[1]Mutual citations and related applications
[2]This application claims the benefit of priority based on dated Korea Patent Application No. 10-2016-0131985 October 2016 and April, all information disclosed in the literature of the Korea patent application are included as part of the specification.
[3]
[4]
Art
[5]
The present invention relates to a vinyl chloride polymer composition, and more particularly to a flowability and excellent thixotropic vinyl chloride polymer composition.
[6]
BACKGROUND
[7]
Vinyl chloride-based polymer is a polymer containing repeating units derived from vinyl chloride monomer (Vinyl Chloride Monomer, VCM) at least 50% by weight, and inexpensive and easy hardness adjustment, application and is applicable to most of the processing device the diverse. Besides, there are widely used in many fields it is possible to provide a molded article excellent physical and chemical properties, such as mechanical strength, weather resistance, and chemical resistance.
[8]
Vinyl chloride-based polymer such is made of different forms depending upon the application. For example, the extrusion process, calendar process, injection process, such as straight-processing vinyl chloride-based polymer is generally prepared by suspension polymerization, the paste processing vinyl chloride polymer, such as dipping, spraying, coating is produced by emulsion polymerization.
[9]
The paste processing is typically followed by drying in a manner that emulsion spray drying a paste for processing the vinyl chloride-based polymer latex obtained by the polymerization to form the final resin particles, and the particles were dispersed in a solvent or a plasticizer coating (reverse roll-coating, knife coating, screen coating, spray coating), gravure and screen printing (gravure and screen printing), rotation casting (rotation casting), shell casting and dipping (shell casting and dipping) and flooring, wallpaper, tarpaulins and right through the same process, gloves, apply to products such as car underbody coatings, sealants, carpet tiles.
[10]
The paste for processing a vinyl-based polymer chloride is alone is used is difficult to apply the lower the workability processed into plastisol form consisting of a number of additives such as heat stabilizers along with conventional plasticizers, wherein in order to make excellent the processability the Plastic adjusting the viscosity of the sol styryl to an appropriate level by, it is important to maintain good flow properties.
[11]
On the other hand, prior to the flow Castle improvement, the plastisol is an external force (shear rate, shear rate) If it is not applied, and maintains the gel (gel) state the plastisol does not flow, an external force (shear rate) is applied to load there is changed in accordance with the sol liquid plastisol, at this time shows a gelatinous the plastisol does not flow when the higher the value that appears in the Bingham yield stress (yield stress bingham) did not external force is applied. In addition, if for the liquid plastisol is lowered viscosity sol receiving the external force, to remove the back external force (shear rate) the plastisol is restored to its original gel state, the Bingham yield stress (bingham yield stress) in this case the more the value is subjected to an external force equal to the value of the Bingham yield stress according to the load, there is given the gel characteristics similar to those of the state of the first plastisol cases, the thixotropic poor, the plastisol processing plastisol of the there is a problem that the viscosity of workability and productivity loss due to change. In addition, when an external force is increased or the external force decreases when, Bingham yield stress is very high, but poor jolhwa when the viscosity is very high, the flow of gel property, when a Bingham yield stress is very low, the gel-holding ability of the plastisol is reduced there is a problem that workability is lowered.
[12]
In order to solve the problems as described above, the plastisol been proposed a plan of adding an additive at the time, such as mineral production possible, but there is a problem of lowering the mechanical properties of the molded article. Therefore, a situation that has developed while preventing the deterioration of the mechanical properties are excellent thixotropic vinyl chloride polymer composition of the molded article is continually required.
[13]
[14]
[Prior art document]
[15]
[Patent Document]
[16]
(Patent Document 1) JP1998-036407 A
[17]
Detailed Description of the Invention
SUMMARY
[18]
The present invention said to be conventionally made in view of solving the problems of the art, while preventing the mechanical properties of the polymer due to the additive of inorganic material such as deterioration, maintain proper viscosity, and the vinyl chloride for the production of thixotropic excellent plastisols to provide a polymer composition and a method for the purpose.
[19]
Problem solving means
[20]
In accordance with one embodiment of the present invention for solving the above problems, and advanced to the present invention is a vinyl-based polymer and include plasticizers, and the vinyl-based polymer chlorinated carbon atoms with respect to the vinyl-based polymer 100 chloride parts by weight of 10 to 18 Chloride Bingham yield stress of the fatty acid 0.05 parts by weight in excess to 2.0 parts by weight it includes the content less than, the Bingham yield stress of the external force increases conditions (bingham yield stress) is 111 Pa excess to 385 is less than Pa, the external force reduction condition (bingham yield stress ) is greater than the 97 Pa to less than 362 Pa, the difference between the Bingham yield stress value of an external force and external force term increases reducing conditions provides a greater than 0 Pa to about 35 Pa or less vinyl chloride polymer composition.
[21]
In addition, the present invention provides a method for producing a vinyl chloride polymer latex comprises a vinyl chloride polymer (S1); In the step of the higher fatty acid having a carbon number of 10 to 18 and stirring was prepared a vinyl chloride-based polymer latex (S2); Dry stirring the vinyl chloride polymer latex by the steps of obtaining a vinyl chloride polymer powder (S3); And to the vinyl-based polymer powder was stirred with a plasticizer comprising the step (S4) for producing a vinyl-based polymer composition chloride chloride, wherein the higher fatty acid is more than 0.05 parts by weight, relative to vinyl said chlorinated polymer to 100 parts by weight (based on solids) is added in an amount of less than 1.0 parts by weight of the (S4) a vinyl-based polymer composition chloride prepared in the step is the Bingham yield stress (bingham yield stress) is 111 and the Pa excess to 385 is less than Pa, the external force reduction condition of increased external conditions Bingham yield stress (bingham yield stress) of 97, and Pa excess to 362 is less than Pa, and the Bingham difference between the yield stress value of the external force increases terms and external force reduction conditions provide a process for producing 0 Pa excess to about 35 Pa or less vinyl polymer composition chloride method .
[22]
Effects of the Invention
[23]
In accordance with the present invention by containing the additive for improving thixotropy in the vinyl chloride polymer plastisol separate maintaining an appropriate viscosity even without input of an additive of inorganic material, etc., and a thixotropic excellent vinyl-based polymer composition and the manufacture thereof chloride in the manufacture It has the effect of providing a way.
[24]
Mode for the Invention
[25]
Hereinafter, the present invention will be described in more detail to aid the understanding of the present invention.
[26]
The terms or words used in the description and claims of the present invention is general and not be construed as limited to the dictionary meanings are not, the inventor accordingly the concept of a term to describe his own invention in the best way on the basis of the principle that can be defined, which must be interpreted based on the meanings and concepts corresponding to technical aspects of the present invention.
[27]
[28]
Vinyl-based polymer composition chloride according to the invention are vinyl chloride-based polymer and include plasticizers, and the polyvinyl chloride-based polymer is high in carbon number from 10 to 18 with respect to the vinyl-based polymer 100 chloride parts by weight of the fatty acid exceeds 0.05 parts by weight to 2.0 parts by weight comprising an amount of unit is less than, Bingham yield stress of the external force increases conditions and (bingham yield stress) is 111 Pa excess to 385 is less than Pa, Bingham yield stress of the external force reduction condition (bingham yield stress) is 97 Pa excess to 362 under Pa and, the difference between the Bingham yield stress value of an external force and external force term increases reducing conditions may be up to more than 0 Pa to about 35 Pa.
[29]
The vinyl chloride-based polymer according to an embodiment of the present invention may comprise a vinyl monomer derived repeat units from 50 to 100%, and the repeating unit derived from the vinyl monomer by weight 0 to 50% by weight of chloride. The vinyl chloride monomer-derived repeating units may be, which means the repeating units formed by the polymerization of vinyl chloride monomer (VCM), the vinyl-based monomer-derived repeating unit is a vinyl monomer wherein the vinyl chloride monomer copolymerizable with the It may be to mean the repeating units formed by the polymerization of vinyl chloride monomer. The vinyl monomer is an olefin compound such as ethylene, propylene, for example; Vinyl esters, unsaturated nitriles such as acrylonitrile, acrylic acids such as vinyl acetate and vinyl propionate; Vinyl methyl ether, vinyl alkyl ethers such as vinyl ethyl ether; It may be at least one member selected from the group consisting of; and acrylic acid, methacrylic acid, itaconic acid, unsaturated acids and anhydrides of these acids such as maleic acid.
[30]
According to one embodiment of the invention, the higher fatty acid contained in the vinyl chloride-based polymer it can be included in a mixed state on the three-dimensional network (network) of the vinyl chloride polymer. That is, on the three-dimensional network in which the main chain of the vinyl chloride polymer entangled with each other is present, may be present in a state in which the higher fatty acid are mixed.
[31]
The higher fatty acid according to the invention may include one or more functional groups or binding species selected from the group consisting of one or more hydroxy groups, at least one unsaturated bond and at least two carboxyl groups, for example. As specific examples, the fatty acid has a carbon number containing a higher fatty acid, one hydroxyl group and one unsaturated bond with a carbon number of 10 to 18 comprising a higher fatty acid, and one unsaturated bond with a carbon number of 10 to 18 containing one hydroxyl group of 10 to 18, a higher fatty acid, and the like of the two carbon atoms of 10 to 18 carbon atoms and a higher fatty acid of 10 to 18 having both a carboxyl group at both ends of the carbon chain of which includes an unsaturated bond of a higher fatty acid. Here, the unsaturated bond may represent a double bond or triple bond between carbon and carbon.
[32]
The higher fatty acid according to an embodiment of the present invention are castor oil fatty acid, dehydrated castor oil fatty acid, hydrogenated castor oil fatty acid, can be at least one member selected from sebacic acid (sebacic acid) and undecyl group consisting of xylene acid, in this case Plastic excellent thixotropy of styryl sol, an excellent processability and productivity.
[33]
The higher fatty acid according to an embodiment of the present invention may be a saponified higher fatty acid. The saponification of the higher fatty acid may represent a degree of saponification (saponification) was higher fatty acids higher fatty acid as a search agent. The gum agent may be an alkali hydroxide, for example.
[34]
The higher fatty acid is for example included as part relative to the vinyl chloride-based polymer to 100 parts by weight 0.05 parts by weight in excess to 2.0 parts by weight, less than 0.1 part by weight to 1.5 parts by weight, 0.1 part by weight to 1.0 part by weight or 0.3 part by weight to 0.7 parts by weight can, and thixotropic within this range, there is an excellent effect.
[35]
[36]
The plasticizer is by increasing the thermoplastic of the polymer to form a plastisol together with vinyl chloride polymer may be an organic additive material for improving the molding processability at a high temperature of the vinyl-based polymer chloride, specific examples wherein the plasticizer is a phosphate ester based plasticizers, aliphatic dibasic acid be at least one member selected from ester-based plasticizers, the group consisting of an epoxy-based plasticizer, and polyester plasticizer, and a more specific example, the plasticizer is dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), diisodecyl phthalate (DIDP) phthalic acid ester plasticizer, trioctyl trimellitate (TOTM), such as, tridecyl trimellitate, such as trimellitic acid ester plasticizer, tri-cresyl phosphate, trioctyl phosphate, etc. a phosphoric acid ester-based plasticizer, dioctyl adipate, diisobutyl having Adipic chamber may be at least one member selected from the group consisting of aliphatic dibasic acid ester plasticizers, epoxy plasticizers and polyester plasticizers such as sulfates.
[37]
According to one embodiment of the invention, the plasticizer may be included in an amount of 1 to 200 parts by weight, 50 to 150 parts by weight, or from 100 to 150 parts by weight relative to the vinyl chloride-based polymer to 100 parts by weight, workability within this range and It has excellent productivity.
[38]
[39]
According to one embodiment of the present invention, the vinyl chloride-based polymer composition is shear rate (shear rate) the Bingham yield stress at the time is increased for 180 seconds at 10 / s to 500 / s (bingham yield stress) than the 111 Pa to 385 Pa lower than, 120 Pa to 380 Pa, or 124 Pa may be to 376 Pa, a shear rate (shear rate) for a 180 sec at 500 / s 10 / s Bingham yield stress (bingham yield stress at the time was reduced to ) of 97 Pa may be greater than to less than 362 Pa, 100 Pa to 360 Pa, or 110 Pa to 350 Pa, this range is within a thixotropic highly effective in.
[40]
As another example, the vinyl chloride-based polymer composition can be the difference between the Bingham yield stress value of the external force increases terms and external force reduction condition 0 Pa excess to about 35 Pa or less, 5 Pa to 35 Pa, or 9 Pa to 32 Pa, the range is excellent in the thixotropic effect.
[41]
According to one embodiment of the present invention, the vinyl chloride-based polymer composition is shear rate (shear rate) to the time increased from 10 / s to 500 / s for 180 seconds Bingham viscosity (bingham viscosity) is greater than 0.841 Pa.s to less than 1.362 Pa.s, 0.850 Pa.s to 1.350 Pa.s, or 0.884 to 1.321 Pa.s it may be Pa.s, shear rate (shear rate) 180 seconds decreased from 500 / s to 10 / s for It may be a Bingham viscosity of time that exceeds the 0.837 Pa.s (bingham viscosity) to less than 1.302 Pa.s, 0.850 Pa.s to 1.290 Pa.s, or 0.852 Pa.s to 1.278 Pa.s, in the range it is excellent in workability and a thixotropic effect.
[42]
As another example, the vinyl chloride-based polymer composition is increased external conditions and the Bingham viscosity difference between the value of the external force reduction conditions than 0 Pa.s to 0.07 Pa.s or less, 0.001 Pa.s to 0.065 Pa.s, or 0.019 Pa may be .s to 0.065 Pa.s, this range is within a thixotropic highly effective in.
[43]
The vinyl chloride-based polymer composition can plastisol jolil In one example, the plastisols can be an indication of the mixture was mixed with a vinyl chloride polymer and a plasticizer to be processed into a molding, a mold or a continuous film by heating, other examples may yet be sangil paste.
[44]
[45]
Vinyl chloride-based polymer composition process according to the invention comprises the steps of producing a vinyl chloride polymer latex comprises a vinyl chloride polymer (S1); In the step of the higher fatty acid having a carbon number of 10 to 18 and stirring was prepared a vinyl chloride-based polymer latex (S2); Dry stirring the vinyl chloride polymer latex by the steps of obtaining a vinyl chloride polymer powder (S3); And to the vinyl-based polymer powder was stirred with a plasticizer comprising the step (S4) for producing a vinyl-based polymer composition chloride chloride, wherein the higher fatty acid is more than 0.05 parts by weight, relative to vinyl said chlorinated polymer to 100 parts by weight (based on solids) is added in an amount of less than 1.0 parts by weight of the (S4) a vinyl-based polymer composition chloride prepared in the step is the Bingham yield stress (bingham yield stress) is 111 and the Pa excess to 385 is less than Pa, the external force reduction condition of increased external conditions Bingham yield stress (yield stress bingham) is greater than 97 Pa, and to less than 362 Pa, the difference between the Bingham yield stress value of an external force and external force term increases decrease condition may be less than 0 Pa to about 35 Pa. When in the above method of production, including higher fatty acid having a carbon number of 10 to 18 Vinyl chloride-based polymer and a plasticizer comprising a according to the present invention, it is possible to manufacture the vinyl-based polymer composition having excellent thixotropic chloride.
[46]
Wherein (S1) producing a vinyl polymer latex chloride in step is the emulsion polymerization method, fine suspension polymerization method, suspension polymerization method or, but may be carried out by the mass polymerization method, an emulsion-polymerized methods or produced by a micro-suspension polymerization chloride in the case of a vinyl-based polymer can be preferably carried out by emulsion polymerization or fine suspension polymerization because they can exhibit a more significant effect on the amount of improved plastisol is required is to use the modified characteristic during processing.
[47]
The emulsion polymerization is polymerized in a high pressure reactor as an example, after the input of such as the primary emulsifier and a water-soluble initiator, it may be carried out by putting such a vinyl chloride type monomer to walk the vacuum of the vacuum reactor and the reaction, during the polymerization the first emulsifier and can be introduced into a separately added second emulsifying agent, the second emulsifier may be continuously added during the polymerization.
[48]
As another example, before placing the vacuum in the autoclave, it is possible to put more additives such as dispersing agents, inhibitors, electrolyte, a molecular weight modifier in addition to the first emulsifiers as needed. At this time, with respect to the vinyl monomer 100 chloride parts by weight of a first emulsifying agent is 0.02 part by weight to 0.4 parts by weight of a water-soluble polymerization initiator is 0.01 parts by weight to 2 parts by weight of the second emulsifying agent is 0.01 part by weight to 6 parts by weight, the polymerization may have 70 parts by weight to 125 parts by weight, the electrolyte portion from 0.0001 part by weight to 3 parts by weight, molecular weight control agents can be used in parts of 0.01 part by weight to 2 parts by weight.
[49]
The first emulsifier and the second emulsifier may be the same or different, respectively, and specific examples of the first emulsifying agent and a second emulsifying agent, respectively, sodium lauryl sulfate, lauryl benzene sulfonate, alpha-olefin sulfonates, sodium lauryl ethoxy federated sulfate, sodium octadecyl sulfate, sodium lauryl ether sulfate and the linear alkyl may be more than one member selected from the benzenesulfonamide group consisting of acid salts, the water-soluble polymerization initiator is the group consisting of one example potassium persulfate, ammonium persulfate and hydrogen peroxide may be at least one species selected from the molecular weight-controlling agent is one example n- butyl mercaptan, n- octylmercapto mercaptan, n- dodecyl silmeo mercaptan, t- dodecyl mercaptan, and the like silmeo, the electrolyte is potassium chloride, sodium chloride, for example , potassium bicarbonate, sodium carbonate, potassium carbonate, potassium hydrogen sulfite, sodium hydrogen sulfite, potassium fatigue of Crataegus, P Loin from Crataegus sodium, tripotassium phosphate, tricalcium phosphate group consisting of sodium phosphate, and potassium phosphate susoyi susoyi sodium may be at least one member selected. The emulsion polymerization can be carried out in a temperature range of 30 ℃ to 70 ℃, for example.
[50]
On the other hand, the vinyl chloride-based polymer composition process according to the invention may comprise the step of the higher fatty acid added prior to the saponification (saponification) a gum agent to fatty acid in the above (S2) step, the polymer in this case, a higher fatty acid there is an effect that is evenly distributed. The gum agent may be an alkali hydroxide, for example, it may be a sodium hydroxide or potassium hydroxide, and specific examples. As another example, the search agent may be used in 0.1 to 5 moles, 0.5 mol to 3 mol, 0.8 mol to 2.5 mol, or a molar ratio of 1 mol to 1.5 mol per 1 mol of the higher fatty acid.
[51]
The vinyl chloride-based polymer production method may further include, dehydration and washing steps prior to the stirring step of the above (S3) drying, for example.
[52]
[53]
Example
[54]
Example 1
[55]
To be polymerized in a high pressure reactor in 500 L 100 parts by weight of a primary emulsifier, sodium lauryl sulfate, 0.01 parts by weight of La added, potassium persulfate (KPS) 0.06 wt parts of walked vacuum to -730 mmHg to the reactor with stirring. Then put in a vacuum reactor, a vinyl monomer (VCM) 100 parts by weight of chloride, the temperature was raised and the reactor temperature was 50 ℃ was subjected to polymerization. A secondary emulsifier and then initiating the polymerization of sodium lauryl sulfate, 1 part by weight of 8 hours continuously added to the reactor, and the chloride of the castor oil fatty acid saponification to the polymerization conversion rate vinyl chloride polymer latex of 80% to 85% of the time over In the vinyl-based polymer to 100 parts by weight 0.5 parts by weight of the preparation (solid basis) was prepared and then stirred for 30 minutes, the emulsion polymerization of vinyl chloride-based polymer latex. Subsequently, spray-drying the produced vinyl chloride polymer latex to prepare a vinyl chloride polymer on the powder.
[56]
Then, the obtained vinyl based polymer 100 chloride on a powder parts by weight, and then mixed in the plasticizer dioctyl phthalate (DOP) 120 parts by weight of producing a vinyl chloride-based polymer composition, this 800 using WERKE mixer of EUROSTAR 社 rpm Due to stir for 10 minutes to prepare a plastisol.
[57]
[58]
Example 2
[59]
The castor oil fatty acid instead of the saponification in the first embodiment, except that the same amount added to the saponification dehydrated castor oil fatty acid was carried out as Example 1.
[60]
[61]
Example 3
[62]
The castor oil fatty acid instead of the saponification in the first embodiment, except that the same amount added to the saponified hardened castor oil fatty acid was carried out as Example 1.
[63]
[64]
Example 4
[65]
Instead of castor oil fatty acid saponification in Example 1, except that the same amount In the saponification the sebacic acid was carried out as Example 1.
[66]
[67]
Example 5
[68]
The castor oil fatty acid instead of the saponification in the first embodiment, except that the same amount In the saponification the undecylenic acid was carried out as Example 1.
[69]
[70]
Example 6
[71]
Sodium as an emulsifier to a reactor of 1 L lauryl sulfate and 0.68 parts by weight of a fatty alcohol 1.36 parts by weight of a mixture prepared by mixing in deionized water 59 parts by weight, oil-soluble initiators include di-2-ethylhexyl peroxydicarbonate and 2.7 part by weight of vinyl chloride then a solution of the charged monomers (VCM) 100 parts by weight, stirred, by operating with a total pressure of 1,400 psi distribution homogenizer in a ratio of 50: 50 respectively at a front end and a rear end, and the reaction was 1 m 3 and then transferred to the reactor , by controlling the reactor internal temperature at 45 ℃ it was subjected to polymerization reaction. After the polymerization conversion rate In 80% to 85% of a vinyl-based polymer 100 chloride a castor oil fatty acid saponification to the vinyl chloride polymer latex at the time of parts by weight (solids basis) compared to 0.5 parts by weight, and stirred for 30 minutes, a fine suspension polymerized vinyl chloride based polymer latex was prepared. Subsequently, spray-drying the produced vinyl chloride polymer latex to prepare a vinyl chloride polymer on the powder.
[72]
Then, the obtained vinyl based polymer 100 chloride on a powder parts by weight, and then mixed in the plasticizer dioctyl phthalate (DOP) 120 parts by weight of producing a vinyl chloride-based polymer composition, this 800 using WERKE mixer of EUROSTAR 社 rpm Due to stir for 10 minutes to prepare a plastisol.
[73]
[74]
Example 7
[75]
The castor oil fatty acid instead of saponification in Example 6, except that the same amount of dehydrated castor oil fatty acid In the saponification was conducted in the same manner as in Example 6.
[76]
[77]
Example 8
[78]
The castor oil fatty acid instead of saponification in Example 6, except that the same amount added to the saponified hardened castor oil fatty acid was carried out as Example 6.
[79]
[80]
Example 9
[81]
Instead of castor oil fatty acid saponification in Example 6, except that the same amount In the saponification the sebacic acid was carried out as Example 6.
[82]
[83]
Example 10
[84]
The castor oil fatty acid instead of saponification in Example 6, except that the same amount In the saponification the undecylenic acid was carried out as Example 6.
[85]
[86]
Comparative Example 1
[87]
The same method as in Example 1, but without the added cost of castor oil fatty acids, saponified vinyl based polymer latex chloride in Example 1, the spray-drying a vinyl chloride polymer latex to prepare a vinyl chloride polymer on the powder as it was performed.
[88]
[89]
Comparative Example 2
[90]
The same method as in Example 1, but without the added cost of castor oil fatty acids, saponified vinyl based polymer latex chloride in Example 6, the spray-drying a vinyl chloride polymer latex to prepare a vinyl chloride polymer on the powder as it was performed.
[91]
[92]
Comparative Example 3
[93]
With the exception of the castor oil fatty acid saponified vinyl chloride-based polymer latex in Example 1 that the added 0.05 parts by weight was carried out as Example 1.
[94]
[95]
Comparative Example 4
[96]
With the exception of the castor oil fatty acid saponified vinyl chloride-based polymer latex in Example 1 that the added 1.0 parts by weight was carried out as Example 1.
[97]
[98]
Experimental Example
[99]
The above-described embodiment and a plastisol prepared in the comparative example in the Peltier plate 40 mm, Gap size 0.5 mm conditions using the Rotational Rheometer AR2000EX of TA Instrument 社 1) by an external force increasing condition, 180 seconds external force in accordance with the time during shear a rate 10 / s bingham yield stress (Pa) measured, and a 2) in the back was increased to 500 / s the plastisol in an external force reduction condition, for 180 seconds the external force with time during the shear rate 500 / s 10 / s to the back in which the measurement bingham yield stress (Pa) of the plastisol decreases, measuring the viscosity (bingham viscosity, Pa.s) measured by the external conditions and increase in the external force reduction conditions it is shown in Table 1 below.
[100]
TABLE 1
division Polymerization method Higher fatty acid type Amount (parts by weight) External growth conditions Reducing external conditions
Bingham yield stress Bingham viscosity Bingham yield stress Bingham viscosity
Example 1 Fine Emulsion Polymerization Castor oil fatty acids 0.5 376 1.321 347 1.278
2 Dehydrated castor oil fatty acids 357 1.289 346 1.229
3 Castor oil fatty acids 352 1.277 335 1.223
4 Sebacic 243 1.156 211 1.107
5 Undecylenic acid 214 1.098 183 1.079
6 Micro suspension polymerization Castor oil fatty acids 167 1.012 147 0.947
7 Dehydrated castor oil fatty acids 154 0.976 142 0.931
8 Castor oil fatty acids 161 0.994 145 0.938
9 Sebacic 130 0.905 119 0.863
10 Undecylenic acid 124 0.884 115 0.852
Comparative Example 1 Fine Emulsion Polymerization - - 86 0.816 49 0.739
2 Micro suspension polymerization - - 53 0.761 31 0.722
3 Fine Emulsion Polymerization Castor oil fatty acids 0.05 111 0.841 97 0.837
4 Castor oil fatty acids 2.0 385 1.362 362 1.302

[101]
[102]
As shown in Table 1, in the case of the vinyl chloride-based polymer composition made according to the present invention, excellent flowability and processability represented a Bingham yield stress and Bingham viscosity of an appropriate level, it was confirmed that excellent thixotropy.
[103]
On the other hand, in the case of Comparative Examples 1 and 2 did not contain the fatty acid in the vinyl chloride polymer, there was confirmed that the polymerization is very low Bingham yield stress and Bingham viscosities regardless, even including a fatty acid in the vinyl chloride polymer, a small amount of in the case of Comparative example 3 also includes a fair level for the Bingham yield stress and Bingham viscosities process has been confirmed that short of. In the case of Comparative Example 4 containing the fatty acid in excess, Bingham yield stress and Bingham viscosities are not good is both very high flowability, so that it was confirmed that the workability is lowered.
[104]
[105]
In this way, according to the present invention the plastisol a maintaining an appropriate viscosity, without injection of additives such as additional mineral in the manufacture, and thixotropic effect are possible an excellent production of vinyl chloride-based polymer composition.

WE CLAIM

[Claim 1]
Vinyl chloride-based polymer and a plasticizer, and wherein the vinyl-based polymer chloride comprises a higher fatty acid having a carbon number of 10 to 18 with respect to the vinyl-based polymer 100 chloride parts by weight of the content less than 0.05 part by weight in excess to 2.0 parts by weight, increase in the external force the Bingham yield stress (bingham yield stress) is 111 Pa excess to 385 is less than Pa, Bingham yield stress of the external force reduction condition is (bingham yield stress) is 97 Pa excess to 362 is less than Pa, the external force increases conditions and external decrease of the condition the difference between the Bingham yield stress value greater than 0 Pa to about 35 Pa or less vinyl chloride polymer composition.
[Claim 2]
The method of claim 1, wherein the vinyl chloride polymer is a vinyl chloride-based polymer composition containing 50 to 100% by weight of repeating units derived from vinyl chloride monomer and a vinyl-based monomer-derived repeating unit of 0 to 50% by weight.
[Claim 3]
According to claim 1, wherein said higher fatty acid is a vinyl chloride-based polymer composition is included in a mixed state on the three-dimensional network (network) of the vinyl chloride polymer.
[Claim 4]
According to claim 1, wherein said higher fatty acid is at least one hydroxy group, at least one unsaturated bond and a vinyl chloride-based polymer composition comprises one or more functional groups or binding species selected from the group consisting of 2 or more carboxyl groups.
[Claim 5]
The method of claim 4, wherein said higher fatty acid is castor oil fatty acid, dehydrated castor oil fatty acid, hydrogenated castor oil fatty acid, sebacic acid (sebacic acid) and selected from undecyl group consisting of xylene acid at least one member to the vinyl-based polymer composition chloride.
[Claim 6]
According to claim 1, wherein said higher fatty acid is a higher fatty acid saponification of the vinyl chloride polymer composition.
[Claim 7]
The method of claim 1 wherein the plasticizer is a phosphate ester-based plasticizers, aliphatic dibasic acid ester plasticizers, epoxy plasticizers and polyester-based one member vinyl chloride-based polymer composition selected from the group consisting of a plasticizer.
[Claim 8]
The method of claim 1, wherein the plasticizer of a vinyl chloride polymer composition that contained an amount of 1 to 200 parts by weight with respect to the vinyl chloride-based polymer to 100 parts by weight.
[Claim 9]
According to claim 1, wherein the vinyl chloride-based polymer composition is shear rate (shear rate) than is the Bingham viscosity of 0.841 Pa.s (bingham viscosity) at the time was increased from 10 / s to 500 / s at 180 sec to 1.362 Pa .s less than the vinyl chloride-based polymer composition.
[Claim 10]
According to claim 1, wherein the vinyl chloride-based polymer composition is shear rate (shear rate) 180 seconds 500 / s at 10 / s exceeds Bingham viscosity of 0.837 Pa.s (bingham viscosity) at the time was reduced to 1.302 Pa for .s less than the vinyl chloride-based polymer composition.
[Claim 11]
Preparing a vinyl chloride polymer comprising the vinyl chloride-based polymer latex (S1); In the step of the higher fatty acid having a carbon number of 10 to 18 and stirring was prepared a vinyl chloride-based polymer latex (S2); Dry stirring the vinyl chloride polymer latex by the steps of obtaining a vinyl chloride polymer powder (S3); And to the vinyl-based polymer powder was stirred with a plasticizer comprising the step (S4) for producing a vinyl-based polymer composition chloride chloride, wherein the higher fatty acid is more than 0.05 parts by weight, relative to vinyl said chlorinated polymer to 100 parts by weight (based on solids) is added in an amount of less than 2.0 parts by weight of the (S4) and the vinyl-based polymer composition chloride produced in step Bingham yield stress of the external force increases conditions (bingham yield stress) is 111 Pa excess to 385 is less than Pa, the external force reduction conditions Bingham yield stress (yield stress bingham) is greater than 97 Pa to 362 Pa and less than, external conditions and increase the difference between the Bingham yield stress value of the external force reduction condition method 0 Pa to about 35 Pa or less than the vinyl chloride-based polymer composition.
[Claim 12]
13. The method of claim 11, wherein the (S1) producing a vinyl chloride polymer latex of the step is the emulsion polymerization method or a vinyl chloride-based polymer composition that is carried out by the fine suspension polymerization method.
[Claim 13]
13. The method of claim 11, wherein (S2) In step higher fatty acid saponification to the previous search topics the higher fatty acid in (saponification) stage vinyl chloride-based polymer composition containing of the manufacturing.
[Claim 14]
The method of claim 13, wherein the gum agent The method of producing a vinyl chloride-based polymer composition that is used in a molar ratio of 0.1 to 5 mol per 1 mol of the higher fatty acid.