JPH04359043A - Plasticizer and halogen-containing resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel plasticizer capable of imparting antistatic properties to a thermoplastic resin, and a halogen-containing resin composition containing this plasticizer.

0002

BACKGROUND OF THE INVENTION Halogen-containing resins such as vinyl chloride resins have various excellent physical properties and electrical insulation properties, and are therefore widely used in various applications such as wire covering materials, wall materials, flooring materials, and automobile interior materials. However, halogen-containing resins are easily charged, and it is difficult to maintain conductivity and antistatic properties.

[0003] When a plasticizer is added for the purpose of softening the halogen-containing resin, the electrical insulation properties are slightly lowered, but it does not provide antistatic performance.In order to satisfy the antistatic performance, antistatic agents and conductive The methods used include kneading substances into molded products or applying antistatic agents to the surface of molded products.

However, products that incorporate antistatic agents have the disadvantage that the antistatic agent sprays out onto the surface of the molded product due to a bleed phenomenon, causing stickiness and adhesion of dirt.
Products mixed with carbon black have the disadvantage of lack of flexibility in coloring and lack of decorative properties. Furthermore, the antistatic effect of those coated with an antistatic agent decreased rapidly over time, and the antistatic effect could not be maintained for a long period of time.

[0005] In addition, in recent years, plasticizers having antistatic properties have been disclosed in Japanese Patent Laid-Open Nos. 59-105037 and 64-435.
Although proposed in Publication No. 51, these plasticizers are
Phthalic acid and trimellitic acid are used as acid components, and their heat resistance and compatibility are insufficient.

[0006]

[Problems to be Solved by the Invention] The present inventor has made efforts to find a plasticizer that does not become sticky or stain due to bleeding phenomenon when used for plasticizing halogen-containing resins, and exhibits antistatic properties over a long period of time. As a result of investigation, the present invention was completed by discovering that the above object can be achieved by reacting biphenyltetracarboxylic acid with an alkylene oxide compound.

[0007] Therefore, the object of the present invention is to provide a plasticizer and antistatic performance that are free from stickiness and dirt adhesion for plasticized halogen-containing resin molded products, have excellent antistatic performance, and have excellent heat resistance and compatibility. The aim is to provide excellent compositions.

[0008]

[Means for Solving the Problems] The gist of the present invention is to provide a plasticizer represented by the following general formula.

[Case 2
] (In the formula, R1, R2, R3 and R4 are alkylene groups having 2 to 4 carbon atoms, and may be the same. R5, R6, R7 and R8 are alkylene groups having 1 to 4 carbon atoms.
-13 alkyl groups, which may be the same. k,
l, m and n are integers of 1 to 7 and may be the same. ) and a halogen-containing resin composition containing the above-mentioned plasticizer.

The present invention will be explained in detail. The plasticizer of the present invention can be easily obtained by a general ester production method by reacting biphenyltetracarboxylic acid or biphenyltetracarboxylic anhydride with a (poly)alkylene glycol monoalkyl ether. The number of carbon atoms of R1, R2, R3 and R4 or the number of carbon atoms of R5, R6, R7 and R8 of the (poly)alkylene glycol monoalkyl ether residue of the plasticizer represented by the above general formula is less than the above range. Large, k, l,
If the numbers of m and n are too large, the compatibility with the halogen-containing resin will be poor and bleeding will occur easily.

Specific examples of (poly)alkylene glycol monoalkyl ether include ethylene glycol monobutyl ether, ethylene glycol monooctyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoheptyl ether, and triethylene glycol. Monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, tetraethylene glycol monoethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monooctyl ether, dipropylene glycol monomethyl ether,
Examples include dipropylene glycol monobutyl ether, butylene glycol monoethyl ether, hexylene glycol monoethyl ether, and the like, and these may be used alone or in combination.

The halogen-containing resin composition of the present invention is obtained by uniformly mixing the above-mentioned plasticizer and halogen-containing resin. The blending ratio of the plasticizer is selected from the range of 20 to 200 parts by weight, preferably 30 to 150 parts by weight, based on 100 parts by weight of the halogen-containing resin. In addition, when the plasticizer of the present invention and a general-purpose plasticizer such as di-2-ethylhexyl phthalate are used together, it is desirable to blend the plasticizer of the present invention in an amount of 10 parts by weight or more, preferably 20 parts by weight or more. If the blending ratio of the plasticizer is less than 20 parts by weight, the antistatic effect will be insufficient, and if it exceeds 200 parts by weight, a bleed phenomenon will easily occur, resulting in stickiness and adhesion of dirt.

The halogen-containing resin used in the present invention includes polyvinyl chloride, polyvinylidene chloride, vinyl chloride,
Examples include copolymers containing vinylidene chloride as a main component and other copolymerizable comonomers. As the copolymerizable comonomer, ethylene, propylene, acrylonitrile, vinyl acetate, maleic acid or its ester, acrylic acid or its ester, methacrylic acid or its ester, etc. can be used. The composition of the present invention also contains additives that are normally added to halogen-containing resins, such as stabilizers,
Antioxidants, flame retardants, lubricants, fillers, ultraviolet absorbers, colorants, surfactants, etc. may be added. Furthermore, the use of an antistatic agent in combination is not prohibited.

[0013]

[Examples and Comparative Examples] Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited by the following Examples. The ester (plasticizer) and the composition were evaluated as follows.

1. Ester value Based on the ester value test method of JIS K 0070. 2.100% Modulus According to JIS K 6301 tensile test method, 2
3°C, relative humidity 50%, and the test sample was pulled using a No. 3 dumbbell at a pulling speed of 200 mm/min3. Heat resistance (loss on heating) It is expressed as the weight loss rate of the resin sheet after heating at 100°C for 120 hours. 4. Surface resistance According to JIS K-6911 (30°C). Measure the surface resistivity using a super megohmmeter. The smaller the value, the better.

5. Volume resistivity according to JIS K-6723 (30°C). The smaller the value, the better. 6. Half-life A high voltage is applied using a STATIC HONESTMETER, and the time required for the potential of the applied charged body to be reduced by half is determined as the half-life. (23℃, relative humidity 50%
). The shorter the time, the better. 7. Compatibility (Loop method) At a temperature of 23°C and a humidity of 50%, fold a sheet with a width of 1 cm, a length of 5 cm, and a thickness of 1 mm, hold it in a jig, and leave it for 24 hours. Visually observe dirt. ○ Paper is not stained △ Slightly stained × Stained

Example 1 294 g (1 mol) of anhydrous biphenyltetracarboxylic acid
, 590 g of ethylene glycol monobutyl ether (5
mol), 120 ml of toluene as an entrainer and 3.13 g of methanesulfonic acid (70% aqueous solution) were placed in a 2-liter flask equipped with a thermometer, nitrogen inlet tube, stirrer, water separator, and reflux condenser, and heated with a nitrogen stream. The mixture is heated under stirring and the temperature of the reaction solution is raised to 140°C to carry out the reaction. During this time, produced water was continuously removed from the system using a water separator, and the reaction was continued until the acid value of the reaction solution was below 1 mgKOH/g. After the reaction is completed, unreacted ethylene glycol monobutyl ether and toluene are recovered by reducing the pressure of the reaction system, and then neutralized, washed with water, and dehydrated under reduced pressure to obtain biphenyltetracarboxylic acid tetrabutoxyethyl ester (Ester I). ) 690g was obtained. The ester value of the obtained ester was 307, and the gas chromatography retention time of the saponified decomposition product was consistent with that of ethylene glycol monobutyl ether. Vinyl chloride resin (average degree of polymerization 1300
), 50 parts by weight of the obtained ester and 3 parts by weight of a barium-zinc liquid stabilizer were mixed thoroughly on two mill rolls whose temperature was adjusted to 160°C by a conventional method (for 5 minutes). ), and then pressed to a predetermined thickness (170° C., preheating for 2 minutes, 200 kg/cm 2 for 5 minutes). The evaluation results are shown in Table 1.

Example 2 294 g (1 mol) of anhydrous biphenyltetracarboxylic acid
, diethylene glycol monoethyl ether 670g (
5 mol), 120 ml of toluene as an entrainer and 3.40 g of methanesulfonic acid (70% aqueous solution) were reacted in the same manner as in Example 1 to obtain tetra(diethylene glycol monoethyl ether) biphenyltetracarboxylate.
754 g of ester (Ester II) was obtained. The ester value of the obtained ester was 283, and the gas chromatography retention time of the saponified decomposition product was consistent with that of diethylene glycol monoethyl ether. Vinyl chloride resin (average degree of polymerization 1300)
Example 1: 50 parts by weight of the obtained ester and 3 parts by weight of a barium-zinc liquid stabilizer were mixed with 100 parts by weight.
Evaluation samples were prepared by processing in the same manner as above. The evaluation results are shown in Table 1.

Example 3 294 g (1 mol) of anhydrous biphenyltetracarboxylic acid
, diethylene glycol monobutyl ether 810g (
5 mol), 120 ml of toluene as an entrainer and 3.88 g of methanesulfonic acid (70% aqueous solution) were reacted in the same manner as in Example 1 to obtain tetra(diethylene glycol monobutyl ether) biphenyltetracarboxylate.
1,020 g of ester (Ester III) was obtained. The ester value of the obtained ester was 248, and the gas chromatography retention time of the saponified decomposition product was consistent with that of diethylene glycol monobutyl ether. Vinyl chloride resin (average degree of polymerization 1
300) 50 parts by weight of the obtained ester and 3 parts by weight of a barium-zinc liquid stabilizer are blended with 100 parts by weight,
Evaluation samples were prepared by processing in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 4 294 g (1 mol) of anhydrous biphenyltetracarboxylic acid
, triethylene glycol monoethyl ether 890g
(5 mol), 120 ml of toluene as entrainer
and 4.16 g of methanesulfonic acid (70% aqueous solution) were reacted in the same manner as in Example 1 to obtain 922 g of biphenyltetracarboxylic acid tetra(triethylene glycol monoethyl ether) ester (Ester IV). The ester value of the obtained ester was 231, and the gas chromatography retention time of the saponified decomposition product was consistent with that of triethylene glycol monoethyl ether. Vinyl chloride resin (average degree of polymerization 13
00) 50 parts by weight of the obtained ester and 3 parts by weight of a barium-zinc liquid stabilizer were mixed with 100 parts by weight, and processed in the same manner as in Example 1 to prepare an evaluation sample. The evaluation results are shown in Table 1.

Example 5 294 g (1 mol) of anhydrous biphenyltetracarboxylic acid
, tetraethylene glycol monoethyl ether 1,1
10g (5 moles), toluene 12 as entrainer
0ml and methanesulfonic acid (70% aqueous solution) 4.91
g was reacted in the same manner as in Example 1 to obtain 1,089 g of biphenyltetracarboxylic acid tetra(tetraethylene glycol monoethyl ether) ester (Ester V). The ester value of the obtained ester was 196, and the gas chromatography retention time of the saponified decomposition product was consistent with that of tetraethylene glycol monoethyl ether. 50 parts by weight of the obtained ester and 3 parts by weight of a barium-zinc liquid stabilizer were blended with 100 parts by weight of vinyl chloride resin (average degree of polymerization 1300), and processed in the same manner as in Example 1 to obtain an evaluation sample. Created. The evaluation results are shown in Table 1.

Example 6 294 g (1 mol) of anhydrous biphenyltetracarboxylic acid
, propylene glycol monooctyl ether 940g
(5 mol), 120 ml of toluene as entrainer
and 4.33 g of methanesulfonic acid (70% aqueous solution) were reacted in the same manner as in Example 1 to obtain 956 g of biphenyltetracarboxylic acid tetra(propylene glycol monooctyl ether) ester (ester VI). The ester value of the obtained ester was 222, and the gas chromatography retention time of the saponified decomposition product was consistent with that of propylene glycol monooctyl ether. Vinyl chloride resin (average degree of polymerization 13
00) 50 parts by weight of the obtained ester and 3 parts by weight of a barium-zinc liquid stabilizer were mixed with 100 parts by weight, and processed in the same manner as in Example 1 to prepare an evaluation sample. The evaluation results are shown in Table 1.

Example 7 294 g (1 mol) of anhydrous biphenyltetracarboxylic acid
, butylene glycol monoethyl ether 590g (5
120 ml of toluene as an entrainer and 3.13 g of methanesulfonic acid (70% aqueous solution) were reacted in the same manner as in Example 1, and 694 g of biphenyltetracarboxylic acid tetra(butylene glycol monoethyl ether) ester (Ester VII) was reacted. Obtained. The ester value of the obtained ester was 307, and the gas chromatographic retention time of the saponified decomposition product was consistent with that of butylene glycol monoethyl ether. Vinyl chloride resin (average degree of polymerization 1300) 10
50 parts by weight of the obtained ester and 3 parts by weight of a barium-zinc liquid stabilizer were added to 0 parts by weight, and processed in the same manner as in Example 1 to prepare an evaluation sample. The evaluation results are shown in Table 1.

Example 8 294 g (1 mol) of anhydrous biphenyltetracarboxylic acid
, 730 g of hexylene glycol monoethyl ether (
5 mol), 120 ml of toluene as an entrainer and 3.63 g of methanesulfonic acid (70% aqueous solution) were reacted in the same manner as in Example 1 to obtain tetra(hexylene glycol monoethyl ether) biphenyltetracarboxylate.
686 g of ester (Ester VIII) was obtained. The ester value of the obtained ester was 267, and the gas chromatography retention time of the saponified decomposition product was consistent with that of hexylene glycol monoethyl ether. Vinyl chloride resin (average degree of polymerization 130
0) 50 parts by weight of the obtained ester and 3 parts by weight of a barium-zinc liquid stabilizer were mixed with 100 parts by weight, and processed in the same manner as in Example 1 to prepare an evaluation sample. The evaluation results are shown in Table 1.

Comparative Example 1 50 parts by weight of di-2-ethylhexyl phthalate (hereinafter abbreviated as DOP) and 3 parts by weight of barium-zinc liquid stabilizer were mixed with 100 parts by weight of vinyl chloride resin (average degree of polymerization 1300). Then, processing was carried out in the same manner as in Example 1 to prepare evaluation samples. The evaluation results are shown in Table 2.

Comparative Example 2 50 parts by weight of diheptyl phthalate (hereinafter abbreviated as DHP) and 3 parts by weight of a barium-zinc liquid stabilizer were blended with 100 parts by weight of vinyl chloride resin (average degree of polymerization 1300). An evaluation sample was prepared by processing in the same manner as in 1. The evaluation results are shown in Table 2.

Comparative Example 3 To 100 parts by weight of vinyl chloride resin (average degree of polymerization 1300), 50 parts by weight of tetra-2-ethylhexyl biphenyltetracarboxylate (hereinafter abbreviated as BTCO) and 3 parts by weight of barium-zinc liquid stabilizer. were blended and processed in the same manner as in Example 1 to prepare evaluation samples. Table 2 shows the evaluation results.
Shown below.

Comparative Example 4 Dibutoxyethyl phthalate (hereinafter referred to as DBE) was added to 100 parts by weight of vinyl chloride resin (average degree of polymerization 1300).
P) and 3 parts by weight of a barium-zinc liquid stabilizer were mixed and processed in the same manner as in Example 1 to prepare an evaluation sample. The evaluation results are shown in Table 2.

Comparative Example 5 192 g (1 mol) of trimellitic anhydride, 472 g (4 mol) of ethylene glycol monobutyl ether, 120 ml of toluene as an entrainer, and 3.40 g of methanesulfonic acid (70% aqueous solution) were prepared in the same manner as in Example 1. The reaction was carried out to obtain 485 g of trimellitic acid tributoxyethyl ester (Ester IX). 50 parts by weight of the obtained ester and 3 parts by weight of a barium-zinc liquid stabilizer were blended with 100 parts by weight of vinyl chloride resin (average degree of polymerization 1300), and processed in the same manner as in Example 1 to obtain an evaluation sample. Created. The evaluation results are shown in Table 2.

Comparative Example 6 192 g (1 mol) of trimellitic anhydride, 536 g (4 mol) of diethylene glycol monoethyl ether, 120 ml of toluene as an entrainer, and 3.40 g of methanesulfonic acid (70% aqueous solution) were added in the same manner as in Example 1. The reaction was carried out to obtain 530 g of trimellitic acid tridiethoxyethyl ester (Ester X). 50 parts by weight of the obtained ester and 3 parts by weight of a barium-zinc liquid stabilizer were blended with 100 parts by weight of vinyl chloride resin (average degree of polymerization 1300), and processed in the same manner as in Example 1 to obtain an evaluation sample. Created. The evaluation results are shown in Table 2.

[0030]

[Table 1]

[0031]

[Table 2]

Claims (2)

[Claims] [Claim 1] A plasticizer represented by the following general formula [Claim 1]
] (In the formula, R1, R2, R3 and R4 are alkylene groups having 2 to 4 carbon atoms, and may be the same. R5, R6, R7 and R8 are alkylene groups having 1 to 4 carbon atoms.
-13 alkyl groups, which may be the same. k,
l, m and n are integers of 1 to 7, and may be the same. ) 2. A halogen-containing resin composition containing the plasticizer of claim 1.