KR20080060752A - Plasticizer composition, preparation method thereof and vinyl chloride resin composition for tape of vehicle cable containing the same - Google Patents

Abstract

A plasticizer composition is provided to obtain a vinyl chloride resin composition for a tape for car cables having eco-friendly characteristics as well as excellent heating loss, transfer resistance, hardness, elongation and tensile strength. A plasticizer composition comprises a polymeric compound that comprises repeating units represented by the formula of -C(O)-R3-C(O)-O-R4-O- and repeating units represented by the formula of -C(O)-R5-C(O)-O-R6-O-, is substituted with any one group selected from R7-O-, R8-C(O)-O-R4-O-, R8-C(O)-O-R6-O-, R8-C(O)-, R7-C(O)-R3-C(O)-O-, and R7-C(O)-R5-C(O)-O-, and has a molecular weight of 500-10,000. In the formulae, each of R3 and R5 is -(CH2)p-, wherein p is an integer of 1-12 and at least one hydrogen atom thereof is optionally substituted with a C1-C8 linear or branched alkyl group; R4 and R6 are different from each other, and each represents -(CH2)q-, wherein q is an integer of 1-18 and at least one hydrogen atom thereof is optionally substituted with a C1-C8 linear or branched alkyl group, or at least one -(CH2)- thereof is optionally substituted with -O- or COO-; and each of R7 and R8 is a C1-C18 linear or branched alkyl group.

Description

Plasticizer composition, preparation method thereof, and vinyl chloride resin composition for automotive wire tape including the same {PLASTICIZER COMPOSITION, PREPARATION METHOD THEREOF AND VINYL CHLORIDE RESIN COMPOSITION FOR TAPE OF VEHICLE CABLE CONTAINING THE SAME}

The present invention relates to a plasticizer composition, a method for manufacturing the same, and a vinyl chloride resin composition for an automotive wire tape including the same, and more particularly, a non-phthalate-based plasticizer composition, a method for preparing the same, and a heating loss including the plasticizer composition. The present invention relates to a vinyl chloride resin composition which is excellent as a tape for automobile wires due to its excellent performance resistance, hardness, elongation and tensile strength.

Vinyl chloride resin is processed by various processing methods such as extrusion molding, injection molding, calendering, and the like, and includes various pipes, electric wires, electromechanical products, toys, films, sheets, artificial leather, tape, food packaging materials, and medical supplies. It is a general purpose resin used in the field. Various processing properties can be imparted to the vinyl chloride resin by appropriately adding various additives such as a plasticizer, a stabilizer, a filler, a pigment, and the like. The types of plasticizers used so far are very diverse and different in use, but they are classified into phthalate esters, adipate esters, phosphate esters and trimellitates. Trimellitate esters and the like, most of which have been used as general purpose plasticizers.

However, the general-purpose and low-viscosity plasticizers used up to now have many problems, and many studies have been conducted to solve them, and various new products have been developed accordingly. Among the physical properties to be imparted by including the plasticizer, the most important are migration resistance, volatility, and extraction resistance. If the above physical properties do not meet the required level, the plasticizer itself in the resin is released to induce the deterioration of the essential properties of the resin, and promotes aging. This drawback is a problem that must be solved for the vinyl chloride resin composition for the electric wire tape used in the hood of the automobile where high heat is present and many chemicals can be generated.

On the other hand, the international environmental atmosphere is to continuously regulate the phthalate-based plasticizers, and as a result, plasticizers used in automotive wire tapes are environmentally friendly and excellent in migration resistance, thereby minimizing the release of plasticizers to the resin surface. It is in a position to apply a plasticizer that can be used.

In addition, as described above, in the case of the vinyl chloride resin composition, various additives may be used in addition to the plasticizer. In order to find a physical property suitable for the purpose of use, finding a suitable composition ratio may be the most important thing.

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a non-phthalate-based plasticizer composition, and a manufacturing method thereof.

In addition, an object of the present invention is to provide a vinyl chloride resin composition suitable as a tape for automobile wires having excellent heating loss, migration resistance, hardness, elongation, tensile strength and the like, including the plasticizer composition.

The present invention also provides a plastisol and a compound prepared from the vinyl chloride resin composition.

In addition, an object of the present invention is to provide a tape for automobile wires prepared from the plastisols and compounds.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention includes a repeating unit represented by the following formula (1) and a repeating unit represented by the formula (2), the terminal is substituted with any one of the following formulas 3 to 8, the molecular weight is 500 to 10,000 It provides a plasticizer composition comprising a high molecular compound, and a method for producing the same.

In Chemical Formulas 1 to 8,

R ₃ and R ₅ are each independently — (CH ₂ ) _p — (where p is an integer of 1 to 12), and at least one hydrogen of — (CH ₂ ) _p − may have 1 to 8 carbon atoms. May be substituted with a straight or branched alkyl group,

R ₄ and R ₆ are different from each other, and-(CH ₂ ) _q- (where q is an integer of 1 to 18), and at least one hydrogen _of- (CH ₂ ) _q -is a straight chain having 1 to 8 carbon atoms. can be substituted with linear or branched alkyl group, or a - (CH _{2) q} - at least one of - (CH ₂₎ -, and can be replaced by -O-, or COO-,

R ₇ and R ₈ are each independently a linear or branched alkyl group having 1 to 18 carbon atoms.

The plasticizer composition may include 10 to 80 mol% of R ₃ and R ₅ , 10 to 80 mol% of R ₄ and R ₆ , and 5 to 20 mol% of R ₇ or R ₈ with respect to the total content of the polymer compound. Do.

The present invention also provides a vinyl chloride resin composition comprising 100 parts by weight of a vinyl chloride resin and 5 to 80 parts by weight of the plasticizer composition.

The vinyl chloride resin composition is a group consisting of 1 to 50 parts by weight of a secondary plasticizer, 0.5 to 7 parts by weight of stabilizer, up to 5 parts by weight of lubricant, up to 10 parts by weight of auxiliary stabilizer, 0.5 to 10 parts by weight of colorant and 5 to 50 parts by weight of filler. It may further comprise one or more additives selected from.

The present invention also provides a plastisol and a compound prepared from the vinyl chloride resin composition.

The present invention also provides a tape for automobile wires made from the plastisols and compounds.

Hereinafter, the present invention will be described in detail.

The plasticizer composition of the present invention includes a polymer compound comprising a repeating unit represented by Formula 1 and a repeating unit represented by Formula 2.

[Formula 1]

[Formula 2]

In Formulas 1 to 2, R ₃ and R ₅ are each independently — (CH ₂ ) _p − (where p is an integer of 1 to 12, preferably an integer of 4 to 8), Specific examples thereof include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene or decylene, and preferably butylene. In addition, in R ₃ and R ₅ , at least one hydrogen of — (CH ₂ ) _p − may be substituted with a straight or branched alkyl group having 1 to 8 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, isoamyl, neopentyl and hex. Practical skills etc. are mentioned.

The R ₃ and R ₅ is preferably included in 10 to 80 mol% based on the total content of the polymer compound of the present invention. If the content is less than 10 mol% or more than 80 mol%, there is a problem that does not satisfy the respective properties required for the tape for the automobile wires.

이며, 나머지 다른 하나가

로 표시되는 3-하이드록시-2,2-디메틸프로필2-하이드록시-2메틸 프로파노에이트(3- hydroxy-2,2-dimethylpropyl2-hydroxy-2methyl propanoate, HPNE)인 것이다. 또한, R₄ 및 R₆에 있어서, -(CH₂)_q-중 적어도 하나의 수소는 탄소수 1 내지 8의 직쇄형 또는 분지형 알킬기로 치환될 수 있으며, 알킬기의 구체적인 예로는, 메틸기, 에틸기, n-프로필기, 이소프로필기, n-부틸기, 이소부틸기, sec-부틸기, t-부틸기, 펜틸기, 이소아밀기, 네오펜틸기, 헥실기 등을 들 수 있다. 또한, -(CH₂)_q- 중 적어도 하나의 -(CH₂)-가 -O- 또는 COO-로 대체될 수 있다. 구체적인 예로는, -CH₂-O-CH₂-, -(CH₂)₂-O-CH₂-, -CH₂-O-(CH₂)₂-, -CH₂-O-(CH₂)₃-, -(CH₂)₂-O-(CH₂)₂-, -(CH₂)₃-O-CH₂-, -CH₂-O-(CH₂)₄-, -(CH₂)₂-O-(CH₂)₃-, -(CH₂)₃-O-(CH₂)₂-, -(CH₂)₄-O-CH₂-, -CH₂-O-(CH₂)₅-, -(CH₂)₂-O-(CH₂)₄-, -(CH₂)₃-O-(CH₂)₃-, -(CH₂)₄-O-(CH₂)₂-, -(CH₂)₅-O-CH₂- 등을 들 수 있다. Further, in the above Chemical Formulas 1 to 2, R ₄ and R ₆ are different from each _{other, - (CH 2) q -} (. Wherein, q is an integer from 1 to 18, preferably an integer of 4 to 8) as Specific examples thereof include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, and the like. Preferably, each of R ₄ and R ₆ is one of

Is the other one

3-hydroxy-2,2-dimethylpropyl2-hydroxy-2methyl propanoate (3-hydroxy-2,2-dimethylpropyl2-hydroxy-2methyl propanoate, HPNE). In addition, in R ₄ and R ₆ , at least one hydrogen of — (CH ₂ ) _q — may be substituted with a linear or branched alkyl group having 1 to 8 carbon atoms. Specific examples of the alkyl group may include a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, isoamyl group, neopentyl group, hexyl group, etc. are mentioned. Further, at least one of-(CH ₂ )-of-(CH ₂ ) _q -may be replaced with -O- or COO-. Specific examples include -CH ₂ -O-CH ₂ -,-(CH ₂ ) ₂ -O-CH _2- , -CH ₂ -O- (CH ₂ ) _2- , -CH ₂ -O- (CH ₂ ) ₃ -,-(CH ₂ ) ₂ -O- (CH ₂ ) ₂ -,-(CH ₂ ) ₃ -O-CH _2- , -CH ₂ -O- (CH ₂ ) ₄ -,-(CH ₂ ) ₂ -O- (CH ₂ ) ₃ -,-(CH ₂ ) ₃ -O- (CH ₂ ) ₂ -,-(CH ₂ ) ₄ -O-CH _2- , -CH ₂ -O- (CH ₂ ) ₅ -,-(CH ₂ ) ₂ -O- (CH ₂ ) ₄ -,-(CH ₂ ) ₃ -O- (CH ₂ ) ₃ -,-(CH ₂ ) ₄ -O- (CH ₂ ) _2- ,-(CH ₂ ) ₅ -O-CH ₂ -and the like.

The molar ratio of R ₄ and R ₆ is 1: x, where x is preferably 0.1 <x <9. If x is less than 0.1, it means that the content ratio of R ₆ is small, and there is a problem of deterioration of workability due to excessive increase of viscosity and crystallization of the material itself, and if it exceeds 9, it means that the content ratio of R ₆ is large. And, there is a problem that the viscosity of the plasticizer is too low.

The R ₄ and R ₆ is preferably included in 10 to 80 mol% based on the total content of the polymer compound of the present invention. At this time, the content of R ₄ and R ₆ of the substituent substituted at the terminal of the polymer compound is included. If the content is less than 10 mol%, that is, in the case of lower alkylene, there is a problem of poor migration resistance and extraction resistance, and if it exceeds 80 mol%, that is, in the case of linear or branched higher alkylene, There is a problem that the physical properties are too large.

Thus, more preferably any one of R ₄ and R ₆ is branched alkylene and the other is alkylene wherein — (CH ₂ ) — of at least one of the alkylenes is replaced with —O— or COO— will be. By including R ₄ and R ₆ having different structures in this way, the overall form of the high molecular compound is formed in a branched form, and an action exhibiting appropriate migration resistance occurs, so that the plasticizer composition containing the high molecular compound is made of vinyl chloride. When applied to the resin composition, there is an effect of improving the heat resistance and chemical resistance.

As described above, the polymer compound including the repeating unit represented by Formula 1 and the repeating unit represented by Formula 2 has a terminal substituted with any one of Formulas 3 to 8.

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In Formulas 3 to 8, R ₃ and R ₅ and R ₄ and R ₆ are the same as defined in Formulas 1 and 2.

이고, R₈은

인 것이다. In addition, in Formulas 3 to 8, R ₇ and R ₈ are each independently a linear or branched alkyl group having 1 to 18 carbon atoms, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, isoamyl group, neopentyl group, hexyl group, isohexyl group, sec-hepsyl group, t-heptyl group, 2-methyl -3dimethylpropyl group, heptyl group, isoheptyl group, sec-heptyl group, t-heptyl group, 2-methyl-3 dimethylbutyl group, 2-dimethyl-3 methylbutyl group, octyl group, nonyl group, isononyl group Etc. can be mentioned. Preferably, R ₇ is

R ₈ is

It is

The R ₇ or R ₈ is preferably included in 5 to 20 mol% based on the total content of the polymer compound of the present invention. If the content is less than 5 mol%, that is, the straight chain or branched lower alkyl group having a carbon number, there is a problem in that the termination of the reaction is not good, and if the content exceeds 20 mol%, that is, the linear or minute carbon atoms In the case of a topographic higher alkyl group, there is a problem in that the molecular weight control is not appropriate.

The polymer compound preferably has a molecular weight of 500 to 10,000. When the molecular weight is less than 500, there is a problem in that it is difficult to obtain a satisfactory performance of the migration resistance, and when it exceeds 10,000, there is a problem in that the molecular weight is increased and the viscosity is increased.

The method for preparing a plasticizer composition of the present invention includes the step of preparing the polymer compound by esterifying a compound represented by Formulas 9 to 12, and a compound represented by Formula 13 or Formula 14 in the presence of a catalyst.

[Formula 9]

HOOC-R ₃ -COOH

[Formula 10]

HO-R ₄ -OH

[Formula 11]

HOOC-R ₅ -COOH

[Formula 12]

HO-R ₆ -OH

[Formula 13]

R ₇ -OH

[Formula 14]

R ₈ -COOH

In Chemical Formulas 9 to 14, R ₃ to R ₈ are the same as defined in Chemical Formulas 1 to 8.

Examples of the compound represented by the formula (9) and the compound represented by the formula (11) include malonic acid, succinic acid, glutaric acid, adipic acid, and the like, but are not limited thereto.

The compound represented by the formula (10) and the compound represented by the formula (12), any one of the two compounds, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, 2-hydroxypropane-2-yl2-hydr 2-hydroxypropane-2-yl2-hydroxy-2methyl propanoate, 2-hydroxy-2-methylpropyl2-hydroxy-2methyl propanoate hydroxy-2methyl propanoate), 3-hydroxy-2,2-dimethylpropyl2-hydroxy-2methyl propanoate, and the like. Other ones include 2-methylpropanediol, 2-methylbutanediol, neopentylglycol, 2-methylhexanediol, 3-methylhexanediol, and the like, but are not limited thereto.

The compound represented by Chemical Formula 13 and the compound represented by Chemical Formula 14 serve to control the molecular weight of the polymer compound, and remain in the terminal group. Examples of the compound represented by the formula (13) include isobutyl alcohol, isopene alcohol, neopentyl alcohol, isohexyl alcohol, isononyl alcohol and the like, and the compound represented by the formula (14) is acetic acid, propionic acid, butyl acid, valeric acid And capuronic acid, and the like, but are not limited thereto.

The compound as described above is added to the flask with a stirrer and condenser together with the catalyst, and then heated to 220 ° C to esterify for 4 to 10 hours to prepare a polymer compound. After the esterification reaction, the unreacted compound and the catalyst can be removed under reduced pressure with a vacuum pump. In addition, the residual acid component not removed can be neutralized by adding NaOH or the like, followed by washing, dehydration and filtration to obtain a final plasticizer composition.

The catalyst serves to promote the reaction, it can be selected according to the temperature of the esterification reaction. In general, the esterification reaction is carried out at 130 to 280 ℃, it is possible to use a variety of catalysts to suit the appropriate temperature. Specific examples thereof include tetra isobutyl titanate, tetra isopropyl titanate, dibutyl tin oxide, paratoluene sulfonic acid, and the like, preferably paratoluene sulfonic acid or tetra isopropyl titanate, and the like. It doesn't happen.

In the esterification reaction, an entrainer may be further used. The entrainment material is an auxiliary material that serves to discharge the H ₂ O produced in the esterification reaction to the outside of the reaction system. Since the esterification reaction is a reversible reaction, when the product water is discharged to the outside of the reaction system, less reverse reaction occurs due to the LeChatlier principle, thereby obtaining a large amount of the desired product. Thus, entrained materials improve the yield of the desired product. Specific examples of the entrained materials include organic solvents containing n-hexane, toluene, xylene and the like, or an inert gas such as nitrogen, and preferably n-hexane, toluene, xylene, nitrogen, and the like. It may be, but is not limited to such. When the entrained material is a liquid, it is used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the total compound represented by Formulas 9 to 14, and in the case of gas phase, it may be used at a ratio of 0.1 to 10 times / hour of the reactor volume. .

After completion of the esterification reaction, post-treatment of the unreacted compound and the catalyst is not particularly limited, but the excess raw material can be removed by a method such as distillation under reduced pressure. In addition, the remaining acid components not removed are neutralized with a basic solution such as NaOH, KOH, Na ₂ CO ₃ aqueous solution, etc., washed with water, and optionally dried under reduced pressure by dehydration. A composition can be obtained.

The vinyl chloride resin composition of the present invention comprises the plasticizer composition and is a composition suitable for application to a tape for automobile wires.

The vinyl chloride resin composition has various excellent properties such as excellent heat loss, migration resistance, hardness, elongation, and tensile strength. In particular, it can solve many problems that may occur when using general purpose plasticizers. In general, in the case of general-purpose plasticizers, due to the low molecular weight and the monotony of the structural change, a large amount of the plasticizer composition applied to the vinyl chloride resin composition according to the present invention has a problem in that it is transferred to the outside. It is easy to use and has various variables of structural design and modeling, which can solve the problem of external transition because it has the advantage of compensating the plasticizer transition and fragile characteristics with various molecular weights and molecular shapes. Therefore, the problem that the transferred plasticizer does not pollute the surroundings does not arise, and it is judged that it is very suitable for the tape for automobile wires.

The vinyl chloride resin composition includes 100 parts by weight of the vinyl chloride resin and 5 to 80 parts by weight of the plasticizer composition, and preferably 15 to 60 parts by weight of the plasticizer composition. When the content of the plasticizer composition is less than 5 parts by weight, the viscosity of the resin itself is high, and thus workability is not good. When the content of the plasticizer composition is more than 80 parts by weight, the intrinsic properties of the vinyl chloride resin may not be expressed.

The vinyl chloride resin composition may further include at least one additive selected from the group consisting of secondary plasticizers, stabilizers, lubricants, auxiliary stabilizers, colorants, and fillers. That is, the additive may be appropriately selected and used depending on the physical properties to be improved in the vinyl chloride resin composition. Specifically, 1 to 50 parts by weight of the secondary plasticizer, 0.5 to 7 parts by weight of the stabilizer, up to 5 parts by weight of the lubricant, up to 10 parts by weight of the auxiliary stabilizer, 0.5 to 10 parts by weight of the colorant and 5 to 50 parts by weight of the filler 1 It may further comprise at least an additive. In the case of including the additive of the above content, it is possible to optimally satisfy the physical properties such as heating loss, hardness, elongation, tensile strength, as well as the performance resistance required in the tape for automobile wires.

Secondary plasticizers are plasticizers that remain in the product after processing to control physical properties, and plasticizers that lower the viscosity during processing and do not remain after processing and do not affect physical properties such as tensile strength or elasticity in the product continuously. Means, it serves to further improve the migration resistance of the vinyl chloride resin composition. Secondary plasticizers have low plasticity as compared to the plasticizers generally used as the main plasticizer corresponding to the plasticizer composition containing the polymer compound of the present invention, but have excellent properties of viscosity lowering ability and viscosity retention performance. In addition, it is possible to reduce the stickiness of the surface of the workpiece by reducing the content of the plasticizer in the workpiece because it does not remain after the end of processing. Examples of secondary plasticizers include dioctyl adipate (DOA), diisononyl adipate (DINA), and diisodecyl adipate (DIDA). The secondary plasticizer is preferably included in an amount of 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the content is less than 1 part by weight, there is a problem that the cold resistance is lowered, and if it exceeds 30 parts by weight, there is a problem that the effect of the primary plasticizer is lowered.

In the vinyl chloride resin composition, HCl is separated from polyvinyl chloride to form a polyene structure, which is a chromophore, to prevent various physical property changes caused by cutting and crosslinking of the main chain. As a stabilizer, Ca-Zn type compound; Ba-Zn compound; Organic Tin compounds such as mercaptide compounds, maleic acid compounds or carboxylic acid compounds; Metallic soap-based compounds such as Mg-stearate, Ca-stearate, Pb-stearate, Cd-stearate or Ba-stearate; Phenolic compounds; Phosphoric acid ester compounds; Or a phosphorous acid ester compound, and the like, and may be selectively used according to the use. The stabilizer is preferably included in an amount of 0.5 to 7 parts by weight, more preferably 1 to 4 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the content is less than 0.5 parts by weight, there is a problem that the thermal stability is lowered.

The auxiliary stabilizer can be used to compensate for heat resistance that can be weakened by adding a plasticizer and a Ca-Zn-based stabilizer, and in addition, can improve heat resistance, transparency and colorability of the vinyl chloride resin composition. Specific examples include epoxy compounds such as epoxide soy bean oil (ESO); Phosphorous acid ester compounds; Phenol derivative compounds such as benzophenone compounds or benzotriazole compounds; Polyhydric alcohols; And β-diketo compounds. The auxiliary stabilizer is preferably included at most 10 parts by weight, more preferably 0.5 to 5 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content exceeds 10 parts by weight, the hardness is high and there is a problem that cold resistance is lowered.

Lubricants can be used to impart lubrication between polymer chains by reducing friction between particles and reducing adhesion in processing vinyl chloride resin. Specific examples thereof include fatty acid compounds such as stearic acid; Fatty acid ester compounds such as butyl ester or octyl stearate; Mixtures of alcohols and fatty acids such as palmityl alcohol or stearyl alcohol; Fatty acid amide compounds such as stearic acid amide or oleic acid amide; Metallic soaps; Hydrocarbon type compounds, such as a paraffin or polyethylene wax, etc. are mentioned, A stearic acid is preferable as an electric wire tape for automobiles. The lubricant is included at most 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the content exceeds 5 parts by weight, the melt viscosity is too low, there is a problem that the workability is lowered.

A coloring agent can be suitably selected and used according to the various color suitable for the use of a vinyl chloride resin composition. Specific examples include titanium oxide (TiO ₂ ), lithopone, iron oxide (Fe ₂ O ₃ ), cadmium red, cadmium sulfur, chromium oxide (Cr ₂ O ₃ ), and the like. The colorant is preferably included in an amount of 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the content is less than 0.5 parts by weight, there is a problem of discoloration for light and heat, and if it exceeds 10 parts by weight, there is a problem that the processing equipment is worn.

A filler can be used in order to improve the productivity of a vinyl chloride resin composition, and the dry touch of a dry state. Specific examples include calcium carbonate, clay, talc or diatomaceous earth. The filler is preferably included in an amount of 5 to 50 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the content is less than 5 parts by weight, there is a problem that the dimensional stability and economic efficiency is lowered, and if the content exceeds 50 parts by weight there is a problem of poor workability.

The method for preparing the vinyl chloride resin composition is not particularly limited, and methods well known in the art may be used.

The present invention provides a plastisol and a compound prepared from the vinyl chloride resin composition.

Usually, the paste vinyl chloride resin is prepared by emulsion polymerization into powder particles having a size of 0.1 to 2 μm. The latex prepared by emulsion polymerization is dried by a spray drying method to prepare a final paste vinyl chloride resin product particle of 5 μm or more. The paste vinyl chloride resin thus prepared is processed and molded into a plastisol or organosol state composed of various additives such as a heat stabilizer together with a conventional plasticizer. Such a plastisol is applied to a product such as a tape for an automobile wire, and is also blended in an optimum ratio to be molded into a compound.

The present invention provides a tape for automobile wires excellent in migration resistance, which is prepared from the plastisol, the compound, or a mixture thereof.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

EXAMPLE

<Production of Plasticizer Composition>

Example 1

In a four-necked 2-liter flask equipped with a stirrer and a condenser, 551.55 g of adipic acid, 278.76 g of neopentylglycol, 3-hydroxy-2,2-dimethylpropyl2-hydroxy-2methyl propanoate (3- hydroxy-2,2-dimethylpropyl2-hydroxy-2methyl propanoate) 136.70 g and 219.99 g of isononyl alcohol were added to 0.45 g of tetraisopropyl titanate as a reaction catalyst, and the temperature was raised to 220 ° C. under stirring in a nitrogen atmosphere. The reaction was carried out for 9 hours while removing the reaction product water.

After the reaction, unreacted adipic acid and excess isononyl alcohol were removed under reduced pressure using a vacuum pump at 150 to 220 ° C., 10% by weight of sodium hydroxide (NaOH) solution and 10% by weight of forget-me-not (Na ₂ SO _4). Neutralization and washing were performed sequentially using a 10H ₂ O) solution to dehydrate under reduced pressure, an adsorbent was added to the reaction product from which water was removed, and filtered through a filter medium to obtain a final polymer plasticizer composition.

Example 2

In Example 1, 518.21 g of adipic acid, 225.43 g of neopentylglycol, 3-hydroxy-2,2-dimethylpropyl2-hydroxy-2methyl propanoate (3-hydroxy-2,2-dimethylpropyl2- Hydroxy-2methyl propanoate) 110.55 g, and 434.40 g of isononyl alcohol was carried out in the same manner as in Example 1 except that 0.49 g of tetraisopropyl titanate as a reaction catalyst was added.

<Vinyl Chloride Resin Composition Preparation>

Example 3

100 parts by weight of polyvinyl chloride resin and 23 parts by weight of the plasticizer composition prepared in Example 1, 23 parts by weight of diisononyl adipate (DINA) as a secondary plasticizer, 3 parts by weight of a Ba-Zn compound as a stabilizer , 1 part by weight of stearic acid as lubricant, 1.5 parts by weight of epoxide soy bean oil (ESO) as auxiliary stabilizer, 3 parts by weight of TiO ₂ as colorant, 20 parts by weight of CaCO ₃ as filler, using an extruder Compounding to prepare a vinyl chloride resin composition.

Example 4

In Example 1, it was carried out in the same manner as in Example 1 except that the secondary plasticizer was used in 25 parts by weight.

Example 5

In Example 1, except that 25 parts by weight of the plasticizer composition, 25 parts by weight of the secondary plasticizer was carried out in the same manner as in Example 1.

Example 6

In Example 1, it was carried out in the same manner as in Example 1, except that 23 parts by weight of the plasticizer composition prepared in Example 2 as a plasticizer composition.

Example 7

In Example 1, the plasticizer composition was used in the same manner as in Example 1, except that 23 parts by weight of the plasticizer composition prepared in Example 2 was used, and 25 parts by weight of the secondary plasticizer was used.

Example 8

In Example 1, 25 parts by weight of the plasticizer composition prepared in Example 2 was used as the plasticizer composition, except that 25 parts by weight of the secondary plasticizer was used in the same manner as in Example 1.

Comparative Example 1

Except for using dioctyl phthalate (DOP) in 25 parts by weight as a plasticizer in Example 1 was carried out in the same manner as in Example 1.

Comparative Example 2

Except that 25 parts by weight of dibutyl phthalate (DBP) as a plasticizer in Example 1 was carried out in the same manner as in Example 1.

Comparative Example 3

Except for using acetyltributyl citrate (ATBC) in 25 parts by weight as a plasticizer in Example 1 was carried out in the same manner as in Example 1.

[Test Example]

The physical properties of the vinyl chloride resin composition prepared in Examples 3 to 8 and Comparative Examples 1 to 3 were measured by the following method, and the results are shown in Table 1 below.

* Tensile strength-According to ASTM D638 method, using a test instrument UTM 4466 (Instron Co., Ltd.) to pull the cross head speed to 200 mm / min, and then measure the point where the specimen is cut, It was calculated by the following equation (1).

 Tensile Strength (kgf / mm2) = Load Value (kgf) / Thickness (mm) × Width (mm)

* Elongation-According to ASTM D638 method, using a test instrument UTM 4466 (Instron Co., Ltd.) pull the crosshead speed to 200 mm / min, and then measure the point where the specimen is cut, Calculated by Equation 2.

Elongation (%) = Length after elongation (mm) / Initial length (mm) × 100

* Hardness-Hardness was measured as an indicator of plasticization efficiency, and the hardness after 5 seconds after the needle of hardness tester C-751400101 (A type) (manufactured by Toyoseiki) was completely lowered to one of the specimens according to ASTM D2240 method. The values were read and tested for 5 specimens for each specimen, and their mean values calculated. At this time, the hardness was measured once immediately after the specimen was prepared, and once more after one day after the specimen was prepared.

* Loss of heating-After working the vinyl chloride resin composition for 3 minutes at 165 ℃ using a roll mill to produce a 0.8 mm thick sheet, this was taken 60 g at 185 ℃ using a roll mill The specimen was fabricated to a thickness of 0.4 mm by working for 10 minutes. Then, after 24 hours, the weight of the specimen was measured, and calculated by the following equation (3).

Loss of heating (% by weight) = 1-(weight after working for 10 minutes at 185 ℃) / 60 g × 100

* Improving resistance-For each specimen prepared, the initial weight (Wi) was measured to four decimal places, and a specimen (3 cm × 3 cm) was put between ABS resin plates in an oven at 70 ° C, and a load of 1 kg was applied. After leaving for 72 hours in the state, the specimen was taken out and stored in a thermostat for 4 hours or more, the weight (Wo) of the specimen was measured, and calculated by the following equation (4).

Shift by weight = (Wi-Wo) / Wi × 100

division Example Comparative example 3 4 5 6 7 8 One 2 3 Tensile Strength (㎏f / ㎠) 3.07 3.25 2.90 2.88 2.89 2.78 2.10 2.12 1.95 % Elongation 492 494 438 498 504 501 605 610 612 Hardness 84 82 87 78 75 77 70 69 69 Loss of heating (% by weight) 0.2868 0.4135 0.2853 0.3963 0.4130 0.3900 0.9253 0.9109 0.9305 Shift amount (% by weight) 0.1416 0.3287 0.1513 0.2932 0.3759 0.3103 0.5349 0.5789 0.6032

As shown in Table 1, the vinyl chloride resin compositions of Examples 3 to 8 according to the present invention are Comparative Examples 1 to 2, including phthalate plasticizers, which are plasticizers most widely used in vinyl chloride resins, and acetyltributyl citrate. Compared with Comparative Example 3 containing a plasticizer, it was confirmed that the physical properties such as tensile strength, elongation, hardness, etc. were excellent, and at the same time, it was excellent in heat loss and migration resistance.

As described above, according to the present invention provides an environment-friendly plasticizer composition with a non-phthalate-based, including the plasticizer composition in an optimal content, excellent heating loss, transition resistance, hardness, elongation, tensile strength and the like for automotive wire tape There is an effect of providing a vinyl chloride resin composition suitable as.

In addition, according to the present invention, there is provided a plistisol and a compound prepared from the vinyl chloride resin composition, and there is an effect of providing a tape for an automobile wire manufactured therefrom.

Claims (18)

A plasticizer composition comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the formula (2), the terminal of which is substituted with any one of the following formulas (3) to (8) and has a molecular weight of 500 to 10,000 ; [Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In Chemical Formulas 1 to 8, R ₃ and R ₅ are each independently — (CH ₂ ) _p — (where p is an integer of 1 to 12), and at least one hydrogen of — (CH ₂ ) _p − may have 1 to 8 carbon atoms. May be substituted with a straight or branched alkyl group, R ₄ and R ₆ are different from each other, and-(CH ₂ ) _q- (where q is an integer of 1 to 18), and at least one hydrogen _of- (CH ₂ ) _q -is a straight chain having 1 to 8 carbon atoms. can be substituted with linear or branched alkyl group, or a - (CH _{2) q} -, at least one of the - (CH ₂₎ -, and can be replaced by -O-, or COO-, R ₇ and R ₈ are each independently a straight or branched alkyl group having 1 to 18 carbon atoms. The method of claim 1, R ₃ and R ₅ is 10 to 80 mol%, R ₄ and R ₆ is 10 to 80 mol%, R ₇ or R ₈ is 5 to 20 mol% with respect to the total content of the polymer compound Plasticizer composition. The method of claim 1, Any one of R ₄ and R ₆

The other one

3-hydroxy-2,2-dimethylpropyl2-hydroxy-2methyl propanoate represented by Plasticizer composition. The method of claim 1, One of R ₄ and R ₆ is branched alkylene, and the other is at least one of alkylene-(CH ₂ )-is alkylene substituted with -O- or -COO- Plasticizer composition. A plasticizer comprising the step of esterifying a compound represented by the following formulas (9) to (12), and a compound represented by the following formulas (13) or (14) in the presence of a catalyst to produce the polymer compound according to claim 1 A method of preparing the composition; [Formula 9] HOOC-R ₃ -COOH [Formula 10] HO-R ₄ -OH [Formula 11] HOOC-R ₅ -COOH [Formula 12] HO-R ₆ -OH [Formula 13] R ₇ -OH [Formula 14] R ₈ -COOH In Chemical Formulas 9 to 14, R ₃ and R ₅ are each independently — (CH ₂ ) _p — (where p is an integer of 1 to 12), and at least one hydrogen of — (CH ₂ ) _p − may have 1 to 8 carbon atoms. May be substituted with a straight or branched alkyl group, R ₄ and R ₆ are different from each other, and-(CH ₂ ) _q- (where q is an integer of 1 to 18), and at least one hydrogen _of- (CH ₂ ) _q -is a straight chain having 1 to 8 carbon atoms. can be substituted with linear or branched alkyl group, or a - (CH _{2) q} -, at least one of the - (CH ₂₎ -, and can be replaced by -O-, or COO-, R ₇ and R ₈ are each independently a linear or branched alkyl group having 1 to 18 carbon atoms. The method of claim 5, The esterification reaction, characterized in that carried out for 4 to 10 hours at 220 ℃ Process for preparing plasticizer composition The method of claim 5, The catalyst is at least one member selected from the group consisting of tetra isobutyl titanate, tetra isopropyl titanate, dibutyl tin oxide and paratoluene sulfonic acid. Method for producing a plasticizer composition. 100 parts by weight of the vinyl chloride resin and 5 to 80 parts by weight of the plasticizer composition according to claim 1, characterized in that Vinyl chloride resin composition. The method of claim 8, The vinyl chloride resin composition is composed of 1 to 50 parts by weight of secondary plasticizer, 0.5 to 7 parts by weight of stabilizer, up to 5 parts by weight of lubricant, up to 10 parts by weight of auxiliary stabilizer, 0.5 to 10 parts by weight of colorant and 5 to 50 parts by weight of filler. Further comprising at least one additive selected from the group Vinyl chloride resin composition. The method of claim 9, The secondary plasticizer is at least one member selected from the group consisting of dioctyl adipate, diisononyl adipate and diisodecyl adipate. Vinyl chloride resin composition. The method of claim 9, The stabilizer is at least one member selected from the group consisting of a Ca-Zn compound, a Ba-Zn compound, an organic Tin compound, a metallic soap compound, a phenol compound, a phosphate ester compound and a phosphite ester compound. By Vinyl chloride resin composition. The method of claim 9, The lubricant is at least one member selected from the group consisting of fatty acid compounds, fatty acid ester compounds, mixtures of fatty acids and alcohols, fatty acid amide compounds, metallic soaps and hydrocarbon compounds. Vinyl chloride resin composition. The method of claim 9, The auxiliary stabilizer is at least one member selected from the group consisting of an epoxy compound, a phosphite ester compound, a phenol derivative compound, a polyhydric alcohol and a β-diketo compound. Vinyl chloride resin composition. The method of claim 9, The colorant is at least one member selected from the group consisting of titanium oxide, lithopone, iron oxide, cadmium red, cadmium sulfur and chromium oxide. Vinyl chloride resin composition. The method of claim 9, The filler is at least one member selected from the group consisting of calcium carbonate, clay, talc and diatomaceous earth. Vinyl chloride resin composition. A vinyl chloride resin plastisol prepared from the vinyl chloride resin composition according to any one of claims 8 to 15. A vinyl chloride resin compound prepared from the vinyl chloride resin composition according to any one of claims 8 to 15. A tape for automobile wire made from a vinyl chloride resin plastisol, a compound or a mixture thereof prepared from the vinyl chloride resin composition according to any one of claims 8 to 15.