JPH01158060A - Polyester plasticizer - Google Patents

Abstract

PURPOSE:To provide a polyester plasticizer composed of a dibasic acid, a specific glycol and a lactone and/or an aliphatic oxycarboxylic acid and effective in imparting a halogen-containing resin with extremely excellent migration resistance and low-temperature flexibility. CONSTITUTION:The objective polyester plasticizer is produced by the thermal catalytic reaction of (A) a dibasic acid (e.g., adipic acid or phthalic anhydride), (B) a glycol of formula I (X is 1-4C hydrocarbon group; R1 is H or 1-4C alkyl; R2 is 1-4C alkyl) (e.g., 2-methyl-1,3-propanediol) accounting for 10-100mol% of the glycol component, (C) a lactone of formula II (Y is 2-17C aliphatic hydrocarbon group) (e.g., beta-propiolactone) and/or a 3-18C aliphatic oxycarboxylic acid (preferably hydrogenated castor oil) in an amount of 10-100mol% based on the component A and, as necessary, (D) a terminal stopper (e.g., monoalcohol).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel polyester plasticizer.

(Prior art and its problems) There are a wide variety of uses for soft vinyl chloride products made by blending plasticizers with polyvinyl chloride resin, but they are used in electrical wire coatings, automobile parts, leather, boots, f-sketches, hoses, etc. Excellent oil resistance and non-migration properties are required, and polyester plasticizers are used as plasticizers to be added to these materials.

However, in these application fields, demands for quality improvement are stricter than in the past, and in particular, wire coating,
For applications such as f-sketches, the required qualities of non-migration and low-temperature flexibility are high, and conventional plasticizers are required to provide internal magnetism.

In order to improve the quality characteristics of polyester plasticizers, for example, JP-A-49-18927 proposes a polyester containing 3-methyl-1,5-bentanediol as a glycol component; Polyester plasticizers using neopentyl glycol as a glycol component are said to be excellent non-migration plasticizers, but they are not sufficiently non-migration and have insufficient low-temperature flexibility.

(Means for Solving the Problems) As a result of intensive research, the present inventors succeeded in greatly improving the non-migration property and low-temperature flexibility, and completed the present invention.

That is, the present invention provides ``(1) glycol with the following general formula [
Glycol 10 100 represented by I] and (2) a lactone represented by the following general formula [river] and/or a carbon number of 3 to
18 aliphatic oxycarboxylic acids to dibasic acids 10~
A polyester plasticizer containing 100 molti as an essential ingredient.

(Note) General formula [■]: HO-CH2- X-CH20H General formula (II) Y C/! . (However, Y202 to C17 are aliphatic hydrocarbon groups).

The polyester plasticizer of the present invention can be prepared by heating and reacting a dibasic acid, the glycol, the cyclic ester and/or the oxcargonic acid, and a monoalcohol or a basic acid as a terminal stopper in the presence of a catalyst. can get.

Glycols of general formula [I] used to produce the polyester of the present invention include 2-methyl-1,3-gulononediol, 2-ethyl-1,3-furopanediol, and 2,2-dimethyl- 1.3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, 2.2-diethyl-1.3-flonodiol,
2-Ethyl-2-n-butyl-1,3-furopanediol, 2-mef-1,4-butanediol, 2-ethyl-1,4-butanediol 1,2-butyl-1,4-butanediol , 2,2-dimethyl-1,4-butanediol, 2-methyl-2-ethyl-1,4-butanediol, 2-)f-1,5-bentanediol, 3-methyl-1,5-bentanediol Diol, 2-ethyl-1.5
- hentanediol, 3-f role-1.5 --e
Examples include tantanediol, 3-methyl-1,6-hexanediol, and the like. In the present invention, the glycol of general formula [■] may be used in combination, and further glycols other than general formula (1) may be used in combination. Such glycols include ethylene glycol, 1,2-7' lono4diol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-bentanediol, 1,4- Examples include bentanediol, 1,5-hexanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, diethylene glycol, and the like.

Examples of lactones represented by the general formula [old] include β-proviolac 5t, r-butyrolactone, δ-ha L/rolactone, γ-valerolactone, ε-caprolactone,
Examples include methyl-e-caprolactone, dimethyl-8-caprolactone, trimethyl-ε-caprolactone, and the like. In addition, examples of aliphatic oxycarboxylic acids having 3 to 18 carbon atoms include lactic acid, ω-oxycaproic acid, ω-oxylauric acid, ω-oxycarboxylic acid, ricinoleic acid, 9-
Examples include hydroxystearic acid, 12-hydroxystearic acid, hydrogenated castor oil fatty acid, hydrogenated castor oil, and the like. Among these, when 12-hydroxystearic acid, hydrogenated castor oil fatty acid and hydrogenated castor oil are used, it shows non-migration, especially non-migration to As resin (acrylonitrile-styrene copolymer), and low-temperature flexibility. The improvement effect is large. In addition, since hydrogenated castor oil undergoes transesterification during the reaction to produce hydrogenated castor oil fatty maric acid, it is used as an effective oxy-7-cardic acid. The above-mentioned lactone and/or the above-mentioned oxy-7 caldic acid has a ratio of 10 to 10% relative to the dibasic acid.
0 molti used. If the amount is less than 10 moles, the effect of improving the non-migration properties and low-temperature flexibility of the composition will be insufficient, and if it exceeds 100 moles, the processability of the composition will decrease.

Examples of dibasic acids include saturated aliphatic dibasic acids such as adipic acid, azelaic acid, and sepacic acid; aromatic dibasic acids such as phthalic acid, inphthalic acid, and terephthalic acid; and anhydrides thereof. Of course, not only one kind of these dibasic acids but also a mixture of two or more dibasic acids can be used.

The monoalcohol or basic acid as the terminal capping agent is specifically a saturated aliphatic alcohol having 2 to 22 carbon atoms, preferably 6 to 18 carbon atoms, or a saturated fatty acid having the same number of carbon atoms, and may be used alone or in a mixture of two or more. Ru. In addition, this polyester may not be used depending on the case. Typical examples of such monoalcohols include butanol, hexanol, inhexanol, heptatool, le-octanol, inoctatool, 2-ethylhexanol, nonanol, innonanol, 2-methyloctatool, decanol, and indecanol. , undecanol,
dodecanol, tridecanol, indridecanol,
Examples include tetradecanol, pentadecanol, hexadecanol, and octadecanol. In addition, monovalent carmenic acids include acetic acid, propionic acid, butyric acid, cabroic acid, caprylic acid, inoctanoic acid, 2-ether-hexanoic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, Examples include aliphatic monovalent carzenic acids and benzoic acids such as linoleic acid and lylunic acid, or aromatic monovalent carmenic acids such as toluic acid, and especially mixed fatty acids derived from coconut oil or palm oil and their hydrogen. Additives are preferably used.

The present polyester can be produced by various methods such as esterification reaction and transesterification reaction as described by those skilled in the art.

For example, when reacting a glycol, a dibasic acid, a lactone and/or an oxycardic acid, and a terminal capper to obtain a polyester with a desired molecular weight, glycol/dibasic W lactone and/or oxycardic acid/terminal The molar ratio of the terminator is important, but this molar ratio is not uniform and depends on the glycol, dibasic acid, lactone and/or
Alternatively, it is necessary to select an appropriate molar ratio depending on the type of oxy-7-cardic acid or terminal capping agent. 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 that can be azeotropically distilled with water, such as toluene or xylene, but is not compatible with it, and the appropriate acid value is obtained. Alternatively, the reaction can be continued by adding a terminal capping agent once the hydroxyl value is obtained. In this case, a monoalcohol as a terminal capping agent can also be used as the solvent.

Polyester production reactions are carried out using acidic catalysts such as sulfuric acid, cynic acid, zinc chloride, sodium bisulfite, dibutyltin oxide, tetraline glovir titanate, tin oxalate, zinc acetate, aluminum, diimbu oz-++a)', -oxidation. It is promoted by metal compound catalysts such as lead, anti-trioxide, and stannous oxide, so it is usually started by heating to a temperature at which water can be distilled off at atmospheric pressure in the presence of these catalysts. Once the distillation is complete or essentially complete, reduce the pressure and continue to remove excess glycol and endcapper.

At the end of the reaction, the pressure is usually 1 to 15111 Hg.

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

Such plasticizers according to the invention are used as plasticizers for synthetic resins, especially heron-containing resins. Such heron-containing resins include vinyl chloride resins, vinylidene chloride resins, chlorinated polyolefins, and the like. Its blending amount is usually 5 to 150 parts by weight per 100 parts of synthetic skin oil. Also, the plasticizer of the present invention is used in the field of processing rodan-containing resins, just like other polyester plasticizers. Used in combination with well-known plasticizers such as phthalates, adipates, trimellitates, epoxidized fatty acid esters, chlorinated fatty acid esters, chlorinated paraffins, phosphate esters, etc. You can also do that.

(Example) Next, the present invention will be specifically explained with reference to Examples, Comparative Examples, and Test Examples, but the present invention is not limited thereto. In addition, all parts in the following Examples and Comparative Examples are parts by weight. shows.

Examples 1 to 4 A reaction vessel was charged with dibasic acid, glycol and lactone and/or oxycargenic acid in the amounts specified in Table 1,
Heating was carried out under stirring in a nitrogen gas stream, and the temperature was raised to 210° C. over 7 hours while continuously distilling off the produced water. After that, a specified amount of monohydric alcohol shown in Table 1 and diptyltin oxide in an amount equivalent to 0.03% of the polyester raw material chamber t (hereinafter referred to as the charged amount) were added as a catalyst, and a reflux condenser was attached. The mixture was heated at a maximum temperature of 220° C. until the acid value became 2 or less, and the produced water was gradually removed using a water separator. After removing excess alcohol and low boiling point under reduced pressure, the mixture was cooled to 100° C. and exposed to F to obtain a polyester plasticizer.

Comparative Examples 1 to 4 For comparison, polyester plasticizers were obtained in the same manner as in Examples using the raw material compositions shown in Table 1.

The properties of the various polyester plasticizers obtained in the above Examples and Comparative Examples are summarized in Table 1.

Test Examples For each plasticizer obtained in Examples and Comparative Examples, press sheets were prepared according to the following basic formulations and molding conditions, and the following physical property tests were conducted. The results are shown in Tables 2 and 3.

(Basic blend) A blend B blend polyvinyl chloride (polymerization degree: 1050) 100 parts 1
Plasticizer of 00 Examples and Reference Examples 50 parts 10
0 parts barium-zinc composite stabilizer (2 parts
2 parts (Note) *: Manufactured by Dainippon Ink and Chemicals Co., Ltd. Part name: Grec MP-5680 (Forming conditions) Roll (6 inch diameter) 165°C x 10 minutes press (1ii + thickness) 170C x 5 minutes (physical property test) l ) Hardness (JIS Sugerink A) r-ru): J
Measured according to IS K-63'01.

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

3) Low temperature flexibility test: Measured according to JIS K-6745. It shows that the lower the temperature, the better the low temperature flexibility.

4) Non-gravity test A test piece was prepared by punching out a 1 μ thick press sheet into a size of 25 x 40 nm.

ABS JR fingerboard made by Japan Synthetic Rubber Co., Ltd., product name JSR-15NP), Hl-PS Wei fingerboard made by Dainippon Ink and Chemicals Co., Ltd., product name Dayx Styrene GH
-9100) and AS [ABS after being sandwiched between fingerboards (back of Asahi Kasei Corporation, product name Stylac 767), then held at 70°C for 72 hours under a load of 0.5 kg/z Resin plate, HI-PS resin plate and A
The state of corrosion caused by the transfer of plasticizer to the resin board was observed and evaluated.

5) Roll processability test The above-mentioned basic composition was kneaded by rolls for 1650.10 minutes, and the agglomeration speed, adhesion and puncture stability against the rolls were comprehensively observed and evaluated.

(Effects of the Invention) The polyester plasticizer of the present invention has excellent non-migration properties and low-temperature flexibility, especially when blended with a resin containing rhodan.

Agent: Patent Attorney Katsutoshi Takahashi

Claims (1)

[Claims] (1) 10 to 100 mol% of a glycol represented by the following general formula [I] as a glycol component; and (2) a lactone and/or a carbon number of 3 to 18 represented by the following general formula [II].
of aliphatic oxycarboxylic acid to dibasic acid.
A polyester plasticizer containing 0 mol% as an essential component. (Note) General formula [I]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, X: C_1 to C_4 hydrocarbon group R_1: R or C_1 to C_4 alkyl group R_2: C_1 to C_4 alkyl group) General formula [II]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, Y: C_2 to C_1_7 aliphatic hydrocarbon group)