JPH02150416A - Polyester plasticizer - Google Patents

Abstract

PURPOSE:To obtain the title plasticizer having excellent migration resistance of ABS resin and hydrolysis resistance by condensing a dibasic acid with a specific alkylene diol. CONSTITUTION:The aimed diol obtained by condensing a dibasic acid (e.g. adipic acid or phthalic acid) with an alkylene diol containing three or more branched chains comprising alkyl groups (e.g. 2,2,4-trimethyl-1,3-pentanediol or trimethyl-1,6-hexanediol). Another diol component such as 1,2-propanediol or 1,6-hexanediol may be used besides the above-mentioned diol.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to polyester plasticizers. Specifically, the present invention relates to a polyester plasticizer having excellent migration resistance and hydrolysis resistance.

(Prior art) Plasticizers are added to plastics to lower their melting temperature or melt viscosity to facilitate molding, and also to impart properties such as flexibility, elasticity, and cold resistance to plastics, making them durable. It is used to make plastics suitable for various uses.

As conventional plasticizers, monomeric plasticizers such as dioctyl phthalate and dioctyl adipate are often used, and polyester plasticizers are preferred for applications that require durability such as oil resistance and migration resistance. .

Polyester plasticizers include, for example, ethylene glycol, 1
．． 3-propanediol, 1,3-butanediol, 1
, polyhydric alcohols such as 4-butanediol and phthalic acid,
Manufactured by condensing polyhydric carboxylic acids such as adipic acid and trimellitic acid and terminal-treating with monohydric alcohol or monohydric carboxylic acid, it has superior oil resistance and migration resistance compared to other plasticizers. However, conventional polyester plasticizers do not have sufficient migration resistance to ABS resin (hereinafter referred to as ABS migration resistance). Furthermore, polyester plasticizers generally have the disadvantage of poor hydrolysis resistance.

(Problems to be Solved by the Invention) The present invention aims to obtain a polyester plasticizer having excellent ABS flGl properties and hydrolysis resistance.

(Means for Solving the Problems) In view of the above circumstances, the present inventors have made repeated studies and found that a polyester binder using a specific diol component has excellent ABS migration resistance and hydrolysis resistance. The present invention was achieved by confirming the following. That is, the gist of the present invention resides in a polyester plasticizer formed by condensing a dibasic acid with an alkylene diol having three or more branched chains consisting of alkyl groups.

The present invention will be explained in detail below.

As the dibasic acid component used in the polyester plasticizer of the present invention, various aliphatic, aromatic, and alicyclic dibasic acids or anhydrides thereof used in the production of conventional polynistyl plasticizers are used.

Specific examples include adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, and anhydrides thereof, and one type or a mixture of two or more of these can be used.

The polyester plasticizer of the present invention has, as a diol component,
The main point is to use an alkylene diol having three or more branched chains consisting of alkyl groups.

The number of carbon atoms in the branched alkyl group is preferably 1 to 4, and specific examples of alkylene diols include, for example, 2°2.4-
) riftyl-1,3-bentanediol, trimethyl-
Examples include 1,6-hexanediol.

In addition to the above-mentioned alkylene diol, other diol components can also be used together, but the alkylene diol having three or more branched chains consisting of alkyl groups is preferably 20 m 11% or more based on the amount of the total diol component. is 30
ii It is necessary to use fi% or more.

Examples of other diol components include 1.2-propanediol, 1.2-butanediol, and 1.3-butanediol! , 4-butanediol, 2,2-dimethyl-1
, 3-propanediol, 1,6-hexanediol and the like.

During production of the polyester plasticizer of the present invention, it is necessary to add a well-known monobasic acid or -hydric alcohol having 4 to 18 carbon atoms as a molecular weight regulator. - Examples of basic acids include caproic acid, caprylic acid, lauric acid, myristic acid, stearic acid, coconut oil fatty acids, etc.
Examples of the -hydric alcohol include hexanol, heptatool, n-octatool, 2-ethylhexanol, nonanol, decanol, undecanol, tridecanol, stearyl alcohol, and the like.

Used when producing the polyester plasticizer of the present invention,
The ratio of the alkylene diol having three or more branched chains consisting of alkyl groups and the dibasic acid varies greatly depending on whether a monobasic acid or a -hydric alcohol is used as the molecular weight regulator; When used together, it is usually desirable to use 0.1 to 4 equivalents of the dibasic acid component per 1 equivalent of the total diol component, although it also depends on the amount. The amount of the alcohol used is preferably 0.02 to 6 equivalents per equivalent of the total diol component, and the amount of the basic acid used is:
It is preferable that the amount is 0.02 to 4 equivalents based on 1 equivalent of all diol components.

More specifically, for example, when using a -hydric alcohol as a molecular weight regulator, the total diol component molar ratio is 20 to 49, the dibase m is 40 to 50 molar ratio, and the -hydric alcohol is 40
2 molar ratio is suitable, and when a basic acid is used as a molecular weight regulator, the total diol component is 40 to 2 molar ratio.
50 molar ratio, dibasic acid 20 to 49 molar ratio, -basic acid 4
A molar ratio of 0 to 2 is preferred.

In order to produce the polyester plasticizer of the present invention, conventionally known methods for producing polyester plasticizers can be employed. That is, it can be produced by either a method of directly condensing the dibasic acid or its anhydride with a diol, or a method of reacting a lower alkyl ester of the dibasic acid with a diol.

For example, a dibasic acid, an alkylene diol having three or more branched chains consisting of alkyl groups, and a monobasic acid or monohydric alcohol as a molecular weight regulator are mixed in the presence or absence of a catalyst, if necessary in a nitrogen atmosphere. The boiling point of the reaction mixture (
The reaction is carried out above the azeotropic point. After the reaction has progressed to a certain extent, the pressure in the system is reduced, and while gradually increasing the degree of vacuum, excess alcohol, molecular weight regulator, etc. are removed. Usually, the temperature at the end of the reaction is about 200°C and the pressure is 1 to 10
mmHg. In addition, at the beginning of the reaction, only the dibasic acid and alkylene diol are used, if necessary, toluene,
It is also possible to carry out the reaction using a solvent such as xylene which is azeotropic with water but not compatible with it, and when a certain degree of acid value or hydroxyl value is obtained, a molecular weight regulator can be added to continue the reaction.

As the catalyst, well-known catalysts such as sulfuric acid, phosphoric acid, p-
) Acid catalysts such as luenesulfonic acid, titanium compounds such as tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetrabutyl titanate, diethyltin dilaurate, dibutyltin oxide, dibutyltin diacetate,
Examples include combinations of tin compounds such as tin oxide, acetates of magnesium, calcium, zinc, etc., and antimony oxide or the above-mentioned titanium compounds.

The polyester plasticizer of the present invention is used as a plasticizer for synthetic resins, particularly halogen-containing synthetic resins such as vinyl chloride resins, vinylidene chloride resins, and chlorinated polyolefins. Examples of the vinyl chloride resin include vinyl chloride homopolymers, copolymers, and mixtures thereof, and regardless of the polymerization method, suspension polymerization products, emulsion polymerization products, and bulk polymerization products are all applicable. As the vinylidene chloride resin, a vinylidene chloride homopolymer or copolymer, or a mixture thereof is used.

The polyester plasticizer of the present invention may be used in combination with other well-known plasticizers used in the field of halogen-containing synthetic resin processing, such as phthalate esters and aliphatic dibasic acids, to the extent that the purpose of the present invention is not impaired. Esters, polyhydric alcohols, basic acid esters, epoxidized fatty acid esters, trimellitic acid esters, chlorinated fatty acid esters, chlorinated paraffins, phosphoric acid esters, or well-known polymer modifiers, It can be used in combination with heat stabilizers, antistatic agents, lubricants, pigments, etc.

When the polyester plasticizer of the present invention is used, for example, in a vinyl chloride resin, it is added in an amount of 5 to 300 parts by weight, preferably 15 to 200 parts by weight, per 100 parts by weight of the vinyl chloride resin. Uniformly mix or knead using a mixer, ball mill, ribbon mixer, change can mixer, super mixer, crusher, mixing roll, Σ blade kneader, Banbury mixer-1 high-speed twin-screw continuous mixer, extruder type kneader, etc. It is molded as a resin composition and used for applications such as films, sheets, containers, flooring materials, and wall materials.

As shown in the examples below, the polyester plasticizer of the present invention has superior AB and B compared to known polyester plasticizers.
Has S migration resistance and hydrolysis resistance.

(Example) The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to the following examples unless it exceeds the gist thereof.

The acid value and hydroxyl value of the polyester plasticizer in the following Examples and Comparative Examples were measured in accordance with JIS 0070, and the viscosity was measured at 25°C using an E-type viscometer (EM type).

Further, the ABS migration resistance and hydrolysis resistance of the polyester plasticizer were measured by blending the polyester plasticizer into the vinyl chloride resin and using the following method.

[Preparation of test piece] The polyvinyl chloride resin to be tested is mixed with a polyester plasticizer and a prescribed stabilizer using a Henschel mixer, kneaded with heated rolls, and then press-molded to create a sheet. It was cut to the specified size.

[ABS migration resistance]: (1) Inland method A test piece with a length of 40 am, a width of 2 mm, a thickness of 1 mm was sandwiched between two ABS resin plates, and a load of 1 kg was applied, and the specimen was heated at 70°C for 96 hours. After leaving it closed, ABS
The surface condition of the resin plate is observed and the degree of migration of the polyester plasticizer in the test piece is visually determined and evaluated.

[Evaluation] ◎: No traces of migration at all O: Some traces of migration ×: Severe migration (2) A length of 40 mm in 200 g of polyester plasticizer for immersion test
An ABS resin plate of mm, width 40 I, thickness 2.5 nun was immersed and left at 70°C for 4 hours.
II. The resin board was taken out, its surface condition was observed, and the degree of transfer of the polyester plasticizer was visually judged, and from the rate of change in charge (%) of the ABS resin board before and after the test,
Determine the degree of migration of polyester plasticizer.

[Evaluation] ◎: Claws remain ○: Some gloss remains △: Claws have disappeared ×: Surface has melted [Hydrolysis resistance]: Circular shape with a radius of 25 mm and a thickness of 1 mm The specimens are immersed separately in previously prepared 1% aqueous soap solution and 5% aqueous caustic soda solution and sealed. This was placed in an oven at 50°C and left for 96 hours, then taken out, the stickiness on the surface of the test piece was wiped off, and the test piece was dried in an oven at 50°C for 24 hours. Measure the weight of the test piece after drying, and determine the weight change rate (%) from the weight of the test piece before the test.

Example 1 Adipic acid 292 was placed in a 1000 ml flask equipped with a thermometer, fractionator tube, nitrogen inlet tube, stirrer, reflux condenser, etc.
277.4 g of 2,2.4-)methyl 1,3-bentanediol and 130 g of 2-ethylhexanol (a molecular weight regulator) were charged, and the temperature was raised to 220°C by heating while stirring under a nitrogen stream. did. Next, 0.024 it of tetraisopropyl titanate was added and the reaction was carried out at the same temperature, and the water produced during that time was continuously distilled out of the system from the fractionating tube, and the acid value of the reaction solution was determined by m g K O
The reaction was continued until It fell below It /8. Thereafter, the pressure inside the system was reduced to 5 mm Hg or less, and the reaction was carried out at 220° C. for 3 hours to obtain the desired polyester plasticizer (referred to as plasticizer A). Table 1 shows the physical properties of the obtained plasticizer A.

Example 2 Adipine [292 g, ) riftyl 1,6-hexanediol 272 g and 2-ethylhexanol 143 g
were reacted under the same conditions as in Example 1 to obtain a polyester plasticizer (referred to as plasticizer B). Its physical property values are shown in Table 1.

Comparative Example 1 Adipic acid 292 g, 2.2-dume. Chiru 1.3
-Propanediol (neopentyl glycol) 187
．． 6 g and 2-ethylhexanol 1308 were reacted under the same conditions as in Example 1 to obtain a polyester plasticizer (referred to as plasticizer C) having physical properties shown in Table 1. Its physical property values are shown in Table 1.

Comparative Example 2 Instead of 2,2,4-trimethyl 1,3-bentanediol in Example 1, 1,3-butanediol and 1
A polyester plasticizer (referred to as plasticizer) was obtained in the same manner using an equal mixture of 4-butanediol.

The physical property values are shown in Table 1.

Table 1 Reference example polyvinyl chloride resin (YM-1100, degree of polymerization 1100
100 parts by weight of the homopolymer (manufactured by Mitsubishi Kasei Vinyl Co., Ltd.), 67 parts by weight of the plasticizer obtained in the above Examples and Comparative Examples, and a Cd-8a stabilizer (L-500, manufactured by Eishin Kasei Co., Ltd.).
parts by weight using a Henschel mixer, and kneaded for 5 minutes with an 8-inch roll at a roll temperature of 170°C to form a sheet.

The obtained sheet was placed in a press molding machine at 180°C and press molded under the conditions of a press pressure of 200 kg/cm2, pressurization for 3 minutes, and cooling for 3 minutes. A test piece was prepared from this press sheet, and ABS migration resistance and hydrolysis resistance were measured. The results are shown in Table 2.

(Effects of the Invention) As shown in Table 2, the polyester superplasticizer of the present invention is more effective than the conventional polyester plasticizer.
It is clear that it has resin migration resistance and hydrolysis resistance, and its practical value is great.

Table 2

Claims (1)

[Claims] (1) A polyester plasticizer formed by condensing a dibasic acid with an alkylene diol having three or more branched chains consisting of alkyl groups.