CN101397377B - Auxiliary plasticizers of PVC and PVC sol composition and products containing the same - Google Patents
Auxiliary plasticizers of PVC and PVC sol composition and products containing the same Download PDFInfo
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- CN101397377B CN101397377B CN2007101516277A CN200710151627A CN101397377B CN 101397377 B CN101397377 B CN 101397377B CN 2007101516277 A CN2007101516277 A CN 2007101516277A CN 200710151627 A CN200710151627 A CN 200710151627A CN 101397377 B CN101397377 B CN 101397377B
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Abstract
A PVC secondary plasticizer, a PVC sol composition containing the secondary plasticizer and a product made from the composition are disclosed. The PVC secondary plasticizer is a dearomatization product with the distillation range of 285-340 DEG C, the aromatic hydrocarbon content of less than 1 weight percent, the power viscosity of 4-8cSt, and the carbon content of alkane of 55-80 percent, and is used for enhancing the processing property of the PVC sol, improving the physical properties of an obtained PVC film, a PVC membrane, and a PVC board, and causing the distribution rate of VOC (volatile organic compound) of the PVC product to be decreased to less than 0.1mg/m <2> question mark hr. Furthermore, the dearomatization product can still effectively reduce the viscosity even under the high filler content and simultaneously reduce the distribution rate of the volatile organic compound. Therefore, the distribution rate of VOC of the PVC floor material, the wallpaper and the membrane which are obtained from the dearomatization product is less than 0.1mg/m <2> question mark hr.
Description
Technical field
The present invention relates to a kind of extender plasticizer of SE (PVC), a kind of PVC sol composition of this extender plasticizer and goods of making by said composition of containing of being used for; Particularly relate to a kind of viscosity of the PVC of minimizing colloidal sol and increase the workability of this colloidal sol and reduce simultaneously significantly extender plasticizer and a kind of PVC sol composition of this extender plasticizer and goods made from said composition of containing through VOC (volatile organic compounds) emission rate of flooring material (floor material), wallpaper and film that this PVC collosol and gelization is made.
Background technology
Usually, because the PVC goods are compared cheap with other material and had good chemical resistance, weathering resistance and flame retardant resistance and the favorable mechanical performance, therefore be applied to various Application Areass.In the PVC goods, flooring material generally has multilayered structure, and wherein, bottom, foam layer, top layer and upper layer are range upon range of each other successively.Also have, the structure of wallpaper is on paper, to apply PVC colloidal sol, and film is the single or multiple lift structure through producing in the last coating colloidal sol of interleaving paper (release paper), gelation subsequently.In making the technology of these goods, used volatility dearomatization compound (dearomatized compound) as extender plasticizer or thinner to reduce dissolved adhesiveness.In addition, used extender plasticizer such as TXIB (2,2,4-trimethylammonium-1,3-pentanediol diisobutyrate) and DOS (dioctyl sebacate).
PVC suitably mixes with after giving this resin treatment performance, as the universal resin that is applied to various Application Areass with the various additives of primary plasticizer and extender plasticizer, UV stablizer and thermo-stabilizer, filler and inner pattern releasing agent applicable that comprise.The various application of PVC comprise as the coating above metallic surface, leatheroid, wallpaper, the gloves etc.Especially, the softening agent that in the polyvinyl chloride resin course of processing, adds is a basic additive of giving various performances of polyvinyl chloride resin and function (comprising workability, snappiness and surface viscosity).
Softening agent has function that reduces the viscosity in the course of processing and give processability and the function of controlling the finished product physicals.The conventional plasticizers that is used for the polyvinyl chloride resin course of processing comprises phthalic ester, hexanodioic acid and trimellitate; The most widely used is phthalic ester, DOP (DOP) and Dinonylphthalate (DINP), and they are classified as primary plasticizer sometimes.Open text No.2005-0026178 of Korean Patent and 2003-0066039 have disclosed the application of ester-based plasticizer.And vinylbenzene (styrenic) verivate that XPA that the open text No.2003-0029528 of Korean Patent discloses and the open text No.2004-007616 of Korean Patent disclose is sometimes also as softening agent.
Simultaneously; Different with the primary plasticizer of staying after the resin treatment in the product with control product physicals; In the resin treatment process, reduce viscosity, and after machining, do not stay in the product and the softening agent that do not change the physicals (for example tensile strength and elasticity) of product can classify as extender plasticizer.Compare with primary plasticizer, extender plasticizer has lower plasticity-, and has the premium properties that reduces and keep viscosity.And, because extender plasticizer do not stay in the resin after the processing, so the surface viscosity of the product after the processing is reduced owing to they have reduced the content of softening agent in the product.
Open text No.1995-0003376 of Korean Patent and the open text No.2005-0182156 of USP disclose the purposes as extender plasticizer with TXIB.In this prior art, used extender plasticizer such as volatility aromatic hydrocarbons or TXIB, under the situation of not considering its environmental hazard, increase economic benefit, but had the problem of higher indoor VOC emission rate.
Summary of the invention
In view of this, contriver of the present invention has addressed and has been present in the problems referred to above of the prior art.Consequently; Contriver of the present invention has developed to be contained as the PVC sol composition low volatility of the extender plasticizer of PVC, that contain aromatic hydrocarbons seldom or aromatic free hydrocarbon product, and finds to utilize flooring material, wallpaper and the film of said sol composition production to have less than 0.1mg/m
2The VOC of hr (volatile organic compounds) emission rate, thus the present invention accomplished.
Therefore, the invention provides the extender plasticizer that is used for the PVC sol composition, said composition can be processed the PVC goods, for example flooring material, wallpaper and film, and these goods have less than 0.1mg/m
2The VOC emission rate of hr.
The present invention also provides the PVC that is used for flooring material, wallpaper and film sol composition; Said composition contains said extender plasticizer; Said extender plasticizer can be reduced in the viscosity of PVC sol composition in the article of manufacture process, thereby improves the processing characteristics of sol composition.
The present invention also provides the PVC goods that utilize said PVC sol composition to produce.
According to an aspect of the present invention; The extender plasticizer of a kind of PVC is provided, this extender plasticizer be boiling range be 285-340 ℃, aromaticity content be lower than 1 weight %, kinetic viscosity be the carbon content of 4-8cSt and paraffinic hydrocarbons be 55-80% take off aromatization product (dearomatized product).
According to a further aspect in the invention, a kind of PVC sol composition is provided, said composition contains: one or more polyvinyl chloride resins of 100 weight parts; The softening agent of 30-70 weight part; The extender plasticizer of 3-20 weight part; With one or more additives of 0.1-150 weight part, said additive is selected from the group of being made up of whipping agent, filler, stablizer, viscosity modifier and dispersion agent.
According to another aspect of the invention, PVC is provided goods, these goods are made by said PVC sol composition, and have less than 0.1mg/m
2The VOC emission rate of hr.
Embodiment
Hereinafter, will do the present invention and describe in further detail.
As stated; The PVC sol composition that the present invention relates to the extender plasticizer of PVC and contain said extender plasticizer; This extender plasticizer can reduce the viscosity of PVC colloidal sol and improve the processing characteristics of PVC colloidal sol; Simultaneously, make through the VOC emission rate of flooring material, wallpaper and film that the PVC collosol and gelization is processed very low.
Be used for extender plasticizer of the present invention for taking off the aromatization product, this boiling range that takes off the aromatization product is 285-340 ℃ a boiling range, and aromaticity content is lower than 1 weight %, and kinetic viscosity is 4-8cSt, and the carbon content of paraffinic hydrocarbons is 55-80%.Lower boiling commonly used in said TXIB that taken off the aromatization products substitution or the prior art takes off the aromatization product; Make and reduce by the smell that resulting goods distributed; And significantly reduced the VOC emission rate of resultant goods; Reduced the processing characteristics of the viscosity of colloidal sol, and reduced the viscosity of using softening agent to bring with raising colloidal sol.
The boiling range of said extender plasticizer is preferably 285-340 ℃.If the over point of said extender plasticizer is lower than 285 ℃, will cause the VOC emission rate to increase, if the full boiling point of said extender plasticizer is higher than 340 ℃, extender plasticizer will be stayed in the resulting goods, causes bleed (bleeding).Said carbon content of taking off the paraffinic hydrocarbons of aromatization product is preferably 55-80%.If the naphthene content that the carbon content of paraffinic hydrocarbons less than 55%, will cause taking off the aromatization product increases and therefore accelerated deterioration,, cause bleed if the carbon content of paraffinic hydrocarbons, is taken off the consistency of aromatization product greater than 80% and will be reduced.Also have, when the carbon content of boiling range and paraffinic hydrocarbons was met, said kinetic viscosity of taking off the aromatization product was in the scope of 4-8cSt.
PVC sol composition of the present invention contains: one or more polyvinyl chloride resins of 100 weight parts; The softening agent of 30-70 weight part; The extender plasticizer of 3-20 weight part; With one or more additives of 0.1-150 weight part, said additive is selected from the group of being made up of whipping agent, filler, stablizer, viscosity modifier and dispersion agent.Said additive preferably uses the whipping agent of 1-5 weight part, the stablizer of the filler of 0-150 weight part and/or 1-5 weight part.
The used polyvinyl chloride resin of the present invention is the commercially available prod, under the situation of multilayered structure, preferably in each layer, uses different types of polyvinyl chloride resin.
In the present invention, softening agent is used for promoting the processing of resin and snappiness is provided for resulting goods.Based on the polyvinyl chloride resin of 100 weight parts, be the 30-70 weight part as the cardinal principle consumption of the phthalic ester of softening agent.If the amount of employed softening agent is less than 30 weight parts, the snappiness of gel product can be very low, if be higher than 70 weight parts, resulting goods can toughness.
In addition, based on the polyvinyl chloride resin of 100 weight parts, the consumption of extender plasticizer is the 3-20 weight part.If the consumption of extender plasticizer is lower than 3 weight parts, the effect that reduces viscosity that is not enough to play will be if its consumption greater than 20 weight parts, will cause package stability to reduce.
As the additive of PVC sol composition, use to be selected from one or more additives in the group of forming by whipping agent, filler, stablizer, viscosity modifier and dispersion agent.Preferably; The filler that can in said sol composition, add the 1-5 weight part, the stablizer of 0-150 weight part, UV absorption agent, viscosity modifier and/or the dispersion agent of 1-5 weight part; To give said compsn other function, still scope of the present invention is not subject to this.
PVC goods of the present invention are processed by the PVC sol composition, and are preferably the form of flooring material, wallpaper, film and sheet material, and these PVC goods have less than 0.1mg/m
2The VOC emission rate of hr.
Used term " VOC emission rate " is meant the total amount of the volatile organic compounds (in the scope from the normal hexane to the n-hexadecane) that gives out from 1 square metre sample in the literary composition.Very high VOC emission rate does not meet the standard of IAQ management decree (Indoor Air Quality Management Act) and can cause the buildings syndromes of causing a disease.
Hereinafter, will describe the present invention in more detail, but scope of the present invention does not receive the restriction of these embodiment with reference to embodiment.
Embodiment 1
Polyvinyl chloride resin (PB-1752 to 100 weight parts; LG Chemical Co.; Ltd.) DOP (the LG Chemical Co. that adds 50 weight parts in; Ltd.), the lime carbonate (OMYA) of 150 weight parts, 15 weight parts is as the SK-EPSOL RD (SK Corp.) of extender plasticizer and the barium-zinc-base stablizer of 3 weight parts (Korea DaeHyup Chemical Co.), in mixing machine, mixed 5-10 minute.When above-mentioned colloidal sol homodisperse, it is applied the thickness of 50 μ m on interleaving paper, in baking oven, remain on 180 ℃ then and carry out gelation.
Embodiment 2
To the another kind of polyvinyl chloride resin (LP-170 of 100 weight parts; LG Chemical Co.; Ltd.) DOP (the LG Chemical Co. that adds 50 weight parts in; Ltd.), the lime carbonate (OMYA) of 150 weight parts, 15 weight parts is as the SK-EPSOL RD (SK Corp.) of extender plasticizer and the barium-zinc-base stablizer of 3 weight parts (Korea DaeHyup Chemical Co.), in mixing machine, mixed 5-10 minute.It is thick that this glue is coated onto interleaving paper 50 μ m, in baking oven, remains on 180 ℃ then and carry out gelation.
Embodiment 3
According to preparing colloidal sol with embodiment 1 identical method.This colloidal sol is coated on the paper, then gelation, and process wallpaper.
Comparative Examples 1
Repeat the step of embodiment 1, different is to use YK-D80 as extender plasticizer.
Comparative Examples 2
Repeat the step of embodiment 1, different is to use YK-D100 as extender plasticizer.
The performance that is used for the extender plasticizer of above embodiment and Comparative Examples is shown in the following table 1.
Table 1
| Extender plasticizer | Molecular weight | Viscosity (cSt) | Boiling range (℃) | |
| Embodiment 1 | SK-EPSOL?RD | 243 | 5.2 | 285-340 |
| Embodiment 2 | SK-EPSOL?RD | 243 | 5.2 | 285-340 |
| Comparative Examples 1 | YK-D80 | 170 | 1.9 | 210-240 |
| Comparative Examples 2 | YK-D100 | 186 | 2.5 | 235-265 |
More than the component and the consumption thereof that use in each embodiment and the Comparative Examples be shown in the following table 2, will in baking oven, be controlled at 180 ℃ by the PVC colloidal sol that these components are formed and carry out gelation.
Table 2
| Embodiment 1 and 3 | Embodiment 2 | Comparative Examples 1 | Comparative Examples 2 | |
| Polyvinyl chloride resin | 100 | 100 | 100 | 100 |
| DOP | 50 | 50 | 50 | 50 |
| CaCO 3 | 150 | 150 | 150 | 150 |
| Extender plasticizer | 15 * | 15 * | 15 ** | 15 *** |
| Stablizer | 3 | 3 | 3 | 3 |
Annotate:
*With SK-EPSOL RD as extender plasticizer;
*With YK-D80 as extender plasticizer;
* *With YK-D100 as extender plasticizer.
Flooring material and wallpaper to making in embodiment 1-3 and Comparative Examples 1 and 2 carry out visual observation, and according to conventional methods, for example measure the ASTM D638 of tensile strength and elongation, measure their physical properties.Observation and measuring result are shown in the following table 3.In table 3; Omitted the measuring result of embodiment 3; Because embodiment 3 is coated on the paper to process wallpaper and to check whether extender plasticizer is transferred on the paper through the colloidal sol that obtains with embodiment 1 to implement, so the analytical results of gel-film is identical between embodiment 1 and 3.
Table 3
Can find out that from the result of top table 3 embodiment 1 and 2 that uses SK-EPSOL RD disclosed by the invention to carry out demonstrates the VOC emission rate less than 0.1mg/m
2Hr compares remarkable reduction with using YK-D80 with the Comparative Examples 1 that YK-D100 carries out with 2.The physicals of embodiment 1 and Comparative Examples 1 and 2 compare, the initial viscosity of embodiment 1 are higher than Comparative Examples 1 and 2 a little, but do not have significant difference.And the tensile strength of embodiment 1 is similar with 2 with Comparative Examples 1 with elongation.In addition, the result of visual observation bleed and frosting shows that embodiment 1 no bleed and frosting shows that embodiment 1 has stable performance.
As stated, the invention provides and take off the aromatization product, this extender plasticizer even still can effectively reduce viscosity under the high filler content very much, and reduce the emission rate of volatile organic compounds simultaneously as extender plasticizer.Therefore, with said VOC emission rate of taking off flooring material, wallpaper and film that the aromatization product makes less than 0.1mg/m
2Hr.
Although described the preferred embodiment of the present invention for purposes of illustration, be understood by those skilled in the art that, under the situation that does not break away from scope of disclosure and essence in the appending claims, can carry out various modifications, interpolation and replacement.
Claims (3)
1. PVC sol composition, said composition contains: the polyvinyl chloride resin of 100 weight parts; The softening agent of 30-70 weight part; The extender plasticizer of 3-20 weight part; One or more additives in the group of forming by whipping agent, filler, stablizer, viscosity modifier and dispersion agent that are selected from the 0.1-150 weight part; Said extender plasticizer be boiling range be 285-340 ℃, aromaticity content less than 1 weight %, kinetic viscosity be the carbon content of 4-8cSt and paraffinic hydrocarbons be 55-80% take off the aromatization product.
2. PVC goods, these PVC goods are processed by the described PVC sol composition of claim 1, and the emission rate of the volatile organic compounds of these goods is less than 0.1mg/m
2Hr.
3. PVC goods according to claim 2, wherein, said goods are the form of sheet, film or plate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101516277A CN101397377B (en) | 2007-09-25 | 2007-09-25 | Auxiliary plasticizers of PVC and PVC sol composition and products containing the same |
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|---|---|---|---|
| CN2007101516277A CN101397377B (en) | 2007-09-25 | 2007-09-25 | Auxiliary plasticizers of PVC and PVC sol composition and products containing the same |
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| CN101397377A CN101397377A (en) | 2009-04-01 |
| CN101397377B true CN101397377B (en) | 2012-11-21 |
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| CN2007101516277A Expired - Fee Related CN101397377B (en) | 2007-09-25 | 2007-09-25 | Auxiliary plasticizers of PVC and PVC sol composition and products containing the same |
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| CN102587218B (en) * | 2011-12-12 | 2014-12-17 | 公安部四川消防研究所 | Composite wallpaper containing polyvinyl chloride |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043153A (en) * | 1988-11-28 | 1990-06-20 | 郑发纲 | Prepare the method for petroleum base softening agent and prepared petroleum base softening agent |
| US6118012A (en) * | 1995-04-27 | 2000-09-12 | Council Of Scientific & Industrial Research | Compound bearing an urethane linkage, which is an addict of ricinoleic esters and an isocynate, useful as a plasticizer for polyvinyl chloride (PVC) and a process for preparing such compound |
| CN1296514A (en) * | 1998-12-11 | 2001-05-23 | 索尔维公司 | Poly epsilon-caprolactone plasticizers and vinylic polymer compositions plastified therewith |
| CN1370790A (en) * | 2000-12-07 | 2002-09-25 | 郭承烨 | Aliphatic polyester compound with highly branched structure as plasticizer for polyvinyl chloride and flexible polyvinyl chloride blend with the compound |
| CN1417309A (en) * | 2002-12-02 | 2003-05-14 | 中国石油化工集团公司 | Friction-increasing grease |
-
2007
- 2007-09-25 CN CN2007101516277A patent/CN101397377B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043153A (en) * | 1988-11-28 | 1990-06-20 | 郑发纲 | Prepare the method for petroleum base softening agent and prepared petroleum base softening agent |
| US6118012A (en) * | 1995-04-27 | 2000-09-12 | Council Of Scientific & Industrial Research | Compound bearing an urethane linkage, which is an addict of ricinoleic esters and an isocynate, useful as a plasticizer for polyvinyl chloride (PVC) and a process for preparing such compound |
| CN1296514A (en) * | 1998-12-11 | 2001-05-23 | 索尔维公司 | Poly epsilon-caprolactone plasticizers and vinylic polymer compositions plastified therewith |
| CN1370790A (en) * | 2000-12-07 | 2002-09-25 | 郭承烨 | Aliphatic polyester compound with highly branched structure as plasticizer for polyvinyl chloride and flexible polyvinyl chloride blend with the compound |
| CN1417309A (en) * | 2002-12-02 | 2003-05-14 | 中国石油化工集团公司 | Friction-increasing grease |
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