JP2002212431A - Antistatic-treated synthetic resin flooring material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antistatic-treated synthetic resin flooring material which does not use a dark-colored electroconductive agent such as carbon black because the agent undesirably limits possible colors for the flooring material, and emits no volatile gas. SOLUTION: The antistatic-treated synthetic resin flooring material comprises an inorganic filler having a coating layer which contains a polymer and/or a copolymer, wherein the polymer has a repeating unit represented by formula (1) (n is an integer of 10 or more, R1 is hydrogen or methyl, and R2 is an alkyl group or an alkyl-substituted phenyl group) and the copolymer has both a repeating unit represented by formula (I) and a repeating unit represented by formula (II) (R3 is hydrogen or methyl, Q is a bivalent linking group, and A is a sulfonic acid group, a phosphoric acid group, a carboxylic acid group or their respective neutralized groups).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-colored antistatic flooring.

[0002]

2. Description of the Related Art When an antistatic flooring material is used in a clean room, it is required that dust generation be as low as possible and that volatile gas be generated as little as possible. When an antistatic flooring is made of a polymer flooring such as a vinyl chloride resin, a method of kneading a surfactant into a resin is inexpensive and effective, and thus is widely used. However, there is a drawback that the electrical resistance value tends to depend on humidity, and sufficient performance cannot be exhibited under low humidity. In addition, many of the surfactants have a low molecular weight, and thus have a drawback that they evaporate for a long time. On the other hand, when a non-polar polymer material such as polyolefin is used, a conductive filler is used because it is difficult to obtain a sufficient antistatic effect by using a surfactant, The representative carbon of the conductive material has a drawback that it is a dark-colored carbon and a light-colored carbon is very expensive.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to use a dark-colored material such as carbon black as a conductivity-imparting agent, which limits the color of the flooring material. An object of the present invention is to provide an antistatic synthetic resin flooring that does not use any material and does not generate volatile gas.

[0004]

The first aspect of the present invention is to provide (a)
General formula (I)

Embedded image (Wherein, n represents an integer of 10 or more, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkyl group or an alkyl-substituted phenyl group), and / or ( B) the repeating unit represented by the general formula (I) and the general formula (II)

Embedded image (Wherein, R ₃ represents a hydrogen atom or a methyl group, and Q represents 2
A represents a sulfonic acid group, a phosphoric acid group, a carboxylic acid group or a group in which these acid groups have been neutralized. A coating layer containing a repeating unit represented by the following formula: The present invention relates to an antistatic synthetic resin flooring characterized by incorporating an inorganic filler having the same.

A second aspect of the present invention is that (a) a first coating layer comprising a cationic copolymer having a constitutional unit of a diallylamine salt and / or an alkyldiallylamine salt and a nonionic vinyl monomer, and (b) (b) I) General formula (I)

Embedded image (Wherein, n represents an integer of 10 or more, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkyl group or an alkyl-substituted phenyl group) polymers and / or having a repeating unit represented by ( B) the repeating unit represented by the general formula (I) and the general formula (II)

Embedded image (Wherein, R ₃ represents a hydrogen atom or a methyl group, and Q represents 2
Represents a valent linking group, and A represents a sulfonic acid group, a phosphoric acid group, a carboxylic acid group or a group in which these acid groups have been neutralized). And an inorganic filler having a layer.

The third aspect of the present invention is (a) the above-mentioned general formula (I)
And / or (b) a copolymer having both the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II), and The antistatic synthetic resin flooring according to claim 1 or 2, comprising at least one salt selected from the group consisting of alkaline earth metal salts.

A fourth aspect of the present invention relates to an antistatic synthetic resin flooring according to any one of claims 1 to 3, wherein the inorganic filler is calcium carbonate.

A fifth aspect of the present invention is that the synthetic resin is a vinyl chloride resin or an olefin resin.
The present invention relates to any of the antistatic synthetic resin flooring materials described above.

The above-mentioned vinyl chloride-based synthetic resin is attractive for its excellent workability, and the olefin-based synthetic resin is attracting attention as a non-halogen resin.

The inorganic filler having a coating layer used in the present invention may be a polymer having a repeating unit represented by the formula (I) and / or a copolymer having a repeating unit represented by the formulas (I) and (II). The surface of the inorganic filler is coated with an antistatic agent containing a polymer, and the particle size of the inorganic filler for forming the coating layer thereon is finely pulverized from several tens of microns to several microns. It is more preferable to use a finely pulverized one having a size of 1 micron or less. In order to pulverize to such a size, a sand mill, ball mill, attritor,
Dry pulverization or wet pulverization using a pulverizer such as a jet mill is usually used. As a method of coating the surface of the inorganic filler with an antistatic agent, for example, in the wet pulverization step of the inorganic filler, a liquid in which the polymer is dispersed in a slurry in advance is added to the inorganic filler, By drying the inorganic filler after grinding,
The surface can be coated with an antistatic agent. Alternatively, it is also preferable to add the polymer to a wet-pulverized or dispersed liquid of the inorganic filler and then dry it to perform surface coating. Alternatively, it is also preferable to apply a surface coating to the pulverized inorganic filler by a method such as spray coating. The ratio of the polymer as the antistatic agent to the inorganic filler is 0.5 to 10 parts by weight based on 100 parts by weight of the inorganic filler.
It is preferable to coat the surface of the inorganic filler in the range of parts by weight.

The surface-coated inorganic filler is used in an effective amount, preferably 30 to 100 parts by weight, based on 100 parts by weight of the resin composition.
It is preferable to use 100 parts by weight.

Preferred examples of the monomer giving a repeating unit represented by the general formula (I) include an alkyl group or an alkyl-substituted phenyl group at one end and a degree of polymerization of 10
The terminal portion of the above poly (oligo) ethylene glycol having an ethyleneoxy group is esterified with a methacryloyl group or an acryloyl group, and as an esterifying agent therefor, methacrylic acid or acrylic acid is particularly preferably used. . As the alkyl group for R ₂ , a linear or branched alkyl group having 1 to 25 carbon atoms is preferable because it shows good miscibility with plastics, rubber and the like. The preferable range of n is about 12 to 50, and preferable properties can be exhibited in this range.

The proportion of the repeating unit represented by the general formula (I) in the polymer having the repeating unit represented by the general formula (I) is preferably in the range of 10% by weight to 100% by weight, and more preferably 50% by weight. The range is more preferably from 100% by weight to 100% by weight.

In the general formula (II), the divalent linking group represented by Q is not particularly limited as long as it is a group linking an acid group A and a radical polymerizable double bond. Are included in this. Examples of preferred monomers of the general formula (II) are given below. Examples of the monomer having a sulfonic acid group include styrene sulfonic acid, vinyl sulfonic acid,
Allylsulfonic acid, methallylsulfonic acid, acrylamidomethylpropanesulfonic acid and salts thereof; monomers having a phosphoric acid group include acid phosphooxyethyl methacrylate, acid phosphooxypropyl methacrylate, and 3-chloro-2-acid phosphooxypropyl methacrylate , Acid phosphooxypolyethylene glycol monomethacrylate, acid phosphooxypolypropylene glycol monomethacrylate and salts thereof; as the monomer having a carboxylic acid group, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride and And salts thereof.

The "groups in which these acid groups are neutralized" in A of the general formula (II) are defined as groups in which these acid groups are neutralized with an alkali metal, an alkaline earth metal, ammonia, an amine or the like. It is. The neutralized form is more conductive than the free acid form.

In the polymer having the repeating unit represented by the general formula (II), the one in which the proportion of the repeating unit represented by the general formula (II) is 50% by weight or less is kneaded into a plastic, a rubber or the like. This is preferable because the dispersibility at that time is good.

In the copolymer having both the repeating units of the general formula (I) and the general formula (II), the repeating unit of the general formula (I) and the general formula (II) has 5 units in the total polymer.
Preferably, it accounts for 0% by weight or more.

In addition to the monomers according to the present invention, styrene derivatives such as styrene, 4-methylstyrene, 4-hydroxystyrene, 4-carboxystyrene, 4-aminostyrene, chloromethylstyrene and 4-methoxystyrene; Such as methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and dodecyl (meth) acrylate Alkyl (meth) acrylates; aryl (meth) acrylates or alkylaryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate; 2-dimethylaminoethyl (meth) acrylate, (meth) acrylate Acrylic acid 2-
Amino group-containing (meth) acrylates such as diethylaminoethyl; or monomers having a quaternary ammonium base such as p-vinylbenzyltrimethylammonium chloride; amino-group-containing monomers such as allylamine and diallylamine; or Monomers having a nitrogen-containing heterocyclic ring such as -vinylpyridine, 2-vinylpyridine, N-vinylimidazole, N-vinylcarbazole; or acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, dimethylacrylamide, diethylacrylamide, N- Acrylamide or methacrylamide derivatives such as isopropyl acrylamide, diacetone acrylamide, N-methylol acrylamide, N-methoxyethyl acrylamide; Vinyl esters such as acrylonitrile, methacrylonitrilo, vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl stearate, and vinyl benzoate; vinyl ethers such as methyl vinyl ether and butyl vinyl ether; Various monomers such as vinylpyrrolidone, acryloylmorpholine, tetrahydrofurfuryl methacrylate, vinyl chloride, vinylidene chloride, allyl alcohol, vinyltrimethoxysilane, and glycidyl methacrylate can be used as a copolymerization monomer.

When such other copolymerizable monomer is further introduced into the polymer, if the other monomer is introduced in a proportion exceeding 50% by weight in the polymer, the antistatic performance is impaired. In some cases, this is not preferable.

Further, a polymer having a repeating unit of the above general formula (I) and / or a general formula (I) and a general formula (I)
It is preferable to add at least one salt selected from the group consisting of an alkali metal salt and an alkaline earth metal salt, particularly a sodium salt, a potassium salt or a lithium salt, to the copolymer having the repeating unit of I). Particularly preferred are lithium salts, which can take the form of chlorides, sulfates, acetates, phosphates, carbonates, perchlorates, trifluoromethanesulfonates and the like.
These alkali metal salts are preferably added to the polymer in a form dissolved in water or other suitable solvent, and several oxyethylene units in the repeating unit represented by the general formula (I) in the polymer are added. And an ion complex, which is a factor for imparting good conductivity.

In the present invention, the polymer having the repeating unit of the above general formula (I) and / or the general formula (I)
In order to stably form a coating layer of a copolymer having a repeating unit of the general formula (II) on the inorganic filler, first, a diallylamine salt and / or an alkyldiallylamine salt are formed on the inorganic filler. It is preferable to form a first coating layer made of a cationic copolymer having an ionic vinyl monomer as a constituent unit.

As the alkali metal salt to be added to the polymer having the repeating unit of the general formula (I) and / or the copolymer having the repeating units of the general formulas (I) and (II), a lithium salt, Sodium salts, potassium salts and the like can be mentioned, and as alkaline earth metal salts, magnesium salts, calcium salts and the like can be mentioned, and lithium salts are particularly preferable. Preferred lithium salts include lithium chloride, lithium sulfate, lithium acetate, lithium phosphate, lithium carbonate, lithium perchlorate,
And lithium trifluoromethanesulfonate. Sodium salts and potassium salts can also be the corresponding salts of the above-mentioned halides and acids. These salts are preferably added to the polymer in a form dissolved in water or other suitable solvent, and several oxyethylene units in the repeating unit represented by the general formula (I) in the polymer are added. An ionic complex is formed, which is a factor for providing good conductivity.

A feature of the present invention is that a polymer having an ionic complex exhibits extremely good conductivity because such a repeating unit forming an ionic complex is present in a side chain in the polymer. There is also a feature. Normally, when an ionic complex is formed with a lithium salt or the like, plasticity, kneading property to rubber or the like is reduced, and uniform kneading may be difficult. The kneading is performed without hindrance.

A coating layer containing a polymer having a repeating unit of the general formula (I) and / or a copolymer having a repeating unit of the general formulas (I) and (II), and a suitable alkali metal salt The inorganic filler of the present invention having a good antistatic performance in both application and kneading applications, but the mixing ratio of the polymer and the alkali metal salt is 100 parts by weight of the polymer based on the alkali. The metal salt is preferably 5 to 100 parts by weight, particularly preferably 1 to 100 parts by weight.
0 to 50 parts by weight are used. The molecular weight of the polymer is preferably in the range of several thousand or more to several million or less, and in this range, the stability after forming a complex with the alkali metal salt is high, for example, plastics for kneading,
When kneaded into rubber or the like and used, it is particularly effective because it shows a very favorable property that the surface resistance does not change at all even if the water washing treatment is repeated.

The cationic copolymer used in the present invention
The structural unit diallylamine {(CH₂= CHC
H₂)₂NH｝ salt and / or alkyldiallylamine
｛(CH ₂= CHCH₂)₂NR｝ (R is an alkyl group)
The molar ratio of the salt of
10/90 to 99/1 (molar ratio:
The same applies hereinafter), preferably 50/50 to 9
9/1, more preferably 80/20 to 98/2.
The intrinsic viscosity of the cationic copolymer is usually 0.05 to
3.00, preferably 0.10 to 1.80, particularly preferred
Or 0.15 to 0.70.

The alkyl diallylamine amine salt used in the present invention includes those having an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. Examples of the salts of diallylamine and alkyldiallylamine include salts with inorganic or organic acids such as hydrochloric acid, sulfuric acid, nitric acid and acetic acid.

The nonionic vinyl monomer used in the present invention includes acrylamide, methacrylamide, N-
Vinylpyrrolidone, (meth) acrylic acid 2-hydroxyethyl ester, (meth) acrylic acid methyl ester,
Ethyl (meth) acrylate, butyl (meth) acrylate and the like can be mentioned. Of these, acrylamide and / or methacrylamide are preferred.

As an example of a method for synthesizing the polymer, the polymer can be obtained by mixing each monomer component as a structural unit and polymerizing in a solvent using a radical polymerization initiator. Examples of the radical polymerization initiator include hydrogen peroxide, ammonium persulfate, potassium persulfate, tertiary butyl hydroperoxide, cumene hydroperoxide,
2,2-azobis (2-amidinopropane) dihydrochloride, 2,2-azobis (2-amidinobutane) dihydrochloride, 2,2-azobis (N-phenylamidinopropane) dihydrochloride, 2,2-azobis (N, Any commonly used radical polymerization initiator such as (N-dimethylamidinopropane) dihydrochloride and azobisvaleronitrile can be used without any particular limitation. As the solvent, water or a mixture of water and a water-soluble organic solvent can be appropriately used. Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, n-propanol, formamide, dimethylformamide, dioxane, acetonitrile, dimersulfoxide, and the like. When the amount of each component used in the polymerization reaction is shown in a usual range, 100 parts by weight of a monomer component as a constituent component is dissolved in 20 to 900 parts by weight of a solvent, and 0.05 to 20 parts by weight of a radical polymerization initiator is dissolved. In addition, if necessary, a polymerization reaction may be carried out using 0.01 to 5 parts by weight of a reducing agent such as sodium acid sulfite and ferrous sulfate. The polymerization temperature is usually 30 to 110 ° C, and the polymerization time is usually 3
The polymerization reaction is preferably carried out while blowing nitrogen gas.

When the polymer thus obtained is dispersed in water with an inorganic filler such as talc, calcium carbonate, diatomaceous earth, kaolin, calcium sulfate, etc., it may be used alone or, if necessary, with another polymer such as sodium polycarboxylate. Can be used in combination with the anionic polymer type dispersant. In the case of this combination system, 20 parts by weight of the polymer of the present invention and 20 parts by weight of another polymer were used.
A mixing ratio of not more than part by weight is preferred. Further, the inorganic filler and the above (a) or (b) which function as an antistatic agent
Is 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight of the polymer with respect to 100 parts by weight of the inorganic filler.

As the means for forming the first coating layer and the second coating layer of the present invention, various known methods can be applied, and a wet pulverization method is particularly preferable. The reason is that the manufacturing process is simple,
In addition, the particle size can be easily adjusted and fine particles can be obtained. The wet pulverization method may be any of a batch method and a continuous method. As a device, a mill using a pulverizing medium such as a sand mill, an attritor, and a ball mill can be used. Since the polymer layer (a) or (b), which functions as an antistatic agent, is anionic, the presence of a cationic copolymer layer in the first layer suppresses the desorption and bleed-out of the antistatic agent. can do.

The olefin resin is not particularly limited, but one of the preferred olefin resins is as follows.

First, (A) the melting point observed by differential scanning calorimetry (DSC) is 80 to 110 ° C., the enthalpy of fusion is 60 to 120 J / g, and the density is 0.87 to 0. 925 g / cc ethylene / α-olefin copolymer having 4 to 12 carbon atoms 10 to 90% by weight
(B) the melting point observed by DSC in the range of 30 to 65 ° C., the melting enthalpy thereof is 40 to 80 J / g, the density is 0.87 to 0.97 g / cc, and the styrene content is 5 to 50. 9% by weight of ethylene-styrene copolymer
It is a polyolefin resin composition comprising 0 to 10% by weight.

The α-olefin copolymer of the component (A) has a melting point in the range of 80 to 110 ° C. observed by DSC,
Preferably in the range of 90-105 ° C, its enthalpy of fusion is 60-120 J / g, preferably 80-100 J / g.
g, density 0.87 to 0.925 g / cc, preferably 0.89 to 0.91 g / cc.

The α-olefin copolymer of the component (A) has a ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC in the range of 1.2 to 4. Calm down, Mn is 10,000-2,000,000
00 is preferred.

The α-olefin copolymer (A) is
(A) ethylene 60 to 95 mol% and (B) carbon number 4-1
It is preferable that the copolymer is a copolymer comprising 5 to 40 mol% of at least one monomer selected from the group consisting of α-olefins (2).

The α-olefin having 4 to 12 carbon atoms includes 1-butene, 1-pentene, 1-hexane, 1-hexane,
Heptene, 4-methyl-1-pentene, 1-octene and the like can be mentioned.

A particularly preferred α-olefin copolymer is an ethylene-octene copolymer, particularly having an octene content of 5 to 30% by weight and an MI value (melt index) of 0.5 to 5.0 g (g / g). 10 min), density 0.
86-0.93 (g / cc) ethylene-octene copolymer is preferred.

The ethylene-styrene copolymer as the component (B) has a melting point observed by DSC in the range of 30 to 65 ° C., preferably 35 to 60 ° C., and its enthalpy of fusion is 40 to 80 J / g, preferably Is 50-70 J / g, density 0.87-0.97 g / cc, styrene content is 5
５０50% by weight, preferably 5-30% by weight of the copolymer.

The ethylene-styrene copolymer of the component (B) has a weight average molecular weight (M
w) and the number average molecular weight (Mn) Mw / Mn is 1.2.
And Mn is in the range of 10,000 to 2,000.
Preferably it is 000.

By polymerizing both the component (A) and the component (B) using a metallocene catalyst, the Mw / Mn becomes 1.
A copolymer having a sharp molecular weight distribution of 2 to 4 can be obtained. When a metallocene catalyst is used, the obtained polymer does not contain residual monomers and low molecular weight components, so that it is suitable as a material for use in a production process of a product that does not like to be mixed with residual monomers and low molecular components from the viewpoint of environmental health.

The mixing ratio of the component (A) and the component (B) is 10 to 90% by weight, preferably 20 to 8% by weight of the component (A).
0% by weight, component (B) 90 to 10% by weight, preferably 8
0 to 20% by weight.

In the present invention, in addition to the above components (A) and (B), other olefin polymers or copolymers may be used in a proportion of not more than 40% by weight, preferably not more than 35% by weight of the total resin. Can be blended.

As for the component (B), the point that other additives cannot be stably blended with the component (A) alone can be solved by blending the component (B) together. For details of the polyolefin resin composition, refer to Japanese Patent Application No. 11-332363.

As the second preferred olefin resin which can be used in the present invention, the following polyolefin resin compositions can be mentioned.

In (A) heat flow rate differential scanning calorimetry (DSC),
A melting peak Tm observed at a temperature rising rate of 0 ° C./min is 90 to 110 ° C., and a copolymer of ethylene and an α-olefin having 4 to 8 carbon atoms is 5 to 75% by weight, preferably 20 to 20%. To 70% by weight, particularly preferably 30 to 70% by weight
[Based on the weight of (A) + (B) + (C)] (B) Propylene having a melting peak Tm of 120 to 140 ° C. observed at a heating rate of 10 ° C./min in DSC. 5 to 75% by weight, preferably 20 to 7%
0% by weight, particularly preferably 20 to 50% by weight [(A) +
(Based on the weight of (B) + (C)]] and (C) 5-20 petroleum resins having a softening point of 90-150 ° C.
% (Based on the weight of (A) + (B) + (C)).

The component (A) α- having 4 to 8 carbon atoms
The copolymer of olefin and ethylene is not particularly limited, but as the α-olefin component, 1-butyne,
1-pentene, 1-hexene, 1-heptene, 1-octene, 2-butene, 2-methyl-butene, 2-hexene, 2-heptene, 3-heptene, 2-octene, 3-
Octene, 4-octene and the like, and in particular, at least one monomer selected from the group consisting of hexene and octene, particularly at least one monomer selected from the group consisting of 1-heptene and 1-octene The copolymer has a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the copolymer measured by GPC of 1.2.
-4, preferably 1.5-2.5, and Mn of 10,000-2,000,000, preferably 27,2.
It is preferably a copolymer of α-olefin having a molecular weight of 000 to 50,000 and ethylene.

In DSC, which is the component (B), 1
As a propylene-based resin having a melting peak Tm observed at a heating rate of 0 ° C./min in the range of 120 ° C. to 140 ° C., the shape of the melting peak is not a steep peak but a peak as gentle as possible. Are preferred.

Examples of the propylene resin include copolymers such as ethylene-propylene random copolymer, ethylene-propylene block copolymer, ethylene-propylene graft copolymer, ethylene-propylene-butylene random copolymer, and propylene. Homopolymers, or a mixture of homopolymers of these monomers, a mixture of a homopolymer and a copolymer, and the like, but these polymers, the shape of the above-mentioned melting peak is gentle. Since it is preferable that the polymer has a mountain shape, it is necessary to use a homopolymer having a gentle molecular weight distribution. Among these, an ethylene-propylene random copolymer is particularly preferred.

The present invention relates to the above component (A),
By mixing the component (B) at a specific ratio of the present invention,
The calenderable temperature range of the entire composition can be in a very wide range from around Tm of the component (A) to around Tm of the component (B), and the component (C)
It is a component for compensating for the non-polarity of the component (A) and the component (B).

The petroleum resin as the component (C) is generally a polymer having a C _{4 to} C ₉ fraction, but may be a homopolymer having a C ₄ fraction or a homopolymer having a C ₉ fraction. in particular it is preferred that the C ₉ fraction homopolymer. The hydrogenation rate of the petroleum resin is 85 to 10 when used for the surface layer of the laminate.
If it is used in a layer other than 0%, it is preferably 65 to 85%, and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC is 1.
2 to 2.0, preferably 1.3 to 1.6,
Mn is 500 to 1,000, preferably 550 to 750
Is preferred.

When the component (A) increases beyond the range [other components, especially the component (B) decrease], the D of the compound increases.
The SC curve becomes a peak of only the component (A). When this compound exceeds the melting point, the melt tension (melting tensile strength) becomes extremely small, and it becomes impossible to take the calendar. On the other hand, when the component (B) increases (other components, particularly the component (A) decreases), the melting peak becomes remarkable in the characteristics of the component (B), and the heat lamination (heat The seal) properties deteriorate. When the component (C) increases beyond the range, the mechanical strength of the molded product decreases, and the dent resistance and tearability of the floor deteriorate. On the other hand, if the amount is less than the specified range, the polarity required for the composition cannot be imparted, and the affinity with the adhesive used for bonding the flooring material to the base material is deteriorated, and the construction cannot be performed. In addition, the affinity for the filler added as necessary to the composition becomes insufficient, and a large amount of the filler cannot be added. For the polyolefin resin composition, see Japanese Patent Application No. 10-238025.

Prior to blending the inorganic filler of the present invention with a polyolefin-based synthetic resin, a masterbatch in which the inorganic filler having the coating layer is dispersed in a maleic acid-modified polyolefin resin is formed. It is preferable to adopt a method of blending this with a polyolefin-based resin that is a main component of the floor material.

For the masterbatch, for example, 100 parts by weight of maleic acid-modified polyolefin resin,
100 to 900 parts by weight of the inorganic fine powder, preferably 20
Suitably, 0 to 600 parts by weight are added. Prior to kneading, mixing of the acid-modified polyolefin with the inorganic powder
Known mixers such as a ribbon blender, a tumble mixer, a Henschel mixer, and a V-type blender can be used, and dry blending may be performed. For kneading, a known kneader, for example, an open roll, a Banbury mixer, a kneader, a single-screw extruder, a twin-screw extruder, or a single-screw reciprocating screw kneader can be used.

The maleic acid-modified polyolefin resin is a resin obtained by modifying a polyolefin resin with an organic acid. Examples of the polyolefin resin include low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultrahigh-molecular-weight polyethylene, ethylene-vinyl acetate copolymer resin, ethylene-ethyl acrylate copolymer resin, and polypropylene. Among them, polyethylene, polypropylene and the like are preferable. The molecular weight of the polyolefin as the main chain in the modified polypropylene resin is usually preferably 1 × 10 ⁵ to 1 × 10 ⁶ , and particularly preferably 2 × 10 ⁵ to 1 × 10 ^6.
× 10 ⁵ to 8 × 10 ⁵ is preferred. As the acid that modifies these polyolefin resins, maleic acid, maleic anhydride, acrylic acid, and low molecular weight compounds containing a carboxylic acid group such as methacrylic acid, low molecular weight compounds containing a sulfonic group such as sulfonic acid, Examples thereof include low molecular weight compounds containing a phospho group such as sulfonic acid, low molecular weight compounds containing a vinyl group, low molecular weight compounds containing a hydroxyl group, and the like. Among these, low molecular weight compounds containing a carboxylic acid group are preferred, and maleic acid, maleic anhydride, acrylic acid and methacrylic acid are particularly desirable. Further, the molecular weight of the acid-modified polyolefin is desirably 1 × 10 ³ to 1 × 10 ⁶ .

The masterbatch is used for polyolefin resins such as polyethylene and polypropylene, particularly for unmodified polyolefin resins. In the polyolefin resin composition of the present invention, based on 100 parts by weight of the resin composition, 1 to 50% by weight of the inorganic filler having the coating layer,
Preferably, the content is 5 to 30% by weight. Therefore, this master batch is used for the polyolefin resin 1
It is preferable to add 1 to 100 parts by weight, particularly 5 to 60 parts by weight, per 100 parts by weight. When producing the resin composition of the present invention, a master batch, a polyolefin resin, and additives to be added as necessary, a commonly known mixing method, for example,
Using a kneader such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, or a kneader, the mixture is kneaded in a heated and molten state. The resin composition of the present invention can be formed by a generally used method without any particular limitation. For example, it is an arbitrary molding method such as extrusion molding, hollow molding, injection molding, sheet molding, and thermoforming. For the master batch, refer to Japanese Patent Application Laid-Open No. Hei 9-118754.

[0056]

The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited thereto.

Synthesis Examples 1 and 2 Using methacryloyl chloride in an equimolar amount to polyethylene glycol monostearate (degree of polymerization of ethylene oxide n = 25, Tokyo Kasei), using THF as a solvent,
A methacrylic acid ester monomer (M-1) was synthesized in the presence of pyridine at 0 ° C. according to a conventional method. In exactly the same way, a monomer (M-2) was synthesized from polyethylene glycol-4-nonylphenyl monoether (n = 15) and methacryloyl chloride. Using the monomers M-1 and M-2 obtained as described above, corresponding polymers P-1 and P-2 were synthesized as follows. Take 20 parts of sodium styrenesulfonate and 80 parts of monomer M-1 or M-2, and add 45 parts of distilled water
0 parts and 50 parts of ethanol, and heated and stirred at 60 ° C. in a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser, and V-50 [2 , 2'-azobis (2-amidinopropane) dihydrochloride, manufactured by Wako Pure Chemical Industries, Ltd.). Polymerization was performed at this temperature for 5 hours to obtain polymer solutions P-1 and P-2 having a weight average molecular weight of about 300,000.

Synthesis Examples 3 to 6 In the same manner as in Synthesis Examples 1 and 2, the compositions shown in Table 1 were polymerized to obtain respective polymer solutions.

[0059]

[Table 1]

MAA = methacrylic acid, SSS = sodium p-styrenesulfonate, QBm = p-vinylbenzyltrimethylammonium chloride, NK-230G = methoxypolyethylene glycol # 1
000 methacrylate (Shin-Nakamura Chemical Co., Ltd., N
K ester M-230G, n = 23), NF-N177E (alkylphenyl polyethylene glycol methacrylate, ethylene oxide polymerization degree n = 1)
6-17, manufactured by Daiichi Kogyo Seiyaku, New Frontea N-17
7E), PM-M = acid phosphooxyethyl methacrylate (Phosmer M manufactured by Unichemical Co., Ltd.), and PM-PE = acid phosphooxypolyethylene glycol methacrylate (Phosmer PE manufactured by Unichemical Co., Ltd.).

Synthesis Example 7 500 parts of diallylamine hydrochloride (60%) and acrylamide (40%) were placed in a reactor (volume: 1 L) equipped with a reflux condenser, a thermometer, a dropping funnel, a stirrer, and a gas inlet tube.
And 15 parts of water, and the temperature in the system was raised to 80 ° C. while flowing nitrogen gas. Using a dropping funnel, 30 parts of a polymerization initiator, ammonium persulfate (25%), was added dropwise with stirring over 4 hours. After completion of the dropwise addition, the reaction was continued for 1 hour to obtain a viscous pale yellow liquid. Take 50g of this, 500
Pouring into ml of acetone resulted in a white precipitate. The precipitate was separated by filtration, washed well twice with 100 ml of acetone, and dried under vacuum to obtain 22.5 g of a white solid. Yield 8
2.0%. In a 1N aqueous solution of NaCl, the intrinsic viscosity of the obtained polymer at 25 ° C. was 0.30 (dl / g),
The weight average molecular weight determined by GPC was 500000.

Synthesis Example 8 200 parts of diallylamine hydrochloride (60%) and acrylamide (40%) were placed in a reactor (1 L capacity) equipped with a reflux condenser, a thermometer, a dropping funnel, a stirrer, and a gas inlet tube.
0 parts and 220 parts of water were added, and the temperature in the system was raised to 60 ° C. while flowing nitrogen gas. Polymerization initiator under stirring,
Forty parts of 2,2-azobis (2-amidinopropane) dihydrochloride (10%) were added in four portions every two hours. The first initiator was added, and after 1.5 hours, 280 parts of acrylamide (18%) was added dropwise from the dropping funnel over 4 hours. After completion of the initiator addition, the reaction was continued for 2 hours to obtain a viscous pale yellow liquid. Take 50g of this, 500m
Pouring into 1 liter of acetone resulted in a white precipitate. The precipitate was separated by filtration, washed well twice with 100 ml of acetone, and dried under vacuum to obtain 11.5 g of a white solid. The yield is 96.
2%. The intrinsic viscosity of the obtained polymer in a 1N aqueous solution of NaCl at 25 ° C. is 1.10 (dl / g),
The weight average molecular weight determined from C was 260,000.

Production Example 1 <Preparation of Inorganic Filler Having Coating Layer> Limestone dry-ground to an average particle size of 5 μm and water were mixed at a weight ratio of 4: 6, and the mixture was mixed with the polymer (polymer). Name P-1 to P
-6) was added in an amount of 3 parts by weight based on 100 parts by weight of limestone, and a wet milled slurry was prepared using a stirring mill. This was dried with a medium fluidized drier to obtain calcium carbonate having a coating layer.

Production Example 2 <Preparation of inorganic filler having first coating layer and second coating layer> Limestone dry-ground to an average particle size of 5 μm and water were mixed in a weight ratio of 4: 6, and this mixture was mixed. The synthesis example 7
Alternatively, 0.06 parts by weight of the cationic polymer of No. 8 was added to 100 parts by weight of limestone, and the mixture was wet-milled using a stirring mill to form a first coating layer. Then, Production Example 1
In the same manner as in the above, polymers having polymer names P-1 to P-6 were added, stirred, and dried by a medium fluidized drier to form a second coating layer.

Examples 1 to 6 Floor materials were manufactured according to the recipe shown in Table 2 below according to a conventional method.

[Table 2]

In the table, gas generation was measured by the static headspace method. Surface resistance value (Ω) and volume resistance value (Ω) can be measured using a fresh sample at 20 ° C and 30% humidity in a greenhouse atmosphere for 24 hours, and then using a TOA Dempa Kogyo Co., Ltd. mega-ohm meter SM-5E. It was measured.

Examples 7 to 12 Floor materials were manufactured according to the recipe shown in Table 3 below according to a conventional method.

[Table 3]

Example 13 A floor material was produced using the inorganic filler having the first coating layer and the second coating layer obtained in Production Example 2 in the same formulation as in Examples 1 to 6. There is no bleed out of the antistatic agent,
Excellent antistatic performance as shown in Examples 1 to 6 for a long time.

Comparative Example A flooring material was manufactured according to a conventional method according to the following formulation. Vinyl chloride resin 100 parts by weight Plasticizer DOP 50 parts by weight Calcium carbonate 100 parts by weight Antistatic agent 3 parts by weight

[0070]

According to the present invention, it is possible to provide an antistatic synthetic resin flooring material which does not generate volatile gas and can be finished in a bright color.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) E04F 15/18 ECA E04F 15/18 ECAV // C08F 290/06 C08F 290/06 299/02 299/02 ( 72) Inventor Takashi Ogawara 1-25-1 Miyagi, Adachi-ku, Tokyo Inside Tajima Corporation (72) Inventor Toshio Fukushima 1-25-1 Miyagi, Adachi-ku, Tokyo Inside Tajima Corporation (72) Inventor Noriyuki Sugimoto 2-8-6 Nishi-Shimbashi, Minato-ku, Tokyo Sumitomo Real Estate Hibiya Building 12th Floor Inside Fimatec Corporation (72) Inventor Ryoji Ito 2-8-6 Nishi-Shimbashi, Minato-ku, Tokyo Sumitomo Real Estate Hibiya 12th floor of Building F-Tech Co., Ltd. F-term (reference) 4J002 AA001 BB001 BB051 BB101 BB121 BB151 BD031 BN031 BP021 DE236 DG056 DJ036 DJ046 FA086 FB266 FD016 FD106 GL00 4J027 AC03 AC06 AJ02 BA04 BA05 BA06 BA07 BA09 BA10 BA11 BA12 BA13 BA14 BA15 BA16 CD01

Claims (5)

[Claims] (1) General formula (I) (Wherein, n represents an integer of 10 or more, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkyl group or an alkyl-substituted phenyl group), and / or ( B) the repeating unit represented by the general formula (I) and the general formula (II) (Wherein, R ₃ represents a hydrogen atom or a methyl group, and Q represents 2
A represents a sulfonic acid group, a phosphoric acid group, a carboxylic acid group or a group in which these acid groups have been neutralized. A coating layer containing a repeating unit represented by the following formula: An antistatic synthetic resin flooring characterized by incorporating an inorganic filler having the same. 2. A first coating layer comprising (a) a cationic copolymer comprising a diallylamine salt and / or an alkyldiallylamine salt and a nonionic vinyl monomer as constituent units, and (b) (a) a general coating formula I) (Wherein, n represents an integer of 10 or more, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkyl group or an alkyl-substituted phenyl group), and / or ( B) the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) (Wherein, R ₃ represents a hydrogen atom or a methyl group, and Q represents 2
Represents a valent linking group, and A represents a sulfonic acid group, a phosphoric acid group, a carboxylic acid group or a group in which these acid groups have been neutralized). A floor material made of an antistatic synthetic resin, comprising an inorganic filler having a layer. 3. A polymer having a repeating unit represented by the general formula (I) and / or (b) a polymer represented by the general formula (II) and a repeating unit represented by the general formula (I) 3. The antistatic synthetic resin according to claim 1, wherein at least one salt selected from the group consisting of an alkali metal salt and an alkaline earth metal salt is blended with a copolymer having a repeating unit. Flooring. 4. The flooring made of an antistatic synthetic resin according to claim 1, wherein the inorganic filler is calcium carbonate. 5. The flooring material according to claim 1, wherein the synthetic resin is a vinyl chloride resin or an olefin resin.