KR20180079152A - Plasticizer composition comprising naturally cardanol base plasticizer and vegetable oil base epoxidated, and polymer resin composition comprising the same - Google Patents

Abstract

The present invention relates to a plasticizer composition including a natural cardanol plasticizer and a vegetable epoxy plasticizer, and a polymer resin composition including the same. According to the present invention, a natural cardanol eco-friendly plasticizer is manufactured with cardanol derived from cashew nut shell liquid (CNSL), and thus, the eco-friendly plasticizer generates less endocrine disrupter than a conventional oil-based phthalate plasticizer. Moreover, mixed with a vegetable epoxy plasticizer, a phthalate-free plasticizer improves basic plasticizing performance such as tensile strength and elongation as well as improving matter properties of a polymer resin product such as thermal reducibility, elongation, aging-resistance, and transmission-resistance when applied to polymer resin such as PVC. As such, the present invention is capable of providing a safe plasticizer in terms of health and environment.

Description

[0001] The present invention relates to a plasticizer composition comprising a natural cardanol-based plasticizer and a vegetable oil-based epoxidizing plasticizer, and a polymeric resin composition comprising the same,

The present invention relates to a plasticizer composition comprising a natural cardanol-based plasticizer and a vegetable oil-based epoxidizing plasticizer, and a polymer resin composition containing the same.

In general, plastic products such as polyethylene, polystyrene, polypropylene and polyvinyl chloride (PVC) are used in various fields such as food packaging, building materials or household appliances, and are indispensable plastic products in daily life.

In particular, PVC is a hard plastic that is difficult to process, and plasticizers are used as an essential additive to improve processability by imparting flexibility when processing. Although various compounds are known as plasticizers that are added to exert such flexibility, most of the plasticizers currently used in the industry are plasticizers such as petroleum phthalate (DOP, DINP, DBP), adipic acid (DINA, DOA, etc.) It is a plasticizer. Such plasticizers are organic ester compounds obtained through the esterification reaction of carboxylic acid and alcohol and are added to thermoplastic such as sheet, PVC film, electric wire and the like to facilitate molding at high temperature, and flexibility, heat resistance, Characteristics and so on. The most commonly used phthalate plasticizers account for 92% of the global plasticizer market, and are mainly used as additives for improving flexibility, durability and cold resistance of PVC and improving processability by lowering the viscosity during melting. From hard products such as hard pipes to soft products that grow smoothly and can be used for food packaging materials, blood bags, flooring materials, etc., they are more closely related to real life than any other materials and are widely used for direct contact with human body. .

However, phthalate plasticizers have good plasticizing effect, but they are endocrine disruptors that cause liver, kidney disorder, and reproductive anomalies. That is, the phthalate plasticizer is easily eluted during use and is pointed out as a cause of environmental hormones and carcinogens, and abnormal symptoms occur in the body. In recent years, the use of phthalate plasticizers has been regulated mainly in EU and the like. In the case of plastics and children's toys especially used in kitchens, phthalate plasticizers are very likely to enter the human body directly. Therefore, even if plastic or plasticizers are used without using plasticizers, the direction of using plastics manufactured using harmless substances .

Due to the prohibition of use of phthalate plasticizers for PVC wraps, patient fluid packs, and children's toys, domestic and overseas plasticizer manufacturers such as BASF, ExxonMobil, Eastman, Ferro, Teknor Apex and Aekyung oil are actively involved in research and development of nonphthalate environmentally friendly plasticizers It is coming out. Although phthalate plasticizers are the most widely used chemicals in the world, the EU and environmental groups recently pointed out environmental and health concerns that the use of phthalate plasticizers is prohibited in the case of exposure to phthalate plasticizers, , And this tendency is spreading all over the world.

Thus, phthalate-free environmentally friendly plasticizers that provide the same properties when added to polymeric resins such as vinyl polymers, polyurethanes, polyvinyl chloride (PVC), and acrylic replace the phthalate plasticizers that are negative for environment and health. The environmentally friendly plasticizer developed by many researchers is environmentally friendly, but due to structural limitations, physical properties are worse than phthalate plasticizers, and the light resistance required in compound formulations, or viscosity required in sheet formulations, bleeding phenomena, It is necessary to improve the physical properties.

On the other hand, in order to produce flooring, wallpaper, and sheet products that require lightfastness as a physical property, a suitable plasticizer should be used in consideration of discoloration. In the case of a PVC compound for wallpaper or sheet, tensile strength, elongation, A plasticizer, a filler, a stabilizer, a viscosity reducing agent, a dispersant, a defoaming agent, a foaming agent and the like are added to the PVC resin in accordance with light fastness, bleeding phenomenon and geling property.

For example, when dioctyl terephthalate, which is low in cost, is used among environmentally friendly plasticizers applicable to PVC, bleeding phenomenon is observed not only because of high viscosity and relatively slow absorption rate of plasticizer, Gelling ability is also not excellent. There is also controversy as to whether it is appropriate to include in the category of environmentally friendly plasticizer in terms of whether terephthalate is a modification of phthalate.

Therefore, in order to cope with environmental hormone problems and environmental regulation due to phthalate plasticizer leakage, many researchers have developed a novel nonphthalate-based plasticizer which is free of phthalic anhydride used in the production of phthalate plasticizers or inhibited the outflow of phthalate plasticizers The research is proceeding to develop a spill suppression technology that can significantly reduce human risks and meet environmental standards.

In the existing nonphthalate substitute plasticizer research, in Patent Document 1, soft polyvinyl chloride was produced by using a linear structure aliphatic polyester compound. The linear structural aliphatic polyester compound is known to be capable of imparting excellent ductility without any possibility of leakage when used as a PVC plasticizer. However, it is well known that the terminal hydroxyl groups of the above linear structure aliphatic polyester compounds are capable of decomposing polyester compounds or promoting hydrolysis by backbiting the carbonyl groups of the main chain. In addition, for the production of a linear structural aliphatic polyester compound, a step of precipitating with cold methanol after the chemical reaction and filtering is required. This is due to the economic burden due to the use of a large amount of organic solvent and environmental pollution such as being thrown away into wastewater, and it is known that the process of precipitation, filtration, washing and drying is prolonged and economic efficiency is problematic. As a result, the polyvinyl chloride produced by using the linear structure aliphatic polyester compound is easily decomposed and discolored by heat, and lacks in economy, commerciality and environment friendliness.

In addition, plant-based epoxidized plasticizers, which are currently used as plasticizers for heat stabilizers, have poor compatibility with PVC and the like in spite of being environmentally friendly and excellent in thermal stability, and thus have limited properties in order to replace phthalate plasticizers.

Accordingly, a technical problem to be solved by the present invention is a natural-based cardanol-based environmentally friendly plasticizer for use in the production of a polymer resin such as PVC, which has a sufficiently large molecular weight and excellent compatibility with a polymer resin, Of course, it is a plasticizer composition having excellent physical properties such as heat resistance and light resistance by being mixed with plant-based epoxidizing plasticizer. Accordingly, in order to produce a natural resin-based polymer resin plasticizer, CNSL (Cashew nut shell liquid) is used as a raw material, and the cardanol contained therein is extracted and purified, and acetylation reaction and epoxidation reaction are continuously carried out, The inventors of the present invention have completed the present invention by confirming that the synergistic effect is improved when the eco-friendly plasticizer derived from danol is economically produced and added to the polymer resin to improve the plasticizing performance of the polymer resin and when used in combination with the plant-based epoxidizing plasticizer.

Korean Patent Publication No. 10-2004-0057792

It is an object of the present invention to provide a plasticizer composition comprising a natural cardanol-based environmentally friendly plasticizer and a vegetable oil-based epoxidizing plasticizer, wherein the plasticizer composition containing plant-based epoxidizing plasticizer in a specific wt% range is significantly improved will be.

Another object of the present invention is to provide a polymer resin composition comprising the above plasticizer composition and a polymer resin, and having remarkably excellent light resistance, solvent resistance, and plasticity.

It is still another object of the present invention to provide a polymer film comprising the polymer resin composition.

In order to achieve the above object,

The present invention relates to an acetylated cardanol plasticizer or an acetylated epoxycadanol plasticizer; And an epoxidized vegetable oil, said plasticizer composition comprising:

Wherein the epoxidized vegetable oil comprises 3 to 70 wt% of the acetylated cardanol plasticizer or acetylated epoxycadanol plasticizer in an amount of 3 to 70 wt% based on 100 wt% of the total plasticizer composition. do.

The present invention also provides a polymer resin composition comprising the vinyl chloride resin composition described above.

Further, the present invention provides a polymer film comprising the above polymer resin composition.

Since the natural-based cardanol-based environmentally friendly plasticizer according to the present invention is produced by using CNSL (Cashew nut shell liquid) -derived cardanol, an eco-friendly plasticizer that does not induce environmental hormone, which is an endocrine disruptor, to be. In addition, when mixed with plant-based epoxidizing plasticizer, not only basic plasticizability such as tensile strength and elongation but also physical properties such as heat loss, aging resistance and anti-skid property of polymeric resin molding are improved when applied to polymeric resin such as PVC, Especially, the phthalate-free plasticizer which is remarkably improved by the addition of the plant-based epoxidized plasticizer in the specific wt% range of the plasticization efficiency (%), which is the most important characteristic as the plasticizer, is prepared and the effect of providing a safe plasticizer in terms of health and environment have.

1 is a graph showing a result of confirming a crystalline / amorphous region ratio through a Fourier transform infrared spectroscope.

Hereinafter, the present invention will be described in detail.

The present invention relates to an acetylated cardanol plasticizer or an acetylated epoxycadanol plasticizer; And an epoxidized vegetable oil, said plasticizer composition comprising:

Wherein the epoxidized vegetable oil comprises 3 to 70 wt% of the acetylated cardanol plasticizer or acetylated epoxycadanol plasticizer in an amount of 3 to 70 wt% based on 100 wt% of the total plasticizer composition. , And the plasticizer composition is preferably used for a vinyl chloride-based polymer.

Herein, the acetylated cardanol-based plasticizer or the acetylated epoxy-based plasticizer may be prepared from CNSL (Cashew nut shell liquid). Cashew nut shell liquid (CNSL) is obtained from the nuts of open cashew nut trees grown in temperate tropical or sub-tropical frost-free conditions.

You can get cashew nuts by roasting a hard shell and then taking out the pellets. The shell, which was wrapped around the cashew nuts used for edible purposes, is called a cashew shell shell, and its thickness is about 3 mm. It is a combo structure containing vegetable oil with a dark brown viscosity. The cashew nut shell contains about 30% to 35% of an aliphatic hydrocarbon-based vegetable oil having a long alkyl chain having a plurality of intramolecular double bonds in the phenol molecular structure, and the oil obtained from the cashew nut shell is a cashew nut shell oil (CNSL) to be. CNSL is a natural non-edible oil extracted from cashew nuts shell. It has chemical resistance, water resistance and flexibility. Basic physical and chemical properties of CNSL are as follows.

Cardanol is an oil obtained by refining CNSL. It is a natural biomaterial with chemical resistance, water resistance and flexibility. Its main component is cardanol, which has the following structure,

The basic physicochemical properties are as follows but are not limited thereto.

The natural cardanol eco-plasticizer of the present invention is represented by the following formula,

This is prepared by subjecting an acetylated cardanol of the following general formula which is produced by reacting with high purity cadanol and acetic anhydride to an epoxy reaction.

In addition, an eco-friendly process for continuously epoxidizing acetic acid, which is a by-product in the production of acetanized cardanol, without further purification, when preparing the natural-based cardanol eco-plasticizer.

On the other hand, the acetylated cardanol plasticizer or the acetylated epoxycananol plasticizer is characterized by containing a compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

R ¹ is a linear or branched alkyl of C _1-10; And

R ² is a hydrocarbon having from 15 to 17 carbon atoms, with or without one or more epoxy groups and containing from 0 to 3 double bonds;

Preferably,

R < ¹ > is methyl; And

이다.R ² is

to be.

The oil may be an epoxidized oil of one or more of soybean oil, rape oil, sunflower oil, palm oil, corn oil, cottonseed oil, castor oil, jatropha oil, coconut oil, palm kernel oil and waste cooking oil thereof. no.

Further, the epoxidized vegetable oil may be contained in an amount of 3 to 70 wt%, more preferably 3 to 62.5 wt%, and 5 to 70 wt%, based on 100 wt% of the total amount of the plasticizer composition, , May be included in an amount of 5 to 62.5 wt%, may be contained in an amount of 10 to 50 wt%, may be included in an amount of 12.5 to 37.5 wt%, may be included in an amount of 16.7 to 37.5 wt%, and may be contained in an amount of 25.0 to 37.5 wt %. ≪ / RTI > Wherein the remainder of the plasticizer composition is the acetylated cardanol plasticizer or the acetylated epoxy caranol plasticizer.

If the epoxidized vegetable oil is contained in an amount of less than 3 wt% based on 100 wt% of the plasticizer composition, the plasticizing efficiency, which is the most important factor of the characteristics of the plasticizer, can not be significantly improved If it is contained in an amount exceeding 70 wt%, the plasticizing efficiency is lowered.

The present invention also relates to a vinyl chloride resin; And

And a polymeric resin composition comprising the plasticizer composition.

The polymer resin composition according to the present invention is prepared by mixing with the above plasticizer composition. The plasticizer composition can be remarkably improved in hardness and elongation at the time of production of the polymer resin compound or sheet than when the plasticizer components are used alone, which can be advantageous for the productivity and workability of the product, and the plasticizing efficiency can be improved. The increase in heat transfer and heat loss can be a fatal flaw in the processability and long-term stability of the final product. In particular, an increase in heating loss may mean that the amount of plasticizer present in the interior decreases. On the other hand, the vinyl chloride resin is preferably polyvinyl chloride (PVC).

The polymeric resin composition may include 1 to 100 parts by weight, 10 to 90 parts by weight, and 20 to 80 parts by weight of the plasticizer composition, based on 100 parts by weight of the vinyl chloride resin. To 70 parts by weight, and may be 32.5 to 60 parts by weight, but not limited thereto.

Further, the present invention provides a polymer film comprising the above polymer resin composition.

The eco-friendly plasticizer, which is a mixture of cardanol eco-plasticizer and plant-based epoxy compound, prepared by the manufacturing method according to the present invention, has a good compatibility with environmental and harmless core materials, environmental compatibility and biocompatibility for elimination of phthalate compounds as an endocrine disruptor Having a large molecular weight and having a large number of carbonyl groups capable of strongly interacting with the polymer resin chain, has excellent compatibility with the polymer resin and a binding force to prevent outflow to the outside of the polymer resin.

In addition, environment-friendly plasticizer mixed with cardanol eco-plasticizer and vegetable oil-based epoxy compound exhibits a three-dimensional structure, and when compared with general linear structure of the same molecular weight, chain entanglement is eliminated, small hydrodynamic volume, Thereby giving excellent softness to the resin. From the stabilization of the oxirane group contained in the plasticizer, the environmentally friendly substitute plasticizer has heat resistance and light resistance that are not readily decomposed or discolored by heat. In addition, it is possible to manufacture environmentally friendly alternative plasticizers of CARADON, which have economic, commercial and eco-friendly economic processes that are applied directly to the epoxidation reaction process without removing the acetic acid produced in the first step reaction. . Therefore, by using an environmentally-friendly substitute plasticizer which is a mixture of the cardanol ecological plasticizer and the vegetable oil-based epoxy compound of the present invention, it is possible to replace the existing plasticizers with each other to provide excellent plasticizing effect to PVC, There is an effect.

Hereinafter, the present invention will be described in detail with reference to Examples and Experimental Examples.

However, the following examples and experimental examples are intended to illustrate the present invention, but the present invention is not limited thereto.

< Manufacturing example  1> Acetylation Cardanol  Preparation of plasticizers ( CARDANOL -Ac)

Cathanol (BC-C-100) and acetic anhydride were added to a three-necked reactor equipped with a thermometer, a condenser, and the mixture was stirred at 100 ° C. After stirring, the mixture was cooled to room temperature, and unreacted acetic anhydride and acetic acid produced were vacuum distilled under vacuum to prepare a compound represented by the following formula (CARDANOL-Ac).

¹ H-NMR analysis: The cadanol-OH proton peak (? 4.7 ppm) disappeared, and the acetyl proton peak (? 2.3 ppm) of acetylated cardanol was newly appeared; FT-IR analysis: the car danol -OH peak (i 3400cm ^{- 1)} will disappear, and the newly found ester peak (1770cm ^-1 i) the acetylation car danol.

< Manufacturing example  2> Acetylation  Epoxy Cardanol  Preparation of plasticizers ( CARDANOL -Ac- Ep )

The acetylated cardanol plasticizer (CARDANOL-Ac) prepared in Preparation Example 1 was added to a 2-neck reactor and stirred in an ice bath. H ₂ O ₂ was dropwise added dropwise for 1 hour, heated to 60 ° C and stirred for 3 hours to prepare a compound represented by the following formula (CARDANOL-Ac-Ep).

¹ H-NMR analysis: The unsaturated proton peak (δ 5-6 ppm) of the acetylated cardanol disappeared and the epoxide proton peak (δ 2.8-3.2 ppm) of the epoxidized acetylated cardanol remained fresh; FT-IR analysis: A peak (i 950 cm ^-1 ) due to the epoxy group appeared newly.

< Example  1> Acetylation  Epoxy Cardanol  Plasticizer ( CARDANOL -Ac- Ep ) And epoxidation expression Production of PVC film using oil-based oil 1

PVC film was prepared by solvent-casting method.

More specifically, 30 parts by weight of the acetylated epoxycadanol plasticizer (CARDANOL-Ac-Ep) prepared in Preparation Example 2 and 2.5 parts by weight of epoxidized soybean oil (ESBO) were added to 100 parts by weight of the PVC resin, % (w / v) solution. The mixture was stirred for 3 hours or more until completely dissolved, and then poured into a PFA (Perfluoroalkoxy) Petri dish and dried at room temperature for 72 hours and in a vacuum oven at 80 ° C for 72 hours.

< Example  2> Acetylation  Epoxy Cardanol  Plasticizer ( CARDANOL -Ac- Ep ) And epoxidation expression Production of PVC film using oil-based oil 2

Except that 30 parts by weight of the acetylated epoxycadanol plasticizer (CARDANOL-Ac-Ep) prepared in Preparation Example 2 and 5 parts by weight of epoxidized soybean oil (ESBO) were used for 100 parts by weight of the PVC resin in Example 1 And the same procedure as in Example 1 was carried out to prepare a PVC film.

< Example  3> Acetylation  Epoxy Cardanol  Plasticizer ( CARDANOL -Ac- Ep ) And epoxidation Plant flow  Manufacture of PVC film using oil 3

Except that 30 parts by weight of the acetylated epoxycadanol plasticizer (CARDANOL-Ac-Ep) prepared in Preparation Example 2 and 10 parts by weight of epoxidized soybean oil (ESBO) were used for 100 parts by weight of the PVC resin in Example 1 And the same procedure as in Example 1 was carried out to prepare a PVC film.

< Example  4> Acetylation  Epoxy Cardanol  Plasticizer ( CARDANOL -Ac- Ep ) And epoxidation expression Manufacture of PVC film using water-based oil 4

Except that 50 parts by weight of the acetylated epoxycadanol plasticizer (CARDANOL-Ac-Ep) prepared in Preparation Example 2 and 2.5 parts by weight of epoxidized soybean oil (ESBO) were used for 100 parts by weight of the PVC resin in Example 1 And the same procedure as in Example 1 was carried out to prepare a PVC film.

< Example  5> Acetylation  Epoxy Cardanol  Plasticizer ( CARDANOL -Ac- Ep ) And epoxidation Plant flow  Manufacture of PVC film using oil 5

Except that 50 parts by weight of the acetylated epoxycadanol plasticizer (CARDANOL-Ac-Ep) prepared in Preparation Example 2 and 5 parts by weight of the epoxidized soybean oil (ESBO) were used for 100 parts by weight of the PVC resin in Example 1 And the same procedure as in Example 1 was carried out to prepare a PVC film.

< Example  6> Acetylation  Epoxy Cardanol  Plasticizer ( CARDANOL -Ac- Ep ) And epoxidation Plant flow  PVC film production using oil 6

Except that 50 parts by weight of the acetylated epoxycadanol plasticizer (CARDANOL-Ac-Ep) prepared in Preparation Example 2 and 10 parts by weight of epoxidized soybean oil (ESBO) were used for 100 parts by weight of the PVC resin in Example 1 And the same procedure as in Example 1 was carried out to prepare a PVC film.

< Example  7> Acetylation Cardanol  Plasticizer ( CARDANOL -Ac) and epoxidation Plant flow  Production of PVC film using oil 1

(W / v) solution in chloroform using 30 parts by weight of acetylated cardanol plasticizer (CARDANOL-Ac) prepared in Preparation Example 1 and 2.5 parts by weight of epoxidized soybean oil (ESBO) . The mixture was stirred for 3 hours or more until completely dissolved, and then poured into a PFA (Perfluoroalkoxy) Petri dish and dried at room temperature for 72 hours and in a vacuum oven at 80 ° C for 72 hours.

< Example  8> Acetylation Cardanol  Plasticizer ( CARDANOL -Ac) and epoxidation Plant flow  PVC film production using oil 2

Except that 30 parts by weight of the acetylated cardanol plasticizer (CARDANOL-Ac) prepared in Preparation Example 1 and 5 parts by weight of the epoxidized soybean oil (ESBO) were added to 100 parts by weight of the PVC resin in Example 7, The same procedure as in Example 7 was followed to prepare a PVC film.

< Example  9> Acetylation Cardanol  Plasticizer ( CARDANOL -Ac) and epoxidation Plant flow  Manufacture of PVC film using oil 3

Except that 30 parts by weight of the acetylated cardanol plasticizer (CARDANOL-Ac) prepared in Preparation Example 1 and 10 parts by weight of the epoxidized soybean oil (ESBO) were added to 100 parts by weight of the PVC resin in Example 7, The same procedure as in Example 7 was followed to prepare a PVC film.

< Example  10> Acetylation Cardanol  Plasticizer ( CARDANOL -Ac) and epoxidation Plant flow  Manufacture of PVC film using oil 4

Except that 50 parts by weight of acetylated cardanol plasticizer (CARDANOL-Ac) prepared in Preparation Example 1 and 2.5 parts by weight of epoxidized soybean oil (ESBO) were used per 100 parts by weight of PVC resin in Example 7, The same procedure as in Example 7 was followed to prepare a PVC film.

< Example  11> Acetylation Cardanol  Plasticizer ( CARDANOL -Ac) and epoxidation Plant flow  Manufacture of PVC film using oil 5

Except that 50 parts by weight of the acetylated cardanol plasticizer (CARDANOL-Ac) prepared in Preparation Example 1 and 5 parts by weight of the epoxidized soybean oil (ESBO) were used per 100 parts by weight of the PVC resin in Example 7, The same procedure as in Example 7 was followed to prepare a PVC film.

< Example  12> Acetylation Cardanol  Plasticizer ( CARDANOL -Ac) and epoxidation Plant flow  PVC film production using oil 6

Except that 50 parts by weight of acetylated cardanol plasticizer (CARDANOL-Ac) prepared in Preparation Example 1 and 10 parts by weight of epoxidized soybean oil (ESBO) were used per 100 parts by weight of the PVC resin in Example 7, The same procedure as in Example 7 was followed to prepare a PVC film.

< Comparative Example  1> Acetylation  Epoxy Cardanol  Plasticizer ( CARDANOL -Ac- Ep ) Alone as PVC film production 1

A 5% (w / v) solution was prepared in chloroform using 30 parts by weight of the acetylated epoxycadanol plasticizer (CARDANOL-Ac-Ep) prepared in Preparation Example 2 per 100 parts by weight of the PVC resin. The mixture was stirred for 3 hours or more until completely dissolved, and then poured into a PFA (Perfluoroalkoxy) Petri dish and dried at room temperature for 72 hours and in a vacuum oven at 80 ° C for 72 hours.

< Comparative Example  2> Acetylation  Epoxy Cardanol  Plasticizer ( CARDANOL -Ac- Ep ) Alone as PVC film production 2

A 5% (w / v) solution was prepared in chloroform using 50 parts by weight of the acetylated epoxycadanol plasticizer (CARDANOL-Ac-Ep) prepared in Preparation Example 2 per 100 parts by weight of the PVC resin. The mixture was stirred for 3 hours or more until completely dissolved, and then poured into a PFA (Perfluoroalkoxy) Petri dish and dried at room temperature for 72 hours and in a vacuum oven at 80 ° C for 72 hours.

< Comparative Example  3> Acetylation Cardanol  Plasticizer ( CARDANOL -Ac) was used alone.

A 5% (w / v) solution was prepared in chloroform using 30 parts by weight of the acetylated cardanol plasticizer (CARDANOL-Ac) prepared in Preparation Example 1 per 100 parts by weight of the PVC resin. The mixture was stirred for 3 hours or more until completely dissolved, and then poured into a PFA (Perfluoroalkoxy) Petri dish and dried at room temperature for 72 hours and in a vacuum oven at 80 ° C for 72 hours.

< Comparative Example  4> Acetylation Cardanol  Plasticizer ( CARDANOL -Ac) alone for PVC film production 2

A 5% (w / v) solution was prepared in chloroform using 50 parts by weight of the acetylated cardanol plasticizer (CARDANOL-Ac) prepared in Preparation Example 1 per 100 parts by weight of the PVC resin. The mixture was stirred for 3 hours or more until completely dissolved, and then poured into a PFA (Perfluoroalkoxy) Petri dish and dried at room temperature for 72 hours and in a vacuum oven at 80 ° C for 72 hours.

< Comparative Example  5> Preparation of PVC film without added plasticizer

A PVC film was prepared using PVC resin.

< Comparative Example  6> DOP  Manufacture of PVC film using plasticizer alone

A 5% (w / v) solution was prepared in chloroform using 30 parts by weight of a commercially available DOP (Dioctyl phthalate) plasticizer for 100 parts by weight of PVC resin. The mixture was stirred for 3 hours or more until completely dissolved, and then poured into a PFA (Perfluoroalkoxy) Petri dish and dried at room temperature for 72 hours and in a vacuum oven at 80 ° C for 72 hours.

< Comparative Example  7> ESBO  Manufacture of PVC film used alone

A 5% (w / v) solution was prepared in chloroform using 30 parts by weight of epoxidized soybean oil (ESBO) commercially available on the market for 100 parts by weight of PVC resin. The mixture was stirred for 3 hours or more until completely dissolved, and then poured into a PFA (Perfluoroalkoxy) Petri dish and dried at room temperature for 72 hours and in a vacuum oven at 80 ° C for 72 hours.

< Comparative Example  8> DOP  Plasticizers and ESBO  Manufacture of used PVC film

A 5% (w / v) solution was prepared in chloroform using 30 parts by weight of commercially available DOP plasticizer and 5 parts by weight of epoxidized soybean oil oil (ESBO) per 100 parts by weight of PVC resin. The mixture was stirred for 3 hours or more until completely dissolved, and then poured into a PFA (Perfluoroalkoxy) Petri dish and dried at room temperature for 72 hours and in a vacuum oven at 80 ° C for 72 hours.

< Comparative Example  9> DOP  Manufacture of PVC film using plasticizer alone

A 5% (w / v) solution was prepared in chloroform using 50 parts by weight of a commercially available DOP (Dioctyl phthalate) plasticizer for 100 parts by weight of PVC resin. The mixture was stirred for 3 hours or more until completely dissolved, and then poured into a PFA (Perfluoroalkoxy) Petri dish and dried at room temperature for 72 hours and in a vacuum oven at 80 ° C for 72 hours.

< Comparative Example  10> ESBO  Manufacture of PVC film used alone

A 5% (w / v) solution was prepared in chloroform using 50 parts by weight of epoxidized soybean oil (ESBO) commercially available on the market for 100 parts by weight of PVC resin. The mixture was stirred for 3 hours or more until completely dissolved, and then poured into a PFA (Perfluoroalkoxy) Petri dish and dried at room temperature for 72 hours and in a vacuum oven at 80 ° C for 72 hours.

< Comparative Example  11> DOP  Plasticizers and ESBO  Manufacture of used PVC film

A 5% (w / v) solution was prepared in chloroform using 50 parts by weight of commercially available DOP plasticizer and 5 parts by weight of epoxidized soybean oil (ESBO) for 100 parts by weight of PVC resin. The mixture was stirred for 3 hours or more until completely dissolved, and then poured into a PFA (Perfluoroalkoxy) Petri dish and dried at room temperature for 72 hours and in a vacuum oven at 80 ° C for 72 hours.

< Experimental Example  1> Evaluation of Mechanical Properties of PVC Film

In order to measure the tensile strength and elongation of the PVC films prepared in Examples 1 to 12 and Comparative Examples 1 to 11, the following experiment was conducted.

More specifically, microtensile bars (ASTM D1708) were fabricated and QURO's universal testing machine (UTM, QRS-S11H) was used. And analyzed at a rate of 10 mm / min using a 100 N load cell at room temperature.

Dynamic mechanical properties were measured by heating a rectangular specimen (7.5 mm × 5.3 mm × 0.30 mm) at -100 ° C to 150 ° C at a rate of 3 ° C / min using a Q-800 dynamic mechanical analyzer from TA.

The dissolution stability of the plasticizer was measured according to ASTM D1239 (Resistance of Plastic Films to Extraction by Chemicals). The PVC film was cut into a square shape (50 mm × 50 mm × 0.30 mm), placed in 500 ml of tertiary distilled water, and stored at 23 ± 2 ° C. and 50 ± 5% relative humidity for 24 hours. After the test, the specimen was completely dried in a vacuum oven at 80 ° C and the weight change was measured.

The initial weight (W ₁ ) was measured to 4 decimal places for each specimen. The specimen was taken out of the oven at 80 ° C with a clamp, and after 72 hours, the specimen was taken out and stored for 4 hours or more in a thermostatic chamber. The specimen weight (W ₂ ) was measured and the heating loss was calculated using the following equation.

[Equation 1]

Weight loss (%) = (W ₁ - W ₂ / W ₁ ) × 100

(In the above formula (1)

W ₁ is the film weight before the test, and W ₂ is the film weight after the test).

The results are shown in Table 1 below.

Experimental group
(Parts by weight, phr) Stress
(MPa) Strain
(%) Tg
(° C) Inner planet
(%) Heat loss
(%) Example 1
(CARDANOL-Ac-Ep / ESBO = 30 / 2.5) 23.9 ± 0.5 549 ± 24 43.2 1.9 ± 0.2 2.0 Example 2
(CARDANOL-Ac-Ep / ESBO = 30/5) 26.0 ± 0.7 548 ± 26 43.5 1.8 ± 0.2 1.5 Example 3
(CARDANOL-Ac-Ep / ESBO = 30/10) 25.5 ± 0.7 544 ± 26 43.6 1.6 ± 0.2 0.8 Example 4
(CARDANOL-Ac-Ep / ESBO = 50 / 2.5) 19.0 ± 0.6 803 ± 10 26.8 2.0 ± 0.2 0.4 Example 5
(CARDANOL-Ac-Ep / ESBO = 50/5) 19.4 ± 0.3 795 ± 9 26.9 1.9 ± 0.2 0.4 Example 6
(CARDANOL-Ac-Ep / ESBO = 50/10) 19.0 ± 1.2 793 ± 16 27.2 1.8 ± 0.2 0.3 Example 7
(CARDANOL-Ac / ESBO = 30 / 2.5) 24.2 ± 1 518 ± 11 57.3 8.3 ± 0.5 3.1 Example 8
(CARDANOL-Ac / ESBO = 30/5) 26.9 ± 0.9 512 ± 10 57.1 8.0 ± 0.5 1.7 Example 9
(CARDANOL-Ac / ESBO = 30/10) 25.9 ± 1 507 ± 18 56.5 7.5 ± 0.4 0.9 Example 10
(CARDANOL-Ac / ESBO = 50 / 2.5) 19.1 ± 0.6 723 ± 10 28.3 9.2 ± 0.8 2.0 Example 11
(CARDANOL-Ac / ESBO = 50/5) 17.4 ± 0.3 715 ± 9 28.4 9.0 ± 0.8 1.2 Example 12
(CARDANOL-Ac / ESBO = 50/10) 18.0 ± 1.2 713 ± 26 29.1 8.8 ± 0.8 0.6 Comparative Example 1
(CARDANOL-Ac-Ep = 30) 25.0 ± 0.5 550 ± 20 42.8 2.0 ± 0.2 2.5 Comparative Example 2
(CARDANOL-Ac-Ep = 50) 19.5 ± 0.3 810 ± 28 26.4 2.3 ± 0.2 0.3 Comparative Example 3
(CARDANOL-Ac = 30) 25.4 ± 1.2 527 ± 20 58.4 8.5 ± 0.6 4.2 Comparative Example 4
(CARDANOL-Ac = 50) 19.1 ± 0.3 730 ± 28 27.4 9.5 ± 0.8 2.3 Comparative Example 5
(Neat PVC) 61.4 ± 0.9 24 ± 11 72.3 0 6.2 Comparative Example 6
(DOP = 30) 25.8 ± 0.7 504 ± 4 58.7 10.9 ± 4.3 3.4 Comparative Example 7
(ESBO = 30) 31.9 ± 1.6 440 ± 19 65.5 <1 0.6 Comparative Example 8
(ESBO / DOP = 5/30) 29.6 ± 1.6 485 ± 24 61.2 8.9 ± 4.3 1.5 Comparative Example 9
(DOP = 50) 17.9 ± 0.5 699 ± 20 29.2 12.9 ± 6.3 2.1 Comparative Example 10
(ESBO = 50) 22.3 ± 1.0 669 ± 14 38.8 <1 0.2 Comparative Example 11
(ESBO / DOP = 5/50) 23.0 ± 0.4 680 ± 22 33.4 9.9 ± 0.8 1.6

As shown in Table 1,

The PVC film prepared by using the cardanol plasticizer and the epoxidized vegetable oil as a plasticizer showed that the PVC film produced by using it alone as a plasticizer exhibited remarkably improved resistance to migration and heating loss.

In particular, the PVC films prepared in Examples 1 to 3 as compared with Comparative Example 1 showed significant improvements in endurance and heating loss as the weight of ESBO added as a plasticizer increased.

In addition, in the PVC films prepared in Examples 4 to 6, as compared with Comparative Example 2, the anti-planarity was remarkably improved as the weight of the ESBO added as the plasticizer increased.

Further, the PVC films prepared in Examples 7 to 9, as compared with Comparative Example 3, showed significant improvement in endurance and heat loss as the weight of ESBO added as a plasticizer increased.

In addition, in the PVC films prepared in Examples 10 to 12, as compared with Comparative Example 4, the increase in weight of ESBO added as a plasticizer significantly improved the in-plane migration and the heating loss.

From this, an acetylated cardanol plasticizer or an acetylated epoxycananol plasticizer according to the present invention; And an epoxidized vegetable oil can be used to produce a polymer film, it is possible to obtain a significantly improved durability and reduction in heating loss so that synergism can be recognized rather than when the plasticizer is used alone .

< Experimental Example  2> through crystalline / amorphous region ratios Plasticization  Efficiency evaluation

In general, plasticizers show excellent mixing with polymer resin, and when plasticized, the crystalline region decreases and the amorphous region increases. This is confirmed by Fourier Transform Infrared Spectrometer (Fourier Transform Infrared Spectrometer). Generally, the peaks showing crystallinity appear at 1427 and 636 cm ^-1 , and the peaks showing amorphousness appear at 1435 and 610 cm ^-1 . The width ratio of the peak is obtained, and as the value is smaller, the amorphous property is greater, which means that the digestion efficiency is higher.

More specifically, 50 parts by weight of a plasticizer composition comprising acetylated epoxycadanol plasticizer (CARDANOL-Ac-Ep) and epoxidized soybean oil (ESBO) prepared in Preparation Example 2 was added to 100 parts by weight of PVC resin, To prepare a 5% (w / v) solution. The mixture was stirred for 3 hours or more until completely dissolved, poured into a PFA (Perfluoroalkoxy) Petri dish and dried at room temperature for 72 hours and then in a vacuum oven at 80 ° C for 72 hours to prepare a PVC film. Then, the crystalline / amorphous area ratio was confirmed by a Fourier Transform Infrared Spectrometer (Agilent / Cary 630 FTIR spectrometer) and the plasticization efficiency was measured. The wt% ratios of the acetylated epoxycadanol plasticizer (CARDANOL-Ac-Ep) and the epoxidized soybean oil (ESBO) contained in the plasticizer composition are shown in Table 2 below.

The plasticization efficiency was calculated by calculating the ratio of crystalline / amorphous regions measured through Fourier transform infrared spectroscopy as follows.

The peak width (A _{1435, amorphous} ) appearing at the width of the peak (A _{1427, crystallinity} ) / 1435 cm ^-1 appearing at A _{1427, crystalline} / A _{1435, amorphous} = 1427 cm ^-1 ,

A _{636, deterministic} / A _{610, the amorphous} = width of the peak appearing at ₆₃₆ cm ^-1 (A _{636, crystalline)} / width of the peak (A _{610, non-crystalline)} that appears at 610 cm ^-1

A manufactured PVC film containing various proportions of epoxycadanol plasticizer (CARDANOL-Ac-Ep) and epoxidized soybean oil (ESBO) was measured and found to have a ratio of A _{1427, crystalline} / A _{1435, amorphous} and A _{636, Crystallinity} / A _{610, amorphous properties} are graphically shown in FIG.

The plasticization efficiency values in Table 2 are the values derived from the A _{1427, crystallinity} / A _{1435, amorphous} graph of FIG. 1 _, and the average values from the A _{636, crystallinity} / A _{610 and amorphous} graphs .

The crystallinity / amorphous area ratios are shown in Fig. 1, and the plasticizing efficiency values derived therefrom are shown in Table 2 below. At this time, the plasticizing efficiency measured when the acetylated epoxycadanol plasticizer (CARDANOL-Ac-Ep) prepared in Preparation Example 2 alone was used was regarded as 100%.

From 100 wt% of the plasticizer composition
Epoxidized soybean oil (ESBO) wt% Plasticization Efficiency (%) 0.0 100 5 105 10 107 12.5 108 16.7 111 25 115 37.5 114 50 110 62.5 107 75 99 87.5 96 100 92

As shown in Table 2,

When using a plasticizer composition comprising 5 to 62.5 wt% of epoxidized soybean oil (ESBO) and acetylated epoxycadanol plasticizer (CARDANOL-Ac-Ep) in an amount of 100 wt% of the plasticizer composition, plasticization Efficiency is significantly improved to such an extent that the synergy effect is recognized.

Particularly, when a plasticizer composition comprising 25 to 37.5 wt% of epoxidized soybean oil (ESBO) and acetylated epoxycadanol plasticizer (CARDANOL-Ac-Ep) is used in an amount of 100 wt% The plasticization efficiency of the resin composition was remarkably improved so that the synergy effect was recognized.

< Experimental Example  3> Evaluation of mixture by Tan delta measurement

A PVC film mixed with a phthalic acid plasticizer (DOP), a commercial plasticizer, and an epoxidation plant-based plasticizer with a cardanol plasticizer was analyzed using a dynamic mechanical analyzer (DMA, TA Instruments / Q-800 DMA). A peak is obtained when the tan delta value (loss elastic modulus / storage elastic modulus, loss modulus / storage modulus) according to temperature is expressed. The temperature range corresponding to half of the peak value is called FWHM (full width at half maximum) , The smaller the value, the better the mixing of the PVC resin and the plasticizer.

Generally, plasticizers with good mixing tend to decrease in value, and plasticizers increase in amount. The FWHM values measured when 100 parts by weight of PVC are treated with different weight parts of phthalic acid plasticizer, cardanol plasticizer and epoxidized vegetable oil plasticizer are shown in Table 3 below. The weight parts used are shown in Table 3 below.

Experimental group FWHM ¹
(° C) Experimental group FWHM ¹
(° C) Comparative Example 1
(CNSL-Ac-Ep = 30) 39 Example 1
(CNSL-Ac-Ep / ESBO = 30 / 2.5) 38 Comparative Example 2
(CNSL-Ac-Ep = 50) 41 Example 2
(CNSL-Ac-Ep / ESBO = 30/5) 35 Comparative Example 3
(CNSL-Ac = 30) 56 Example 3
(CNSL-Ac-Ep / ESBO = 30/10) 32 Comparative Example 4
(CNSL-Ac = 50) 57 Example 4
(CNSL-Ac-Ep / ESBO = 50 / 2.5) 40 Comparative Example 5
(Neat PVC) 29 Example 5
(CNSL-Ac-Ep / ESBO = 50/5) 37 Comparative Example 6
(DOP = 30) 58 Example 6
(CNSL-Ac-Ep / ESBO = 50/10) 34 Comparative Example 7
(ESBO = 30) 61 Example 7
(CNSL-Ac / ESBO = 30 / 2.5) 56 Comparative Example 8
(DOP / ESBO = 30/5) 60 Example 8
(CNSL-Ac / ESBO = 30/5) 55 Comparative Example 9
(DOP = 50) 60 Example 9
(CNSL-Ac / ESBO = 30/10) 52 Comparative Example 10
(ESBO = 50) 73 Example 10
(CNSL-Ac / ESBO = 50 / 2.5) 57 Comparative Example 11
(DOP / ESBO = 50/5) 66 Example 11
(CNSL-Ac / ESBO = 50/5) 56 Example 12
(CNSL-Ac / ESBO = 50/10) 54

¹ FWHM (full width at half maximum) Temperature range when you have half the value of Tan delta peak maximum

As shown in Table 3,

FWHM was increased by 2 and 6 ° C when phthalic acid plasticizers were mixed with epoxidized vegetable oil based plasticizers (Comparative Examples 8 and 11) when phthalic acid plasticizers alone were used (Comparative Examples 6 and 9), while camaranol plasticizers and epoxidized In the case of Example 5 in which the vegetable oil based plasticizer was mixed, it was decreased by 1 占 폚 compared to the case of the case of the cardanol plasticizer alone treatment at 4 占 폚 and that of Example 11 was lower than that of the cardanol plasticizer alone treatment. This means that the synergistic effect of the epoxidized cardanol plasticizer and the epoxidized vegetable oil plasticizer increases the mixing property when the epoxidized vegetable oil plasticizer is added.

Taking into account the results proved in Experimental Examples 1 to 3 of the present invention,

The addition of epoxidized vegetable oil to an acetylated cardanol plasticizer or an acetylated epoxycadanol plasticizer resulted in an increase in deodorant and heating loss (Table 1) and mixing properties (Table 3) in proportion to the content of epoxidation vegetable oils But,

In the plasticization efficiency (%), which is the most important factor when evaluating the performance as a plasticizer, only about 5 to 62.5 wt% of epoxidized vegetable oil based on 100 wt% of the entire plasticizer composition is sufficient to allow synergy If the plasticizing efficiency is significantly improved and the epoxidized vegetable oil is contained in an amount of less than 5 wt% or more than 62.5 wt%, the plasticizing efficiency is not improved to such an extent that synergy is recognized, or rather the unexpected effect Respectively.

Claims (10)

Acetylated cardanol plasticizers or acetylated epoxycadanol plasticizers; And an epoxidized vegetable oil, said plasticizer composition comprising:
Wherein the epoxidized vegetable oil comprises 3 to 70 wt% of the acetylated cardanol plasticizer or acetylated epoxycadanol plasticizer in an amount of 3 to 70 wt% based on 100 wt% of the total plasticizer composition.
The method according to claim 1,
Wherein the plasticizer composition is a vinyl chloride-based polymer.
The method according to claim 1,
Wherein the epoxidized vegetable oil comprises 25.0-37.5 wt% of the acetylated cardanol plasticizer or acetylated epoxycadanol plasticizer as much as 100 wt% of the total plasticizer composition.
The method according to claim 1,
Wherein the acetylated cardanol plasticizer or acetylated epoxycananol plasticizer comprises a compound represented by the following Formula 1:
[Chemical Formula 1]

(In the formula 1,
R ¹ is a linear or branched alkyl of C _1-10; And
R ² is a hydrocarbon having 15 to 17 carbon atoms, with or without an epoxy group, and containing 0 to 3 double bonds.
5. The method of claim 4,
R &lt; ¹ &gt; is methyl; And
R ² is

&Lt; / RTI &gt;
The method according to claim 1,
Wherein the oil is an epoxidized oil of at least one of soybean oil, rapeseed oil, sunflower oil, palm oil, corn oil, cottonseed oil, castor oil, jatropha oil, coconut oil, palm kernel oil and waste cooking oil thereof.
Vinyl chloride resin; And
A polymer resin composition comprising the plasticizer composition of claim 1.
8. The method of claim 7,
Wherein the vinyl chloride resin is polyvinyl chloride (PVC).
8. The method of claim 7,
Wherein the polymer resin composition comprises 1 to 100 parts by weight of the plasticizer composition of claim 1 based on 100 parts by weight of the vinyl chloride resin.
A polymer film comprising the polymer resin composition of claim 7.

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