JPS62185738A - Conductive resin composition and conductive floor sheet - Google Patents

Abstract

PURPOSE:To obtain a composition which can give a molding which can be freely colored and has a sufficient antistatic property, by adding a specified plasticizer and an electrolyte to a copolymer of vinyl chloride with a monomer having a hydrophilic group and a reactive double bond. CONSTITUTION:A resin composition prepared by adding a plasticizer of the formula and an electrolyte to a copolymer of vinyl chloride with a monomer having a hydrophilic group and a reactive double bond in the molecule. Said resin composition can give an electroconductive floor sheet by laminating a first floor sheet comprising this composition with a second sheet made of a resin composition formed by adding at least one member selected from among carbon black, carbon fiber, metal powder and metal fiber to a rubber or a plastic and having an electric conductivity larger than that of the first sheet. This floor sheet can show a still more improved antistatic property and is useful for improving the appearance of a floor.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of application for industrial production] The present invention provides a conductive resin composition which can be freely colored and which can yield a molded article having sufficient antistatic performance.
The present invention also relates to a conductive floor sheet using this resin composition.

[Prior Art] As a measure to prevent static electricity from forming on rubber or plastic molded products, it is necessary to lower the electrical resistance of the molded product and quickly ground the static electricity generated by friction to dissipate it. It is.

The following methods are known so far to lower the electrical resistance of rubber or plastic.

(+) A method of adding highly conductive metal powder such as silver, copper, stainless steel, nickel, etc. or m1it to rubber or plastic.

(2) A method of adding carbon black or carbon fiber to rubber or plastic.

(3) Do you add surfactants called antistatic agents or similar substances to rubber or plastic? Man.

[Problems to be Solved by the Invention] Although the method (+) is very effective in preventing electrostatic charging, it cannot be colored freely and is limited to metallic colors.

Moreover, it is very expensive and lacks economic efficiency.

Furthermore, it is desirable that the 7fi resistance of the molded product be within a certain range to prevent the risk of electric shock from low-voltage electricity, but such products can be manufactured stably using metal powder or metal powder. It is very difficult to do so.

In method (2), carbon black is often used as an inexpensive conductivity imparting agent, but it has the drawback that the hue is limited to black.

Further, even with this method, it is difficult to industrially and stably produce molded products that are free from the risk of electric shock due to low voltage electricity.

Method (3) has the advantage of being able to be colored freely, but it has poor compatibility with rubber and plastics, and it incorporates a surfactant that easily absorbs moisture. It is obtained by letting air escape from the surface, and relies on surface resistance, which is easily affected by environmental conditions, and lacks stability in antistatic performance.Especially in low humidity conditions. In the environment, the antistatic effect will be considerably reduced.Also, the duration of the antistatic performance will be short.

On the other hand, in recent years, in semiconductor parts such as IC, LS, 1, etc. and electronic equipment factories, etc., in order to prevent production failures due to the adsorption of micron and submicron dust due to the generation of static electricity, and in OA rooms etc. The use of conductive floors is being considered to prevent computer malfunctions and circuit damage caused by static electricity.

In this case, from the viewpoint of aesthetics, it is preferable to use a sheet obtained by the method (3), which can be colored freely, but it is difficult to use it alone due to concerns about its antistatic performance. As a countermeasure for this, turn the sheet obtained by method (3) on the front side,
It is convenient to use a sheet in which the highly conductive sheet obtained by method (1) or (2) is stacked on the π side.

In such a laminated sheet, static electricity charged on the front side is transferred to the back side? IiP! However, in this case, the volume resistance is more important than the surface resistance, and in the case of the sheet made by method (3) in which a surfactant or a similar antistatic agent is added, the volume resistance is more important than the surface resistance. The resistance cannot be lowered, and a sufficient antistatic effect cannot be obtained.

The present invention has been made based on the above, and provides a conductive resin composition that can be colored in any color and realizes a molded product having excellent antistatic performance, and a conductive floor sheet that has excellent antistatic performance. The purpose is to provide the following.

[Means for Solving the Problems] The conductive resin composition of the present invention is a copolymer of vinyl chloride and a monomer having a hydrophilic group and a reactive double bond in the molecule with the general formula %) ( i (wherein, X is an aliphatic or alicyclic dibasic acid residue having 2 to 8 carbon atoms;
~15 straight chain or branched alkyl group, A is 2~15 carbon atoms
4 represents an alkylene group, and rrl and n are integers of 1 to 7, which may be the same or different. However, A+R
The total number of carbon atoms is 5 to 17. ) It is characterized by containing a plasticizer and an electrolyte represented by:

In addition, the conductive floor sheet of the present invention is a copolymer of vinyl chloride and a monomer having a hydrophilic group and a reactive double bond in the molecule. 2 to 8 aliphatic or alicyclic dibasic acid residues, R is the same or different, and has 3 to 3 carbon atoms;
15 linear or branched alkyl groups, A has 2 to 4 carbon atoms
represents an alkylene group, and m and n are integers of 1 to 7, which may be the same or different. However, the total number of carbon atoms in HeR is 5 to 17. ) A first sheet made of a resin composition containing a plasticizer and an electrolyte, and a resin made of rubber or plastic containing at least one of carbon black, carbon fiber, metal powder, or metal fiber. It is characterized in that it is formed by laminating a second sheet made of a composition and having a higher conductivity than the first sheet.

In the present invention, monomers having a hydrophilic group and a reactive double bond in the molecule to be copolymerized with vinyl chloride include (
3-sulfopropyl)-acrylic acid ester potassium salt, (3-sulfopropyl)-methacrylic acid ester potassium salt, bis(3-sulfopropyl)-itaconic acid ester potassium salt, N-(3-sulfopropyl)-N −
Methacroyloxyethyl-N,N-dimethyl-ammonium-betaine, N-(3-sulfopropyl)-N-
methacroylamidopropyl-N,N-dimethyl-ammonium-betaine, 1-(3-sulfobyl)-
Examples include 2-vinyl-viridinium 11- and human tine: Hydrophilic groups and reactivity in the molecule with vinyl chloride 21! The content of the latter monomer in a copolymer with a monomer having a bond (hereinafter referred to as "vinyl chloride copolymer") is 0.5 to
The content is preferably in the range of 20% by weight; if it is less than 0.5% by weight, it tends to be difficult to obtain good electrical resistance, and if it exceeds 20% by weight, the compatibility with plasticizers becomes poor and mechanical There is a tendency for the strength of the target to decrease. The method for obtaining such a vinyl chloride copolymer is not particularly limited;
Either suspension polymerization method or emulsion polymerization method may be used.

In the present invention, the plasticizer represented by the general formula % is a linear or branched aliphatic alcohol having 3 to lδ carbon atoms and an alkylenoxide having 2 to 4 carbon atoms.
Alcohol obtained by addition of ~7 moles and alkylene oxide have a total carbon number of 5 to 17.
It can be easily obtained by a general ester production method by reacting a l-1-syl compound with an aliphatic or alicyclic dibasic acid.

The number of carbon atoms in alcohol, the number of moles added to alkylene oxide, and the total number of carbon atoms in alcohol and fullkylene oxide are:
If the amount is outside the range specified in the present invention, the effect as a plasticizer or electrical resistance will be insufficient.

Examples of plasticizers represented by the above general formula include propatool with 1 to 7 moles of ethylene oxide, 1 to 4 moles of propylene oxide, or 1 to 3 moles of butylene oxide, and butanol with 1 to 6 moles of ethylene oxide or 1 to 4 moles of propylene oxide. or 1 to 3 moles of butylene oxide, 1 to 5 moles of ethylene oxide in hexanol, 1 to 3 moles of propylene oxide, or 1 to 2 moles of butylene oxide,
Heptatool contains 1 to 5 moles of ethylene oxide or 1 to 3 moles of propylene oxide or 1 to 2 moles of butylene oxide, and octatool contains 1 to 4 moles of ethylene oxide or 1 to 3 moles of propylene oxide or 1 to 1 mole of butylene oxide.
2 moles of nonanol, 1 to 4 moles of ethylene dioxide or 1 to 2 moles of brobylene oxide or 1 to 2 moles of butylene oxide, 1 to 3 moles of ethylene oxide or decanol.

1 to 2 moles of propylene oxide or 1 mole of butylene oxide, 1 to 2 moles of ethylene oxide or 1 mole of propylene oxide or 1 mole of butylene oxide in dodecanol;
Examples include compounds in which 1 mole of ethylene oxide or 1 mole of propylene oxide is added to tetradecanol, and compounds in which 1 mole of ethylene oxide is added to pentadecanol.

The amount of the plasticizer represented by the above general formula added to the vinyl chloride copolymer is not particularly limited as long as the desired volume resistivity is obtained, but it is 5 to 100 parts by weight per 100 parts by weight of the vinyl chloride copolymer. A range of is preferred. If it is less than 5 parts by weight, it will be difficult to obtain the desired volume resistivity, and if it exceeds 100 parts by weight, it will lead to deterioration of compatibility and mechanical properties, making it unsuitable for use in the field of thermoplastic resins. There is sex.

Examples of the electrolyte include lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, zinc chloride, barium chloride, sodium sulfate, potassium sulfate, lithium citrate, and lithium bromide. However, unstable oxidizing or reducing electrolytes such as nitrates or hexavalent chromates are unsuitable for the present invention.

The appropriate amount of electrolyte to be added is 0.01 to 5 parts by weight per 100 parts by weight of the vinyl chloride copolymer; less than 0.01 parts by weight has little effect on lowering the electrical resistance, and 5 mm parts reduces the electrical resistance. The decrease in is almost saturated.

In the present invention, in addition to the above components, D
Plasticizers such as OP, other compounding agents such as stabilizers, antioxidants, crosslinking agents, vulcanizing agents, vulcanization aids, lubricants, processing aids,
Flame retardants, fillers, colorants, ultraviolet absorbers, etc. can be used as appropriate, and the composition can be made without any practical problems.

The conductive composition thus obtained can be formed into a sheet and used as an antistatic sheet for floors or desks. Further, it can be used as curtain fabric or wallpaper, and furthermore, it can be dissolved or dispersed in a solvent and used as an antistatic paint.

The sheet made of the conductive composition of the present invention is laminated with a conventionally known conductive sheet, that is, a sheet made of rubber or plastic containing carbon black, carbon fiber, metal powder, metal a male, etc. to impart conductivity. By doing so, the -F' antistatic performance can be improved, and it is also useful for improving the aesthetic appearance.

[Example] A compound kneaded using two electrically heated rolls was molded using a high-pressure steam press according to the compounding ratio shown in Table 1 to form a sheet with a thickness of 1 mm.

The results of measuring the volume resistivity of this sheet are
Shown in the bottom column of the table.

The volume resistivity is based on the Japan Rubber Association standard 5RIS230.
4 and its explanation.

From Table 1, Examples 1 to 4 within the scope of the present invention all have sufficient electrical resistance to prevent electrostatic charging.

Comparative Examples 1 and 2 used polyvinyl chloride and a plasticizer outside the scope of the present invention, and added a commercially available antistatic agent, so the electrical resistance was large and no antistatic effect could be expected.

Example 5 As shown in FIG. 1, a sheet in which colored conductive Nl and conductive layer 2 were laminated was produced.

Color conductive layer 1 was prepared by kneading a composition containing 1 part by weight of phthalocyanine green, which is a green colorant, in addition to the composition of Example 1, using two electrically heated rolls, and then kneading the composition using a steam press.
．． It was produced by molding to a thickness of 5 mm.

The conductive layer 2 is made of a composition of 100 parts by weight of polyvinyl chloride resin, 70 parts by weight of dioctyl phthalate, 80 parts by weight of carbon black, and 5 parts by weight of other stabilizers, etc. It was produced by molding to a thickness of 2.5 mm in the same manner as in the case.

The volume resistivity of this conductive N2 was 3×10 2 Ω-Cm.

Next, the color conductive layer l and the conductive! ! 2 was laminated using a steam press to produce a laminated sheet with a colored surface as shown in FIG. 1.

Comparative Example 3 Color conductive Nl was added to 100 parts by weight of polyvinyl chloride resin, 50 parts by weight of dioctyl phthalate, and a nonionic antistatic agent (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Resist) 141) 2
A laminated sheet was prepared in the same manner as in Example 5, except that the composition was prepared by adding 6 parts by weight of ffLa part and other stabilizers.

The results of measuring the electrical resistance of the laminated sheets produced in Example 5 and Comparative Example 3 are shown in Table 2.

The electrical resistance was measured as shown in FIG. That is, a direct current f is applied to the copper plate 4 connected to the conductive layer 2.
Apply voltage with i5, and electrode 3 of 60 m n]φ
The current flowing through the main stream was measured at -17, and the TL electrical resistance was calculated from Ohm's law. It is a 6C1 voltmeter.

The laminated 1-sheet of Comparative Example 3 in Table 2 had high electrical resistance, and the lamination effect was not exhibited.

[Effects of the Invention] As explained above, according to the present invention, a molded article that can be colored in any color and has excellent antistatic performance can be realized.

Further, by laminating the sheet obtained from the composition of the present invention with a black conductive sheet containing carbon black or the like and having excellent conductivity, a colored sheet having even better antistatic performance can be realized.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram of one embodiment of the laminated sheet according to the present invention, and FIG. 2 is an explanatory diagram of one embodiment of the laminated sheet according to the present invention. It is an explanatory view of a measuring method of 4 air resistance. 1: Conductive colored sheet, 2: Conductive sheet.

Claims (2)

[Claims] (1) A copolymer of vinyl chloride and a monomer having a hydrophilic group and a reactive double bond in the molecule has a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X is a carbon number of 2 to 8 R is an aliphatic or alicyclic dibasic acid residue having 3 to 3 carbon atoms, which may be the same or different;
15 linear or branched alkyl groups, A has 2 to 4 carbon atoms
represents an alkylene group, and m and n are integers of 1 to 7, which may be the same or different. However, the total carbon number of A+R is 5 to 17. ) A conductive resin composition characterized by containing a plasticizer and an electrolyte represented by: (2) A copolymer of vinyl chloride and a monomer having a hydrophilic group and a reactive double bond in the molecule has a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X is a carbon number of 2 to 8 R is an aliphatic or alicyclic dibasic acid residue having 3 to 3 carbon atoms, which may be the same or different;
15 linear or branched alkyl groups, A has 2 to 4 carbon atoms
represents an alkylene group, and m and n are integers of 1 to 7, which may be the same or different. However, the total carbon number of A+R is 5 to 17. ) A first sheet made of a resin composition containing a plasticizer and an electrolyte, and a resin made of rubber or plastic containing at least one of carbon black, carbon fiber, metal powder, or metal fiber. An electrically conductive floor sheet, characterized in that it is formed by laminating a second sheet made of a composition and having a higher electrical conductivity than the first sheet.