CN101775183B - Low-toxicity white-light bonded crystal board and manufacturing method thereof - Google Patents
Low-toxicity white-light bonded crystal board and manufacturing method thereof Download PDFInfo
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Abstract
The invention relates to a low-toxicity white-light glued crystal board and a manufacturing method thereof. The crystal board comprises the following materials: 100 polyvinyl chloride, 40-60 dioctyl phthalate, 1.8-2.5 liquid barium-zinc stabilizer, 0.2-0.6 crylic acid processing agent, 0.05-0.08 pigment and 0.3-0.6 PHR nontoxic organic phosphate. A process comprises the following processes of: anautomatic metering process, a high-speed mixing process, a cooling and stirring process, a planet extruder plastifying process, a filtering process, a four-roller calendering process, a calendering cooling process, a bait recycling manufacture process, a calendering winding process, a gluing material feeding process, a gluing and preheating gluing process, a gluing and cooling edge cutting process, a gluing winding process and a finished product packaging and warehousing process. The invention meets the requirements of EN71Part3, RoHS and PAHs in European Union and standard ASTM F963-08 in America and has the advantages of elasticity superior to that of glass, high surface transparency and brightness, good planeness and small water wave of a membrane surface, approximately colourless single gluing membrane and characteristics of the glass.
Description
Technical field
The invention belongs to a kind of SE calendering bonded crystal board; Relate to particularly that a kind of to meet approximate glass, water wave that 4.3.5.2 among the EN71Part3 of European Union, RoHS, PAHs and the USS ASTM F963-08 requires little, can reach white, pass through, the low-toxicity white-light bonded crystal board of bright appearance and preparation method thereof.
Background technology
SE (hereinafter to be referred as PVC) resin is one type of strong polar polymer, and its Intermolecular Forces is big, thereby has caused the softening temperature of polyvinyl chloride resin and melt temperature higher, generally needs 160～210 ℃ of ability processing.The replacement chloro that contains in the PVC molecular structure in addition causes the polyvinyl chloride resin dehydrochlorination reaction easily; Thereby cause the DeR of PVC; PVC is to thermoae instability, and the temperature rising can promote the PVC dehydrochlorination reaction greatly, and indicating characteristic is a series of by the colour-change of clear, colorless to black.In order to widen its work range, satisfy the requirement of the goods transparency and brightness, thermo-stabilizer, the mutual synergistic combination of oxidation inhibitor must be arranged in the system.Because will guarantee to meet above-mentioned low toxicity requirement, must not have the existence of cadmium in the stable system simultaneously, the employing barium-zinc liquid stabilizer all not as the cadmium barium-zinc liquid stabilizer, is prone to cause that the xanthochromia and the transparency descend aspect thermostability and initial coloration.Be to guarantee color and luster, brightness, the transparency and the hypotoxic requirement of low toxicity goods, must form by rational prescription, fixed process conditions and production control procedures guarantee, avoid the instability of temperature to cause the influence of the appearance property of goods.
At present, the production of PVC calendering process of lamination is usually thick sheet using the following formula and process: formula composition: PVC, DOP, stabilizers, pigments; process: measurement step, high-speed mixing step, the mixing step, rolling step turbine (two), a filtration step, calendering process, the cooling step, the coiling process, lamination feeding process, preheating lamination process, fitting the cooling process, fitting coiling process, finished packaging process.This complete processing Production Flow Chart is long, wayward, and stabilizing agent dosage is big, material is long heat-up time.The low toxicity PVC applying sheet that adopts this complete processing to produce, transparency and brightness are all relatively poor, and the more difficult control of transparent light goods color is difficult to reach white, passes through, bright low-toxicity white-light bonded sheet appearance standard.
Summary of the invention
The present invention provides a kind of approximate glass that 4.3.5.2 requires among the EN71Part3 of European Union, RoHS, PAHs and the USS ASTM F963-08 that meets for solving the technical problem that exists in the known technology; PVC film surface finish is high, water wave is little, and that outward appearance has is white, pass through, the low-toxicity white-light bonded crystal board of bright characteristics and preparation method thereof.
The technical scheme that the present invention takes for the technical problem that exists in the solution known technology is: a kind of low-toxicity white-light bonded crystal board and preparation method thereof, and wherein, low-toxicity white-light bonded crystal board comprises following prescription (measure unit is a weight unit):
SE 100
DOP 40～60
Liquid barium zinc stabilizer 1.8～2.5
Acrylic process aids 0.2～0.6
Pigment 0.05～0.08;
Also include nontoxic phosphoesterase 30 .3～0.6PHR in the prescription.
Described SE adopts the K65 resin.
Described acrylic process aids employing molecular weight is 1,500,000 acrylic process aids.
Described pigment is selected purple powder SF-7088B for use.
The manufacture craft of low-toxicity white-light bonded crystal board of the present invention comprises the following operation of carrying out successively:
1) automatic gauge operation is imported and is measured by the prescription consumption of the low-toxicity white-light bonded crystal board of assigning;
2) mixed at high speed operation, mixing time is 400～450 seconds, makes the abundant phase mutual diffusion of each component in the prescription be prepared into the dry mash of homogeneous;
3) cooling and stirring operation makes the material cooling through feed recirculated cooling water or refrigerated water to stirrer, and temperature of charge is dropped to below 80 ℃, can stir the diffusion of strengthening each component for a long time and the degraded that does not cause material also includes the process to the storage vat storing;
4) planet extruder plasticizing operation;
5) filter operation; Adopt 20 orders, 60 orders, 150 or 200 orders, four layers of stainless (steel) wire of 20 purposes to filter, the filter temperature is controlled at 165～185 ℃;
6) four-roll calendaring operation;
7) calendering refrigerating work procedure, the cutting edge bait that is produced in this refrigerating work procedure is sent into the 8th operation, and all the other finished products get into the 9th operation;
8) bait returns the system operation, and the product after this operation is pulverized is sent into the 3rd operation and continued subsequent handling;
9) calendering coiling process;
10) material process in the applying is according to the number of plies material loading of processing requirement by setting;
11) applying preheating bonding process; Preheating wheel temperature: 160～170 ℃; Fit and take turns temperature: 160～170 ℃;
12) applying cooling cutting edge operation;
13) applying coiling process;
14) finished product packing warehouse-in;
The extruder temperature of described planet extruder plasticizing operation is set at 175～200 ℃.
In the described four-roll calendaring operation, the rolling press temperature is set at:
Front-wheel: 192～198 ℃
Last wheel: 192～198 ℃
Middle wheel: 188～192 ℃
Lower whorl: 175～182 ℃.
Step 9 in the winding step of the take-up speed of 22 to 32 m / min.
As described in step 13 step bonding winding up speed of 10 to 15 m / min.
Every hand material is controlled at 15～20% of formulation weight with the interpolation of prescription clout in the 3rd operation.
Advantage and positively effect that the present invention has are: white-light laminated crystal board of the present invention and preparation method thereof; Having fills a prescription meets the requirement of 4.3.5.2 among the EN71Part3 of European Union, RoHS, PAHs and the USS ASTM F963-08; The characteristics that manufacture craft is advanced, shortened technical process; Reduce the time of material plasticizing heating, improved production efficiency.Adopt the produced product of the present invention; Meet the requirement among the 4.3.5.2 among the EN71Part3 of European Union, RoHS, PAHs and the USS ASTM F963-08, elasticity is superior to glass, and degree is passed through on the surface, brightness is high; And the film surface finish is good, water wave is little; Monolithic applying film color is approximate colourless, and the transparency of film is high, has the characteristics of glass.
Description of drawings
Fig. 1 is the manufacture craft schema of the PVC sheet of prior art;
Fig. 2 is a low-toxicity white-light bonded crystal board manufacture craft schema of the present invention.
Embodiment
For further understanding summary of the invention of the present invention, characteristics and effect, the following examples of giving an example now, and conjunction with figs. specifies white-light laminated crystal board of the present invention and preparation method thereof as follows:
White-light laminated crystal board of the present invention comprises following prescription (measure unit is a weight unit):
SE 100
DOP (DOP) 40～60
Liquid barium zinc stabilizer 1.8～2.5
Acrylic process aids 0.2～0.6
Pigment 0.05～0.08;
White-light laminated crystal board of the present invention can also be to comprise following prescription (measure unit is a weight unit):
SE 100
DOP (DOP) 40～60
Liquid barium zinc stabilizer 1.8～2.5
Nontoxic phosphoesterase 30 .3～0.6
Acrylic process aids 0.2～0.6
Pigment 0.05～0.08;
SE recited above adopts heat-resisting good K65 resin (as: Tai Wantai moulds S65S, the Japanese TK1000 of SHIN-ETSU HANTOTAI, Japanese ocean TH1000, clock deep pool S1001, Ning Botai moulds S65, Shandong QS1000F, Taurus SLP1000); It is 1,500,000 acrylic process aids that described acrylic process aids adopts molecular weight, can improve the intensity of melt, reduces difficulty of processing and improves the appearance of goods; It is the purple powder of SF-7088B that described pigment is selected model for use, and the yellow keynote that can eliminate PVC bleaches goods, and can improve the brightness of goods.
Stablizer adopt liquid barium zinc have heat-resistant stability good, pass through degree and the outstanding advantage of brightness; Nontoxic SULPHOSUCCINIC ACID ESTER and stablizer be collaborative can improve stability and goods in the production pass through degree, brightness is further promoted, and is met the low toxic and environment-friendly requirement.
As shown in Figure 2, the manufacture craft of low-toxicity white-light bonded crystal board of the present invention comprises the following operation of carrying out successively:
1) automatic gauge operation is imported and is measured by the prescription consumption of the low-toxicity white-light bonded crystal board of assigning;
SE 100
DOP (DOP) 40～60
Liquid barium zinc stabilizer 1.8～2.5
Acrylic process aids 0.2～0.6
Pigment 0.05～0.08;
Perhaps:
SE 100
DOP (DOP) 40～60
Liquid barium zinc stabilizer 1.8～2.5
Nontoxic phosphoesterase 30 .3～0.6
Acrylic process aids 0.2～0.6
Pigment 0.05～0.08;
2) mixed at high speed operation, mixing time is 400～450 seconds, makes the abundant phase mutual diffusion of each component in the prescription be prepared into the dry mash of homogeneous;
3) cooling and stirring operation; Through lowering the temperature to stirrer feeding recirculated cooling water or refrigerated water; Temperature of charge is dropped to below 80 ℃; Can stir material for a long time, not cause the diffusion of strengthening each component of prescription under the situation of material degraded, every hand material adds with the prescription clout and is controlled at formulation weight 15～20%; In the cooling and stirring operation, also include process to the storage vat storing;
4) planet extruder plasticizing operation; The planet extruder is a state-of-the-art now PVC plasticizing equipment, two section planet screw extruders that present embodiment adopts German ENTEX company to produce.The extruder temperature of described planet extruder plasticizing operation is 175～200 ℃, and in the planet extruder plasticizing operation, material is issued to plasticizing effect in the intense shear effect of multiscrew, and the plasticizing temperature rise of material mainly leans on this shearing action to accomplish.And short (10～30 seconds) heated time of fusion time is short, can guarantee that the plasticizing of material evenly reduces the danger of material xanthochromia and physicals decline;
5) filter operation; Described filtration operation adopts 20 orders, 60 orders, 150 or 200 orders, four layers of stainless steel filtering net of 20 purposes, and the filter temperature is set at 165～185 ℃;
6) four-roll calendaring operation, wherein, the rolling press temperature is set at:
Front-wheel: 192～198 ℃
Last wheel: 192～198 ℃
Middle wheel: 188～192 ℃
Lower whorl: 175～182 ℃
The hot-galvanizing that middle wheel, lower whorl adopt Germany to produce is taken turns, and surfaceness (Ra) is less than 0.005;
7) calendering refrigerating work procedure, the bait that is produced in this refrigerating work procedure is sent into the 8th operation, and all the other finished products get into the 9th operation;
8) bait returns the system operation, and the product after this operation is pulverized is sent into the 3rd operation and continued subsequent handling;
9) coiling step; said step of winding up speed of 22 to 32 m / min;
10) material process in the applying is according to the number of plies material loading of processing requirement by setting;
11) applying preheating bonding process, wherein, preheating wheel temperature: 160～170 ℃; Fit and take turns temperature: 160～170 ℃;
12) applying cooling cutting edge operation;
13) coiling step of laminating, said step of winding up speed of 10 to 15 m / min.
14) finished product packing warehouse-in;
In the manufacture craft process of low-toxicity white-light bonded crystal board of the present invention, also to accomplish following requirement:
1. the buying of control material, various starting material must meet above-mentioned low toxicity standard, and every batch of raw material must be tested the goods characteristics by laboratory needle, guarantee the accuracy of prescription.
2. raw-material weighing is guaranteed accurately to pack with the low toxicity film, is responsible for examination at random by the special messenger.
3. produce preceding 15 hand material with the clear car of low toxicity prescription, other clouts are forbidden to reclaim.
4. per tour special messenger is responsible for visual appearancies such as color, brilliant assorted point are followed the trail of inspection when producing.
5. changed a filtering net in per two hours in producing, guarantee that product colour is stable.
6. the strict processing condition of assigning of carrying out guarantee product consistence from the beginning to the end.
7. clout guarantees that in crushing process inclusion-free sneaks into, the quantitative weighing pack.
8. clout is when returning system, and every hand material feed back amount is controlled at 15～20% of formulation weight, and special messenger's accounting of making an inventory is arranged.
10. the consistence of low-toxicity white-light goods is guaranteed in scheduling rationally, does equipment and environmental health well, and stopping has impurity to sneak into aborning.
Provide specific examples below:
Instance 1:
1) selects: Japanese ocean TH1000 SE 100kg
DOP (DOP) 40kg
Liquid barium zinc stabilizer 2.2kg
Nontoxic phosphoesterase 30 .5kg
Molecular weight is 1,500,000 acrylic process aids 0.5kg
Model is the violet pigment 0.06kg of SF-7088B
Set electronic scale and begin metering by above-mentioned prescription, SE, DOP, liquid barium zinc stabilizer and nontoxic SULPHOSUCCINIC ACID ESTER enter high mixer successively after accomplishing;
2) carry out mixed at high speed, mix and drop into processing aid and pigment successively after 120 seconds, total mixing time is 400 seconds;
3) carry out cooling and stirring, the material after the mixed at high speed is entered stirrer carry out cooling and stirring, lower the temperature through feeding recirculated cooling water to stirrer, temperature drops to below 80 ℃, enters storage vat.Every hand system of returning is with prescription clout 25kg;
4) give the planet extruder through worm conveyor with the mass transport of storage vat, plastify, the extrusion temperature of planet extruder is set at 175 ℃;
5) material after the plasticizing of planet extruder is filtered through filter, adopt 20 orders, 60 orders, 200 orders, four layers of stainless steel filtering net of 20 purposes, the filter temperature is set at 165 ℃;
6) carry out four-roll calendaring, wherein, the rolling press temperature is set at:
Front-wheel: 192 ℃
Last wheel: 192 ℃
Middle wheel: 188 ℃
Lower whorl: 180 ℃;
7) product after the calendering carries out cooling and shaping through refrigerating work procedure, and cutting edge as requested, and the bait after the cutting edge is sent into the 8th operation, and all the other finished products get into the 9th operation;
8) bait is pulverized after wind and deliver to the 3rd operation continuation subsequent handling;
9) after cooling and molding products for coiling, winding speed of 22 m / min;
10) 5 number of layers of setting according to the product requirement material loading of fitting, promptly material is batched in 5 volume calenderings on the make-up machine;
11) through rigging machine the material article of 5 individual layers being fitted is one deck, and wherein, the preheating wheel temperature of rigging machine is 170 ℃; The wheel temperature of fitting is 170 ℃;
12) goods after the applying are finalized the design through refrigerating work procedure, and according to the order requirements cutting edge;
13) after setting the cooling products for coiling up speed of 11 m / min.
14) finished product packing warehouse-in;
Instance 2:
1) select: Tai Wantai moulds S65S SE 100kg
DOP (DOP) 50kg
Liquid barium zinc stabilizer 2kg
Nontoxic phosphoesterase 30 .3kg
Molecular weight is 1,500,000 acrylic process aids 0.3kg
Model is the violet pigment 0.05kg of SF-7088B
Set electronic scale and begin metering by above-mentioned prescription, SE, DOP, liquid barium zinc stabilizer and nontoxic SULPHOSUCCINIC ACID ESTER enter high mixer successively after accomplishing;
2) carry out mixed at high speed, mix and drop into processing aid and pigment successively after 120 seconds, total mixing time is 420 seconds;
3) carry out cooling and stirring, the material after the mixed at high speed is entered stirrer carry out cooling and stirring, lower the temperature through feeding recirculated cooling water to stirrer, temperature drops to below 80 ℃, enters storage vat.Every hand system of returning is with prescription clout 25kg;
4) give the planet extruder through worm conveyor with the mass transport of storage vat, plastify, the extrusion temperature of planet extruder is set at 178 ℃;
5) material after the plasticizing of planet extruder is filtered through filter, adopt 20 orders, 60 orders, 200 orders, four layers of stainless steel filtering net of 20 purposes, the filter temperature is set at 165 ℃;
6) carry out four-roll calendaring, wherein, the rolling press temperature is set at:
Front-wheel: 195 ℃
Last wheel: 195 ℃
Middle wheel: 188 ℃
Lower whorl: 178 ℃;
7) product after the calendering carries out cooling and shaping through refrigerating work procedure, and cutting edge as requested, and the bait after the cutting edge is sent into the 8th operation, and all the other finished products get into the 9th operation;
8) bait is pulverized after wind and deliver to the 3rd operation continuation subsequent handling;
9) after cooling and molding products for coiling, winding speed of 20 m / min;
10) 4 number of layers of setting according to the product requirement material loading of fitting, promptly material is batched in 4 volume calenderings on the make-up machine;
11) through rigging machine the material article of 4 individual layers being fitted is one deck, and wherein, the preheating wheel temperature of rigging machine is 160 ℃; The wheel temperature of fitting is 165 ℃;
12) goods after the applying are finalized the design through refrigerating work procedure, and according to the order requirements cutting edge;
13) after setting the cooling products for winding, the winding speed of 12 m / min.
14) finished product packing warehouse-in;
Instance 3:
1) selects: Shandong QS1000F SE 100kg
DOP 60kg
Liquid barium zinc stabilizer 1.8kg
Molecular weight is 1,500,000 acrylic process aids 0.3kg
Model is the purple powder pigment 0.05kg of SF-7088B
Set electronic scale and begin metering by above-mentioned prescription, SE, DOP and liquid barium zinc stabilizer enter high mixer successively after accomplishing;
2) carry out mixed at high speed, mix and drop into processing aid and pigment successively after 120 seconds, total mixing time is 450 seconds;
3) carry out cooling and stirring, the material after the mixed at high speed is entered stirrer carry out cooling and stirring, lower the temperature through feeding recirculated cooling water to stirrer, temperature drops to below 80 ℃, enters storage vat.Every hand system of returning is with prescription clout 25kg;
4) plastify to the planet extruder mass transport of storage vat through worm conveyor, the extrusion temperature of planet extruder is set at 175 ℃;
5) material after the plasticizing of planet extruder is filtered through filter, adopt 20 orders, 60 orders, 150 orders, four layers of stainless steel filtering net of 20 purposes, the filter temperature is set at 165 ℃;
6) carry out four-roll calendaring, wherein, the rolling press temperature is set at:
Front-wheel: 195 ℃
Last wheel: 195 ℃
Middle wheel: 188 ℃
Lower whorl: 175 ℃;
7) product after the calendering carries out cooling and shaping through refrigerating work procedure, and cutting edge as requested, and the bait after the cutting edge is sent into the 8th operation, and all the other finished products get into the 9th operation;
8) bait is pulverized after wind and deliver to the 3rd operation continuation subsequent handling;
9) after cooling and molding products for coiling, winding speed of 18 m / min;
10) 6 number of layers of setting according to the product requirement material loading of fitting, promptly material is batched in 6 volume calenderings on the make-up machine;
11) through rigging machine the material article of 6 individual layers being fitted is one deck, and wherein, the preheating wheel temperature of rigging machine is 160 ℃; The wheel temperature of fitting is 160 ℃;
12) goods after the applying are finalized the design through refrigerating work procedure, and according to the order requirements cutting edge;
13) after setting the cooling products for winding, the winding speed of 10 m / min.
14) finished product packing warehouse-in;
Be respectively to limiting the regulation of material below among the EN71Part3 of European Union, RoHS, PAHs and the USS ASTM F963-08.
1.EN71 requiring the following 8 heavy metal species amounts of shifting out not surpass, Part3 and ASTM F963-08 require to limit:
Plumbous (Pb)＜90mg/kg
Arsenic (As)＜25mg/kg
Antimony (Sb)＜60mg/kg
Barium (Ba)＜1000mg/kg
Cadmium (Cd)＜75mg/kg
Chromium (Cr)＜60mg/kg
Mercury (Hg)＜60mg/kg
Selenium (Se)＜500mg/kg
2.RoHS requiring following substances content can not exceed requirement limits
Cadmium (Cd)＜100mg/kg
Mercury (Hg)＜1000mg/kg
Plumbous (Pb)＜1000mg/kg
Sexavalent chrome (Cr
6+)＜1000mg/kg
PBBs (PBBs)＜1000mg/kg
Polybromodiphenyl ether (PBDEs)＜1000mg/kg
3.PAHs (polynuclear aromatics) comprising:
Naphthalene, acenaphthylene, acenaphthene, fluorenes, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, bend, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (a) pyrene, indenes benzene (1,2,3-cd) pyrene, dibenzo (a, n) anthracene, benzo (ghi) north (perylene); Require 16 kinds of polynuclear aromatics content＜10mg/kg and benzo (a) pyrene content＜1mg/kg;
Low-toxicity white-light bonded crystal board of the present invention and preparation method thereof meets above-mentioned each item requirement fully.
Claims (6)
1. the making method of a low-toxicity white-light bonded crystal board is characterized in that, comprises the following operation of carrying out successively:
1) automatic gauge operation is imported and is measured by the prescription consumption of the low-toxicity white-light bonded crystal board of assigning;
2) mixed at high speed operation, mixing time is 400～450 seconds, makes the abundant phase mutual diffusion of each component in the prescription be prepared into the dry mash of homogeneous;
3) cooling and stirring operation makes the material cooling through feed recirculated cooling water or refrigerated water to stirrer, and temperature of charge is dropped to below 80 ℃, stirs the diffusion of strengthening each component and the degraded that does not cause material also includes the process to the storage vat storing for a long time;
4) planet extruder plasticizing operation;
5) filter operation; Adopt 20 orders, 60 orders, 150 or 200 orders, four layers of stainless (steel) wire of 20 purposes to filter, the filter temperature is controlled at 165～185 ℃;
6) four-roll calendaring operation;
7) calendering refrigerating work procedure, the cutting edge bait that is produced in this refrigerating work procedure is sent into the 8th operation, and all the other finished products get into the 9th operation;
8) bait returns the system operation, and the product after this operation is pulverized is sent into the 3rd operation and continued subsequent handling;
9) calendering coiling process;
10) material process in the applying is according to the number of plies material loading of processing requirement by setting;
11) applying preheating bonding process; Preheating wheel temperature: 160～170 ℃; Fit and take turns temperature: 160～170 ℃;
12) applying cooling cutting edge operation;
13) applying coiling process;
14) finished product packing warehouse-in;
The prescription of described low-toxicity white-light bonded crystal board is following, and measure unit is a weight unit:
2. the making method of low-toxicity white-light bonded crystal board according to claim 1 is characterized in that, the extruder temperature of described planet extruder plasticizing operation is set at 175～200 ℃.
3. the making method of low-toxicity white-light bonded crystal board according to claim 1 is characterized in that, in the described four-roll calendaring operation, the rolling press temperature is set at: front-wheel: 192～198 ℃
Last wheel: 192～198 ℃
Middle wheel: 188～192 ℃
Lower whorl: 175～182 ℃.
As claimed in claim 1, wherein the lamination white crystal board production, characterized in that the winding step as described in step 9 of the take-up speed of 22 to 32 m / min.
5 according to claim 1, wherein the bonded toxic white crystal board production, characterized in that the step 13 of the winding lamination step up speed of 10 to 15 m / min.
6. the making method of low-toxicity white-light bonded crystal board according to claim 1 is characterized in that, every hand material is controlled at 15～20% of formulation weight with the interpolation of prescription clout in the 3rd operation.
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|---|---|---|---|---|
| CN1127270A (en) * | 1995-01-16 | 1996-07-24 | 连云港市电化厂 | Making method for low density polyvinyl-chloride plate material |
| JP3377754B2 (en) * | 1998-09-28 | 2003-02-17 | アキレス株式会社 | Transparent soft film or sheet made of polyvinyl chloride resin composition |
| JP2004123962A (en) * | 2002-10-04 | 2004-04-22 | Takiron Co Ltd | Molded product of polyvinyl chloride resin |
-
2010
- 2010-02-11 CN CN2010101088967A patent/CN101775183B/en active Active
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| Publication number | Publication date |
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| CN101775183A (en) | 2010-07-14 |
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