JPH062858B2 - Polyester plasticizer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyester plasticizers. More specifically, a diol having an alkyl group having 3 to 4 carbon atoms 2
-It relates to a polyester plasticizer using ethyl, 2-alkyl 1,3-propanediol.

A soft vinyl chloride product obtained by blending a polyvinyl chloride resin with a plasticizer has excellent performance and is therefore used for various purposes. In general, phthalates such as DOP are widely used as plasticizers used in the production of soft vinyl chloride products, but when the plasticizers used are transferred to other materials, there are often drawbacks.

For this reason, polyester plasticizers have come to be used as plastics having a low migration property. This polyester plasticity is roughly classified into various adipate-based, phthalate-based, and sebacate-based polyester plasticizers, which are currently on the market.

However, polyester plasticizers generally have poor water resistance (prone to hydrolysis), and a so-called bleeding phenomenon occurs in which the polyester plasticizer is blended and the polyester plasticizer blows out to the surface of a soft vinyl chloride product ( Hereinafter referred to as burritability).
Further, a polyester plasticizer using neopentyl glycol as a siol is known, but it is still insufficient in terms of water resistance, bleeding property and migration property.

The present inventors have diligently studied to improve these drawbacks. As a result, when a polyester plasticizer using 2-ethyl, 2-alkyl1,3-propanediol having an alkyl group having 3 to 4 carbon atoms as a diol component is used as a soft vinyl chloride product, water resistance is improved. It was found that the bleeding property and the plasticizer migration property were significantly improved, and the present invention was completed.

As is clear from the above description, the object of the present invention is that the diol component has an alkyl group having 3 to 4 carbon atoms.
The use of ethyl, 2-alkyl 1,3-probandiol provides polyester plasticity with improved water resistance, bleeding and migration.

The present invention has the following configurations.

(1) Aliphatic dicarboxylic acid (A) and 2-ethyl, 2-alkyl 1,3-wherein the alkyl group has 3 to 4 carbon atoms
Propanediol (B) or a mixed diol (B) of the diol with a diol selected from propylene glycol, butanediol, pentanediol, hexanediol and a mixture of two or more thereof, and a monovalent aliphatic alcohol ( C) to the molar ratio (A) :( B):
(C) = a polyester plasticizer obtained by reacting at a ratio of 3: 3: 2: to 6: 6: 2, having a viscosity of 3000 measured at 25 ° C. using a single cylinder rotary viscometer. ~
7,000 cp polyester plasticizer for halogen containing resins.

The polyester plasticizer of the present invention comprises an aliphatic dicarboxylic acid (A), an aliphatic diol (B) and a monovalent aliphatic alcohol (C) (A) :( B) :( C) = 3: 3: 2:
It is obtained by heating reaction in the presence of a catalyst at a molar ratio of ˜6 :: 6: 2.

As the aliphatic dicarboxylic acid used, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid or the like can be used alone or in a mixture of two or more thereof.

Aliphatic diols include 2-ethyl, 2-alkyl 1,3
A diol in which the alkyl of propanediol has 3 to 4 carbon atoms, a mixture of these diols, and a mixture of the diol and another diol such as propylene glycol, butanediol, pentanediol, or hexanediol can be used.

At this time, the 2-ethyl, 2-alkyl 1,
The content of 3-propanediol is preferably equimolar or more to other diols.

Usual aliphatic alcohols such as hexanol, hebutanol, n-octanol, 2-ethylhesanol, stearyl alcohol and cetyl alcohol may be used as the aliphatic alcohol. Particularly, higher aliphatic alcohols having 6 to 16 carbon atoms are preferable.

The polyester plasticizer of the present invention is used as a plasticizer for halogen-containing resins such as polyvinyl chloride resin and polyvinylidene chloride resin. The polyvinyl chloride resin to be used is not limited depending on the polymerization method, and a suspension polymerization product, an emulsion polymerization product, a bulk polymerization product or the like obtained by any polymerization method may be used. Further, a vinyl chloride homopolymer or copolymer, or a mixture of two or more thereof may be used. As the polyvinylidene chloride resin, a vinylidene chloride homopolymer or copolymer or a mixture of two or more thereof is used.

Further, in the present invention, soft vinyl chloride resin, additives such as a vinylidene chloride soft resin, such as polymer modifiers, heat stabilizers, antistatic agents, lubricants, pigments, etc. It can be used within a range that does not damage it.

The various properties of the obtained polyester plasticizer were measured for oxidation, saponification value and hydroxyl value. The viscosity was measured at a temperature of 25 ° C. using a B type viscometer (BL type).

Further, regarding the water resistance, bleeding property and migration property of the obtained polyester plasticizer, the polyester plasticizer to be tested and the necessary stabilizer are mixed in a polyvinyl chloride resin with a conventional mixing device such as a Henschel mixer (trade name). After mixing and kneading with a heating roll, a sheet was formed by press forming, and a predetermined test piece was prepared from this sheet and tested.

As a result, the water resistance, bleeding and migration of the soft polyvinyl chloride resin product using the polyester plasticizer of the present invention is greatly improved as compared with the soft polyvinyl chloride resin product using the conventional polyester plasticizer. It was confirmed that the polyester plasticizer of the present invention is a polyester plasticizer having excellent water resistance, bleeding resistance and migration resistance.

The present invention will be specifically described below with reference to the present invention and comparative examples. The acid value and saponification value hydroxyl value measured in Examples and Comparative Examples were measured according to JIS K8004, and the tensile test was measured according to JIS K6723. The hardness was measured according to JIS K6301 (spring type hardness test A type), and the specific gravity was measured according to ASTM D792.

The viscosity was measured using a B-type viscometer (Vismetron (trademark), manufactured by Shibaura System Co., Ltd.) at a temperature of 25 ° C.

The water resistance, bleeding, migration test and heat stability test of the obtained polyester plasticizer were carried out by the following methods.

Water resistance test piece (JIS K7113 No. 2 type test piece) in advance at 90 ° C
Immerse in a stainless steel container containing hot water heated above and seal. This is placed in an oven at 100 ° C, left for 48 hours, then taken out, the stickiness on the surface of the test piece is wiped off, and then dried in an oven at 100 ° C for 2 hours. After drying, the weight of the test piece is measured to determine the rate of change in weight with the weight of the test piece before the test.

Bleedability test A test piece with a length of 60 mm, a width of 30 mm and a thickness of 1 mm was heated to 70
The surface state of the test piece is observed with time by keeping it at a constant temperature and humidity of 80 ° C. and a relative humidity of 80%, and the presence or absence of bleeding and the degree thereof are determined.

Transferability test A test piece with a length of 50 mm, a width of 50 mm, and a thickness of 1 mm is sandwiched between an ABS resin plate or an AS resin plate, a load of 1 kg is applied, and the sample is left at 70 ° C for 168 hours. Calculate migration.

Regarding transfer to an acrylic coated plate, a test piece is sandwiched between acrylic coated plates, left for 240 hours at a load of 1 kg, a temperature of 70 ° C. and a relative humidity of 80%, and the transferability is calculated from the weight change before and after the test.

Thermal stability test A test piece having a length of 30 mm, a width of 25 mm, and a thickness of 1 mm is put in a gear oven at 180 ° C., and the colored state of the test piece is observed every 10 minutes for comparison.

Example 1, Comparative Example 1 Various polyester plasticizers were synthesized as follows.

(1) Adipic acid 205.5 gr. , Dimethylol heptane (abbreviated as DMH, 2-n-butyl, 2-ethyl 1,
3-propanediol) 241.5 gr. , 2-ethylhexanol 83.2 gr. A thermometer, nitrogen inlet tube,
A flask having an inner volume of 1 equipped with a stirrer, a water separator and a reflux condenser was charged and heated while stirring in a nitrogen stream. When the temperature of the reaction solution reached 140 ° C, tetraisopropyl titanate was used as a catalyst. 0.1 gr. The reaction was carried out by controlling the temperature at 200 ° C. until the acid value of the reaction solution reached about 20 (mgKOH / gr.) While continuously adding water to the outside of the system by using a water separator. The reaction time was 2.5 hours. Then, this reaction system is 2-3
Under a reduced pressure of mmHg, a transesterification reaction was performed at 220 ° C. for 2.5 hours to obtain a predetermined polyester plasticizer.

(2) Adipic acid 275.4 gr. DMH 163.7 gr., 1,6-hexanediol 120.7 gr. A predetermined polyester plasticizer was obtained from 2,4-ethylhexanol 104.0 gr. Under the same reaction conditions as in the above (1).

As Comparative Example 1, (1) adipic acid 314.5 gr., Neopentyl glycol (NPG
Abbreviated) 267.4 gr.,-Ethylhexanol 108.6 gr. Were reacted under the same reaction conditions as in the above (1) to obtain a predetermined polyester plasticizer.

Two types of commercially available adipate polyester plasticizers were taken as comparative examples. The various properties of the various polyester plasticizers thus obtained are summarized in Table 1.

Example 2 and Comparative Example 2 In order to investigate the water resistance, bleeding property and migration property of the polyester plasticizer according to the present invention, 100 parts by weight of a polyvinyl chloride resin (a homopolymer having a Nipolit SM degree of polymerization of 1300) was synthesized in Example 1. 90 parts by weight of various polyester plasticizers,
As a stabilizer, 4 parts by weight of dibasic lead sulfate and 1 part by weight of lead stearate were mixed by a Henschel mixer, and the roll temperature was adjusted to 16
The mixture was kneaded with an 8-inch roll at 0 ° C. for 7 minutes. The obtained sheet is put into a breathing machine at 170 ° C and a breathing pressure of 150 kg / c.
Press molding was carried out under the conditions of m ² pressure for 3 minutes and cooling for 3 minutes, and a predetermined test piece was prepared from the obtained press seal and subjected to various tests. In addition to the water resistance, bleeding and migration tests, general performances such as tensile test, thermal stability, specific gravity and hardness were also measured. As Comparative Example 2, two kinds of polyester plasticizers synthesized in Comparative Example 1 and commercially available adipate polyester plasticizers were selected to prepare test pieces in the same manner as in Example 2, and various tests similar to those in Example 2 were performed. did. The results are summarized in Table 2.

As can be seen from Table 2, it was confirmed that the polyester plasticizer according to the present invention was greatly improved in water resistance, bleeding property and migration property as compared with the polyester plasticizers given in Comparative Examples. It was also confirmed that general performance such as tensile strength, specific gravity, hardness, and thermal stability was almost the same as that of the commercial product, and the performance was equivalent to that of the conventional product.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References Society of Detroleum Engineers Journal 19 (1963-9) (English) P984-991

Claims (2)

[Claims] 1. An aliphatic dicarboxylic acid (A) and a 2-ethyl, 2-alkyl-1,3-propanediol (B) having an alkyl group having 3 to 4 carbon atoms or the diol,
A molar ratio (A) of a mixed diol (B) with a diol selected from propylene glycol, butanediol, pentanediol, hexanediol and a mixture of two or more thereof and a monohydric aliphatic alcohol (C):
(B): (C) = Polyester plasticizer obtained by reacting at a ratio of 3: 3: 2 to 6: 6: 2, which was measured at a temperature of 25 ° C using a single cylinder rotational viscometer. Viscosity 30
A polyester plasticizer for a halogen-containing resin, which is from 00 to 7000 cp. 2. The polyester plasticizer for a halogen-containing resin according to claim 1, wherein the aliphatic dicarboxylic acid is succinic acid, glutaric acid, azelaic acid, sebacic acid or a mixture of two or more thereof.