JPH01113472A - Coating composition containing carbon black - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in longterm storage stability and can give a coating excellent in antistatic property, evenness of coloration, abrasion resistance, heat resistance, etc., by mixing carbon black treated with a (modified) polyamine with a binder. CONSTITUTION:Carbon black (a) having a functional group such as -COOH, -OH or a group of the formula on the surface is mixed under agitation with a (modified) polyamine (b) of an MW >=200, having a polyalkylenepolyamine moiety [e.g., (modified) polyethyleneimine] at a weight ratio of component (a) to component (B) of 100/1-1000 at 0-300 deg.C to obtain component (A) comprising component (a) surface-treated with component (b). Component A is mixed with at least one binder (B) selected from among a thermoplastic resin, a thermosetting resin and a reactive resin each of which has an average MW of 1000-1000000 in such an amount that 1-300 pts.wt. component (a) is present per 100pts.wt. component (B), and, optionally, a solvent (C).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to coating compositions containing Carginbra. In more detail, binder 01) Carbon black is not uniformly dispersed in the solution, and carbon black has excellent affinity with the binder, so it can be used on the surface of plastics such as films, fibers, molded products, metals, etc. A carbon black-containing coating composition which, when applied to a surface, provides a coating that has stable antistatic properties and uniform coloring properties, and also has excellent abrasion resistance, heat resistance, blocking resistance, lubricity, etc. .

[Conventional technology]

Conventionally, plastics such as films and fibers, antistatic properties, coloring properties, abrasion resistance, heat resistance,
A coating composition containing an inorganic or organic filler selected depending on the purpose of use in a binder solution is applied to impart blocking resistance, lubricity, etc. Among them, carbon black (hereinafter referred to as CB) is used as a filler.
Coating compositions containing CB have excellent antistatic properties, so there is a great deal of potential demand for them, but ordinary CB has poor dispersibility in coating compositions and poor affinity with binders. , CB precipitates during storage of the solution, and when the coating composition is applied to the surface of a near stick molded product or metal, it does not achieve the desired antistatic properties, coloring properties, abrasion resistance, heat resistance, and anti-blocking properties. It has the disadvantage that it is not possible to stably obtain softness and slipperiness.

Regarding this problem, JP-A-61-5515-8 describes a method of using a specific resin as a dispersant, and JP-A-52-96 discloses a method using a specific resin as a dispersant.
No. 505 proposes a method using grafted CB obtained by polymerizing a polymerizable monomer in the presence of a specific CB.

[Problem that the invention seeks to solve]

However, although the former of these methods slightly improves the dispersibility of CB in the liquid, it does not improve the dispersion stability during long-term storage, and the latter method produces grafted CB. Despite the complexity and high cost of the process, the efficiency of grafting is low and the dispersibility is not improved as much as expected. Furthermore, the coating composition obtained by either method is insufficient in antistatic properties, uniform coloration, abrasion resistance, lubricity, etc.

[Means and effects for solving the problems] The present inventors have conducted extensive research in view of the above-mentioned current situation, and have found that CB treated with a specific resin has a significant effect on the dispersibility in the liquid of the coating composition and the pine finish. As a result, the coating composition containing the treated CB and binder has long-term storage stability, and can be used on various plastics, molded products, metals, etc. The present inventors have discovered that a coating with excellent properties can be obtained when applied to a surface, leading to the completion of the present invention.

That is, the present invention relates to polyamine 0 and/or polyamine modified products (hereinafter referred to as
The present invention relates to a CB-containing coating composition containing CB (1) and binder 01) treated with one or more of the following:

CB in the present invention refers to CB manufactured by a commonly known method such as a contact method, a 7 Arness method, a thermal method, etc.
Coatings obtained using treated CB have been achieved by the fact that CB can be treated uniformly and with high bonding properties due to its particularly good affinity with CB surface polymers). This is preferred because the composition has improved durability.

In the present invention, polyamine (a) of Tellimer (6) used for surface treatment of CB is a polymer having a molecular weight of 200 or more, preferably 300 or more, and having a polyalkylene borea gun moiety, and is a polymer formed by ring-opening polymerization of an aziridine compound. The homopolymer, copolymer, propolymer, and polypolymer obtained by For example, ■ polyethylene imine and polypropylene imine obtained by homopolymerizing ethylene imine and propylene imine, respectively, ■ codelimer obtained by copolymerizing these aziridine compounds, ■ polycondensation of aliphatic or aromatic dicarboxylic acid and diethylene triamine. mono-amide polyamine obtained by graft polymerization of a polyamide polyamine as a reactant and further an aziridine compound; Among them, polyethyleneimine is preferred because it is inexpensive and industrially available.

In addition, the polyamine modified product (b) of the polymer) refers to a modified product derived from these 4 amines (-), such as a reaction product of a polyamine and an epihalohydrin, a reaction product of a polyamine and an α-olefin oxide, etc. Is the reactant polyamine and aliphatic, and b is an aromatic cal? A part which is a reaction product with phosphoric acid or its anhydride, a part which is a reaction product of a polyamine and a furkyl halide, a part which is a reaction product of a polyamine and a furkyl halide, a part which is a reaction product of a polyamine and an alkylene oxide, among others. For the reasons mentioned above, it is preferable that the polyamine is polyethyleneimine.

In the present invention, the method for obtaining CB treated with polymer) is not particularly limited, and for example, a method of stirring and mixing polymer particles and CB, or a method of synthesizing CB treated with polymer in the presence of CB, etc. good. More specifically, for example, (1) one or more CB and one or more /IJ j-(6
) and a method of surface treatment by stirring and mixing under a temperature condition of θ°C to 300°C, preferably 20 to 250°C, (2)
one or more CB and one or more polymers) in a suitable solvent at a temperature of 0°C to 300°C, preferably 20°C to 250°C.
(3) Ring-opening polymerization of ethyleneimine in the presence of one or more types of CB in a suitable solvent and further modification as necessary. However, in the present invention, it is preferable to use method (2) for the following reasons. Namely, according to method (1) or (2), the secondary agglomeration state is Since the CB is crushed to a state close to primary particles or missing particles, the resulting CB has a fine and uniform particle size.In addition, the CB that has been previously processed into a polymer
A coating composition using the above has particularly excellent physical properties.

When obtaining the treated CB in the present invention, there is no limit to the ratio of CB to the polymer, but the surface treatment of the CB is uniformly performed to firmly bond the CB to the polymer, and the resulting treated CB is The ratio of binder (to CB and the polymer to improve dispersibility with respect to 10) is 1 by weight.
It is preferable to set it as 00/1 to 100/1000, and 10
A range of 075 to 1001500 is more preferable.

The binder ω) in the present invention is a thermoplastic resin, a thermosetting resin, or a reactive resin that can form a film by coating on various substrates, and may be one or both of these resins depending on the application. Mixtures of the above are used. As thermoplastic resins, those having an average molecular weight of about 1,000 to 1,000,000 are preferably used, and specific examples thereof include vinyl chloride polymers, vinyl chloride-based resins such as vinyl chloride-vinylidene chloride copolymers; vinyl acetate. Vinyl ester resins such as polymers, vinyl acetate-ethylene copolymers, vinyl acetate-methyl methacrylate polymers: (meth)acrylic ester clear polymers, (meth)acrylic ester-7crylonitrile copolymers , (meth)acrylic acid ester resin such as (meth)acrylic acid ester-styrene copolymer;
Styrene resins such as styrene polymers, styrene-butadiene copolymers, and styrene-tutadiene-acrylonitrile copolymers; poly(ξ-caglolactam); polyamide resins such as condensates of adipic acid and hexamethylene diamine; terephthal condensate of acid and ethylene glycol,
Polyester resins such as condensates of adipic acid and ethylene glycol; polyethylene, chlorinated polypropylene,
Carmexyl modified - lyethylene, polyisobutylene, ?
Examples include polyolefin resins such as ribtazoene; cellulose acetate, cellulose globionate, cellulose derivatives containing nidotetracellulose; and other butyral resins. These resins may be commercially available products or may be synthesized by commonly known methods.

Thermosetting resins or reactive resins are those that can form a crosslinked structure due to addition reaction, condensation reaction, etc. during the film formation process or after film formation by heating active energy ray irradiation, drying, or other means. For example, 7-enol resins such as resins, resol resins; 7-enol resins such as urea resins, melamine resins, and denzoguanamine resins; various alky resins, and unsaturated polyester resins;
Examples include thermosetting acrylic resins; urethane-modified resins such as isocyanate group-containing polyesters and incyanate group-containing polyethers; polyamine resins;

The above binder) should be selected depending on the adhesion and wettability to the substrate to be coated, the hardness, flexibility, chemical resistance, stain resistance, weather resistance, etc. required of the coating. can be,
They may be used alone or in combination of two or more, taking into consideration the intended use of the coating composition.

The CB-containing coating composition of the present invention is treated with the above-mentioned specific /9 mer and contains CB (I) and a binder ω), and its forms include solvent-free type, lysate type, and dispersion type. It can be obtained by any conventionally known method. For example, (1) a method of gradually adding and mixing treated C B (()) to a solution of binder (()) in a suitable solvent (e.g., water, alcohol, acetone, toluene, etc.); A method of adding and mixing the treated CB (1) to a dispersion of the binder (1), (2) A method of adding an appropriate solvent after mixing the binder (10) and the treated C B (1), (2) A suitable method. Liquid binder Q [
) and the treated C B (i).

The ratio of the treated CB (1) and binder (10) in the CB-containing coating composition is not particularly limited, but it is important to fully express the characteristics of the CB-containing coating composition and to achieve the performance as a coating. Binder so as not to damage it ω)
It is preferable that the amount of CB contained in the treated CB (1) is 1 to 300 parts by weight, or 5 to 100 parts by weight per 100 parts by weight.

In addition to the above-mentioned components, the CB-containing coating composition of the present invention may contain additives conventionally known to coating compositions as long as they do not impair the effect.

Examples of such additives include metal soaps, dispersion aids such as surfactants, film-forming aids, antistatic agents, antifoaming agents, and inorganic fillers such as silica, talc, calcium carbonate, and titanium oxide. , polyethylene, I-retetrafluoroethylene, and amino resin powder.

〔Effect of the invention〕

The carbon black-containing coating composition of the present invention thus obtained contains the treated C B (1) and the binder ω.
), but the treated CB (1) has excellent dispersibility in the liquid of the coating composition and excellent affinity with the binder aI), resulting in good long-term storage stability. 4. To provide a coating that has stable antistatic properties and uniform coloration when applied to various base materials, and has excellent abrasion resistance, heat resistance, blocking resistance, lubricity, etc. Can be done.

Therefore, the CB-containing coating composition of the present invention can be suitably used for coating for the purpose of protecting or modifying the surface of base materials such as various glass molded products, metals, wood, paper, and inorganic materials. .

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples in any way. In addition, parts in the examples indicate parts by weight.

Reference Example 1 20 parts of MA-10OR (manufactured by Mitsubishi Kasei Co., Ltd.) as CB and Epomin ■5P-300Ca, which is monoethylene ion with a molecular weight of 30,000, were added to Ugaplastomill (manufactured by Toyo Seiki Co., Ltd.). (manufactured by Kogyo@) was charged, mixed with the mixture for 20 minutes at a temperature of 100 to 200° C. while stirring, and then cooled and pulverized to obtain a treated CB.

This is referred to as processing CB (1).

Reference Example 2 Instead of polyethyleneimine in Reference Example 1, molecular weight 100
A CB was obtained which was treated in the same manner as in Reference Example 1, except that a thorine-modified resin was used for polyethyleneimine containing 0.00 cationic nitrogen and 5.2 ml/11 of cationic nitrogen. This is referred to as processing CB (2).

Reference Example 3 SP-300 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) 30 parts of polyethyleneimine/ethylene oxide modified resin to which an average of 2 mol of diethylene oxide was added per 1 mol of K nitrogen and CB
30 parts of Asahi ÷ 60 (manufactured by Asahi Cargan Co., Ltd.) was mixed with 30 parts of Asahi ÷ 60 (manufactured by Asahi Cargan Co., Ltd.) using a gelato mill at 100 to 200°C for 20 minutes, then cooled and pulverized to obtain a treated CB.

This is referred to as processing CB (3).

Reference Example 4 A mixture of 10 parts of SP-300, 20 parts of MA-600 (manufactured by Mitsubishi Kasei Corporation) as CB, and 70 parts of pure water was added to 1111 parts.
C treated by wet dispersion using Dyno Mill (C Co., Ltd., manufactured by Shinmaru Enterprises) using glass beads of the same diameter.
An aqueous dispersion of B was obtained. This is referred to as processing CB (4).

Comparative Reference Example I A mixture of 20 parts of MA-600 and 80 parts of pure water as CB was dispersed in the same manner as in Reference Example 4 to obtain an aqueous slurry of untreated CB for comparison. This is referred to as comparison CB (1).

Examples 1-3. Comparative Example 1 Using saturated polyester resin (trade name: Pylon-200, manufactured by Toyobo Co., Ltd.) as a binder ([), treated CB (1) and untreated CB obtained in Reference Example are shown in (Table 1). The formulations were mixed to obtain CB-containing coating compositions of the present invention and for comparison.

20/10/10) to a viscosity of 16-17 seconds (
A black paint of 7 ord cup ÷ 4) was sprayed onto an aluminum plate using a spray gun so that the film thickness after drying was 25 μm, and the test piece was dried at room temperature. The test results (
Table 2) shows the results.

The test method is as follows.

Coloring property: The uniformity of the coloring property of the coating film was visually evaluated.

O: Uniform, ×: Uneven or dull.

Gloss: Gloss was measured at 60°.

Adhesion: After cutting 100 squares in a width of 1.0 mm and pressing cellophane tape on it, it was rapidly peeled off and the remaining state of the coating film was evaluated on a 10-point scale.

10 points: remaining 100;, 9 points: remaining 99-90, ---
--------- Coefficient of friction (3.3 cm)
/s@a) μ was measured.

Antistatic bisurface electrical resistance was measured.

Abrasion resistance: JIS
According to the L-108445R method, the wear state after 100 reciprocations was visually evaluated.

O: No wear;

(Table 1) Formulation (Table 2) As is clear from the test results (Table 2), 1. The present invention has good dispersibility, uniform coloring, excellent adhesion, slipperiness, etc. I understand.

Example 4, Comparative Example 2 Vinyl chloride vinyl acetate copolymer (trade name: 400X-11OA
, manufactured by Nippon Zeon Co., Ltd.), - Refletan (product name: 2).

I-Ran 2301, manufactured by Japan I Refletan Co., Ltd.), terisocyanate (trade name: Coronate L, manufactured by Nippon Polyurethane Co., Ltd.) and OMEK solution KCB were mixed in the formulation shown in (Table 3) K, and CB of the present invention and comparative CB were mixed. A containing coating composition was obtained.

The obtained CB-containing coating composition was coated on an ethylene terephthalate film so that the film thickness after drying was 1.5 μm, and dried to obtain a test piece. The test results are also included (
Table 3) shows the results.

(Table 3) As is clear from the formulation and test results (Table 3), the present invention has good dispersion and
It can be seen that it has excellent antistatic properties, slippery properties, abrasion resistance, etc.

Examples 5 to 8, Comparative Examples 3 to 4 Epoxy ester water-dispersed resin (trade name: Alloron 5
(manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) and CB in the formulation shown in Table 4 to obtain CB-containing coating compositions for the present invention and comparison.

The obtained CB-containing coating 1 product was coated on a polished mild steel plate to a dry film thickness of 30 μm, and dried to obtain a test piece. The test results are shown in Table 4.

-214t7t9-tetramethyl-5-7″syn-4,
7-Diol 8 Manufactured by Shin Kagaku Kogyo (E) As is clear from (Table 4), the CB-containing coating composition of the present invention has good dispersibility of CB even in an aqueous medium, and the coating film can be uniformly colored. It can be seen that it has excellent gloss, adhesion, corrosion resistance, etc.

Claims (1)

[Claims] 1. Polyamine (a) and/or polyamine modified product (
A carbon black-containing coating composition comprising carbon black (I) treated with one or more of b) and a binder (II). 2. The carbon black-containing coating composition according to claim 1, wherein the polyamine (a) is polyethyleneimine. 3. The carbon black-containing coating composition according to claim 1, wherein the modified polyamine (b) is a modified polyethyleneimine.