JPH0339349A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition, containing a specific polyether ester amide, acrylic polymer and acrylic multistage polymer, having permanent antistatic properties and excellent in optical characteristics represented by the total light transmittance. CONSTITUTION:A resin composition composed of (A) 1-35 pts.wt. polyether ester amide composed of (A1) a >=6C aminocarboxylic acid or lactam or a salt of a >=4C diamine with a dicarboxylic acid, (A2) a poly(alkylene oxide)glycol having 400-4000 average molecular weight and (A3) a 4-16C dicarboxylic acid, (B) 98-5 pts.wt. acrylic polymer consisting essentially of methyl methacrylate and (C) 1-60 pts.wt. multistage (multilayered) polymer alternately having elastic layers and nonelastic layers around an acrylic polymer core material. Alternatively, a composition prepared by blending 100 pts.wt. aforementioned composition with 0.5-5 pts.wt. metal sulfonate or 0.1-20 pts.wt. light diffusion agent.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an antistatic resin composition that has permanent antistatic properties and excellent optical properties represented by total light transmittance.

(Prior Art) Synthetic polymer materials are used in a wide range of fields due to their excellent properties. By imparting antistatic properties to these materials, their uses can be further expanded. That is, it is extremely useful for applications such as copying machine parts, various dust-proof parts, various lighting covers, displays, screens for ProgeXion televisions, etc. in which damage caused by static electricity is to be prevented.

Methods for improving the antistatic properties of synthetic polymer materials include, for example, Japanese Unexamined Patent Publications No. 55-36237 and No. 56-1207.
No. 51 discloses that a hydrophilic rubber-like polymer obtained by copolymerizing a conjugated diene or/and an acrylic ester with a vinyl monomer having an alkylene oxide group is added with a vinyl monomer or a vinylidene monomer. It is disclosed that a polymer obtained by graft polymerization has been achieved as a practical antistatic agent.

JP-A-60-23435 discloses that a resin having semi-permanent antistatic properties can be obtained by mixing a polyamide elastomer and a modified vinyl polymer containing a carboxyl group.

Furthermore, JP-A-60-170646 discloses a method for improving wear resistance by blending a polyamide elastomer into a styrene resin, and JP-A-62250049 discloses a method for adding a specific polyamide elastomer to an ABS resin. A method for imparting semi-permanent antistatic properties by blending is disclosed.

In addition, a method for imparting semi-permanent antistatic properties by blending a specific polyetheramide elastomer was disclosed in JP-A-62-
It is disclosed in JP 119256, JP 62-241945, JP 62-256855, JP 62-11759, JP 63-33456, JP 63-95251, and the like.

(Problem to be Solved by the Invention) The antistatic resin obtained by graft polymerizing a monomer to a hydrophilic rubber-like polymer disclosed in JP-A-55-36237 is a special hydrophilic rubber. Since the method uses a polymorphic polymer, the production method is complicated, and the resulting resin has poor mechanical properties, so it is not completely satisfactory.

Furthermore, when a modified vinyl polymer containing a carboxyl group and a boria elastomer are mixed as disclosed in JP-A-60-23435, there is reactivity between both polymers, and the modified vinyl polymer is Due to the large amount blended, moldability is poor and the reproducibility of physical properties is poor.

On the other hand, Japanese Unexamined Patent Publication No. 62-250049, No. 62-24
No. 1945, No. 62-256855, No. 62
Although the composition consisting of a specific polyether ester amide and a specific graft polymer disclosed in Publication No. 11759 etc. has excellent semi-permanent antistatic properties, it does not have the above-mentioned properties due to the use of a specific graft polymer. Similarly, they have drawbacks such as complicated manufacturing methods and low optical properties, particularly low total light transmittance.

In addition, although the method disclosed in JP-A-62-119256 has excellent transparency and total light transmittance, it has low mechanical properties, especially flexural modulus, and lacks surface hardness, so it is prone to scratches. There is a problem to be said.

(Means for Solving the Problem) The present inventors aimed to provide an antistatic resin composition that has permanent antistatic properties and has excellent optical properties represented by total light transmittance. As a result of extensive studies, it was discovered that the above object could be achieved by mixing a specific polyether ester adsorbent with an acrylic resin, and the present invention was achieved.

That is, the present invention is; (A) (a) a salt of an aminocarboxylic acid or lactam having 6 or more carbon atoms, or a diamine and a dicarboxylic acid having a number average molecular weight of 400 or more, (bl number average molecular ff 1400 to 4.000); f!
iJ (7'rukylene oxide) glycol, (c) dicarboxylic acid having a number average molecular weight of 400 to 16, 1 to 35 parts by weight of polyether ester amide prepared from IJI from the above (a), (b), and (c), ■Acrylic polymer 98 to 5 parts by weight, ■Acrylic multistage polymer 1 to 60 parts by weight, the above, ■,
■A thermoplastic resin and an acid compound made of thermoplastic resin.

(B) Additionally, to 100 parts by weight of the above constituent components (1) and (2), (1) to 5 parts by weight of a metal salt of sulfonic acid, or/and (1) to 20 parts by weight of light-diffusing IPIO, are added. It is a mature plastic resin-containing acid compound.

The present invention will be explained in detail below.

The M paraboloid of the present invention essentially consists of (1) a specific polyether ester amide and (2) an acrylic polymer.

Structure of the polyether ester adduct in the present invention
(a) Aminocarboxylic acids or lactams having 6 or more carbon atoms, or salts of diamines and dicarboxylic acids having a number average molecular weight of 400 or more, include ω-aminocaproic acid, ω-
Aminocarboxylic acids such as acarinoenanthate, ω-aminocaprylic acid, ω-aminopergonic acid, ω-acunocabric acid and 11-aminoundecanoic acid, 12-aminododecanoic acid; caprolactam, enantholactam, capryllactam and laurolactam, etc. lactams; salts of diamine-dicarboxylic acids such as hexamethylenediamine-adipate, hexamethylenediamine-sebacate or hexamethylenediamine-isophthalate are used, especially caprolactam, 12-amide dodecanoic acid,
Hexamethylenediamine-adipate is preferably used.

Further, (a) an aminocarboxylic acid or lactam having 6 or more carbon atoms, or a salt of diamine and dicarboxylic acid having a number average molecular weight of 400 or more is used in an amount of 10 to 70% by weight as a constituent unit of the polyether ester amide. If it is less than 10% by weight, the mechanical properties of the polyether ester resin will be poor, and if it exceeds 70% by weight, the resulting resin will have poor antistatic properties, which is not preferred.

Other constituents of polyether ester amide (
b) As poly(alkylene oxide) glycol,
Polyethylene glycol, poly(12-propylene oxide) glycol, poly(1°3-propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol,
Block or random copolymers of ethylene oxide and propylene oxide and block or random copolymers of ethylene oxide and tetrahydrofuran are used. Among these, polyethylene glycol is particularly preferably used because of its excellent antistatic properties.

The number average molecular weight of poly(alkylene oxide) glycol is 400 to 4,000. In particular, it is used in the range of 600 to 2,000. If the number average molecular weight is less than 4.0, the mechanical properties of the resulting polyether ester amide will be poor, and if the number average molecular weight exceeds 4,000, antistatic properties will be insufficient, which is not preferred.

Other constituents of polyether ester amide (
c) Dicarboxylic acids having 4 to 16 carbon atoms include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,
6-dicarboxylic acid, naphthalene 2,7-dicarboxylic acid,
Aromatic dicarboxylic acids such as diphenyl-4,6'-dicarboxylic acid, diphenoxyethanedicarboxylic acid or sodium 3-sulfoisophthalate; 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid or dicyclohexyl-4 , 4°-dicarboxylic acid; Aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid or dodecanedioic acid (decanedicarboxylic acid); in particular terephthalic acid, isophthalic acid; , 1,4-cyclohexanedicarboxylic acid, sebacic acid, adipic acid, and dodecanedicarboxylic acid are preferably used from the viewpoint of polymerizability, color tone, and physical properties.

(c) poly(alkylene oxide) glycol and (c)
The dicarboxylic acids are reacted at a molar ratio of 1:1, but the charging ratio is usually changed depending on the type of dicarboxylic acid used.

There are no particular limitations on the method of polymerizing polyether ester a
c) React dicarboxylic acid to create a polyamide prepolymer with carboxylic acid groups at both ends, and add (b) poly(
A method of reacting glycol (alkylene oxide) under vacuum, (b), each of the compounds (a), 0)), and (c) above is charged into a reaction tank and pressurized at high temperature in the presence or absence of water. A method of producing a carboxylic acid-terminated polyamide prepolymer by reacting and then proceeding with polymerization under normal pressure or reduced pressure; A known method can be used, such as charging the components into a reaction tank, melting and mixing, and then proceeding with polymerization all at once under high vacuum.

The acrylic polymer (2) used in the present invention includes, in particular, resins mainly composed of methyl methacrylate, including homopolymers of methyl methacrylate, methyl methacrylate and methyl acrylate, ethyl acrylate, n-propyl acrylate, etc. , isopropyl acrylate, butyl acrylate, acrylonitrile, acrylic acid, methacrylic acid, vinylpyridine, vinylmorpholine, vinylpyridonetetrahydrofurfuryl acrylate, N,N-dimethylaminoethyl acrylate, N
, a copolymer with any one or more of copolymerizable monomers such as N-dimethylacrylamide, 2-hydroxyacrylate, ethylene glycol monoacrylate, glycerin monoacrylate, maleic anhydride, styrene or α-methylstyrene, or Mixtures of methyl methacrylate homopolymers and the above copolymers are included.

In any of the above cases, the proportion of methyl methacrylate contained in the polymer is preferably 50% by weight or more, more preferably 80% by weight or more. If the proportion of methyl methacrylate is less than 50% by weight, the mechanical properties, especially the flexural modulus, will deteriorate, which is not preferable.

The acrylic multistage (multilayer) polymer (2) used in the present invention is disclosed in JP-A-53-58554 and JP-A-55-94.
It is disclosed in Japanese Patent No. 917, Japanese Patent No. 61-32346, etc., but to briefly explain, it is manufactured by a multi-step sequential polymerization method in which elastic layers and inelastic layers are alternately formed around an acrylic polymer elastic layer. It is a multi-stage polymer.

More specifically, the acrylic multi-stage ( An acrylic type polymer having a weight average particle size of preferably 0.1 to 1μ, and an intermediate layer between an elastic layer and an inelastic layer in which alkyl methacrylate gradually increases. Multistage (multilayer) polymers are also effective.

The blending ratio of polyether ester adduct (2) in the present invention is 1 to 35 parts by weight, preferably 5 to 25 parts by weight, and more preferably 8 to 20 parts by weight.

If the amount is less than 13!1 parts, the antistatic property will be poor, and if it is more than 35 parts by weight, the mechanical properties, especially the flexural modulus after immersion in water, will be deteriorated, which is not preferable.

The blending ratio of the acrylic multistage polymer (2) is 1 to 60 parts by weight, preferably 5 to 40 parts by weight.

If it is less than 1 part by weight, the improvement in impact resistance is insufficient, and if it is less than 60 parts by weight, the flexural modulus decreases, which is not preferable.

In the present invention, in order to further exhibit the antistatic effect, it is effective to add a metal salt of sulfonic acid as component (2). Specific examples thereof include alkali metal salts or alkaline earth metal salts of aromatic sulfonic acids such as p-)luenesulfonic acid, dodecylbenzenesulfonic acid, dodecyl diphenyl ether disulfonic acid, naphthalenesulfonic acid, and a condensate of naphthalenesulfonic acid and formalin. Salts; or specific carboxylic acids such as stearic acid, lauric acid, and polyacrylic acid, and alkali or alkaline earth metal salts such as diphenyl phosphite and diphenyl phosphate. Among these, sodium salts and potassium salts are particularly preferred.

The blending amount of the component (■) is the total amount of the above-mentioned components (■) and (■): 10
0.1 to 5 parts by weight is preferable to 0 parts by weight, 0.1
If the amount is less than 5 parts by weight, the effect of use will not be fully exhibited, and if it exceeds 5 parts by weight, the surface of the molded product may become rough or colored, which is not preferable.

The light diffusing agent used in the present invention is an inorganic light diffusing agent, such as 5lO with a weight average particle size of 0.5 to 20μ.
z (trade name Tospar 2 manufactured by Toshiba Silicone Co., Ltd.), CaC01 of 0.5 to 15μ, Ba of 0.5 to 15μ
5O, 0.5-20μ quartz powder, 0.5-20μ
Examples of organic light diffusing agents include Japanese Patent Publication No. 62-31741,
Examples include organic polymer fine particles disclosed in JP 63-291002 and JP 63-29001.

These light diffusing agents may be used alone or in combination of two or more, regardless of whether they are inorganic or organic. In particular, organic light diffusing agents are excellent in high transmittance and high diffusivity, so when using a light diffusing agent, it is desirable to make them an essential component.

The amount of component (1) added is preferably in the range of 0.1 to 20 parts by weight; if it is less than 0.1 part by weight, the light diffusion effect will not be sufficient, and if it is more than 20 parts by weight, the total light transmittance will decrease. Poor optical properties.

The thermoplastic resin composition of the present invention contains specific components (1) to (4) in a specific number surrounded by rectangles A-D shown in FIG. The resin composition of the present invention may contain other components such as pigments, dyes, reinforcing agents, fillers, and mold release agents within a range that does not impair its physical properties. , a heat stabilizer, an antioxidant, a nucleating agent, a light stabilizer, an ultraviolet absorber, a plasticizer, and other polymers can be contained in any process such as a kneading process or a molding process.

The resin m-acid of the present invention thus obtained is molded by a known method generally used for thermoplastic resins, such as injection molding, extrusion molding, blow bottom molding, vacuum molding, etc. It can be made into a molded body.

(Examples) In order to explain the present invention more specifically, Examples and Comparative Examples will be described below, but these do not limit the scope of the present invention.

In addition, after the finally obtained resin &Il product was molded by injection molding, various physical properties were measured by the following test methods.

(1) Tensile strength: Measured at 23° C. and 55% RH using a 1/8-inch dumbbell piece according to ASTM D638.

However, since many elastomers do not have a yield point, the tensile strength was measured in an absolutely dry state using a dumbbell piece with a thickness of 11 m.

(2) Flexural modulus: Measured at 23"C and 55% RH using a 1/4 inch thick test piece according to ASTM D790.

(3) Surface specific resistance value: Using 2tx40φ disk, room temperature 23°C1 temperature 50%R
Measured under H atmosphere. A super insulation resistance meter 5M-10 model manufactured by Toa Denpa Kogyo ■ was used for the measurement.

(4) Flap adhesion test: The 1/8 inch thick flat plate used for surface resistivity measurement was heated to 23°C.
℃, relative humidity of 50% for 3 months, and then placed in a Dart Chamber (model 200) manufactured by Condo Scientific ■ under the conditions of a blower of 10 f/mIn, a temperature of 23℃, and a relative humidity of 50%. The test was conducted for 30 minutes, and the presence or absence of lumps was visually observed.

(5) Total light transmittance: Total light transmittance was measured using a 2t×10φ disk.

Toyo Sei I for measurement! @Used a haze meter manufactured by the manufacturer.

In addition, parts and percentages in the examples indicate parts by weight and percentages by weight, respectively.

Reference Example 1 Preparation of polyether ester amide; A-1; 26 parts of caprolactam, number average molecular weight of i, o
73 parts of polyethylene glycol and 9 parts of adipic acid were mixed with 0.0 parts of "Irganox" 1010 (antioxidant).
15 parts of antimony trioxide catalyst and 0.15 parts of antimony trioxide catalyst were charged into a reaction vessel equipped with a helical ribbon stirring blade, the mixture was replaced with nitrogen, heated and stirred at 240°C for 60 minutes to obtain a transparent homogeneous solution, and then heated to 260°C. 4 under conditions of 0.5 PengHg or less
After polymerization for a period of time, a viscous and transparent polymer was obtained.

A pellet-shaped polyether ester amide (A-1) was prepared by discharging the polymer onto a cooling belt and pelletizing it.

A-2: 28 parts of nylon 6.6 salt (AH salt), 70 parts of polyethylene glycol with a number average molecular weight of 1600, and 8 parts of adipic acid were used, and the polymerization time was 4 hours.
Polyether ester amide (A-2) was prepared in exactly the same manner as A-1).

A-3: (A
-1) Polyether ester amide (A-
3) was prepared.

Reference Example 2 Preparation of acrylic multi-stage polymer: B-1 = 250 parts of ion-exchanged water, 1 part of sulfosuccinic acid ester sodium salt, and 10.05 parts of sodium formaldehyde sulfoxylate were placed in a reaction vessel equipped with a cooler, and nitrogen was added. After stirring under air flow, 10 parts MMA, 0.05 parts AM
Prepare A.

CHP is dissolved in MMA in an amount of o, i% relative to MMA. All monomers added in subsequent steps also contain 0.1% CHP for each monomer, unless otherwise specified.

The reaction vessel was stirred at a rotational speed of 20 rpm under a nitrogen stream, heated to 70°C, and stirred for 30 minutes to form a layer (A).
) polymerization is completed. Continued l.

A mixture of 1 part MMA, 10 parts BuA, and 0.10 parts AMA is added over 10 minutes and held for an additional 40 minutes to complete the second stage polymerization. Next, 38 parts of BuA
, 0.20 parts of AMA, 20 parts of BD were added over 10 minutes and held for an additional 40 minutes to complete polymerization of the third layer. Next, 10 parts of MMA, 1
When the fourth layer component consisting of 0 parts of BuA and 0.10 parts of AMA was cleaned for 10 minutes and held for an additional 50 minutes, the rubber layer (
The polymerization of B) is completed.

Furthermore, an outermost layer (c) component consisting of 10 parts of MMA and 0.03 parts of n-03H was added and polymerized for 10 minutes to form an acrylic multi-stage polymer (B-1) consisting of 5 layers. .

By observing the sampled samples after the completion of polymerization of each layer using an electron microscope, it was confirmed that no new particles were generated during the polymerization of each layer, and complete seed polymerization was performed.

The obtained emulsion undergoes coagulation, coagulation, and solidification reactions using aluminum chloride, and is then treated with il! After filtering, washing with water, and drying, an acrylic multi-stage polymer (Bl) was obtained.

The abbreviations are as follows.

Methyl methacrylate: MMA Butyl acrylate: BuA Allyl methacrylate): AMA l,3-butylene dimethacrylate: BD Cumene hydroperoxide: CHPn-octyl mercaptan: n-〇SH (Examples 1 to 7 and Comparative Examples 1 to 3 ) The polyether ester amide prepared above, the acrylic multi-stage polymer prepared above, and the acrylic polymer (trade name Delpera 8ON, manufactured by Asahi Kasei Corporation) were mixed in the blending ratio shown in Table 1. Hindered Phenol Stable 1fII (trade name: Sanol LS) is mixed and used as a stabilizer.
770 Nisankyo ■) 065 parts by weight, ultraviolet absorber (trade name Tinuvin P: manufactured by Ciba Geigy) 0.3 parts by weight, heat stabilizer (trade name Phosphite 16 Days: manufactured by Ciba Geigy) 0.2 parts by weight After blending using a tumbler, the resin was melt-kneaded using a vented extruder 1 (40 mφ) at a resin temperature of 250 ''C, and pelletized.Then, it was tested using an injection molding machine at a cylinder temperature of 260 ℃ and a mold temperature of 60 ℃. The bottom shape of each piece was measured, and each physical property was measured.

Note that the surface resistivity value was measured on injection molded products under the following conditions.

■ Immediately after molding, wash with detergent “Mama Lemon” (manufactured by Lion Oil ■) aqueous solution, then thoroughly wash with distilled water, and then
After removing moisture from the surface, it was heated at 55%RH and 23°C for 24 hours.
The humidity was adjusted for a period of time and measured.

■ After molding, leave it at 50% RH 123°C for 100 days, wash with a detergent "Mama Lemon" aqueous solution, then thoroughly wash with distilled water, remove surface moisture,
%RH123°Ct' 24 hours left v4 wet and measured.

(Effects of the present invention) The acrylic resin composition of the present invention is composed of an acrylic resin, an acrylic multistage polymer, and a polyether ester admixture elastomer, and has excellent permanent antistatic properties. In addition, it has characteristics such as good optical properties and low cost, and can be used as a material and molded rod that can prevent electrostatic charging in various parts such as lighting equipment, home appliances such as equipment nameplates, and office equipment electronics products. Very suitable for use.

[Brief explanation of drawings]

FIG. 1 shows the composition range of each component constituting the resin composition of the present invention.
The range surrounded by is the &Il precept area of the present invention. (1 other person)

Claims (3)

[Claims] (1) [1] (a) Aminocarboxylic acid or lactam having 6 or more carbon atoms, or salt of diamine and dicarboxylic acid having 4 or more carbon atoms, (b) Poly(alkylene oxide) having a number average molecular weight of 400 to 4,000 ) glycol, (c) dicarboxylic acid having 4 to 16 carbon atoms, 1 to 35 parts by weight of a polyether ester amide composed of the above (a), (b), and (c), [2] 98 to 98 parts by weight of an acrylic polymer 5 parts by weight, [3] 1 to 60 parts by weight of acrylic multistage polymer, [1]
], [2], and [3]. (2) [1] (a) Aminocarboxylic acid or lactam having 6 or more carbon atoms, or salt of diamine and dicarboxylic acid having 4 or more carbon atoms, (b) Poly(alkylene oxide) having a number average molecular weight of 400 to 4,000 Glycol, (c) dicarboxylic acid having 4 to 16 carbon atoms, 1 to 35 parts by weight of polyether ester amide composed of the above (a), (b), and (c), [2] Acrylic polymer 98 to 5 parts by weight, [3] 1 to 60 parts by weight of acrylic multistage polymer, the above (1
100 parts by weight of a resin mixture consisting of ), (2), and (3), and [4] 0.1 to 5 parts by weight of a metal salt of sulfonic acid.
Thermoplastic resin composition. (3) [1] (a) Aminocarboxylic acid or lactam having 6 or more carbon atoms, or salt of diamine and dicarboxylic acid having 4 or more carbon atoms, (b) Poly(alkylene oxide) having a number average molecular weight of 400 to 4,000 Glycol, (c) dicarboxylic acid having 4 to 16 carbon atoms, 1 to 35 parts by weight of polyether ester amide composed of the above (a), (b), and (c), [2] Acrylic polymer 98 to 5 Parts by weight, [3] 1 to 60 parts by weight of acrylic multistage polymer, [1]
], [2], and [3] 100 parts by weight of a resin mixture; [4] A thermoplastic resin composition comprising 0.1 to 20 parts by weight of a light diffusing agent.