CN108806827A - Conductive agent for synthetic resin, conductive resin composition, and conductive flooring material - Google Patents
Conductive agent for synthetic resin, conductive resin composition, and conductive flooring material Download PDFInfo
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- CN108806827A CN108806827A CN201810374919.5A CN201810374919A CN108806827A CN 108806827 A CN108806827 A CN 108806827A CN 201810374919 A CN201810374919 A CN 201810374919A CN 108806827 A CN108806827 A CN 108806827A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F15/00—Flooring
- E04F15/02—Flooring or floor layers composed of a number of similar elements
- E04F15/10—Flooring or floor layers composed of a number of similar elements of other materials, e.g. fibrous or chipped materials, organic plastics, magnesite tiles, hardboard, or with a top layer of other materials
- E04F15/105—Flooring or floor layers composed of a number of similar elements of other materials, e.g. fibrous or chipped materials, organic plastics, magnesite tiles, hardboard, or with a top layer of other materials of organic plastics with or without reinforcements or filling materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F2290/00—Specially adapted covering, lining or flooring elements not otherwise provided for
- E04F2290/02—Specially adapted covering, lining or flooring elements not otherwise provided for for accommodating service installations or utility lines, e.g. heating conduits, electrical lines, lighting devices or service outlets
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- Engineering & Computer Science (AREA)
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Abstract
The present invention relates to a conductive agent for synthetic resin, a conductive resin composition containing the conductive agent for synthetic resin, and a conductive flooring material formed using the conductive resin composition. The conductive agent for synthetic resin can provide a molded article having excellent coloring properties, suitable conductivity to the molded article, and no stickiness on the surface of the molded article. The conductive agent for synthetic resin of the present invention contains a specific quaternary ammonium salt and a specific diol compound.
Description
【Technical field】
The present invention relates to a kind of synthetic resin conductive agent, the electroconductive resin containing the synthetic resin conductive agent combination
Object and the electrically plank shaped using the conductive resin composition.
【Background technology】
Synthetic resin has used in various fields at present, wherein being widely employed as the flooring material in building goods, materials and equipments.It closes
The property inherently charged at resin, old place plank also often need to take antistatic measure.Especially semiconductor is relevant
Workshop, computer room etc., other than it must be prevented from the floor for the building that electrostatic causes failure, with the general of electronic equipment
And it is also required to static countermeasure in common workplace etc..Therefore, it is 10 that flooring board can be assigned sheet resistance by, which expecting at present,4~
106The suitably electrically conductive property of Ω or so.In the past in terms of assigning conductive synthetic resin, it is thus proposed that carbon black or conducting fibre
(for example, see Japanese Unexamined Patent Publication 4-289373 bulletins).However, be difficult in these known technologies by such as flooring board this
The molding of the built-in material of class carries out the problem of required coloring.Also it has been proposed that surface is lived in terms of synthetic resin antistatic agent
Property agent (for example, see Japanese Unexamined Patent Publication 4-198239 bulletins and special open 2005-154575 bulletins).However, known in these
Although can brightly be coloured in technology, 10 can not be decreased below by the sheet resistance of the molding of gained by having7Ω, and
Surfactant can overflow and be easy to lead to the problem of viscous stick on surface if the blend amount for promoting surfactant.
【Invention content】
Problems to be solved by the invention
Project to be solved by this invention is, provides a kind of synthetic resin conductive agent, containing the synthetic resin conductive agent
Conductive resin composition and the electrically plank that is shaped using the conductive resin composition.The synthetic resin is with leading
The coloring for the molding that electric agent obtains is excellent, and can assign molding electric conductivity appropriate, while on the surface of molding
It does not generate viscous glutinous.
Means for solving the problems
It is that present inventor is studied in order to solve the above problems as a result, it has been found that, contain specific quaternary ammonium salt and specific glycol
The composition of compound is highly suitable as synthetic resin conductive agent.
Also that is, the present invention relates to a kind of synthetic resin conductive agents, which is characterized in that shown in following chemical formula 1
Diol compound shown in quaternary ammonium salt and following chemical formula 3.Also, the present invention relates to one kind containing the synthetic resin conductive agent
Conductive resin composition and the electrically plank that is shaped using the conductive resin composition.
Chemical formula 1：
In chemical formula 1,
R1：The group of organic group shown in aliphatic alkyl and following chemical formula 2 selected from carbon number 8~16,
R2, R3：The aliphatic alkyl of carbon number 1~4,
Y：There is 1~5 (poly-) alkylidene oxide its (poly-) being made of the oxyalkylene units of carbon number 2~4 in molecule
The residue after all hydroxyls is removed in aklylene glycol,
X-：The group for the alkylsulfonate ion base that carbon number selected from chlorion base, high chloro acid ion's base and alkyl is 1~4.
Chemical formula 2：
R4CONHR5-
In chemical formula 2,
R4：The aliphatic alkyl of carbon number 7~15,
R5：The alkylidene of carbon number 1~5.
Chemical formula 3：
In chemical formula 3,
A：The alkylidene of carbon number 2~4,
m：1~10 integer.
First, it is illustrated with conductive agent (hereinafter referred to as conductive agent of the invention) for synthetic resin of the present invention.
The conductive agent of the present invention contains quaternary ammonium salt shown in above-mentioned chemical formula 1 and diol compound shown in above-mentioned chemical formula 3.
Quaternary ammonium salt used in the conductive agent of the present invention is by X in quaternary ammonium cation base and chemical formula 1-Shown in anion
Base is constituted.The quaternary ammonium cation base of a wherein side is：1) R in chemical formula 11For the aliphatic alkyl of carbon number 8~16, R2And R3
For the aliphatic alkyl of carbon number 1~4, Y is (poly-) oxygen for being made of the oxyalkylene units of carbon number 2~4 with 1~5
The quaternary ammonium cation base when residue after all hydroxyls is removed in its (poly-) aklylene glycol of change alkylidene；2) in chemical formula 1
R1For organic group, R shown in chemical formula 22And R3For the aliphatic alkyl of carbon number 1~4, Y is with 1~5 by carbon number 2~4
The residue after all hydroxyls is removed in its (poly-) aklylene glycol of (poly-) alkylidene oxide that oxyalkylene units are constituted
When quaternary ammonium cation base.The aliphatic alkyl of carbon number 8~16 can enumerate octyl, nonyl, decyl, dodecyl, myristyl,
Cetyl, iso-octyl, 2- ethylhexyls, isodecyl, Permethyl 99A base, different myristyl etc.；Organic group shown in chemical formula 2
Caprylamide methyl, decyl amide methyl, lauramide methyl, myristamide methyl, palmitamide methyl, 2- caprylamide second can be enumerated
Base, 2- decyl amide ethyl, 2- lauramides ethyl, 2- myristamides ethyl, 2- palmitamides ethyl, 3- caprylamides propyl, 3-
Decyl amide propyl, 3- lauramides propyl, 3- myristamides propyl, 3- palmitamides propyl, 4- caprylamides butyl, 4- decyl amide
Butyl, 4- lauramides butyl, 4- myristamides butyl, 4- palmitamides butyl, 5- caprylamides amyl, 5- decyl amide amyl,
5- lauramides amyl, 5- myristamides amyl, 5- palmitamide amyls etc..Wherein again with R1For the aliphatic of carbon number 12~14
Alkyl, R4For the aliphatic alkyl and R of carbon number 11~135For propyl when chemical formula 2 shown in organic group it is preferable.Also, chemistry
R in formula 12And R3The aliphatic alkyl of the carbon numbers such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl group 1~4 can be enumerated,
In again it is preferable with methyl.In addition the Y in chemical formula 1 can be enumerated：1) ethylene glycol, propylene glycol, trimethylene, tetramethylene two
It is removed in the aklylene glycol of the oxyalkylene units with 1 carbon number 2~4 in alcohol equimolecular residual after all hydroxyls
In base, 2) polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, (poly-) second (poly-) propylene glycol equimolecular
The residue after all hydroxyls is removed in the polyalkylene glycol of oxyalkylene units with 2~5 carbon numbers 2~4, wherein
It is again preferable to remove the residue after all hydroxyls in ethylene glycol.
X in the chemical formula 1 of another party-Shown in anion base can enumerate：1) chlorion base, 2) high chloro acid ion's base, 3)
Pyrovinic acid ion radical, ethylsulfonic acid ion radical, propyl sulfonic acid ion radical, isopropyl azochlorosulfonate acid ion base, butyl sulfonic acid ion radical,
The alkylsulfonate ion base that the carbon number of the alkyl such as isobutyl group azochlorosulfonate acid ion base is 1~4, wherein again preferable with high chloro acid ion's base.
The concrete example of quaternary ammonium salt shown in chemical formula 1 described above can enumerate the high chlorine of 2- hydroxyethyl dimethyl octyl ammoniums
Hydrochlorate, 2- hydroxyethyl dimethyl nonyl ammoniums perchlorate, 2- hydroxyethyl dimethyl decyl ammoniums perchlorate, 2- hydroxyethyls
Dimethyl dodecyl base ammonium perchlorate, 2- hydroxyethyl dimethyl tetradecyl base ammoniums perchlorate, 2- hydroxyethyl dimethyl
Cetyltrimethyl ammonium perchlorate, 2- hydroxyethyl dipropyl octyl ammonium salts hydrochlorate, 2- hydroxyethyl dipropyl decyl ammoniums chlorate,
3- hydroxypropyl dimethyl dodecyl base ammoniums perchlorate, tetraethylene glycol dimethyl tetradecyl base ammonium metilsulfate, 2- hydroxyls
Ethyl dimethyl -3- caprylamide propyl ammoniums perchlorate, 2- hydroxyethyl dimethyl -3- pelargonamide propyl ammoniums perchlorate, 2-
Hydroxyethyl dimethyl -3- decyl amide propyl ammoniums perchlorate, 2- hydroxyethyl dimethyl -3- lauramide propyl ammonium perchloric acid
Salt, 2- hydroxyethyl dimethyl -3- myristamide propyl ammoniums perchlorate, 2- hydroxyethyl dimethyl -3- palmitamide propyl
Ammonium perchlorate, 2- hydroxyethyl dipropyl -3- caprylamide propyl ammoniums hydrochloride, 2- hydroxyethyl dipropyl -3- decyl amide third
Base ammonium chlorate, 3- hydroxypropyl dimethyl -3- lauramide propyl ammoniums perchlorate, tetraethylene glycol dimethyl -3- myristoyls
Amine propyl ammonium metilsulfate etc., wherein again with 2- hydroxyethyl dimethyl dodecyl base ammoniums perchlorate, 2- hydroxyethyls two
Methyltetradecylphosphine base ammonium perchlorate, 2- hydroxyethyl dimethyl -3- lauramide propyl ammoniums perchlorate, 2- hydroxyethyls two
Methyl -3- myristamide propyl ammonium perchlorate is preferable.
One kind can be used alone in quaternary ammonium salt shown in chemical formula 1 described above, but is preferably and uses two kinds or more, and
Preferably (R1For carbon number 8~16 aliphatic alkyl when chemical formula 1 shown in quaternary ammonium salt)/(R1To have shown in chemical formula 2
Quaternary ammonium salt shown in chemical formula 1 when machine base)=80/20~20/80 (mass ratio) ratio mixture.
Diol compound can be enumerated used in the conductive agent of the present invention：1) ethylene glycol, propylene glycol, trimethylene,
Aklylene glycol in the chemical formulas such as tetramethylene glycol 3 when m=1；2) polyethylene glycol, polypropylene glycol, polytrimethylene glycol,
In polytetramethylene glycol, (poly-) second (poly-) propylene glycol equimolecular with 2~10 carbon numbers 2~4 oxyalkylene units it
Polyalkylene glycol in chemical formula 3 when m=2~10, wherein the poly- Asia preferably in ethylene glycol and chemical formula 3 when m=2~6
Alkyl diol, more preferably ethylene glycol.
The conductive agent of the present invention contains above-mentioned quaternary ammonium salt described above and above-mentioned diol compound, preferably (quaternary ammonium
Salt)/the content ratio of (diol compound) is 99.9/0.1~80/20 (mass ratio), more preferably (quaternary ammonium salt)/(glycol chemical combination
Object) containing than for 99.5/0.5~90/10 (mass ratio).
The present invention conductive agent can to the vinylites such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyester,
Condensation resins such as polyamide etc., various thermoplastic resins assign electric conductivity, wherein again with to polychlorostyrene used in flooring board etc.
Vinylite is more useful.
Then, it is said for conductive resin composition of the present invention (hereinafter referred to as resin combination of the invention)
It is bright.The resin combination of the present invention contains the conduction of polyvinyl chloride resin, plasticizer, calcium carbonate and present invention mentioned above
Agent.
Polyvinyl chloride resin used in the resin combination of the present invention can enumerate the homopolymer or chlorine of vinyl chloride monomer
Vinyl monomer is formed by copolymer with the other monomers that can be copolymerized with it.Other monomers can enumerate vinyl acetate, ethylene, third
Alkene, butylene, 1- amylenes, butadiene, styrene, α-methylstyrene, acrylonitrile, protochloride ethylene, cyaniding Asia ethylene, alkyl second
Alkene ethers, generating vinyl carboxylate esters, aryl ethers, dialkyl group Malaysia acids, fumaric acid esters, N- ethylene Pyrrolizidines ketone, ethylene pyrrole
Pyridine, vinyl silane class, alkyl-acrylates, alkyl methacrylate etc..Polychlorostyrene second used in the composition of the present invention
Alkene system resin can be the graft copolymerizations such as ethane-acetic acid ethyenyl-chloride graft polymer, vinyl chloride-urethane copolymers
Object.Wherein polyvinyl chloride resin is again with the copolymer of the homopolymer of vinyl chloride monomer, vinyl chloride monomer and vinyl acetate monomer
Preferably.Polyvinyl chloride resin is usually 500~4000 using average degree of polymerization, and preferably 600~2000, wherein more preferably
It is 700~1200.
Plasticizer is selected from used in the resin combination of the present invention：1) phthalic acid ester system plasticizer, 2) aliphatic
At least one of dicarboxylic ester system plasticizer and 3) trimellitic acid ester system plasticizer.Phthalic acid ester system plasticizer can
Enumerate two-n- monooctyl esters of phthalic acid, di-2-ethylhexyl phthalate, diisononyl phthalate, phthalic acid
Diisodecyl ester, diphenyl phthalate etc..Aliphatic dicarboxylic acid ester system plasticizer can enumerate two-n- monooctyl esters of adipic acid, oneself two
Sour two -2- ethylhexyls, Diisooctyl Sebacate etc..Trimellitic acid ester system plasticizer can enumerate trimellitic acid three-
N- monooctyl esters, three -2- ethylhexyls of trimellitic acid etc..Wherein plasticizer is again with di-2-ethylhexyl phthalate, adjacent benzene two
Formic acid dinonyl, diisooctyl phthalate, di-2-ethylhexyl adipate, three -2- ethylhexyls of trimellitic acid compared with
It is good.
Calcium carbonate includes used in the resin combination of the present invention：1) untreated calcium carbonate, 2) fatty acid surface processing
Calcium carbonate, 3) it is above-mentioned 1) and above-mentioned mixture 2).Untreated calcium carbonate has average grain diameter obtained by the crushing such as natural limestone
0.5~10 μm of heavy type, the synthesis type by 0.02~2 μm of grain size obtained by chemical reaction, commercially available product can be enumerated
Softon2200, Softon2600, Softon3200, BF-200, BF-300 (are all the quotient of standby northern dusting industrial group above
The name of an article), Whiton B (trade name of shiraishi calcium corporation).Wherein in terms of untreated calcium carbonate, but with average grain diameter be 1~
5 μm of heavy type is preferable.Fatty acid surface processing calcium carbonate is the calcium carbonate by above-mentioned untreated heavy type or synthesis type
Surface is with the aliphatic acid of 2~6 mass % is handled and obtains person, and commercially available product can enumerate Lighton S-4, and (standby north dusting industry is public
Take charge of the trade name of system), calcene CC, calcene CCR, Vigot10, Vigot15 (be all the commodity of shiraishi calcium corporation above
Name).Wherein in terms of fatty acid surface handles calcium carbonate, and to be surface-treated with the saturated fatty acid of carbon number 12~22
Calcium carbonate it is preferable, the calcium carbonate being surface-treated with the saturated fatty acid of carbon number 16~18 is more preferably.The fatty acid surface
0.02~10 μm of person, preferably 0.02~5 μm of person can be used by handling the average grain diameter of calcium carbonate.Calcium carbonate described above
It can be used alone, wherein again with (fatty acid surface processing calcium carbonate)/(untreated calcium carbonate)=80/20~20/80 (quality
Than) ratio mixture it is preferable.These calcium carbonate in the range of not undermining the effect of the present invention can and with clay, talcum
Deng.
The resin combination of the present invention is configured to, relative to above-mentioned polyvinyl chloride resin composition 100 described above
Mass parts, the conductive agent containing 15~60 mass parts of above-mentioned plasticizer, 50~500 mass parts of above-mentioned calcium carbonate and aforementioned present invention
5~30 mass parts.
In order to which in response to other purposes, resin combination of the invention can use other additives, the additive that can enumerate
Stabilizer, colorant, UV resistant agent, antioxidant, age resister, processing aid, filler, lubricant, weather resisting agent etc., this
The usage amount of other a little additives is preferably a small amount of as possible.Aforementioned stable agent can enumerate zinc stearate, barium stearate, stearic acid
The epoxides such as metallic soaps, the epoxidised soybean oils such as calcium, ricinoleic acid barium, calcium laurate, calcium oleate, phosphorous acid diphenyl
Last of the ten Heavenly stems ester, triphenyl phosphite, phosphorous acid three (nonyl benzene) ester, phosphorous acid tridecane ester, phosphorous acid three (2- ethyl hexyls) ester, phosphorous
The organic phosphites system stabilizers such as sour tristearate, phosphorous acid octyl diphenyl ester, dibutyl tin laurate, two fourth of maleic acid
The tin system such as Ji Xi, thiol organotin, organotin sulfonamide stabilizer, dibutyl tin bis- (ethyl maleates), the bis- (horses of dibutyl tin
Carry out acid butyl ester), dibutyl tin bis- (maleic acid tridecyl ethyl esters), the organotins such as dibutyl tin bis- (maleic acid 2- ethylhexyls)
Maleate system stabilizer etc., these stabilizers can be used alone or mix two or more use.When using stabilizer, this makes
Dosage is preferably per the ratio that 100 parts by weight of polyvinyl chloride resin are 0.5~10 parts by weight, the ratio of more preferably 1~5 parts by weight
Example.Also, above-mentioned colorant can use commercially available product.
The resin combination of the present invention can be by using kneading machines such as roll-type kneading machine, Ban Buli mixing machines, extruders
The conductive agent etc. of polyvinyl chloride resin described above, plasticizer, calcium carbonate and the present invention are kneaded and prepared.
If the resin combination of the present invention is configured to the sheet material of 2.0mm thickness, the sheet material can become at 20 DEG C and
Sheet resistance value under 55%RH atmosphere is 1 × 104~9 × 106Ω.The sheet resistance value can be surveyed according to JIS K6911
It is fixed.
Finally, it is illustrated for electrically plank of the present invention (hereinafter referred to as flooring board of the invention).This hair
Bright flooring board be using aforementioned present invention resin combination by thickness be configured to 1~3mm molding and winner.Shape energy
Enough use forming process well known to calendaring molding, press molding, extrusion molding etc..Electrically plank is lamination of the present invention
Will use aforementioned present invention conductive composition and method described above forming thickness be 0.5~1.5mm sheet material as table
Layer, and it is bonded and winner with liner sheet material etc..
Invention effect
The present invention from the description above has effects that as follows：The coloring of the molding of gained is excellent, and can assign forming
Object sheet resistance is 104~106The electric conductivity appropriate of Ω or so does not generate viscous glutinous on the surface of molding.
Hereinafter, in order to which the composition of the present invention and effect is more specific, therefore enumerate embodiment etc., but the present invention does not limit
In these embodiments.Wherein, in following Examples and Comparative Examples, part indicates that mass parts, % indicate mass percent.
【Specific implementation mode】
1 (preparation of conductive agent) is distinguished in experiment
Embodiment 1
0.4 part of 4.8 parts of quaternary ammonium salt (A-1), 4.8 parts of quaternary ammonium salt (B-1) and diol compound (D-1) are mixed, prepared real
Apply the conductive agent (E-1) of example 1.
Embodiment 2~25 and comparative example 1~7
In the same manner as example 1, prepare embodiment 2~25 and comparative example 1~7 conductive agent (E-2)~(E-25) and
(e-1)~(e-7).By the content of the conductive agent of above prepared each example including embodiment 1 arrange and it is shown in table 1 and
Table 2.
Table 1
Table 2
In table 1 and table 2,
* 1：(R1For carbon number 8~16 aliphatic alkyl when chemical formula 1 shown in quaternary ammonium salt)/(R1Shown in chemical formula 2
Quaternary ammonium salt shown in chemical formula 1 when organic group) mass ratio
A-1：2- hydroxyethyl dimethyl dodecyl base ammonium perchlorate
A-2：2- hydroxyethyl dimethyl tetradecyl base ammonium perchlorate
A-3：2- hydroxyethyl dimethyl decyl ammonium perchlorate
A-4：2- hydroxyethyl dimethyl hexadecyl base ammonium perchlorate
A-5：2- hydroxyethyl dimethyl octyl ammonium perchlorate
A-6：2- hydroxyethyl dimethyl dodecyl base ammonium metilsulfates
a-1：2- hydroxyethyl dimethyl stearyl ammonium perchlorate
B-1：2- hydroxyethyl dimethyl -3- lauramide propyl ammonium perchlorate
B-2：2- hydroxyethyl dimethyl -3- myristamide propyl ammonium perchlorate
B-3：2- hydroxyethyl dimethyl -3- decyl amide propyl ammonium perchlorate
B-4：2- hydroxyethyl dimethyl -3- palmitamide propyl ammonium perchlorate
B-5：2- hydroxyethyl dimethyl -3- caprylamide propyl ammonium perchlorate
b-1：2- hydroxyethyl dimethyl -3- stearamide propyl ammonium perchlorate
b-2：Dimethyl -3- lauramide propyl amine diethyl sulfide hydrochlorates
D-1：Ethylene glycol
D-2：Polyoxyethylene glycol (m=5)
d-1：PEG-1000 (Sanyo is melted into corporation)
d-2：The ethylene oxide 15mol addition products of oleyl alcohol
d-3：Addition product=50/50 ethylene oxide 13mol (mass ratio) of ethylene oxide 5mol addition products/oleyl alcohol of tetradecyl alchohol
d-4：The ethylene oxide 13mol addition products of oleic acid
2 (preparations of conductive resin composition) are distinguished in experiment
Embodiment 26
By as 100 parts of the ryuron of polyvinyl chloride resin (average degree of polymerization 800) (P-1), as plasticizer
25 parts of di-2-ethylhexyl phthalate (K-1), the stearic acid surface processing calcium carbonate (M-1)/untreated as calcium carbonate
10 parts of throwings of the conductive agent (E-1) prepared by 1 are distinguished in 160 parts of the mixture of calcium carbonate (N-1)=50/50 (mass ratio) and experiment
Enter kneading machine, then further adds 1.5 parts of barium-zinc system liquid stabilisers, barium-zinc system powder stabilizer as stabilizer
0.5 part, 3 parts of epoxidised soybean oil and as colorant 1 part of GBG-2156 (green, the trade name of Japanese pigment corporation) into
Row is kneaded, and prepares the conductive resin composition (R-1) of embodiment 26.
Embodiment 27~50 and comparative example 8~19
In a manner of identical with embodiment 26, the conductive resin composition (R- of embodiment 27~50 and comparative example 8~19 is prepared
2)~(R-25) and (r-1)~(r-12).The content of the conductive resin composition of each example including embodiment 26 is whole
Manage and be shown in table 3 and table 4.
Table 3
Table 4
In table 3 and table 4,
* 2：(calcium carbonate is handled by the fatty acid surface that the saturated fatty acid of carbon number 12~22 is surface-treated)/(do not locate
The calcium carbonate of reason) mass ratio
P-1：Ryuron (average degree of polymerization 800)
P-2：Ryuron (average degree of polymerization 1050)
P-3：Vinyl chloride-vinyl acetate copolymer (average degree of polymerization 700)
P-4：Vinyl chloride-vinyl acetate copolymer (average degree of polymerization 900)
P-5：Vinyl chloride-vinyl acetate copolymer (average degree of polymerization 1100)
K-1：Di-2-ethylhexyl phthalate
K-2：Diisononyl phthalate
K-3：Diisooctyl phthalate
K-4：Di-2-ethylhexyl adipate
K-5：Three monooctyl ester of trimellitic acid
M-1：Stearic acid handles calcium carbonate (0.08 μm of average grain diameter)
M-2：Stearic acid handles calcium carbonate (2.2 μm of average grain diameter)
M-3：Palmitic acid handles calcium carbonate (0.08 μm of average grain diameter)
M-4：Lauric acid handles calcium carbonate (0.08 μm of average grain diameter)
M-5：Behenic acid handles calcium carbonate (2.2 μm of average grain diameter)
m-1：Modified fat acid handles calcium carbonate (1.8 μm of average grain diameter)
m-2：Carbon black
m-3：Carbon fiber (13 μm of fiber footpath, average fiber grow 0.3~0.4mm)
N-1：Untreated calcium carbonate (product name：Whiton B, shiraishi calcium corporation)
N-2：Untreated calcium carbonate (product name：Softon2200, shiraishi calcium corporation)
n-1：Talcum (LMR, talcum industrial group of Fuji system)
E-1~E-25, e-1~e-7：Conductive agent recorded in table 1 and table 2
3 (the electrically formings and evaluation of plank) are distinguished in experiment
Embodiment 51
The conductive resin composition (R-1) prepared by 2 is distinguished using experiment, thickness 2.0mm is configured to by calendaring molding
Electrically plank.
Embodiment 52~75 and comparative example 20~31
In a manner of identical with embodiment 51, the conduction of the embodiment 52~75 and comparative example 20~31 recorded in table 5 is shaped
Property flooring board.Following coloring, conduction are evaluated for the electrically plank of each example of the forming including embodiment 51
Property and non-stick stickiness.Result is arranged and is shown in table 5.
Coloring
The tone of the electrically plank of forming is to visually observe, and And is with following benchmark evaluations.
◎：No obscure or discoloration, is presented distinctness, and coloring is obviously excellent.
○：Though some obscure or discolorations, are presented distinctness, coloring is excellent.
△：There are obscure or discoloration, presentation to lose distinctness, coloring is bad.
╳：Black, coloring are obviously bad.
Electric conductivity
By the electrically plank of forming under conditions of 20 DEG C and relative humidity 55% damping 24 hours, then in the same terms
It is lower to measure sheet resistance value using resistance value measurement device (trade name SM-8220, SME-8310 of Zhi Motor Corporations)
(Ω)。
Non-stick stickiness
By the electrically plank of forming under conditions of 20 DEG C and relative humidity 55% damping 24 hours, then to visually observe
The appearance on surface, touches, and And is with following benchmark evaluations.
◎：Spilling without conductive agent, also without viscous glutinous.
○：Though the spilling of some conductive agents, without viscous glutinous.
△：The spilling for having conductive agent has viscous glutinous.
╳：The spilling of conductive agent is serious, hence it is evident that viscous glutinous.
Table 5
It can clearly be learnt by the result of the table 5 corresponding to 1~table of table 4, use the electric conductivity of the conductive agent containing the present invention
Oil/fat composition and electrically plank its coloring for shaping is excellent, and be 10 with sheet resistance4~106Ω's or so is appropriate
Electric conductivity, while not generating on surface viscous glutinous.
Claims (13)
1. a kind of synthetic resin conductive agent, which is characterized in that contain quaternary ammonium salt and following chemical formula shown in following chemical formula 1
Diol compound shown in 3,
Chemical formula 1：
In chemical formula 1,
R1：The group of organic group shown in aliphatic alkyl and following chemical formula 2 selected from carbon number 8~16,
R2、R3：The aliphatic alkyl of carbon number 1~4,
Y：There is (poly-) alkylidene oxide its (poly-) being made of the oxyalkylene units of 1~5 carbon number 2~4 in molecule
The residue after all hydroxyls is removed in aklylene glycol,
X-：The group for the alkylsulfonate ion base that carbon number selected from chlorion base, high chloro acid ion's base and alkyl is 1~4；
Chemical formula 2：
R4CONHR5-
In chemical formula 2,
R4：The aliphatic alkyl of carbon number 7~15,
R5：The alkylidene of carbon number 1~5；
Chemical formula 3：
In chemical formula 3,
A：The alkylidene of carbon number 2~4,
m：1~10 integer.
2. synthetic resin conductive agent as described in claim 1, wherein the mass ratio of quaternary ammonium salt/diol compound is 99.9/
0.1~80/20.
3. synthetic resin conductive agent as claimed in claim 1 or 2, wherein X-For high chloro acid ion's base.
4. synthetic resin conductive agent according to any one of claims 1 to 3, wherein R1For the aliphatic of carbon number 12~14
Alkyl, R4For the aliphatic alkyl of carbon number 11~13.
5. synthetic resin conductive agent as described in any one of claims 1 to 4, wherein quaternary ammonium salt is (R1For carbon number 8~16
Aliphatic alkyl when chemical formula 1 shown in quaternary ammonium salt)/(R1Shown in the chemical formula 1 shown in chemical formula 2 when organic group
Quaternary ammonium salt) be 80/20~20/80 mass ratio mixture.
6. such as synthetic resin conductive agent according to any one of claims 1 to 5, wherein diol compound is ethylene glycol.
7. such as synthetic resin conductive agent according to any one of claims 1 to 6, it to be used for polyvinyl chloride resin.
8. a kind of conductive resin composition, which is characterized in that relative to 100 mass parts of polyvinyl chloride resin, contain plasticising
15~60 mass parts of agent, 50~500 mass parts of calcium carbonate and synthetic resin according to any one of claims 1 to 7 are conductive
5~30 mass parts of agent,
The plasticizer is selected from phthalic acid ester system plasticizer, aliphatic dicarboxylic acid ester system's plasticizer and trimellitic acid ester system
At least one of plasticizer.
9. conductive resin composition as claimed in claim 8, wherein saturated fat of the calcium carbonate containing useful carbon number 12~22
The fatty acid surface that acid is surface-treated handles calcium carbonate.
10. conductive resin composition as claimed in claim 9, wherein calcium carbonate is the saturated fat with carbon number 12~22
Fatty acid surface processing calcium carbonate/untreated calcium carbonate that acid is surface-treated is the mixed of 80/20~20/80 mass ratio
Close object.
11. the conductive resin composition as described in claim 9 or 10, wherein fatty acid surface processing calcium carbonate is to use carbon
The fatty acid surface that the saturated fatty acid of number 16~18 is surface-treated handles calcium carbonate.
12. a kind of electrically plank, which is characterized in that use the electroconductive resin described in any one of claim 8~11
Composition and molding that the thickness that shapes is 1~3mm.
13. a kind of lamination electrically plank is 2 layers or more, which is characterized in that surface layer is using in claim 8~11
Any one of them conductive resin composition and electrically plank that the thickness that shapes is 0.5~1.5mm.
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| JP2017089279A JP6870848B2 (en) | 2017-04-28 | 2017-04-28 | Conductive agents for synthetic resins, conductive resin compositions and conductive flooring materials |
| JP2017-089279 | 2017-04-28 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115003746A (en) * | 2020-01-24 | 2022-09-02 | 株式会社Tbm | Biodegradable resin composition and molded article |
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| JP7232149B2 (en) * | 2019-08-02 | 2023-03-02 | 花王株式会社 | Polyurethane composition |
| CN117836366A (en) * | 2021-09-30 | 2024-04-05 | 日本瑞翁株式会社 | Vinyl chloride resin composition, vinyl chloride resin molded body, and laminate |
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Also Published As
| Publication number | Publication date |
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| TWI762625B (en) | 2022-05-01 |
| JP2018188493A (en) | 2018-11-29 |
| CN108806827B (en) | 2021-02-26 |
| TW201841877A (en) | 2018-12-01 |
| JP6870848B2 (en) | 2021-05-12 |
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