JPS60263949A - Electroconductive paint composition - Google Patents

Abstract

PURPOSE:To obtain an electroconductive paint for covering defects providing superior surface smoothness by constituting with electroconductive powder, polyfunctional (meth)acrylate oligomer, and a compd. having a (meth)acryloxy group and an acidic group. CONSTITUTION:The electroconductive paint is constituted with electroconductive powder, a polyfunctional (meth)acrylate oligomer, and a compd. having a (meth)acryloyloxy group and an acidic group. Further, an electroconductive metal oxide is used for the electroconductive powder which may be used also in the state covering the surface of an insulative pigment. The paint is liquid at ordinary temp. and may contain a thermal or photopolymerization initiator. The oligomer used in this compsn. is fluidous liquid capable of penetrating into pores and filling the pores. Further, the compd. having the (meth)acryloxyloxy group and the acidic group is cured by copolymerizing with the oligomer in the curing stage by the effect of the (meth)acryloyloxy group, and the acidic group has reactivity with the surface of a metal to enhance the adhesive strength.

Description

[Detailed description of the invention] Introduction - Volume 1, November 1, Vol.
Regarding.

Background of the Invention Conventionally, conductive paints have been used to provide electrical conductivity by coating on non-conductive surfaces.

Such conductive paints include powders and P1 fibers of conductive substances such as carbon, aluminum, nickel, copper, gold flakes, acrylic resin, alkyd resin, epoxy resin, phenol, etc. Typical examples include resins, polyester resins, silicone resins, resins with rubber threads, etc. dispersed therein.

The Tt-conducting substances and AI types of resins used vary depending on the application, and are selected taking into consideration the required short-temperature resistance, the material of the substrate to be coated, the color of the paint, cost, etc. .

17 However, conventional conductive materials are used as paints! In No. 0, ζnIW is formed by dispersing a phase diluted with a solvent, then drying the solvent, and curing the resin. That is, in paints, non-volatile components are of the li'jl type. If the non-volatile content is solid, it will naturally lose its fluidity when the solvent evaporates, but the quality of the surface smoothness of the paint will greatly affect the fluidity of the paint.1. ．． Generally speaking, the easier it is to flow, the better the smoothness. - Also, when there are small dents or holes in the object to be coated, the greater the fluidity of the # phase, the more effective it is in filling and smoothing the holes. ′=1〃, even if the nuclear material is a porous substrate, flow! The smoothness improves when I+Il is large. In other words, when a paint with solid non-volatile content diluted with a solvent is applied to a porous base, the solvent penetrates into the base, and the fluidity of the finish is slowly lost, resulting in no smooth finish. 1. Although the purpose of conductive paint is to achieve special effects such as conductivity and property, it also has surface smoothness, for example.
Smoothness is required while imparting conductivity to a defective or porous substrate.'f1. Desired in case of inconvenience.

Problems to be Solved by the Invention The object of the present invention is to break out the defects and obtain a coating material with excellent surface smoothness and properties.

Means for Solving the Problems The present invention provides (8) a barrel, a sex powder, and (B) a multifunctional (meta-functional) powder.
) Acrylate oligomer °-1 (C) It is composed of a conductive coating composition consisting of a compound having a (meth)acryloyloxy group and an acidic group, the conductive powder may be a conductive metal oxide, and the conductive The surface of the insulating pigment may be coated with a metallic oxide. Further, the paint can be liquid at room temperature, the paint can contain a thermal polymerization initiator or a nine-polymerization initiator, and the paint can contain an organic solvent. In order to obtain properties, K should improve the fluidity of the paint, as mentioned above. Therefore, the present invention, first and foremost, (A
) Conductive powder is dispersed in (B) polyfunctional (meth)acrylate oligomer. The polyfunctional acrylate 1 oligomer is C, l-12=c-COO (R, tel" + acryloyl R oxyno, (, j moka CIhfx et al. methacryloyloxy group), - An oligomer having a plurality of (meth)acryloyloxy groups in one molecule that is oxidized in the depletion method is v:) Mura.Hereinafter, the acryloyloxy group will be explained as a representative, but the same applies to the methacryloyloxy group. The difference between the two is that the former has higher reactivity.

Each f111. There are several known types, including epoxy acrylate, polyester acrylate, polyurethane acrylate, and polyether acrylate. In order to obtain fluidity, these are preferably liquid at room temperature [7] However, even if they are not liquid, they can be made liquid by adding other low molecular weight polyfunctional acrylates. Such low molecular weight polyfunctional acrylates include d, (poly)ethylene glycol diacrylate (borifubuD hylene glycol diacrylate, imhenthyl glycol cyacrylate, bunalen glycol = 1-) + diacrylate, -
Examples include xanediolnoacrylate, trimethylolpropane triacrylate, and tetramethylolmethanetetraacrylate.

Since these polyfunctional acrylate oligomers are liquid even without using 69 shavings, they have good fluidity and have seedlings that penetrate well into small holes. Also,
In the case of a solid resin that uses a solvent, the volume decreases greatly due to evaporation of the solvent1-2, and even if the hole is filled, the hole may be re-formed due to shrinkage.
In some cases, it is extremely rare.

Next, regarding the powder used in the present invention, since the purpose is fluidity as a paint, it is better to use a fine powder rather than a fiber-like one. As a color powder, carphone black is suitable (although it is superficial, it is suitable for sewing tables that reduce light colors), tin oxide, antimony oxide, indium oxide, lead oxide, bleached copper, etc. In addition, those containing tin oxide, antimony oxide, and oxidation] 1': For lead, those doped with aluminum, gallium, etc. are used.

In addition, if you want to obtain the properties of a paint as a paint, you can also use an insulating pigment with a 4-electrolic gold oxide on the surface. Examples include titanium oxide coated with tin oxide containing antimony oxide, zinc oxide, calcium carbonate, aluminum oxide, barium sulfate, barium carbonate, etc. 1 and 4 electrically conductive powders do not lose their conductivity. An insulating pigment may be mixed within the range. This is suitable for improving the color tone, dispersibility, coatability, cost, etc. of the paint.

Here, just dispersing conductive powder in (meth)acrylate oligomer is good for materials such as water barrels and paper, but Jingu does not have good adhesion to metals, i.e. Originally, monomers of polyfunctional (meth)acrylate oligomers have very poor adhesion to metals.Therefore, in the present invention, factors b') that improve adhesion are added to each layer. As a result of investigation, it was found that it is good to have an acidic group. Therefore, the present invention is further characterized in that it contains (C) a compound having a (meth)acryloyloxy group and an acidic group.

The (meth)acryloyloxy group is copolymerizable with the polyfunctional (meth)-acrylate oligomer and is intended to be integrated during curing. The acidic group has reactivity with the metal surface and activates the surface of the metal to improve the tightness. 3. The acidic group 1 to 1 is typically a carboxyl group. (
Examples of the compound C) include the following.

(R is Izunemo H or CH3) CI-(z=CR-COOH CH2CH2ligoma-CH2CH20CO◇C00HC
H2=C'R-CO(1-CH2CH20CO-COO
HCH2=CR-C(jo-C)COOHCH2-CR
-COO-CH2O(2CO lido1CH2=CR-C
Ol, j-CH2CH20COCH2CH2COOH, each of which is a single compound, but the present invention depends on the use of (meth)acryloyloxy, l, I;, and I static or radical groups.

The ratio of (C) to (13) is about 1 to 50%,
'i,':' FCli 5~40 X 141EL
f A:s /) t, small 4 E1 has a direct elbow I'
, 1: σ, effective bed or ino) is not formed, and there is a large amount of lL, ′, hardening properties are insufficient in the warehouse. the minimum f within
J shishi 1 good on r3.

(A), depending on the resistivity of the target i% film! 1+eru. If there is a large amount of powder, the strength of the coating film will generally be insufficient, or the surface will be rough due to poor dispersion, so the desired resistivity of the coating film may be affected.
It is a good idea to occupy Naruheku powder within the surrounding area.

To disperse the powder, a conventional method such as a whole mill, a land mill, a round mill, an attritor, or a roll mill hook is used.
) may be dispersed, or (C) may be mixed after (A) is dispersed in (B). If the viscosity of the dispersion is high, a suitable organic solvent can be used. Furthermore, since this paint is originally liquid, only a small amount of organic solvent can be used.
Adding too much liquid has the opposite effect on covering defects 1. A curing method using rc irradiation with ionizing radiation such as an electron beam, in which the dispersion is applied as a paint to the substrate and then hardened. Then, it can be cured as it is. In the case of thermal curing, dimensional or UV curing, an initiator is added which generates radicals by heat or VJ-UV radiation, respectively.

d-cyclohexanone peroxide as a thermal polymerization initiator,
inobutyryl peroxide, penzoyl peroxide,
Parachlorobenzoyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, t-butyl peroxide/benzoate, t-butyl hydroperoxide, lauroyl peroxide, di-t-butino[bar-oxide] cumene hydroperoxide, dicumyl peroxide , azobisisobutyronitrile, etc. Photopolymerization initiators include benzyl, benzophenone, acetophenone,
Benzoin alkyl ethers, alkyl anthraquinones.

Chloranthraquinones, benzanthrone, etc. are used. The amount added is about 1 to 5% based on the resin content.

According to the experimental results, adhesion to Kinzo was better achieved by curing rapidly over a short period of time or slowly over a long period of time. Therefore, heat curing is more preferable.

The physical resistivity of the coating film after curing varies depending on the purpose and conductivity, and if it is to prevent static electricity, it is 106 to 101.
Approximately 30cm 10-1 to 104 for a heating element
Ωem level, 10-2 to 1040c for electrodes
About m is preferable. If low resistance is desired, the content of conductive powder must be increased, but metal powder may also be used.

In addition to the effects of the invention, the above-mentioned conductive paint has good surface smoothness and can fill all four parts of the substrate well. And, 1. has a strong compactness to the /i genus. Therefore, it is effectively used to improve the surface properties of metal-rich materials whose surface is uneven.

Example 1 100 parts (11
(Okibe, hereinafter referred to as 1υ) was prepared. This is a viscous liquid with a viscosity of about 10 pa, s at room temperature. This was mixed with 50 parts of methyl ethyl ketone, 1 υ, and 10 parts of antimony oxide.
In a ball mill, add 200 parts of titanium oxide powder (average particle size 0.4μ) whose surface is coated with tin oxide containing %.
When rlJ+, it was dispersed.

In this dispersion, CH2=C-COO-CH2CH20COCH2CH2
-COOH...(1) 25 parts of CHa and 5.7 parts of benzoyl peroxide were added to prepare a conductive class.

On the other hand, I prepared a 50μ piece of aluminum press sheet as a base, and the surface had numerous scratches about 5μ deep. The coating film (iL) was cured using PA at 140°C for 10 minutes using the above coating material and wire bar.
2μ thick d9. I made a short I and J. The duck beak property with the thread body was 10-00 by the cross-cut method, and it was strong.

, the resistance is 108Ωem, the grain surface roughness is 0.5μ, and the smoothing field is II.

This sheet with squares and blinds can be widely applied to electrophotographic JR photoconductors, electrostatic recording media, lithographic F1/original plates, etc.

However, on the other hand, when compound (1) Th was not added, the adhesion of the number 1 material was examined after curing, and it was O/100, and peeled off at a rate of 8. .

Example 12 Ephoxy acrylate oligomer (trade name: V 550
2. Manufactured by Dainippon Ink, viscosity 4j2-3Pa, liquid of about S) 80 parts, 2-methoxyethanol 40 parts, conductive zinc oxide (part name: Zinc White No. 1, manufactured by Hon Itochemical Sou 3) 2
00 parts Keball mill for 3 hours. After dispersion, 25 parts of the compound CHa (I C0OH, 1 part of 2-ethylanthraquinone,
A paint was prepared by adding 10 parts of methyl ethyl ketone.

This was applied to the same sheet as in Example 1, and irradiated with ultraviolet light for 3 seconds using a 4KWX pressure water scissors lamp to cure it for 10 minutes.
A conductive layer having a thickness of μ was formed. The adhesion was 100/100, the resistivity was 1070, and the maximum surface roughness was 06μ, which were almost the same results as in Example 1.

On the other hand, when compound (2) was not added, the adhesion was examined after curing and found to be O/100.

Patent applicant: Canon Co., Ltd. Agent: Patent attorney Yu Karino

Claims (6)

[Claims] (1) (A) a groove-shaped powder, (B) a polyfunctional (meth)acrylate oligomer, and (C) a compound having a (meth)acryloyl ochre group and an acid +/4 group. conductive paint composition. (2) The conductive component composition according to claim 1m, wherein the conductive powder is a conductive metal oxide. (3) The conductive coating composition according to claim W, wherein the conductive powder is obtained by nucleating a conductive metal oxide on the surface of an insulating pigment. (4) The conductive paint composition according to claim 1, wherein the nonvolatile content of the paint is liquid at room temperature. (5) The conductive monochromatic paint silk composition according to claim 1, wherein the paint contains a thermal polymerization initiator or a photo-11+ polymerization initiator. (6) Claim 1 in which the paint contains a cloth solvent
2# lightning paint composition described in section 2.