JP3082231B2 - Plasticizer and halogen-containing resin composition containing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel polyester plasticizer using glyceride as an essential reaction component constituting polyester and a halogen-containing resin composition containing the same.

[Prior art and its problems] Polyester plasticizers are generally known to have excellent durability with polyesters obtained by reacting dibasic acids, glycols and, if necessary, monohydric alcohols or monobasic acids. ing.

Therefore, halogen-containing resins such as vinyl chloride resin plasticized with polyester are widely used in various applications such as electric wire coating, automobile parts, leather, boots, gaskets and hoses. However, the demand for quality improvement in these application fields has been stricter than in the past, and especially in applications such as wire coating and gaskets, excellent low-temperature flexibility,
Non-migratory properties are required, and it is difficult to deal with conventional plasticizers.

In order to improve the low-temperature flexibility of the polyester-based plasticizer, the molecular weight may be reduced, but properties such as non-migration property and oil resistance deteriorate with the decrease in the molecular weight. Also,
By increasing the molecular weight, properties such as non-migration and oil resistance are improved, but as the molecular weight increases, the viscosity becomes higher, the handling 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. Conventionally, the selection and combination of the types of dibasic acids, glycols and monohydric alcohols or monobasic acids, which are the constituent components of the polyester plasticizer, have been required. Improvements have been attempted by devising.

For example, U.S. Pat. No. 4,220,57 proposes, in summary, that polyesters quenched with a mixture of a monobasic acid and a monohydric alcohol have improved low temperature properties as plasticizers for vinyl chloride resins. In addition, Japanese Patent Publication No. 61-41936 summarizes a monobasic carboxylic acid having a side chain of 30% or more at the α-position with a polycarboxylic acid and a polyhydric alcohol or a mixed alcohol of a polyhydric alcohol and a monohydric alcohol. It is stated that the polyester obtained by co-condensation can be used as a plasticizer for vinyl chloride resin to improve the deficiency of cold resistance and other physical properties.

However, although these polyester-based plasticizers show improvement in cold resistance, they are not yet satisfactory,
In addition, the non-migratory property to other resins such as ABS resin and polystyrene resin cannot be said to be sufficiently satisfied. That is, since the non-migratory property is not sufficient, the molecular weight of the polyester must be increased, and therefore, a vicious cycle inferior in handling workability due to the increase in viscosity cannot be avoided.

As described above, the conventional polyester plasticizers could not satisfy properties such as low-temperature flexibility and non-migration property at a high level and at the same time in a well-balanced manner.

[Means for Solving the Problems] The present inventors have studied a polyester plasticizer which does not have the above-mentioned disadvantages, has a good balance of low-temperature flexibility, non-migration and other physical properties, and is highly improved. Was completed.

That is, the present invention uses at least one kind of glyceride, dibasic acid, or diol selected from mono-, di-, or triglyceride as an essential constituent component of the polyester, and the amount of glyceride used in the polyester is 2 to 50.
% By weight, wherein the polyester-based plasticizer for a halogen-containing resin, preferably glyceride, is a triglyceride, preferably the triglyceride is selected from at least one of animal and vegetable oils and fats or hardened oils thereof. That the triglyceride is preferably selected from coconut oil, palm oil and palm kernel oil or at least one of their hardened oils;
A halogen-containing resin composition comprising the polyester-based plasticizer for a halogen-containing resin according to any one of the above.

(Structure) The plasticizer of the present invention contains at least one kind of mono-, di- or triglyceride as an essential component, a dibasic acid component, a glycol component, and 1
It is a polyester obtained by reacting the components of a polyester comprising a polyhydric alcohol or a monobasic acid.

However, triglycerides are preferred for effectively practicing the invention in these glycerides.

Further, among the triglycerides, animal and vegetable fats and oils or the hardened oils thereof which can more effectively carry out the present invention are preferable.

The glycerides used to make up the polyesters of the present invention are, for example, the natural triglycerides palm oil, palm oil, palm kernel oil, cocoa butter, wax, olive oil, kapok oil, castor oil, dehydrated castor oil, rapeseed oil Oils, oils such as rice bran oil, cottonseed oil, soybean oil, safflower oil, flaxseed oil, tung oil, beef tallow, lard oil, cod oil and the like, and hardened oils of animal and vegetable fats and oils obtained by hydrogenating them. Used as one kind or a mixture of two or more kinds. In addition, monoglyceride and diglyceride can be obtained by a generally known transesterification reaction of the above-mentioned fats and oils and glycerin. Further, monoglyceride, diglyceride, and remaining triglyceride produced by adjusting the ratio of fats and oils to be transesterified to glycerin can be obtained at a ratio in accordance with the production fraction of glycerolysis. These can be separated and used as individual glycerides, but it is technically and economically preferable to use them as a mixture. It is not necessary to separate and remove glycerin remaining in glycerolysis.

Further, as glycerides, monobasic acids having 6 to 22 carbon atoms or acetic acid, butyric acid, isobutyric acid, heptanoic acid, isooctanoic acid, 2-ethylhexanoic acid, nonanoic acid and isostearic acid derived from the above-mentioned fats and oils or hydrogenated oils thereof. Mono-, di- and triglycerides obtained from the synthesized monobasic acids of number 2 to 18 and glycerin or mixtures thereof can also be used.

Furthermore, as a result of the fatty acid composition being moderately distributed in animal and vegetable oils and fats, coconut oil whose quality performance is even more highly satisfactory,
Palm oil and palm kernel oil or their hydrogenated oils can be particularly preferably used.

Examples of the dibasic acid component used to construct the polyester of the present invention include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc. Aliphatic dibasic acids, aromatic dibasic acids such as phthalic acid, isophthalic acid or terephthalic acid, and alicyclic dibasic acids such as tetrahydrophthalic acid and hexahydrophthalic acid or anhydrides and esterified products thereof. . Of course, these dibasic acids may be used alone or in a mixture of two or more.

Glycol components used to constitute the polyester 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, 1,1
Examples thereof include aliphatic glycols having 2 to 18 carbon atoms such as 2-octadecanediol and polyalkylene glycols such as diethylene glycol and dipropylene glycol. These glycols are used as one kind or as a mixture of two or more kinds.

A monohydric alcohol or a monobasic acid is used as needed to constitute the polyester 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, tetradecanol, and hexadecanol. Examples thereof include monohydric alcohols having 4 to 18 carbon atoms such as decanol and octadecanol, which can be used alone or as a mixture of two or more. Examples of the monobasic acid include the above-mentioned aliphatic monobasic acid having 6 to 22 carbon atoms derived from the above-mentioned animal or vegetable fats or the hardened oil thereof and the above-mentioned synthetic monobasic acid having 2 to 18 carbon atoms.
It can be used as a species or a mixture of two or more.

Furthermore, the polyester of the present invention may be modified with glycerin, diglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, trimellitic acid, pyromellitic acid or other trihydric or higher polyhydric alcohols and polybasic acids as necessary. You may use as. Ε-caprolactone, methyl ε-caprolactone, β
Lactones such as -methyl δ-valerolactone or epoxidized methyl, butyl and octyl stearate can also be appropriately used as a modifier.

The polyester plasticizer of the present invention is obtained by reacting at least one selected from mono, di or triglyceride with each of the above-mentioned components as an essential component, and has a molecular weight of 600 to 10,000, preferably 1,000 to 5,000. It is suitable.

Such a polyester containing glyceride as an essential component can be produced by various methods.

For example, the above-mentioned glyceride, dibasic acid component, glycol component, and optionally used polyester components such as monohydric alcohol or monobasic acid are reacted together or two to three kinds, and then the remaining components are reacted. To give the target polyester. Glyceride is suitably esterified or transesterified during these reactions to produce the desired polyester.

Since the reaction of the polyester of the present invention is accelerated by a metal catalyst such as an acid catalyst such as paratoluenesulfonic acid and phosphoric acid, tetraisopropyl titanate, tetrabutyl titanate, dibutyltin oxide, dioctyltin oxide and zinc chloride, the reaction is usually performed. It is desirable to carry out the reaction in the presence of these catalysts. Usually, the reaction is 10
It is obtained by heating to 0 to 250 ° C, preferably 130 to 250 ° C.

The amount of the glyceride used in the present invention is 2 to 50% by weight, preferably 5 to 40% by weight in the polyester component. If the amount of glyceride used is less than 2% by weight,
If the properties such as low-temperature flexibility and non-migratory property are insufficient, and if it exceeds 50% by weight, the non-migratory property is insufficient and the gelling performance is reduced.

The polyester plasticizer of the present invention thus obtained has properties that cannot be obtained by simply reacting glycerin and monobasic acid in the polyesterification component, such as low-temperature flexibility and relatively low viscosity. In addition, properties such as non-migration properties can be satisfied at a high level and at the same time in a well-balanced manner. In addition, this plasticizer is excellent in promoting production efficiency such as shortening the reaction time since mono-, di- or triglyceride in which a part or all of glycerin is already esterified is an essential reaction component. In particular, animal and vegetable oils and fats which are triglycerides or their hardened oils are more preferable in terms of economy.

Such a polyester plasticizer is particularly suitable as a plasticizer for a halogen-containing resin. Examples of the halogen-containing resin include a vinyl chloride resin, a vinyl chloride-vinyl acetate copolymer resin, a vinylidene chloride resin, a vinyl chloride-vinylidene chloride copolymer resin, and a chlorinated polyolefin resin.

The amount of the plasticizer is usually 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 of a halogen-containing resin, for example, phthalates such as DOP, adipic esters such as DOA, TOTM
Such as trimellitic esters, pyromellitic esters, epoxidized animal and vegetable oils, epoxidized fatty acid esters, chlorinated paraffins, phosphate esters, and polyester plasticizers other than the plasticizer of the present invention. be able to.

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

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, these "parts" all mean "parts by weight".

<Production of Polyester Plasticizer> Example 1 A reaction vessel was charged with 730 parts of adipic acid, 649 parts of 3-methyl-1,5-pentanediol, 331 parts of coconut oil, and coconut oil fatty acids.
52 parts and 0.53 part of dibutyltin oxide corresponding to 0.03% of the polyester component as a catalyst are charged all at once, and while stirring in a nitrogen stream, water generated at 140 to 230 ° C. is distilled off to reduce the acid value to 15 or less. The reaction was carried out for 8 hours until complete.

Then, the reaction was carried out at 220 to 230 ° C. for 5 hours under reduced pressure of 100 to 5 mmHg while removing distillate. Thereafter, filtration was performed to obtain a polyester having the following properties.

Viscosity (25 ° C., cps); 1910 Acid value; 0.66 Example 2 A reaction vessel was charged with 730 parts of adipic acid and 1,3-butanediol 90.
And 531 parts of 3-methyl-1,5-pentanediol were charged and reacted for 5 hours while stirring at 140 to 230 ° C. in a nitrogen stream while distilling off water produced.

Next, 330 parts of coconut oil and 0.17 parts of tetraisopropyl titanate were added, and the mixture was reacted at 220 to 230 ° C under reduced pressure of 100 to 5 mmHg for 5 hours while removing distillates. Thereafter, filtration was performed to obtain a polyester having the following properties.

Viscosity (25 ° C., cps); 3070 acid value; 0.26 Example 3 730 parts of adipic acid, 1,4-butanediol 19
4 parts, neopentyl glycol 130 parts, 3-methyl 1,5-
189 parts of pentanediol and 210 parts of palm oil were charged and reacted under stirring for 5 hours at 140 to 230 ° C. while distilling off water generated at 140 to 230 ° C. Then 2-ethylhexanol
Add 156 parts and 0.48 part of dibutyltin oxide corresponding to 0.03% of the polyester component as a catalyst, and add 220 to 230 ° C.
The reaction was continued until the acid value became 15 or less. At that temperature
The reaction was carried out for 6 hours while removing the distillate under reduced pressure of 100 to 5 mmHg. Thereafter, filtration was performed to obtain a polyester having the following properties.

Viscosity (25 ° C., cps); 2010 Acid value; 0.26 Example 4 730 parts of adipic acid and 1,3-butanediol 68 were added to a reaction vessel.
149 parts of 1,4-butanediol, 130 parts of neopentyl glycol, 189 parts of 3-methyl1.5-pentanediol and 343 parts of palm kernel oil are charged and stirred in a nitrogen stream at 140 to 23.
The reaction was carried out at 0 ° C. for 5 hours while distilling off the generated water.
Next, 65 parts of 2-ethylhexanol and 0.5 part of dibutyltin oxide were added and reacted at 220 to 230 ° C. until the acid value became 15 or less. In addition, at that temperature under reduced pressure of 100-5 mmHg,
The reaction was carried out for 6 hours while removing the distillate. Thereafter, filtration was performed to obtain a polyester having the following properties.

Viscosity (25 ° C., cps); 3010 Acid value; 0,40 Monoglyceride 15%, diglyceride 44
%, Triglyceride 40% and glycerin 1%. 180 parts of this mixture, 730 parts of adipic acid, 1,
212 parts of 3-butanediol and neopentyl glycol 24
Charge 4 parts into a reaction vessel and stir in a nitrogen stream, 140-230
The reaction was carried out for 5 hours while distilling off water produced at ° C.

Next, 195 parts of 2-ethylhexanol and 0.16 parts of tetraisopropyl titanate were added and reacted until the acid value became 15 or less. Further, the mixture was reacted at that temperature under reduced pressure of 100 to 5 mmHg for 6 hours while removing distillate, and then filtered to obtain a polyester having the following properties.

Viscosity (25 ° C., cps); 3140 Acid value; 0.14 Example 6 A reaction vessel was charged with 1010 parts of sebacic acid and 1,3-butanediol 2
70 parts, neopentyl glycol 208 parts and coconut hardened oil 200
The reaction was carried out for 5 hours while distilling off water produced at 140 to 220 ° C. while stirring the mixture in a nitrogen stream. Next, 130 parts of 2-ethylhexanol and 0.1 parts of tetraisopropyl titanate were added.
8 parts were added and reacted at 220 to 230 ° C. until the acid value became 15 or less. Further, the mixture was reacted at that temperature under reduced pressure of 100 to 5 mmHg for 6 hours while removing distillate, and then filtered to obtain a polyester having the following properties.

Viscosity (25 ° C., cps); 2520 acid value; 0.33 Example 7 A reaction vessel was charged with 730 parts of adipic acid, 276 parts of neopentyl glycol, 313 parts of 3-methyl-1,5-pentanediol, 313 parts of hardened coconut oil and 464 parts of coconut oil. Ethylhexanol (65 parts) was charged and reacted under stirring in a nitrogen stream at 140 to 230 ° C. while distilling off water produced until the acid value became 30 or less.

Next, 0.18 parts of tetraisopropyl titanate was added and 22
The reaction was carried out at 0 to 230 ° C under reduced pressure of 100 to 5 mmHg for 7 hours while removing distillate. Then, filtration was performed to obtain a polyester having the following properties.

Viscosity (25 ° C., cps); 2050 acid value; 0.23 Example 8 A reaction vessel was charged with 730 parts of adipic acid, 286 parts of neopentyl glycol, 325 parts of 3-methyl-1,5-pentanediol, 596 parts of hardened coconut oil, and 596 parts of tetraisopropyl. 0.2 parts of titanate was charged and reacted under stirring in a nitrogen stream at 140 to 230 ° C. while distilling off generated water until the acid value became 15 or less. Next, the mixture was reacted at that temperature for 6 hours while removing the distillate under reduced pressure of 100 to 5 mmHg, followed by filtration to obtain a polyester having the following properties.

Viscosity (25 ° C., cps); 1830 acid value; 0.41 Comparative Examples 1 to 3 Comparative Examples 1 to 3 except that glyceride was omitted from the polyester components in the amounts specified in Table 1 for comparison.
In this case, a polyester plasticizer was obtained by the method of Example 1, and in Comparative Examples 2-3, by the method of Example 3.

<Evaluation of polyester-based plasticizer> Example 9 A sheet was prepared from the plasticizers obtained in Examples 1 to 8 according to the following basic composition and molding conditions, and a physical property test was performed. The results are shown in Tables 2 and 3 together with the physical property test results of the plasticizers obtained in Comparative Examples 1 to 3.

(Basic blend) Polyvinyl chloride resin (degree of polymerization 1050); 100 parts Plasticizer; 50 or 80 parts Barium / zinc powder stabilizer ^* ; 2 parts * Dainippon Ink and Chemicals, Inc. Product name: Grec MP- 568C (Molding conditions) Roll (diameter 6 inches); 165 ° C x 10 minutes Press (1mm thickness); 170 ° C x 5 minutes (Physical property test) 1) Hardness (JIS spring A scale); Measured according to JISK-6301.

2) Tensile test: Measured according to JISK-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 1 mm-thick press sheet punched into a size of 25 mm x 40 mm was used as a test piece. It is made of ABS resin plate (manufactured by Nippon Synthetic Rubber Co., Ltd .; trade name: JSR-15NP) and HI
-Polystyrene resin plate (Dainippon Ink and Chemicals, Inc.)
Manufactured by Dick Styrene GH-9100)
Sandwich with the same resin plate, then 0.5kg / cm
After holding at 70 ° C. for 72 hours under a load of ^2, the erosion state due to the transfer of the plasticizer to the resin plate was visually observed and evaluated.

Evaluation conditions ：: no erosion due to migration of plasticizer (good) ：: slight erosion is observed.

×: Erosion due to migration of plasticizer is clearly observed (poor) ××: Very poor.

5) Thermal aging test: Measured according to JISK-6723.

However, the test conditions were 120 ° C. for 120 hours. The results were shown as a residual elongation rate (%) and a weight reduction rate (%) with respect to the normal state after the test.

6) High-humidity bleeding test A 0.3mm-thick roll sheet was used as a 40mm x 100mm test piece.
The bleed state of the test piece after 2 days at 0 ° C. and 98% RH was visually observed and evaluated.

：: No bleeding 7) Brabender gelling test 55 g of a homogeneous mixture of the above basic composition was sampled, preliminarily dried at 50 ° C for 1 hour, filled into a Brabender plastic coder, and jacket temperature was 150 ° C and 30r. The time from starting rotation at .pm to reaching the maximum torque was shown.

[Effects of the Invention] The polyester-based plasticizer of the present invention has extremely excellent low-temperature flexibility and non-migratory property at the same time as compared with conventionally known polyester-based plasticizers. Furthermore, since other physical properties are improved in a well-balanced manner, it is extremely useful not only in the production of a plasticizer as a plasticizer of a vinyl chloride resin but also in the field of applied processing.

────────────────────────────────────────────────── (5) References JP-A-51-63803 (JP, A) JP-A-47-43590 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 63/00-63/91 C08L 27/00-27/24 C08L 67/00-67/02

Claims (5)

(57) [Claims] 1. A glyceride selected from mono-, di- or triglycerides is used as an essential constituent of the polyester, a dibasic acid or a diol, and the amount of glyceride used in the polyester is 2 to 50% by weight. A polyester plasticizer for a halogen-containing resin, which is: 2. The polyester plasticizer for a halogen-containing resin according to claim 1, wherein the glyceride is triglyceride. 3. A polyester plasticizer for a halogen-containing resin according to claim 1, wherein the triglyceride is selected from at least one of animal and vegetable fats and oils and hardened oils thereof. 4. The polyester-based plastic for a halogen-containing resin according to claim 3, wherein the triglyceride is selected from at least one of coconut oil, palm oil, palm kernel oil and hydrogenated oil thereof. Agent. 5. A halogen-containing resin composition comprising the polyester plasticizer for a halogen-containing resin according to any one of claims 1 to 4.