JPH0859948A - Transparent antistatic resin composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition not causing lowering in strength stiffness and useful for illuminators, etc., by blending a specific amount of a copolymer containing a 6-membered ring acid anhydride unit into a composition composed of an acrylic resin, an AS resin and a polyetheresteramide. CONSTITUTION: This resin composition is obtained by blending 100 pts.wt. of a resin composition composed of (A) 2-90wt.% of an acrylic resin, (B) 2-90wt.% of a copolymer of a vinyl cyanide and an aromatic vinyl, (C) 5-50wt.% of a copolymer containing at least >=3wt.% of a 6 membered ring acid anhydride unit and having 0.01-1dl/g reduced viscosity at 25 deg.C in acetone and (D) 3-30wt.% of polyetheresteramide with (E) 0.01-5 pts.wt. of at least one of an organic electrolyte and an inorganic electrolyte, and has <=0.02 refractive index difference between the mixture of these components A to C and the component D.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition having excellent permanent antistatic performance and excellent transparency, such as lighting equipment, equipment nameplates, electronic products, home electric appliances, The present invention relates to a resin composition suitable as a material capable of preventing electrostatic charge in various parts such as OA equipment.

[0002]

2. Description of the Related Art Acrylic resins, AS resins, and PS resins, which are typical typical transparent resins, have excellent transparency and rigidity, and thus are used as materials for various parts such as electronic products, home electric appliances, and office automation equipment. Widely used as. However, since these resins have a large surface resistivity and are easily charged by friction or the like, they have drawbacks such as dust and dirt adhering to the outer appearance, or electronic parts causing troubles due to static electricity. There is. Under such circumstances, it is desired to develop a material having excellent transparency and antistatic properties.

As a method of imparting an antistatic property to an acrylic resin, for example, a method of kneading a surfactant or coating it on the surface is known. In such a method, the charge existing on the surface is charged. The antistatic agent is easily removed by washing with water or wiping with a cloth and cannot impart a permanent antistatic property. As a method for imparting a permanent antistatic property, there are disclosed in JP-A-55-36237 and JP-A-62-1.
Japanese Patent Laid-Open No. 19256 and Japanese Patent Laid-Open No. 63-63739 are proposed.

Further, a transparent permanent antistatic composition comprising a polyamide-imide elastomer and an acrylic resin is disclosed in JP-A-2-255573. However, this composition tended to have reduced strength and rigidity. On the other hand, JP-A-5-279536 and JP-A-6-100747 have been proposed as methods for improving these. Although the composition obtained by these methods does not have a decrease in strength and rigidity, it has a problem that the transparency is significantly decreased by water absorption, which is a large limitation in practical use.

[0005]

DISCLOSURE OF THE INVENTION According to the present invention, there is no reduction in strength and rigidity, and there is little reduction in transparency when absorbing water.
It is an object to provide a transparent antistatic resin composition.

[0006]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies to overcome the drawbacks of conventional transparent antistatic resins, and as a result, a composition comprising an acrylic resin, an AS resin and a polyetheresteramide. In addition, by blending a specific amount of a copolymer containing a 6-membered cyclic anhydride represented by the following formula (I), there is no reduction in strength and rigidity, and there is little reduction in transparency due to water absorption. The present invention has been completed by finding that a new antistatic resin composition can be obtained.

That is, the present invention relates to (A) acrylic resin 2
To 90% by weight, (B) a copolymer of vinyl cyanide and an aromatic vinyl, 2 to 90% by weight, (C) at least 3% by weight or more of a 6-membered cyclic anhydride unit represented by the following formula (I). A copolymer 5 which is a copolymer contained and has a reduced viscosity in acetone at 25 ° C. of 0.01 to 1 deciliter / g.
~ 50% by weight, and

[0008]

Embedded image

(D) Polyether ester amide 3 to 3
0% by weight, based on 100 parts by weight of the resin composition,
(E) An antistatic resin composition comprising 0.01 to 5 parts by weight of at least one selected from organic electrolytes and inorganic electrolytes, and (A) + (B) +
The transparent antistatic resin composition is characterized in that the difference between the refractive index of the mixture of (C) and the refractive index of the component (D) is 0.02 or less.

In the composition of the present invention, the acrylic resin used as the component (A) is, for example, 40% by weight of vinyl monomer unit copolymerizable with 60% by weight or more of polymethylmethacrylate and methylmethacrylate unit. % Or less, and these may be used alone or in combination of two or more. As the copolymerizable vinyl monomer unit, acrylic acid and methacrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl methacrylate and t-butylcyclohexyl methacrylate, aromatic vinyl compounds, Examples thereof include vinyl cyanide compounds.

In the composition of the present invention, the copolymer of vinyl cyanide and aromatic vinyl used as the component (B) is 15 to 40% by weight of vinyl cyanide units and 85 to 60% by weight of aromatic vinyl units. % Copolymer. In particular, the ratio of vinyl cyanide to aromatic vinyl is preferably 18 to 25% by weight of vinyl cyanide units.
When the vinyl cyanide unit content is less than 15% by weight or more than 40% by weight, it becomes difficult to obtain a homogeneous transparency when mixed with the component (A). Examples of vinyl cyanide constituting the copolymer include acrylonitrile and methacrylonitrile. As the aromatic vinyl, for example,
Examples thereof include styrene and α-methylstyrene.

In the composition of the present invention, the copolymer containing a 6-membered cyclic acid anhydride unit used as the component (C) is a copolymer containing at least one ethylenically unsaturated monomer unit. It is united. Examples of the ethylenically unsaturated monomer unit include esters of acrylic acid and methacrylic acid such as methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl methacrylate and t-butylcyclohexyl methacrylate, styrene,
In addition to aromatic vinyls such as α-methylstyrene, usual radical-polymerizable monomers such as methacrylic acid, acrylic acid, vinyl chloride, vinyl acetate and acrylonitrile can be used. Among these ethylenically unsaturated monomer units, methyl methacrylate, methacrylic acid, styrene and α-methylstyrene are particularly preferable. The methyl methacrylate unit improves the mechanical strength and oil resistance of the copolymer containing the 6-membered cyclic anhydride unit. The methacrylic acid unit improves the heat resistance of the copolymer. The styrene unit improves its mechanical strength, water resistance and the like. Furthermore, α
-Methylstyrene units improve their water resistance and at the same time their heat resistance.

The composition of this copolymer is as follows: 6-membered cyclic anhydride unit 3 to 85% by weight, methyl methacrylate unit 13 to 95
It is preferable that the content is 1% to 70% by weight of aromatic vinyl units and 1% to 20% by weight of methacrylic acid units. More preferably, it is 5 to 50% by weight of a 6-membered cyclic acid anhydride unit, 15 to 88% by weight of a methyl methacrylate unit, 5 to 50% by weight of an aromatic vinyl unit and 2 to 10% by weight of a methacrylic acid unit.

Furthermore, this copolymer is
The reduced viscosity at 5 ° C is 0.01 to 1 deciliter / g, preferably 0.05 to 0.5 deciliter / g. When the reduced viscosity is less than 0.01 deciliter / g, the mechanical strength of the composition becomes insufficient, and 1 deciliter / g
If it exceeds, the moldability will be deteriorated. The content of this copolymer must be 5 to 50% by weight. When the content is less than 5% by weight, the transparency is greatly reduced when absorbing water, and when it exceeds 50% by weight, the antistatic performance is poor. The preferred content is 10 to 40% by weight.

In the composition of the present invention, the polyether ester amide used as the component (D) is composed of the following three components (a), (b) and (c). First, the component (a) is an aminocarboxylic acid having 6 or more carbon atoms, a lactam or a salt of a dicarboxylic acid having 6 or more carbon atoms and a dicarboxylic acid. Specific examples thereof include aminocarboxylic acids such as ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminobergonic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, caprolactam and enantolactam. And diamine-dicarboxylic acid salts such as hexamethylenediamine-adipate, hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate, especially caprolactam, 12-aminododecanoic acid, hexamethylene- Adipate is preferably used.

A salt of an aminocarboxylic acid having 6 or more carbon atoms, a lactam, or a dicarboxylic acid having 6 or more carbon atoms and a dicarboxylic acid is a constitutional unit of a polyether ester amide.
It is used in the range of 6 to 60% by weight. If this amount is less than 36% by weight, the strength of the polyether ester amide will be low and the mechanical properties will be low when kneaded with an acrylic resin or the like. On the other hand, when it exceeds 60% by weight, the affinity with the resin is deteriorated and the antistatic effect is insufficient.

Next, the component (b) is poly (alkylene oxide) glycol, such as polyethylene glycol, poly (1,3-propylene oxide) glycol, poly (1,2-propylene oxide) glycol, poly (tetramethylene oxide). ) Glycol, poly (hexamethylene oxide) glycol, a block or random copolymer of ethylene oxide and propylene oxide, etc. are used. Among these, the number average molecular weight of poly (alkylene oxide) glycol is preferably 200 to 6000, and more preferably 250 to 4000. When the number average molecular weight is less than 200, the mechanical properties of the obtained polyetheresteramide are poor, and when the number average molecular weight is more than 6000, the antistatic effect is insufficient.

Further, the component (c) has 4 to 20 carbon atoms.
Dicarboxylic acid, terephthalic acid, isophthalic acid,
Naphthalene-2,6-dicarboxylic acid, naphthalene-2,
Aromatic dicarboxylic acids such as 7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, sodium 3-sulfoisophthalate, 1,
Examples thereof include alicyclic dicarboxylic acids such as 2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4'-dicarboxylic acid, and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid and dodecanedioic acid, and particularly terephthalic acid. Acids, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, adipic acid and dodecanedioic acid are preferably used in terms of polymerizability, color tone and physical properties.

The poly (alkylene oxide) glycol and the dicarboxylic acid react with each other in a 1: 1 molar ratio in the reaction, but the charging ratio is usually changed depending on the kind of the dicarboxylic acid used. The method for polymerizing the polyether ester amide is not particularly limited, and for example, aminocarboxylic acid or lactam is reacted with dicarboxylic acid to synthesize a polyamide prepolymer having dicarboxylic acid groups at both ends, and poly (alkylene oxide) glycol is added to the polyamide prepolymer. Under a vacuum, after charging each compound of the above-mentioned raw material into a reaction tank, proceeding the polymerization in the presence of water, and charging the compound of the above-mentioned raw material into the reaction tank at the same time, followed by melting and mixing under high vacuum. A known method such as a method of advancing polymerization all at once can be used.

The content of the polyether ester amide needs to be in the range of 3 to 30% by weight based on the total weight of the components (A), (B), (C) and (D). If this amount is less than 3% by weight, a sufficient antistatic effect cannot be obtained. If it exceeds 30% by weight, the rigidity is lowered. Furthermore, the components (A), (B), (C) and (D) must satisfy the following formulas (1) and (2) in order for the composition to exhibit transparency.

[0021]

[Equation 1]

In the composition of the present invention, in order to further improve its antistatic performance, dodecylbenzenesulfonic acid, p-toluenesulfonic acid, dodecyldiphenyletherdisulfonic acid, naphthalenesulfonic acid and naphthalenesulfonic acid are used as the component (E). Aromatic sulfonic acids such as condensates of formalin, alkyl sulfonic acids such as lauryl sulfonic acid, organic carboxylic acids such as stearic acid, lauric acid and polyacrylic acid, organic phosphoric acids such as diphenyl phosphite and diphenyl phosphate, and these At least one selected from the alkali metal salts and alkaline earth metal salts of can be used. Among these, lithium salt, sodium salt and potassium salt are preferable. This amount is
The amount is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the resin composition containing the components (A), (B), (C) and (D). If the amount is less than 0.01 parts by weight, the antistatic performance is low, and if it exceeds 5 parts by weight, the heat resistance is lowered, or the appearance is deteriorated during molding, which is not preferable.

In the composition of the present invention, an acrylic multi-layer structure rubber, MB may be added, if necessary, as long as the transparency is not impaired.
An impact resistance imparting agent such as S or the like can be added. Further, similarly, as long as the transparency is not impaired, pigments, dyes,
Reinforcing agents, fillers, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, release agents, plasticizers and the like can be added. The composition of the present invention is a known method generally used for molding a thermoplastic resin, for example, injection molding, extrusion molding, blow molding, vacuum molding, inflation molding,
It can be formed by a method such as film forming or sheet forming.

[0024]

The present invention will be described in more detail with reference to the following examples. The physical properties of the composition and the elastomer were determined according to the methods described below. (1) Using a flat plate having a surface resistivity of 5 cm × 9 cm and a thickness of 2.5 mm, and using a super super insulation meter SM-10E type manufactured by Toa Denpa Kogyo Co., Ltd., after molding, it was 24 at 23 ° C. and 50% RH. It was measured after adjusting the time condition. (2) Haze 5 cm × 9 cm, using a flat plate having a thickness of 2.5 mm, measured by a haze meter SM-3 type manufactured by Suga Test Instruments Co., Ltd. under the following conditions. (A) Initial value: Measured after conditioning for 24 hours under conditions of 23 ° C. and 50% RH after molding. (B) When absorbing 3% water ... After molding, the sample is immersed in ion-exchanged water at 23 ° C., the water absorption rate and Haze are measured every 24 hours, and a graph of water absorption rate and Haze is prepared. From this graph,
Read Haze at 3% water absorption.

(3) Relative Viscosity of Polyether Esteramide Measured in meta-cresol at 30 ° C. under the condition of 0.5% by weight / volume. [Production Example of Polyetheresteramide (D-1 to 3)] Production of (D-1) 50 parts by weight of caprolactam, 45 parts by weight of polyoxyethylene glycol having a number average molecular weight of 1000 and 7 parts by weight of adipic acid were added to Irganox 1076. (Antioxidant) 0.
2 parts by weight and 0.1 part by weight of an antimony trioxide catalyst were charged into a reaction vessel equipped with a helical ribbon stirring blade, and after nitrogen substitution, the mixture was heated and stirred at 240 ° C. for 60 minutes to obtain a transparent homogeneous solution. Polymerization was carried out at 260 ° C. under the conditions of 0.5 mmHg or less for 4 hours to obtain a viscous and transparent polymer. The polymer was discharged on a cooling belt in a gut form and pelletized to obtain a pelletized polyether ester amide (D-1). The relative viscosity of this elastomer was 2.04. Production of (D-2) 60 parts by weight of nylon 6,6 salt (AH salt), 33 parts by weight of polyoxyethylene glycol having a number average molecular weight of 600, and 8.7 parts by weight of adipic acid were used (D-1). Polyether ester amide (D-2) was produced by the same method as described above. The relative viscosity of the obtained elastomer was 1.96.

Production of (D-3) 45 parts by weight of caprolactam, 45.2 parts by weight of polyoxyethylene glycol having a number average molecular weight of 600 and 13.0 parts by weight of terephthalic acid were added to 0.2 parts of Irganox 1076 (antioxidant). Parts and 0.1 part by weight of an antimony trioxide catalyst were charged into a reaction vessel equipped with a helical ribbon stirring blade, the atmosphere was replaced with nitrogen, and the mixture was heated with stirring at 260 ° C. for 60 minutes to obtain a transparent homogeneous solution. Then, 0.09 parts of tetra-n-butyl zirconate was added, and then 0.5 at 260 ° C.
Polymerization was carried out for 5 hours under a condition of mmHg or less to obtain a viscous and transparent polymer. The polymer was discharged onto a cooling belt in a gut shape and pelletized to obtain a pelletized polyether ester amide (D-3). The relative viscosity of this elastomer was 2.09. Further, this elastomer maintained a transparent state even after standing for 200 days.

[6-membered cyclic anhydride unit-containing copolymer (C)
Production of] methyl methacrylate 72.9% by weight, α-methylstyrene 13.5% by weight, methacrylic acid 3.6% by weight, ethylbenzene 10.0% by weight, 1,1, -di-t
A mixed solution consisting of 300 ppm of ert-butylperoxy-3,3,5, -trimethylcyclohexanone and 1000 ppm of n-octyl mercaptan was prepared,
The mixed solution was continuously fed at a rate of 0.5 liter / hr to a jacketed complete mixing reactor having an inner volume of 2 liters to carry out polymerization at 125 ° C. Furthermore, the polymerization liquid is added to 26
It was continuously fed to a high temperature devolatilizer set to 0 ° C. to remove unreacted materials and form a 6-membered cyclic acid anhydride unit. The composition of the copolymer was analyzed by neutralization titration, an infrared spectrophotometer and a nuclear magnetic resonance analyzer. As a result, 85% by weight of methyl methacrylate unit and 8% by weight of α-methylstyrene unit were added.
Membered acid anhydride unit 4% by weight, methacrylic acid unit 3% by weight
Met. Further, 0.150 g of this copolymer was dissolved in acetone to prepare a 50 ml solution, and the reduced viscosity was measured at 25 ° C., and it was 0.15 deciliter / g.

[0028]

Examples 1 to 4 and Comparative Examples 1 to 4 Acrylic resin (copolymer of methyl methacrylate and methyl acrylate) (A)
(Asahi Kasei Co., Ltd. Delpet (trade name) 80
N), AS resin (B) (containing 20% by weight of acrylonitrile, Styrac (trade name) T8 manufactured by Asahi Kasei Kogyo Co., Ltd.)
707), 6-membered acid anhydride unit-containing copolymer (C), polyetheresteramide (D-1 to 3), sodium dodecylbenzenesulfonate (E), acid-modified resin (F)
(Asahi Kasei Co., Ltd. Delpet (trade name) 980
N) was mixed in the ratio shown in Table 1 and pelletized at a cylinder temperature of 250 ° C. and a screw rotation speed of 150 rpm using a same-direction twin-screw extruder (manufactured by Toshiba Machine Co., Ltd. TEM-35B). After drying the pellets at 90 ° C. for 3 hours, a test piece was prepared using an injection molding machine (EPN-55 manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. The properties of the obtained test piece were measured and evaluated according to the methods described above. The results are shown in Table 1. As is clear from Table 1, by mixing a 6-membered cyclic acid anhydride unit-containing copolymer (C) in a specific amount, a transparent antistatic resin composition with little decrease in transparency upon water absorption can be obtained. You can

[0029]

[Table 1]

[0030]

The composition of the present invention comprises an acrylic resin, A
A composition comprising an S resin and a polyether ester amide in which a specific amount of a copolymer containing a 6-membered cyclic acid anhydride unit is blended, and the strength and rigidity are not reduced.
Also, it is a transparent antistatic resin composition with little decrease in transparency when absorbing water, and various trays such as medical cassettes, document boxes, IC trays, lighting covers, showcases, tableware, dials. Parts for covers, car interior and exterior products, TV stand doors, bird cages, insect cages, vegetable storage boxes in refrigerators, meter nameplates, VTR cassette windows, computer magnetic tape containers, VTR cassette cases,
It is preferably used for applications such as CD cases, MFD cases, MD cases, ornaments and trays.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C08L 77/12 LQS 101/06 LSY

Claims (1)

[Claims] 1. (A) 2 to 90% by weight of an acrylic resin,
(B) Copolymer of vinyl cyanide and aromatic vinyl 2 to
90% by weight, (C) a copolymer containing at least 3% by weight of a 6-membered cyclic anhydride unit represented by the following formula (I), and having a reduced viscosity in acetone at 25 ° C. of 0.01 ~
5 to 50% by weight of the copolymer, which is 1 deciliter / g, 0.01 to 5 parts by weight of at least one selected from (E) organic electrolyte and inorganic electrolyte with respect to 100 parts by weight of a resin composition consisting of (D) 3 to 30% by weight of polyether ester amide. It is an antistatic resin composition that is blended, and the difference between the refractive index of the mixture of (A) + (B) + (C) and the refractive index of the component (D) is 0.02 or less. A transparent antistatic resin composition comprising: