KR20160119615A - Plasticizer, resin composition and method for preparing them - Google Patents

Abstract

The present invention relates to a plasticizer composition, a resin composition, and a production method thereof. By improving disadvantageous physical properties occurred due to structural shortcomings, it is possible to provide a plasticizer and a resin composition containing the same, which can improve physical properties such as viscosity, bleeding phenomenon, and gelling properties required in a sheet treatment when used as the plasticizer in the resin composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a plasticizer composition, a resin composition, and a process for producing the same. BACKGROUND ART [0002]

The present invention relates to a plasticizer composition, a resin composition containing the same, and a process for producing the same.

Typically, plasticizers react with alcohols with polycarboxylic acids such as phthalic acid and adipic acid to form the corresponding esters. Also, in consideration of domestic and foreign regulations of phthalate plasticizers which are harmful to human body, studies on plasticizer compositions that can replace phthalate plasticizers such as terephthalate, adipate, and other high molecular weight have continued.

On the other hand, a suitable plasticizer should be used in consideration of discoloration in order to produce products such as flooring, wallpaper, and sheet industries requiring lightfastness as a physical property. In the case of PVC compound for wallpaper or sheet, plasticizer, filler, stabilizer, viscosity reducing agent, dispersant, antifoaming agent, foaming agent, etc. are added to PVC resin according to tensile strength, elongation, light resistance, bleeding phenomenon, And so on.

For example, when diisononyl isophthalate is applied to a plasticizer composition applicable to PVC, a bleeding phenomenon is observed not only due to a high viscosity and a relatively low absorption rate of the plasticizer, It was not outstanding.

Therefore, there is a continuing need to develop a product that is superior to the diisononyl isophthalate or a product of a novel composition containing diisononyl isophthalate, which can be applied as a plasticizer to a vinyl chloride resin.

Accordingly, the inventors of the present invention have continued to carry out research on plasticizers, and have ascertained a plasticizer composition capable of improving poor physical properties caused by structural limitations, and completed the present invention.

That is, an object of the present invention is to provide a plasticizer which can improve physical properties such as light resistance required in a compound preparation when used as a plasticizer of a resin composition, viscosity required in sheet formulation, bleeding phenomenon, gelation property, Compositions.

According to an embodiment of the present invention, there is provided an isophthalate-based compound; And diisononyl phthalate, wherein the weight ratio of the isophthalate compound to the diisononyl phthalate is 1:99 to 99: 1.

The weight ratio of the isophthalate compound to the diisononyl phthalate may be 1:99 to 7: 3, and the weight ratio of the isophthalate compound to the diisononyl phthalate may be 1: 9 to 5: 5.

The isophthalate compound may have a terminal group independently selected from alkyl groups having 1 to 12 carbon atoms.

The isophthalate compound may include a compound represented by the following general formula (1).

[Chemical Formula 1]

The plasticizer composition may further comprise an additive, and the additive may be included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the isophthalate-based compound.

The additive may be selected from the group consisting of di-2-propylheptyl phthalate, diisodecyl phthalate, pyrolytic carbon, epoxy fatty acid methyl ester (eFAME), acetyl tributyl citrate (ATBC), tributyl citrate (TBC) (DOM), and dioctyl adipate (DOA).

According to another embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: preparing an isophthalate compound and a diisononyl phthalate; And blending the isophthalate compound and diisononyl phthalate in a weight ratio of 1:99 to 99: 1 to obtain the plasticizer composition described above.

According to another embodiment of the present invention, there is provided a thermoplastic resin composition comprising 100 parts by weight of at least one resin selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane and thermoplastic elastomer And 5 to 150 parts by weight of the above-mentioned plasticizer composition.

The resin composition may be applied as a compound formulation or a sheet formulation.

The resin composition may be applied to manufacture at least one selected from the group consisting of electric wire, flooring, automobile interior material, film, sheet, wallpaper and tube.

The plasticizer composition according to an embodiment of the present invention can improve properties such as plasticization efficiency, tensile strength and elongation when used in a resin composition, and can provide excellent physical properties such as anti-planarity and resistance to volatility have.

Hereinafter, the present invention will be described in detail.

First, the present invention has a technical feature in providing a plasticizer composition capable of improving poor physical properties that have been caused by structural limitations.

According to one embodiment of the present invention, a plasticizer composition containing an isophthalate-based compound can be provided. Specifically, it is possible to provide a plasticizer composition comprising 1 to 99% by weight, 1 to 80% by weight, and 20 to 70% by weight, based on the total weight of the composition, of the isophthalate compound.

The isophthalate compound is not limited and may be one having an independently selected terminal group among alkyl groups having 1 to 12 carbon atoms, 3 to 11 carbon atoms, 4 to 10 carbon atoms, 8 to 10 carbon atoms, 8 to 9 carbon atoms, or 8 carbon atoms have.

Specifically, the isophthalate compound may include a compound represented by the following formula (1), i.e., diisononyl isophthalate.

[Chemical Formula 1]

According to an embodiment of the present invention, the plasticizer composition may include an isophthalate compound, and may further include another second phthalate compound in addition to the compound. As described above, in the case of the resin prepared from the plasticizer composition in which the isophthalate compound and the second phthalate compound are mixed together, the tensile strength and the tensile strength of the resin prepared from the plasticizer composition containing the isophthalate- , Elongation and the like can be more excellent.

The second phthalate compound may have a terminal group independently selected from alkyl groups having 1 to 12 carbon atoms, 3 to 11 carbon atoms, 4 to 10 carbon atoms, 8 to 10 carbon atoms, 8 to 9 carbon atoms, or 8 carbon atoms.

Specifically, the second phthalate compound may include a compound represented by the following formula (2), i.e. diisononyl phthalate.

(2)

The isophthalate compound and the second phthalate compound may be contained in the plasticizer composition in a weight ratio of 1:99 to 99: 1, preferably 1:99 to 7: 3, or 1: 9 to 1: 5: 5. ≪ / RTI >

The plasticizer composition may further comprise an additive. The additive may include 1 to 30 parts by weight of the additive, based on 100 parts by weight of the isophthalate-based compound. The additive may be mixed with the isophthalate compound alone to improve the physical properties such as stress characteristics of the resin composition. However, even if only a small amount of the additive is included in the mixed plasticizer composition, a compound having excellent physical properties can be produced.

Such additives include, for example, di-2-propylheptyl phthalate, diisodecyl phthalate, pyrolysis carbon (pyro-C), epoxy fatty acid methyl ester (eFAME), acetyl tributyl citrate (ATBC), tributyl citrate (TBC), dioctyl malate (DOM), or dioctyl adipate (DOA).

In the present invention, the plasticizer composition may be prepared by a blending method. The blending method may be as follows.

An isophthalate compound and a second phthalate compound are prepared.

The plasticizer composition may be prepared by blending the isophthalate compound and the second phthalate compound (for example, diisononyl phthalate) in a weight ratio of 1:99 to 99: 1.

In the blend production method, the isophthalate compound may be prepared by adding isophthalic acid to an alcohol, adding a catalyst, and reacting in an atmosphere of nitrogen; Removing unreacted alcohol and neutralizing the unreacted acid; And dehydration and filtration by vacuum distillation.

The alcohols used in the blending process may be in the range of 150 to 500 mole%, 200 to 400 mole%, 200 to 350 mole%, 250 to 400 mole%, or 270 to 330 mole% based on 100 mole% of isophthalic acid Lt; / RTI >

Further, the alcohol used in the blending process may be in the range of 150 to 500 mol%, 200 to 400 mol%, 200 to 350 mol%, 250 to 400 mol%, or 270 to 330 mol% based on 100 mol% of isophthalic acid Lt; / RTI >

The catalyst used in the blending process may be any catalyst that can be used in the esterification reaction without any particular limitation. Examples of the catalyst include sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, paratoluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, Metal catalysts such as aluminum sulfate, lithium fluoride, potassium chloride, cesium chloride, calcium chloride, iron chloride and aluminum phosphate, metal oxides such as heteropoly acid, natural / synthetic zeolites, cationic and anion exchange resins , Tetra alkyl titanate, and organic polymers such as a polymer thereof. As a specific example, the catalyst may use tetraalkyl titanate.

The amount of the catalyst to be used may vary depending on the type of catalyst. For example, in the case of a homogeneous catalyst, 0.01 to 5 wt%, 0.01 to 3 wt%, 1 to 5 wt%, or 2 to 4 wt% And in the case of a heterogeneous catalyst, it may be in the range of 5 to 200 wt%, 5 to 100 wt%, 20 to 200 wt%, or 20 to 150 wt% of the total amount of reactants.

The reaction temperature may be in the range of 180 to 280 ° C, 200 to 250 ° C, or 210 to 230 ° C.

The plasticizer composition thus prepared may be used in an amount of 5 to 150 parts by weight, 40 to 40 parts by weight, and preferably 40 to 50 parts by weight, based on 100 parts by weight of a resin such as ethylene-vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane or thermoplastic elastomer, To 100 parts by weight, or from 40 to 50 parts by weight, and can provide a resin composition which is effective both in compounding prescription and / or in sheet prescription.

According to an embodiment of the present invention, the resin composition may further include a filler.

The filler may be used in an amount of 0 to 300 parts by weight, preferably 50 to 200 parts by weight, more preferably 100 to 200 parts by weight, based on 100 parts by weight of the resin.

According to one embodiment of the present invention, the filler may be a filler known in the art, and is not particularly limited. For example, a mixture of at least one selected from the group consisting of silica, magnesium carbonate, calcium carbonate, wax, talc, magnesium hydroxide, titanium dioxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, aluminum silicate, magnesium silicate and barium sulfate.

Further, according to one embodiment of the present invention, the resin composition may further contain other additives such as a stabilizer, if necessary.

The other additives such as the stabilizer may be, for example, 0 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the resin.

The stabilizer that can be used according to one embodiment of the present invention may be, for example, a calcium-zinc-based stabilizer such as calcium-zinc complex stearate, but is not particularly limited thereto.

The resin composition can be applied to various fields but can be applied to, for example, electric wire, flooring, automobile interior material, film, sheet, wallpaper, or tube manufacturing.

Example

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention may be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

Manufacturing example  One: Diisononyl Of isophthalate (DINIP)  Produce

495.0 g of purified isophthalic acid (PIA), 1298.3 g of isononyl alcohol (INA) (PIA: INA) were added to a four-liter three liter reactor equipped with a stirrer, a condenser, a decanter, a reflux pump, 1.54 g (0.31 part by weight with respect to 100 parts by weight of PIA) of a titanium-based catalyst (TIPT, tetraisopropyl titanate) was added as a catalyst and the temperature was gradually raised to about 170 占 폚. Generated water began to be generated at about 170 ° C. The esterification reaction was continued for about 4.5 hours while the nitrogen gas was continuously supplied at a reaction temperature of about 220 ° C and at normal pressure. When the acid value reached 0.01, the reaction was terminated.

After completion of the reaction, distillation extraction is carried out under reduced pressure for 0.5 to 4 hours in order to remove unreacted raw materials. Steam extraction is carried out under reduced pressure for 0.5 to 3 hours using steam to remove unreacted raw materials to a certain level or lower, the reaction liquid temperature is cooled to about 90 캜, and neutralization treatment is performed using an alkali solution . Further, washing may be carried out, and then the reaction liquid is dehydrated to remove moisture. The filter material was added to the reaction liquid from which the water had been removed, stirred for a certain period of time, and filtered to obtain 1243.3 g (yield: 99.0%) of diisononyl isophthalate.

Manufacturing example  2: Diisononyl Phthalates (DINP)  Produce

Diisononylphthalate was obtained in the same manner as in Preparation Example 1, except that phthalic acid was used instead of isophthalic acid in the esterification reaction.

Example  One: Blending  Manufacturing 1

The diisononyl isophthalate prepared in Preparation Example 1 and the diisononyl phthalate prepared in Preparation Example 2 were mixed at a weight ratio of 30:70 to obtain a plasticizer composition.

Example  2: Blending  Manufacturing 2

The diisononyl isophthalate prepared in Preparation Example 1 and the diisononyl phthalate prepared in Preparation Example 2 were mixed at a weight ratio of 50:50 to obtain a plasticizer composition.

Example  3: Blending  Manufacturing 3

The diisononyl isophthalate prepared in Preparation Example 1 and the diisononyl phthalate prepared in Preparation Example 2 were mixed at a weight ratio of 70:30 to obtain a plasticizer composition.

Example  4: Blending  Manufacturing 4

The diisononyl isophthalate prepared in Preparation Example 1 and the diisononyl phthalate prepared in Preparation Example 2 were mixed at a weight ratio of 90:10 to obtain a plasticizer composition.

Comparative Example  One

DINIP prepared in Preparation Example 1 was used alone as a plasticizer.

Comparative Example  2

DINP prepared in Preparation Example 2 was used alone as a plasticizer.

Comparative Example  3

DIDP sold as a commercial product as a plasticizer was used alone.

Experimental Example  One: Compound  Production and performance evaluation

With reference to ASTM D638, the plasticizer compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were respectively prepared as test specimens through the following methods.

50 parts by weight of the plasticizer composition prepared in the above Examples and Comparative Examples, 5 parts by weight of RUP 144 (Adeka Korea) as an additive, 5 parts by weight of Omya 1T (Omiya) as an additive were added to 100 parts by weight of a polyvinyl chloride resin (PVC (LS100) And 0.3 phr of St-A (di-isocyanurate) were mixed and mixed at 1300 rpm at 100 占 폚. The specimens were processed at 175 ° C for 4 minutes using a roll mill and at a temperature of 185 ° C for 3 minutes (low pressure) and 2 minutes 30 seconds (high pressure) using a press, Respectively.

The specimens were subjected to hardness, tensile strength, elongation rate, sheet heating loss, accelerated weathering (QUV), stress and fusion test in the following manner. Table 1 shows the results of the performance evaluation of each of the test specimens.

<Property Test Items>

Hardness measurement

ASTM D2240 was used to measure the shore hardness, 3T 10s, at 25 占 폚.

The tensile strength tensile strength measurement

A cross head speed was pulled at 200 mm / min (1T) using a UTM (manufacturer; Instron, model name: 4466) according to the ASTM D638 method, and the point at which the specimen was cut was measured . The tensile strength was calculated as follows:

Tensile strength (kgf / cm ² ) = load value (kgf) / thickness (cm) x width (cm)

Elongation elongation rate

After pulling the cross head speed at 200 mm / min (1T) using the U.TM according to the ASTM D638 method, the point at which the specimen was cut was measured and the elongation was calculated as follows:

Elongation (%) = length after elongation / initial length x 100.

Measurement of migration loss

Test specimens having a thickness of 2 mm or more were obtained in accordance with KSM-3156. PS plates were attached to both surfaces of the test pieces, and a load of 1 kgf / cm ² was applied. The specimens were left in a hot air circulating oven (80 ° C) for 72 hours, taken out and cooled at room temperature for 4 hours. After removing the PS attached to both sides of the test piece, weights were measured before and after leaving in the oven, and the amount of loss of migration was calculated by the following equation.

(%) = (Initial weight of test piece at normal temperature-weight of test piece after leaving oven) / initial weight of test piece at room temperature} x 100

Sheet heating volatile loss measurement

The prepared specimens were worked at 100 DEG C for 168 hours, and then the specimens were weighed.

Weight loss (weight%) = initial specimen weight - (100 ℃, weight of the specimen after 168 hours of operation) / initial specimen weight × 100.

Claims (11)

Isophthalate-based compounds; And a diisononyl phthalate,
Wherein the weight ratio of the isophthalate compound to the diisononyl phthalate is from 1:99 to 99: 1.
The method according to claim 1,
Wherein the weight ratio of the isophthalate compound to the diisononyl phthalate is from 1:99 to 7: 3.
3. The method of claim 2,
Wherein the weight ratio of the isophthalate compound to the diisononyl phthalate is from 1:99 to 5: 5.
4. The method according to any one of claims 1 to 3,
Wherein the isophthalate compound has an independently selected end group among the alkyl groups having 1 to 12 carbon atoms.
4. The method according to any one of claims 1 to 3,
Wherein the isophthalate compound comprises a compound represented by the following general formula (1).
[Chemical Formula 1]

The method according to claim 1,
The plasticizer composition further comprises an additive,
Wherein the additive is contained in an amount of 1 to 30 parts by weight based on 100 parts by weight of the isophthalate-based compound.
The method according to claim 6,
The additive may be selected from the group consisting of di-2-propylheptyl phthalate, diisodecyl phthalate, pyrolytic carbon, epoxy fatty acid methyl ester (eFAME), acetyl tributyl citrate (ATBC), tributyl citrate (TBC) Wherein the plasticizer composition comprises at least one selected from the group consisting of terephthalate (TOM) and dioctyl adipate (DOA).
Preparing an isophthalate-based compound and diisononyl phthalate; And
And mixing the isophthalate compound and the diisononyl phthalate in a weight ratio of 1:99 to 99: 1 to obtain the plasticizer composition of claim 1.
Based on 100 parts by weight of at least one resin selected from the group consisting of ethylene-vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane and thermoplastic elastomer,
A resin composition comprising 5 to 150 parts by weight of the plasticizer composition of claim 1.
10. The method of claim 9,
Wherein the resin composition is applied in a compound formulation or a sheet formulation.
10. The method of claim 9,
Wherein the resin composition is applied to the production of at least one selected from the group consisting of electric wire, flooring, automobile interior material, film, sheet, wallpaper and tube.