JPH03111441A - Plasticizer and halogenated resin composition containing same - Google Patents

Abstract

PURPOSE:To obtain a plasticizer excellent in properties such as prevention of migration and low temperature flexibility and suitable as a plasticizer especially for vinyl chloride resin by using 1,12-octadecanediol as the essential component. CONSTITUTION:A polyester plasticizer is obtained by using 1,12-octadecanediol as the essential component which constitutes the polyester. When compared with a conventional known polyester plasticizer, this plasticizer is very excellent in properties such as low temperature flexibility and prevention of migration and can be desirably used as a plasticizer for vinyl chloride resin.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel polyester plasticizer containing 1,12-octadecanediol as an essential component and a halogen-containing resin composition containing the same.

(Prior art and its problems) Soft vinyl chloride products, which are made by blending plasticizers with vinyl chloride resin, have a wide variety of uses, but they have excellent oil resistance in applications such as electric wire coatings, automobile parts, leather, boots, gaskets, and hoses. Polyester-based plasticizers are used as plasticizers to be added to these materials, as they are required to have good elasticity and non-migration properties.

However, in these application fields, demands for quality improvement have been stricter than before, and in particular, for applications such as electric wire coatings and gaskets, the required quality of low temperature flexibility and non-migration is high, making it difficult to meet the requirements with conventional plasticizers. .

Various improvement methods have been proposed to improve the quality characteristics of polyester plasticizers.

For example, JP-A-49-18927 proposes a polyester plasticizer containing 3-methyl 1,5-bentanediol as a glycol component. Although this polyester plasticizer is effective in improving plasticization efficiency and low-temperature flexibility when blended with vinyl chloride resin, it cannot be used in cases where a higher degree of low-temperature flexibility is required. Moreover, this plasticized vinyl chloride resin has insufficient non-migration properties when it comes into contact with other resins.

In order to improve the low-temperature flexibility of polyester plasticizers, it is possible to lower their molecular weight, but there is a limit due to the balance with other physical properties, and properties such as non-migration properties decrease as the molecular weight decreases. do.

Similarly, in order to improve the non-migration properties of polyester plasticizers, their molecular weight may be increased, but as a result,
It becomes highly viscous, resulting in poor handling and workability, and properties such as low-temperature flexibility deteriorate.

As described above, conventional polyester plasticizers have not been able to satisfy properties such as low-temperature flexibility and non-migration properties to a high degree and at the same time in a well-balanced manner.

(Means for Solving the Problem) As a result of intensive research into polyester plasticizers that do not have the above drawbacks, the present inventors found that polyester containing 1,12-octadecanediol as an essential component constituting polyester was used in vinyl chloride resin. The present inventors have discovered that when blended, properties such as non-migration and low-temperature flexibility are well-balanced and extremely excellent, leading to the completion of the present invention.

That is, the present invention provides a plasticizer characterized by using 1,12-octadecanediol as an essential component constituting a polyester, and a halogen-containing resin composition containing the same.

(Constitution) The plasticizer of the present invention is a glycol component containing 1.12-octadecanediol as an essential component, a dibasic acid component and a monohydric alcohol used as necessary, or a polyester containing a basic acid as a constituent component. It is.

1 used to constitute the polyester of the present invention,
Glycol components that may be used in combination with 12-octadecanediol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,
2-butylene glycol, 13-butylene glycol,
1.4-butylene glycol, neopentyl glycol, 1.5-bentanediol, 3-methyl 1,5-bentanediol, 1,6-hexanediol, 2,2.4
-trimethyl 1,3-bentanediol, 2ethyl L3
Examples include aliphatic glycols such as -hexanediol and 2-methyl 1.9nonanediol, and polyalkylene glycols such as diethylene glycol and dipropylene glycol. These glycols may be used alone or as a mixture of two or more.

Dibasic acid components used to constitute polyester include aliphatic dibasic acids such as succinic acid, maleic acid, fumaric acid, geltaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and phthalic acid. , aromatic dibasic acids such as isophthalic acid or terephthalic acid, alicyclic dibasic acids such as tetrahydrophthalic acid and hexahydrophthalic acid, or anhydrides and esters thereof. Of course, these dibasic acids may be used alone or in a mixture of two or more.

A monohydric alcohol or a monobasic acid is used as necessary to constitute the polyester, but it is usually preferable to use these components from the viewpoint of product design of the polyester.

Examples of the monohydric alcohol component include butanol, hexanol, isohexanol, heptatool, isoheptatool, octatool, isooctatool, 2-ethylhexanol, nonanol, isononanol, 2-
Methyl octatool, decanol, indecanol, undecanol, dodecanol, tridecanol, tetradecanol, hexadecanol, octadecanol and the like are used singly or in a mixture of two or more.

Basic acids include acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, isooctanoic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid,
Examples include linoleic acid, wasillic acid, and 12-hydroxystearic acid, which may be used singly or in a mixture of two or more.

Furthermore, the polyester can contain trihydric or higher polyhydric alcohols and polybasic acids such as glycerin, pentaerythritol, trimellitic acid, and pyromellitic acid as constituent components, if necessary. In addition, lactones having 3 to 12 carbon atoms such as ε-caprolactone, methyl ε-caprolactone, β-methyl δ-valerolactone,
Epoxidized methyl, butyl and octyl stearate esters can also be used as modifiers, if appropriate.

The polyester plasticizer of the present invention preferably has a number average molecular weight of 600 to 20,000 and is obtained by condensing the above-mentioned components with 1,12-octadecanediol as an essential component.

Such polyesters can be produced by various known esterification methods. For example, when reacting the glycol, dibasic acid and -hydric alcohol or monobasic acid used to obtain a polyester with a desired molecular weight,
Although their molar ratio is important, this molar ratio is not uniform and it is necessary to select an appropriate molar ratio depending on the type of glycol, dibasic acid, -hydric alcohol, or monobasic acid used. In addition, at the initial stage of the reaction, only the glycol and the dibasic acid are reacted in the presence or absence of a solvent capable of azeotroping with water such as toluene or xylene, and when the appropriate acid value or hydroxyl value is obtained, m The reaction can be continued by adding alcohol or monobasic acid. Further, the target polyester can be obtained by reacting polyester components such as glycol, dibasic acid, -hydric alcohol, or monobasic acid all at once, or by reacting two of them as appropriate and then reacting the remaining one.

The polyester production reaction is promoted by acid catalysts such as sulfuric acid, paratoluenesulfonic acid, and phosphoric acid, and metal compound catalysts such as tetraisopropyl titanate, tetrabutyl titanate, dibutyltin oxide, dioctyltin oxide, and zinc chloride. Usually, it is preferable to carry out the reaction in the presence of these catalysts.

The plasticizer according to the present invention produced in this manner has superior properties such as low temperature flexibility and non-migration properties compared to conventional polyester plasticizers.

(2) The content of 12-octadecanediol is preferably in the range of 2 to 50% by weight in the polyester component.

1. If the content of 12-octadecanediol in the polyester component is less than 2% by weight, properties such as low temperature flexibility and non-migration will be insufficient, and if it exceeds 50% by weight, lubricity will increase and gelation will occur. Performance decreases.

The polyester plasticizer of the present invention is used as a plasticizer for synthetic resins, especially halogen-containing resins.

Examples of such halogen-containing resins include vinyl chloride resins, vinyl chloride-vinyl acetate copolymer resins, vinylidene chloride resins, vinyl chloride-vinylidene chloride copolymer resins, and chlorinated polyolefin resins. The amount of plasticizer blended is usually 5 to 150 parts by weight, more preferably 20 to 100 parts by weight, per 100 parts by weight of the halogen-containing resin.

In addition, the plasticizer according to the present invention may be a well-known plasticizer used in the field of processing halogen-containing resins, such as phthalate esters, just like other polyester plasticizers.
Can be used in combination with adipic acid esters, trimellitic acid esters, pyromellitic acid esters, epoxidized fatty acid esters, chlorinated fatty acid esters, chlorinated paraffins, and polyester plasticizers other than the plasticizer of the present invention. can. Furthermore, it can be used in combination with stabilizers, fillers, pigments and other additives used in the field of processing halogen-containing resins.

Next, the present invention will be specifically explained using Examples, Comparative Examples, and Test Examples. Note that all of these "parts" mean "parts by weight."

Examples 1 to 6 The dibasic acid and glycol components of the polyester components in the amounts specified in Table 1 were placed in a reaction vessel, heated under stirring in a nitrogen gas stream, and the produced water was continuously distilled off. The temperature was raised to 220°C over a period of 3 hours. After that, a specified amount of m alcohols or monobasic acids and an amount of dibutyltin oxide corresponding to 0.03% by weight of the polyester constituents were added as a catalyst, and a reflux condenser was attached, and the reaction was carried out at a maximum temperature of 220°C (However, When using a monohydric alcohol, the acid value is 3 or less; when using a -basic acid, the acid value is 1.
(Heating was continued until the temperature decreased to 5 or less, followed by a dehydration reaction.)

Next, after carrying out the reaction under reduced pressure and removing the distillate,
A polyester plasticizer was obtained by filtration.

Comparative Examples 1 to 3 For comparison, polyester plasticizers were obtained in the same manner as in the Examples using polyester components in the amounts specified in Table 1.

The properties obtained in the above Examples and Comparative Examples are also summarized in Table 1.

/ / / Test Examples Sheets were prepared using the plasticizers obtained in Examples and Comparative Examples according to the following basic formulations and molding conditions, and physical property tests were conducted.

The results are shown in Tables 2 and 3.

(Basic formulation) Polyvinyl chloride (degree of polymerization: 1050); 100 parts Plasticizer for Examples and Comparative Examples; 50 or 80 parts Barium-zinc composite stabilizer 0; 2 parts 9 Manufactured by Dainippon Ink and Chemicals Co., Ltd. Product name: Gretz MP-5680 (Forming conditions) Roll (6 inch diameter): 165℃XIO minute press (1
Fin thickness): 170℃ x 5 minutes (physical property test) ■) Hardness (JIS spring A scale); JIS K
Measured according to -6301.

2) Tensile test: Measured according to JIS K-6723.

3) Low temperature flexibility test; Measured according to JIS K-61454). It was shown that the lower the temperature, the better the low temperature flexibility.

Non-migration test H1w thick press sheet 25n x 40n
A test piece was punched out to a size of . ABS resin board (manufactured by Japan Synthetic Rubber Co., Ltd.; trade name JSR-15NP), II-PS resin board (manufactured by Dainippon Ink and Chemicals Co., Ltd.; trade name Dick Styrene GH-9100) and AS resin board ( Asahi Kasei (
Co., Ltd. (product name: STYLAC 767) was sandwiched between the same resin plates in a sandwich shape, and then heated at 70°C under a load of 1 kg/-.
After holding the resin plate for 72 hours, the state of corrosion caused by the transfer of the plasticizer to the resin plate was observed and evaluated.

Evaluation criteria: ○: Good with no corrosion due to plasticizer migration) △: Slight corrosion observed ×: Erosion due to plasticizer migration is obvious (bad) ××: Very poor (effect of the invention) Polyester plasticizers have extremely superior quality characteristics, such as low-temperature flexibility and non-migration, compared to conventionally known polyester plasticizers, and are used as plasticizers for vinyl chloride resins in applied processing fields. Great value.

Claims (1)

[Claims] 1. As essential components constituting polyester, 1, 12
- A polyester plasticizer characterized by using octadecanediol. 2. A halogen-containing resin composition containing the plasticizer according to claim 1.