → low speed mixer → planetary forcing machine → single screw rod extruding filter → calendering main frame → liquid (deionized water) cooling tank → annealing insulation wheels → cooling wheels → reeling machine.
Entering the liquid cooling groove from the high temperature polrvinyl chloride product that comes out of calendering main frame is quickly cooled to below 80 ℃, enter annealing insulation wheels afterwards, under the effect of annealing insulation wheels, temperature of articles maintains 105～110 ℃ scope and carries out anneal, becomes finished product afterwards behind cooling wheels, reeling machine.
2, the making method of the hard polrvinyl chloride product of high glossiness according to claim 1 is characterized in that the cooling tank temperature is 50～60 ℃.
3, the making method of the hard polrvinyl chloride product of high glossiness according to claim 2 is characterized in that goods are 2～5 seconds in the time that cooling tank stops.
4, the making method of the hard polrvinyl chloride product of high glossiness according to claim 1 and 2 is characterized in that annealing insulation wheels are divided into Qian Ban district, later half district, and the temperature in Qian Ban district is 120～140 ℃, and the temperature in later half district is 105～125 ℃.
5, the making method of the hard polrvinyl chloride product of high glossiness according to claim 4 is characterized in that goods are 13～15 seconds in the time that annealing insulation wheels stop.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101323208A CN100422256C (en) | 2006-12-26 | 2006-12-26 | Method for fabricating products of rigid polyvinyl chloride with high glossiness |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101323208A CN100422256C (en) | 2006-12-26 | 2006-12-26 | Method for fabricating products of rigid polyvinyl chloride with high glossiness |
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| Publication Number | Publication Date |
|---|---|
| CN101003653A true CN101003653A (en) | 2007-07-25 |
| CN100422256C CN100422256C (en) | 2008-10-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101323208A Active CN100422256C (en) | 2006-12-26 | 2006-12-26 | Method for fabricating products of rigid polyvinyl chloride with high glossiness |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102555136A (en) * | 2010-12-29 | 2012-07-11 | 佛山市天安塑料有限公司 | Manufacturing method of high-transparency polypropylene calendered sheet |
| CN102649310A (en) * | 2011-02-23 | 2012-08-29 | 海洋王照明科技股份有限公司 | Forming process and forming equipment for PC thin-wall part |
| CN107057229A (en) * | 2017-05-12 | 2017-08-18 | 佛山市天进塑胶有限公司 | A kind of PVC film gloss application sheet |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5134185A (en) * | 1990-07-18 | 1992-07-28 | Lindner Robert A | Lubricant system for polyvinylchloride, polyvinylchloride articles, and a method for manufacturing the same |
| CN1302066C (en) * | 2005-01-13 | 2007-02-28 | 佛山市天安塑料有限公司 | Method for fabricating hard products of PVC not containing any plasticizer |
-
2006
- 2006-12-26 CN CNB2006101323208A patent/CN100422256C/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102555136A (en) * | 2010-12-29 | 2012-07-11 | 佛山市天安塑料有限公司 | Manufacturing method of high-transparency polypropylene calendered sheet |
| CN102649310A (en) * | 2011-02-23 | 2012-08-29 | 海洋王照明科技股份有限公司 | Forming process and forming equipment for PC thin-wall part |
| CN107057229A (en) * | 2017-05-12 | 2017-08-18 | 佛山市天进塑胶有限公司 | A kind of PVC film gloss application sheet |
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| Publication number | Publication date |
|---|---|
| CN100422256C (en) | 2008-10-01 |
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| C56 | Change in the name or address of the patentee |
Owner name: GUANGDONG TIAN'AN NEW MATERIAL CO., LTD. Free format text: FORMER NAME: TIANAN PLASTIC CO., LTD., FOSHAN CITY |
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Address after: 528200 Guangdong Province, Foshan city Chancheng District Nanzhuang Jili Industrial Park Xinyuan Road No. 30 Patentee after: Guangdong Tianan New Material Co., Ltd. Address before: 528000 five peak four road, Chancheng District, Guangdong, Foshan Patentee before: Foshan Tianan Plastic Co., Ltd. |
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Application publication date: 20070725 Assignee: ANHUI TIAN'AN NEW MATERIALS CO., LTD. Assignor: Guangdong Tianan New Material Co., Ltd. Contract record no.: 2018440000024 Denomination of invention: Method for fabricating products of rigid polyvinyl chloride with high glossiness Granted publication date: 20081001 License type: Common License Record date: 20180319 |
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