JPH09208770A - Transparent resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent resin composition having excellent antistatic effect without losing transparency. SOLUTION: This transparent resin composition having an antistatic property is obtained by blending (a) 100 pts.wt. of a transparent resin composition comprising 100-20wt.% of styrene unit, 0-80wt.% of methyl methacrylate unit, 0-80wt.% of acrylonitrile unit and 0-20wt.% of monomer copolymerizable with more than one of the above units with (b) 0.5-6.0 pts.wt. of a polyglycerin fatty ester having high monoesterified content synthesized from a fatty acid or a glycerin fatty ester with glycidol, (c) 0.05-4.0 pts.wt. of a phosphorus compound expressed by the formula: R<1> O-P: (OR<2> ) and (OR<3> )} (R<1> , R<2> and R<3> are each a 6-22C alkyl group or aryl group), and (d) 0.5-5.0 pts.wt. of a polyalkyleneglycol, as necessary.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a transparent resin composition having an excellent antistatic property.

[0002]

2. Description of the Related Art Since many transparent resin compositions have a strong charging property, static electricity induced by contact or friction is unlikely to escape and disappear. Therefore, the resin surface in use is easily soiled, resulting in a loss of a beautiful appearance. In order to correct this drawback, various studies such as an addition kneading type which mainly uses a surfactant and a surface coating type which mainly uses a silicon compound are being advanced.

However, at present, a sufficient effect cannot be obtained with the addition kneading type without impairing the transparency. In addition, although a certain degree of effect can be expected in the surface coating type, it is generally difficult to use because it is disadvantageous in cost.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a transparent resin composition having an excellent antistatic effect.

[0005]

Therefore, the present inventors have arrived at the present invention as a result of diligent studies on these problems, and a specific polyglycerin fatty acid ester and a specific phosphorus compound, or further a polyalkylene glycol. It has been found that an excellent antistatic effect can be obtained and the transparency can be maintained by adding the resin to a specific resin composition, and the present invention has been completed.

That is, the present invention provides "(a) styrene unit 100 to 20% by weight, methyl methacrylate unit 0 to 80".
100% by weight of a resin composition having a transparency of 0 to 80% by weight of an acrylonitrile unit and 0 to 20% by weight of a monomer copolymerizable therewith, (b) a fatty acid or glycerin fatty acid ester and glycidol 0.5 to 6.0 parts by weight of a synthesized polyglycerin fatty acid ester having a high monoesterification rate, (c) the following general formula (1) 0.05 to 4.0 parts by weight of a phosphorus compound represented by the formula: wherein R ¹ , R ² and R ³ are an alkyl group having 6 to 22 carbon atoms or an aryl group, and optionally (d) It is a transparent resin composition having antistatic properties, which is obtained by blending 0.5 to 5.0 parts by weight of polyalkylene glycol.

Hereinafter, the present invention will be described in detail.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The transparent resin which is the component (a) in the resin composition of the present invention is 100 to 20% by weight of styrene unit, 0 to 80% by weight of methyl methacrylate unit, 0 to 80% by weight of acrylonitrile unit. %, And 0 to 20% by weight of a monomer copolymerizable therewith, the resin is transparent.

Examples of the copolymerizable monomer include acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate, methacrylic acid esters such as ethyl methacrylate and cyclohexyl methacrylate, cyclohexyl maleimide and the like. Examples thereof include maleimide compounds, methacrylonitrile, vinyl toluene and other vinyl compounds. These may be polymerized by any of known polymerization techniques such as (continuous) bulk polymerization, suspension polymerization, emulsion polymerization and solution polymerization.

The polyglycene fatty acid ester which is the component (b) in the resin composition of the present invention is synthesized from fatty acid or glycerin fatty acid ester and glycidol, and the polyglycene fatty acid ester has a high content of monofatty acid ester form. It is a fatty acid ester mixture.

Conventionally, as a method for producing polyglycerin fatty acid ester, (1) esterification reaction of polyglycerin and fatty acids [JAOCS (Journal of American OilC
hemists' Society) Vol. 58, p. 878 (1981), JP-A-6-41007, etc.], (2) transesterification reaction between polyglycerin and fatty acid esters, (3) polyglycerin and fats and oils Transesterification reaction with compounds, (4) Addition polymerization reaction of glycidol and fatty acid monoglycerides [US Pa
tent 4,515,775], (5) Addition polymerization reaction of glycidol with fatty acids (see JP-A-51-65705, etc. is known. In the present invention, "fatty acid or glycerin fatty acid ester was synthesized from glycidol The "polyglycerin fatty acid ester having a high monoesterification rate" is produced by the method (5).

Examples of the starting fatty acid used include fatty acids having 7 to 22 carbon atoms. The fatty acid may be a saturated fatty acid or an unsaturated fatty acid, may be a linear fatty acid or a fatty acid having a side chain, and may be a substituted fatty acid having a carbon chain substituted with a hydroxyl group. Specific examples of these fatty acids include caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, Examples thereof include behenic acid, erucic acid, ricinoleic acid, hydroxystearic acid and the like. These may be used alone or in any combination of two or more.

The molar ratio of glycidol to fatty acid in the addition polymerization reaction of glycidol and the above fatty acid is
1-100, preferably 1-50, more preferably 1
It is good to choose in the range of ~ 10.

When the molar ratio is less than 1, mold releasability cannot be imparted to the transparent resin, and conversely, the molar ratio is
When it is 100 or more, the ratio of the hydrophilic group to the hydrophobic group becomes too high in the polyglycerin fatty acid ester, and the compatibility with the resin having transparency is deteriorated, which is not preferable.

The addition polymerization reaction of the above fatty acid and glycidol is preferably carried out in the presence of a phosphoric acid-based acidic catalyst and, if necessary, a solvent. The phosphoric acid-based acidic catalyst used here is phosphoric acid or phosphoric acid ester. Specifically, phosphoric acid, phosphoric anhydride, polyphosphoric acid, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphoric acid such as triphosphoric acid, tetraphosphoric acid, methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, butyl acid. Phosphate, 2-
Examples thereof include acidic phosphoric acid esters such as ethylhexyl acid phosphate. The acidic phosphoric acid ester may be a monoester body, a diester body or a mixture thereof. Among the catalysts listed above, phosphoric acid and acidic phosphoric acid esters are particularly preferable.

The above catalysts may be used alone or in combination of two or more. The amount of the catalyst used was 0.
It is preferable to select in the range of 01 to 10% by weight. If it is less than 0.01% by weight, the reaction rate is too slow, and if it exceeds 10% by weight, the effect is not reached even if a large amount of the catalyst is used, and an addition polymer of glycidol is by-produced. Absent. In the above range of the amount of catalyst used, 0.1-5
% By weight is particularly preferred. The addition polymerization reaction can be carried out without a solvent, but a solvent may be used. As the solvent that can be used, aromatic hydrocarbons having 6 to 9 carbon atoms, particularly halogenated toluene such as benzene, toluene and trifluorotoluene, aliphatic ketones having 3 to 9 carbon atoms, especially methyl isopropyl ketone , Methyl isobutyl ketone, diethyl ketone, di-isobutyl ketone, and the like. Besides, ethers such as diisopropyl ether are also suitable. These solvents may be used alone or as a mixture of two or more kinds. When a solvent is used, the amount used is preferably as small as possible from the viewpoint of recovery operation after completion of the reaction, and particularly preferably twice the total amount of the reaction raw materials.

The reaction temperature varies depending on the presence or absence of a solvent, the type and amount of the catalyst, etc., but it is preferably selected in the range of 50 to 180 ° C. If the temperature is lower than 50 ° C, the reaction rate is too slow, and if it exceeds 180 ° C, not only the coloring of the product becomes severe, but also glycidol is decomposed to cause a side reaction, which is not preferable. In the above temperature range, 70 to 160 ° C is preferable, and 140 to 160 ° C is particularly preferable.

The addition polymerization reaction is preferably carried out by mixing the fatty acid, the solvent and the catalyst in a reaction vessel, heating the mixture to the reaction temperature, and then adding glycidol little by little with stirring. The reaction can be carried out continuously or batchwise.

When a solvent is used and its boiling point is below the reaction temperature, it is advantageous to carry out under pressure.
It is desirable to carry out the addition polymerization reaction in an inert gas atmosphere such as nitrogen gas.

By the above reaction, glycidol is addition-polymerized with the fatty acid to produce a polyglycerol fatty acid ester having a higher degree of polymerization. The product is a monofatty acid ester form,
The polyglycerin fatty acid ester is a mixture of di-fatty acid ester body and tri-fatty acid ester body, and according to the above reaction, one having a large content ratio of mono fatty acid ester body is obtained. That is, the polyglycerin fatty acid ester used in the present invention has a content of 70% or more represented by the peak area ratio of the monofatty acid ester compound detected by an ultraviolet absorption detector by a column chromatography analysis method. .

It is of course possible to use a mixture of two or more compounds within the scope of the present invention.

A well-known method can be used to prepare a composition by incorporating the fatty acid ester of polyglycene into the transparent resin used in the present invention.

For example, it is a method of kneading each component in a molten state, and the melt kneading is only a method of using a kneading device such as a commonly used uniaxial or biaxial extruder or various kneaders. Instead, there is a method of directly kneading during a melt processing operation such as injection molding and extrusion molding. In addition, the monomer or syrup containing methyl methacrylate as the main component,
There is a method in which the pentaerythritols and the polyglycene fatty acid ester are added and mixed, and this is polymerized by a known method such as a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method.

The polyglycerin fatty acid ester is preferably added in an amount of 0.5 to 6.0 parts by weight based on 100 parts by weight of the transparent resin composition.
It is preferably 1.0 to 5.0 parts by weight. The addition amount is 6.
If the amount exceeds 0 parts by weight, the mold surface may become dirty during molding,
There is a problem that bleeding occurs after molding and the appearance is impaired, which is not preferable. If the amount added is less than 0.5 part by weight, a sufficient antistatic effect cannot be obtained.

The phosphorus compound which is the component (c) in the resin composition of the present invention is specifically tributyl phosphite,
Triisooctyl phosphite, tribenzyl phosphite, triphenyl phosphite, phenyl didecyl phosphite, diphenyl isodecyl phosphite, trisnonyl phenyl phosphite, tridecyl phosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite Examples include fights. Particularly preferred phosphorus compounds include tridecyl phosphite,
Tristearyl phosphite and distearyl pentaerythritol diphosphite.

The addition amount of the phosphorus compound is 0.05 to 4.0 parts by weight, preferably 1.0 to 3.0 parts by weight. If the addition amount of the phosphorus compound exceeds 4.0 parts by weight, it is not preferable because it causes defects in appearance such as sticking to the mold and soiling the molded product. If the addition amount is less than 0.05 parts by weight, a sufficient antistatic effect cannot be obtained, which is not preferable.

Further, the polyalkylene glycol which is the component (d), which is optionally added to the resin composition of the present invention, can be more effectively used in combination with the polyglycerin fatty acid ester and the phosphorus compound for the antistatic property. Express. Specific examples include polyethylene glycol and polypropylene glycol. Their molecular weight is 20
It is 0 to 1500, more preferably 300 to 1000. If the molecular weight is less than 200, the compatibility with the resin is poor and bleeding easily occurs, and if it exceeds 1500, the antistatic effect is low, which is not preferable.

The amount of these polyalkylene glycols added is 0.5 to 5.0 parts by weight, preferably 1.0 to
It is 4.0 parts by weight. If the addition amount exceeds 5.0 parts by weight, bleeding occurs, which is not preferable.

The method for producing a transparent resin composition having antistatic properties according to the present invention includes polyglycerin fatty acid ester, phosphorus compound, polyalkylene glycol which is an optional component and transparent resin, Brabender, Henschel mixer, tumbler, etc. A method of mixing with a commonly used mixer and kneading with an extruder to form pellets or sheets, or forming a mixture or pellets with a molding processing machine such as an injection molding machine, a compression molding machine, or an extrusion molding machine. There are no particular restrictions.

In carrying out the present invention, if necessary, additives such as an ultraviolet absorber, a heat stabilizer, an antioxidant, a lubricant, a release agent, a dye and pigment can be added, and at the time of polymerization and mixing. ,
It may be at any time such as melt kneading.

Examples The present invention will be described in detail below with reference to examples, but the contents of the present invention are not limited thereby. The antistatic performance in the examples was performed by the following method.

1. Charge voltage, half-life: Honest meter S-
4104 (Shishido Shokai) 2. Surface resistivity: Surface resistivity meter TR-8601 (Takeda Riken) [Reference Example 1] 4 with 1 liter capacity equipped with stirrer, thermometer, temperature controller, reflux condenser, dropping cylinder, nitrogen gas introduction pipe, etc. In a two-necked flask, stearic acid 0.5 mol (284.49 g) and phosphoric acid (purity 85% product) 0.0
622 g was charged, and the internal temperature was heated to 140 ° C. with stirring. Next, while maintaining the internal temperature at this temperature and stirring, 3.0 mol (222.24 g) of glycidol was added dropwise over 5 hours, and the reaction was continued until the oxirane concentration in the system became 0.1% or less. .

Reference Example 2 4.0 mol of glycidol (2
The same as the example described in Reference Example 1 except that 96.32 g) was used.

Reference Example 3 5.0 mol of glycidol (3
The same as the example described in Reference Example 1 except that 70.40 g) was used.

Reference Example 4 0.5 mol of lauric acid (10
0.16 g) and 3.0 mol of glycidol (222.24)
The same as the example described in Reference Example 1 except that g) was used.

Example 1 4.0 parts by weight of hexaglycerin monostearate obtained in Reference Example 1 synthesized from fatty acid or glycerin fatty acid ester and glycidol in 100 parts by weight of a transparent resin composed of 100% by weight of styrene unit. Department, tristearyl phosphite [Johoku Chemical Industry Co., Ltd.
Manufactured JP-318E] by 2.0 parts by weight was mixed with a Henschel mixer, and pelletized with an extruder having a cylinder diameter of 40φ (manufactured by Nakatani Machinery).

This pellet was injected into an injection molding machine (Nippon Steel N
70A type) was fitted with a flat plate mold [200L × 70W × 3t (mm)], and molded at a cylinder temperature of 240 ° C. and a mold temperature of 50 ° C. As a result of measuring the electrification voltage, half-life and surface resistivity of the molded flat plate, the maximum electrification voltage is 400V and the half-life is 4.2.
The surface specific resistance was 72 × 10 ¹² Ω, which showed good antistatic performance.

Example 2 4.0 parts by weight of hexaglycerin monostearate obtained in Reference Example 1 synthesized from fatty acid or glycerin fatty acid ester and glycidol in 100 parts by weight of a transparent resin consisting of 100% by weight of styrene unit. Department, tristearyl phosphite [Johoku Chemical Industry Co., Ltd.
Manufactured by JP-318E] and 2.0 parts by weight of polyethylene glycol having a molecular weight of 300 were pelletized in the same manner as in Example 1.

The pellets were evaluated in the same manner as in Example 1. As a result of measuring the charged voltage, half-life and surface resistivity of the molded flat plate, the maximum charged voltage was 380 V and the half-life was 3.
The surface resistivity was 56 × 10 ¹² Ω for 2 seconds, showing a very good antistatic performance.

Comparative Example 1 8.0 parts by weight of hexaglycerin monostearate obtained in Reference Example 1 synthesized from 100 parts by weight of a transparent resin consisting of 100% by weight of styrene unit and fatty acid or glycerin fatty acid ester and glycidol. Department, tristearyl phosphite [Johoku Chemical Industry Co., Ltd.
Manufactured by JP-318E] and 6 parts by weight of polyethylene glycol having a molecular weight of 1000 were pelletized by the same method as in Example 1. The pellets were evaluated in the same manner as in Example 1.

The electrification voltage, half-life and surface resistivity of the molded flat plate were measured. As a result, the maximum electrification voltage was 380 V, the half-life was 2.2 seconds, and the surface resistivity was 38 × 10 ¹² Ω. Although it is high, the additive bleeds on the surface of the molded product and the appearance is significantly impaired.

<Examples 3 to 5, Comparative Examples 2 and 3> Polyglycerin synthesized from fatty acid or glycerin fatty acid ester in the proportions shown in Tables 1 and 2 and glycidol in the resin having the composition shown in Tables 1 and 2 The fatty acid ester, phosphorus compound and polyalkylene glycol were mixed, and the mixture was pelletized, molded and evaluated in the same manner as in Example 1.

As shown in Tables 1 and 2, the sample in which each additive was mixed had a low maximum electrification voltage, a good half-life and a good surface resistivity.

Table 1 Example 3 4 5 6 Blend composition Monomer composition St / MMA St / AN St / MMA / MA St / MMA / MA / CHMI (wt%) 50/50 60/40 40/56/4 10/70/5/15 Polyglycerin fatty acid ester MS08 MS08 MS08 MS08 (weight part) 4 4 4 4 Phosphorus compound DP SP DP DP SP (weight part) 2 1 3 1 PAG 3E 10E 10P − (weight part) 0.5 1 2 Physical properties Maximum charging voltage (V) 420 420 440 410 Half-life 4.2 5.3 4.0 3.9 Surface resistivity 55 72 69 85 (× 10 ¹² Ω) Table 2 Comparative example 2 3 Composition composition Monomer composition St / MMA St / MMA (% by weight) ) 50/50 50/50 polyglycerol fatty acid ester MS08 (parts by weight) 4 - phosphorus compound SP (parts by weight) - 2 PAG (parts by weight) - - physical properties maximum band voltage (V) 500 540 half-life 92 210 <specific surface Resistance 1800 36000 (× 10 ¹² Ω) The abbreviations in the table are as follows.

St: Styrene MMA: Methyl Methacrylate AN: Acrylonitrile MA: Methyl Acrylate CHMI: Cyclohexyl Maleimide MS08: Octaglycerin Monostearate (Reference Example 2) MS10: Decaglycerin Monostearate (Reference Example 3) ) MS06: Hexaglycerin monolaurate (Reference Example 4) DP: Tridecyl phosphite SP: Tristearyl phosphite PAG: Polyalkylene glycol 3E: Polyethylene glycol molecular weight 300 10E: Polyethylene glycol molecular weight 1000 10P: Polypropylene glycol Molecular weight 1000

[0046]

As described above, the transparent resin composition of the present invention has a short charging half-life and a low surface resistivity, so that the obtained molded product is impaired in appearance due to dirt such as dust. Never. Since the composition of the present invention has such advantages, it can be suitably used in the field of lighting fixtures such as louvers, covers and parts for electronic devices, meter covers and the like.

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Claims (6)

[Claims] 1. From (a) 100 to 20% by weight of a styrene unit, 0 to 80% by weight of a methyl methacrylate unit, 0 to 80% by weight of an acrylonitrile unit, and 0 to 20% by weight of a monomer copolymerizable therewith. Resin composition 1 having the following transparency
00 parts by weight, (b) 0.5 to 6.0 parts by weight of polyglycerin fatty acid ester having a high monoesterification rate synthesized from fatty acid or glycerin fatty acid ester and glycidol, (c) the following general formula (1) 0.05 to 4.0 parts by weight of a phosphorus compound represented by the formula: wherein R ¹ , R ² and R ³ are an alkyl group having 6 to 22 carbon atoms or an aryl group, and optionally (d) A transparent resin composition having an antistatic property obtained by blending 0.5 to 5.0 parts by weight of a polyalkylene glycol. 2. The transparent resin composition having an antistatic property according to claim 1, wherein the transparent resin composition is a styrene homopolymer. 3. A transparent resin composition having an antistatic property according to claim 1, wherein the transparent resin composition comprises a copolymer of styrene and methyl methacrylate. 4. The transparent resin composition having an antistatic property according to claim 1, wherein the transparent resin composition is a styrene / acrylonitrile copolymer. 5. The transparent resin composition having an antistatic property according to claim 1, wherein the transparent resin composition is a terpolymer of styrene, methyl methacrylate and methyl acrylate. 6. The transparent resin composition having an antistatic property according to claim 1, wherein the transparent resin composition is a quaternary copolymer of styrene, methyl methacrylate, methyl acrylate and cyclohexylmaleimide.