JPH07331230A - Antistatic composition for resin and antistatic resin composition - Google Patents

Abstract

PURPOSE:To obtain an antistatic composition which is useful in a variety of plastics, particularly for high-rigidity polypropylene (PP) by using a mixture of a specifically mixed fatty acid glyceride with an alkyldiethanolamine so that specific requirements are satisfied. CONSTITUTION:This antistatic composition comprises (A) a fatty acid glyceride mixture of monoglycerides, diglycerides and/or triglycerides where the acyl groups have 8-20 carbon atoms and the content of the monoglycerides is 85-95wt.% and (B) an alkyldiethanolamine of a 8-20C alkyl wherein the weight ratio of A/B is 9/1-2/B, the difference in carbon number is 0-4 between the acyl group occupying the most proportion among the acyl groups in the component A and the alkyl group occupying the most proportion among the alkyl groups in the component B, the most proportion is more than 65 mole % of the total acyl groups and more than 65 mole of the total alkyl groups and there are one or more couples that the carbon number of the acyl groups in the component A is the same as that of the alkyl groups in the component B.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an antistatic agent composition for various plastics, particularly an antistatic agent composition useful for high rigidity polypropylene, and an antistatic agent composition containing the antistatic agent composition. It relates to a high-rigidity polypropylene resin composition.

[0002]

2. Description of the Related Art In recent years, in polypropylene resins, which can be said to be a representative of general-purpose resins, research has been conducted to improve their performance.
Recently, a high-rigidity polypropylene resin has been newly provided by increasing the crystallinity as compared with the conventional one, and making the material thinner, lighter, and shortening the molding cycle. On the other hand, polypropylene, which has been widely used in the past, has a large electric insulating property and thus is easily charged with electricity, which causes many problems such as processing troubles in the manufacturing process, electric shock, and dust adhesion when a molded product is used. Therefore, it is particularly desired to impart excellent antistatic properties to polypropylene resins. To address this problem, it is industrially practiced to knead an antistatic agent into polypropylene resin. For example, a method of blending polyoxyethylene alkylamine and polyhydric alcohol fatty acid ester (Japanese Patent Publication No.
4-925), a polyoxyethylene alkylamine and a fatty acid monoglyceride are mixed and melt-extruded,
A method of subjecting a film obtained by biaxial stretching to corona discharge treatment (JP-A-48-54155) and a method of using an alkyldiethanolamine fatty acid ester (JP-A-58).
No. 191729), a method using alkylamine and / or alkylamide and glycerin monoester (JP-A-60-58444), and a method using alkyldiethanolamine fatty acid ester and glycerin monofatty acid ester (JP-A-54). No. 48866), a method of using alkyldiethanolamide and glycerin monofatty acid ester in combination (Japanese Patent Publication No. 64-11214).
Issue gazette) etc. However, since the high-rigidity polypropylene described above has an increased crystallinity as compared with the conventional polypropylene, these known techniques cannot give a desired effect to the high-rigidity polypropylene.
In particular, development of a fast-acting antistatic agent that exhibits an antistatic effect in about one day after molding is desired.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a resin having an antistatic effect which is superior to that of conventional antistatic agents for resins, and which can impart an excellent antistatic effect to polypropylene having high rigidity. It is an object to provide an antistatic agent composition. Another object of the present invention is to provide a high-rigidity polypropylene resin composition having an excellent antistatic effect.

[0004]

According to the present invention, when a conventionally known mixture of glycerin fatty acid ester and alkyldiethanolamine is selected in a state in which both structures, weight ratios and carbon number distribution in the mixture are specified. This was done based on the finding that the above-mentioned problems can be efficiently achieved. That is, the present invention is (A) a mixed glycerin fatty acid ester of monoester, diester and / or triester of glycerin and fatty acid, wherein the acyl group in the mixed glycerin fatty acid ester has 8 carbon atoms.
To 20 and the content of monoester is 85 to 95
(B) a mixed glycerin fatty acid ester, which is in a weight%.
An antistatic agent composition for resins comprising a mixture of (A) and (B), which is a mixture with an alkyldiethanolamine having an alkyl group having 8 to 20 carbon atoms and which satisfies the following requirements. provide. (I) The weight ratio of (A) / (B) is in the range of 9/1 to 2/8, and (ii) the carbon number of the acyl group occupying the maximum proportion of the acyl group in (A) and ( The difference from the carbon number of the alkyl group occupying the maximum proportion of the alkyl group in B) is in the range of 0 to 4, (iii) the maximum proportion is 65 mol% or more of all the acyl groups, and all the alkyl groups And (iv) the carbon number of the acyl group in (A) and (B)
At least one set having the same number of carbon atoms as the alkyl groups therein exists.

In the present invention, the flexural modulus according to JIS K7203 and the surface hardness according to JIS K7202 (R scale) are 1.8 in the case of a homopolymer, respectively.
× 10 ⁴ kg / cm ² or more and 110 or more, and in the case of a block polymer 1.2 × 10 ⁴ kg / cm ² or more and 90 or more, respectively, and a melt flow rate based on JIS K7210 of 0.1 to 100 g / 10. The amount of the antistatic agent composition is 0.05 to 100 parts by weight per 100 parts by weight of the polypropylene resin.
An antistatic resin composition containing 3.0 parts by weight is provided.

Specific examples of the glycerin fatty acid ester of the component (A) used in the present invention include glycerin mono,
Di, tricaprylate, glycerin mono, di, tricaprate, glycerin mono, di, trilaurate, glycerin mono, di, trimyristate, glycerin mono,
Di, tripalmitate, glycerin mono, di, trioleate, glycerin mono, di, tristearate, glycerin mono, di, tribehenate, glycerin palm fatty acid mono, di, triester, glycerin tallow fatty acid mono, di, triester, glycerin Examples include hardened tallow fatty acid mono-, di-, and triesters. In the present invention, monoesters, diesters of glycerin and fatty acids and / or
Alternatively, a mixed glycerin fatty acid ester consisting of triesters is used, and in particular, the content of monoester is 85-95.
% By weight (hereinafter abbreviated as%), preferably 87 to 95
% Mixed glycerin fatty acid ester is used. In the mixed glycerin fatty acid ester, the balance other than the monoester is a diester, a triester or a mixture thereof. In the present invention, the mixed glycerin fatty acid ester is used as described above, and the desired effect cannot be obtained with a monoester of 100%.

Specific examples of the alkyldiethanolamine of the component (B) used in the present invention include octyldiethanolamine, decyldiethanolamine, lauryldiethanolamine, myristyldiethanolamine, cetyldiethanolamine, stearyldiethanolamine, behenyldiethanolamine, coconut fatty acid diethanolamine, tallow fatty acid diethanolamine, Examples include hardened tallow fatty acid diethanolamine and the like, or a mixture of two or more kinds. Alkyldiethanolamine is usually produced by adding 2 moles of ethylene oxide to a monoalkylamine, and therefore has a certain degree of variation in the tertiary amine value. In the present invention, it is preferable to use one having a tertiary amine value of 96 mol% or more, and particularly preferably one having a tertiary amine value of 97 mol% or more.

In the present invention, it is important that the weight ratio of the components (A) and (B) used is 9/1 to 2/8, and more preferably 8/2 to 6 /. It is 4. If it is out of this range, the preferable interaction between the components (A) and (B) is lost, and the immediate effect of the antistatic effect is lowered. Further, in the present invention, it is important to specify the carbon number distribution of the acyl group and the alkyl group of the components (A) and (B) in order to exert a preferable interaction between them. It is important that all of these carbon numbers are in the range of 8 to 20, and preferably 10 to 18. Further, the difference between the carbon number of the acyl group which occupies the maximum proportion of the acyl group in (A) and the carbon number of the alkyl group which occupies the maximum proportion of the alkyl group in (B) is within the range of 0 to 4. Is also important, and particularly preferably 0-2. In this case, the maximum ratio is 65 mol% or more of all acyl groups or 65 mol% or more of all alkyl groups, preferably 70 mol% or more. Further, there is at least one set in which the number of carbon atoms of the acyl group in (A) and the number of carbon atoms of the alkyl group in (B) are the same, and preferably the carbon number of all the acyl groups in (A). It is preferred that the number corresponds to the carbon number of the alkyl group in (B).

The antistatic agent composition for resins of the present invention is a general-purpose
Not only propylene resin but also other thermoplastic resin and thermosetting resin
It also has an excellent antistatic effect on chemical resins,
In particular, the flexural modulus based on JIS K7203 and JI
The surface hardness based on SK7202 (R scale) is
1.8 × 10 for mopolymer^Fourkg / cm² that's all
(Preferably 1.8 × 10^Four~ 2.5 × 10^Fourkg / cm² )
And 110 or more (preferably 110 to 120), and
1.2 x 10 in the case of block polymer^Fourkg / cm ² that's all
(Preferably 1.2 × 10^Four~ 1.5 × 10^Fourkg / cm²)
And 90 or more (preferably 90 to 100) and JI
Melt flow rate based on SK7210 is 0.1-1
Polypropylene resin that is 00g / 10min, that is, high
Excellent antistatic effect for rigid polypropylene resin
Can be granted. Such high rigidity polypropylene
Resins are, for example, Mitsui Petrochemical Co., Ltd. and Tonen Chemical
It can be easily obtained as a commercial product from Co., Ltd.

When the antistatic agent of the present invention is added to the resin, the method is not particularly limited, but the component (A) and the component as the antistatic agent composition of the present invention are added to the target resin. (B) may be added separately, or both may be mixed in advance and then added. Furthermore, it may be added after forming a high-concentration master batch. In particular, it is effective to add both after melt mixing in advance. The amount of the antistatic agent composition added to the resin may be arbitrary, but the antistatic agent composition of the present invention is added in an amount of 0.05 to 3.0 parts by weight, preferably 0.1 to 100 parts by weight of the resin. It is recommended to use 2.0 parts by weight.

The antistatic resin of the present invention exerts an antistatic effect without being restricted by a molding processing method such as inflation, casting, extrusion molding, injection molding, or a form of a molded product such as a film, a sheet or a fiber. . Incidentally, other additives, for example, glass fibers or potassium titanate-based whiskers for further increasing rigidity, talc, inorganic fillers such as calcium carbonate or aromatic polyamide-based organic fibers, etc. within a range that does not impair the effects of the present invention. The organic filler, the lubricant, the antioxidant, the ultraviolet absorber, the light stabilizer, the antiblocking agent, the pigment, etc. may be used in combination.

[0012]

EFFECTS OF THE INVENTION Conventionally, it took a long time to develop an antistatic effect for highly crystalline polypropylene resins, but the present invention adversely affects the original appearance and other physical properties of highly crystalline polypropylene resins. Has immediate effect without
Further, there is provided an antistatic agent composition for a resin, which has low mold stainability and bleeding property, is stable over time, and can impart sufficient antistatic properties. Next, the present invention will be described with reference to examples, but the present invention is not limited to the examples.

[0013]

【Example】

Example 1 Flexural modulus based on JIS K7203 22000 kg / c
For each of the polypropylene homopolymer resins (manufactured by Tonen Chemical Co., Ltd.) having a m ² of 113, a surface hardness of 113 according to JIS K7202 (R scale), and a melt flow rate of 23 g / 10 minutes according to JIS K7210, each listed in Table 1. The components were kneaded under the conditions below using a 36 mm twin-screw extruder manufactured by Nakatani Machinery so that each of them would be 0.4% (relative to resin) to prepare strand-cut pellets having a diameter of about 3 mm and a length of about 4 mm. . C1: 200 ° C, C2: 220 ° C, C3: 230 ° C, C
4: 230 ° C (barrel temperature) Die temperature: 220 ° C, screw rotation speed: 150-2
00 rpm Next, the above pellets were 78 × 78 × 1.6 m under the following conditions using a TS-150 type injection molding machine manufactured by Nissei Plastic Industry Co., Ltd.
A flat plate of m was prepared and the following physical properties were evaluated. C1: 200 ° C, C2: 210 ° C, C3: 230 ° C (barrel temperature) Die temperature: 220 ° C, injection pressure: 1t / cm ²

The performance of the obtained resin was evaluated by the following method, and the evaluation results are also shown in Table 1. (Measurement of surface resistance value) Immediately after molding the injection molded plate, 20
Hire made by Mitsubishi Petrochemical every other day under conditions of ℃ and humidity of 60%
Using the sta H-210 type resistance measuring device, the printing voltage is 500V.
The surface resistance value was calculated by multiplying by. Surface resistance 1 × 10 ¹³ Ω
When it is less than the above, the antistatic effect is good. Antistatic Criterion ◎: surface resistivity less than 1 × 10 ¹² Ω ○: surface resistivity 1 × 10 ¹² Ω or more 1 × 10 ¹³ Omega less ×: Evaluation of surface resistivity 1 × 10 ¹³ or more (mold fouling properties ) The mold after 25 shots of injection molding was visually observed. Criteria for evaluation of mold contamination ○: No cloudiness of the mold Δ: Some cloudiness of the mold ×: Cloudiness of the mold (Evaluation of bleeding property) The test piece was left in a constant temperature and humidity chamber at 20 ° C. × 60% RH, Two months after the molding, the surface appearance was visually observed. Bleedability evaluation standard ○: Surface gloss △: Cloudy ×: Gravel

[0015]

[Table 1] Table 1 Attached table Belt A / B Upper: weight ratio A component / all A + all B added surface charge type lower weight: weight ratio B component / all A + all B amount Antifouling | Amount A acyl group or B alkyl Carbon number of the group Anti-decontamination No ratio 10 12 14 16 18 20 (%) (Ω) Characteristic 1 9/1 0.9 0.4 5x10 ¹² ○ ○ ○ 0.1 2 8/2 0.8 0.4 2x10 ¹¹ ◎ ○ ○ 0.2 3 8/2 0.08 0.72 0.4 3x10 ¹¹ ◎ ○ ○ 0.02 0.18 4 8/2 0.08 0.72 0.1 6x10 ¹² ○ ○ ○ 0.02 0.18 5 6/4 0.56 0.04 0.4 5x10 ¹¹ ◎ ○ ○ 0.37 0.03 6 6/4 0.6 0.4 4x10 ¹¹ ◎ ○ ○ 0.4 7 4/6 0.4 0.4 2x10 ¹² ○ ○ ○ 0.6 8 2/8 0.2 0.4 3x10 ¹² ○ ○ ○ 0.8 9 8/2 0.8 0.4 1x10 ¹² ○ ○ ○ 0.2 10 8/2 0.24 0.56 0.4 2x10 ¹² ○ ○ ○ 0.06 0.14 11 8/2 0.24 0.56 3.0 3x10 ¹¹ ◎ ○ ○ 0.06 0.14 12 6/4 0.6 0.4 3x10 ¹² ○ ○ ○ 0.4 13 6/4 0.18 0.42 0.4 2x10 ¹² ○ ○ ○ 0.12 0.28 14 4/6 0.1 0.3 0.4 4x10 ¹² ○ ○ ○ 0.1 0.5 15 4/6 0.04 0.36 0.4 1x10 ¹² ○ ○ ○ 0.06 0.54 16 2/8 0.02 0.18 0. 4 5x10 ¹² ○ ○ ○ 0.08 0.72 17 8/2 0.56 0.04 0.02 0.18 0.4 7x10 ¹² ○ ○ ○ 0.19 0.01

Component (A) composition: No. 1-8 No. 9-17 Monoester content 89% 90% Di- and triester content 11% 10% (B) Component composition (No. 1-17): Tertiary amine content
97% Secondary amine content 3% Comparative Example 1 Example 1 except that the components and addition amounts shown in Table 2 were adopted.
The performance was evaluated in the same manner as. The results are also shown in Table 2.

[0017]

[Table 2] Table 2 Attached table Belt A / B Upper: weight ratio A component / all A + all B added surface charge type lower weight: weight ratio B component / all A + all B amount Antifouling | Amount A acyl group or B alkyl Number of carbon atoms of the group Anti-decontamination No. ratio 10 12 14 16 18 20 (%) (Ω) Property 1 8/2 0.8 0.02 9x10 ¹³ × ○ ○ 0.2 2 8/2 0.08 0.72 4.0 7x10 ¹⁰ ◎ × × 0.02 0.18 3 9.5 0.95 0.4 3x10 ¹³ × △ ○ /0.5 0.05 4 1/9 0.03 0.07 0.4 5x10 ¹³ × ○ △ 0.27 0.63 5 0/10 0.4> 10 ¹⁴ × ○ △ 0.3 0.7 6 10/0 0.3 0.7 0.4> 10 ¹⁴ × △ △ 7 7/3 0.21 0.49 0.4 5x10 ¹³ × △ △ 0.09 0.21 8 6/4 0.18 0.42 0.4 8x10 ¹³ × △ △ 0.12 0.28 9 8/2 0.4 0.08 0.32 0.4 1x10 ¹³ × ○ ○ 0.2 10 8/2 0.28 0.02 0.15 0.35 0.4 2x10 ¹³ × ○ ○ 0.06 0.14

Composition of component (A): No. 1, 2, 9 No. 3, 4, 6, 7 No. 8 Monoester content 89% 90% 75% Di- and triester content 11% 10% 25% ( Composition of component B): No. 1 to 5 and 8 to 10 No. 7 tertiary amine content 97% 90% secondary amine content tell content 3% 10%

Claims (2)

[Claims] 1. A mixed glycerin fatty acid ester of (A) monoester, diester and / or triester of glycerin and fatty acid, wherein the acyl group in the mixed glycerin fatty acid ester has 8 to 20 carbon atoms, A mixture of a mixed glycerin fatty acid ester having a monoester content of 85 to 95% by weight and (B) an alkyldiethanolamine having an alkyl group having 8 to 20 carbon atoms, which satisfies the following requirements: An antistatic agent composition for resins, which comprises a mixture of (A) and (B). (I) The weight ratio of (A) / (B) is in the range of 9/1 to 2/8, and (ii) the carbon number of the acyl group occupying the maximum proportion of the acyl group in (A) and ( The difference from the carbon number of the alkyl group occupying the maximum proportion of the alkyl group in B) is in the range of 0 to 4, (iii) the maximum proportion is 65 mol% or more of all the acyl groups, and all the alkyl groups And (iv) the carbon number of the acyl group in (A) and (B)
At least one set having the same number of carbon atoms as the alkyl groups therein exists. 2. The flexural modulus according to JIS K7203 and the surface hardness according to JIS K7202 (R scale) are 1.8 × 10 ⁴ kg / cm in the case of a homopolymer, respectively.
² or more and 110 or more, 1.2 × 10 ⁴ kg / cm ² or more and 90 or more in the case of block polymer, respectively, and J
Melt flow rate based on IS K7210 is 0.1-
An antistatic resin composition comprising 0.05 to 3.0 parts by weight of the antistatic agent composition according to claim 1 per 100 parts by weight of 100 g / 10 min polypropylene resin.