CN1177894C - Vinyl chloride serial paste resin composition and disposable gloves - Google Patents
Vinyl chloride serial paste resin composition and disposable gloves Download PDFInfo
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- CN1177894C CN1177894C CNB011243325A CN01124332A CN1177894C CN 1177894 C CN1177894 C CN 1177894C CN B011243325 A CNB011243325 A CN B011243325A CN 01124332 A CN01124332 A CN 01124332A CN 1177894 C CN1177894 C CN 1177894C
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- softening agent
- vinyl chloride
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Abstract
The invention provides a vinyl chloride paste resin composition which comprises 100 pts.wt. vinyl chloride paste resin and 50-120 pts.wt. plasticizer comprising 50-95 wt.% citric ester plasticizer and/or glycerin ester plasticizer and 5-50 wt.% polyester plasticizer having a viscosity at 23 deg.C of 100 mPa.s or higher and lower than 1,000 mPa.s. The vinyl chloride paste resin composition which is prepared by using a non-phthalic ester plasticizer, has excellent tensile strength and 100% modulus almost equal to those of a vinyl chloride paste resin composition prepared by using a phthalic ester plasticizer, and can be molded under the conventional processing conditions and to provide a molded article obtained therefrom.
Description
The present invention relates to vinyl chloride serial paste resin composition and formed body thereof.In more detail, the present invention relates to be suitable for vinyl chloride pasty resin composition and the disposable glove that disposable glove is used etc.
Disposable glove is meant the gloves of throwing away after the usefulness of using in food, medical field etc., the about 80-150 μ m of central authorities of flat portion of hand is thick.
The manufacturing of this disposable glove generally is such working method: flood fingerprint types such as promoting pottery in the plastisol (hereinafter referred to as colloidal sol) that 50 ℃ of following viscosity being made up of the vinyl chloride pasty resin composition are about 70-300mPas after, remove remaining colloidal sol, by the gelation manufacturing.
In the past, as the softening agent of disposable glove, generally used phthalic ester series softening agent, for example phthalic acid-2-ethylhexyl (DOP), phthalic acid two-n-butyl ester (DBP) etc. with the vinyl chloride pasty resin composition.
; phthalic acid-2-(ethyl hexyl) ester (DOP); butyl benzyl phthalate (BBP); phthalic acid two-n-butyl ester (DBP); phthalic acid two-n-pentyl ester (DPP); dipropyl phthalate (DPRP); dicyclohexyl phthalate (DCHP); the phthalic ester of diethyl phthalate (DEP) etc. is under a cloud to be the material (so-called environmental hormone) of disorderly internal secretion effect; purposes instant food at disposable glove; in the medical field, wish to replace the softening agent of these phthalic ester series with the softening agent of wholesomeness excellence.
For this reason; for example studied the Tributyl O-acetylcitrate (ATBC) of citrate series softening agent; but because along with the viscosity of plastisol reduces; initial stage gel voltinism accelerates; under prior art processing conditionss such as processing temperature, carry out dip forming, then the thickness of the outward appearance of goods and goods produces change etc.; in order to obtain and former equal goods, must study, adjust processing conditions.In addition, because the hardness (100% modulus) of gloves increases the vicissitudinous tendency of the characteristic of goods or quality.
On the other hand; the viscosity that produces colloidal sol under the situation with the glycerine diacetyl list laurate of glyceryl ester series softening agent too reduces; and because the increase that is changed significantly in time of viscosity; in the keeping that must adjust colloidal sol, storage requirement, the problem of processing aspect also is easy to generate.In addition, similarly,, also bring the characteristic of goods or the problem of quality change in order to increase gloves hardness.
The objective of the invention is to use non-phthalic ester series softening agent, provide keep and use phthalic ester series softening agent disposable glove equal or better rerum natura and can be at the working method of prior art or the vinyl chloride pasty resin composition and the disposable glove of processing conditions compacted under.
The result that the inventor studies repeatedly with keen determination, discovery contains at least a softening agent of citrate series softening agent and glyceryl ester series softening agent and viscosity more than or equal to 100mPas, can achieve the above object less than the vinyl chloride pasty resin composition of the polyester series softening agent of 1000mPas, and the result has finished the present invention.
Promptly, the present invention relates in 100 weight part vinyl chloride pasty resins, cooperation is the vinyl chloride serial paste resin composition (claim 1) of the softening agent of the 50-120 weight part formed less than the polyester series softening agent of 1000mPas more than or equal to 100mPas by 23 ℃ the viscosity of 50-95 weight % citrate series softening agent and/or glyceryl ester series softening agent and 5-50 weight %, polyester is that the viscosity of 23 ℃ in softening agent is the vinyl chloride serial paste resin composition (claim 2) of claim 1 record of 100-500mPas, the K value of vinyl chloride pasty resin is the claim 1 or 2 vinyl chloride serial paste resin compositions of putting down in writing (claim 3) of the vinyl chloride pasty resin of 65-75, by the tensile strength that has cooperated matrix band is 10-16MPa, and 100% modulus is the disposable glove (claim 4) that the vinyl chloride serial paste resin composition of the non-phthalic ester series softening agent of 4-5MPa is made, the disposable glove of claim 4 record, wherein vinyl chloride serial paste resin composition is in 100 weight part vinyl chloride serial paste resins, and cooperating 23 ℃ viscosity by 50-95 weight % citrate series softening agent and/or glyceryl ester series softening agent and 5-50 weight % is more than or equal to 100mPas, the composition (claim 5) of the softening agent of the 50-120 weight part of forming less than the polyester series softening agent of 1000mPas, the viscosity that the polyester series softening agent is 23 ℃ is the disposable glove (claim 6) of claim 5 record of 100-500mPas, the K value of vinyl chloride pasty resin is the disposable glove (claim 7) that the claim 4-6 of the vinyl chloride pasty resin of 65-75 puts down in writing.
Among the present invention,, use vinyl chloride pasty resin separately, or as required, add the vinylchlorid blending resin therein and use as vinyl chloride pasty resin.
Vinyl chloride pasty resin is meant by in the presence of water-soluble polymerization initiator, in the aqueous medium that contains emulsifying agent etc., emulsion polymerization or independent vinyl chloride monomer or vinyl chloride monomer and the copolymerizable monomeric mixture of inoculation emulsion polymerization, perhaps by in the presence of oil-soluble polymerization initiator, by fine suspension polymerization, the method of spraying drying latex etc. obtains after the polymerization, and primary particle diameter is the vinyl chloride serial polymer (hereinafter referred to as vinyl chloride serial emulsion polymerization body) of 0.1-5 μ m.
The vinylchlorid blending resin is by in the aqueous medium of pbz polymer series suspension stabilizer etc., in the presence of oil-soluble polymerization initiator, vinyl chloride monomer that suspension polymerization is independent or vinyl chloride monomer and copolymerizable monomeric mixture, make soup compound dehydration after the polymerization with centrifuge etc., obtain by methods such as air stream drying, the dryings that flows again.With improvement pasty state flow of sol etc. is purpose, cooperates vinylchlorid blending resin (vinyl chloride serial suspension polymerization body) as required in vinyl chloride serial paste resin.The cooperation ratio of vinylchlorid blending resin is 0-50 weight %, especially the 0-10 weight % of whole vinyl chloride serial resins normally.Preferably mismatch the vinylchlorid blending resin, use vinyl chloride pasty resin separately.
As above-mentioned vinyl chloride serial emulsion polymerization body and vinyl chloride suspension polymerization body, the independent polymer of preferred usually use vinylchlorid, but they also can be vinylchlorid and the monomeric copolymer copolymerizable with it.The monomeric content that can close with chloroethylene copolymer in vinyl chloride serial emulsion polymerization body and the vinyl chloride serial suspension polymerization body is 0-10 weight % normally.As the monomer that can close with chloroethylene copolymer, usually if be used for the monomer of the copolymerization of vinylchlorid, then have no particular limits, for example can list the ethene ethers etc. of the olefines, isobutyl vinyl ether, octyl group Vinyl Ether etc. of vinyl esters such as vinyl acetate, vinyl laurate, stearic acid vinyl ester, ethene, propylene, iso-butylene etc.
Vinyl chloride pasty resin and vinylchlorid blending resin were widely used in the past, can buy the described resin of various grades from market, can use in the present invention.
Among the present invention, " vinyl chloride serial paste resin " is meant independent vinyl chloride pasty resin and cooperated the vinyl chloride pasty resin of vinylchlorid blending resin.
Because the tensile strength of the resin that the K value is low is low, the resin polymerization productivity that the K value is high is bad, and cost improves, and in the vinyl chloride serial paste resin composition of prior art, uses vinyl chloride pasty resin and the vinylchlorid blending resin of K value 70-80 usually.But, becoming at phthalic ester under the situation of other softening agent such as ATBC or glycerine diacetyl mono-laurate prior art, it is big that 100% modulus of the moulding product that obtain becomes, and goods have the tendency of hardening.Use the polyester series softening agent even merge therein, 100% modulus of the moulding product that obtain is still high, the resin degree of crystallization height that the K value is high, goods hardening.
Among the present invention, if use the low vinyl chloride serial paste resin of K value 65-75, owing to adopt this resin, tensile strength is big, obtain the little moulding product of 100% modulus, so can access the goods of rerum natura with quality identical with the goods of the phthalic ester series plasticizer DOP that uses prior art.And can select productivity good, the resin that cost is cheap kills two birds with one stone.
In addition, based on ISO1628-2, implement the K pH-value determination pH of resin.
The amount that is used for softening agent of the present invention with respect to 100 weight part vinyl chloride pasty resins, is the 50-120 weight part, preferred 70-100 weight part.If the amount of softening agent less than 50 weight parts, then needs more thinner, and has the tendency of the problem that produces the hardening of moulding product.Even the products thickness attenuation is limbered up,, be not preferred owing to, the bad tendency of product qualitative change is arranged by producing the fraction defective height that pin hole brings.On the contrary, if greater than 120 weight parts, then, not preferred because the goods that have the seepage of product strength reduction and softening agent to bring are worth the tendency that becomes bad yet.
Among the present invention, make as any one of the citrate of main plasticizer series softening agent or glyceryl ester series softening agent, amount with respect to whole softening agent, reach 50-95 weight %, perhaps, merging under the situation of using citrate series softening agent and glyceryl ester series softening agent, make the amount of its total amount with respect to whole softening agent, reach 50-95 weight %, with itself and 5-50 weight % viscosity ratio, 23 ℃ more than or equal to 100mPas, use together less than the polyester series softening agent of 1000mPas.
As citrate series softening agent; can list triethyl citrate, tributyl citrate, CitroflexA-2, Tributyl O-acetylcitrate, ethanoyl citric acid three-2-ethylhexyl, ethanoyl citric acid-n-octyl group ester in the last of the ten Heavenly stems, citric acid distearyl ester, citric acid three stearyl esters etc.; though there is no particular limitation to it, preferably use Tributyl O-acetylcitrate (ATBC).Citrate series softening agent may be used alone, two or more kinds can also be used in combination.
As glyceryl ester series softening agent; can list; glycerine diacetyl mono-laurate, glycerine diacetyl list ricinoleate ester, glycerine ethanoyl butyl mono-laurate, glycerine dibutyl mono-laurate, glycerine ethanoyl dilaurate etc.; there is no particular limitation to it, but preferably use glycerine diacetyl mono-laurate as plasticizer for polyvinyl chloride.Glyceryl ester series softening agent can use separately, also can carefully close use more than 2 kinds.
Be used for softening agent of the present invention as previously mentioned, at least a softening agent of being selected from the group that citrate series softening agent and glyceryl ester series softening agent are formed by 50-95 weight % and 23 ℃ the viscosity of 5-50 weight % are more than or equal to 100mPas, form less than the polyester series softening agent of 1000mPas.
General polyester series softening agent is the condenses of hexanodioic acid and glycol, in the vinyl chloride serial resin combination of prior art, in order to improve oil-proofness or non-moving property,, use the viscosity under 23 ℃ to be the softening agent of 1000-6000mPas as complementary softening agent.In contrast, use in the present invention than the polyester series softening agent condensation degree of the general use of prior art viscosity little, 23 ℃ be greater than 100mPas less than 1000mPas, the polyester series softening agent of preferred 100-500mPas.As the specific examples of such polyester series softening agent, can list PN-160 (rising sun electrochemical industry system), PN-150 (rising sun electrochemical industry system), PN-170 (rising sun electrochemical industry system), PX-811 (rising sun electrochemical industry system), W-1000 (big Japanese ink chemical industry system), W-1200 (big Japanese ink chemical industry system) etc.The polyester series softening agent can use separately, also can be used in combination more than 2 kinds.
Under the situation of using the low polyester series softening agent of viscosity ratio 100mPas, seepage is many, and this polyester series softening agent lacks practicality.On the contrary, if greater than the high viscosity of 1000mPas, then because to set colloidal sol many to the dilution dosage of processing viscosity, cost has just increased.
In addition,, use taper-flat-panel systems (φ=6.0cm, α=2 °), implement the softening agent viscosimetric analysis down at 23 ℃ based on ISO3219.
Vinyl chloride serial paste resin composition of the present invention can contain the normally used various additives of prior art.Disposable glove of the present invention is meant except that vinylchlorid paste resin, softening agent with the vinyl chloride pasty resin composition, cooperate the various additives of the general stablizer that uses of the industry, thinner, other necessity and obtain the composition of disposable glove, so common cooperation is had no particular limits.
As thinner, generally use 2,2,4-trimethylammonium-1,3-pentanediol diisobutyrate (TXIB) or n-paraffinic hydrocarbons etc.
As the disposable glove that adopts such vinyl chloride serial paste resin composition moulding, the tensile strength of measuring with matrix band is 10.0-16.0MPa, preferred 13.0-15.0MPa, and 100% modulus is 3.0-5.0MPa, preferred 4.0-5.0MPa.
Embodiment
Describe the present invention in detail below by embodiment, the present invention is not subjected to the restriction of following embodiment.
Embodiment 1-4 and comparative example 1-4
Table 1
Weight part
| Vinyl chloride pasty resin (Kanegafuchi Chemical Industry Co., Ltd system PSM-71, PSH-31) | 100 |
| Softening agent (with reference to table 2 and table 4) | 90 |
| Ca-Zn stablizer (Asahi Denka Kogyo K. K's system, 38) | 3 |
| Epoxidised soybean oil (Asahi Denka Kogyo K. K's system, 0-130P) | 3 |
| Thinner (Kyowa Hakkokogyo Co., Ltd's system, キ ョ-ワ ノ-Le D:TXIB) | X |
The described cooperation of employing table 1 mixes, and the thinner with the amount of Table 4 is carried out the mixture standing and defoaming 1 hour that viscosity adjusts, and obtains plastisol.Measure the characteristic of the plastisol that obtains with following method.The results are shown in table 4.
Viscosity measurement
The viscosimetric analysis of plastisol is the measuring method that adopts the apparent viscosity of the Kreuk Fei Erde rotary viscosimeter of ISO2555, measures temperature and carries out under 50 ℃ of average actual processing collosol temperatures.
The tensile strength measuring method
Behind the about 200 μ m of coating on the sheet glass, make sheet with gelation in 4 minutes down at 200 ℃.JIS K 7113 according to the rules prepares dumbbell shaped JIS3 test film by this sheet, using high-performance universal testing machine (self-registering instrument, Shimadzu Seisakusho Ltd.'s system) under the 200mm/min test rate, measures 100% modulus (MPa), tensile strength (MPa) and elongation (%).
Initial stage gel voltinism measuring method
Use Rheometer AR500 (TA Instruments society system), when giving the 3Pa shear-stress, with 10 ℃/minute, the intensification from 25 ℃ to 95 ℃ is measured the temperature that viscosity increases, as the initial stage gelling temperature.
The softening agent that uses is shown in table 2.In addition, the viscosity of these softening agent is shown in table 3.Viscosimetric analysis is based on ISO3219, use taper-flat-panel systems (φ=6.0cm, α=2 °), implements down at 23 ℃.
Table 2
| DOP | Phthalic acid 2-ethylhexyl | Kyowa Hakkokogyo Co., Ltd's system |
| ATBC | Acetyl tributyl citrate ester | Sanken Chemical Co., Ltd's system |
| PL-012 | Glycerine diacetyl mono-laurate | Reason is ground VITAMIN Industrial Co., Ltd system |
| PX-811 | Low-viscosity polyester series softening agent | Asahi Denka Kogyo K. K's system |
| PN-250 | The polyester series softening agent | Asahi Denka Kogyo K. K's system |
Table 3
(mPa·s)
| シェアレ-ト | 1 | 10 | 100 |
| DOP | 69 | 62 | 64 |
| ATBC | - | 37 | 35 |
| PL-012 | - | 30 | 31 |
| PX-811 | 160 | 187 | 189 |
| PN-250 | 4710 | 4720 | - |
As can be seen from Table 4, compare with the DOP cooperation of comparative example 1, in order to make the viscosity unanimity, the ATBC of comparative example 2 cooperates becomes the few cooperation of thinner amount, and 100% modulus rerum natura increases.In addition, the initial stage gelling temperature is also shifted to low temperature side.It is in order to make the viscosity unanimity, to become the few cooperation of thinner too that the PL-012 of comparative example 3 cooperates, 100% modulus rerum natura height, and the initial stage gelling temperature is a low temperature, viscosity changes in time to have and becomes big tendency.
In addition, in comparative example 4, in order to make the levels of viscosity unanimity, and with the cooperation of general polyester series softening agent, dilution dosage must be more than 2 times.
In contrast, in the cooperation of the use of the merging shown in the embodiment 1,2,4 low-viscosity polyester series softening agent, with cooperating identical dilution dosage to reach setting viscosity with the DOP of comparative example 1, viscosity changes little in time, 100% modulus rerum natura is with low uncertainty, and the initial stage gelling temperature is also identical.Therefore, need not significantly to change processing conditions etc., and the goods of the same quality that can be maintained.
From embodiment 3 as can be seen, be 72 PSM-71 with respect to the K value of embodiment 1, be 76 PSH-31 displacement with the K value, 100% modulus rerum natura might increase.Thereby, requiring under the low condition of modulus, use the little softening agent of K value relatively good.
Table 4
| Comparative example | Embodiment | ||||||||
| 1 | 2 | 3 | 4 | 1 | 2 | 3 | 4 | ||
| Use resin | PSM -71 | PSM -71 | PSM -71 | PSM -71 | PSM -71 | PSM -71 | PSH -31 | PSM -71 | |
| The K value | 72 | 72 | 72 | 72 | 72 | 72 | 76 | 72 | |
| Cooperate | DOP | 90 | - | - | - | - | - | - | - |
| ATBC | - | 90 | - | 63 | - | 63 | 63 | 31.5 | |
| PL-012 | - | - | 90 | - | 63 | - | - | 31.5 | |
| PX-811 | - | - | - | - | 27 | 27 | 27 | 27 | |
| PN-250 | - | - | - | 27 | - | - | - | - | |
| TXIB | 20 | 10 | 5 | 45 | 20 | 15 | 15 | 17 | |
| Viscosity | 1Hr | 160 | 170 | 160 | 150 | 150 | 150 | 170 | 160 |
| 24Hr | 230 | 250 | 260 | 190 | 200 | 200 | 220 | 210 | |
| 72Hr | 510 | 430 | Can't measure | 420 | 270 | 310 | 320 | 300 | |
| Rerum natura | 100% modulus | 3.8 | 4.6 | 4.8 | 4.0 | 4.2 | 4.3 | 4.6 | 4.3 |
| Tensile strength | 12.7 | 14.4 | 13.9 | 13.4 | 14.6 | 13.6 | 15.0 | 14.0 | |
| Elongation | 458 | 397 | 416 | 418 | 428 | 417 | 400 | 415 | |
| The initial stage gelling temperature | 70.8 | 68.7 | 67.8 | 71.8 | 70.8 | 70.8 | 71.8 | 70.7 | |
Vinyl chloride pasty resin composition of the present invention uses the non-phthalic ester series softening agent of wholesomeness excellence, provide the tensile strength that keeps identical with the disposable glove that uses phthalic ester series softening agent, 100% modulus and excellence that can moulding under the processing conditions of prior art formed body.
Claims (4)
1. vinyl chloride serial paste resin composition, in the K value is in the 100 weight part vinyl chloride serial paste resins of 65-76, the softening agent that cooperates the 50-120 weight part to be made up of more than or equal to 100mPas, less than the polyester series softening agent as the condenses of hexanodioic acid and glycol of 1000mPas the viscosity under 50-95 weight % citrate series softening agent and/or glyceryl ester series softening agent and 5-50 weight % 23 ℃.
2. the described vinyl chloride serial paste resin composition of claim 1, wherein the viscosity of polyester series softening agent under 23 ℃ is 100-500mPas.
3. disposable glove, make by vinyl chloride serial paste resin composition, described vinyl chloride serial paste resin composition is to obtain for cooperating 50-120 weight part softening agent in the vinyl chloride serial paste resin of 65-76 in 100 weight part K values, described softening agent by the viscosity under 50-95 weight % citrate series softening agent and/or glyceryl ester series softening agent and 5-50 weight % 23 ℃ more than or equal to 100mPas, form less than the polyester series softening agent of 1000mPas as the condenses of hexanodioic acid and glycol.
4. the described disposable glove of claim 3, wherein the viscosity of polyester series softening agent under 23 ℃ is 100-500mPas.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000165256A JP2001342316A (en) | 2000-06-02 | 2000-06-02 | Vinyl chloride paste resin composition and disposable glove |
| JP165256/2000 | 2000-06-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1328086A CN1328086A (en) | 2001-12-26 |
| CN1177894C true CN1177894C (en) | 2004-12-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011243325A Expired - Fee Related CN1177894C (en) | 2000-06-02 | 2001-06-01 | Vinyl chloride serial paste resin composition and disposable gloves |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2001342316A (en) |
| CN (1) | CN1177894C (en) |
| TW (1) | TWI288158B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4832131B2 (en) * | 2006-03-23 | 2011-12-07 | オカモト株式会社 | PVC gloves |
| JP4908888B2 (en) * | 2006-03-23 | 2012-04-04 | オカモト株式会社 | PVC gloves |
| US8022127B2 (en) * | 2009-03-24 | 2011-09-20 | Eastman Specialties Holdings Corporation | Plastisols containing glycerol esters as plasticizers |
| JP6148570B2 (en) * | 2013-08-08 | 2017-06-14 | リケンテクノス株式会社 | Medical radiation sterilized vinyl chloride resin composition and medical device comprising the same |
| CN104387699A (en) * | 2014-11-07 | 2015-03-04 | 苏州维泰生物技术有限公司 | Medical PVC paste material and preparation method thereof |
| CN105255065A (en) * | 2015-11-17 | 2016-01-20 | 雅安市晶强板业有限公司 | Green environment-friendly composite paint-free decorative material and production technology thereof |
| CN113956583A (en) * | 2016-11-23 | 2022-01-21 | 唐山川欧森塑料制品有限公司 | Method for producing polyvinyl chloride disposable gloves |
| CN107955290B (en) * | 2017-11-17 | 2020-05-08 | 中红普林（北京）医疗用品高新技术研究院有限公司 | Disposable PVC gloves and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3229656A1 (en) * | 1982-08-09 | 1984-02-09 | Henkel KGaA, 4000 Düsseldorf | ADHESIVE PRE-GEL PLASTIC |
| JPS62256852A (en) * | 1986-04-30 | 1987-11-09 | Mitsubishi Kasei Vinyl Co | Plastisol composition |
| JP2529568B2 (en) * | 1987-04-21 | 1996-08-28 | 日本ゼオン株式会社 | Resin molded product |
| JPH01110549A (en) * | 1987-10-23 | 1989-04-27 | Sumitomo Chem Co Ltd | Fomable plastisol composition |
| EP0347769A1 (en) * | 1988-06-20 | 1989-12-27 | The B.F. Goodrich Company | Modification of vinyl dispersion resins for improved elasticity |
| JPH08127691A (en) * | 1994-10-28 | 1996-05-21 | Aisin Chem Co Ltd | Poly(vinyl chloride) plastisol composition |
| JPH08269282A (en) * | 1995-03-31 | 1996-10-15 | Nippon Zeon Co Ltd | Vinyl chloride resin plastisol composition and vinyl chloride resin granule for paste processing |
-
2000
- 2000-06-02 JP JP2000165256A patent/JP2001342316A/en active Pending
-
2001
- 2001-05-28 TW TW90112774A patent/TWI288158B/en not_active IP Right Cessation
- 2001-06-01 CN CNB011243325A patent/CN1177894C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001342316A (en) | 2001-12-14 |
| CN1328086A (en) | 2001-12-26 |
| TWI288158B (en) | 2007-10-11 |
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