JPS596255A - Electrically conductive aqueous resin composition - Google Patents

Abstract

PURPOSE:To provide the titled resin compsn. having excellent storage stability and capable of forming an electrically conductive film having excellent gloss and strength, by blending electrically conductive carbon black with an aq. dispersion of a cationic polyurethane. CONSTITUTION:A polyol such as polyethylene adipate polyol is reacted with a diisocyanate such as diphenylmethane diisocyanate. The resultant NCO-terminated prepolymer is reacted with a chain extender having at least one tertiary amino group and at least two zerewitinoff-active hydrogen groups such as N- methyldiethanolamine. Then the reaction product is reacted with a quaternizing agent to form a cationic polyurethane. 5-100pts.wt. electrically conductive carbon black is blended with 100pts.wt. aq. dispersion of said polyurethane.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides conductive aqueous (δ It has drawbacks such as fire danger and deterioration of work environment due to the use of water. Minute 1"1t and (
Since each type of koji is well known, it is easy to think of mixing both of them.
If 1, the combination of the aniline type or the aniline nicked yarn will coagulate even with a single force, or it will become in a state with H<1 (minute agglomeration or thixo-lr-r 1-nick property). In addition, the gloss of the coated object obtained by applying the entire mixture was poor due to 1μ, and the strength of the stone contact was also less than 1 minute. A strong reaction of Q adjacent to A'1 in the field r〒 results in an even lower F.

The purpose of the present invention is to provide a conductive resin composition with extremely excellent stability.

Misfired IJI &: J coating (good gloss L1 when IJ is applied)
It has 9 electric properties which are excellent for coating objects, and this jH7 electric property allows electromagnetic waves,
lη: Shielding effect, anti-static II-effect Water excellent in snow (111
The purpose is to provide 1) 11 liquor fat compositions.
゜Kilight 1 is a conductive material that exhibits excellent contact strength.
111 resin composition.

In fact, the present invention "C" is excellent in production 11 without thickening during mixing during sealing, and generates static electricity on the coated object when applied.
1. The overall purpose is to provide a conductive thin ice 111 resin composition that does not cause electric shock.

The present invention has been made as a result of extensive research and research in order to achieve the objective described in L.
I found that the -1 target was not achieved. However, when using an anionic aqueous dispersion of BORIUREXI, the viscosity thickens slowly during mixing during manufacturing, the coated object is charged with static electricity, and furthermore, the peel strength is low and the adhesion strength is poor. The result was that it was inferior.

The end of the final year J was completed with the discovery of this substance.

In other words, conductive carbon fluff is added to the aqueous dispersion of L-force J-on-li to conductive carbon fluff.
It relates to an aqueous resin composition.

The composition of the present invention can be used for various adhesives or adhesives. It can be used in the field of coating, such as anti-static adhesive for 11 helds, printed circuit interconnection adhesive, radio wave shielding paint, conductive floor adhesive or coating, etc. Useful.

Furthermore, by incorporating the composition of the present invention into an open-cell foam, for example, a soft polyurethane foam, the composition can be used to increase the electrical conductivity.
Polyurethanes with secondary properties such as polyols, diisocyanates, and molecules containing at least one tertiary amino group and 2
Device 1. a chain extender with tzelevitinoff activity and 4
tl) by reacting with a grading agent.

In [A-1], as the polyol No. 11, various polygomer polysubols, polygotyl polyols, and their derivatives can be used. Polyesworupolyuken -
As the acid component, for example, adipic acid, superric acid, sebacic acid, aliphatic dicarboxylic acid having 4 to 20 carbon atoms such as gracilic acid, ralefucuric acid, isophthalic acid, etc.
J brezi glycol, zo[J pyrene glycol, pentyl glycol, 8A 7 tyrene glycol, aliphatic digyl having 1 to 6 carbon atoms, diethylene glycol, schizo τJ birezi glycol, etc. (7) Oehler It is possible to use polyethylene glycols, suberl glycols, N-argyldial alcohols such as N-methyljetanolamine, polyethylene glycols, polyethylene glycols, polycaprolactone polyols, etc. enemy,
Specific examples include polybutylene adipate polyol, polybutylene adibate polyol, adipate polyols of polyurethane "l birecyadibate polyol", delefcuric acid polyol (e.g. Teibosha, 1lfi product name Byron RUX, Byron RV-2 (
+ ()L), polycaprolactone polyol (eg, Daicel Chemical Co., Ltd., product name: Plaxel 212, Zolaxel 220), and snow.

L1 Bo IJ is a specific example of Ushida polyether polyol.
, I xylene glycol, polyethylene glycol
Pyrene polyol, polyol, polyol, etc. can be mentioned.
Toboli A-le (e.g., West Germany, Pai-T, /l/ (
l, Product name Tesmo Fen 2020 E),
Forabtal 1-mboli sub-ruple (e.g., 11 Kibo Tatsu, product name G 1000, G-2000, G-3000, Idemitsu Right Bu Kagaku, 1lfj product name 1) oly b (I R-4
51 (Tr(T), polybentadi 1° emboliol,
Examples include castor-based polyols.

Examples of diisocyanates used for misfires include 1, diphenylmexylisodiane-1-(Ml)I), 1-recipitylisodiane-1-(Ml)I), -1. 'I) I), 1-lysine diinocyanate (To I), Preferred are socyphnate (IPl, )I), hegysomethyleneisocyane-1.(rID+), dicyc[7hexylmethanecyisocyanate (HMDI), and the like.

A part of the inocyanate was mixed with a blocking agent.
Ivy can also be used for historical purposes.

As a chain extender in the chain extension agent 1, a chain extender containing at least one tertiary amine 7 group in the molecule is used.

Examples of compounds having at least one tertiary amine group in the molecule and a tzelevitinoff activity in the molecule in Section 14 include N methyldiec/-71/7E, N
-diyldiethanolamine, N-]] 1:L dirubiperazine, N-phenyldi-r-diethanolamine% = '6
6, which can be mentioned, 11-7 wooden bones:' is 1; other than armor extender K jlJ
A conventional chain extender is also used, and a suitable example is the general formula % (R'& M is a straight chain or V1 branched alkylene group having 2 to 10 carbon atoms; They may be connected by atoms.R2 is a group having 2 to 10 carbon atoms, and is a branched alkylene group or an alicyclic group.A and B are groups that form an aromatic ring. .) It is expressed in 1. Examples include aliphatic diols, aliphatic diamines, aromatic diols, and aromatic diamines.

Preferred examples of aliphatic diols include ethylene glycol, propylene glycol, butramethylene glycol, hexamethylene glycol, neopentyl glycol, diethylene glycol, -dipropylene glycol, etc. Specific examples include ethylenediamine, 1,6-hexamethylenediamine, and inphorondiamine.

Examples of the aromatic diol A include chloride, and examples of the aromatic diamine B include 4I.

In the present invention, at least 1 (7 solid 'tertiary amide groups and 2 probes 1.
- Rekhdinov's candy (L1) The chain extender used in L1 is quaternized in advance with a quaternizing agent, and the chain extender used in L1 is quaternized with a quaternizing agent. By turning it into a quaternary male, the 7. Boliurekun water, 11 min.
The quaternizing agent is attached to the 3° timber frame j
(I) For example, t1 dimethyl sulfate, di-7-thyl sulfate, sialyl/Mi, acid, p2 chemical compound, methyl chloride, iodide, sialyl, [I argyl saponide, Other stories from Besijiruk include: ``Nora, I''' You can bring good luck by using the algylating agent of the god of snow.

In the final completion, each component U1, the objective ♂ water, l'1 force]' IJp can be determined from a wide range depending on the tidal liquid.
However, for example, the chemical power of the ll'i hydrogen group and the NCO group of diisocyanate 1, which are contained in polysubstituted hydrogen groups, is 111. 14. Good pressure<
&:t 0.95~1. It is better to react within the range that results in I. Quaternization in polyurekun, fc7 my y group; l; +J combination U, jlJj 1. 'y ;I? ■
per noma, 01 mm per iii', / 1 or more'' - and -
Preferably.

-4 Tamoto Hikari 1 has the ability to use an inert distillate that does not react with NGO groups, and can be recovered by distillation if necessary. In addition, a known flexun biocatalyst, an aqueous antifoaming agent (e.g. 1
・It is also optional to use λ such as 5M-5512 made of silicon.

-1. Examples of solvents include acetone, methyl ethyl ketone, acetic acid nibble, propionate methyl Other examples include dimethyl porn, amides, dimethyl sulfoxide, etc., and these solvents may be used at any stage of the reaction of the present invention.

The aqueous polycrethane dispersion e of Fudou 111 can be produced by various methods, such as the Fushishot method and the prepolymer method. In the prepolymer method, for example, a polyol and a diisocyanate are reacted to create an NGO-terminated prepolymer, then a chain extender is added and reacted, and when chain extended tMIJ that is not quaternized is used, the following A quaternizing agent is applied to -C1. After cooling the resulting polymer, water is added with vigorous stirring, and the solvent is then distilled off to form a milky white emulsion. In this case, Water may be added while removing the shavings.The prepolymerization reaction is preferably performed at a temperature of approximately 60 to 130°C.Also, the quaternization reaction is preferably performed at a temperature of approximately 40 to 100°C.
A temperature of 1J at °C is suitable.

In Kinoi IJ, fiI et al fr, Taboriurekun Mizui! It is also possible to blend one dispersion with other emulsions. Examples of other emulsions include vinyl acetate/vinyl chloride copolymer emulsion (e.g., Denki Kagaku Kogyo Co., Ltd., trade name Tenriki Techs AC-20), ethylene/u "Hycobolymer emulsion (e.g. Denki Kagaku Kogyo Co., Ltd., trade name Tenriki Tetsu) Tenka E
VA Tex) I can raise snow. Another misfire
Polyurethane aqueous dispersion iCJ:1. , T Goulenediamine, Die J-Lentriamis,...V Zamethylenediamine snow aliphatic polyamine water/M (Ik t
(You can also use Jl.

Conductive purpose of water valve I11. The water-1'l-1 grease-resistant composition is made by interposing a conductive carbon grain in the above-mentioned aqueous water dispersion. Conductive carbon blanks are not limited to cow, q, k, but a wide range of famous ones. ) and acetylene blank ¥7. Carbon blank formulation 111': 1, Tun IIl
Ratio of approximately 5 to 100 parts per 100 parts of polymer, η
r', 1: It is recommended to use approximately 10 to 50 parts, and within this range, excellent results can be obtained in Ii conductivity 1 (6 peaks, 11 J branches, 1 strong resistance, contact I''-T strong bending). When dispersing crushed carbon black, VC&J2 may be added to the aqueous dispersion of crushed polycretane, but after preparing the aqueous dispersion of the crushed carbon blank,
It is better to add t. When preparing this aqueous dispersion of carbon black, it is preferable to use Kachikun Kyokai 411 active agent, Noecho Kyoukai 1111 activator, etc.

Mixing of the aqueous polyurethane solution and carbon black can be carried out using various known stirring devices.
17 Electrolyte aqueous resin emulsion contains known thickeners, preservatives,
Associate colloid agents, such as polyvinylpyrrolidone, polyurethane aqueous solution (BASF, Colafral 850 (1)
, Hydroxyl cellulose, Meglucel
In addition, it is also possible to increase its viscosity and stabilize it during long-term storage.

]17? Since the aqueous resin composition has an excellent dispersion effect of cationic polyurethane or carbon black, it can be easily mixed and dispersed.
As a result, it exhibits extremely stable 41'l. Table 1 ``11'' of coated objects subjected to tII by applying the composition of the present invention
Good gloss and film strength, 11 thoroughly ionic properties
The skin 1IIA, which is obtained by the synergistic action of polycrethane and conductive carbon black, has excellent conductivity.
f1 and does not attract static electricity. In addition, the composition Q of the present invention has excellent adhesive strength and exhibits high peel strength despite V being filled with all inorganic substances. Another advantage is that the non-exploding composition does not thicken and is therefore easy to manufacture, and can also be applied into a cylinder by spraying or the like.

Below, I will give an example of the unexploded search 1 and explain the theory 1. Hereinafter, 1' 1ils indicates a weight of 111 parts.

(]) 1 sheet liquid for conductive I11 carbon blank (A,
) in 90 parts of water and 2 parts of Tsukumin 24P (Kagyo Atlas Co., Ltd., Kadion Kaikyoku 611 Sex Agent), and stirred with a homogenizer. !, C) Add 10 parts kllj5 and stir for 30 minutes. Carbon black if? [A dispersion with excellent storage stability and a UJ of about 10 wt% was prepared.

(2) 3f'l NZ force - bomb blank dispersion (
(So (13)'s blue water 90 r' + (s, Perex o t゛-1' (IE I:,]' Truss Co., anionic interface 21 ■ 1 property agent) 2 + tl (and 10 carbon blacks) A dispersion liquid with a carbon black concentration of about 10 wt% and excellent 1V stability was prepared in the same manner as in Example 1-1.

(3) Manufacture of Kadion l'l polyurethane emulsion (+) 1-1 Manufactured by Kiboriurekun 1) (1)) MDI
75! (c) N-methyldiethanolamine 107 g (d) 1,4-butanediol 5.4 g (e) Dimethyl sulfuric acid 113 g Stirring equipment) 6, #ii 1 counter total, 11 separators equipped with Contin-2-1 nitrogen rod tube (a) and (b) in a bull flask
Add the ingredients and react at 80°C for 1 hour. Next, add 504It of methyl ethyl ketone (MEK), (c) and 0.
d) Add component f) and reflux M E K in nitrogen atmosphere 1:
In the infrared absorption spectrum, NCO (absorption is no longer detected).Then, after cooling to 70°C, (
e Add Tsukibobun and stir for 30 minutes, then add water 3791 and M
When EK'5 is distilled off, solid content is 40 wL%, viscosity is 120
The milky white emulsion (1) at cps/25°C is t(
Example 1-4 and Examples 1-9 of 1-9 conducted by J et al.
An IT1 aqueous lumber composition was obtained. Table 2 shows the properties of the obtained at products.

In Table 1, emulsion (A) is Tenryokutex A.
C20 (nonion type), emulsion (+-1) &
: J Tenka EVA, 7'x (Nonion Quitub),
Gomarjohn (c) Heinbranir I) r-N
(Bayer, Horikurekun Emulsion, Anion Tights), Emulsion (d) Hatisan Resin A-2
50 (Teikoku Kagaku Sangyo, polyacrylic acid-1-thread emulsion, Aniba Tsutaib), carbon blank dispersions (C) and (■)) are SonoL Sono1. Hun S I”
Black 8062 and 8091 (Toniiro Yuusha, Kesochin J blank concentration] Owc% aniline dispersion).

In Table 2, the surface gloss was determined by making a film of 0.05 mm or more on a glass plate and using a gloss meter S manufactured by Toyo Seiki Co., Ltd.
Measured at -60K. In addition, for a dispersion that can produce a good film of gold, the mixture is 1 o or lXVc to 1 part water.
By adding 50 parts, diluting it, and spraying it on a glass plate, it was also possible to make a sympathetic ``2''.

Examples and comparative examples of 1. The composition was applied at a solid content of -r l 50 g/nf (li L
, lh iCA: 'J-T-StellG'fit
ri 'c1) i 111-190 `` C and 111!

? ! The width of the test Fl was 2.5 or +.
,, Island/(” Using the newly manufactured Go!-Graph IM100, 23-C1 R ■ 1 SHE 7 de speed 50 Dragon /
Peeling was carried out at least 180 times under conditions of min. I made a belt-shaped sample 11 with a width of 5 (m) and a length of 30 ('m), and made it with 1ff and 4 mm of polygon.

The results are shown in Table 3. Table 8. Figure 1 shows the amount of carbon blank added to 100 parts of polymer and the amount of peeling. The relationship between the strengths is shown for the case where the cationized polycrethane emulsion of the present invention is used (curve 4iA) and the case where Denka EVA Tex is used (curve B). Strong 1g or stick d) is superior, and Teru Kokichi is Kawaru.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the entire relationship between 111 and peel strength 1y of the carbon blank. (hereinafter "-") Special feature 1;'1 Applicant: Toyo Rubber Co., Ltd.
Immediate patent attorney 1) + 1 Vertical 1 figure □ fo 2 o 30') 0 50 ho 0 reamer - 100 parts] and carbon fiber 7 shi b calories (xk 7.) 389
−

Claims (4)

[Claims] (1) A conductive aqueous resin composition in which conductive 1'1 Horn Silk is blended into Kabuon 1-1 Voliclekne aqueous dispersion. , (2) Kachinic polycrete water 1f1 dispersion,
At least one tertiary amino group in the polyol, diisocyanate 1-13) r-
2. The composition according to claim 1, which is obtained from a chain extender and a quaternizing agent having a non-I'lri property. (3) The composition according to claim 2, wherein the 1-kichintencho agent is quaternized in advance by quaternization. (4) Qrq Box 2 of the claim that after copolymerizing in the 1. tree-spreading agent Kepolycretane, it is then quaternized with a quaternizing agent.
The composition described in Section.