JPH01113473A - Coating composition containing carbon black - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in long-term storage stability and can give a coating excellent in antistatic property, lubricity, etc., by mixing carbon black treated with poly(oxazoline) and/or its modified product 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 at 0-400 deg.C with poly(oxazoline) obtained by using, as principal components, at least one 2-oxazoline selected from among 2-ethyl-2-oxazoline, 2-phenyl-2- oxazoline and 2-cyclohexyl-2-oxazoline and/or its modified product in an amount corresponding to a component (a) to component (b) ratio of 100/1-1000 to obtain component A comprising component (a) surface-treated with component (b). Component A is mixed with a binder (B) selected from among a thermoplastic resin, a thermosetting resin and 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 100 pts.wt. component (B) and, optionally, a solvent (C).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to carbon black-containing coating compositions. More specifically, the binder 0) carden plastic is not uniformly dispersed in the solution, and the binder has excellent affinity with the carin black, which makes it suitable for use with glass moldings such as films and fibers, and metals. When applied to the surface,
The present invention relates to a carton black-containing coating composition that provides a coating that has stable antistatic properties and uniform coloring properties, and is also excellent in abrasion resistance, heat resistance, blocking resistance, slipperiness, etc.

[Conventional technology]

It has traditionally been used in binder solutions to impart antistatic properties, coloring properties, abrasion resistance, heat resistance, blocking resistance, lubricity, etc. to the surfaces of plastic molded products such as films and fibers, and metals. A coating composition containing selected inorganic or organic fillers is applied. Among them, car as a filler? Coating compositions containing carbon black (hereinafter referred to as CB) have excellent antistatic properties, so there is great potential demand for them. Due to poor affinity, CB may precipitate during storage of the solution. It has the disadvantage that it cannot stably obtain properties such as hardness, blocking resistance, and lubricity.

Regarding this problem, JP-A-61-55158 describes a method of using a specific resin as a dispersant, JP-A-52-96.
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 improves the dispersibility of CB in liquid to some extent, it does not improve the dispersion stability during long-term storage, and the latter method does not improve the dispersion stability in long-term storage. 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. In addition, the coating composition obtained by either method is insufficient in antistatic properties, uniform coloration, abrasion resistance, lubricity, etc.

[Means and effects for solving the problem] The present inventors have conducted intensive research in view of the above-mentioned current situation, and have found that CB treated with a specific resin has a good dispersibility in the liquid of the coating composition and a binder. As a result, the coating composition containing the treated CB and binder has long-term storage stability. The present inventors have discovered that a coating with excellent properties can be obtained when the method is carried out, and the present invention has been completed.

That is, the present invention provides C (
The present invention relates to a CB-containing coating composition comprising 1) and a binder (If).

As the CB in the present invention, CBs manufactured by commonly known methods such as the contact method, the 7 Arness method, and the thermal method can be used, but in particular, the CB? Due to its particularly good affinity with the reamer (4), CB can be treated uniformly and with high bonding properties, and coating compositions obtained using the resulting treated CB have excellent durability. This is preferable because it results in an improved product.

In the present invention, the polymer (A
), poly(oxazoline) (a) is the following - maximum (in the formula, R1, R2, R5, R4, R5 each independently represents hydrogen, halogen, alkyl, aralkyl, phenyl, substituted phenyl) ) is the substitution 2-
It is a homopolymer or copolymer of oxazoline, and is easily available because it is a 2-substituted-2-oxazoline (in the formula R2==R
3: A homopolymer or copolymer of R'=R5=H).

, specific examples of flJ (oxazoline) (a) include poly(2-oxazoline), poly(2-methyl-2-oxazoline), poly(2-ethyl-2-oxazoline), poly(2-innorovir-2- oxazoline), poly(2
-cyclohexyl-2-oxazoline), or poly(2
-phenyl-2-oxazoline), etc., 2
-Copolymer of ethyl-2-oxazoline and 2-phenyl-2-oxazoline, copolymer of 2-ethyl-2''-oxazoline and 2-cyclohexyl-2-oxazoline, 2- Copolymer of ethidoxazoline and ethyleneimine 3'', copolymer of 2-ethyl-2-oxazoline and propylene oxide, 2-finyl-2
- copolymers of oxazoline and tetrahydrofuran, and the like. Among these, one or more selected from 2-ethyl-2-oxazoline, 2-phenyl-2-oxazoline, and 2-cyclohexyl-2-oxazoline because they are easily available industrially and have excellent treatment effects. Isu (oxazoline) obtained using the 2-oxazoline monomer as a main component is preferred.

In addition, the modified poly(oxazoline) (b) among the polymers in the present invention includes partial hydrolysates of the above-mentioned oxazolines (a), these partial hydrolysates, and alkylenes such as ethylene oxide and propylene oxide. Examples thereof include oxides and/or graft reaction products with alkylene imines such as ethylene imine and propylene imine.

As mentioned above, when obtaining the polymer prisoner in the present invention,
Alkylene imines such as ethyleneimine and propylene imine, alkylene oxides such as ethylene oxide and propylene oxide, etc. may be used as the copolymerization component of 2-oxazoline without departing from the purpose of the present invention. It is preferable to use these alkylene imines and alkylene oxides in an amount of 50 mole or less based on all monomers.

In order to obtain the CB treated in the present invention, a method of stirring and mixing CB and polymer particles, a method of polymerizing 2-oxazoline monomer in the presence of CB, etc. may be used, and specific embodiments thereof include: , for example (1) one or more types of CB and one or more types of 4-rimers),
A method of surface treatment by stirring and mixing at a temperature of 0°C to 400°C, preferably 20°C to 350°C, (2) one or more CBs and one or more polymers (g) in a suitable solvent. 2-oxazoline in the presence of one or more CBs in a suitable solvent. Methods such as ring-opening polymerization of monomers as essential components can be mentioned, but in the present invention, method (1) or (2) is preferable for the following reasons.

That is, according to the method (1) or (2), during the treatment, CB in a secondary agglomerated state is crushed to primary particles or a state close to primary particles, so the obtained CB has a fine and uniform particle size. It is. Furthermore, since the polymer CA) is prepared in advance, it is easy to control the molecular weight, and a particularly high molecular weight polymer (4) can be easily obtained.

As a result, C processed by method (2) or (2)
The coating composition using B has particularly excellent physical properties.

When obtaining the treated CB in the present invention, the ratio of CB to the polymer (A) is not limited, but the surface treatment of the CB is uniformly performed to firmly bond the CB and the polymer (4), and the resulting treatment In order to improve the dispersibility of CB in the binder (It), the ratio of CB to the polymer (A) is preferably 100/1 to 100/1000 by weight, preferably in the range of 10015 to 1001500. I really like it.

The binder (n) used in the present invention is a thermoplastic resin, a thermosetting resin, or a reactive resin that can form a film by applying it to a substrate. One type or a mixture of two or more of these can be used. Thermoplastic resins have an average molecular weight of about 10 to 1 million, and specific examples thereof include vinyl chloride polymers, vinyl chloride-based resins such as vinyl chloride-vinylidene chloride copolymers; vinyl acetate polymers, and acetic acid. Vinyl ester resins such as vinyl-ethylene copolymer, vinyl acetate-methyl methacrylate copolymer: (meth)acrylic acid ester hexapolymer, (meth)acrylic acid ester-acrylonitrile copolymer, (meth)acrylic (Meth)acrylic acid ester resins such as acid ester-styrene copolymers: Styrene polymers, styrene-based resins such as styrene-butadiene copolymers, styrene-butadiene-acrylonitrile copolymers; poly(ε-caprolactam) , polyamide resins such as a condensate of adipic acid and hexamethylene diamine; polyester resins such as a condensate of terephthalic acid and ethylene glyconyl, a condensate of adipic acid and ethylene glycol; polyethylene, chlorinated polypropylene, Cal?
Polyolefin resins such as xyl-modified I-lyethylene, polyisobutylene, and polybutadiene; cellulose derivatives such as cellulose acetate, cellulose propionate, and nitrocellulose; and butyral resins.

These commercially available resin stocks may be used as they are, or those synthesized by commonly known methods can be used.

Thermosetting resins or reactive resins may 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. Specifically, for example, phenolic resins such as novolac resins and resol resins; amine resins such as urea resins, melamine resins, and benzoguanamine resins; various alkyd resins; polyester resins; thermosetting acrylic resins; isocyanate group-containing polyesters. , urethane modified resins such as isocyanate group-containing polyethers; polyamine resins; epoxy resins and the like.

The above binder (If) 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. These are used alone or in combination of two or more types, taking into consideration the intended use of the Nobuki composition.

The CB-containing coating composition of the present invention contains CB (1) treated with the above-mentioned specific polymer and a binder ([I), and its forms include solvent-free type, solution type,
It may be of any dispersed type and can be obtained by conventionally known methods. For example, ■ Binder (I
A method of gradually adding and mixing the treated C B (1) to a solution of I) in a suitable solvent (e.g., water, alcohol, acetone, toluene, etc.) in a dispersion of the binder (■). A method of adding and mixing the treated CB (I); (2) A method of adding an appropriate solvent after mixing the binder Q[) and the treated C B (1); (2) A method of curing by an appropriate means. Liquid binder (I
Examples include a method of mixing n and treated C B (1).

The ratio of treated C B (I) and binder ■ in the CB-containing coating composition is not particularly limited, but it is necessary to fully express the characteristics of the CB-containing coating composition while impairing the performance as a coating. Binder (II)
It is preferable that the amount of CB contained in the treated CB (1) is 1 to 300 parts by weight, particularly 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, inorganic fillers such as silica, talc, calcium carbonate, and titanium oxide, Examples include organic fillers such as polyethylene, polytetrafluoroethylene, and amine resin powder.

〔Effect of the invention〕

The CB-containing coating composition of the present invention thus obtained contains the treated CB (1) and the binder (I[), and the treated CB (1) has good dispersibility in the liquid of the coating composition. Due to its excellent affinity with binder (II), it has good long-term storage stability, has stable antistatic properties and uniform coloration when applied to various substrates, and has excellent abrasion resistance. It is possible to provide a coating with excellent heat resistance, anti-blocking properties, slip properties, etc.

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 plastic moldings, metals, wood, paper, and inorganic materials.

[Example] 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. Incidentally, in the examples, "part" indicates a part by weight, and "ch" indicates a percentage by weight.

Reference example 1 Po! with a weight average molecular weight of 200,000! 40 parts of J (2-'ethyl-2-oxazoline) and 20 parts of MA-10OR (manufactured by Mitsubishi Chemical Industries, Ltd.) as CB were heated at 160°C using a Laboplastomill (manufactured by Toyo Seiki Co., Ltd.) at 100°C. Example 2 Poly(2-ethyl-2-oxazoline) and poly(2-cyclohexyl) having a weight average molecular weight of 80,000 Reference Example 3 60 parts of 2-ethyl-2-oxazoline and 2-phenyl-
40 parts of 2-oxazoline and 30 parts of an oxazoline copolymer (weight average molecular weight 50,000) obtained from Asahi
Poly(2- Dissolve 20 parts of ethyl-2-oxacyly/) in 80 parts of deionized water, and dissolve 1 part of concentrated hydrochloric acid.
．． After adding 8 ml and reacting at a temperature of 100°C for 7 hours, the generated propionic acid was distilled off and diluted with water to obtain 20% of poly(2-ethyl-2-oxazoline) partial hydrolyzate hydrochloride. An aqueous solution was obtained.

A 20% aqueous solution of the above poly(2-ethyl-2-oxazoline) partial hydrolyzate hydrochloride was treated with anion exchange resin Amberlite IRA-410 (manufactured by Organo Co., Ltd.), dried, and pulverized. -ethyl-2-oxazoline) partial hydrolyzate was obtained.

The same procedure as in Reference Example 1 was carried out except that the above poly(2-ethyl-2-oxazoline) partial hydrolyzate was used as the poly(2-ethyl-2-oxazoline) glue. Reference Example 5 5 parts of ethyleneimine was added to $50 parts of a 20% aqueous solution of poly(2-ethyl-2-oxazoline) partial hydrolyzate hydrochloride obtained in Reference Example 4 at a temperature of 80°C. After reacting for a period of time, the mixture was dried and pulverized to obtain an ethyleneimine grafted product of poly(2-ethyl-2-oxazoline).

25 parts of the ethyleneimine grafted product of the above poly(2-ethyl-2-oxazoline) and CB! - MA-60
Example 1
~5. Comparative Example 1 A saturated polyester resin (trade name: Pylon) was mixed in the formulation shown in Table 1 to obtain CB-containing coating compositions for the present invention and for comparison.

20/10/10), the viscosity was 16-17 seconds (
Ford Kaf≠4) black paint was sprayed on 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) K is shown.

The test method is as follows.

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

○：Uniform ×: Uneven or glossy Gloss: Gloss was measured at 60'.

Adhesion = 1! The breadth of the width was cut into 100 squares, and the remaining state of the coating film when it was rapidly peeled off after being crimped with Selchive was evaluated using the 10 point scale.

10 points: 100 remaining, 9 points: 99-90 remaining, ---
--- ・The coefficient of friction is the coefficient of kinetic friction (3,3af
/I・Shuntoki) μ was measured.

Antistatic property: Measure the surface electrical resistance.Abrasion resistance: Using a Gakushin dyeing abrasion toughness tester, JIS, -L-108
According to the 445R method, the wear condition after 100 reciprocations was visually evaluated. was evaluated with a grain of salt.

(Table 1) Mixture (Me 2) Test results It turns out that it is excellent.

Example 6, Comparative Example 2 Vinyl chloride-vinyl acetate copolymer (trade name: 400X-11OA.

Nippon Zeon Co., Ltd.), polyurethane (product name: 2,/
CB was mixed in the MEK solution of Run 2301 (manufactured by Nippon Polyurethane Co., Ltd.) and polyisocyanate (trade name: Coronet L% (manufactured by Nippon Polyurethane Co., Ltd.)) in the proportion shown in Table 3, and used for the present invention and comparison. A CB-containing coating composition was obtained.

The obtained CB-containing coating composition was applied to a polyethylene 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, lubricity, abrasion resistance, etc.

Examples 7 to 9, Comparative Example 3 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 (K) to obtain CB-containing coating compositions for the present invention and comparison.

The resulting CB-containing coating composition was applied to a polished mild steel plate to a dry film thickness of 3.
It was coated so as to have a thickness of 0μ and dried to obtain a test piece. The test results are shown in (Table 4).

(Rin 4) $ 2.4,7.9-tetramethyl-5-decyne-4,
7-Diol 8 Manufactured by Shin Kagaku Kogyo Co., Ltd. (Table 4) As is clear from the results, the CB-containing coating composition of the present invention has good dispersibility of CB even in an aqueous medium, and the coating film has uniform coloration. It can be seen that the material has excellent properties such as light adhesion and corrosion resistance.

Claims (1)

[Claims] 1. Contains carbon black (I) and binder (II) treated with one or more of poly(oxazoline) (a) and/or modified poly(oxazoline) (b) A carbon black-containing coating composition. 2. The treated carbon black is mixed with carbon black and one or more of poly(oxazoline) (a) and/or modified poly(oxazoline) (b) at 0°C to 40°C.
The carbon black-containing coating composition according to claim 1, which is obtained by stirring and mixing at a temperature of 0°C. 3. Poly(oxazoline) (a) is 2-ethyl-2-oxazoline, 2-phenyl-2-oxazoline and 2-
The carbon black-containing coating composition according to claim 1, which is obtained by using as a main component one or more 2-oxazoline monomers selected from cyclohexyl-2-oxazoline. 4. Poly(oxazoline) modified product (b) is 2-ethyl-
A modified product of poly(oxazoline) (a) obtained using as a main component one or more 2-oxazoline monomers selected from 2-oxazoline, 2-phenyl-2-oxazoline and 2-cyclohexyl-2-oxazoline. A carbon black-containing coating composition according to claim 1.