JPH0762180A - Plasticizer and halogen-containing resin composition containing the same - Google Patents

Abstract

(57) [Summary] [Structure] In a polyester plasticizer comprising an acid component and a glycol component, an unsaturated fatty acid residue contained in the polyester is used by using animal or vegetable fats and oils or unsaturated fatty acids derived from the fats and oils. A polyester plasticizer and a halogen-containing resin composition containing the same, wherein a carbon-carbon bond between an α, β-ethylenically unsaturated compound and α-β is formed. [Effect] The polyester plasticizer of the present invention is modified by the reaction between the unsaturated group of the unsaturated fatty acid component and the α, β-ethylenically unsaturated compound, so that the polyester plasticizer of the present invention is better than conventional polyester plasticizers. In particular, low temperature flexibility and non-migration property are extremely excellent at the same time. Further, since it is improved in balance with respect to other physical properties as well, it is of great utility in the field of applied processing, not to mention the production of a plasticizer as a plasticizer for a vinyl chloride resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is characterized in that unsaturated fatty acids are used to form carbon-carbon bonds between unsaturated fatty acid residues of polyester and α, β-ethylenically unsaturated compounds. And a halogen-containing resin composition containing the same and having excellent balance in low-temperature flexibility and non-migration property.

[0002]

Polyester plasticizers are generally known to have excellent durability as polyesters obtained by reacting a dibasic acid, a glycol and optionally a monohydric alcohol or a monobasic acid. .

Therefore, halogen-containing resins such as vinyl chloride resin plasticized with polyester are widely used for various applications such as electric wire coating, automobile parts, leather, boots, gaskets and hoses. However, in these fields of application, there has been a strong demand for quality improvement, and particularly in applications such as electric wire coatings and gaskets, excellent low-temperature flexibility and non-migratory property are required, and conventional plasticizers are difficult to meet.

In order to improve the low temperature flexibility of the polyester plasticizer, its molecular weight may be lowered, but as the molecular weight is lowered, properties such as non-migration property and oil resistance are deteriorated. Further, by increasing the molecular weight, properties such as non-migration property and oil resistance are improved, but as the molecular weight increases, the viscosity becomes high and the workability becomes poor, and the properties such as low temperature flexibility deteriorate.

As described above, there is a limit in terms of the balance of physical properties only by designing the molecular weight, and selection of the types of dibasic acid, glycol and monohydric alcohol or monobasic acid, which have been conventionally used as constituent components of polyester plasticizers. Improvements have been attempted by devising combinations.

[0006] For example, US Pat.
In summary, it is proposed that polyesters quenched with a mixture of monobasic acid and monohydric alcohol have improved low temperature properties as plasticizers for vinyl chloride resins. Further, in Japanese Patent Publication No. 61-41936, a monobasic carboxylic acid having a side chain of 30% or more at the α-position is polyvalent carboxylic acid and polyhydric alcohol or a mixed alcohol of polyhydric alcohol and monohydric alcohol. The polyester obtained by co-condensing is a plasticizer for vinyl chloride resin and is capable of improving the defects of cold resistance and other physical properties.

Further, the applicant has filed an application for a polyester type plasticizer using coconut oil or the like as Japanese Patent Application Laid-Open No. 4-132756.

However, although these polyester plasticizers are recognized to have improved cold resistance, they are not yet satisfactory, and their non-migratory properties against other resins such as ABS resin, AS resin and polystyrene resin are also sufficiently satisfied. I can't say that That is, since the non-migrating property is not sufficient, the molecular weight of the polyester must be increased, and therefore a vicious cycle in which the handling workability is poor due to the increase in viscosity cannot be avoided.

[0009]

As described above, the conventional polyester plasticizers cannot satisfy the properties such as low-temperature flexibility and non-migrating property at a high degree and at the same time in good balance.

[0010]

DISCLOSURE OF THE INVENTION The inventors of the present invention have studied the polyester plasticizer which has the above-mentioned drawbacks and has a good balance of low-temperature flexibility, non-migratory property and other physical properties, and highly improved. Has been completed.

That is, according to the present invention, an unsaturated fatty acid component is used in a polyester plasticizer comprising an acid component and a glycol component, and the unsaturated fatty acid residue and the α, β-ethylenically unsaturated compound contained in the polyester are used. The present invention provides a polyester-based plasticizer characterized by forming a carbon-carbon bond with and a halogen-containing resin composition containing the same. Preferably, the unsaturated fatty acid component is derived from animal and vegetable oils or fats or oils thereof, preferably the unsaturated fatty acid component is oleic acid, linoleic acid, linolenic acid, conjugated linoleic acid or eleostearic acid. It is selected from at least one kind, and preferably the α, β-ethylenically unsaturated compound is selected from at least one kind of maleic acid, fumaric acid, itaconic acid and their anhydrides and esters. is there.

(Structure) The plasticizer of the present invention comprises a dibasic acid component, a glycol component, and optionally a monohydric alcohol or a monobasic acid other than unsaturated fatty acid, which contains an unsaturated fatty acid component as an essential component. For polyester, α, β
A polyester obtained by using an ethylenically unsaturated compound to form a carbon-carbon bond between an unsaturated fatty acid residue of the polyester and an α, β-ethylenically unsaturated compound.

The unsaturated fatty acid component used for constituting the polyester modified with the unsaturated fatty acid component of the present invention is preferably an animal or vegetable oil or fat, or an oil or fat derived from the oil or fat, or contained therein. Fatty acids, for example oleic acid, linoleic acid, linolenic acid, monoenoic acids such as conjugated linoleic acid or eleostearic acid, dienoic acids, polyenoic acids, conjugated dienoic acids or conjugated polyenoic acids, and linseed oils containing any of these , Safflower oil, soybean oil, cottonseed oil, rice bran oil, rapeseed oil, dehydrated castor oil, tung oil, castor oil, kapok oil, olive oil,
Examples thereof include animal and vegetable oils and fats such as palm oil, palm oil, palm kernel oil, beef tallow, lard and cod oil, and fatty acids thereof, and they are used as one kind or as a mixture of two or more kinds. Further, oleic acid, linoleic acid, linolenic acid, conjugated linoleic acid, eleostearic acid or fatty acid esters of the above-mentioned animal and vegetable oils and fats can also be used.

Of these, highly unsaturated group-containing oils and fats, such as linseed oil, safflower oil, soybean oil or fatty acid components thereof, conjugated unsaturated group-containing oils and fats, such as dehydrated castor oil, tung oil or fatty acid components thereof, are each alone. Alternatively, they can be mixed and used particularly preferably. Further, fats and oils having relatively low unsaturation degree and different fatty acid chain lengths are appropriately distributed, for example, coconut oil, palm oil, palm kernel oil or its fatty acid component, the unsaturated group concentration is separated and improved by purification. However, it is not particularly necessary to separate and improve the degree of unsaturation, but rather, for adjustment of the degree of unsaturation, it is mixed with the above-mentioned highly unsaturated group-containing oil or fat or conjugated unsaturated group-containing oil or fat. Is preferably used.

These oils and fats or fatty acid components thereof are
During the reaction of the polyester, it can be easily modified by transesterification or direct esterification to give a polyester containing unsaturated fatty acid residues.

Examples of the dibasic acid component used for constituting the polyester modified with the unsaturated fatty acid component of the present invention include carbon such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid and dodecanedicarboxylic acid. Aliphatic dibasic acids having a number of 4 to 12, aromatic dibasic acids such as phthalic acid, isophthalic acid or terephthalic acid, and alicyclic dibasic acids such as hexahydrophthalic acid, or anhydrides or esters thereof. . Of course, these dibasic acids may be used alone or as a mixture of two or more.

Examples of the glycol component used for constituting the polyester modified with the unsaturated fatty acid component of the present invention include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,
2-butanediol, 1,3-butanediol, 2-methyl 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl 1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl 1,3-pentanediol, 2-ethyl 1,3-hexanediol,
2-Methyl 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol and other aliphatic glycols having 2 to 18 carbon atoms and polyethylene glycols such as diethylene glycol and dipropylene glycol. Examples include alkylene glycol. These glycols are used alone or as a mixture of two or more.

If necessary, a monohydric alcohol or a monobasic acid is used for constituting the polyester modified with the unsaturated fatty acid component of the present invention.

Examples of the monohydric alcohol include butanol, hexanol, isohexanol, heptanol, octanol, isooctanol, 2-ethylhexanol, nonanol, isononanol, 2-methyloctanol, decanol, isodecanol, undecanol, dodecanol, tridecanol, tetra. Decanol, hexadecanol, octadecanol, etc. 4 carbon atoms
To 18 monohydric alcohols can be used, and they can be used alone or as a mixture of two or more.

In addition to the fatty acids derived from the above-mentioned oils and fats, the monobasic acid has 2 to 18 carbon atoms such as acetic acid, butyric acid, isobutyric acid, heptanoic acid, isooctanoic acid, 2-ethylhexanoic acid, nonanoic acid and isostearic acid. Synthetic monobasic acids can be mentioned, and they can be used alone or as a mixture of two or more.

Further, the polyester modified with the unsaturated fatty acid component of the present invention may optionally contain glycerin, diglycerin, trimethylolpropane, pentaerythritol,
Trivalent or higher polyhydric alcohols such as dipentaerythritol, trimellitic acid and pyromellitic acid, and polybasic acids may be used as modifiers. Further, lactones such as ε-caprolactone, methyl ε-caprolactone, β-methyl δ-valerolactone or epoxidized methyl stearate, butyl and octyl esters, and hardened oils of the aforementioned animal and vegetable oils and fats may also be appropriately used as a modifier. You can also

The polyester modified with the unsaturated fatty acid component of the present invention is obtained by reacting the above-mentioned oil or fat or its fatty acid component as an essential constituent with each of the above-mentioned components,
Molecular weight 600-10000, preferably 1000-50
A range of 00 is preferred.

The polyester modified with such an unsaturated fatty acid component can be produced by various methods. For example,
The above-mentioned oils and fats or fatty acid components thereof, dibasic acid components,
Targets by reacting the glycol component and polyester constituent components such as monohydric alcohol or monobasic acid other than unsaturated fatty acid, which is used as necessary, in one batch or two or three species and then reacting the remaining ingredients. The polyester can be obtained.

That is, the fats and oils or the fatty acid components thereof are appropriately transesterified or esterified during these reactions, and the carbon-carbon bond with the α, β-ethylenically unsaturated compound required for product design is formed. A pre-formed polyester is obtained. Since the polyesterification reaction is promoted by an acid catalyst such as paratoluenesulfonic acid and phosphoric acid, a metal catalyst such as tetraisopropyl titanate, tetrabutyl titanate, dibutyltin oxide, dioctyltin oxide, and zinc chloride, these are usually used. It is desirable to react in the presence of a catalyst in a stream of an inert gas such as nitrogen gas. Also, the reaction is usually 100
It is obtained by heating to ˜250 ° C., preferably 130 to 250 ° C.

The unsaturated fatty acid content in the polyester component is 2 to 50% by weight, preferably 5 to 40% by weight.
Is appropriate. When the content of unsaturated fatty acid is less than 2% by weight, the concentration of unsaturated group necessary for forming a carbon-carbon bond with the α, β-ethylenically unsaturated compound is not sufficient, resulting in compatibility. , Non-migration property, oil resistance, etc. are insufficient, and when it exceeds 50% by weight, it is convenient in that the reaction amount with the α, β-ethylenically unsaturated compound is increased, but it exceeds 50% by weight. Even if it is not necessary, the effect of the present invention can be sufficiently exhibited, so that it is not necessary to increase the amount.

When the α, β-ethylenically unsaturated compound forming a carbon-carbon bond is an acid anhydride, the OH group remaining in the polyester undergoes a side reaction due to ring opening of the OH group and the acid anhydride. In the case of an ester, it easily causes a side reaction of transesterification with OH group and de-alcohol. If this side reaction occurs frequently, a polyester having a viscosity higher than necessary is produced, leading to a reduction in workability. In order to suppress this side reaction as much as possible, the product design should control the content of OH groups remaining in the polyester component.

The α, β-ethylenically unsaturated compound which forms a carbon-carbon bond with the polyester modified with the unsaturated fatty acid component thus obtained is, for example, acrylic acid, methacrylic acid or crotonic acid. Dibasic acids such as basic acids, maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, mesaconic acid and their anhydrides, alkyl esters of these monobasic acids and dibasic acids having 1 to 18 carbon atoms, etc. Is mentioned. Typical alkyl groups constituting these esters are methyl, ethyl, n
-Propyl, isopropyl, n-butyl, isobutyl,
n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, isoundecyl, n-dodecyl, Examples thereof include isododecyl, n-tridecyl, isotridecyl, n-tetradecyl, isotetradecyl, pentadecyl, hexadecyl, octadecyl and the like. Furthermore, as the α, β-ethylenically unsaturated compound, aromatic ethylenically unsaturated compounds such as styrene, α-methylstyrene and vinyltoluene can also be used. Of these, technically and economically maleic acid,
Fumaric acid, itaconic acid, their anhydrides or their alkyl esters can be preferably used.

The polyester plasticizer of the present invention is prepared by reacting the above-mentioned α, β-ethylenically unsaturated compound with a polyester containing an unsaturated fatty acid residue modified with the above-mentioned unsaturated fatty acid component to form a carbon-carbon bond. Obtained by forming.

When the double bond of the unsaturated fatty acid residue of the polyester is conjugated, a carbon-carbon bond is mainly produced by the Diels-Alder reaction, and when it is non-conjugated, it becomes a double bond rather than the Diels-Alder reaction. Carbon to form a carbon-carbon bond. For the formation of this carbon-carbon bond, a Lewis acid type catalyst such as boron fluoride or an organic peroxide such as benzoyl peroxide or t-butyl peroxide may be used in that it lowers the reaction temperature, but it may be used for polymerization or the like. Considering adverse effects, the reaction by heating alone is preferable. Therefore, in an inert gas stream such as nitrogen gas, 10
Heat to 0-280 ° C, preferably 180-260 ° C to form carbon-carbon bonds. If the unreacted α, β-ethylenically unsaturated compound remains, it may be removed from the reaction system by distillation under reduced pressure. If an acid anhydride or a carboxyl group remains in the polyester, the esterification may be continued by adding alcohol in a later step, if necessary, in practical use. However, esterification of the remaining carboxyl group leads to complication of the manufacturing process and is not a good method for improving efficiency in production.

Therefore, as the α, β-ethylenically unsaturated compound, an alkyl ester having 1 to 15 carbon atoms of maleic acid, fumaric acid or itaconic acid, which does not need to be esterified in the subsequent step, can be particularly preferably used.

The content of the α, β-ethylenically unsaturated compound of the present invention is 0.2 times the molar amount of the unsaturated fatty acid residue.
It is suitable to be 10 to 10 times mol, preferably 0.5 to 5 times mol. If it is less than 0.2 times by mole, the non-migrating property is insufficient, and if it exceeds 10 times by mole, low temperature flexibility is insufficient.

The polyester-based plasticizer of the present invention obtained through such a reaction is more compatible than conventional plasticizers,
Properties such as low-temperature flexibility and non-migration property can be satisfied at a high level and at the same time with good balance. Further, by forming a carbon-carbon bond between a polyester containing an unsaturated fatty acid residue modified with an unsaturated fatty acid component and an α, β-ethylenically unsaturated compound, hydrogenation is performed to reduce the degree of unsaturation. Further, properties such as heat resistance and heat aging resistance can be further improved.

Such polyester plasticizers are suitable as plasticizers for synthetic resins, particularly halogen-containing resins.
Examples of the halogen-containing resin include vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, vinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer resin, and chlorinated polyolefin resin.

The plasticizer content of the present invention is generally 10 to 150 parts by weight, preferably 20 to 100 parts by weight, per 100 parts by weight of the halogen-containing resin.

The plasticizer of the present invention is a well-known plasticizer used in the field of processing halogen-containing resins, for example, phthalic acid ester based compounds such as di (2-ethylhexyl) phthalate, dinormal butyl phthalate and diisononyl phthalate. Trimellitic acid ester type such as tri (2-ethylhexyl) trimellitate, pyromellitic acid ester type such as tetra (2-ethylhexyl) pyromellitate, aliphatic dibasic acid ester type such as di (2-ethylhexyl) adipate, tricresyl It can be used in combination with a plasticizer such as a phosphate ester type such as phosphate, an epoxy type such as epoxidized soybean oil, a polyester type other than the present invention, and a chlorinated paraffin type.

Furthermore, it can be used in combination with stabilizers, fillers, pigments and other additives used in the field of processing halogen-containing resins.

Next, in order to further clarify the characteristics of the present invention, specific description will be given with reference to examples. In addition, "part" in the sentence
All "%" indicate weight basis.

[0038]

【Example】

<Production of Polyester Plasticizer> Example 1 730 parts of adipic acid, 338 parts of 1,3-butanediol and 295 parts of 1,6-hexanediol were charged in a reaction vessel at once, and stirred at 140 to 140 ° C in a nitrogen stream. The reaction was carried out for 5 hours while distilling off water produced at 230 ° C.

Next, 297 parts of linseed oil fatty acid and 0.15 part of tetraisopropyl titanate were added to 220 to 23.
The mixture was reacted at 0 ° C. under reduced pressure of 100 to 5 mmHg for 7 hours while removing the distillate.

Further, 510 parts of di2-ethylhexyl maleate was added and the reaction was carried out at 250 ° C. for 6 hours. (The progress of the addition reaction of the fatty acid maleic di-2-ethylhexyl, IR characteristic absorption of maleic di-2-ethylhexyl 1210Cm ^-1 and C = C of the characteristic absorption 1650 cm ^-1
It was confirmed by the decrease of. ) Then 220-230 ℃
The distillate was removed under reduced pressure of 100 to 5 mmHg. Then, filtration was performed to obtain a polyester having the following properties.

Viscosity (25 ° C., cps); 2820 acid value; 0.35

Example 2 A reactor was charged with 730 parts of adipic acid, 649 parts of 3-methyl-1,5-pentanediol, 440 parts of linseed oil and 0.53 parts of dibutyltin oxide as a catalyst, and stirred in a nitrogen stream. Under the conditions below, the reaction was carried out for 8 hours while distilling off the water produced at 140 to 230 ° C. until the acid value became 15 or less.

Next, 100 to 5 mmHg at 220 to 230 ° C.
The reaction was continued for 5 hours under reduced pressure while removing the distillate. Furthermore, 510 parts of di2-ethylhexyl maleate was added and the reaction was carried out at 250 ° C. for 6 hours. (The progress of the addition reaction of di-2-ethylhexyl maleate to fatty acid is shown by the characteristic absorption of IR of di2-ethylhexyl maleate 1210
Confirmation was made by the reduction of the characteristic absorption of cm ^-1 and C = C 1650 cm ^-1 . ) Then 100 ~ 5mm at 220 ~ 230 ℃
The distillate was removed under reduced pressure of Hg. Then, filtration was performed to obtain a polyester having the following properties.

Viscosity (25 ° C., cps); 2380 acid value; 0.66

Example 3 A reaction vessel was charged with 730 parts of adipic acid, 248 parts of 1,3-butanediol, 248 parts of 1,4-butanediol and 310 parts of dehydrated castor oil, and the mixture was stirred in a nitrogen stream at 140 ° C.
The reaction was carried out for 5 hours while distilling off water produced at ˜230 ° C.

Then, 46 parts of 2-ethylhexanol and 0.17 part of tetraisopropyl titanate are added and 220
The reaction was carried out at ˜230 ° C. under reduced pressure of 100˜5 mmHg for 5 hours while removing the distillate. Further, 425 parts of di2-ethylhexyl fumarate was added and the reaction was carried out at 250 ° C. for 2 hours. (The progress of the addition reaction of di-2-ethylhexyl fumarate to fatty acids is
Characteristic absorption of R 1300 cm ^-1 and characteristic absorption of C = C 165
Confirmation was made by a decrease of 0 cm ^-1 . ) Then 220-2
The distillate was removed under reduced pressure of 100 to 5 mmHg at 30 ° C.
Then, filtration was performed to obtain a polyester having the following properties.

Viscosity (25 ° C., cps); 3130 acid value; 0.16

Example 4 730 parts of adipic acid, 248 parts of 1,3-butanediol, 248 parts of 1,4-butanediol, 166 parts of coconut oil and 220 parts of linseed oil were charged into a reaction vessel and stirred in a nitrogen stream, While distilling off the water produced at 140-230 ° C, 5
The reaction was carried out over time. Next, 0.48 part of dibutyltin oxide was added as a catalyst and the reaction was carried out at 220 to 230 ° C. until the acid value became 15 or less. Furthermore, at that temperature, 100 to 5 mm
The reaction was carried out for 6 hours under reduced pressure of Hg while removing the distillate.
Further, add 342 parts of dibutyl fumarate, and add 4 at 250 ° C.
The reaction was carried out over time. (The progress of the addition reaction of the fatty acid dibutyl fumarate was performed to confirm the reduction of the IR characteristic absorption of dibutyl fumarate 1300 cm ^-1 and C = C of the characteristic absorption 1650 cm ^-1.) Then 220 to 230 ° C. In 1
The distillate was removed under reduced pressure of 00 to 5 mmHg. Then, filtration was performed to obtain a polyester having the following properties.

Viscosity (25 ° C., cps); 2010 acid value; 0.32

Example 5 A reaction vessel was charged with 730 parts of adipic acid, 162 parts of 1,3-butanediol, 162 parts of 1,4-butanediol, 198 parts of neopentyl glycol and 443 parts of soybean oil with stirring in a nitrogen stream. The reaction was carried out for 5 hours while distilling off water produced at 140 to 230 ° C. Next, 0.5 part of dibutyltin oxide is added and the acid value is 15 at 220 to 230 ° C.
Reacted until below. Furthermore, at that temperature 100 ~
The mixture was reacted for 6 hours under a reduced pressure of 5 mmHg while removing the distillate. Further, 680 parts of di-2-ethylhexyl itaconate was added and the reaction was carried out at 250 ° C. for 8 hours. (The progress of the addition reaction of the fatty acids of itaconic di-2-ethylhexyl, was confirmed by a decrease in the IR characteristic absorption of itaconic di-2-ethylhexyl 1290Cm ^-1 and C = C of the characteristic absorption 1650 cm ^-1. ) Then 10 at 220-230 ° C
The distillate was removed under reduced pressure of 0 to 5 mmHg. Then, filtration was performed to obtain a polyester having the following properties.

Viscosity (25 ° C., cps); 2860 acid value; 0.44

Example 6 A reactor was charged with 1010 parts of sebacic acid, 248 parts of 1,3-butanediol, 286 parts of neopentyl glycol, 133 parts of soybean oil and 100 parts of hardened coconut oil, and the mixture was stirred at 140 to 140 ° C. in a nitrogen stream. The reaction was carried out for 5 hours while distilling off water produced at 220 ° C. Next, 0.18 part of tetraisopropyl titanate was added and reacted at 220 to 230 ° C. until the acid value became 15 or less. Furthermore, at that temperature 100 to 5 mmHg
The mixture was reacted for 6 hours under reduced pressure while removing the distillate. Furthermore, 342 parts of dibutyl fumarate was added and the reaction was carried out at 250 ° C. for 5 hours. (The progress of the addition reaction of the fatty acid dibutyl fumarate was performed to confirm the reduction of the IR characteristic absorption of dibutyl fumarate 1300 cm ^-1 and C = C of the characteristic absorption 1650 cm ^-1.) Then 220 to 230 ° C. In 10
The distillate was removed under reduced pressure of 0 to 5 mmHg and then filtered to obtain a polyester having the following properties.

Viscosity (25 ° C., cps); 2540 acid value; 0.31

Comparative Examples 1 to 3 Polyester plasticizers were obtained by the method of Example 2 except that unsaturated dibasic acids were removed from the polyester constituents in the amounts specified in Table 1 for comparison.

<Evaluation of Polyester Plasticizer> Example 7 Sheets were prepared from the plasticizers obtained in Examples 1 to 6 according to the following basic composition and molding conditions, and physical properties were tested. The results of the physical property tests of the plasticizers obtained in Comparative Examples 1 to 3 are shown in Tables 2 to 5.

(Basic composition) (Physical property test) Polyvinyl chloride resin (polymerization degree 1050): 100 parts Plasticizer: 50 parts or 8
0 parts Barium / zinc powder composite stabilizer ^* ; 2 parts ^* Dainippon Ink and Chemicals Co., Ltd. product name: GREC MP-568C (molding condition) roll (diameter 6 inches); 165 ° C x 10 minutes Press (1 mm Thickness); 170 ℃ x 5 minutes

(Physical property test) 1) Hardness (JIS spring A scale); JISK-
It measured according to 6301.

2) Tensile test: Measured according to JIS K-6723. 3) Low temperature flexibility test: Measured according to JISK-6745. The lower the temperature, the better the low temperature flexibility.

4) Non-migration test: A press sheet having a thickness of 1 mm was punched into a size of 25 mm × 40 mm to obtain a test piece. ABS resin plate (Nippon Synthetic Rubber Co., Ltd.)
Manufactured; trade name JSR-15NP), HI-polystyrene resin plate (manufactured by Dainippon Ink and Chemicals, Inc .; trade name Dick Styrene GH-9100) and AS resin plate (manufactured by Asahi Kasei Co., Ltd .; trade name Stylak 767). Each about,
Sandwiched with the same resin plate, then 0.5k
The state of erosion due to the transfer of the plasticizer to the resin plate after the load of g / cm ² was kept at 70 ° C. for 72 hours and then visually observed and evaluated.

Evaluation conditions ○: No erosion due to transfer of plasticizer (good) Δ: Slight erosion is observed.

X: Clearly erosion due to migration of plasticizer is recognized (bad) XX: Very bad.

5) Heat aging test: Measured according to JIS K-6723. However, the test conditions were 120 ° C. × 120 hours. The results are shown by the residual elongation rate (%) and the weight loss rate (%) after the test.

6) High humidity bleeding test: A roll sheet having a thickness of 0.3 mm was used as a 40 mm × 100 mm test piece, and the bleeding state of the test piece after 20 days at 70 ° C. and 98% RH was visually observed and evaluated.

◯: Indicates that there is no bleed

[0065]

[Table 1]

[0066]

[Table 2] (Plasticizer 50 parts blended)

[0067]

[Table 3] (Plasticizer 50 parts blended)

[0068]

[Table 4] (80 parts of plasticizer)

[0069]

[Table 5] (Plasticizer 80 parts blended)

[0070]

The polyester plasticizer of the present invention is modified by the reaction between the unsaturated group of the unsaturated fatty acid component and the α, β-ethylenically unsaturated compound to give a conventionally known polyester plasticizer. In particular, the low temperature flexibility and non-migration property are extremely excellent at the same time. Further, since it is improved in balance with respect to other physical properties as well, it is of great utility in the field of applied processing, not to mention the production of a plasticizer as a plasticizer for a vinyl chloride resin.

Claims (5)

[Claims] 1. A polyester plasticizer comprising an acid component and a glycol component, wherein an unsaturated fatty acid component is used, and the unsaturated fatty acid residue and α, β contained in the polyester are used.
-A polyester-based plasticizer characterized by forming a carbon-carbon bond with an ethylenically unsaturated compound. 2. The polyester plasticizer according to claim 1, wherein the unsaturated fatty acid component is derived from animal and vegetable oils and fats or oils and fats thereof. 3. The polyester plasticizer according to claim 1, wherein the unsaturated fatty acid component is selected from at least one of oleic acid, linoleic acid, linolenic acid, conjugated linoleic acid and eleostearic acid. 4. An α, β-ethylenically unsaturated compound is maleic acid, fumaric acid, itaconic acid and their anhydrides,
The polyester plasticizer according to claim 1, which is selected from at least one kind of esters. 5. A halogen-containing resin composition comprising the plasticizer according to any one of claims 1 to 4. [0000]