KR840001692B1 - Antistatic resin compositi - Google Patents

Abstract

An antistatic resin compsn. comprises 100parts base redin and 0.1-5 parts anionic surfactant. The base resin comprises (a) 7-100 parts graft copolymer obtd. by graft-polymerizing 5-95% ethylenically unsatd. monomer onto 5-95% rubber trunk polymer and (b) 0-93 parts theremoplastic resin. The rubber trunk polymer is a copolymer of 30-90% conjugated diene or alkyl acrylate to impart elasticity, 10-70% polyalkylene oxide monomer having 4-500 alkylene oxide gen. plus an ethylenic unsaturation, and 0-50% ethylenically unsatd. monomer. The rubber polymer comprises 5-80% of the total (a) + (b). All parts and % are by wt. The compsn. has a permanent antistatic property, good mechanical strength and heat resistance.

Description

Antistatic resin composition

The present invention grafts ethylenically unsaturated monomers onto a low-intermittent rubbery polymer composed of conjugated dienes and alkyl acrylates containing from 10 to 70% by weight of monomers having from 4 to 500 alkylene oxide groups. Antistatic properties obtained by mixing a graft copolymer obtained by polymerization alone or a mixture of a thermoplastic resin compatible with the graft copolymer and a small amount of anionic surfactant It relates to a resin composition.

In general, plastics have a high electrical resistivity and tend to be easily charged by friction or peeling. Because of the above reasons, plastics are easy to attract dust or dirt, so that various annoying things occur such as damaging the appearance of molded articles, sheets, films, and fibers made of plastics.

The method of imparting antistatic property to such a plastic which is easy to charge has been examined, and can be roughly classified as follows.

1. How to put antistatic agent in plastic

2. Method of applying antistatic agent (surfactant) to the surface of plastic

3. Method of applying silicone compound on the surface of plastic

4. How to chemically improve the molecular structure of plastic

In the above method, the method of incorporating the antistatic agent into the plastic cannot successfully impart a permanent antistatic effect, and the antistatic effect is lost if the antistatic agent present on the surface of the plastic is removed by washing or friction. .

Exceptionally, internal intercalating antistatic agents suitable for use in polyethylene, polypropylene and polyvinyl chloride have been put to practical use. However, this antistatic agent is accompanied by some problems as follows. That is, one requires a considerable time until the antistatic effect is restored after cleaning, and the other is that if the antistatic agent excessively penetrates the surface of the plastic, dirt or dust adheres thereon. Another problem is that an antistatic agent that is satisfactory for transparent and rigid plastics has not yet been put to practical use. Moreover, this method requires an intercalation process step of the antistatic agent.

When the method of applying the antistatic agent to the surface of the plastic is used, the antistatic effect is greatly reduced by cleaning.

The method of applying the silicon compound to the surface of the plastic provides an excellent and substantially permanent antistatic effect, but is disadvantageous in terms of process efficiency and economy.

The method of chemically improving the molecular structure of plastics by introducing a hydrophilic group by a polymerization method or the like in the plastic generally requires a considerable amount of hydrophilic introduction to obtain many antistatic effects. Therefore, the increased hygroscopicity deteriorates the mechanical and other properties of plastics.

As a result of earnestly examining the method for producing the resin which has a permanent antistatic property which is not reduced by washing | cleaning, the rubbery interpolymer with low cost resistance was obtained. In addition, the inventors have found that the resin composition obtained by mixing an anionic surfactant in a resin composed of a graft copolymer having a rubber interpolymer has a permanent antistatic effect. The present invention has been completed based on the new findings above.

That is, the antistatic resin composition according to the present invention comprises (i) 30 to 90% by weight of an elastic-imparting monomer selected from the loop composed of conjugated diene, alkyl acrylate and mixtures thereof, and (ii) ethylene 10 to 70% by weight of a polyalkylene monomer which is a monomer having 4 to 500 alkylene oxide groups together with an unsaturated compound, and (iii) a copolymer which is composed of 1 to 500% by weight of one or more ethylenically unsaturated monomers copolymerizable with the elasticity-providing monomer. 7 to 100 parts by weight of the graft copolymer (A) obtained by graft polymerization of 5 to 95% by weight of one or more ethylenically unsaturated monomers to 5 to 95% by weight of the rubber interpolymer and a thermoplastic resin compatible with the graft copolymer (B) It is a composition which consists of 100 weight part of resin (1) consisting of 0-93 weight part and anionic surfactant (2) 0.1-5 weight part.

The antistatic resin containing the conventional antistatic agent is considered to exhibit an antistatic effect mainly due to the antistatic agent which exists in the surface of a resin molding, and the antistatic effect is reduced by washing | cleaning or ignorance. However, the resin composition according to the present invention has a permanent antistatic effect. Although the action and the mechanism which produce such an antistatic effect are not clear, the use of a special graft polymer is mentioned as one of the main factors.

That is, in the graft copolymer or a mixture thereof with a thermoplastic resin, a graft component resin is used as a matrix component during the processing of a rubber interpolymer, which is a copolymer of a monomer having an alkylene oxide group and a conjugated diene or an alkyl acrylate. Or disperse alternately in the mixture of the graft resin and the thermoplastic resin, and the charge is thought to be reduced mainly due to diffusion through the inter-rubber polymer phase. The presence of the monomer component with the alkylene oxide group is believed to facilitate the diffusion or transfer of charge through the interrubber polymer. The user of such graft-containing resins is the subject of pending US Patent Application No. 72,846 (Masaki OHYA et al).

The addition of anionic surfactants is another major factor in which moldings made of the resin composition of the present invention impart extremely good permanent antistatic properties. In the antistatic resin composition of the present invention, like the conventional antistatic agent-added antistatic resin, the antistatic property is not actually lowered by washing or ignorance. This is because the added anionic surfactant is not present on the surface of the molded article and exhibits antistatic properties, as in the conventional antistatic agent-added antistatic resin, and is adsorbed to the rubber-containing polymer containing the alkylene oxide group described above. The polymer itself is thought to enhance the diffusion attenuation function of the charged charge. Particularly excellent anionic surfactants and permanent antistatic properties compared to nonionic or cationic surfactants are that anionic surfactants are particularly effectively adsorbed onto the rubber-based polymers to enhance the diffusion function of the rubber-to-rubber polymers. It is because it is strong.

In the resin composition according to the present invention, even though the moisture absorption rate of the rubber-to-rubber polymer phase is increased, the absorption rate of the geopolymer phase is hardly changed, so that the mechanical strength or heat resistance is hardly deteriorated.

As mentioned above, monomers having alkylene oxide groups need to be present in the intergum polymer. If it is not an intergum polymer and only exists as one component of a random copolymer, even if an antistatic agent is added, a polymer having excellent antistatic properties as in the present invention cannot be obtained.

The intergranular polymer of the present invention comprises 30 to 90% by weight, preferably 50 to 90% by weight, more preferably 60 to 90% by weight and 4 to 500, of an elastic-imparting monomer selected from conjugated dienes, alkyl acrylates and mixtures thereof. To 70% by weight, preferably 10 to 50% by weight, most preferably 10 to 40% by weight and, if necessary, at least one copolymerization of polyalkylene oxide monomer containing two alkylene oxide groups and having an ethylenically unsaturated bond It is a rubbery copolymer which consists of 0 to 50 weight%, preferably 0 to 45 weight% of possible ethylenically unsaturated monomers.

The interrubber polymer is mainly composed of conjugated diene and or alkyl acrylate as an elastic-imparting monomer.

As the conjugated diene, 1,3-butadiene, isoprene, chloroprene and 1,3-pentadiene can be used.

As the alkyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate and nonyl acrylate can be used.

The amount of conjugated diene and or alkyl acrylate should be at least 30% by weight, preferably at least 50% by weight, particularly preferably at least 60% by weight of the intergum polymer. If less than this amount, the glass transition temperature of the rubber-to-rubber polymer cannot be sufficiently lowered, so that the antistatic effect is small. On the contrary, when this amount is not 90% by weight or less, the amount of polyalkylene oxide monomers inevitably becomes small, so that the desired antistatic effect cannot be obtained.

In addition to the ethylenically unsaturated group, the polyalkylene oxide monomer has a polyalkylene oxide chain represented by the following structural formula:

m+n

500을 채우는 정수이고, 특히 R₂및 R₃의 적어도 한쪽이 수소인 에틸렌 옥사이드기를 4개 이상을 된 폴리에틸렌 옥사이드 블럭을 가진 것이 바람직하다.Wherein R ₂ and R ₃ are hydrogen or an alkyl group having 1 to 4 carbon atoms, and the same or different groups, m and n are 4

m + n

It is preferable to have a polyethylene oxide block having four or more ethylene oxide groups which are integers which fill 500 and in particular at least one of R ₂ and R ₃ is hydrogen.

Preferred polyalkylene monomers are at least one monomer represented by any one of the following structural formulas (2) to (4):

Wherein R ₁ is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is hydrogen, an alkyl group having 1 to 9 carbon atoms, a phenyl group, SO ₃ Me, SO ₂ Me, PO ₃ Me ₂ ,

Each R ₄ , R ₅ , and R ₆ is hydrogen or an alkyl group of 1 to 9 carbon atoms, Me is hydrogen, Na, Li or K, and R ₂ , R ₃ , m and n are represented by the formula (1) The same meaning as.

이며, p 및 q는 4

p+q

500을 채우는 정수이고, R₁∼R₃, X, Me, m 및 n은 위에서 정의된 바와 같다.In formula, Z is hydrogen, a C1-C40 alkyl group, a C3-C6 cycloalkyl group, a phenyl group, or

P and q are 4

p + q

Is an integer filling 500 and R ₁ to R ₃ , X, Me, m and n are as defined above.

Wherein R ₁ and R ₂ , m and n are as defined above and R ₁₁ is hydrogen or an alkyl group having 1 to 4 carbon atoms.

As mentioned above, it is especially preferable that at least one of R <_2> and R <_3> is hydrogen and has 4 or more ethylene oxide groups among the monomers represented by said structural formula (2)-(4).

Of course, in addition to the monomers represented by the structural formulas (2) to (4), it is also possible to use similar monomers having an ethylenically unsaturated bond and a polyalkylene oxide group and capable of lowering the volumetric electrical resistivity of the rubbery polymer.

The number of alkylene oxide groups in the polyalkylene oxide monomer is preferably 4 to 500, preferably 6 to 50, particularly preferably 9 to 50. When the number of alkylene oxide groups is less than 4, it is difficult to impart antistatic properties. On the other hand, when the number of alkylene oxide groups is more than 500, it is difficult to dissolve in water or other monomers during polymerization, and the polymerizability is also poor.

In addition, when the amount of the polyalkylene oxide monomer is not contained in the rubber-based polymer 10% by weight or more, sufficient antistatic properties cannot be imparted.

In addition, when it is not 70% by weight, preferably 50% by weight, and most preferably 40% by weight or less, the polymerization and obtained in the formation of the intergum polymer or the polymerization in the graft polymerization and the formation or the graft polymerization of the obtained polymer are obtained. Post-treatment of the polymer such as stones is difficult.

Known monomers can be used as the ethylenically unsaturated monomer copolymerizable with the elastic-imparting monomer used as necessary in the preparation of the rubber interpolymer.

For example, alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, acrylamide, methacrylamide, vinyl acetate, unsaturated nitrile, aromatic vinyl monomer, alkyl vinyl ether, alkyl vinyl ketone, 2-hydroxyethyl ( Meta) acrylate, diacetone acrylamide, vinyl chloride, vinylidene chloride, itaconic acid, alkyl itaconic acid, isobutene, 2-acid phosphoxyethyl methacrylate, 3-chloro-2-acid phosphoxyethyl methacrylate And one or more monomers such as sodium styrene sulfonate.

As the ethylenically unsaturated monomer copolymerizable with the elastic-imparting monomer, antistatic properties are further increased by selecting a monomer having a large polarity such as acrylonitrile or an anionic substituent such as sulfonic acid group, phosphoric acid group or carboxylic acid base. Is improved.

These copolymerizable ethylenically unsaturated monomers are used in the range of 50 weight%, preferably 45 weight% or less of the monomer mixture which provides a rubbery interpolymer. If this range is exceeded, the glass transition temperature rises, thereby losing the rubbery properties.

In addition, the rubber-containing polymer may be a crosslinking agent, as necessary, for example, at least one of an ethylenically unsaturated group such as a vinyl group, a 1,3-butadienyl group, an acryl group, a methacryl group, an aryl group, or the like. 0-10 weight% of polyfunctional monomers which have more than one can be contained. In particular, polyfunctional monomers containing 4 to 500, preferably 9 to 50 polyalkylene glycool groups are preferred because they act as crosslinking agents and also as antistatic impurity agents.

A well-known monomer can be used as an ethylene monomer used at the time of graft superposition | polymerization to such an rubber interpolymer. For example, alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, acrylamide, methacrylamide, vinyl acetate, unsaturated nitrile, aromatic vinyl, conjugated diene alkyl vinyl ether, alkyl vinyl ketone, 2-hydroxy Ethyl (meth) acrylate, (alkoxy) polyethylene glycol (meth) acrylate. One or more monomers may be used such as diacetone acrylamide, vinyl chloride, vinylidene chloride, itaconic acid, alkyl itaconic acid and isobutene.

The ratio of the inter-rubber polymer and the geopolymer in the graft copolymer is in the range of 5 to 95% by weight, preferably 8 to 80% by weight, the latter is 5 to 95% by weight, and preferably 20 to 92% by weight. Used as When the rubber interpolymer is less than 5% by weight, it is difficult to impart antistatic properties. When the rubber interpolymer is more than 95% by weight, the graft copolymer is lost when used alone and mixed with a compatible thermoplastic resin. Even when used, it is difficult to give compatibility.

The antistatic resin composition of the present invention is 7 to 100 parts by weight of the graft copolymer (A) as described above, preferably 10 to 100 parts by weight, particularly preferably 10 to 90 parts by weight of the graft copolymer (A). ), An antistatic agent selected from anionic surfactants is added to a resin obtained by mixing 0 to 93 parts by weight, preferably 0 to 90 parts by weight, and particularly preferably 10 to 90 parts by weight of a thermoplastic resin (B) compatible with It is a composition formed by.

The amount of the surfactant is 0.1 to 5 parts by weight, preferably 0.2 to 5 parts by weight, particularly preferably 0.3 to 3 parts by weight based on 100 parts by weight of the resin. When the amount is 0.1 parts by weight or less, the effect of improving the antistatic property is small. On the other hand, when the amount is 5 parts by weight or more, the surfactant is exuded excessively on the resin molded surface, which is not preferable. In the case of the mixture of the graft copolymer and the thermoplastic resin, the intergranular polymer needs to be present in an amount of 5 to 80% by weight, preferably 5 to 60% by weight, particularly preferably 10 to 60% by weight.

Examples of thermoplastic resins that can be used with the graft copolymers include, for example, polyethylene, polypropylene, polyvinyl chloride, lidene aromatic vinyl polymers, nitrile resins, polymethyl methacrylates and copolymers thereof, acrylonitrile-styrene- Butadiene resin, acrylonitrile-styrene resin, polycarbonate, polyamide resin, polyester resin, fluorine resin and the like are used, but other thermoplastic resins (compatibility with graft copolymer) may be used. Of course it can.

As the anionic surfactant used in the present invention, one or more known ones can be used. For example, the following salts are preferable. Namely, succinic acid dialkyl sulfonate, alkylbenzene sulfonate, fatty acid salt, alkyl sulfate, alkyl sulfonate, alkylnaphthalene sulfonate, phosphate salt, fatty acid ethyl carbonate, aliphatic alcohol sulfate, polyoxyethylene phosphate, and the like. This ether sulfate phosphate, polyoxyethylene phosphate, etc. are contained, and alkali metal salts are especially preferable.

The resin composition according to the present invention having excellent antistatic properties is formed by conventional processing methods such as injection molding, extrusion molding, compression molding or vacuum molding. Therefore, this resin composition can be manufactured from plastic molded articles, sheets, films, pipes, fibers and the like.

The resin composition according to the present invention is an electrical appliance (for example, a cassette tape recorder case, a front cover of a television tube, a record flavor cover, a magnetic disk cover, an electric dust collector cover, a key board of an instrument cover, an IC element storage container, IC device assembly mats and jigs, etc., packaging products (e.g., doll cases, cans, bottles, packaging films, perspective panels, photo film cases, photo film bases), acoustic materials (e.g. For example, audio discs, video discs, tape recorder tapes, etc., building materials (e.g., wall materials, flooring materials, panels, window materials and pipes, etc.), lighting equipment (e.g., lighting covers, displays ( suitable for use in displays, etc. and in general plastics requiring antistatic properties.

In order to further illustrate the nature and utility of the present invention, for the following examples, these examples should not be understood to limit the wall of the present invention.

Samples were measured one week after molding and one week after washing, as described in Example 1, after adjusting the moisture content. As a result of the measurement, the resin composition according to the present invention was found to have sufficient antistatic properties immediately after molding or immediately after washing. Therefore, the antistatic property achieved by the present invention is not because the antistatic agent is exuded to the surface of the resin composition with time, nor is it due to moisture absorption or washing after molding.

The sample used in the Example was manufactured by the molding method which heat-presses the resin powder. However, all of the moldings by mixing with a heating roll and then by pressing or molding using an extruder showed almost the same values.

Example 1

In a 10ℓ stainless steel autoclave with a stirring blade

(A) 12 parts of 1,3 butadiene

Methyl acrylate 4 parts

Methoxypolyethylene glycol methacrylate 4 parts

(The average number of ethylene oxide groups is approximately 23)

Diisopropylbenzene hydroperoxide0.04part

Formaldehyde sodium sulfoxylate 0.02part

Ferrous Sulfate, 7 hydrochloride 0.0008 parts

0.0012 parts of ethylenediaminetetraacetic acid disodium salt

0.01 part sodium pyrophosphate

0.2 parts of sodium dodecylbenzenesulfonate

Deionized Water 60 parts

The aqueous solution consisting of was adjusted to pH 7 with an aqueous sodium hydroxide solution, sufficiently substituted with nitrogen, and stirred at 40 ° C. for 20 hours. A rubber latex having an average particle size of 0.08 mu was obtained in a yield of 99%.

(B) 40 parts of the rubber latex (10 parts of the rubber interpolymer)

Methyl metal acrylate 80 parts

Normal octyl mercaptan 0.64

Potassium Persulfate 0.064parts

Sodium hydrogen sulfite0.16part

Sodium dodecylbenzenesulfonate0.8part

240 parts of deionized water

Was added, nitrogen-substituted, and the mixture was stirred at 50 ° C. for 20 hours to recover the graft copolymerized latex, precipitated with an aqueous solution of aluminum sulfate, adjusted to pH 7 with sodium pyrophosphate solution, dehydrated and washed for 24 hours at 55 ° C. Dried over. A white powder having a yield of 97% was obtained. 100 parts of this graft copolymer powder was impregnated with 0.5 part of sodium dioctyl sulfobacteate as a 10% aqueous solution, and sufficiently dried.

Next, the powder was mixed for 3 minutes in a roll having a surface temperature of 140 ° C., and then press-molded at 200 ° C. and 20 kg / cm 2 for 5 minutes to form a test piece having a thickness of 0.6 to 0.8 mm. After one week of storage at the standard state of RH, antistatic properties were determined by measuring the half-life of the large voltage using a static honest meter, and the results are shown in Table 1. . In addition, the measurement conditions of the static onist miter are as follows.

Applied () Voltage 8,000V Measuring Temperature 23 ℃

Sample rotation speed 1,300 rpm Application time 1 minute

Humidity 55 ~ 55% RH

Detergency resistance After washing the sample surface sufficiently with aqueous solution of Detergent Mama Lemon (Lion Oil Company), wash it in distilled water sufficiently and then keep it for 1 week under 50% RH, 23 ℃ The adjusted samples were measured for half-life of the large voltage using a static onist miter, and the results are shown in Table 1.

Comparative Example 1

The same graft copolymer powder as that used in Example 1 was prepared without the addition of sodium dioctylsulfate succinate, and the test specimens were made in the same manner as in Example 1, and the humidity was controlled. Was measured, and the results are shown in Table 1.

TABLE 1

Example 2

The polymerization was carried out in the same manner as in the copolymerization method of Example 1, but in the composition of the rubber-to-rubber polymer, 12 parts of 1,3-butadiene were made into 9 parts, methyl acrylate was added into butyl acrylate and methoxy polyethylene glycol methacrylate (ethylene 4 parts of an average of about 23 oxide groups were replaced with 4 parts of copper (an average of about 9 ethylene oxide groups), while 80 parts of methyl methacrylate was 68 parts of methyl methacrylate and butyl acrylate in the graft composition. With 8 parts and 4 parts of styrene, 0.64 parts of normal octyl mercaptan was replaced with 0.48 normal dodecyl mercaptan to prepare a graft copolymer.

100 parts of this copolymer was also impregnated with 0.5 part of sodium decylbenzene sulfonate as a 10% swimming solution, and after sufficiently drying, a test piece was made in the same manner as in Example 1 to measure the half-life of the large voltage, and the results are shown in Table 2. .

Comparative Example 2

The graft copolymer prepared in the same manner as in Example 2 was used to prepare a test specimen in the same manner as in Example 1 without adding sodium dodecylbenzene sulfonate, and the results were shown in Table 2. same.

TABLE 2

EXAMPLES 3 AND 4

Using the rubber-to-rubber polymer and the geopolymer of the same composition as in Example 2, the graft copolymers having the ratios of each described in Table 3 were prepared in the same manner as in Example 1, and the results are shown in Table 3. As shown.

0.5 parts of sodium dodecyl benzenesulfonate in 100 parts of each copolymer was added and dried in the form of a 10% aqueous solution, and then a large voltage was measured using the same method as in Example 1 (Table 3).

TABLE 3

[Examples 5-11]

A test piece was prepared in the same manner as in Example 1 except that 0.5 parts of the surfactants listed in Table 4 were added to the graft polymer used in Example 2, and the half-life of the large voltage was measured using a static ornithometer. As shown in Table 4.

TABLE 4

[Examples 12 to 22]

The composition of the monomer used in the graft polymer in Example 1 was modified as shown in Table 5, and 0.5 part of dioctylsulfo sodium succinate was added to 100 parts of each graft copolymer to prepare a sample in the same manner as in Example 1. The samples were evaluated for static elimination by static onion miters, and the results are shown in Table 5.

TABLE 5

The symbols used in Table 5 and the following tables indicate the following meanings.

But… … 1.3-butadiene

MA… … Methyl acrylate

MMA… … Methyl methacrylate

St… … Styrene

BA… … Butyl acrylate

M1... … Methoxy polyethylene glycol methacrylate (average number of ethylene oxide groups is 23)

M2... … Methoxypolyethylene glycosmethacrylate (the average number of ethylene oxide groups nine)

TDM… … Third decyl mercaptan

NOM… … Normal octyl mercaptan

DVB… … Divinylbenzene

CI… … Polyethylene glycol dimethacrylate (average number of ethylene oxide groups is 23)

EDMA… … Ethylene Glycol Dimethacrylate

OA… … Octyl acrylate

Comparative Examples 3 to 6

The commercial antistatic grade resin of Table 6 was measured in the same manner as in the above Example by using a static onist miter to measure the half-life of the large voltage is shown in Table 6.

TABLE 6

* 1 AS resin: Acrylonitrile-styrene copolymer

* 2 ABS resin: acrylonitrile-butadiene-styrene copolymer

[Comparative Examples 7-12]

Composition of the monomer of Example 2 A sample was made in the same manner as in Example 2, except that the composition was changed as shown in Table 7, and the half-life of the large voltage was measured using a static onist miter, and the results are shown in Table 7. .

In addition, as surfactant, 0.5 part of sodium dodecylbenzene sulfonate was added.

TABLE 7

[Examples 23 to 27]

Except that the monomer composition was changed as shown in Table 8, 0.5 parts of sodium dodecylbenzenesulfonate was added to 35 parts of the graft copolymer obtained in the same manner as in Example 1, and the mixture was sufficiently uniformly mixed with a Henchel mixer. After mixing the mixture with 65 parts of thermoplastic plastics as shown in Table 8 for 3 minutes in a roll at 160 ° C., a target was prepared in the same manner as in Example 1, and the half-life of the large voltage was obtained by using a static onit miter. The measurement results are shown in Table 8.

TABLE 8

* 1 polymethyl methacrylate resin

* 2 Acrylonitrile-butadiene-styrene resin

* 3 Acrylonitrile-Styrene Resin

* 4 polystyrene-based resin

* 5 polymethyl methacrylate resin

EXAMPLES 28,29 and 30

Graft copolymer and polyvinyl chloride compound used in Example 15 (100 parts of polyvinyl chloride of average degree of polymerization 700, 20 parts of dibutyltin mercaptide, 2.3 parts of dibutyltin maleate polymer, 0.7 parts of stearyl alcohol, 0.2 parts of butyric acid glycol montanate) were mixed at the ratio shown in Table 9, 0.5 parts of sodium dioctyl sulfoacetate was added to 100 parts of each resin, and the mixture was mixed with a thermal roller at 1.6 ° C. for 3 minutes, followed by mixing with Example 1 The large voltage was measured in the same manner, and the results are shown in Table 9.

TABLE 9

Comparative Examples 13 to 16

A sample was prepared in the same manner as in Example 23, except that 0.5 part of sodium dodecylbenzenesulfonate was replaced with 0.5 part of the surfactant shown in Table 10, and the half-life of the large voltage was measured using a static onist miter, and the results are shown in Table 10. As shown.

TABLE 10

[Comparative Examples 17-20]

A test piece was made in the same manner as in Example 2 except that 0.5 parts of the surfactants listed in Table 11 were added to the graft copolymer used in Example 2, and the half-life of the large voltage was measured with a static onit miter. Is as shown in Table 11.

TABLE 11

[Examples 31 and 32]

The sample was prepared in the same manner as in Example 1, except that the monomer composition of the graft copolymer was changed as shown in Table 12, and 0.5 part of sodium dioctylsulfoacetate was added to each 100 parts by weight of the obtained graft copolymer. Was prepared. The antistatic properties of each sample were evaluated by a static onist miter, and the results are shown in Table 12.

TABLE 12

Remarks:

M3... … Polyethylene Glycool Acrylate

(The average number of ethylene oxide groups is 23)

M4... … Gamethok Cipolyethyl ngelycohol acrylate

(15 average number of ethylene oxide groups)

[Examples 33 and 34]

Samples were prepared in the same manner as in Example, except that the monomer composition of the graft copolymer was changed as described in Table 13. The results of measuring the half-life of the high voltage using the static onist miter are shown in Table 13.

TABLE 13

Remarks:

M5... … Ethoxy Polyethylene Glycool Acrylate

(The average number of ethylene oxide groups is 15)

M6... … Ethoxy polyethylene glycol methacrylamide

(The average number of ethylene oxide groups is 23)

Claims (1)

100 parts by weight of the following resin (1) and 0.1 to 5 parts by weight of anionic surfactant (2), wherein the resin (1) is elastically selected from a group consisting of (i) conjugated diene, alkyl acrylate and mixtures thereof 30 to 90% by weight of imparting monomer, (ii) 10 to 70% by weight of polyalkylene oxide monomer having 4 to 500 alkylene oxide groupings and having an ethylenically unsaturated bond, and (iii) Graft 95, 5 to 95% by weight of one or more ethylenically unsaturated monomers to 5 to 5-95% by weight of a rubber interpolymer having 0 to 50% by weight of at least one ethylenically unsaturated monomer copolymerizable with the elastomeric monomer. 7 to 100 parts by weight of the graft copolymer (A) obtained by copolymerization, and 0 to 93 parts by weight of thermoplastic resin (B) having compatibility with the graft copolymer (A), and the inter-rubber polymer Graft Copolymer (A) and Thermoplastics Antistatic resin composition characterized by comprising 5 to 80% by weight of the total amount of the resin (B).