JPS6141936B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new and useful plasticizer for vinyl chloride resins. Conventionally, di-2-ethylhexyl phthalate (hereinafter referred to as
(abbreviated as DOP) is used. Although this type of plasticizer has excellent compatibility with resin, it easily evaporates and migrates, so the major drawback is that the plasticizer gradually oozes out onto the surface of the molded product due to changes in environmental conditions. There is. As a result, various problems may occur, such as curing and deterioration during storage of the molded product, migration of plasticizer to the packaging material, and, in the case of wire coating materials, a decrease in electrical insulation.
In addition, since recent soft PPVC molded products have generally been used for harsh purposes, polyester is increasingly used as a plasticizer, but it does not have the drawbacks mentioned above. Although it has well-balanced physical properties, its cold resistance is extremely poor, so in practical use, it is recommended to use it in combination with DOP and di-2-ethylhexyl adipate (hereinafter abbreviated as DOA), which is a cold-resistant plasticizer. Therefore, the disadvantages caused by DOP and DOA cannot be avoided. Regarding the cold resistance of such polyester,
Various improvement methods have been proposed to balance other physical properties, but no satisfactory method has yet been found. For example, when one or both ends of polyester are blocked with oleic acid, stearic acid, lauric acid, pelargonic acid, etc., although good cold resistance is achieved, there is a significant decrease in UV stability.
This causes phenomena such as a decrease in hardness, resistance to cold agents, a decrease in heat aging resistance, and a decrease in photoselectivity. Furthermore, a method has been reported in which a specific dibasic acid and a polyhydric alcohol are used to react with a polyester, and then the end is blocked with a monobasic carboxylic acid or a monohydric alcohol ((a) JP-A No. 47-32315, (b) JP-A-Sho. 49-598853), but these are low temperature,
Durability and strength performance under harsh conditions such as high temperature, high humidity, and ultraviolet irradiation are insufficient.
In other words, (a) has the same performance as conventional sebacic acid-based polyester, and has the disadvantages of being a linear polyester, which bleeds easily, and has low durability and strength under the harsh conditions mentioned above. have or
Since (b) also produces linear polyester, it tends to bleed, and has the disadvantages of low durability and strength as described above, and poor Zeid temperature. The present invention was made to solve the above-mentioned drawbacks of such polyesters. That is, the present inventors prepared a polyhydric carboxylic acid (A) having 2 to 10 carbon atoms and a polyhydric alcohol having 3 to 10 carbon atoms, or a mixed alcohol of this polyhydric alcohol and a monohydric alcohol having 1 to 18 carbon atoms ( B), and general formula (1)

[Formula] (2) R ₁ —CH ₂ —COOH (However, R ₁ , R ₂ , and R ₃ each have 8 to 8 carbon atoms.
(1) alone or in a mixture with (2) containing at least 30% of (1), with a total carbon number of 10 to 24, preferably a total carbon number of 12 Of the three components of ~19 carboxylic acids (C), (A)
10 to 60% by weight, (B) 10 to 60% by weight, (C) 5 to 60% by weight
By blending polyester with a molecular weight of 800 to 12,000, which is obtained by co-condensation by mixing in a weight percent range, with vinyl chloride resin, it improves cold resistance and other physical properties, which were the drawbacks of conventional polyester plasticizers. We have discovered that poor balance can be dramatically improved, leading to the present invention. If necessary, plasticizers, stabilizers, lubricants, antioxidants, ultraviolet absorbers, and stabilizers other than those mentioned above may be added depending on the final use of the vinyl chloride resin molded product containing the polyester of the present invention as a plasticizer. There is no problem in using additives, dyes, fragrances, fungicides, and insecticides in combination. In addition, the polyester of the present invention can be used without affecting the degree of polymerization of vinyl chloride resin, and can be used in cellulose resins, polyvinyl alcohol, polyvinyl acetate resins, polyamide resins, polyolefin resins, vinylidene dichloride resins, acrylic resins, synthetic resins, etc. As a plasticizer for rubber, blend resins of these resins and polyvinyl chloride resins, and copolymer resins of vinyl chloride and vinyl acetate, higher alkyl vinyl esters, higher alkyl vinyl ethers, ethylene, acrylates, acrylonitrile, vinylidene chloride, etc. Although vinyl chloride resin can also be used, vinyl chloride resin has the most remarkable effect in achieving the object of the present invention. Among the three components constituting the polyester of the present invention, component A includes malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, ethylmalonic acid, butylmalonic acid, hexylmanic acid, phthalic anhydride, Examples include isophthalic acid, terephthalic acid, trimeltic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, malic acid, tartaric acid, citric acid, isomalic acid, and the like. Alcohols used for component (B) include ethylene glycol, 1.2-propylene glycol, trimethylene glycol, glycerin, φ-butylene glycol, diethylene glycol, trimethylolpropane, diglycerin, pentaerythritol, dipentarythritol, and 2.3.4-pentane. Polyhydric alcohols such as triol, dipropylene glycol, triethine glycol, tetraethylene glycol, tripropylene glycol, 1.4-butanediol, 1.6-hexanediol, 1.3-butanediol, methanol, ethanol, propanol, butanol, n-amyl alcohol , n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-nonyl alcohol, n-decyl alcohol, n-lauryl alcohol, n-cetyl alcohol, n-octadecyl alcohol, etc., or normal primary saturated alcohols such as these. Of these, isoprimary saturated alcohols, secondary and tertiary saturated alcohols, furfuryl alcohol, cyclohexanol, benzyl alcohol, 3-methylcyclohexanol, 2
-Phenylethanol, 2-phenoxyethanol, cyclohexylethanol, 2-phenyl-
2-propanol, cinnamic alcohol, 3-phenyl-1-propanol, cumin alcohol,
2-ethyl-β-phenylethyl alcohol, 1
-Methyl-4-isopropenyl-2-cyclohexanol, α-terpineol, diphenylmethanol, 3.5.5-trimethylhexanol, alphaanol #79, oxanol #78, Linibol #79, Linibol #911, Oxocol #710, etc. can give. The polyester of the present invention can be easily obtained by esterifying the above-mentioned components in a conventional manner in a one-step or two-step reaction to obtain a polyester having a molecular weight of 800 to 12,000. When the molecular weight is less than 800,
It exhibits properties similar to low-molecular plasticizers such as DOP and DOA, and exhibits significant oozing, poor migration resistance and cold resistance, and does not lose its properties as a polyester.Moreover, when the molecular weight is 12,000 or more, it becomes highly viscous. It has poor compounding workability with vinyl chloride resin and poor plasticizing efficiency in terms of physical properties, making it undesirable as a plasticizing agent. Next, a typical synthesis example of the polyester of the present invention will be shown, but this production method is merely an example, and the present invention is not limited by these production methods, as it can be synthesized by other production methods. do not have. The general analytical method for the polyester of the present invention obtained in the synthesis example is as follows:
The hue depended on the appearance. The acid value and specific gravity (25°C) are based on the standard oil and fat analysis test method (Japan Oil Chemists' Association) and the viscosity (25°C).
℃) was measured using a B-type viscometer, and the molecular weight was measured using the benzene freezing point depression method. Synthesis Example 1 In a 10 four-necked flask, 343gr of a monobasic carboxylic acid with 21 to 24 carbon atoms represented by general formula (1), 112gr butylmalonic acid, 1470gr trimethic acid, 100gr trimethylene glycol, and tetrabutyl titanium.
5.9gr was blended and a dehydration reaction was carried out at 190-198°C for 4 hours. When the acid value became constant, 910g of n-octanol was added, and a dehydration reaction was carried out at the azeotropic temperature of n-octanol and water. After theoretical dehydration, 220g of n-octanol was added.
Stirring was continued at °C, and the reaction was terminated when the viscosity became constant. Added 0.1% activated carbon and 0.2% activated clay,
The appearance of the product after heating at 120°C was a pale yellow transparent liquid with an acid value of 1.1, a specific gravity of 1.057, a viscosity of 61,200 centipoise, and a molecular weight of 8,550 to 8,650. Synthesis Example 2 184 gr of monobasic mixed carboxylic acid with 10 to 12 carbon atoms with linear chain ratio of 47%, 112 gr of 1.6-hexanediol, 68 gr of propylene glycol, pyromellitic acid
229gr and isobutanol 67gr, synthesis example 1
reacted accordingly. Appearance: pale yellow transparent liquid, acid value
1.2, specific gravity 1.06, viscosity 198,000 centiboise, and molecular weight 11,450 to 11,550. Synthesis Example 3 According to Synthesis Example 1, 146gr of monobasic mixed carboxylic acid having 12 to 15 carbon atoms with a linear chain rate of 700%, 195gr adipic acid, 150gr 1,3-butanediol, 0.34gr calcium acetate, and 0.34gr tetrabutyl titanium. I reacted. Appearance: pale yellow transparent liquid, acid value 1.0, specific gravity 1.028,
The viscosity was 460 centiboise and the molecular weight was 1250-1350. Synthesis Example 4 300 gr of basic carboxylic acid with 11 to 13 atoms represented by general formula (1), 105 gr of trimellitic acid, 135 gr of 1,3-butanediol, 0.2 gr of dibutyltin oxide
was mixed and heated to 198℃, and after 5 hours, the amount of dehydration was 58
ml, the acid value was 1.9, and 4 hours after raising the temperature to 230℃,
The reaction has ended. Appearance: pale yellow transparent liquid, acid value
1.1, specific gravity 1.02, viscosity 350 centipoise, molecular weight
It was between 950 and 1000. Synthesis Example 5 275gr monobasic carboxylic acid with 50% linear chain ratio of 16 to 19 carbon atoms, 332gr tetrahydrophthalic acid, 264gr glutaric acid, 477gr diethylene glycol, zinc powder
0.2gr was blended and the reaction was carried out according to Synthesis Example 1. Appearance: pale yellow transparent liquid, acid value 1.3, specific gravity 1.088, viscosity
It had a centipoise of 1650 and a molecular weight of 2350-2450. The following examples specifically demonstrate the advantageous and groundbreakingly excellent test results of the polyester of the present invention as a plasticizer component for vinyl chloride resin molded products; However, the present invention is not limited in any way. Example 1 The polyesters of the present invention obtained in Synthesis Examples 1 to 5 were kneaded into polyvinyl chloride resin and tested under the following conditions. The results are shown in Table 2. Compounding conditions Polyvinyl chloride resin (P1100) 100 parts by weight Inventive polyester 50 Organic calcium-zinc salt composite stabilizer 1 Film forming conditions Film forming process, two calender rolls 6 inches in outer diameter x 12 inches in width, rotation speed front roll 18rpm
Rear roll 20rpm, surface temperature 160℃, kneading time 10
Minutes, molding, hydraulic press machine 160℃ x 10 minutes (However, pressure x time = 40Kg/cm ² x 5 minutes, 80
Kg/cm ² x 3 minutes, 120Kg/cm ² x 2 minutes Physical property test conditions Tensile test - JISK-6723, sheet 1.1mm thick No. 3 dumbbell, 24℃ measurement (TS: tensile strength, 100% modulus, 100% M, EL : Elongation) Tensile test after heating - Measurement of weight loss after 120 hours in a gear oven at 120°C and tensile test (however, it is shown as the residual percentage relative to room temperature) Oil resistance test - Measurement of weight loss after 48 hours immersion in JISC23202 insulating oil at 70°C and tensile test (shown as residual percentage relative to normal condition) Hardness - JISA type Shore hardness tester, 24℃, 15
Seconds Cold resistance temperature - Krashberg low temperature flexibility temperature Zeitization temperature - JIS K6723 Migration resistance - A film with a thickness of 0.2 mm and a diameter of 10 cm was sandwiched between various resin plates of a thickness of 3 mm and a diameter of 15 cm and tested under the following conditions. The surface condition of each resin side and the weight loss of the sample film before and after the test were measured. Polystyrene (GP): 100℃ x 0.5Kgcm ² x 30 days Polystyrene (HI): 100℃ x 0.5Kg/30 days Polyethylene (medium/low pressure): 100℃ x 0.5Kg/cm ² x
30 days PVC (soft): 100 parts by weight of PVC (1100), sheet containing 1 part by weight of organic calcium-zinc composite stabilizer, 80℃ x 0.5Kg/cm ² × 7 days PVC (hard): 100 parts by weight of PVC (1100) Sheet containing 1 part by weight each of organic calcium-zinc salt composite stabilizer and dioctyltin marureate laurate stabilizer, 80℃ x 0.5Kg/cm ²
× 7 days Rubber (vulcanized product): 80°C × 0.5 Kg/cm ² × 3 days Solvent resistance - A sample film with a thickness of 0.2 mm and 10 cm × 10 cm was immersed and dried under the following conditions, and then the weight loss was measured. Water: 90°C x 2 days → Drying at 110°C x 4 days 1% ABS aqueous solution: 90°C x 2 days → Drying at 110°C
4 days MEK: 25℃ x 30 days → drying at 50℃ x 24 hours Parkrene: 25℃ x 1 day → drying at 50℃ x 24 hours Xylene: 25℃ x 1 day → drying at 50℃ x 24 hours Comparative example 1 Polyvinyl chloride 100 parts by weight of resin (1100) and 1 part by weight of organic calcium-zinc salt composite stabilizer
50 parts by weight of each of DOP or polyesters A to C were kneaded and the same test as in Example 1 was conducted. The results are shown in Table 1. In addition, polyesters A to C were synthesized as follows. A predetermined amount of dibasic carboxylic acid, diol, monobasic carboxylic acid, and 1.5% by weight of tetrabutyl titanium based on the total amount charged were placed in a four-necked flask, and a dehydration reaction was performed at 190 to 198°C for 4 hours. Summer. After the dehydration reaction was completed, the reaction was carried out at 220°C until the viscosity became constant. After the reaction, 0.1% of activated carbon and 0.2% of activated clay were added and filtered at 120°C to obtain polyesters A to C. Table 1 shows the synthesis conditions for polyesters A to C and the physical properties of the obtained polyesters A to C.

【table】

【table】

[Table] Example 2 The polyesters of the present invention obtained in Synthesis Examples 1 to 5 were made into polyvinyl chloride sheets and subjected to a fogging test under the following conditions. The results are shown in Table 3. (Composition) Polyvinyl chloride resin (1100) 100 parts by weight Polyester of the present invention 60 parts by weight Dioctyltin laurate 1 part by weight Calcium stiarate 0.5 parts by weight Zinc stearate 0.5 parts by weight Film forming molding conditions Test conditions same as Example 1 Cloudy The value was measured using HAZE METER. Comparative Example 2 60 parts by weight of DOP or polyesters A to C were blended with 100 parts by weight of polyvinyl chloride resin (11000), 1 part by weight of dioctyltin laurate, 0.5 parts by weight of calcium stearate, and 0.5 parts by weight of zinc stearate, and polyvinyl chloride A fogging test was conducted in the same manner as in Example 2 using a sheet. The results are shown in Table 3. Example 3 The polyesters of the present invention obtained in Synthesis Examples 1 to 5 were tested to form polyvinyl chloride sheets under the following conditions. The results are shown in Table 4. (Blend) Polyvinyl chloride resin (1050) 100 parts by weight Polyester of the present invention 80 Calcium stearate 1 Zinc stearate 1 Heavy calcium carbonate 20 (Film formation molding conditions) Same as Example 1 (sample sheet) Thickness 3 m/ A press sheet of 4 cm x 4 cm was used. (Test condition)

【table】

[Table] Forced exudation humidity test High temperature and humidity: 40℃ x 98% RH x 100 hours Ultraviolet irradiation: 10W x 2 lines x 15cm x 60 hours Evaluation criteria - ○: Good, △: Slight oozing, ×: Significant leaching Sun exposure Test The sample sheet was left outdoors so that it was exposed to sunlight vertically. (February 1951 to January 1952) Changes in the sheet surface were observed after one year. Evaluation criteria - ○: Very slight discoloration to light brown △: Discoloration to slightly light brown ×: Comparative example with brown discoloration and significant surface contamination 3 100 parts by weight of polyvinyl chloride resin (1050), 1 part by weight of calcium stearate, stearin 1 part by weight of acid lead, 20 parts by weight of heavy calcium carbonate
80 parts by weight of each of DOP, DOPA, or polyesters A to C were blended to form a polyvinyl chloride sheet in the same manner as in Example 3, and a test was conducted. The results are shown in Table 4.

Claims (1)

[Scope of Claims] 1. Polyhydric carboxylic acid (A) having 2 to 10 carbon atoms, and 3 carbon atoms
~10 polyhydric alcohol or a mixed alcohol (B) of this polyhydric alcohol and a monohydric alcohol having 1 to 18 carbon atoms, and general formula (1) [Formula] (2) R ₁ -CH ₂ -COOH ( However, R ₁ , R ₂ , and R ₃ each have 8 to 8 carbon atoms.
22, 4-21, 1-11 alkyl group), (1) alone or in a mixture with (2) containing at least 30% of (1), a carboxylic acid (C) having a total carbon number of 10 to 24
A polyester with a molecular weight of 800 to 12,000 obtained by co-condensing the three components (A): 10 to 60% by weight, (B) 10 to 60% by weight, and (C): 5 to 60% by weight. A plasticizer for vinyl chloride resin, characterized by comprising: