JPH11302445A - Antistatic plasticizer and chlorine-containing resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a plasticizer which improves compatibility with chlorine- containing resins and antistatic properties by adding one or more compounds selected from alkali metal salts and alkaline earth metal salts to a dibasic acid diester. SOLUTION: An antistatic plasticizer is obtained by adding 0.05-10 pts.wt. of one or more compounds comprising a cation part of an alkali metal or alkaline earth metal such as Na and Ca and an anion part such as Cl and CO3 to 100 pts.wt. of a compound of the formula. 100 pts.wt. of a chlorine-containing compound such as polyvinyl chloride and chlorinated polyethylene is blended with 0.1-100 pts.wt. of the compound of the formula, alkali metal salts and the like to obtain a composition. The compound of the formula is obtained by reacting a dibasic acid such as adipic acid and phthalic acid and an alcohol such as 2-(2-butoxyethoxy)ethanol and 2-butoxyethanol. In the formula, X is a 2-8C alkylene, a dibasic acid residue or the like; R1 and R2 are each a 1-9C alkyl; A is a 2-4C alkylene; and n is 1-7.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasticizer having an antistatic property and a chlorine-containing resin composition having an improved antistatic property using the plasticizer.

[0002]

2. Description of the Related Art In recent years, it has become important to prevent the chargeability of a chlorine-containing resin, and in order to achieve this,
Conventionally, a method of applying a surfactant or the like to the surface of a resin molded product or kneading the same into a resin is known. However, in the former method, the antistatic property is significantly reduced after a long period of time, so that it is difficult to put to practical use, while in the latter method, the persistence of the antistatic effect is slightly superior to that of the former method, but the plasticizer is used. There is a problem that the surfactant or the like bleeds or impairs the transparency of the molded product over a long period of time because the compatibility between the surfactant and the surfactant is poor.

[0003] Among these problems of the antistatic agent, there is an antistatic plasticizer which solves dispersibility and compatibility. This is because a plasticizer, which is an essential component for various processing of a chlorine-containing resin, is given an antistatic property. For example, JP-A-59-105027 and JP-A-60-105
No. 181142, JP-A-62-109841, and JP-A-64-9258.
However, these plasticizers have a problem that the compatibility with the chlorine-containing resin and the antistatic performance are insufficient.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in consideration of the above-mentioned conventional problems, and has been made in consideration of the above-mentioned problems. It is intended to provide a plasticizer and a chlorine-containing resin composition using the same.

[0005]

Means for Solving the Problems The present inventors have made various studies in view of the above situation, and as a result, have found that a chlorine-containing resin contains a compound represented by the following general formula (3) and an alkali metal salt. And at least one compound selected from alkaline earth metal salts, and an antistatic plasticizer and a chlorine-containing resin composition using the same have been found.

Therefore, the present invention is characterized in that one or more compounds selected from the group consisting of alkali metal salts and alkaline earth metal salts are added to the compound represented by the following general formula (3). And

[0007]

Embedded image [In formula 3, X is an alkylene group having 2 to 8 carbon atoms, an aromatic group or an alicyclic dibasic acid residue, and R ₁ and R ₂ are the same or different linear or branched C _{1 to} C 9 groups. An alkyl group, A is an alkylene group having 2 to 4 carbon atoms, and n is 1 to 7
Are respectively shown. ]

[0008] Here, while the chargeability prevention performance is exhibited by the action of the (AO), compatibility with chlorine-containing resins is improved by the action of the R _2. Therefore, the compatibility with the chlorine-containing resin and the antistatic performance are sufficiently exhibited.

In the above formula 3, R ₂ is (AO) _n
When the diester has the same composition as R ₁ , the compatibility with the chlorine-containing resin is deteriorated, and the molded product may become cloudy. In addition, the compound represented by Chemical Formula 3 becomes water-soluble,
In some cases, it cannot be used as a plasticizer. But,
In the above Chemical Formula 3, since the (AO) _n R ₁ and R ₂ do not have the same composition, the above problem does not occur.
However, when R ₂ and (AO) _n R ₁ simultaneously use a diester having the same composition and a compound represented by the above formula 3,
The above problems are not too great and fall within the scope of the present invention.

Further, the compound represented by the formula (3) constituting the antistatic plasticizer of the present invention is obtained by adding an alkylene oxide having 2 to 4 carbon atoms to a linear or branched aliphatic alcohol having 1 to 8 carbon atoms. It can be obtained by a general ester production method using an alcohol obtained by addition of about 7 mol, another higher alcohol and a dibasic acid as raw materials. In this case, the ratio of the esterification reaction with the alcohol to 1 mol of the dibasic acid is desirably 0.01 to 1.0 mol. This is because the ratio of the esterification reaction with alcohol is 0.0
When the amount is less than 1 mol, the antistatic property is not sufficiently exhibited, while the ratio of the esterification reaction with alcohol is 1.0%.
This is because if it exceeds mol, R ₂ and (AO) _n R ₁ may be diesters having the same composition.

In addition, in the production of the above ester, when an alkylene oxide is added to an alcohol, the added molar amount may be distributed without being unitary, but in the case of the present invention, the addition molar amount may be within a range included in the general formula. For example, not only a single substance but also a mixture of different addition molar amounts are included in the present invention without any change in performance. Examples of such additives include 1 to 7 moles of ethylene oxide or 1 to 4 moles of propylene oxide or 1 to 4 moles of butylene oxide in propanol.
3 mol, 1 to 6 mol of ethylene oxide or 1 to 3 mol of propylene oxide for butanol, 1 to 2 mol of ethylene oxide for hexanol, 1 to 5 mol of ethylene oxide for pentanol or 1 to 3 mol of propylene oxide or 1 to 2 mol of butylene oxide, octanol A hydroxyl compound obtained by adding 1 to 5 moles of ethylene oxide or 1 to 3 moles of propylene oxide or 1 to 2 moles of butylene oxide to nonanol, and 1 to 4 moles of ethylene oxide or 1 to 2 moles of propylene oxide or 1 to 2 moles of butylene oxide to nonanol. Can be In addition, among these compounds,
2- (2-butoxyethoxy) ethanol obtained by adding 2 moles of ethylene oxide to 1 mole of butanol, and 2 moles obtained by adding 1 mole of ethylene oxide to 1 mole of butanol.
-Butoxyethanol has a particularly good balance between antistatic properties and processability.

In addition, examples of the dibasic acid according to the above formula 3 include carboxylic acids such as adipic acid, sebacic acid and phthalic acid, and carboxylic anhydrides thereof.

According to a second aspect of the present invention, in the first aspect, the alkali metal salt and the alkaline earth metal salt have a cation moiety of Li, Na, K, M
g, Ca, wherein the anion site is Cl, Br, I, BF ₄ ,
It is selected from the compounds of PF ₆ , ClO ₄ , NO ₃ , and CO ₃ , and contains at least one of these alkali metal salts and alkaline earth metal salts.

With the above configuration, the above-mentioned effects are further exhibited. Here, the alkali metal salt and the alkaline earth metal salt are preferably 0.05 to 10 parts by weight, particularly 0.1 to 5 parts by weight based on 100 parts by weight of the compound represented by the above formula (3). It is preferred that If the amount of the alkali metal salt is less than 0.05 parts by weight, the antistatic effect is insufficient, while if the amount of the alkali metal salt is more than 5 parts by weight, the chlorine-containing resin composition becomes powdery or liquid. This is because there is a problem that oozes out.

Further, in order to achieve the above object, a chlorine-containing resin composition using the antistatic plasticizer of the present invention comprises a compound represented by the following general formula (4) and an alkali metal salt and an alkali metal salt. One or more compounds selected from the group consisting of earth metal salts are added.

[0016]

Embedded image [In formula 4, X is an alkylene group having 2 to 8 carbon atoms, an aromatic group or an alicyclic dibasic acid residue, and R ₁ and R ₂ are the same or different linear or branched C _{1 to} C 9 groups. An alkyl group, A is an alkylene group having 2 to 4 carbon atoms, and n is 1 to 7
Are respectively shown. ]

Here, as the chlorine-containing resin used in the present invention, polyvinyl chloride, post-chlorinated polyvinyl chloride,
Polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride -Isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-urethane copolymer, vinyl chloride-acrylate copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride- Styrene-acrylonitrile terpolymer, vinyl chloride
Butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid Ester copolymers, vinyl chloride-acrylonitrile copolymers, vinyl chloride copolymers such as vinyl chloride-maleimide copolymers, and the above resins and α-olefin polymers such as polyethylene, polypropylene, polybutene, and poly-3-methylbutene. Copolymer or ethylene-vinyl acetate copolymer, polyolefin such as ethylene-propylene copolymer and copolymers thereof, polystyrene, acrylic resin, polyurethane, copolymer of styrene and other monomers, acrylonitrile-styrene- Butadiene copolymer, acrylate Styrene - butadiene copolymer, methacrylic acid ester - styrene - such as a blend of butadiene copolymer. The chlorine-containing resin may be obtained by any of conventionally known polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization and the like.

Further, the composition of the present invention can be prepared by a technique used for processing a chlorine-containing resin composition, for example, injection molding, extrusion, extrusion blow molding, calender rolling,
Applicable to all rotational molding and similar techniques.

Further, the composition of the present invention may contain an ester plasticizer such as a phthalate ester plasticizer, an adipic ester plasticizer, or a polyester plasticizer, a phosphate ester plasticizer, a chlorine plasticizer, or the like. Other plasticizers and the like can be appropriately used depending on the application. In addition, if necessary, the composition of the present invention may contain, for example, a crosslinking agent, a filler, a pigment, a foaming agent, an antistatic agent, an antifogging agent, an anti-playout agent, a surface treatment agent, a lubricant, and a flame retardant. , A fluorescent agent, a fungicide, a bactericide, a photodegradation agent, a non-metal stabilizer, a processing aid, a release agent, and the like.

Further, in the invention according to claim 4, in the invention according to claim 3, the ratio of the compound represented by the above general formula (4) to 100 parts by weight of the chlorine-containing resin is 0.
It is characterized by being restricted to 1 to 100 parts by weight, especially 5 to 50 parts by weight.

The reason for this restriction is that when the proportion of the compound represented by Chemical Formula 4 is less than 0.1 part by weight, the effect of adding the compound is not sufficiently exhibited, while the proportion of the compound represented by Chemical Formula 4 is reduced. If it exceeds 100 parts by weight, the amount of the compound added may be too large and the compound may ooze out.

[0022]

Embodiments of the present invention will be described below. First, ethylene oxide 2 was added to 1 mole of butanol.
After adding moles to synthesize 2- (2-butoxyethoxy) ethanol, 1.0 mole of the 2- (2-butoxyethoxy) ethanol was added to phthalic anhydride (PHA) 1 which is a kind of polycarboxylic acid. 0.0 mol and 1.0 mol of octyl alcohol (OcA), which is another alcohol, is heated at 120 ° C. in an acid catalyst to release moisture, thereby preventing the antistatic shown in the following chemical formula 5. Synthetic plasticizer was synthesized.

[0023]

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Next, 100.0 parts by weight of polyvinyl chloride (PVC) having a polymerization degree of 1000, 40 parts by weight of a plasticizer, 10 parts by weight of an antistatic plasticizer shown in Chemical formula 5, and DOP [bis (2-ethylhexyl) ) Is phthalate,
30 parts by weight} and LiClO ₄ (2.0 parts by weight based on 100 parts by weight of the antistatic plasticizer shown in Chemical Formula 5)
After mixing 1.0 part by weight of calcium stearate, 1.0 part by weight of zinc stearate, and 3.0 parts by weight of epoxidized soybean oil with a mixing roll at 160 ° C. for 5 minutes, press molding (temperature : 165 ° C, pressure: 40kg /
cm ² , time: 7 minutes) to prepare a sheet of the chlorine-containing resin composition.

[0025]

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[0026]

EXAMPLES Example 1 In Example 1, the chlorine-containing resin composition shown in the above embodiment of the present invention was used. The chlorine-containing resin composition thus prepared is hereinafter referred to as “resin composition A1 of the present invention”.

Example 2 The use of isononyl alcohol (INA) as another alcohol gives
And the amount of the antistatic plasticizer was adjusted to 10 parts by weight with respect to 100 parts by weight of PVC.
A chlorine-containing resin composition was prepared in the same manner as in Example 1 except that the amount of DOP was 30 parts by weight and the amount of DOP was 30 parts by weight based on 100 parts by weight of PVC.

[0028]

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The chlorine-containing resin composition thus prepared is hereinafter referred to as a resin composition A2 of the present invention.

Example 3 An antistatic plasticizer represented by the following formula 8 was synthesized by using sebacic acid (SA) as a polycarboxylic acid, and the compounding amount of the antistatic plasticizer was adjusted to 100 parts by weight of PVC. 20 parts by weight to
In addition, the amount of DOP is 20 per 100 parts by weight of PVC.
Example 1 except for using LiI (0.5 parts by weight per 100 parts by weight of the antistatic plasticizer shown in Chemical formula 8) as an alkali metal salt or an alkaline earth metal salt.
In the same manner as in the above, a chlorine-containing resin composition was prepared.

[0031]

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The chlorine-containing resin composition thus prepared is hereinafter referred to as “resin composition A3 of the present invention”.

Example 4 An antistatic plasticizer represented by the following formula 9 was synthesized by using sebacic acid (SA) as a polycarboxylic acid and using butyl alcohol (BuA) as another alcohol. The compounding amount of this antistatic plasticizer was 5 parts by weight with respect to 100 parts by weight of PVC, the compounding amount of DOP was 35 parts by weight with respect to 100 parts by weight of PVC, and the addition amount of LiClO ₄ was as shown in Chemical formula 9. A chlorine-containing resin composition was prepared in the same manner as in Example 1 except that the amount was 0.5 part by weight based on 100 parts by weight of the preventive plasticizer.

[0034]

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The chlorine-containing resin composition thus prepared is hereinafter referred to as “resin composition A4 of the present invention”.

Example 5 Adipic acid (AA) was used as a polycarboxylic acid, and INA was used as another alcohol.
Is used to synthesize an antistatic plasticizer represented by the following chemical formula (1), and MgCO ₃ (an antistatic plasticizer 1 represented by the chemical formula (1)) as an alkali metal salt or an alkaline earth metal salt.
A chlorine-containing resin composition was prepared in the same manner as in Example 1 except that 3.0 parts by weight based on 00 parts by weight was used.

[0037]

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The chlorine-containing resin composition thus prepared is hereinafter referred to as Resin Composition A5 of the present invention.

COMPARATIVE EXAMPLE 1 A compound represented by the general formula 1 (antistatic plasticizer) was not added, and the compounding amount of DOP was 40 parts by weight with respect to 100 parts by weight of PVC.
A chlorine-containing resin composition was prepared in the same manner as in Example 1 above. The chlorine-containing resin composition thus prepared is hereinafter referred to as Comparative resin composition X1.

COMPARATIVE EXAMPLE 2 The compound represented by the general formula 1 (antistatic plasticizer) was not added, and the compounding amount of DOP was 40 parts by weight with respect to 100 parts by weight of PVC.
A chlorine-containing resin composition was prepared in the same manner as in Example 1 except that iClO ₄ was not added. The chlorine-containing resin composition thus prepared was hereinafter referred to as Comparative Resin Composition X2.
Called.

Comparative Example 3 Dipentaoxyethylene glycol sebacate synthesized from 1.0 mol of sebacic acid and 2.0 mol of pentaoxyethylene glycol was synthesized. When 100 parts by weight of polyvinyl chloride and 40 parts by weight of the diester were kneaded under the same conditions as in Example 1, no compatibility was observed. Therefore, it is clear that the compound synthesized in this way is inappropriate as an antistatic plasticizer, and the following experiment was not conducted.

[Experiment] It is generally known that the antistatic performance is directly related to the electrical volume resistivity of the formed chlorine-containing resin composition sheet. Therefore,
Inventive resin compositions A1 to A5 and comparative resin composition X1
The volume resistivity at X2 was measured according to JIS K6723, and the results are shown in Tables 1 and 2 below.

[0043]

[Table 1]

[0044]

[Table 2]

As is clear from Tables 1 and 2, the resin compositions A1 to A5 of the present invention have low volume resistivity,
In contrast to the excellent antistatic properties, the comparative resin composition X
At 1.X2, it is recognized that the volume resistivity is large and the antistatic property is inferior. Although not shown in Tables 1 and 2, the resin compositions A1 to A5 of the present invention show good transparency, and at the same time, bleed from a plasticizer sheet (at 80 ° C. and 80% humidity for 4 days). After standing).

[0046]

As described above, the antistatic plasticizer of the present invention has excellent antistatic properties, and the antistatic property of a chlorine-containing resin composition using this antistatic plasticizer is remarkable. To improve. In addition, the antistatic plasticizer of the present invention has an effect of being excellent in compatibility with a chlorine-containing resin.

Claims (4)

[Claims] 1. An antistatic method characterized in that one or more compounds selected from the group consisting of alkali metal salts and alkaline earth metal salts are added to a compound represented by the following general formula: Plasticizer. Embedded image [In formula 1, X is an alkylene group having 2 to 8 carbon atoms, an aromatic group or an alicyclic dibasic acid residue, and R ₁ and R ₂ are the same or different linear or branched C _{1 to} C 9 groups. An alkyl group, A is an alkylene group having 2 to 4 carbon atoms, and n is 1 to 7
Are respectively shown. ] 2. The alkali metal salt and the alkaline earth metal salt have a cation site of Li, Na, K, Mg, C
a, the anion site is Cl, Br, I, BF ₄ , P
F _6, are selected from ClO _4, NO _3, CO _3, compound, and the alkali metal salts thereof and alkaline earth metal salts are contained at least one or more, according to claim 1
The antistatic plasticizer as described. 3. An antistatic method characterized in that one or more compounds selected from the group consisting of alkali metal salts and alkaline earth metal salts are added to a compound represented by the following general formula: A chlorine-containing resin composition using a plasticizer. Embedded image [In formula 2, X is an alkylene group having 2 to 8 carbon atoms, an aromatic group or an alicyclic dibasic acid residue, and R ₁ and R ₂ are the same or different linear or branched C _{1 to} C 9 groups. An alkyl group, A is an alkylene group having 2 to 4 carbon atoms, and n is 1 to 7
Are respectively shown. ] 4. The ratio of the compound represented by the general formula shown in Chemical Formula 2 to 100 parts by weight of the chlorine-containing resin is from 0.1 to 0.1.
The chlorine-containing resin composition using the antistatic plasticizer according to claim 3, which is regulated to 100 parts by weight, particularly 5 to 50 parts by weight.