JPS62185734A - 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, a phosphoric ester 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 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 a phosphoric ester and an electrolyte are added to a polymer component containing a polyvinyl chloride resin and an acrylonitrile/butadiene copolymer. An example of said plasticizer 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. Examples of said electrolyte are zinc chloride and lithium chloride.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Fields] 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 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.

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

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

(3) A method in which a surfactant called an antistatic agent or something similar is added to rubber or plastic.

[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 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.

Also, is this method also low pressure? It is difficult to industrially and stably produce molded products that are free from the risk of electric shock due to Tj air.

Although method (3) has the advantage of being able to be colored freely, it incorporates a surfactant that has poor compatibility with rubber and plastics and easily absorbs moisture, and bleeds onto the surface to lower surface resistance and reduce static electricity. It is obtained by releasing electricity from the surface, and relies on surface resistance, which is an electrical resistance that is easily affected by environmental conditions, and lacks stability in antistatic performance. In particular, the antistatic effect will be considerably reduced in a low humidity environment. Moreover, the duration of antistatic performance is short.

On the other hand, in recent years, semiconductor parts such as IC, LSI, etc. and electronic equipment factories are being used to prevent production failures due to the attraction of micron and submicron dust particles due to the generation of static electricity, and in office automation rooms, etc. The use of conductive floors is being considered to prevent computer malfunctions and circuit damage.

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 the sheet having high conductivity obtained by method (+) or (2) on the back side.

In such a laminated sheet, static electricity charged on the front side is transferred to the back side? ttF! 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 has a poly-7 component containing a polyvinyl chloride resin and an acrylonitrile-butadiene copolymer, and a compound having the general formula COO(AO). III R Coo (AO)n R (wherein, X is an aliphatic or alicyclic dibasic acid residue having 2 to 8 carbon atoms;
15 linear or branched alkyl groups, A has 2 to 4 carbon atoms
represents a fullkylene 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. ) It is characterized by containing a plasticizer represented by the following, a phosphoric acid ester, and an electrolyte.

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 or a dibasic acid residue of the aliphatic type, R is a linear or branched alkyl group having 3 to 15 carbon atoms, which may be the same or different, and A is a straight chain or branched alkyl group having 2 carbon atoms.
~4 alkylene groups are represented, respectively, 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 consisting of a resin composition containing a plasticizer represented by the following formula, a phosphoric acid ester, and a delyte of U'', and a rubber or plastic containing carbon black, carbon fiber,
It is characterized by being laminated with a second sheet having higher conductivity than the first sheet, which is made of a resin composition containing at least one of metal powder or metal fiber.

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. It may be a polymer or a graft copolymer with other resin materials. 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.

There are no particular restrictions on the acrylonitrile-butadiene copolymer, but it is desirable to have a high acrylonitrile content from the viewpoint of electrical resistance, and the molecular weight and presence or absence of partial crosslinking 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 acrylonitrile-butadiene copolymer content is 5% by weight 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.

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 alkylene 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 6 moles of ethylene oxide in hexanol, or propylene oxy!・1 to 3 moles or 1 to 2 moles of butylene oxide, 1 to 2 moles of ethylene oxide in hebutanol, 1 to 3 moles of propylene oxide, or 1 to 3 moles of butylene oxide
2 moles of ethylene oxide or 1 to 4 moles of propylene oxide or 1 to 2 moles of butylene oxide in octatool, 1 to 4 moles of ethylene oxide or 1 to 2 moles of propylene oxide or 1 to 2 moles of butylene oxide in nonanol, or 1 to 2 moles of butylene oxide in decanol. 1 to 3 moles of ethylene oxide 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 or 1 mole of butylene oxide in dodecanol, 1 mole of ethylene oxide or 1 mole of propylene oxide in tetradecanol, 1 mole of ethylene oxide or 1 mole of propylene oxide in dodecanol, Examples include compounds in which 1 mole of ethylene oxide is added to decanol.

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 5ffi parts, it becomes difficult to obtain the desired volume resistivity, and 10 parts
(Exceeding the lffi part may lead to deterioration of compatibility and deterioration of mechanical properties, making it unsuitable for use in the field of thermoplastic resins.

The properties of the phosphoric acid ester are not particularly limited, but it is desirable that the phosphoric acid ester is liquid at room temperature and has low volatility.

For example, cresyl diphenyl phosphate, di(2,3-dibromopropyl) 2,3-dichloropropyl phosphate, di(2-ethylhexyl) phosphate, dioctyl phosphate, triamyl phosphate, phosphate acid tributoxyethyl ester, phosphate tri(
Examples include 2-chloroethyl) ester, tri(chloropropyl) phosphate, tricresyl phosphate, tri(2,3-dibromopropyl) phosphate, and tri(dichloropropyl) phosphate.

The amount of added acid of the phosphoric acid ester is preferably in the range of 5 to 100 parts by weight based on 100 parts by weight of the polymer component containing the polyvinyl chloride resin and the acrylonitrile-butadiene JF small aggregate. At about 100 parts by weight, the volume resistivity becomes almost saturated, and even if the amount is increased beyond this, the electrical resistance will hardly change, and on the contrary, the compatibility will deteriorate and the mechanical properties will deteriorate. It may not be suitable for use in the field of thermoplastic resins.

As electrolytes, lithium chloride, lithium sulfate, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, zinc chloride, barium chloride, sodium sulfate, f
l[Potassium, lithium citrate, lithium bromate, etc. 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, (
'3, 01 The lower part of the AT part has little effect on lowering the resistance of Electric 11, and 5 parts by weight is 25. The decrease in air resistance is almost saturated.

In the present invention, in addition to the above components, D
Plasticizers such as OP, 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 fiber, etc. to impart conductivity. By doing so, the -Ji antistatic performance can be improved, and it is also useful for improving the aesthetic appearance.

[Example 2] According to the compounding ratios shown on each side of Table 1, the compound was kneaded using two electrically heated rolls and molded using a high-pressure steam press to produce 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 SR+5230 according to the Japan Rubber Association standard.
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 scope 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, color conductive rF! ! l and conductive layer 2
A laminated sheet was prepared.

Color conductive Fl 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 electrically heated rolls, and then kneading the composition using a steam press.
．． It was produced by molding to a thickness of 5 mm.

Guide? tFI2 consists of 100 parts by weight of polyvinyl chloride resin, 70 parts by weight of dioctyl phthalate, and 8 parts by weight of carbon black.
0 parts by weight, and 5 parts by weight of other stabilizers etc. are added to the color guide layer! 2.5ro in the same way as in the case of
It was produced by molding to a thickness of m.

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

Next, color conductive j'jl! 1 and conductive N2 were laminated using a steam press to produce a laminated sheet with a colored surface as shown in FIG. 1.

Comparative Example 3 Color conductive layer 1 was prepared by adding 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., Resistit '141) 2
A laminate sheet was produced in the same manner as in Example 5, except that the composition was prepared by adding 6 parts by weight of other stabilizers and the like.

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 voltage is applied by the DC power supply 5 to the G1 plate 4 connected to the conductive layer 2, and a voltage of E30 mmφ is applied to the G1 plate 4 connected to the conductive layer 2. The pole 3ζ
The flow rate was measured using a main current meter 7, and the electrical resistance was calculated from Ohm's law. 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. 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 a method for measuring the electrical resistance of the laminated 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 represented by the following formula, a phosphoric acid ester, and an electrolyte. (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, a phosphoric acid ester, and an electrolyte represented by 1. A conductive floor sheet comprising a second sheet having a higher conductivity than the first sheet made of a resin composition containing the resin composition.