JPS62185733A - Electroconductive resin composition and electroconductive floor sheet - Google Patents

Abstract

PURPOSE:To form an electroconductive resin 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 polymer component containing a polyvinyl chloride resin and an acrylonitrile/butadiene copolymer. CONSTITUTION:This electroconductive resin composition is formed by adding a plasticizer (b) of the formula (wherein X is a 2-8 C aliphatic or alicyclic dibasic acid residue, R groups may be the same or different and are each a 3-15 C linear or branched alkyl group, A is a 2-4 C alkylene group, and m and n may be the same or different and are each an integer of 1-7, provided that the total number of carbon atoms of A and R is 5-17) and an electrolyte (c) are added to a polymer component (a) containing a polyvinyl chloride resin and an acrylonitrile/butadiene copolymer. An example of plasticizer (b) is a compound formed by an addition reaction of 1-7mol of ethylene oxide, 1-4mol of propylene oxide or 1-3mol of butylene oxide with propanol. An example of electrolyte (c) is zinc chloride.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides a conductive resin composition that can be freely colored and that can produce molded articles 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 in rubber or plastic molded products, it is necessary to lower the electrical resistance of the molded product.
The purpose is to quickly ground and dissipate static electricity generated by friction.

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

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

(2) Rubber or plastic with carbon black or carbon &! How to add fiber.

(3) Go1. Another method is to add a surfactant called an antistatic agent or something similar to the plastic.

[Problem to be Solved by the Invention The method (1) is very effective for electrostatic charging prevention +L, but it cannot be colored in any desired color and is limited to metallic colors. Moreover, it is very expensive and lacks economic efficiency.

Furthermore, it is desirable that the electrical resistance of the molded product be within a certain range to prevent the risk of electric shock due to low-voltage electricity, but it is difficult to stably manufacture such a product using metal powder or metal fiber. is extremely difficult.

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.

Although method (3) has the advantage of being able to be colored freely, it has poor compatibility with rubber and plastics.

This is achieved by incorporating a surfactant that easily absorbs moisture and letting it bleed onto the surface to lower the surface resistance and dissipate static electricity from the surface.It relies on surface resistance, an electrical resistance that is easily affected by environmental conditions. Lack of stability in antistatic performance. In particular, the antistatic effect will be considerably reduced in a low humidity environment. In addition, the antistatic performance lasts for a short time between stations.

On the other hand, in recent years, semiconductor parts such as ICs and LSIs, electronic equipment factories, etc. have been increasing the number of micrometers due to the generation of static electricity (in order to prevent production failures due to adsorption of dirt and dust in units of 1 micron and submicron units, and in OA rooms, etc.). In recent years, the use of conductive floors has been 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 conceivable to use a sheet laminated with a highly conductive sheet obtained by method (1) or (2) on the back side.

In such a laminated sheet, static electricity charged on the front side leaks to the conductive layer on the back side and is grounded, but in this case, volume resistance is more important than surface resistance, and surfactants and similar charged The sheet produced by method (3), in which something called an inhibitor was added, could not lower the volume resistance;
A sufficient antistatic effect will not 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 has a polymer component containing a polyvinyl chloride resin and an acrylonitrile-butadiene copolymer containing the general formula % (%) (in the formula, X is an aliphatic or alicyclic dibasic acid residue having 2 to 8 carbon atoms, and R is a carbon tgW1 which may be the same or different.
A represents a linear or branched alkyl group having 13 to 15 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and ff1n represents the same -
or an integer from 1 to 7 which may be different. However, A+
The total carbon number of R 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 has a polymer component containing a polyvinyl chloride resin and an acrylonitrile-butadiene copolymer with the general formula %) (wherein, X is an aliphatic group having 2 to 8 carbon atoms or an alicyclic dibasic acid residue, R is the same or different carbon F13;
~15 linear or branched alkyl groups, A is carbon F12
~/L represents an alkylene group, and m 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. ) A first sheet made of a resin composition containing a plasticizer and an electrolyte represented by
! A second sheet having higher conductivity than the first sheet made of a resin composition containing at least one of 1t.
It is characterized by being made by laminating sheets of.

In the present invention, the polyvinyl chloride resin may be any resin that normally contains 50% by weight or more of vinyl chloride, such as a polymer of vinyl chloride, or a copolymer of vinyl chloride and a monomer copolymerizable therewith. Either a combination or a graft copolymer with other resin materials may be used. Although the average degree of polymerization of the polyvinyl chloride resin is not particularly limited, it is preferably 2,000 or more for good mechanical strength.

Although there are no particular restrictions on the acrylonitrile-butadiene copolymer, one with a high acrylonitrile content is desirable from the viewpoint of electrical resistance, and the molecular weight, presence or absence of partial crosslinking, etc. should be selected depending on the intended use. good.

The content ratio of polyvinyl chloride resin and 7-acrylonitrile-butadiene copolymer is 95 to 2 in terms of weight ratio of polyvinyl chloride resin/acrylonitrile-butadiene copolymer.
A range of 075 to 80 is desirable. If the acryl nitrile-butadiene copolymer content is 51 ifft% or less, electrical resistance tends to increase. When it exceeds 80% by weight, raw rubber-like properties become noticeable, processability tends to be poor and it is difficult to obtain a product with a smooth surface, and vulcanization becomes necessary, increasing the number of manufacturing steps.

In the present invention, the plasticizer represented by the general formula:
Easily obtained by a general ester production method by reacting an alcohol obtained by addition of ~7 moles, a terminal hydroxyl compound having a total carbon number of 5 to 17 alkylene oxide, and an aliphatic or alicyclic dibasic acid. be able to.

If the number of carbon atoms in alcohol, the number of moles of alkylene oxide (1), and the total number of carbon atoms in alcohol and alkylene oxide are 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 oxy F' or 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 1 mole of propylene oxide. ~4 moles or 1 to 3 moles of butylene oxide,
Hexanol with 1 to 5 moles of ethylene oxide, 1 to 3 moles of propylene oxide, or 1 to 2 moles of butylene oxide, and heptatool with 1 to 5 moles of ethylene oxide or propylene oxide! , ~3 moles to 'rt butylene oxide 1 to 2 moles, octatool to ethylene oxide l~
4 mol or 1-3 mol of propylene oxide or 1-2 mol of butylene oxide, 1 mol of ethylene oxide in nonanol
~4 moles or 1 to 2 moles of propylene oxide or 1 to 2 moles of butylene oxide, 1 to 3 moles of ethylene oxide in decanol or 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 in dodecanol Or butylene oxy! Examples include compounds in which 1 mole of ethylene oxide or 1 mole of propylene oxide is added to tetradecanol, and 1 mole of ethylene oxide is added to pentadecanol.

The amount of the plasticizer represented by the above general formula added to the polymer component containing the polyvinyl chloride resin and the acrylonitrile-butadiene copolymer is not particularly limited as long as the desired volume resistivity is obtained; The range of 5 to 100 parts by weight is preferred. If it is less than 5 parts by weight, it becomes difficult to obtain the desired volume of 11 (resistivity),
Exceeding 0 weight tun toden may lead to deterioration of compatibility and deterioration of mechanical properties, making it unsuitable for use in the field of thermoplastic resins.

Examples of the electrolyte include lithium chloride, lithium sulfate, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, zinc chloride, barium chloride, sodium FIR acid, 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 amount of electrolyte added is 10% of the polymer component containing polyvinyl chloride resin and acrylonitrile-butadiene copolymer.
0.01 to 5 parts by weight is appropriate for 0 parts by weight,
．． Below 0.01 parts by weight, there is almost no effect of lowering the electrical resistance, and at 5 parts by weight, the reduction in electrical resistance 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 can be InN with a conventionally known conductive sheet, that is, a sheet made of rubber or plastic containing carbon black, carbon fiber, metal powder, metal fiber, 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 Example 6 in Table 1 to produce a sheet with a thickness of 1 mm.

The results of the measurements of the volume 1 degree centigrade resistivity of this sheet are shown in the lower column of Table 1.

The volume resistivity is determined by the Japan Rubber Association standard SR [5230
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.

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

Example 5 As shown in FIG. 1, a sheet was prepared in which color conductive Nl and conductive 1tff2 were laminated.

Color guidance M, TI! il was prepared by kneading a composition containing 1 part by weight of phthalocyanine green, a green coloring agent, in addition to the composition of Example 1 using two electric heated rolls, and molding it to a thickness of 0.5 mm using a steam press. It was made by

Conductive layer N2 was prepared using a composition 11 in which 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 were mixed in the same manner as in the case of color conductive layer 1. It was produced by molding it to a thickness of 2.5 mm.

The volume resistivity of this conductive layer 2 was 3×10 2 Ω-cm.

Next, the colored conductive layer] and the conductive M2 were laminated using a steam press to produce a laminated sheet with a colored surface as shown in FIG.

Comparative Example 3 Color conductive layer 1 was mixed with 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
) 2ffiffi parts, other stabilizers, etc. 611! A laminated sheet was produced in the same manner as in Example 5, except that it was produced using a composition in which the following parts were mixed.

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, the conductivity r! A voltage was applied to the copper plate 4 connected to i2 using a DC power supply 5, and the current flowing through the 60 mmφ electrode 3 was measured using a t-current meter 7, and the electrical resistance was calculated from the law of . 6 is a voltmeter.

The laminated 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. 2 is an explanatory diagram of an example of a laminated sheet in the 11th FHJ Kizu Jinmei, and FIG. 2 is an explanatory diagram of a method for measuring the electrical resistance of the laminated J-sheet. 1: Conductive colored sheet, 2: Conductive sheet.

Claims (2)

[Claims] (1) Polyvinyl chloride resin and acrylonitrile
Polymer components containing butadiene copolymers have general formulas▲mathematical formulas, chemical formulas, tables, etc.▼ (wherein, X is an aliphatic or alicyclic dibasic acid residue having 2 to 8 carbon atoms, may be the same or different and have a carbon number of 3 to
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) Polyvinyl chloride resin and acrylonitrile
Polymer components containing butadiene copolymers have general formulas▲mathematical formulas, chemical formulas, tables, etc.▼ (wherein, X is an aliphatic or alicyclic dibasic acid residue having 2 to 8 carbon atoms, may be the same or different and have a carbon number of 3 to
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.