JP6649581B2 - Vinyl chloride paste sol composition containing low viscosity plasticizer - Google Patents

Description

  The present invention is a vinyl chloride-based sol having properties required for paste sols, that is, low viscosity, excellent storage stability, and excellent properties of molded articles such as heat resistance, cold resistance and flexibility. More specifically, the present invention relates to a paste sol composition and a molded article thereof, and more specifically, a vinyl chloride paste sol composition containing a plasticizer for paste sol containing a low-viscosity phthalic acid diester and / or trimellitic acid triester, and a molded article thereof. About.

  The vinyl chloride paste sol composition is obtained by dispersing a vinyl chloride resin for paste sol in a liquid component containing a plasticizer as a main component together with a filler and other compounding agents to form a paste sol. . The obtained paste sol is molded by a method such as coating molding, spray molding, immersion molding, rotational molding, slush molding, spread molding, calendar molding, extrusion molding, and the like, and then heated and melted to form a target molded body. Obtainable. The above paste processing method is widely used because of its ease of processing.

  The paste sol is required to be roughly divided into two performances, that is, a performance as a paste sol and a performance as a molded body after processing the paste sol. The performance as the first paste sol is required to be excellent in processability, that is, to have an appropriate viscosity characteristic (low viscosity) and storage stability as a paste sol, that is, to have excellent sedimentation and viscosity stability. . As the performance of the second molded body, not only the flexibility but also various characteristics such as heat resistance for automobile parts and electronic materials, and cold resistance to withstand use in cold regions, etc. It has been demanded.

  Among the above-mentioned compounding agents, especially plasticizers, the performance as a paste sol such as the flow characteristics and viscosity stability of the sol, and the basic properties such as heat resistance, cold resistance and flexibility of the obtained molded body. It has a great influence on the properties, the choice of which is very important.

  As typical plasticizers for paste sols, for example, phthalate ester-based plasticizers for vinyl chloride represented by di-2-ethylhexyl phthalate (DOP) and diisononyl phthalate (DINP) are known. Is used regularly. In applications requiring heat resistance, for example, trimellitic acid ester-based plasticizers for vinyl chloride represented by tri-2-ethylhexyl trimellitate (hereinafter, referred to as “TOTM”) are widely known. Used (Patent Document 1)

  The above-mentioned general-purpose phthalates and trimellitates are inexpensive, and it is difficult to replace them with other plasticizers due to their well-balanced performance after molding. It cannot be said that sol properties such as viscosity are always sufficient, and improvement thereof has been desired.

  Until now, various methods have been studied to improve the sol properties, that is, to reduce the viscosity. For example, a method of blending a hydrocarbon compound such as alkylbenzene, mineral spirit, paraffin, an anionic surfactant, a polyoxyethylene alkylphenol ether, a sorbitan fatty acid ester or a glycerin fatty acid ester, or a thickening agent is already practical. Most of them have high volatility, and low volatile organic compounds (VOCs), which make it difficult for organic compounds to be volatilized indoors such as interior materials such as wallpaper and flooring materials in recent years. It is no longer possible to cope with this trend, and measures to cope with it are required (Patent Documents 2 to 5). Although a method using a plasticizer having a relatively low viscosity such as benzoate has been proposed, it can be said that the performance after molding is more satisfactory than the phthalate or trimellitate in terms of performance. There is no present. Therefore, development of a low-viscosity phthalate ester or trimellitate ester suitable for a paste sol that does not decrease in performance after molding has been desired.

JP-A-5-279485 JP 2005-232381 A JP 2007-31664 A JP 2010-536991 A JP 2011-79935 A

  An object of the present invention is to solve the above-mentioned problems, that is, a low-viscosity phthalic acid diester and / or triol having improved sol properties without impairing post-molding properties such as heat resistance, cold resistance and flexibility. Plasticizer for vinyl chloride paste sol containing melitic acid triester, and chlorinated vinyl chloride-based molded body having excellent sol properties containing the plasticizer and excellent heat resistance, cold resistance and flexibility. An object of the present invention is to provide a vinyl paste sol composition.

  In view of this situation, the present inventors have conducted intensive studies to solve the above problems, and as a result, a phthalic acid diester and a trimellitic acid triester composed of an ester with a saturated alcohol having a specific structure have been conventionally used. It is found that it has a lower viscosity than phthalic acid diester and trimellitic acid triester, and as a result, it has excellent sol characteristics by containing a plasticizer containing the low viscosity phthalic acid diester and trimellitic acid triester The present inventors have found that a vinyl chloride-based molded article having good heat resistance, cold resistance and flexibility and a vinyl chloride resin-based paste sol composition as a raw material thereof can be obtained, and have completed the present invention.

  That is, the present invention provides the following plasticizer for a low-viscosity vinyl chloride paste sol, a vinyl chloride paste sol composition containing the plasticizer, and a vinyl chloride paste sol molded product thereof. .

[Item 1] A vinyl chloride paste sol composition containing a vinyl chloride resin for a paste and a plasticizer, wherein the plasticizer has a viscosity of not more than 70 mPa · s at 20 ° C. and / or phthalic acid diester. Alternatively, a vinyl chloride paste sol composition characterized by being a low-viscosity plasticizer composed of trimellitic acid triester having a viscosity measured at 20 ° C. of 200 mPa · s or less.

[Item 2] The vinyl chloride according to [Item 1], wherein the plasticizer is a phthalic acid diester represented by the following general formula (1) and / or a trimellitic acid triester represented by the following general formula (2). -Based paste sol composition.

[Wherein, R ¹ and R ² are the same or different and each is a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is mainly composed of a saturated aliphatic alcohol having 9 carbon atoms. A straight-chain saturated aliphatic alcohol having 9 or more carbon atoms having a content in the saturated aliphatic alcohol of 60% by weight or more and a branched-chain saturated aliphatic alcohol having 9 carbon atoms having a content of 40% by weight or less, And the linear ratio of the saturated aliphatic alcohol is 60% or more. ]

[Wherein, R ³ , R ⁴ and R ⁵ are the same or different and each is a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is a saturated aliphatic alcohol having 9 carbon atoms. As a main component, a saturated aliphatic alcohol having a carbon number of 9 and a content of 60% by weight or more and a branched saturated aliphatic alcohol having a carbon number of 9 and 40% by weight or less are contained. And the linear ratio of the saturated aliphatic alcohol is 60% or more. ]

[Item 3] The saturated aliphatic alcohol is mainly composed of a saturated aliphatic alcohol having 9 carbon atoms, and the content in the saturated aliphatic alcohol is 70% by weight or more and is a linear saturated aliphatic having 9 carbon atoms. Item 3. The vinyl chloride-based resin according to [2], which contains an alcohol and 30% by weight or less of a branched saturated aliphatic alcohol having 9 carbon atoms, and the saturated aliphatic alcohol has a linear ratio of 70% or more. Paste sol composition.

[Item 4] The saturated aliphatic alcohol is composed mainly of a saturated aliphatic alcohol having 9 carbon atoms, and a content of 75 to 98% by weight in the saturated aliphatic alcohol is a linear saturated fatty acid having 9 carbon atoms. [3] The vinyl chloride paste according to [3], which contains an aliphatic alcohol and 2 to 25% by weight of a branched saturated aliphatic alcohol, and the linear ratio of the saturated aliphatic alcohol is 75 to 98%. Sol composition.

[Item 5] The vinyl chloride paste sol composition according to any one of [Item 1] to [Item 4], wherein the viscosity of the phthalic acid diester at 20 ° C is in the range of 40 to 70 mPa · s.

[Item 6] The vinyl chloride paste sol composition according to any one of [Item 1] to [Item 4], wherein the viscosity of the trimellitic acid triester at 20 ° C is in the range of 100 to 200 mPa · s.

[Item 7] A vinyl chloride resin molded article molded using the vinyl chloride paste sol composition according to any one of [Item 1] to [Item 6].

[Item 8] A plasticizer for a vinyl chloride paste sol comprising a phthalic acid diester represented by the following general formula (1) and / or a trimellitic acid triester represented by the following general formula (2).

[Wherein, R ¹ and R ² are the same or different and each is a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is mainly composed of a saturated aliphatic alcohol having 9 carbon atoms. A straight-chain saturated aliphatic alcohol having 9 or more carbon atoms having a content in the saturated aliphatic alcohol of 60% by weight or more and a branched-chain saturated aliphatic alcohol having 9 carbon atoms having a content of 40% by weight or less, And the linear ratio of the saturated aliphatic alcohol is 60% or more. ]

[Wherein, R ³ , R ⁴ and R ⁵ are the same or different and each is a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is a saturated aliphatic alcohol having 9 carbon atoms. As a main component, a saturated aliphatic alcohol having a carbon number of 9 and a content of 60% by weight or more and a branched saturated aliphatic alcohol having a carbon number of 9 and 40% by weight or less are contained. And the linear ratio of the saturated aliphatic alcohol is 60% or more. ]

  The vinyl chloride paste sol composition of the present invention is characterized by containing a low-viscosity plasticizer composed of a phthalic acid diester or trimellitic acid triester having a specific structure, and has excellent sol properties and heat resistance. This is a vinyl chloride paste sol composition from which a vinyl chloride paste having good cold resistance and flexibility can be obtained. By using the vinyl chloride paste sol composition, moldability is greatly improved and heat resistance is improved. In addition, a vinyl chloride resin molded product having good cold resistance and flexibility can be easily obtained.

<Vinyl chloride paste sol composition>
The vinyl chloride-based paste sol composition of the present invention is obtained by blending a low-viscosity plasticizer made of an ester having the following structure, which is also excellent in performance after molding, into a vinyl chloride-based resin for paste sol. .

[Plasticizer]
The plasticizer according to the present invention is characterized by having a lower viscosity than conventional phthalic diesters and trimellitic triesters. Specifically, the viscosity measured at 20 ° C. is In this case, it is 70 mPa · s or less, and in the case of trimellitic acid triester, it is 200 mPa · s or less.

  If the viscosity measured at 20 ° C. is within the above range, the above-mentioned viscosity reducing agent is not blended, or the blending is so small that the performance after molding is not affected, and the processability is excellent. Good sol properties are obtained.

More specifically, the plasticizer according to the present invention is a phthalic acid diester represented by the following general formula (1) (hereinafter, referred to as “the present ester 1”) or a trimellit represented by the following general formula (2). It is called an acid triester (hereinafter, this ester 2). )).

[Wherein, R ¹ and R ² are the same or different and each is a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is mainly composed of a saturated aliphatic alcohol having 9 carbon atoms. A straight-chain saturated aliphatic alcohol having 9 or more carbon atoms having a content in the saturated aliphatic alcohol of 60% by weight or more and a branched-chain saturated aliphatic alcohol having 9 carbon atoms having a content of 40% by weight or less, And the linear ratio of the saturated aliphatic alcohol is 60% or more. ]

[Wherein, R ³ , R ⁴ and R ⁵ are the same or different and each is a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is a saturated aliphatic alcohol having 9 carbon atoms. As a main component, a saturated aliphatic alcohol having a carbon number of 9 and a content of 60% by weight or more and a branched saturated aliphatic alcohol having a carbon number of 9 and 40% by weight or less are contained. And the linear ratio of the saturated aliphatic alcohol is 60% or more. ]

  The present ester 1 and the present ester 2 can be easily obtained by esterifying a specific acid component and an alcohol component according to a conventional method, preferably in an atmosphere of an inert gas such as nitrogen in the absence of a catalyst or in the presence of a catalyst. Is obtained. In addition, although it can be produced by a transesterification reaction using a known method, an esterification reaction will be described below as an example of a method for producing the ester 1 and the ester 2.

[Alcohol component]
The specific alcohol component used in the present invention is a saturated aliphatic alcohol having a saturated aliphatic alcohol having 9 carbon atoms as a main component, and the ratio of the saturated aliphatic alcohol having 9 carbon atoms as a main component is determined in the present invention. In the saturated aliphatic alcohol used, preferably at least 60% by weight (60 to 100% by weight), more preferably at least 70% by weight (70 to 100% by weight), particularly preferably at least 80% by weight (80 to 100% by weight) ) Is recommended.

  It is recommended that the saturated aliphatic alcohol has a linear ratio of 60% or more, preferably 70% or more, more preferably 80% or more. Further, the content of the linear saturated aliphatic alcohol having 9 carbon atoms is 60% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more in the saturated aliphatic alcohol used in the present invention. And the content of a branched saturated aliphatic alcohol having 9 carbon atoms (eg, 2-methyloctanol) is 40% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less. It is recommended that it be less than weight percent.

  As the details of the embodiment of the saturated aliphatic alcohol used in the present invention, the saturated aliphatic alcohol is mainly composed of a saturated aliphatic alcohol having 9 carbon atoms (preferably 60% by weight or more). It contains a straight-chain saturated aliphatic alcohol having 9 carbon atoms and a content of 60% by weight or more and a saturated aliphatic alcohol of 40% by weight or less, and the linear ratio of the saturated aliphatic alcohol is 60% or more. . In a more preferred embodiment, the saturated aliphatic alcohol contains a saturated aliphatic alcohol having 9 carbon atoms as a main component (preferably, 70% by weight or more), and a carbon content of 70% by weight or more in the saturated aliphatic alcohol. An embodiment comprising a linear saturated aliphatic alcohol of the formula 9 and a branched saturated aliphatic alcohol having a carbon number of 9 and not more than 30% by weight, and the linear ratio of the saturated aliphatic alcohol is 70% or more. In a particularly preferred embodiment, the saturated aliphatic alcohol contains a saturated aliphatic alcohol having 9 carbon atoms as a main component (preferably 80% by weight or more), and the content in the saturated aliphatic alcohol is 80% by weight. It contains the above-mentioned straight-chain saturated aliphatic alcohol having 9 carbon atoms and not more than 20% by weight of a branched-chain saturated aliphatic alcohol having 9 carbon atoms, and the linear ratio of the saturated aliphatic alcohol is 80% or less. It is recommended in a manner more.

  When the linear chain ratio is 60% or more and the content of the linear aliphatic saturated alcohol having 9 carbon atoms is 60% by weight or more, while maintaining good heat resistance, cold resistance and flexibility, The sol characteristics can be improved.

  In the present specification and claims, the linear chain ratio of the saturated aliphatic alcohol is a ratio (weight ratio) of the linear alcohol in the saturated aliphatic alcohol, and from the viewpoint of the effect of the present invention, Specifically, it can be said that the ratio is occupied by a linear alcohol having 7 to 11 carbon atoms, and can be specifically determined by a method of analyzing by gas chromatography.

  Specific examples (commercially available products) of the above-mentioned aliphatic saturated alcohol having an aliphatic saturated alcohol having 9 carbon atoms as a main component include a linear nonanol of about 80% by weight or more and a branched chain of about 20% by weight or less. Linenball 9 (trade name) manufactured by Shell Chemicals, which is a mixture of nonanol, and Oxair n, which is a mixture of about 90% by weight or more of linear nonanol and about 10% by weight or less of branched nonanol. -Nonanol and the like.

  The above-mentioned saturated aliphatic alcohol having 9 carbon atoms can be produced, for example, by (1) a step of producing an aldehyde having 9 carbon atoms by a hydroformylation reaction of 1-octene and carbon monoxide with hydrogen, and (2) a step of producing an aldehyde having 9 carbon atoms. Can be produced by a production step comprising a step of hydrogenating the aldehyde of the above to reduce to an alcohol.

In the hydroformylation reaction as the step (1), for example, an aldehyde having 9 carbon atoms can be produced by reacting 1-octene, carbon monoxide and hydrogen in the presence of a cobalt catalyst or a rhodium catalyst.

The hydrogenation in the step (2) can be reduced to an alcohol by hydrogenating an aldehyde having 9 carbon atoms under hydrogen pressure in the presence of a noble metal catalyst such as a nickel catalyst or a palladium catalyst.

[Esterification reaction]
The esterification reaction according to the present invention means an esterification reaction between the alcohol component and phthalic acid or anhydride thereof, or trimellitic acid or anhydride thereof.When the esterification reaction is performed, the alcohol component is For example, based on 1 mol of phthalic acid or its anhydride, preferably 2.05 mol to 4.00 mol, more preferably 2.10 mol to 3.00 mol, particularly 2.15 to 2.50 mol, It is preferable to use 3.05 to 4.00 mol, more preferably 3.10 to 3.80 mol, particularly 3.15 to 3.60 mol, per 1 mol of trimellitic acid or its anhydride. Recommended.

  When a catalyst is used for the esterification reaction, examples of the catalyst include mineral acids, organic acids, Lewis acids and the like. More specifically, examples of the mineral acid include sulfuric acid, hydrochloric acid, and phosphoric acid, and examples of the organic acid include p-toluenesulfonic acid and methanesulfonic acid. Examples of the Lewis acid include an aluminum derivative, a tin derivative, Examples thereof include a titanium derivative, a lead derivative, and a zinc derivative, and one or more of these can be used in combination.

  Among them, p-toluenesulfonic acid, tetraalkyl titanate having 3 to 8 carbon atoms, titanium oxide, titanium hydroxide, fatty acid tin having 3 to 12 carbon atoms, tin oxide, tin hydroxide, zinc oxide, zinc hydroxide, Lead oxide, lead hydroxide, aluminum oxide and aluminum hydroxide are particularly preferred. The amount used is, for example, preferably 0.01% by weight to 5.0% by weight, more preferably 0.02% by weight to 4.0% by weight, based on the total weight of the acid component and the alcohol component, which are the raw materials for ester synthesis. It is recommended to use% by weight, in particular from 0.03% to 3.0% by weight.

  The esterification temperature is, for example, 100 ° C. to 230 ° C., and the reaction is usually completed in 3 hours to 30 hours.

  There are no particular restrictions on phthalic acid or its anhydride and trimellitic acid or its anhydride, which are the acid components of the raw material of the present ester, and commercially available ones that are commonly used can be used. From the viewpoint of the esterification reaction, it is most recommended to use the above-mentioned phthalic anhydride or trimellitic anhydride.

  In the esterification, a water entrainer such as benzene, toluene, xylene, and cyclohexane can be used to promote the distillation of water produced by the reaction.

  In addition, when oxygen-containing organic compounds such as oxides, peroxides, and carbonyl compounds are generated by oxidative deterioration of raw materials, formed esters, and organic solvents (water entrainers) during the esterification reaction, heat resistance, weather resistance, and the like are adversely affected. Therefore, it is desirable to carry out the reaction in the system under an atmosphere of an inert gas such as nitrogen gas or a stream of an inert gas under normal pressure or reduced pressure. After completion of the esterification reaction, it is recommended to remove excess raw material under reduced pressure or normal pressure.

  The present ester obtained by the above esterification method may be subsequently purified, if necessary, by a base treatment (neutralization treatment) → water washing treatment, liquid-liquid extraction, distillation (reduced pressure, dehydration treatment), adsorption treatment and the like. .

  Examples of the adsorbent used in the adsorption treatment include activated carbon, activated clay, activated alumina, hydrotalcite, silica gel, silica alumina, zeolite, magnesia, calcia, and diatomaceous earth. These can be used alone or in combination of two or more.

  The purification treatment after the esterification may be carried out at normal temperature, but may also be carried out by heating to about 40 to 90 ° C.

<Vinyl chloride paste sol composition>
In the vinyl chloride paste sol composition of the present invention, the above-mentioned present ester 1 and / or present ester 2 (hereinafter collectively referred to as “present ester”) are blended as a plasticizer in a vinyl chloride resin for paste. It can be obtained by:

[Vinyl chloride resin for paste]
The vinyl chloride resin for the paste used in the present invention is a homopolymer of vinyl chloride or vinylidene chloride and a copolymer of vinyl chloride or vinylidene chloride, and the production method is performed by a conventionally known polymerization method. Suspension polymerization in the presence of an oil-soluble polymerization catalyst, and emulsion polymerization in an aqueous medium in the presence of a water-soluble polymerization catalyst. The polymerization degree of these vinyl chloride resins is usually 300 to 6000, preferably 400 to 5000, and more preferably 700 to 4500. If the degree of polymerization is too low, heat resistance and the like tend to decrease, while if it is too high, moldability tends to decrease.

  In the case of a copolymer, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1- Α-olefins having 2 to 30 carbon atoms such as tridecene and 1-tetradecene, acrylic acid and its esters, methacrylic acid and its esters, maleic acid and its esters, vinyl acetate, vinyl propionate, and alkyl vinyl ether; Polyfunctional monomers such as vinyl compounds and diallyl phthalate; copolymers of these mixtures with vinyl chloride monomers; ethylene-acrylate copolymers such as ethylene-ethyl acrylate copolymer; and ethylene-methacrylate copolymers Polymer, ethylene-vinyl acetate copolymer (EVA), chlorinated polyether Len, butyl rubber, crosslinked acrylic rubber, polyurethane, butadiene-styrene-methyl methacrylate copolymer (MBS), butadiene-acrylonitrile (α-methyl) styrene copolymer (ABS), styrene-butadiene copolymer, polyethylene, poly Examples include methyl methacrylate and a graft copolymer obtained by grafting a vinyl chloride monomer to a mixture thereof.

[Vinyl chloride paste sol composition]
The content of the present ester in the vinyl chloride-based paste sol composition is appropriately selected depending on the use, but is usually 1 to 300 parts by weight, preferably 100 parts by weight, based on 100 parts by weight of the vinyl chloride resin for the paste. Is 5 to 200 parts by weight. If the amount is less than 1 part by weight, it is difficult to obtain a predetermined plasticizing effect, and if the amount exceeds 300 parts by weight, bleeding on the surface of the molded article is severe, which is not preferable in any case. However, when a filler or the like is added to the above-mentioned vinyl chloride-based paste sol composition, the filler itself can absorb oil so that the plasticizer can be added beyond the above range. For example, when 100 parts by weight of calcium carbonate is blended as a filler with respect to 100 parts by weight of a vinyl chloride resin for a paste, about 1 to 500 parts by weight of the present ester can be blended.

  In the vinyl chloride paste sol composition, other known plasticizers can be used in combination with the present ester within the range in which the effects of the present invention are exhibited. Also, if necessary, known stabilizers, stabilizing aids, antioxidants (antiaging agents), ultraviolet absorbers, light stabilizers such as hindered amines, fillers, coloring agents, and the like which are usually used for plastics, Additives such as processing aids, lubricants, flame retardants, antistatic agents, diluents, thinners, thickeners, foaming agents, and adhesives can be blended within the range of achieving the effects of the present invention.

  Other plasticizers and additives other than the present ester may be blended together with the present ester, alone or in combination of two or more.

  Known plasticizers that can be used in combination with the present ester include, for example, benzoic acid esters such as diethylene glycol dibenzoate, phthalic acid esters outside the scope of the present invention, di-2-ethylhexyl adipate (DOA), adipin Aliphatic dibasic acid esters such as diisononyl acid (DINA), diisodecyl adipate (DIDA), di-2-ethylhexyl sebacate (DOS), diisononyl sebacate (DINS), and trimellitic acid esters outside the scope of the present invention , Pyromellitic esters such as tetra-2-ethylhexyl pyromellitic acid (TOPM), phosphoric esters such as tri-2-ethylhexyl phosphate (TOP) and tricresyl phosphate (TCP), and pentaerythritol Alkyl esters of polyhydric alcohols, adipic acid, etc. Polyesters having a molecular weight of 800 to 4000 synthesized by polyesterification of dibasic acid and glycol, epoxidized esters such as epoxidized soybean oil and epoxidized linseed oil, diisononyl 1,2-cyclohexanedicarboxylate (DINCH) and the like. Alicyclic dibasic acid esters, fatty acid glycol esters such as 1.4-butanediol dicaprate, tributyl acetylcitrate (ATBC), trihexyl acetylcitrate (ATHC), triethylhexyl acetylcitrate (ATEHC), butyryl citrate Citrates such as trihexyl acid (BTHC), isosorbide diesters, chlorinated paraffins obtained by chlorinating paraffin wax or n-paraffin, chlorinated fatty acid esters such as chlorinated stearic acid ester, oleic acid Higher fatty acid esters such as chill and the like. When compounding the plasticizer which can be used together, the compounding amount is recommended to be about 1 to 300 parts by weight based on 100 parts by weight of the vinyl chloride resin for paste.

  Stabilizers include lithium stearate, magnesium stearate, magnesium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc octylate, zinc laurate, zinc ricinoleate, stearic acid Examples thereof include metal soap compounds such as zinc, organic tin compounds such as dimethyltin bis-2-ethylhexylthioglycolate, dibutyltin maleate, dibutyltin bisbutylmaleate, and dibutyltin dilaurate, and antimony mercaptide compounds. When a stabilizer is compounded, it is recommended that the amount of the stabilizer be about 0.1 to 20 parts by weight based on 100 parts by weight of the vinyl chloride resin for the paste.

  Examples of the stabilizing aid include phosphite compounds such as triphenyl phosphite, monooctyl diphenyl phosphite and tridecyl phosphite, beta diketone compounds such as acetylacetone and benzoylacetone, glycerin, sorbitol, pentaerythritol, and polyethylene glycol. Examples include polyol compounds, perchlorate compounds such as barium perchlorate and sodium perchlorate, hydrotalcite compounds, zeolites and the like. When a stabilizing aid is compounded, it is recommended that the stabilizing aid be mixed in an amount of about 0.1 to 20 parts by weight based on 100 parts by weight of the vinyl chloride resin for the paste.

  Examples of the antioxidant include 2,6-di-tert-butylphenol, tetrakis [methylene-3- (3,5-tert-butyl-4-hydroxyphenol) propionate] methane, 2-hydroxy-4-methoxybenzophenone and the like. Phenol compounds, sulfur compounds such as alkyl disulfide, thiodipropionate, benzothiazole, trisnonylphenyl phosphite, diphenylisodecyl phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) ) Phosphate-based compounds such as phosphite, and organometallic-based compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate. When an antioxidant is blended, it is recommended that the amount of the antioxidant be about 0.2 to 20 parts by weight based on 100 parts by weight of the vinyl chloride resin for the paste.

  Examples of the ultraviolet absorber include salicylate compounds such as phenyl salicylate and p-tert-butylphenyl salicylate; benzophenone compounds such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-n-methoxybenzophenone; Examples thereof include benzotriazole-based compounds such as 5-methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole, as well as cyanoacrylate-based compounds. When an ultraviolet absorber is blended, it is recommended that the blending amount of the ultraviolet absorber be about 0.1 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin for the paste.

  As hindered amine light stabilizers, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1 , 2,2,6,6-pentamethyl-4-piperidyl sebacate (mixture), bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1- Dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate, bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidyl) decandioate and 1,1-dimethylethyl Reaction product of hydroperoxide and octane, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidino Mixture of carboxylic acid and higher fatty acid, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6- (Pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, poly [ {(6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl)} (2,2,6,6-tetramethyl-4-piperidyl) Imino {hexamethylene} (2,2,6,6-tetramethyl-4-piperidyl) imino}, dibutylamine • 1,3,5-triazine • N, N′-bis (2,2,6,6 -Tetramethyl- Polycondensate of 4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, N, N ', N ", N'"- Tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1 , 10-diamine, etc. When a light stabilizer is compounded, it is recommended that the compounding amount of the light stabilizer is about 0.1 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin for paste.

  Fillers include metal oxides such as calcium carbonate, silica, alumina, clay, talc, diatomaceous earth, ferrite, fibers and powders such as glass, carbon and metal, glass spheres, graphite, aluminum hydroxide, barium sulfate, and magnesium oxide. , Magnesium carbonate, magnesium silicate, calcium silicate and the like. When the filler is compounded, it is recommended that the compounding amount of the filler be about 1 to 150 parts by weight based on 100 parts by weight of the vinyl chloride resin for the paste.

  Examples of the coloring agent include carbon black, lead sulfide, white carbon, titanium white, lithopone, bittern, antimony sulfide, chrome yellow, chrome green, phthalocyanine green, cobalt blue, phthalocyanine blue, molybdenum orange, and the like. When a coloring agent is blended, it is recommended that the blending amount of the coloring agent is about 1 to 100 parts by weight based on 100 parts by weight of the vinyl chloride resin for the paste.

  Examples of the processing aid include liquid paraffin, polyethylene wax, stearic acid, stearic acid amide, ethylene bisstearic acid amide, butyl stearate, calcium stearate and the like. When the processing aid is compounded, it is recommended that the amount of the processing aid is about 0.1 to 20 parts by weight based on 100 parts by weight of the vinyl chloride resin for the paste.

  Examples of the lubricant include silicone, liquid paraffin, paraffin wax, metal salts of fatty acids such as metal stearate and metal laurate, fatty acid amides, fatty acid waxes and higher fatty acid waxes. When a lubricant is compounded, it is recommended that the amount of the lubricant be about 0.1 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin for the paste.

  As the flame retardant, aluminum hydroxide, antimony trioxide, magnesium hydroxide, inorganic compounds such as zinc borate, cresyl diphenyl phosphate, trischloroethyl phosphate, trischloropropyl phosphate, trisdichloropropyl phosphate and the like Examples thereof include phosphorus compounds and halogen compounds such as chlorinated paraffin. When a flame retardant is compounded, it is recommended that the compounding amount of the flame retardant is about 0.1 to 20 parts by weight based on 100 parts by weight of the vinyl chloride resin for the paste.

  As the antistatic agent, alkyl sulfonate type, alkyl ether carboxylic acid type or dialkyl sulfosuccinate type anionic antistatic agent, polyethylene glycol derivatives, sorbitan derivatives, nonionic antistatic agents such as diethanolamine derivatives, alkylamidoamine type, alkyl Examples thereof include quaternary ammonium salts such as dimethylbenzyl type, cationic antistatic agents such as alkylpyridinium type organic acid salts and hydrochlorides, and amphoteric antistatic agents such as alkylbetaine type and alkylimidazoline type. When the antistatic agent is compounded, it is recommended that the amount of the antistatic agent be about 0.1 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin for the paste.

  Examples of the diluent include 2,2,4-trimethyl-1,3-pentanediol diisobutyrate and low-boiling aliphatic and aromatic hydrocarbons. When a diluent is compounded, it is recommended that the compounding amount of the diluent be about 1 to 50 parts by weight based on 100 parts by weight of the vinyl chloride resin for paste.

  Examples of the viscosity reducing agent include various nonionic surfactants, sulfosuccinate anionic surfactants, silicone compounds having surface activity, soybean oil lecithin, monohydric alcohols, glycol ethers, polyethylene glycols, etc. Is exemplified. When a viscosity reducing agent is blended, it is recommended that the blending amount of the viscosity reducing agent is about 0.1 to 20 parts by weight based on 100 parts by weight of the vinyl chloride resin for paste.

  As the thickener, synthetic fine powder silica type, bentonite type, ultrafine precipitated calcium carbonate, metal soap type, hydrogenated castor oil, polyamide wax, polyethylene oxide type, vegetable oil type, granular acid ester type surfactant, nonionic type interface Activators and the like are exemplified. When a thickener is compounded, it is recommended that the compounding amount of the thickener be about 1 to 50 parts by weight based on 100 parts by weight of the vinyl chloride resin for paste.

  Examples of the blowing agent include organic blowing agents such as azodicarbonamide and oxybisbenzenesulfonyl hydrazide, and inorganic blowing agents such as sodium bicarbonate. When a foaming agent is blended, it is recommended that the blending amount of the foaming agent is about 0.1 to 30 parts by weight based on 100 parts by weight of the vinyl chloride resin for the paste.

  Examples of the adhesive include commercially available adhesives such as urethane, acrylate, imide, amide, epoxy, and silicone. When an adhesive is compounded, it is recommended that the amount of the adhesive be about 0.05 to 50 parts by weight based on 100 parts by weight of the vinyl chloride resin for the paste.

  The vinyl chloride-based paste sol composition of the present invention comprises the present ester, a vinyl chloride-based resin for paste and various additives as required, for example, a pony mixer, a butterfly mixer, a planetary mixer, a ribbon blender, a kneader, a dissolver, and a twin-screw mixer. By stirring with a high-speed mixer such as a Henschel mixer or a super mixer, or a mixing and kneading machine such as a three-roll mill, a vinyl chloride paste sol composition can be obtained.

<Vinyl chloride paste sol molded body>
The vinyl chloride paste sol composition according to the present invention is formed by coating molding, spray molding, dip molding, rotational molding, slush molding, spread molding, calendar molding, extrusion molding, or the like, and then heated and melted. It can be molded into a molded article of a desired shape.

  The shape of the molded body is not particularly limited, for example, rod-shaped, sheet-like, film-like, plate-like, cylindrical, circular, elliptical or toys, special shapes such as toys, ornaments, for example, star-shaped, A polygonal shape is exemplified.

  The molded body thus obtained is used for automobile interior materials, body sealers, automobile parts such as underbody coats, wallpaper, cushion floors, tile carpets, other flooring materials, PVC steel sheets, marking films, canvas, waterproof sheets, can coats, It is useful for can seals, sealers, seal tapes, toys, boots, gloves, food models, leather, erasers, medical gloves, medical tubes, blood bags, infusion bags, artificial baits, fishing net floats, and the like.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, the symbol of the compound in an Example and a comparative example, and the measurement of each characteristic are as follows.

(1) Composition and Linearity of Saturated Aliphatic Alcohol The composition and linearity of the saturated aliphatic alcohol in the plasticizer used in Examples and Comparative Examples of the present invention and as a raw alcohol component of the esterification reaction are determined by the production thereof. Was measured by gas chromatography (hereinafter abbreviated as GC). The method of measuring the raw material alcohol by GC is as follows.
<< GC measurement conditions >>
Model: Gas chromatograph GC-17A (manufactured by Shimadzu Corporation)
Detector: FID
Column: Capillary column ZB-1 30m
Column temperature: Raised from 60 ° C to 290 ° C. Heating rate = 13 ° C./min Carrier gas: Helium Sample: 50% acetone solution Injection volume: 1 μl
Quantification: Quantification was performed using 1-hexanol as an internal standard substance.
In selecting the internal standard, it was previously confirmed that 1-hexanol was less than the detection limit by GC in the raw material alcohol.
In the esterification reaction described above, there is no difference in reactivity depending on the structure of the raw material alcohol within the scope of the present invention, and the composition ratio of the saturated fatty alcohol which is the raw material alcohol used and the saturated fatty alcohol in the present ester It has been previously confirmed that there is no difference in the composition ratio.

(2) Evaluation of physical properties of ester The ester obtained in the following production example was analyzed by the following method.
Ester value: Measured according to JIS K-0070 (1992).
Acid value: Measured according to JIS K-0070 (1992).
Number of colors: The number of colors in Hazen was determined by measuring according to JIS K-0071 (Hazen) (1998).
Viscosity: The viscosity at 20 ° C. (mPa · s) was measured at 60 rpm using a B-type viscometer manufactured by Tokyo Keiki Co., Ltd. in accordance with JIS Z-8803 (2011). The rotor is no. 2 (B8L type) was used.

(3) Sol viscosity of vinyl chloride paste composition 70 parts by weight of a plasticizer is added to 100 parts by weight of a vinyl chloride resin for paste (degree of polymerization: 1100, trade name "Zest P22", manufactured by Shin Daiichi PVC Co., Ltd.) The mixture was handled and mixed until a vinyl chloride paste sol composition was obtained. The sol viscosity (Ps · s) of the obtained vinyl chloride paste sol composition was measured with a B-type viscometer (rotor No. 4 (B8H type), 5 rpm, value after 1 minute). The paste sol composition was aged for 7 days at a temperature of 25 ° C. and a humidity of 60%, and the sol viscosity (Pa · s) was measured immediately after adjustment (initial sol viscosity) and after aging for 7 days (7 days after sol viscosity). .

(4) Preparation of Vinyl Chloride Paste Sol Composition and Preparation of Vinyl Chloride Sheet Made Thereof 100 parts by weight of a vinyl chloride resin for paste (degree of polymerization 1100, trade name "Zest P22", manufactured by Shin Daiichi PVC Co., Ltd.) 0.9 and 0.6 parts by weight of calcium stearate (manufactured by Nacalai Tesque Co., Ltd.) and zinc stearate (manufactured by Nacalai Tesque Co., Ltd.) were blended as stabilizers, and the mixture was stirred and mixed with a mortar mixer. 70 parts by weight of the agent were added, and the mixture was handled and mixed until it became uniform to obtain a vinyl chloride paste sol composition. The prepared paste sol composition is coated on a stainless steel plate to a thickness of about 1 mm, heated in an oven at 185 ° C. for 15 minutes to gel, cooled, and obtained, a vinyl chloride sheet (vinyl chloride-based paste sol molded body) It measured using.

[Evaluation of physical properties of resin]
(4) Tensile properties: The 100% modulus, breaking strength, and breaking elongation of the sheet were measured according to JIS K-6723 (1995). The smaller the value of the 100% modulus, the better the flexibility, and the breaking strength and breaking elongation are measures of the practical strength of the material. Generally, the larger the value, the more practical strength. Can be said to be excellent.

(5) Cold resistance: Measured using a Crashberg tester in accordance with JIS K-6773 (1999). The lower the softening temperature (° C), the better the cold resistance. The soft temperature here refers to a temperature at a low temperature limit at which a predetermined torsional rigidity (3.17 × 10 ³ kg / cm ² ) is obtained in the above measurement.

(6) Heat resistance: Based on the evaluation of loss on evaporation and sheet coloring.
a) Volatilization loss: After heating the sheet at 150 ° C. for 30 minutes and 60 minutes in a gear oven, the weight change of the sheet was measured, and the weight loss rate (% by weight) was calculated by the following (Equation 2), and the weight was calculated. The rate of decrease was used as the volatilization loss. It can be said that the smaller the value of volatilization loss, the higher the heat resistance.
Volatilization loss (%) = ((weight before test−weight after test) / weight before test) × 100 (Formula 2)
b) Sheet coloring: The degree of coloring after heating the sheet at 150 ° C. for 30 minutes and 60 minutes in a gear oven was visually evaluated in four stages.
◎: no coloring, ○: slight coloring, Δ: coloring, ×: strong coloring

[Production Example 1]
In a 2 L four-necked flask equipped with a thermometer, a decanter, a stirring blade, and a reflux condenser, 74.1 g (0.5 mol) of phthalic anhydride and 173.1 g of a saturated aliphatic alcohol (manufactured by Shell Chemicals: Lineball 9). (1.2 mol) and 0.2 g of tetraisopropyl titanate as an esterification catalyst were added, and the esterification reaction was carried out at a reaction temperature of 190 ° C. The reaction was carried out until the acid value of the reaction solution reached 0.5 mgKOH / g while refluxing the alcohol under reduced pressure to remove the generated water out of the system. After completion of the reaction, unreacted alcohol was distilled off under reduced pressure, and then neutralized, washed with water and dehydrated according to a conventional method to obtain 178 g of a desired phthalic acid diester (hereinafter, referred to as "ester 1"). .
The obtained ester 1 had an ester value of 267 mgKOH / g, an acid value of 0.07 mgKOH / g, a color number of 10, and a viscosity (20 ° C.) of 58 mPa · s.

[Production Example 2]
Except that 164.4 g (1.14 mol) of n-nonyl alcohol and 8.7 g (0.06 mol) of isononyl alcohol were added instead of 173.1 g of a saturated aliphatic alcohol (manufactured by Shell Chemicals: Lineball 9). By carrying out in the same manner as in Production Example 1, 180 g of phthalic acid diester (hereinafter, referred to as “ester 2”) was obtained.
The obtained ester 2 had an ester value of 267 mgKOH / g, an acid value of 0.02 mgKOH / g, a color number of 20, and a viscosity (20 ° C.) of 50 mPa · s.

[Production Example 3]
Instead of 173.1 g of a saturated aliphatic alcohol (manufactured by Shell Chemicals: Lineball 9), 121.2 g (0.84 mol) of n-nonyl alcohol and 51.9 g (0.36 mol) of isononyl alcohol were used. (Mol)) to obtain 174 g of phthalic acid diester (hereinafter referred to as "ester 3").
The obtained ester 2 had an ester value of 265 mgKOH / g, an acid value of 0.02 mgKOH / g, a color number of 20, and a viscosity (20 ° C.) of 63 mPa · s.

[Production Example 4]
In a 2 L four-necked flask equipped with a thermometer, a decanter, a stirring blade, and a reflux condenser, 96.1 g (0.5 mol) of trimellitic anhydride and 259 g of a saturated aliphatic alcohol (Lineball 9 manufactured by Shell Chemicals, Inc.) (1.8 mol) and 0.3 g of tetraisopropyl titanate as an esterification catalyst, and the esterification reaction was carried out at a reaction temperature of 190 ° C. The reaction was performed until the acid value of the reaction solution reached 0.5 mgKOH / g while refluxing the alcohol under reduced pressure to remove the generated water out of the system. After completion of the reaction, unreacted alcohol is distilled out of the system under reduced pressure, and then neutralized, washed with water and dehydrated according to a conventional method to obtain 245 g of the desired trimellitic acid triester (hereinafter referred to as “ester 4”). Obtained.
The obtained ester 4 had an ester value: 285 mgKOH / g, an acid value: 0.01 mgKOH / g, a color number: 10, and a viscosity (20 ° C.): 150 mPa · s.

[Production Example 5]
Same as Production Example 4 except that 245 g (1.7 mol) of n-nonyl alcohol and 14 g (0.1 mol) of isononyl alcohol were added instead of 259 g of a saturated aliphatic alcohol (manufactured by Shell Chemicals: Lineball 9). By carrying out, 242 g of trimellitic acid triester (hereinafter referred to as “ester 5”) was obtained.
The obtained ester 5 had an ester value: 283 mgKOH / g, an acid value: 0.04 mgKOH / g, a color number: 20, and a viscosity (20 ° C.): 150 mPa · s.

[Production Example 6]
Same as Production Example 4 except that 173 g (1.2 mol) of n-nonyl alcohol and 87 g (0.6 mol) of isononyl alcohol were added instead of 259 g of a saturated aliphatic alcohol (manufactured by Shell Chemicals: Lineball 9). By carrying out, 240 g of trimellitic acid triester (hereinafter, referred to as “ester 6”) was obtained.
The obtained ester 6 had an ester value: 282 mg KOH / g, an acid value: 0.05 mg KOH / g, a color number: 20, and a viscosity (20 ° C.): 180 mPa · s.

[Production Example 7]
Trimellitic acid triester was prepared in the same manner as in Production Example 4 except that 234.4 g (1.8 mol) of 2-ethylhexanol was added instead of 259 g of a saturated aliphatic alcohol (manufactured by Shell Chemicals: Lineball 9). (Hereinafter, referred to as "ester 7") 204 g was obtained.
The obtained ester 7 had an ester value of 309 mgKOH / g, an acid value of 0.04 mgKOH / g, a color number of 10, and a viscosity (20 ° C.) of 310 mPa · s.

[Production Example 8]
The same procedure as in Production Example 4 was carried out except that 259.7 g (1.8 mol) of isononyl alcohol was used instead of 259 g of a saturated aliphatic alcohol (manufactured by Shell Chemicals: Lineball 9) to obtain a trimellitic acid triester ( Hereinafter, this is referred to as “ester 8”.) 236 g was obtained.
The obtained ester 8 had an ester value: 285 mgKOH / g, an acid value: 0.03 mgKOH / g, a color number: 10, and a viscosity (20 ° C.): 310 mPa · s.

[Production Example 9]
Except that 285 g of isodecyl alcohol (1.8 mol) was added instead of 259 g of a saturated aliphatic alcohol (manufactured by Shell Chemicals: Lineball 9), the same procedure as in Production Example 4 was carried out to obtain a trimellitic acid triester (hereinafter, referred to as “trimellitic acid triester”). 250 g was obtained.
The obtained ester 9 had an ester value of 264 mgKOH / g, an acid value of 0.03 mgKOH / g, a color number of 20, and a viscosity (20 ° C.) of 610 mPa · s.

[Example 1]
Using the phthalic acid diester (ester 1) obtained in Production Example 1, the above “(3) Preparation of sol viscosity of vinyl chloride paste sol composition” and “(4) Preparation of vinyl chloride paste sol composition and Preparation of a Vinyl Chloride Paste Sol ", a polyvinyl chloride paste sol composition was prepared, and then a vinyl chloride sheet was prepared from the obtained vinyl chloride paste sol composition. A test and a heat resistance test were performed. Table 1 shows the obtained results.

[Example 2]
A vinyl chloride paste sol composition was prepared in the same manner as in Example 1 except that the ester 2 was used instead of the ester 1, and then a vinyl chloride sheet was prepared. A cold resistance test and a heat resistance test were performed. Table 1 shows the obtained results.

[Example 3]
A vinyl chloride paste sol composition was prepared in the same manner as in Example 1 except that ester 3 was used instead of ester 1, and then a vinyl chloride sheet was prepared. A cold resistance test and a heat resistance test were performed. Table 1 shows the obtained results.

[Example 4]
A vinyl chloride paste sol composition was prepared in the same manner as in Example 4 except that ester 4 was used instead of ester 1, and then a vinyl chloride sheet was prepared. A cold resistance test and a heat resistance test were performed. Table 1 shows the obtained results.

[Example 5]
A vinyl chloride paste sol composition was prepared in the same manner as in Example 1 except that ester 5 was used instead of ester 1, and then a vinyl chloride sheet was prepared. A cold resistance test and a heat resistance test were performed. The results obtained are shown in Table 1.

[Example 6]
A vinyl chloride-based paste sol composition was prepared in the same manner as in Example 1 except that ester 6 was used in place of ester 1, and then a vinyl chloride sheet was prepared. A cold resistance test and a heat resistance test were performed. Table 1 shows the obtained results.

[Comparative Example 1]
The procedure was performed in the same manner as in Example 1 except that di-2-ethylhexyl phthalate (manufactured by Shin Nippon Rika Co., Ltd., Sansosizer DOP, viscosity (20 ° C.): 77 mPa · s) was used instead of ester 1, A vinyl chloride-based paste sol composition was prepared, and then a vinyl chloride sheet was prepared and subjected to sol viscosity measurement, tensile test, cold resistance test and heat resistance test. Table 1 shows the obtained results.

[Comparative Example 2]
A vinyl chloride paste was prepared in the same manner as in Example 1 except that diisononyl phthalate (manufactured by Nippon Rika Co., Ltd., Sansosizer DINP, viscosity (20 ° C.): 84 mPa · s) was used instead of ester 1. The sol composition was prepared, and then a vinyl chloride sheet was prepared and subjected to sol viscosity measurement, tensile test, cold resistance test and heat resistance test. Table 1 shows the obtained results.

[Comparative Example 3]
A vinyl chloride paste was prepared in the same manner as in Example 1 except that diisodecyl phthalate (Sanso Sizer DIDP, manufactured by Shin Nippon Rika Co., Ltd., viscosity (20 ° C.): 140 mPa · s) was used instead of ester 1. The sol composition was prepared, and then a vinyl chloride sheet was prepared and subjected to sol viscosity measurement, tensile test, cold resistance test and heat resistance test. Table 1 shows the obtained results.

[Comparative Example 4]
A vinyl chloride-based paste sol composition was prepared in the same manner as in Example 1 except that ester 7 was used instead of ester 1, and then a vinyl chloride sheet was prepared. A cold resistance test and a heat resistance test were performed. Table 1 shows the obtained results.

[Comparative Example 5]
A vinyl chloride paste sol composition was prepared in the same manner as in Example 1 except that ester 8 was used instead of ester 1, and then a vinyl chloride sheet was prepared. A cold resistance test and a heat resistance test were performed. Table 1 shows the obtained results.

[Comparative Example 6]
A vinyl chloride paste sol composition was prepared in the same manner as in Example 1 except that the ester 9 was used instead of the ester 1, and then a vinyl chloride sheet was prepared. A cold resistance test and a heat resistance test were performed. Table 1 shows the obtained results.

From the results in Table 1, the vinyl chloride-based paste sol composition containing a phthalic acid diester of the present invention (Example) is a vinyl chloride-based paste sol composition containing a general-purpose phthalic acid diester currently used (Comparative Example). It can be seen that the viscosity is lower than that of. This result indicates that the use of the phthalic acid diester of the present invention is excellent in sol properties, that is, the processability of the obtained paste sol composition. This result correlates with the viscosity of the ester itself, that is, the fact that the low viscosity of the ester itself contributes to the improvement of the properties of the obtained paste sol, that is, the processability. Furthermore, the vinyl chloride paste sol molded article obtained from the vinyl chloride paste sol containing the phthalic acid diester of the present invention has good flexibility, and excellent cold resistance and heat resistance. I understand. This result shows that the use of the phthalic acid diester of the present invention is very superior in performance after molding. Similarly, the vinyl chloride paste sol composition containing a trimellitic acid triester of the present invention (Example) is a vinyl chloride paste sol composition containing a commonly used trimellitic acid triester (Comparative Example). It can be seen that the viscosity is lower than that of ()). This result indicates that the use of the trimellitic acid triester of the present invention has excellent sol properties, that is, excellent processability of the obtained paste sol composition. This result correlates with the viscosity of the ester itself, that is, the fact that the low viscosity of the ester itself contributes to the improvement of the properties of the obtained paste sol, that is, the processability. Furthermore, the vinyl chloride paste sol molded article obtained from the vinyl chloride paste sol containing the trimellitic acid triester of the present invention has good flexibility, and has excellent cold resistance and heat resistance. You can see that there is. This result shows that the use of the trimellitic acid triester of the present invention is very superior in terms of performance after molding.

The vinyl chloride paste sol composition of the present invention has excellent sol properties, and can be used as a vinyl chloride paste sol having excellent heat resistance, cold resistance and flexibility, and a molded article obtained from the vinyl chloride paste sol. Is very useful in various applications, such as automotive materials such as leather, building materials such as wallpaper and flooring, as well as sealing materials, undercoat materials, toys, gloves, footwear, and medical applications.

Claims (8)

A vinyl chloride paste sol composition containing a vinyl chloride resin for a paste and a plasticizer, wherein the plasticizer has a viscosity of not more than 70 mPa · s at 20 ° C. and / or a phthalic acid diester having a viscosity of not more than 70 mPa · s. A vinyl chloride paste sol composition characterized by being a low-viscosity plasticizer comprising a trimellitic acid triester having a measured viscosity of 200 mPa · s or less. The vinyl chloride paste sol composition according to claim 1, wherein the plasticizer is a phthalic acid diester represented by the following general formula (1) and / or a trimellitic acid triester represented by the following general formula (2). .

[Wherein, R ¹ and R ² are the same or different and each is a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is mainly composed of a saturated aliphatic alcohol having 9 carbon atoms. A straight-chain saturated aliphatic alcohol having 9 or more carbon atoms having a content in the saturated aliphatic alcohol of 60% by weight or more and a branched-chain saturated aliphatic alcohol having 9 carbon atoms having a content of 40% by weight or less, And the linear ratio of the saturated aliphatic alcohol is 60% or more. ]

[Wherein, R ³ , R ⁴ and R ⁵ are the same or different and each is a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is a saturated aliphatic alcohol having 9 carbon atoms. As a main component, a saturated aliphatic alcohol having a carbon number of 9 and a content of 60% by weight or more and a branched saturated aliphatic alcohol having a carbon number of 9 and 40% by weight or less are contained. And the linear ratio of the saturated aliphatic alcohol is 60% or more. ] The saturated aliphatic alcohol is mainly composed of a saturated aliphatic alcohol having 9 carbon atoms, and the content in the saturated aliphatic alcohol is 70% by weight or more and 30% by weight of a linear saturated aliphatic alcohol having 9 carbon atoms. %. The vinyl chloride paste sol composition according to claim 2, wherein the composition contains a saturated aliphatic alcohol having 9 or less carbon atoms and a linear chain ratio of the saturated aliphatic alcohol is 70% or more. The saturated aliphatic alcohol is mainly composed of a saturated aliphatic alcohol having 9 carbon atoms, and a content of 75 to 98% by weight in the saturated aliphatic alcohol is a linear saturated aliphatic alcohol having 9 carbon atoms. The vinyl chloride-based paste sol composition according to claim 3, wherein the composition contains about 25% by weight of a branched saturated aliphatic alcohol, and the linear ratio of the saturated aliphatic alcohol is 75 to 98%.   The vinyl chloride paste sol composition according to any one of claims 1 to 4, wherein the viscosity of the phthalic acid diester at 20 ° C is in the range of 40 to 70 mPa · s.   The vinyl chloride paste sol composition according to any one of claims 1 to 4, wherein the viscosity of the trimellitic acid triester at 20 ° C is in the range of 100 to 200 mPa · s.   A vinyl chloride resin molded article molded using the vinyl chloride paste sol composition according to any one of claims 1 to 6. A plasticizer for a vinyl chloride paste sol comprising a phthalic acid diester represented by the following general formula (1) and / or a trimellitic acid triester represented by the following general formula (2).

[Wherein, R ¹ and R ² are the same or different and each is a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is mainly composed of a saturated aliphatic alcohol having 9 carbon atoms. A straight-chain saturated aliphatic alcohol having 9 or more carbon atoms having a content in the saturated aliphatic alcohol of 60% by weight or more and a branched-chain saturated aliphatic alcohol having 9 carbon atoms having a content of 40% by weight or less, And the linear ratio of the saturated aliphatic alcohol is 60% or more. ]

[Wherein, R ³ , R ⁴ and R ⁵ are the same or different and each is a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is a saturated aliphatic alcohol having 9 carbon atoms. As a main component, a saturated aliphatic alcohol having a carbon number of 9 and a content of 60% by weight or more and a branched saturated aliphatic alcohol having a carbon number of 9 and 40% by weight or less are contained. And the linear ratio of the saturated aliphatic alcohol is 60% or more. ]