JPH0363588B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to plasticizer compositions useful as plasticizers for thermoplastic resins and as coating solvents or diluents. Conventionally, phthalate ester plasticizers represented by di(2-ethylhexyl) phthalate (DOP) have been frequently used to plasticize thermoplastic resins such as vinyl chloride resins. This type of plasticizer cannot be said to have sufficient physical properties such as volatility resistance, non-migration, and oil resistance, and in order to compensate for this, recently, trimellitic acid ester plasticizers such as trialkyl trimellitate,
Alternatively, considerable amounts of polyester plasticizers have been used. However, vinyl chloride resin compositions plasticized using trialkyl trimellitate have poor oil resistance, and although the plasticizer does not migrate well to ABS resin that has come into contact with the vinyl chloride resin composition, polystyrene The polyester is inferior to the vinyl chloride resin composition, and the polyester becomes brittle in contact with the vinyl chloride resin composition. On the other hand, although vinyl chloride resin plasticized with a polyester plasticizer has excellent oil resistance, the non-migration of the plasticizer to ABS resin is insufficient. Furthermore, polyester plasticizers
Generally, they have poor compatibility with vinyl chloride resins, and when used in large quantities or for long periods of time, the plasticizer oozes out, impairing the physical properties of the vinyl chloride resin composition. This phenomenon is particularly noticeable when lead-based stabilizers are used, and the current situation is that lead-based stabilizers cannot be used. Furthermore, all of the plasticizers are inferior in terms of non-staining properties, and a plasticizer with good non-staining properties has been desired. In order to produce a vinyl chloride resin composition with excellent non-migration, non-staining, oil resistance, compatibility, and low-temperature properties, the inventors have synthesized and studied various plasticizers to be added thereto. However, a plasticizer using a combination of trialkyl trimellitate (hereinafter referred to as trialkyl trimellitate) and a polymer of trialkyl trimellitate does not impair the above-mentioned properties, and a vinyl chloride resin composition having excellent physical properties can be obtained. The present invention was completed based on this discovery. That is, an object of the present invention is to provide a plasticizer composition useful as a plasticizer for thermoplastic resins and as a paint solvent or diluent. Therefore, the gist of the present invention is to provide 60 to 15% by weight of trialkyl trimellitate and the general formula [In the formula, R is an optionally branched alkyl group having 1 to 18 carbon atoms or a substituent, and X is a methylene group optionally having a branched chain having 1 to 20 carbon atoms. Alternatively, the polymethylene group may contain an ether bond in the main chain of the polymethylene group. n
represents an integer from 1 to 10, respectively. ] The plasticizer composition consists of 40 to 85% by weight of trimellitic acid ester polymer. To explain the present invention in detail, trialkyl trimellitate, which is an essential component of the present invention, specifically includes trimethyl trimellitate, triethyl trimellitate, tripropyl trimellitate, tributyl trimellitate, tributyl trimellitate, and trimethyltrimelitate. pentyl trimellitate, triheptyl trimellitate trioctyl (including 2-ethylhexyl) trimellitate,
Trinonyl trimellitate, tridecyl trimellitate, n-octyl-n-decyl trimellitate, triisodecyl trimellitate, tridodecyl trimellitate, tripentadecyl trimellitate, triotadecyl trimellitate, mono Examples include those produced by the esterification reaction of trimellitic acid with monohydric alcohols such as heptyldioctyl trimellitate and mono-n-octyl-di-(2-ethylhexyl) trimellitate, mixed monohydric alcohols, etc. One or two of these
Used as a mixture of more than one species. Among these, an esterification product of a monohydric alcohol having about 4 to 12 carbon atoms and trimellitic acid is most suitable.
The ester may contain a monoalkyl form and a dialkyl form. In the trimellitate polymer represented by the general formula [], which is one component, R in the formula is a methyl group,
Ethyl group, propyl group, butyl group, pentyl group,
Branches with 1 to 18 carbon atoms such as hexyl group, heptyl group, octyl group (including 2-ethylhexyl group), nonyl group, decyl group, dodecyl group, pentadecyl group, octadecyl group, benzyl group, phenethyl group, chloroethyl group, etc. It is an alkyl group which may have a chain or a substituent, and these are residues derived from a monohydric alcohol, and R in the structural formula may be the same or different. Also, X in the formula
are methylene group, ethylene group, propylene group, butene group, pentene group, hexene group, heptene group,
Polymethylene groups which may have a branched chain having 1 to 20 carbon atoms, such as octene group, nonene group, decene group, pentadecene group, and octadecene group, and further include diethylene glycol, triethylene glycol, tetraethylene glycol, etc. It is an alcohol residue derived from a dihydric alcohol such as polypropylene glycol such as polyethylene glycol, dipropylene glycol, and tripropylene glycol, and may have an ether bond in the main chain of the polymethylene group. And n is 1 to 10
It is preferable to be a trimellitic acid ester dimer or tetramer represented by an integer of n=1 to 3, and in particular, the total amount of dimer and trimer is 70% by weight or more. is preferable. As the amount of high polymer increases, the plasticizing efficiency of the thermoplastic resin tends to deteriorate when used as a plasticizer. The plasticizer composition of the present invention is a mixture of trimellitate and trimellitate polymer as described above. The mixing ratio of both is 60 to 15% by weight, especially 50 to 25% by weight, and 40 to 25% by weight of the latter, based on the total amount of the plasticizer composition.
85% by weight, especially in the range 50-75% by weight. When the trimellitate polymer of general formula [] is less than 40% by weight, thermoplastic resins, especially vinyl chloride resins, tend to have poor physical properties such as non-migration and oil resistance when plasticized. The plasticizer composition of the present invention is produced by the following method. 1. Trialkyl trimellitate and trimellitate polymer are manufactured separately and mixed after manufacture. 2. Add monohydric alcohol and dihydric alcohol to trimellitic acid and simultaneously perform an esterification reaction. 3 Add dihydric alcohol to trimellitate and perform transesterification. The plasticizer composition produced by the above production method 2 contains 100 to 300 mol%, preferably 120 to 290 mol% of a monohydric alcohol such as butanol, heptanol, 2-ethylhexanol, etc., based on trimellitic acid.
and dihydric alcohols such as ethylene glycol, butanediol, hexanediol, diethylene glycol, etc. 5 to 100 mol%, preferably 10
It can be obtained by carrying out an esterification reaction with trimellitic acid in the range of ~90 mol%. In addition, the above 3
The plasticizer composition produced by the production method involves reacting trialkyl trimellitate with 5 to 100 mol%, preferably 5 to 90 mol% of dihydric alcohol, and transesterifying the monohydric alcohol while washing away the monohydric alcohol. Manufactured by carrying out a reaction. Conditions for the esterification reaction and transesterification reaction, such as reaction temperature and whether or not to use a catalyst, can be selected as appropriate. Preferably, the reaction is carried out at 180°C or higher, preferably at 200°C or higher, in the presence of an ester catalyst such as dibutyltin oxide. is desirable. By varying the amount of diol added, the average molecular weight of all esters can be varied and trimellitate and trimellitate polymers can be brought into the preferred range of the plasticizer compositions of the present invention. The plasticizer composition of the present invention can be used as a plasticizer for thermoplastic resins such as vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, vinyl butyral resin, methyl methacrylate resin, or as a solvent or diluent for paints. . For example, when the plasticizer composition of the present invention is used for vinyl chloride resin, it is added in an amount of 20 to 300 parts by weight, preferably 30 to 200 parts by weight, per 100 parts by weight of vinyl chloride resin, and the plasticizer composition is added in a tumble mixer, a box type mixer, ball mill, ribbon mixer, chain mixer,
Super mixer, crusher, mixing roll,
The resin composition is uniformly mixed or kneaded using a Σ blade kneader, a Banbury mixer, a high-speed twin-screw continuous mixer, an extruder type kneader, or the like. The resin composition is used for applications such as films, sheets, containers, flooring materials, wall materials, and PVC steel plates. The plasticizer composition of the present invention has good compatibility with thermoplastic resins, particularly vinyl chloride resins and vinylidene chloride resins, and can also be used in combination with lead-based stabilizers. Even when a thermoplastic resin composition plasticized using the plasticizer composition of the present invention comes into contact with ABS resin or polystyrene, the ester in the composition remains
It does not transfer to ABS resin and polystyrene (non-migration), and the composition has excellent heat resistance, oil resistance, and non-staining properties.In addition, there is little change in rigidity over a wide temperature range, so-called rigidity It has extremely low temperature dependence and excellent low-temperature properties. The plasticizer composition of the present invention will be explained in detail below using production examples and usage examples, but the present invention is not limited to the following production examples and usage examples unless the gist thereof is exceeded. Production Example 1 A predetermined molar ratio of the dihydric alcohol listed in Table 1 was added per 1 molar ratio of trioctyl trimellitate (TOTM), and 0.05% by weight of dibutyltin oxide was added.
(vs. TOTM + dihydric alcohol), temperature
The transesterification reaction was carried out at 220° C. and under a vacuum of 10 mmHg or less while removing the produced 2-ethylhexanol. The reaction time is about 2 to 3 hours. Since the catalyst dibutyltin oxide was dissolved in the produced ester, the purification process was omitted and the product was made. The composition of the produced ester was measured by gel permeation chromatography (GPC), and the acid value of the produced ester was measured and is listed in Table 1.

[Table] 1,4-butanediol (1,4-BG), which is a dihydric alcohol, was prepared in large quantities, expecting that it would be distilled off together with 2-ethylhexanol (2EH), which has a low boiling point and is produced. The addition of 1,4-BG has a decreased amount of TOTM and an increased proportion of trimellitate polymer. It can be seen that the amount of ester polymer produced can be controlled by adjusting the amount of dihydric alcohol added. Production Example 2 A transesterification reaction was carried out in the same manner as in Production Example 1 using a predetermined molar ratio of dihydric alcohol 1,6-hexanediol (1,6-HG) and 1 molar ratio of various trialkyl trimellitates. The amount charged and the composition of the reaction product are shown in Table 2.

[Table] Production example 3 384 g of trimellitic acid in 2 four-necked flask
(2 mol), the monohydric alcohols listed in Table 3 and 2
In the presence of 0.05% by weight of dibutyltin oxide catalyst (based on the amount of produced ester), the vacuum level is 1 mmHg and the temperature is 200 to 220°C.
The esterification reaction was carried out for 4 hours while distilling off the produced water. The composition and acid value of the produced ester are also listed in Table 3.

[Table] The effect of the ester produced in the above production example as a plasticizer is shown in the following usage example. Usage example 1 After mixing 100 parts by weight of vinyl chloride resin (average degree of polymerization of about 1050), 67 parts by weight of the ester shown in Table 4, and 1 part by weight of a cadmium-barium stabilizer, the mixture was rolled at a pressure of 6 kg/ ^cm2. Knead for 5 minutes, then
Press molding was performed at a temperature of 180° C. for 5 minutes to obtain a pressed sheet. The ester of the present invention was evaluated using the sheet and is also listed in Table 4. Also for comparison
TOTM only and polyester plasticizer (consisting of adipic acid, butanediol 2EH, molecular weight approx.
2000) was similarly tested.

【table】

[Table] Usage example 2: 100 parts by weight of vinyl chloride resin with a degree of polymerization of about 1300, 70 parts by weight of the ester used in usage example 1, 10 parts by weight of filler, 0.5 parts by weight of barium stabilizer, and 5 parts by weight of lead stabilizer. The composition was formed into a sheet by kneading. The bleedability of the ester when a lead-based stabilizer was used in combination with the sheet was investigated and is shown in Table 5. In the test, the sample was left in an oven at a temperature of 70°C and a humidity of 100% for a predetermined period of time, and the presence or absence of ester bleed was observed. ○ Mark: No bleed. × Mark: Significant bleeding.

[Table] As is clear from the above Usage Examples 1 and 2, the plasticizer composition of the present invention is superior in various physical properties compared to ordinary trimellitate plasticizers and polyester plasticizers.

Claims (1)

[Claims] 1. 60-15% by weight of trialkyl trimellitate and general formula [Wherein, R is an optionally branched alkyl group having 1 to 18 carbon atoms or a substituent, and X is a methylene group optionally having a branched chain having 1 to 20 carbon atoms. Alternatively, the polymethylene group may contain an ether bond in the main chain of the polymethylene group. n
represents an integer from 1 to 10, respectively. ] Trimellitic acid ester polymer 40 represented by
~85% by weight of a plasticizer composition.