JPH0224293B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to polyester plasticizers modified with epoxidized oils. Polyester plasticizers are polyesters with a linear structure obtained by reacting dicarboxylic acids and glycols, and usually monocarboxylic acids or monohydric alcohols as terminal terminators under polyesterification conditions, and have a molecular weight of 600 to 10,000. It is a common product and is known to have excellent durability. Therefore, halogen-containing resins such as vinyl chloride resins plasticized with polyester are widely used in a wide variety of applications such as electric wire coatings, automobile parts, leather, boots, gaskets, hoses, and tubes. In addition, such polyester plasticizers are used in fields other than halogen-containing resins, such as paint resins such as acrylic, melamine, or urea; synthetic rubbers such as chlorobutadiene, butadiene-styrene, or butadiene-acrylonitrile polymers;
It is also used to impart appropriate plasticity and processability to cellulose derivatives such as nitrocellulose, ethylcellulose, or cellulose acetate; and polyurethane resins. However, in these application fields, demands for quality improvement have become more stringent than before, and it has become difficult for conventional plasticizers to be applied to harsh uses and processing conditions. Therefore, the emergence of an economical plasticizer with high quality characteristics is highly desired. In order to improve the quality characteristics of polyester plasticizers, for example, Japanese Patent Publication No. 48-35956 discloses that olefins having 6 to 18 carbon atoms or alkyl groups having 4 to 16 carbon atoms, which have unsaturated double bonds epoxidized, A method for producing a polyester plasticizer using glycidyl ether as part or all of the glycol component has been proposed. When this polyester plasticizer is blended with a halogen-containing resin, the low-temperature properties can be particularly improved. In this case, it is not possible to obtain a product with sufficiently improved heat resistance stability. As a result of intensive research into polyester plasticizers that do not have the above-mentioned drawbacks, the present inventors have found that epoxidized oil-modified polyesters obtained by reacting polyesters with an acid value of 2 to 50 with epoxidized oils, such as vinyl chloride resins, etc. The inventors have discovered that properties such as heat resistance, non-migration, oil or gasoline resistance, and heat aging resistance are extremely excellent when blended with a halogen-containing resin, leading to the completion of the present invention. That is, the present invention is a polyester plastic modified with an epoxidized oil, which is made by reacting a polyester with an acid value of 2 to 50 and an epoxidized oil, and contains 2 to 40% by weight of the epoxidized oil. provide the agent. When plasticizing halogen-containing resins such as vinyl chloride resins, the polyester plasticizer of the present invention provides properties that cannot be obtained by simply blending a mixture of polyester and epoxidized oil, such as roll kneading and Brabender kneading. Excellent dynamic heat resistance and processing properties such as roll processing. Also,
Such compositions have excellent effects on properties such as oven heat resistance, non-migration to ABS resins or polystyrene resins, non-extractability to animal and vegetable oils or organic solvents, and heat aging resistance. The polyester plasticizer modified with the epoxidized oil of the present invention is, for example, a polyester consisting of a dihydric carboxylic acid, a glycol, and an optionally used monohydric carboxylic acid or monohydric alcohol, which has an acid value of 50 to 2. After reaching the range, preferably 30 to 5, a predetermined amount of epoxidized oil is added to esterify the carboxyl groups in the polyester component and the epoxy groups in the epoxidized oil component. When the acid value of the polyester component that reacts with the epoxidized oil exceeds 50, it tends to gel. Furthermore, if the amount of epoxidized oil that modifies the polyester component exceeds 40% by weight, undesirable effects of the epoxidized oil such as decreased bleed resistance will become significant. Furthermore, if the acid value of the polyester is less than 2 or the amount of modification of the epoxidized oil is less than 2% by weight, the amount of the epoxidized oil that reacts with carboxyl groups will be small, making it impossible to obtain a high-performance plasticizer. In the present invention, the content of epoxidized oil in the plasticizer is preferably 5 to 30% by weight. In terms of stoichiometry, the epoxidized oil component that chemically bonds with the polyester component is preferably used in such a ratio that epoxy groups remain in the resulting polyester plasticizer. For this purpose, the epoxidized oil preferably contains at least two or more epoxy groups per molecule on average. Also, the amount of epoxy groups in the epoxidized oil is 1.1 to 10 equivalents, preferably 2 equivalents per 1 equivalent of carboxyl groups in the polyester.
It is preferable to blend the polyester and epoxidized oil so that the amount is 6 equivalents. If the amount of such epoxy groups is less than 1.1 equivalents, the content of epoxy groups in the polyester component modified with epoxidized oil will be small, reducing its effectiveness as a plasticizer, and if it exceeds 10 equivalents, unreacted The remaining amount of epoxidized oil becomes large, and its performance as a plasticizer deteriorates. The amount of this epoxidized oil may be outside the above-mentioned range as long as it does not essentially depart from the purpose of the present invention. Therefore, the type and amount of epoxidized oil should be appropriately determined depending on the balance of properties. In addition, especially if a small amount of terminal capping agent is used,
Or, when modifying polyester that is not used at all, it is necessary to design a polyester with an appropriate molecular weight and acid value to prevent the formation of gel-like substances.
In addition, it is necessary to incorporate the appropriate amount of epoxidized oil. The epoxidized oils used to modify polyester are usually oils with an iodine value of 80 or higher, such as vegetable oils such as soybean oil, linseed oil, safflower oil, olive oil, rapeseed oil, sunflower oil, corn oil, cottonseed oil, rice bran oil, etc. Alternatively, those obtained by epoxidizing fish oil such as pollock cod oil can be mentioned, and these can be used singly or as a mixture of two or more. Such epoxidized oils can be economically produced on an industrial scale by an in-situ method using hydrogen peroxide and a lower organic acid, or a peracetic acid method using peracetic acid produced by autooxidation of acetaldehyde. Among these, epoxidized soybean oil and epoxidized linseed oil are practically preferred. Divalent carboxylic acids that can be used to constitute the polyesters modified with the epoxidized oils of the invention include, for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dodecanedicarboxylic acid. Aliphatic dicarboxylic acids such as acids; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid or terephthalic acid and alicyclic dicarboxylic acids such as tetrahydrophthalic acid or hexahydrophthalic acid or their anhydrides. and esterified products.
Of course, these divalent carboxylic acids can be used alone or in a mixture of two or more, but adipic acid and phthalic anhydride are particularly preferred. In addition, examples of the glycol used to constitute the polyester component include ethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol.
Propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol,
Neopentyl glycol, 3-methyl-1,5-
Examples include aliphatic glycols such as pentanediol, 1,6-hexanediol or 2-ethyl-1,3-hexanediol, and polyalkylene glycols such as diethylene glycol and dipropylene glycol. used. Particularly preferred are aliphatic glycols having 2 to 6 carbon atoms. The polyester component modified with epoxidized oil in the present invention may contain a terminal capping agent as a component, and monohydric alcohol or monohydric carboxylic acid is usually used. Examples of monohydric alcohols include butanol, hexanol, isohexanol, heptanol, octanol, isooctanol, 2-ethylhexanol, nonanol,
Monohydric alcohols having 4 to 18 carbon atoms such as isononanol, 2-methyloctanol, decanol, isodecanol, undecanol, dodecanol, tridecanol, isotridecanol, tetradecanol, pentadecanol, hexadecanol and octadecanol are mentioned. They can be used singly or as a mixture of two or more. Practically 6~
Monohydric alcohols with 13 straight or side chains are preferred. In addition, monovalent carboxylic 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, Aliphatic monocarboxylic acids such as linoleic acid or linolenic acid and aromatic monocarboxylic acids such as benzoic acid or toluic acid
monohydric carboxylic acids, which are used singly or in a mixture of two or more, preferably monovalent carboxylic acids having 2 to 16 carbon atoms, especially mixed fatty acids derived from coconut oil or palm oil and hydrogenated products thereof. is preferably used. The polyester modified with the above-mentioned epoxidized oil may contain a small amount of trihydric or higher polyhydric carboxylic acid or polyhydric alcohol as a constituent component, if necessary. In this way, each raw material used as a component constituting the polyester and its usage amount are appropriately selected depending on the performance of the finally obtained plasticizer. The molecular weight of the polyester modified with the epoxidized oil of the present invention is from 600 to 10,000, preferably from 1,000 to
A range of 5000 is preferred. Such polyesters can be made by various esterification methods known to those skilled in the art. At that time, in order to obtain a polyester having a desired molecular weight, it is important to select the molar ratio of dicarboxylic acid, glycol, and, if necessary, a terminal capping agent when reacting with them. For its production, for example, in the early stage of the reaction, only the dihydric carboxylic acid and the glycol are esterified in the presence or absence of a solvent capable of azeotroping with water, such as toluene or xylene, and the water produced by distillation is distilled. A polyester component having a target acid value can be obtained by carrying out the reaction at a temperature where the desired acid value or hydroxyl group value is obtained, by adding a terminal capper and further proceeding with the reaction. In addition, polyester forming components such as dihydric carboxylic acid, glycol, and terminal capping agent are reacted all at once, or two of them are reacted as appropriate, and then the remaining one is reacted to obtain a polyester having a target acid value. You can also do that. The esterification reaction of the components constituting the polyester can be carried out using general catalysts such as acidic catalysts such as sulfuric acid, paratoluenesulfonic acid, or phosphoric acid; and metal compound catalysts such as zinc chloride, zinc acetate, lead oxide, tetraisopropyl titanate, and dibutyltin oxide. Preferably, the reaction is carried out in the presence of a known esterification catalyst. The reaction between the above polyester and epoxidized oil is as follows:
The temperature at which esterification is normally carried out, e.g. 80
It can be carried out by heating at ~260°C, preferably 100-250°C, more preferably 130-230°C, for example, the esterification promoting catalyst during the polyester synthesis, cyclic amines such as imidazole, tributylamine, etc. tertiary amines, quaternary ammonium salts such as tetramethylammonium chloride,
Preferably, the reaction is carried out in the presence of a Lewis acid, a Lewis base, and the like. Various modification methods can be used to modify the polyester with epoxidized oil. Examples include the methods shown below. After obtaining the target acid value of polyester in a polyesterification reaction vessel, a predetermined amount of epoxidized oil is added in the same reaction vessel, and the polyester component and epoxidized oil component are reacted and modified. A method of obtaining a polyester component with a target acid value in a polyesterification reaction container, and then reacting the polyester component with a predetermined amount of epoxidized oil component in a different reaction container or storage container to modify the polyester component. A method of plasticizing halogen-containing resins such as vinyl chloride resins by reacting a polyester component with a predetermined amount of epoxidized oil component before roll processing or dry blending using a Henschel mixer. This method involves adding a polyester component and an epoxidized oil component separately and modifying the polyester component and epoxidized oil component by reacting them during plasticization. Especially considering the efficiency aspect,
The first method above is preferred. Furthermore, the method for modifying polyester with epoxidized oil can also be carried out by various methods shown below. For example, there is a method in which a carboxyl group of a polyester component and an epoxy group in an epoxidized oil component are subjected to addition esterification, a method in which an ester group in a polyester component and an ester group in an epoxidized oil component are transesterified, and the like. In particular, it is preferable to use the first method. In addition, as another method, a method of addition etherification of the hydroxyl group of the polyester component and the epoxy group of the epoxidized oil component can be mentioned, but it can be carried out as a side effect during the esterification reaction or transesterification reaction. It's a method. The polyester plasticizer modified with the epoxidized oil of the present invention is a synthetic resin, such as a halogen-containing resin;
Paint resins such as acrylic, melamine, and urea; synthetic rubbers such as chlorobutadiene, butadiene-styrene, or butadiene-acrylonitrile polymers; cellulose derivatives such as nitrocellulose, ethylcellulose, or cellulose acetate; plastics such as polyurethane resins used as an agent. In particular, it is effective as a plasticizer for halogen-containing resins because of its excellent roll heat resistance and non-migration properties.
Suitable examples of such halogen-containing resins include chlorine-containing resins such as polyvinyl chloride, polyvinylidene chloride, chlorinated polyolefin, vinyl chloride-vinyl acetate copolymer resin, and vinyl chloride-vinylidene chloride copolymer resin. When the polyester plasticizer of the present invention is blended into a synthetic resin, the amount used is usually about 5 to 200 parts by weight, preferably 20 to 200 parts by weight, per 100 parts by weight of the halogen-containing resin.
100 parts by weight is suitable. The polyester plasticizer of the present invention may also be a known plasticizer used in the field of processing halogen-containing resins, such as phthalic acid esters such as di-2-ethylhexyl phthalate; adipic acid such as di-2-ethylhexyl adipate. Esters; trimellitic acid esters such as tri-2-ethylhexyl trimellitate; pyromellitic acid esters such as tetra-2-ethylhexylpyromellitate; epoxidized fatty acid esters such as epoxidized butyl stearate and epoxidized soybean oil ;
Chlorinated paraffins; can be used in combination with phosphoric acid esters and polyester plasticizers other than the polyester plasticizer of the present invention. Furthermore, the polyester plasticizer of the present invention can be used in combination with other additives such as stabilizers, fillers, and pigments. Next, the present invention will be explained in detail using Examples, Comparative Examples, and Test Examples. Note that all parts and percentages in the examples are based on weight. Examples 1 to 4 Divalent carboxylic acids and glycols in amounts specified in Table 1 were charged into a reaction vessel, and the temperature was raised to 220°C over 7 hours while stirring in a nitrogen gas stream. After that, a specified amount of monohydric alcohol shown in Table 1 and dibutyltin oxide in an amount equivalent to 0.03% of the weight of the polyester raw material (hereinafter referred to as the amount charged) as a catalyst were added, and a reflux condenser was attached to the temperature at a maximum temperature of 222°C. Heating was continued at a temperature of During this time, the reaction was carried out for about 7 hours while removing the water produced to obtain the predetermined acid value shown in Table 1. Next, an amount of tetraisopropyl titanate corresponding to 0.01% of the charged amount and a specified amount of epoxidized oil shown in Table 1 were added, and the mixture was reacted for 2 hours at a temperature of 180 to 210°C under a maximum reduced pressure of 5 mmHg for epoxidation. An oil-modified polyester plasticizer was obtained. The properties of such plasticizers are shown in Table 1. Comparative Example 1 In Example 1, 65 parts of 2-ethylhexanol was added instead of 260 parts of epoxidized soybean oil,
The reaction was carried out under exactly the same conditions as in Example 1 except that the total amount was 221 parts. In addition, acid value 0.85, viscosity Z-
It took 11 hours to obtain a polyester plasticizer with a viscosity of Z ₁ . The properties of the obtained plasticizer are shown in Table 1.

[Table] Examples 5 to 10 The amounts of dihydric carboxylic acid, glycol, and terminal stopper specified in Table 2 were placed in a reaction vessel, and the temperature was raised to 220°C over 7 hours while stirring in a nitrogen gas stream. did. Thereafter, an amount of tetraisopropyl titanate corresponding to 0.025% of the charged amount was added as a catalyst, and the mixture was maintained at a temperature of 200 to 220°C under reduced pressure of 60 mmHg at maximum until a predetermined acid value was reached. Next, add the specified amount of epoxidized oil shown in Table 2 to make a maximum of 5 mm.
A polyester plasticizer modified with epoxidized oil was obtained by reacting at a temperature of 180 to 220° C. for 2 hours under reduced pressure of Hg. The properties of such plasticizers are shown in Table 2.

[Table] Comparative Examples 2 and 3 Comparative plasticizers were prepared by mixing the polyester plasticizer obtained in Comparative Example 1 with the epoxidized soybean oil shown in Table 1. However, Comparative Example 2 is one in which the content of epoxidized soybean oil in the plasticizer is 10%, and 20%
This was designated as Comparative Example 3. Test Example Sheets were prepared using the plasticizers obtained in Examples and Comparative Examples according to the following basic formulations and molding conditions. (Basic formulation) (Polyvinyl chloride (degree of polymerization; 1050) 100 parts Plasticizer of Examples and Comparative Examples 50 parts *Barium-zinc stabilizer 2 parts) (Note) *: Manufactured by Dainippon Ink and Chemicals Co., Ltd. , Product name M-159 (Forming conditions) Roll (diameter 6") 165℃ x 10 minutes Press (1mm thickness) 170℃ x 5 minutes The following physical property tests were conducted on the basic composition and these sheets. Results are shown in Table 3. 1. Hardness (JIS Spring A Scale): Measured according to JIS-K6301. 2. Tensile test: Measured according to JIS-K6723. 3. Heat aging test: Measured according to JIS-K6723. However, the test conditions were 120°C x 120 hours.
The results were shown as weight loss rate (%) and remaining elongation rate (%) with respect to the normal state after the test. 4. Roll Heat Resistance Test The above basic formulation was adjusted to a sheet thickness of 0.4 mm using heated rolls at 180°C and continued kneading. The kneaded material deteriorates over time and strongly adheres to the roll surface, making it difficult to remove it from the roll if kneading is continued. In this way, the elapsed time (minutes) from the start of kneading until the kneaded material starts to show stickiness to the rolls is shown. The longer the time, the better the roll heat resistance. 5. Roll processability test The above-mentioned basic composition was subjected to roll kneading at 165° C. for 10 minutes, and the agglomeration speed, adhesion and bank stability against the roll were comprehensively observed and evaluated. 6 Oven Heat Resistance Test A 40 mm x 100 mm test piece of a roll sheet with a thickness of 0.3 mm was left in a gear type heat aging tester maintained at 170° C. After 90 minutes, the test piece was taken out and the degree of discoloration of the test piece was observed and evaluated. 7 Gasoline Extraction Resistance Test A 0.3 mm thick roll sheet was immersed in gasoline as a 40 mm x 100 mm test piece, and the weight loss of the test piece after immersion was expressed as a percentage. The test conditions were 24 hours at 23°C. 8. Soybean oil extraction resistance test A 40 mm x 100 mm test piece of a rolled sheet with a thickness of 0.3 mm was immersed in soybean oil, and the weight loss of the test piece after immersion was expressed as a percentage. The test conditions were 70°C for 24 hours. 9 ABS non-migration test A test piece was prepared by punching out a 1 mm thick press sheet into a size of 6 mm x 38 mm. 2mm thick
ABS resin plate (manufactured by Japan Synthetic Rubber Co., Ltd., product name JSR
ABS15) with sand german scissors, then 0.5
After being kept at 70℃ for 72 hours with a load of Kg/ ^cm2
The ABS resin board was observed and the state of corrosion due to plasticizer migration was observed and evaluated. 10 Polystyrene non-migration test The same conditions as in the ABS non-migration test except that a 2 mm thick polystyrene plate (manufactured by Dainippon Ink Chemical Co., Ltd., trade name: Deitz Styrene CR-3500) was used instead of the ABS resin plate. A test was conducted and an observation evaluation was made. 11 High-humidity bleed test A 40 mm x 100 mm test piece made of a 0.3 mm thick roll sheet was left in a constant temperature and humidity chamber at 98% RH, and the degree of bleed was observed and evaluated after 10 days.

【table】

[Table] Example 11 and Comparative Example 14 A polyester plasticizer was obtained in the same manner as in Example 1 using the raw materials and amounts shown in Table 3. Thereafter, sheets were prepared and tested in the same manner as in the test example. The results are shown in Table 4.

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1. A polyester plasticizer modified with epoxidized oil, which is produced by reacting a polyester with an acid value of 2 to 50 and an epoxidized oil, and contains 2 to 40% by weight of the epoxidized oil.