JPH09328597A - Antistatic acrylic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an acrylic resin composition having excellent permanent antistatic properties and persistent good transparency by mixing an acrylic resin with a specified cationic copolymer and a specified tert. amine or quat. ammonium salt. SOLUTION: This composition contains 100 pts.wt. acrylic resin (A), 0.5-20 pts.wt. linear cationic copolymer (B) comprising 80-98mol% polyolefin structural units represented by formula I (wherein R<1> is H or methyl) and 2-20mol% acrylamide or acrylate structural units represented by formula II (wherein Y is -O- or -NH-; R<2> is ethylene or propylene; R<3> and R<4> are each methyl; R<5> is methyl, ethyl or the like; and X<-> is a halide ion or the like) and having a weight-average molecular weight of 1,000-50,000 and 0.1-5.0 pts.wt. tert. amine salt represented by formula III (wherein R<7> is a 1-18C alkyl; R<8> and R<9> are each a 1-4C alkyl; and Z is hydrochloric acid, acetic acid or the like) or quat. ammonium salt (C) represented by formula IV or V.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic resin composition excellent in permanent antistatic property, which is used as a material for packaging materials such as sheets and cases and parts for home electric appliances.

[0002]

2. Description of the Related Art Acrylic resins (a generic name for polymer resins of acrylic acid and its derivatives, including methacrylic resins and copolymers with other monomers such as styrene)
Has been conventionally used as a material for packaging materials such as sheets and cases, lighting equipment, home electric appliance parts, instrument covers and the like. However, these thermoplastic resins generally have a large electric resistance and have a serious drawback that they are easily charged by friction and attract dust.

Therefore, in recent years, the following method has been proposed as a method for imparting an antistatic property to a thermoplastic resin.
That is, (a) a method of applying an antistatic agent on the resin surface and then drying, (b) a method of kneading the internal addition type antistatic agent into the resin, and (c) a method of applying a silicone compound to the resin surface, (D) A method of modifying the resin itself has been proposed.

However, in the above method (a), a surfactant solution is used as an antistatic agent, and such an antistatic agent is easily removed from the resin surface by washing. The protective ability could not be provided.

In the method (b), glycerin fatty acid ester is used as the internal addition type antistatic agent,
Sorbitan fatty acid ester, alkyldiethanolamide, sodium alkylbenzenesulfonate, quaternary salt of alkylimidazole and the like are used. When these internal addition type antistatic agents are used, even if the antistatic agent on the resin surface is lost by washing, a new antistatic agent bleeds sequentially from the inside, so the antistatic ability lasted for a relatively long period of time. .

However, in the method using the above-mentioned internal addition type antistatic agent, it takes a long time for the antistatic ability to be restored after the resin surface is washed, and when the antistatic agent bleeds out excessively. However, there is a problem in that the resin surface becomes sticky and dust and the like tend to adhere to the resin surface. Furthermore, since these antistatic agents have low molecular weight, they are volatilized by the heat during molding processing at high temperature, which results in the economical disadvantage of having to add more antistatic agents than necessary, There is a problem that it is difficult to adjust the effective amount of the inhibitor.

In order to solve the above-mentioned drawbacks of the internal addition type antistatic agent, recently, polymethylmethacrylate having 20-80 mol% of methoxy groups modified with diethanolamine (JP-A-1-170603), alkoxypolyethylene. A graft copolymer of glycol methacrylate (Japanese Patent Publication No. 58-39860), a styrene-maleic anhydride copolymer imide-modified and then quaternized and cationized (Japanese Patent Publication No. 1-29820),
Comb type copolymer of high molecular weight monomer in which polymethylmethacrylate having carboxyl group at the terminal is converted to methacryloyl group with glycidylmethacrylate and aminoalkylamyl ester or acrylamide and its quaternized cation modification Product (JP-A-62-
No. 121717), polyether ester amide elastomers (JP-A-60-23435), and other polymer compounds having antistatic functional groups have been proposed as internal addition type antistatic agents.

However, even if any of the above-mentioned polymer compounds is used as the internal addition type antistatic agent, the physical properties of the resin such as transparency, strength and elongation are deteriorated, and further, the antistatic ability of the resin and its durability are obtained. There were problems such as insufficient properties and water resistance.

Further, Japanese Patent Application Laid-Open No. 5-78543 discloses a method of adding an electrolyte to a polyethylene glycol derivative having a specific composition as a transparent permanent antistatic composition, which is water-resistant and obtained. There was still a problem in the heat resistance of the resin composition.

Further, in the above method (c), the antistatic ability lasts semipermanently, but since the silicone compound used is expensive and the working efficiency at the time of coating is poor, it is very disadvantageous in terms of cost. It was

Further, in the above method (d), a hydrophilic group is introduced into the resin, but it is necessary to introduce a considerable amount of the hydrophilic group in order to impart a sufficient antistatic ability. However, when the hydrophilic group is introduced in this manner, the moisture absorption resistance of the resin itself and the mechanical properties thereof may be deteriorated.

[0012]

As described above, the conventional antistatic acrylic resin composition is still insufficient in antistatic ability and durability, water resistance, physical properties of resin and the like. there were.

In the method of kneading or coating the antistatic agent, the antistatic effect is exhibited by the antistatic agent layer bleeding out or adhering to the resin surface.
If the antistatic agent layer comes off due to friction, washing with water, etc., there is a problem that the antistatic effect is lost. In particular, in a system in which an alkyldiethanolamine or the like which is commonly used in an acrylic resin is kneaded, the abrasion resistance and water resistance of the resin are greatly reduced.

Further, in the method of kneading the antistatic agent,
The antistatic agent often bleeds out excessively, and there is a problem of deterioration of the surface condition of the resin such as stickiness or powder blowing on the resin surface or deterioration of printing characteristics on the resin surface.

More specifically, Japanese Patent Laid-Open No. 7-138442.
In the publication, a similar cationic copolymer is added to an acrylic resin to raise a certain effect, but there is a decrease in transparency over time, which is considered to be due to progress of crystallization of the cationic copolymer. I was seen.

<Purpose of the Invention> The present invention has been made in view of the above-mentioned problems of the prior art. The object of the present invention is to provide excellent permanent antistatic property and long-term transparency of the resin itself. It is to provide a good acrylic resin composition.

[0017]

The acrylic resin composition according to claim 1 of the present invention comprises an acrylic resin as a matrix resin and the following cationic copolymer 0.5 to 100 parts by weight thereof. ˜20 parts by weight and 0.1 to 5 parts by weight of the following tertiary amine salt or quaternary ammonium salt are added.

The above-mentioned cationic copolymer has 80 to 9 polyolefin structural units represented by the general formula (1) in the molecule.
8 mol%, acrylamide or acrylate structural unit represented by general formula (2) 2 to 20 mol%, and acrylate structural unit represented by general formula (6) 0.3 to 15 mol% as required. With a weight average molecular weight of 1,
It is a linear cationic copolymer having a molecular weight of 000 to 50,000, and each structural unit may be regularly arranged or irregularly arranged.

[0019]

[Chemical 7]

Embedded image The tertiary amine salt or quaternary ammonium salt is a tertiary amine salt represented by the general formula (3) or a quaternary ammonium salt represented by the general formulas (4) and (5). is there.

[0020]

Embedded image

Embedded image

Embedded image The conventional internal addition type antistatic agent bleeds out on the resin surface to form a hygroscopic layer and leaks static electricity generated thereby, whereas the cationic copolymer added to the resin composition of the present invention is , A continuous layer is formed in the matrix resin, and the leakage of static electricity occurs due to the movement of the charge accompanying the movement of the counter ion of the cationic group in the copolymer molecule. Therefore, the cationic copolymer of the present invention has a higher rate of leakage of static electricity than the conventional internal addition type antistatic agent. Further, in the resin composition of the present invention, since the cationic copolymer does not exist in a high concentration near the surface of the resin which is easily influenced by external factors, friction of the resin surface, loss of antistatic effect due to washing with water, etc. occurs. Absent.

The compounded tertiary amine salt or quaternary ammonium salt is added to the cationic copolymer,
It exhibits the effect of a plasticizer and inhibits its crystallization, thus preventing the decrease in transparency over time.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The constitution of the cationic copolymer used in the resin composition of the present invention will be described in more detail below.

In the cationic copolymer used in the resin composition of the present invention, the polyolefin structural unit represented by the general formula (1) is contained in the molecule in an amount of 80 to 98 mol%. When it is less than 80 mol%, the compatibility with the matrix resin is deteriorated and the physical properties of the resin composition are remarkably lowered. On the other hand, if the content exceeds 98 mol%, sufficient antistatic ability cannot be obtained. From the viewpoint of compatibility and antistatic ability, the content ratio of the polyolefin structural unit is preferably 85 to 97.5 mol%.

In the cationic copolymer used in the resin composition of the present invention, the acrylate structural unit represented by the general formula (6) has 0.3 to 15 mol% in the molecule.
It is contained. By containing such an acrylate structural unit, the compatibility between the cationic copolymer and the matrix resin is improved. When the content ratio of the acrylate structural unit of the general formula (6) exceeds 15 mol%, the physical properties of the resin composition are deteriorated, and the content ratio of the acrylate structural unit of the general formula (6) is 1 to 1 from the viewpoint of compatibility. Thirteen
About mol% is preferable.

In the general formula (6) of the acrylate structural unit, R ⁶ represents a C ₁ -C ₄ alkyl group, and R ⁶ may be the same or different for each structural unit.

Further, in the cationic copolymer used in the resin composition of the present invention, the acrylamide or acrylate structural unit represented by the general formula (2) has 4 units.
A cationic acrylamide or acrylate structural unit in the form of a quaternary ammonium salt.
20 mol% is contained. When this content is less than 2 mol%, the resin composition lacks antistatic ability, and when the content exceeds 20 mol%, the compatibility of the cationic copolymer with the matrix resin deteriorates. From the viewpoint of antistatic ability and compatibility, the content ratio of the acrylamide or acrylate structural unit of the general formula (2) is 3 to 15
Mol% is preferred.

In the general formula (2) of the acrylamide or acrylate structural unit, R ² represents an ethylene group or a propylene group, and these may be mixed in one molecule, and R ³ and R ⁴ are methyl groups. Represents R
⁵ represents a C ₁ -C ₄ lower linear alkyl group such as a methyl group or an ethyl group, or an arylalkyl group such as a benzyl group, from the viewpoint of easy production and good antistatic ability. Further, X ⁻ is Cl ⁻ , Br ⁻ , I ^−.
Halide ion such as CH ₃ SO ₃ ⁻ , CH ₃ OS
O ₃ ⁻ or CH ₃ CH ₂ OSO ₃ ⁻ , CH ₃ CH ₂ S
Represents O ₃ ⁻ .

The weight average molecular weight of the above-mentioned cationic copolymer is measured by gel permeation chromatography, and the weight average molecular weight in terms of polystyrene is used to measure the super high temperature G.
PC method (Kinukawa, "Polymer Papers Vol. 44, No. 2," 139
~ 141, 1987), but the weight average molecular weight is in the range of 1,000 to 50,000. When the weight average molecular weight is less than 1,000, the cationic copolymer becomes waxy, the handling property is deteriorated, and further, there is a problem that the adhesiveness of the resin surface is increased due to excessive bleed-out, and the weight average molecular weight is increased. Is 5
When it exceeds 50,000, the problem that the compatibility with the matrix resin is deteriorated occurs. The preferred weight average molecular weight of the cationic copolymer is 3,000 to 30,000.
0.

The method for producing the cationic copolymer used in the resin composition of the present invention is, for example, an ethylene-acrylic acid ester copolymer obtained by copolymerizing ethylene and an acrylic acid ester by a high pressure polymerization method. The method described in JP-A-60-79008 discloses hydrolysis and thermal degradation at the same time to obtain a desired molecular weight, and the ethylene-acrylic acid ester-acrylic acid copolymer obtained is converted into an acrylamide copolymer. In this case, the above-mentioned cationic copolymer is obtained by amidating with N, N-dialkylaminoalkylamine and then cation-modifying with a known quaternizing agent to isolate the above cationic copolymer. In the case of an acrylate copolymer, After esterification with N, N-dialkylalkanolamine instead of N, N-dialkylaminoalkylamine, Cationically modified with quaternizing agents isolated are those of obtaining the cationic copolymer.

In the resin composition of the present invention, the added amount of the above-mentioned cationic copolymer is practically 0.5 to 100 parts by weight of the acrylic resin which is the matrix resin.
Although it is 20 parts by weight, when the addition amount is less than 0.5 parts by weight, it is difficult to obtain the required antistatic property. On the contrary, when the addition amount exceeds 20 parts by weight, the mechanical properties of the resin are ,
In particular, the impact strength decreases. From the viewpoint of the balance between the antistatic property and the mechanical properties of the resin, the addition amount of the cationic copolymer is particularly preferably 5 to 20 parts by weight relative to 100 parts by weight of the matrix resin.

The tertiary amine salt used in the present invention is represented by the general formula (3), and can be obtained by the neutralization reaction of the equimolar acid with the tertiary amine.

The tertiary amines used here include
Dodecyldimethylamine, tridecyldimethylamine,
Octadecyl dimethyl amine, octyl dimethyl amine, myrcyl dimethyl amine, oleyl dimethyl amine, etc. are mentioned, As an acid, hydrochloric acid, acetic acid, methanesulfonic acid, ethanesulfonic acid, phosphoric acid, hypophosphorous acid, nitric acid,
Examples thereof include perchloric acid, toluenesulfonic acid, benzenesulfonic acid and the like.

The quaternary ammonium salt has the general formula (4):
The compound represented by the formula (5) is obtained by subjecting the general formula (4) to a quaternization reaction of a tertiary amine with an alkylating reagent according to a conventional method. The tertiary amines used here are trialkylamines such as dodecyldimethylamine, tridecyldimethylamine, octadecyldimethylamine, octyldimethylamine, myrsityldimethylamine and oleyldimethylamine. Examples of the alkylating agent include alkyl halides such as benzyl chloride, methyl chloride and methyl iodide, and esters such as diethyl sulfate, dimethyl sulfate, methyl toluenesulfonate, ethyl toluenesulfonate, methyl methanesulfonate, methyl methanesulfonate and ethyl methanesulfonate. Compounds and the like.

Regarding the general formula (5), N, N-dialkylalkylenediamines such as N, N-dimethylethylenediamine, N, N-dimethylpropylenediamine and aliphatic carboxylic acids such as octyl acid and decanoic acid are used. After amidation with dodecanoic acid, octadecanoic acid, etc.,
As an alkylating agent, alkyl halides such as benzyl chloride, methyl chloride, and methyl iodide, and ester compounds such as diethyl sulfate, dimethyl sulfate, methyl toluenesulfonate, ethyl toluenesulfonate, methyl methanesulfonate, and methyl methanesulfonate. It is obtained by carrying out a quaternization reaction in.

Further, these tertiary amine salts and quaternary ammonium salts can be used alone or in combination of two or more kinds, and the compounding amount thereof is 0.1 to 5.0 parts by weight.

If the amount is less than 0.1 part by weight, it is difficult to maintain the transparency, and if the amount exceeds 5.0 parts by weight, bleeding out from the matrix resin occurs and the surface condition is deteriorated. Considering these points, 0.3-3.0
A blending amount of parts by weight is particularly preferable.

In the resin composition of the present invention, an acrylic resin is used as the matrix resin, but the type thereof is not particularly limited. Specific examples of the acrylic resin, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, methyl methacrylate-methyl acrylate copolymer, Methyl methacrylate-ethyl methacrylate copolymers, methyl methacrylate-butyl methacrylate copolymers, methyl methacrylate-ethyl acrylate copolymers and other alkyl acrylate compounds such as methyl, ethyl, propyl and butyl Examples thereof include homopolymers and copolymers. These acrylic resins may be used alone, or 2
You may combine more than one, and the production method thereof is not particularly limited, and known suspension polymerization method, emulsion polymerization method,
A bulk polymerization method or the like is used.

The method for producing the resin composition of the present invention includes:
The cationic copolymer, the tertiary amine salt, and the quaternary ammonium salt may be added to the acrylic resin in a known amount by a known method, for example, using a twin-screw extruder.

Additives may be added to the composition of the present invention as needed, but a heat stabilizer and / or a weathering agent is particularly used. As a heat stabilizer, tetrakis (2,4-di-t
-Butylphenyl) 4,4'-biphenylene diphosphonite, distearyl pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite, 3,4,5,6-dibenzo-1 , 2-oxaphosphane-2-oxide, trisnonylphenylphosphite, 4,4'-butylidene bis (3-methyl-6)
-T-butylphenyldi-tridecylphosphite) and other phosphorus-based stabilizers and tetrakis [methylene-3 (3,5-
t-Butyl-4-hydroxy-phenyl) propionate] methane, 2,6-di-t-butyl-4-methyl-
Phenol-based stabilizers such as phenol and 2-t-butyl-4-methoxyphenol and sulfur-containing stabilizers such as mercaptopropionic acid ester can be used, and among these, phosphorus-based stabilizers are preferable.

Examples of weathering agents such as ultraviolet absorbers and light stabilizers include 2- (2'-hydroxy-3 ', 5'.
-Di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t
-Amylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2-N-benzotriazol-2-yl)
Phenol], 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dicumylphenyl) phenylbenzotriazole, 2- (2'-hydroxy- Triazole-based UV absorbers such as 5'-t-octylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperazinyl) sebacate, poly [[6- (1,
1,3,3-tetramethylbutylimino) 1,3,5-
Triazine-2,4-diyl]-[4- (2,2,6,
6-Tetramethylpiperidinyl) -imino]-[4-
2,2,6,6-tetramethylpiperidinyl) -imino]] and the like are used.
Among them, triazole-based ones are effective, and among them, those imparting particularly excellent weather resistance and transparency include
2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazole-
2-yl) phenol].

The heat stabilizer and the weather resistance agent are preferably added in an amount of 0.01 to 3.0 parts by weight based on 100 parts by weight of the acrylic resin.

Other additives include nonionic or cationic surfactants, polymers having a polyoxyethylene chain, such as polyoxyethylene and polyethylene glycol, which are polycondensed with an ester bond, an amide bond or an imide bond. An antistatic agent of a molecular weight or a high molecular weight which is polyadded with a urethane bond or an epoxy ester (ether) bond may be simultaneously added within a range not exceeding the addition amount of the cationic copolymer of the present invention.

[0043]

【Example】

<Synthesis of Cationic Copolymer> Specific synthesis examples A to C of the cationic copolymer used in the resin composition of the present invention will be described below.

Synthesis Example A In a 1 liter four-necked flask equipped with a thermometer, a stirrer, a dropping funnel and a Dean-Stark water separator, 400 ml of xylene, ethylene / ethyl acrylate / acrylic acid copolymer (ethylene / 150 g of ethyl acrylate / acrylic acid = 93/3/4) and 1.0 g of paratoluenesulfonic acid were charged. Next, 21.1 g of N, N-dimethylaminopropylamine was charged, and water produced by heating to 140 ° C. using an oil bath was continuously removed by azeotropic distillation with xylene. The reaction was continued for an hour, and the amidation reaction was continued until no azeotropic formation of water was observed.

458 g of the obtained reaction product was cooled to 80 ° C., and 31.1 g of diethylsulfate was added to the reaction mixture through a dropping funnel.
It was dripped gradually over time. During this period, heat generation was observed, but the reaction temperature was maintained at 90 ° C. by cooling, and after completion of dropping, aging reaction was performed at 100 ° C. for 4 hours. The reaction product obtained here was poured into a large amount of methanol, and the generated precipitate was collected and dried to obtain a cationic polymer A. When the weight average molecular weight of the polymer A was measured,
It was 300.

Synthesis Example B In a 1-liter four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a Dean-Stark water separator, 400 ml of xylene and an ethylene / acrylic acid copolymer (ethylene / acrylic acid = 91 / 9) 150 g and 1.0 g of paratoluenesulfonic acid were charged. Next, 38.5 g of N, N-dimethylaminoethylamine was charged, and water generated by heating to 140 ° C. using an oil bath was continuously removed by azeotropic distillation with xylene, and further at 140 ° C. for 17 hours. The amidation reaction was continued until the azeotropic distillation of the produced water was not observed.

The obtained reaction product was cooled to 80 ° C., and 72.0 g of methyl iodide was gradually added dropwise thereto over 1 hour. During this time, an exotherm was observed, but the reaction temperature was maintained at 90 ° C by cooling, and after completion of dropping, the reaction temperature was 4 ° C at 100 ° C.
A time aging reaction was performed. The reaction product obtained here was poured into a large amount of n-hexane, and the produced precipitate was collected and dried to obtain a cationic polymer B. The weight average molecular weight of Polymer B was measured to be 22,000.

Synthesis Example C In a 1-liter four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a Dean-Stark water separator, 400 ml of xylene, ethylene / ethyl acrylate / acrylic acid copolymer (ethylene / 150 g of ethyl acrylate / acrylic acid = 93/3/4) and 1.0 g of paratoluenesulfonic acid were charged. Next, 21.1 g of N, N-dimethylaminopropylamine was charged, and water produced by heating to 140 ° C. using an oil bath was continuously removed by azeotropic distillation with xylene. The reaction was continued for an hour, and the amidation reaction was continued until no azeotropic formation of water was observed.

458 g of the obtained reaction product was cooled to 80 ° C., and 15.5 g of benzyl chloride was added thereto from a dropping funnel.
It was dripped gradually over time. During this period, heat generation was observed, but the reaction temperature was maintained at 90 ° C. by cooling, and after completion of dropping, aging reaction was performed at 100 ° C. for 4 hours. The reaction product obtained here was poured into a large amount of methanol, and the produced precipitate was collected and dried to obtain a cationic polymer C. When the weight average molecular weight of the polymer C was measured,
500.

Synthesis Example D In a 1-liter four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a Dean-Stark water separator, 400 ml of xylene, ethylene / ethyl acrylate / acrylic acid copolymer (ethylene / 150 g of ethyl acrylate / acrylic acid = 93/3/4) and 1.0 g of paratoluenesulfonic acid were charged. Next, 18.41 g of N, N-dimethylaminoethanol was charged and heated to 140 ° C. using an oil bath to continuously remove water produced by azeotropy with xylene, and further at 140 ° C. for 17 hours. The amidation reaction was continued until the azeotropic distillation of the produced water was not observed.

437 g of the obtained reaction product was cooled to 80 ° C., and methyl methanesulfonate 2 was added thereto through a dropping funnel.
2.2 g was gradually added dropwise over 1 hour. During this time, an exotherm was observed, but the reaction temperature was lowered to 90 ° C by cooling.
After completion of the dropping, an aging reaction was carried out at 100 ° C. for 4 hours. The reaction product obtained here was poured into a large amount of methanol, and the generated precipitate was collected and dried to obtain a cationic polymer D. The weight average molecular weight of Polymer D was 5,300.

<Evaluation Method of Various Physical Properties of Resin Composition> Various physical properties of the obtained resin composition were measured by the following methods. The following electrical characteristics 1 to 8 are measured after controlling the humidity at a temperature of 20 ° C. and a relative humidity of 60% for 24 hours or more.

Surface Specific Resistance The surface specific resistance when a voltage of 500 V was applied to the test piece of the resin composition was measured with a mega ohm meter (manufactured by Toa Denpa Co., Ltd.).

Charge voltage decay rate With a static Honest meter (made by Shishido Trading Co., Ltd.),
The time required for applying a voltage of 10,000 V × 30 seconds to the test piece of the resin composition and halving the initial voltage was shown in seconds.

Abrasion resistance A test piece of the resin composition was rubbed 80 times with water-soaked gauze and then dried, and the appearance change and surface resistivity of the test piece were measured by the same method as described above.

Water Resistance A test piece of the resin composition was boiled in boiling water for 2 hours and then dried, and the surface specific resistance value of the test piece was measured by the same method.

A haze number of 50 × 50 × 1 mm was measured using a haze meter manufactured by Nippon Denshoku Kogyo Co., Ltd.

Weather resistance A 2 mm thick flat plate obtained by injection molding was compliant with JIS A1.
In accordance with S. 415, it is 5 with Suga Test Instruments Co.
The accelerated exposure test of 00 hr was performed, and the yellowing degree (ΔYI) and total light transmittance before and after the test were measured according to JIS K
7103 and JIS K7105. Moreover, the haze number after the test was measured. The yellowing degree (ΔYI) was measured with reference to an additive-free matrix resin (acrylic resin).

<Concrete Acrylic Resin Composition> A concrete example of the resin composition of the present invention and a concrete comparative example for comparison and comparison therewith will be described below.

Examples 1 to 9 Methyl methacrylate resin (Acrypet MD, manufactured by Mitsubishi Rayon Co., Ltd.), methyl methacrylate / methacrylic acid which is a synthetic product in a laboratory, in a twin-screw extruder equipped with a constant amount supply device. The resin of ethyl = 90 mol / 10 mol and methyl methacrylate / isobutyl methacrylate = 90 mol / 10 mol, and the cationic polymers A to D obtained in the above Synthesis Example and the tertiary amine salt or quaternary ammonium salt described later. Was added in a specified amount and pelletized (Table 1). The pellets were molded with an injection molding machine to give test pieces, and various physical properties were measured. The results are shown in Table 2.

Comparative Examples 1 to 6 Examples 1 to 6 using lauryl diethanolamine and polyether ester amide instead of the cationic polymer
Test pieces of the resin composition were prepared in the same manner as in Example 9 (Table 1), and various physical properties were measured. The results are shown in Table 2.

[0062]

[Table 1]

[Table 2] From Table 1, when the cationic polymer A, B, C or D was added to the acrylic resin, an acrylic resin composition having excellent antistatic properties, abrasion resistance, water resistance, and long-term transparency was obtained. .

When lauryl diethanolamine was added to the resin in place of the cationic polymers A, B, C and D, the surface resistivity of the resin was almost the same value, but the abrasion resistance and water resistance were greatly reduced.

Examples 10 to 17 Using polymethylmethacrylate as a matrix resin, the cationic polymers A to D obtained in the above synthesis example
Then, a test piece was prepared by pelletizing in the same manner as in Examples 1 to 9 except that the heat stabilizer and the weather resistance agent shown in Table 3 were used.
For this test piece, the surface specific resistance value and the degree of yellowing before and after the weather resistance test and the haze number after the weather resistance test were measured. The results are shown in Table 3.

[0065]

[Table 3] The heat stabilizer and weatherproofing agent used here are shown below.

Thermal stabilizer Sandstab P-EPQ (Sandoz
Company): Tetrakis (2,4-di-t-butylphenyl)
-4,4'-Biphenylene diphosphonate Adeka Stab 2112 (Asahi Denka): Tris-
(2,4-di-t-butylphenyl) phosphite Adekastab 260 (Asahi Denka Co., Ltd.): 4,4′-butylidene bis (3-methyl-6-t-butylphenyldi-)
Tridecyl phosphite) Weathering agent ADEKA STAB LA-31 (Asahi Denka Co., Ltd.): 2,2'-
Methylenebis [4 '-(1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] Tinuvin 327 (Diva Geigy): 2- (2'-
Hydroxy-3 ', 5'-di-t-butylphenyl)-
5-Chlorobenzotriazole Tinuvin 328 (Diva Geigy): 2- (2'-
Hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole Tinuvin P (Diva Geigy): 2- (2′-hydroxy-5′-methylphenyl) benzotriazole Tinuvin 234 (Diva Geigy): 2- ( 2'-
Hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenylbenzotriazole The tertiary amine salt or quaternary ammonium salt used here is shown below.

[Chemical 12] As shown in Table 3, when a heat stabilizer and a weather resistance agent are used in combination with the cationic polymer of the present invention, excellent heat stability and weather resistance in antistatic performance and transparency performance can be obtained.

[0067]

The conventional internal addition type antistatic agent bleeds out on the surface of the resin to form a moisture absorption layer, and the static electricity generated thereby is leaked, whereas the cation added in the resin composition of the present invention. The sexual copolymer forms a continuous layer in the matrix resin, and the leakage of static electricity occurs due to the movement of charges due to the movement of the counter ion of the cationic group in the copolymer molecule. Therefore, the cationic copolymer of the present invention has a higher rate of leakage of static electricity than the conventional internal addition type antistatic agent. Further, in the resin composition of the present invention, since the cationic copolymer does not exist in a high concentration near the surface of the resin which is easily influenced by external factors, friction of the resin surface, loss of antistatic effect due to washing with water, etc. occurs. Absent.

The compounded tertiary amine salt or quaternary ammonium salt is added to the cationic copolymer,
It exhibits the effect of a plasticizer and inhibits its crystallization, thus preventing the decrease in transparency over time.

Claims (3)

[Claims] Claims: 1. To 100 parts by weight of (A) acrylic resin, (B) 80 to 98 mol% of a polyolefin structural unit represented by the following general formula (1) and the following general formula (2). Acrylamide or acrylate structural unit 2-20
0.5 to 20 parts by weight of a linear cationic copolymer having a weight average molecular weight of 1,000 to 50,000, and (C) a tertiary amine represented by the following general formula (3). 0.1 to 5.0 parts by weight of at least one of a salt, a quaternary ammonium salt represented by the following general formula (4), and a quaternary ammonium salt represented by the following general formula (5): An acrylic resin composition characterized by being added. Embedded image (R ¹ represents a hydrogen atom or a methyl group.) (Y represents -O- or -NH-, R ² represents an ethylene group or a propylene group, R ³ and R ⁴ represent a methyl group, R ⁵ represents a lower linear alkyl group such as a methyl group and an ethyl group. or an arylalkyl group such as a benzyl group, further, X ^- halide _ion, CH 3 OSO ₃ ^- or _{^{CH 3 CH 2 OSO 3 - CH}} 3 SO 3 -, CH 3 C
H ₂ SO ₃ ^- represents a. R ² may be the same or different for each structural unit. ) (R ⁷ is a C ₁ -C ₁₈ alkyl group, R ⁸ and R ⁹ are C ₁
~ C ₄ alkyl group, Z represents hydrochloric acid, acetic acid, methanesulfonic acid, ethanesulfonic acid, phosphoric acid, hypophosphorous acid, nitric acid, perchloric acid, toluenesulfonic acid, benzenesulfonic acid. ) [Chemical 4] (R ¹⁰ is a C ₁ -C ₁₈ alkyl group, R ¹¹ , R ¹²
Is a C ₁ -C ₄ alkyl group, R ¹³ is a C ₁ -C ₄ alkyl group or a benzyl group, X ⁻ is Cl ⁻ , Br.
⁻ , Halide ions such as I ⁻ , CH ₃ SO ₃ ⁻ , C
^{_{H 3 CH 2 SO 3 -,}} CH 3 OSO 3 - or _CH 3 C
H ₂ OSO ₃ ^- represents a. ) (R ¹⁴ is a C _{1 to} C ₁₈ alkyl group, and R ¹⁵ is a C ₁ to C ₁₈ alkyl group.
C ₄ alkylene group, R ¹⁶ and R ¹⁷ are C _{1 to} C ₄ alkyl groups, R ¹⁸ is a C _{1 to} C ₄ alkyl group or a benzyl group, and X ⁻ is Cl ⁻ , Br ⁻ , I ^−. Halide ions such as CH ₃ SO ₃ ⁻ , CH ₃ CH ₂ SO ₃
^-, _{CH 3} OSO 3 ^- or _{CH 3 CH} 2 OSO 3 ^- represents a. ) 2. The cationic copolymer of (B) contains 0.3 parts of an acrylate structural unit represented by the following general formula (6).
The acrylic resin composition according to claim 1, wherein the acrylic resin composition contains 15 to 15 mol%. [Chemical 6] ^{(R 6} represents an alkyl group of _C 1 _{~C 4.)} 3. A heat stabilizer and / or a weathering agent is added in an amount of 0.01.
The acrylic resin composition according to any one of claims 1 to 2, which comprises -3.0 parts by weight.