KR830000513B1 - Antistatic resin composition - Google Patents

Abstract

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Description

Antistatic resin composition

) 디엔 및/또는 아크릴산에스테르로 이루어지는 전기저항율이 작은 고무줄기(幹) 중합체에 비닐단량체 또는 비닐리덴단량체를 그라프트 공중합해서 얻어지는 세정에 의해서 제전성이 실제상 전혀 저하하지 않는 그라프트 공중합체 단독 또는 이 그라프트 공중합체와 상용(相溶)할 수 있는 열가소성(熱可塑性) 수지와의 혼합물로 이루어지는 조성물에 관한 것이다.The present invention is conjugated with 1 to 50% by weight monomer having 4 to 500 alkylene oxide groups

Graft copolymer alone in which the antistatic property is not substantially reduced by cleaning obtained by graft copolymerization of a vinyl monomer or a vinylidene monomer on a rubber stem polymer having a small electrical resistivity composed of a diene and / or an acrylic acid ester. The composition which consists of a mixture of this graft copolymer and the compatible thermoplastic resin.

In general, plastics have a large electrical resistivity, are easily charged by frictional peeling, suck up dust, and damage the appearance, causing various problems in the fields of molded articles, sheets, films, and fibers.

As such, methods for imparting antistatic properties to plastics that are easily charged are being examined, and they can be classified as follows.

)법1. Internal interlocking of antistatic agent

)method

2. Surface coating method of antistatic agent (surfactant)

3. Surface coating method of silicon compound

4. Chemical Modification of Plastic Structure

Among them, the internal method of antistatic agent is not successful in permanent antistatic, and if the antistatic agent on the surface is removed by means of washing, friction, etc., the antistatic effect is lost. Exceptionally, internally interlocking antistatic agents for polyethylene, polypropylene, and polyvinyl chloride have been used commercially, but need time to recover the antistatic effect after cleaning. When there is too much bleeding on the surface, there are disadvantages such as adhesion of dust and the like that have not yet been put to practical use in transparent and hard products. There is also a difficulty in that a step of adding an antistatic agent is required.

In the method of applying the surfactant to the surface, the antistatic effect is greatly reduced by washing.

The method of coating the silicon compound on the surface is excellent in antistatic effect and semi-permanent antistatic effect can be expected, but there are disadvantages in terms of poor work efficiency and cost.

Chemical modification of the structure of the plastic is a method of introducing a hydrophilic group into the plastic by polymerization and other methods, but in general, in order to exhibit an antistatic effect, it is necessary to include a large amount of hydrophilic groups. Iii) adversely affect mechanical properties or other physical properties.

)디엔 및 또는 아크릴산에스테르 50∼99중량%로 이루어지는 공중합체가 적합한 것을 발견하고, 본원 발명을 완성한 것이다.The inventors of the present application have made a thorough investigation for the purpose of making a resin having a permanent antistatic property which does not lower the antistatic property by washing. As a result, a rubber monomer polymer having a small volume specific resistivity is obtained, and a vinyl monomer or a vinylidene monomer The graft copolymer alone obtained by graft polymerization or a mixture of such a graft copolymer with a resin compatible with the graft copolymer has a permanent antistatic effect and as a rubber polymer, 4 to 500 alkylene oxide groups 1 to 50% by weight monomer having conjugated (

The copolymer which consists of 50-99 weight% of dienes and or acrylic acid ester is found suitable, and this invention is completed.

Although the antistatic agent can be improved by adding the antistatic agent as well as the resin composition according to the present invention, it is not necessary to add the antistatic agent substantially. Since the polyalkyl oxide group is chemically bonded to the rubber stem polymer, the antistatic property does not decrease even under severe washing conditions.

In addition, since the matrix resin does not need to be hydrophilically modified, even if the rubber phase is hygroscopic, the overall physical properties are hardly affected. In addition, by appropriately limiting the particle size, the addition amount, the refractive index and the like of the rubber phase, it is also possible to obtain a transparent resin composition having a high impact strength.

For a method for producing a resin composition having antistatic properties in copolymerization of a monomer containing a polyalkylene oxide, see, for example, Japanese Patent Application Laid-Open No. 48 (Sec. 1973) -18521, Patent Publication No. 51 (Sec. 1976) -29526, Japanese Patent Application Laid-Open No. 50 (SEC 1975) -78842 and the like. However, these are all random copolymers of monomers containing polyalkylene oxides or mixtures of these random copolymers with other polymers, and when the amount of monomers containing polyalkylene oxides is small, the effect is small. There is a flaw that it takes.

In contrast, in the present invention, the monomer having a polyalkylene oxide group needs to exist as a structural unit of the rubber stem polymer. The antistatic effect of the composition of the present invention is that the rubber stem polymer is dispersed in a bridged state in a matrix resin formed of a thermoplastic resin and a branched polymer compatible with the branched polymer or the graft copolymer in the molded body. It is presumed that this is mainly caused by diffusion and attenuation through the rubber stem polymer phase. In the case of the present invention, the absorption rate of the branched polymer phase hardly changes even if the moisture absorption rate of the rubber stem polymer is increased, for example, so that a decrease in mechanical strength or heat resistance is hardly seen.

As described above, the monomer having an alkylene oxide group needs to be present in the rubber stem polymer. If it is not a rubber stem polymer and only exists as one component of a random copolymer, a polymer having excellent antistatic properties as in the present invention cannot be obtained at the same amount.

The rubber stem polymer of the present invention is 50 to 99% by weight of conjugated diene and / or acrylic acid ester, 4 to 500 alkylene oxide groups and monomers having ethylenically unsaturated bonds (hereinafter referred to as polyalkylene oxide monomers) 1 to 50 It is a rubbery copolymer which consists of 0 to 49% of a weight% and the 1 or more types of copolymerizable vinyl monomer or vinylidene monomer as needed.

The rubber stem polymer is mainly composed of conjugated diene and / or acrylic esters. As the conjugated diene, 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene and ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, acrylonyl and the like are used.

The conjugated diene and the acrylate ester account for 50 to 99% by weight of the rubber stem polymer in total. Less than 50% by weight can not sufficiently lower the glass transition temperature of the rubber stem polymer and the antistatic effect is small. If the content exceeds 99% by weight, the amount of polyalkylene oxide monomers inevitably becomes small, so that the desired antistatic effect cannot be obtained.

Polyalkylene oxide monomers in addition to ethylene unsaturated bonds

m+n

500을 충족시키는 정수)것이며, 특히 R₂, R₃의 적어도 한쪽이 H인 에틸렌옥사이드기를 4개이상으로 이루어지는 에틸렌옥사이드블록을 갖는 것이 바람직하게 사용된다.Wherein R ₂ and R ₃ are selected from hydrogen or an alkyl group having 1 to 4 carbon atoms or other groups; m, n are 4

m + n

And an ethylene oxide block composed of four or more ethylene oxide groups in which at least one of R ₂ and R ₃ is H is particularly preferably used.

Moreover, as a polyalkylene oxide monomer, 1 or more types of monomers represented by following structural formula (2) or (3) are preferable.

또는

이며, R₄, R₅, R₆,는 수소 또는 탄소수 1∼9의 알킬기, Me는 수소, Na, Li 또는 K를 나타내며, R₂, R₃및 m, n은 식(1)에 있어서와 동일한 의미를 나타낸다. 또는Wherein 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,

or

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

In formula, Z is hydrogen, a C1-C40 alkyl group, a C3-C6 cycloalkyl group, a phenyl group, or

이며 K, Li는 4

K +Li

500, R₁∼R₆, X, Me는 상기와 동일한 의미를 지닌다.

K and Li are 4

K + Li

500, R ₁ to R ₆ , X, and Me have the same meanings as above.

Among the monomers represented by the formulas (2) and (3) as described above, at least one of R ₂ and R ₃ is H, and those having an ethylene oxide block composed of four or more ethylene oxide groups are particularly preferably used.

Of course, in addition to the monomer represented by the formula (2) or (3), a similar monomer having an ethylene unsaturated bond and a polyalkylyl oxide group and which can lower the volumetric electrical resistivity of the rubber stem polymer obtained by copolymerization with conjugated diene and / or acrylic acid. It is also possible to use.

In the polyalkylene oxide monomer, 4 to 500 alkylene oxide groups are required, and more preferably 6 to 50, especially 9 to 50. When the number of alkylene oxides is less than 4, it is difficult to impart antistatic properties. Moreover, when it is more than 500, when superposing | polymerizing, it is difficult to melt | dissolve in water or a monomer, and also a polymerizability worsens.

If the monomer having a polyalkylene oxide group is less than 1% by weight in the rubber stem polymer, antistatic properties cannot be imparted. Moreover, when it exceeds 50 weight%, it will cause difficulty in the formation of a rubber | gum stem polymer or superposition | polymerization in graft copolymerization, and post-treatment of the obtained polymers, a salt stone, and the like.

As the vinyl monomer or vinylidene monomer copolymerizable with the conjugated diene or acrylate ester used as needed for the production of the rubber stem polymer, a known monomer can be used.

For example, methacrylic acid alkyl ester, acrylic acid, methacrylic acid, acrylamide, methacrylamide, vinyl acetate, unsaturated nitrile, aromatic vinyl monomer, alkyl vinyl ether, alkyl vinyl ketone, 2-hydroxyethyl (meth) acrylic acid ester , Diacetone acrylamide, vinyl chloride, vinylidene chloride, itaconic acid, itaconic acid alkyl ester, isobutene, 2-acid hose epoxy ethyl methacrylate, 3-chloro-2-acid hose poloxyl methacrylate And one or more monomers such as sodium styrene sulfonate can be used.

When the copolymerizable vinyl monomer or vinylidene monomer is selected, a polar monomer such as acrylonitrile or a monomer including an anionic substituent such as a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, and the like may further improve antistatic properties.

These copolymerizable vinyl monomers or vinylidene monomers are used in an amount of up to 49% by weight in the monomer mixture imparting the rubber stem polymer. If it exceeds 49% by weight, the glass transition temperature becomes high, and the rubbery property is lost.

In addition, the rubber stem polymer may contain, if necessary, an ethylenically unsaturated group such as a vinyl group 1,3-butadienyl group, an acryl group, a methacryl group, or an aryl group as a crosslinking agent in a range of up to 10% by weight. The polyfunctional monomer which has 2 or more types of 1 or more of can also be used. In particular, the polyfunctional monomer further having 4 to 500, preferably 9 to 50 polyalkylene glycolol groups is preferable because it functions as a crosslinking agent and also as an antistatic agent.

The graft copolymer excellent in the antistatic property of the present invention is obtained by graft polymerizing the vinyl monomer or the vinylidene monomer to the rubber stem polymer thus obtained.

As a vinyl monomer or vinylidene monomer used for graft polymerization, a well-known monomer can be used. For example, alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, acrylamide, methacrylamide, vinyl acetate, unsaturated nitrile, aromatic vinyl monomer, conjugated diene, alkyl vinyl ether, alkyl vinyl ketone, 2 -At least one kind of hydroxyethyl (meth) taacrylic acid ester, (alkoxy) polyethylene glycol (meth) acrylic acid ester, diacetone acrylamide, vinyl chloride, vinylidene chloride, itaconic acid, itaconic acid alkyl ester, isobutene Monomers can be used.

The ratio of the rubber stem polymer and the branched polymer in the graft polymer is in the range of 5 to 80% by weight, preferably 8 to 70% by weight, the latter is 20 to 95% by weight, preferably 30 to 92% by weight. Used. When the rubber stem polymer is less than 5% by weight, it is difficult to impart antistatic properties. When the rubber stem polymer is more than 80% by weight, the stiffness of the graft copolymer is lost and the moldability deteriorates.

In addition, although the composition in this and the composition in the rubber stem polymer mentioned above are calculated | required on the basis of a starting monomer, since the polymerization rate in each step is 90% or more, it is considered to exist as an equivalent composition also in the composition of this invention. Can be.

The graft copolymer excellent in antistatic properties of the present invention is conventional graft polymerization method such as emulsion polymerization method, suspension polymerization method and bulk polymerization method in the presence of a radical generator. The emulsion polymerization method is the most preferred method for controlling the particle size or dispersibility of the rubber stem polymer.

In the case of polymerizing the branched polymer, the monomers may be polymerized by adding all of them at once, or in the case of a large polymerization fever, or in the case of monomer combinations having different monomer reactivity ratios, the polymers may be polymerized by partial addition polymerization or continuous addition polymerization according to a known method. The target graft copolymer can be made.

The antistatic resin composition of the present invention may be a graft copolymer alone composed of a rubber stem polymer containing a polyalkylene oxide group thus obtained, but 0 to 90 wt% of the graft copolymer and other thermoplastic resins having good usability. An excellent antistatic resin composition is also obtained by mixing parts with 10 to 100 parts by weight of this rubber copolymer. However, the rubber stem polymer needs to be present in an amount of 5 to 80% by weight, preferably 8 to 60% by weight, based on the total amount of the graft copolymer and the thermoplastic resin. When the rubber stem polymer is 5% by weight or less, it is difficult to impart antistatic properties. When 80% by weight or more, heat resistance and moldability deteriorate.

Examples of the thermoplastic resin used with the graft copolymer include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, aromatic vinyl polymer, nitrile resin, polymethyl methacrylate and copolymers thereof, acrylonitrile-styrene Butadiene resin, acrylonitrile-styrene resin-polycarbonate, polyamide resin, polyester resin, fluorine resin, etc. are used, but of course, if the resin is compatible with the graft copolymer, other thermoplastic resins may be used. It goes without saying that it is used.

The composition of the present invention can be easily transparent by controlling the refraction of the rubber stem polymer and the branched polymer or the graft copolymer and the thermoplastic resin, but is not necessarily limited to the transparent article.

The resin composition excellent in the antistatic property of this invention can apply the conventional processing methods, such as the injection molding method, the extrusion molding method, the compression molding method, or the vacuum molding method. Therefore, plastic molded articles, sheets, films, pipes, fibers and the like can be produced.

Specific applications include, for example, electrical appliances (e.g. cassette type tape recorder cases, TV tube front covers, record player covers, electrical cleaner receivers, instrument covers, IC element storage containers, etc.), packaging products (e.g., doll care company). , Cans, bottles, packaging films, etc., acoustic materials (e.g. audio discs, video discs, tape recorder tapes, etc.), building materials (e.g. wall materials, flooring, panels, window materials, etc.) (E.g., lighting cover, display, etc.), and other plastics are suitable for the use that requires antistatic properties.

Next, an Example demonstrates this invention.

The part and% in an Example shall show a weight part and weight%, respectively.

The measurement conditions of the samples were measured one week after molding and one week after washing as described in Example 1, but the present invention has antistatic properties immediately after molding or immediately after washing.

Therefore, the antistatic property in the present invention is not expressed because the components for the antistatic agent after the moisture absorption after the molding or washing with water bleed on the surface with time.

In addition, although the sample in the Example is made with the shaping | molding method which heat-presses powder, even if shaping | molding by the method of pressing after kneading with a heating roller or shaping | molding using an extrusion molding machine, it shows the same value roughly.

Example 1

(A) In a 10ℓ stainless steel autoclave with a stirring spring.

The aqueous solution which consisted of was adjusted to pH with sodium hydroxide aqueous solution, was fully substituted with nitrogen, and stirred at 40 degreeC for 20 hours.

A rubber latex having an average particle diameter of 0.08 µ was obtained in a yield of 99%.

(B) 40 parts of the rubber latex (10 parts of the rubber stem polymer)

Was added and nitrogen-substituted, stirred at 50 ° C. for 20 hours, the graft copolymerized latex was taken out, precipitated with aluminum sulfate aqueous acid, adjusted to pH 7 with aqueous sodium pyrophosphate solution, and dried at 55 ° C. for 24 hours after dehydration washing. I was. A white powder was obtained with a yield of 97%. The powder was press-molded at 200 ° C. and 200 kg / cm ² for 5 minutes to make a test piece having a thickness of 0.6 to 0.8 mm. The test piece was stored at 23 ° C. and 50% RH for one week, and then a static one-meter ( The half-life of the large voltage was measured and antistatic property was determined using the Shishido Corporation. The results are shown in Table 1. In addition, the measurement conditions of the static one-meter.

Washing resistance: After washing the sample surface sufficiently with aqueous solution of detergent Maremon (KKK), wash it in distilled water sufficiently, and then store the sample under the condition of 50% RH, 23 ℃ for 1 week and adjust the humidity to the sample. The half-life of the large voltage was measured using a stmeter.

The results are shown in Table 1.

Example 2

A sample was made in exactly the same manner as in Example 1 except that the acrylonitrile and methyl acrylate of Example 1 were changed to 81 parts of methyl methacrylate and 9 parts of methyl acrylate, and the half-life of the large voltage was measured with a citicone nest meter. The results are shown in Table 1.

[Examples 3, 4, 5]

Using a rubber stem polymer and a branched polymer of the same composition as in Example 2, the graft copolymers having the ratios shown in Table 2 were respectively polymerized in the same manner as in Example 1. Table 1 shows the results obtained in the same manner as in Example 1.

TABLE 1

TABLE 2

[Examples 6-18]

Except changing the composition of the monomer of Example 1 as shown in Table 3, the sample was produced by the method similar to Example 1, and the result measured by the static onestometer is shown in Table 3.

[Comparative 1-7]

Except changing the composition of the monomer of Example 1 as shown in Table 4, the sample was produced by the same method as Example 1, and the result measured by the static one-meter is shown in Table 4.

TABLE 3

In Table 3 and the following table

But… 1,3-butadiene

MA… Methyl acrylate

MMA… Methyl methacrylate

St… Styrene

AN… Acrylonitrile

BA… Butyl acrylate

M ₁ . Methoxypolyethylene glycol methacrylate (the average number of ethylene oxide groups is 23)

M ₂ . Methoxy polyethylene glycol methacrylate (the average number of ethylene oxide groups is nine)

M ₃ . Methoxypolyethylene glycol methacrylate (the average number of ethylene oxide groups is 40)

M ₄ . Methoxypolyethylene glycol acrylate (the average number of ethylene oxide groups is 23)

M ₅ . Polyethylene glycol acrylamide (the average number of ethylene oxide groups is 23)

TDM… Teresa dodecyl Mertan

NDM… Nomaldodecylmertantan

DVB… Divinylbenzene

C ₁ . Polyethylene glycol dimethacrylate (the average number of ethylene oxide groups is 23)

TABLE 4

The symbols used for the monomerity are shown in Table 3.

Example 19

To 80 parts of rubber latex (20 parts as a rubber stem polymer) same as that used in Example 17, 80 parts of methyl methacrylate including 0.8 parts of normaldodecylmerethane was continuously added as a molecular weight regulator (about 5 hours from the start of addition to the end). While graft polymerization. The obtained graft copolymer was sampled by the method similar to Example 1, and the result measured by the static one-meter is shown next.

[Examples 20 to 22]

Except for the composition, 40 parts by weight of the graft copolymer shown in Table 5 obtained in the same manner as in Example 1 and 60 parts by weight of the thermoplastic plastic shown in Table 5 were kneaded with a thermal roller at 170 ° C. for 3 minutes, and then the same as in Example 1 A sample was made by the method, and the result measured by the static one-meter is shown in Table 5.

TABLE 5

^{* 1} Polymethyl methacrylate resin

^{* 2} Acrylonitrile-butadiene-styrene resin

^{* 3} Acrylonitrile-styrene resin

[Examples 23-25]

Except for the composition, each part by weight of the graft copolymer shown in Table 6 and the polyvinyl chloride compound (average degree of polymerization 700, dioctyl sulphate 2PHR, spare alcohol 0.8PHR, butyric acid butyrate) Glycool 0.2PHR Addition: Each weight part of the abbreviation, PVC, was kneaded for 3 minutes with a thermal furnace at 160 ° C., and a sample was prepared in the same manner as in Example 1, and the result measured by a static one-meter was shown in Table 6 Shown in

TABLE 6

^* Normal octyl mercaptan

The same shall apply to the following tables.

[Examples 26 to 31]

Except changing the composition of the monomer of Example 1 as shown in Table 7, the sample was produced by the same method as Example 1, and the result measured by the static one-meter is shown in Table 7.

TABLE 7

MAA… Methacrylic acid, IA... Itaconic acid, SS Styrene sulfonate

[Examples 32 to 35]

20 parts of the graft copolymer shown in Table 8 and 80 parts of the thermoplastic plastic shown in Table 8 were kneaded for 3 minutes with a thermal kneader at 220 to 270 ° C, and then pressed at 220 to 280 ° C and 200 kg / cm ² for 3 minutes. Table 8 shows the results of the measurement with a static one-meter.

[Comparative Examples 8-11]

Except not adding a graft copolymer, a sample was produced by the same method as Examples 32-35, and the result measured by the static one-meter is shown in Table 8.

TABLE 8

^{* 1} polyester copolymer, ^{* 2} polycarbonate, ^{* 3} nylon 12, ^{* 4} polyvinylidene fluoride

Example 36

Molding dies were attached to an extrusion molding machine with the same resin as that used in Example 26, and a T-die extrusion sheet having a thickness of about 100 mu was molded, wherein the resin temperature was 205 占 폚 at the T-die exit. The sheet was measured with a steric onestometer, and the half-life of the large voltage was 1 second with or without water treatment.

Example 37

An injection molding machine of the same resin as used in Example 31 was used to make an injection molding having a size of 100 × 150 × 30 mm. At this time, the resin temperature was 210 ° C and the mold temperature was 60 ° C. The center part of this injection molded product was cut out to a size of 40 × 50 × 3 mm, and measured with a static one nest meter as a test piece. The half-life of the large voltage was as follows.

1 second

1 second washing

[Comparative Examples 12, 13, 14]

The MMA copolymer (A) and the MMA copolymer (B) of the composition shown below are also latex mixed in a resin weight ratio shown in Table 9 and sufficiently stirred and mixed, followed by salting, heat treatment, water washing, It dried and obtained the white powder in 99% yield.

From this powder, the sample was produced by the method similar to Example 1, and the desiccability was evaluated. The results are shown in Table 9.

TABLE 9

Claims (1)

Conjugate

50 to 99% by weight of diene and / or acrylic acid ester, and 1 to 50% by weight of polyalkylene oxide monomer which is a monomer having 4 to 500 alkylene oxide groups and an ethylenically unsaturated bond, and one or more kinds of conjugated ones as necessary. Graft 20 to 95% by weight of one or more vinyl monomers or vinylidene monomers to 5 to 80% by weight of a rubber stem polymer comprising a copolymer of a vinyl monomer or a vinylidene monomer copolymerizable with a diene or an acrylate ester. 10-100 weight part of graft copolymers obtained by copolymerization, and 0-90 weight part of thermoplastic resins compatible with the graft copolymer, wherein the rubber stem polymer is a total amount of the graft copolymer and the thermoplastic resin. Antistatic resin composition, characterized in that 5 to 80% by weight of.