JP4611665B2 - Paint composition - Google Patents

Description

  The present invention relates to a coating composition having a function of preventing contamination.

  Polyurethane resins are excellent in strength, abrasion resistance, adhesion and the like, and are widely used as various coating resins. The excellent physical properties of these polyurethane resins are produced by the strong cohesive strength of urethane bonds with hydrogen bonding properties, but on the other hand, the highly polar urethane bonds are hydrophilic and oleophilic, which makes it easy for contaminants to adhere and prevent contamination. There is a disadvantage that it is inferior.

  In order to improve the above drawbacks, a polyurethane resin in which a polysiloxane segment is introduced into a urethane resin skeleton has been devised (for example, Patent Documents 1 and 2). However, although these polyurethane resins impart water repellency to the coating film and improve the anti-staining function, they do not impart oil repellency, so they are vulnerable to oil stains and have insufficient performance as a resin for stain-resistant paints. A fluorine-based compound is known as a representative material exhibiting oil repellency on the surface. In order to impart oil repellency to the polyurethane resin, a method of adding a fluorine-based additive is conceivable. However, the fluorine component is caused by a problem of compatibility between the polyurethane resin and the fluorine-based additive, or a problem that strength is lowered. It is difficult to increase the content of and sufficient performance cannot be obtained. On the other hand, a method of copolymerizing a fluorine component in a polyurethane skeleton has also been devised (Patent Documents 3 and 4, etc.). However, these methods use a single-terminal diol having a perfluoroalkyl group, which is difficult to produce on an industrial scale, as a raw material, and there is a problem in practical use on an industrial scale.

Japanese Patent Publication No. 7-53789 Japanese Patent Publication No. 7-33427 Japanese Examined Patent Publication No. 43-26518 JP-A 61-252220

  Accordingly, an object of the present invention is to provide a coating composition that solves the above-mentioned problems of the prior art and exhibits water repellency, oil repellency, antifouling property and the like with an inexpensive material and a simple method.

  The above object is achieved by the present invention described below. That is, the present invention is a reaction product of a fluorine-containing compound having an active hydrogen-containing group, a polyisocyanate, and a compound having an active hydrogen-containing group, wherein a perfluoroalkyl group and at least two A coating composition comprising a compound having an active hydrogen-containing group as a film-forming component is provided. In the present invention, the term “perfluoroalkyl group” means both “perfluoroalkyl group” and “perfluoroalkenyl group”.

In the coating composition of the present invention, the film forming component is preferably a compound represented by the following general formula (1).

In the coating composition of the present invention, the fluorine-containing compound having an active hydrogen-containing group is preferably at least one selected from the following compound group.

  In the coating composition of the present invention, the film forming component has a number average molecular weight of 500 to 20,000; the film forming component is introduced from the Rf group of the fluorine-containing compound having an active hydrogen-containing group. The film-forming component contains 1 to 75% by mass of a polysiloxane segment derived from a polysiloxane compound having at least one active hydrogen-containing group; It is preferable to contain a curing agent such as

  ADVANTAGE OF THE INVENTION According to this invention, the coating composition which shows water repellency, oil repellency, and antifouling property with an inexpensive material and a simple method can be provided.

Next, the present invention will be described in more detail with reference to preferred embodiments. The coating composition of the present invention is characterized by a film-forming component contained in the coating composition. The film-forming component used in the present invention (hereinafter sometimes referred to as “the film-forming component of the present invention”) can be produced, for example, by the following steps.
(1) First, a polyisocyanate and a fluorine-containing compound having an active hydrogen-containing group are reacted in a group ratio in which one or more isocyanate groups are excess in a molecule of the product, preferably in the range of 2 to 3 To obtain reaction product A.
(2) A compound having at least two active hydrogen-containing groups (for example, a polyhydric alcohol) is added to the obtained reaction product A in an unreacted active hydrogen in one molecule of the reaction product B obtained by the reaction. The reaction is performed at a group ratio of at least 2, preferably 3 to 10, containing groups.
The film forming component of the present invention can be produced by the above steps.

  Further, the polysiloxane compound having at least one active hydrogen-containing group in the molecule together with the fluorine-containing compound used in the step (1), the ratio (mol) with the fluorine-containing compound is 0.99: 0.01-0. By adding and reacting at a ratio of .01: 0.99, the polysiloxane segment can be incorporated into the film-forming component, and further functionality can be imparted to the film-forming component.

Examples of the fluorine-containing compound used in the present invention include the following compounds.
(1) Alcohol type

上記のエポキシ化合物はポリオール、ポリアミド、ポリカルボン酸などとの活性水素基含有化合物と反応させて末端水酸基を有するようにして使用する。 (2) Epoxy type

The above epoxy compound is used so as to have a terminal hydroxyl group by reacting with an active hydrogen group-containing compound such as polyol, polyamide or polycarboxylic acid.

(3) Amine type

(4) Carboxylic acid type

  The fluorine-containing compounds having an active hydrogen-containing group listed above are examples of preferable compounds used in the present invention, and are not limited to these examples in the present invention. Accordingly, not only the above-exemplified compounds but also other known compounds that are commercially available and can be obtained from the market can be used in the present invention. Particularly preferred fluorine-containing compounds in the present invention are the alcohol type fluorine compounds exemplified above.

  As the polyisocyanate used in the present invention, any conventionally known polyisocyanate can be used. For example, toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1 are preferable. , 3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanate-diphenyl ether, methylene diisocyanate, 4,4′-methylene bis (phenyl isocyanate), Julylene diisocyanate, 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4,4'-diisocyanate dibenzyl, 1,4-tetramethylene diisocyanate 1,6-tetramethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,5-tetrahydronaphthalene diisocyanate, etc. Is mentioned.

  The reaction between the polyisocyanate and the fluorine-containing compound having an active hydrogen-containing group is carried out in such a ratio that at least one, preferably two or more NCO groups remain in the product after the reaction. Accordingly, polyisocyanates having 3 or more isocyanate groups in the molecule are particularly preferred, and the above polyisocyanate multimers and adducts with other compounds, as well as low molecular weight polyols and polyamines become terminal isocyanates. And urethane prepolymers reacted with. These are exemplified below with structural formulas, but are not limited thereto.

  The reaction between the polyisocyanate and the fluorine-containing compound having an active hydrogen-containing group is carried out in such a ratio that one or more, preferably two to three, isocyanate groups remain in one molecule of the reaction product. If the number of remaining isocyanate groups is less than one, it becomes impossible to introduce active hydrogen-containing groups thereafter, and if too many isocyanate groups are left, the coating film will be formed when gelation or coating is performed in the next step. The problem of becoming brittle arises.

  Moreover, in order to exhibit sufficient stain resistance for the coating film formed from the coating composition of the present invention, the fluorine content based on the Rf group in the film forming component as the final product is 3 to 80 mass. %, Preferably 10 to 50% by mass.

  Furthermore, in another embodiment of the present invention, a film forming component containing a polysiloxane segment derived from a polysiloxane having at least one active hydrogen-containing group in the film forming component is used as the film forming component. be able to. By introducing the polysiloxane segment into the film-forming component, the surface smoothness of the resulting coating film is improved and the dirt removal performance is improved. When the content of the polysiloxane segment is excessively increased, the fluorine content is relatively decreased and the oil repellency of the coating film is decreased. Therefore, the content of the polysiloxane segment in the film forming component is 1 to 75% by mass. The amount is preferably 3 to 20% by mass.

  The polysiloxane compound used in the production of the above-mentioned polysiloxane segment-containing film forming component is a polysiloxane compound having at least one active hydrogen-containing group in the molecule, for example, an amino group, an epoxy group, a hydroxyl group, a mercapto group, a carboxyl group, etc. The preferred compounds include, for example, the following compounds.

(1) Amino-modified polysiloxane

(2) Epoxy-modified polysiloxane

(3) Alcohol-modified polysiloxane

(4) Mercapto-modified polysiloxane

(5) Carboxyl-modified polysiloxane

  The polysiloxane compounds having active hydrogen-containing groups listed above are preferred compounds used in the present invention, and the present invention is not limited to these exemplified compounds. Accordingly, not only the above-exemplified compounds but also any other compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention. Particularly preferred compounds in the present invention are polysiloxane compounds having one hydroxyl group or amino group.

  As a compound having an active hydrogen-containing group that reacts with the remaining unreacted isocyanate group after the reaction between the polyisocyanate and a fluorine-containing compound having an active hydrogen-containing group, and further a polysiloxane compound having an active hydrogen-containing group. Any known compound can be used as long as it has two or more active hydrogen-containing groups (for example, hydroxyl group, amino group, etc.) capable of reacting with an isocyanate group, but two or more in one molecule of the film-forming component. In order to introduce the unreacted active hydrogen-containing group, a trifunctional or higher functional compound is particularly preferable. As the active hydrogen-containing group, a hydroxyl group, an amino group, a thiol group, and a carboxyl group can be used, but a hydroxyl group-containing compound and an amino group-containing compound are more preferable, and the molecular weight of the compound to be used is not particularly limited, A range of 20,000 is preferred. Preferred examples are shown below, but are not particularly limited thereto.

  Examples of the hydroxyl group-containing compound include low-molecular glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol; Polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol; polyester polyols obtained from dibasic acids such as adipic acid, maleic acid, terephthalic acid and glycols; various glycols and polyols Lactone-based polyester polyols obtained by ring-opening polymerization of lactone-based compounds; polycarbonate polyols; polyether poly (polytetramethylene glycol, polyethylene glycol, polypropylene glycol, etc.) Lumpur acids; polyol compounds such as silicone polyols having a siloxane bond in the molecule.

  Examples of the amino group-containing compound include aliphatic diamine compounds such as methylene diamine, ethylene diamine, trimethylene diamine, hexamethylene diamine, and octamethylene diamine; diethylene triamine, dipropylene triamine, triethylene tetramine, and tetraethylene pentamine. Aliphatic polyvalent amine: phenylenediamine, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 4,4′-methylenebis (phenylamine), 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl Aromatic diamine compounds such as sulfone; cycloaliphatic diamine compounds such as cyclopentadiamine and cyclohexyldiamine; polyoxypropylene ether triamine, polyoxytetramethylene ether triamine What polyamine compounds and the like.

  Further, a compound containing a hydroxyl group and an amino group can also be used as a preferred compound, for example, amino alcohols such as diethanolamine, dipropanolamine, dihexanolamine, 1-aminopropane glycol, diethanolaminomethylamine, diethanolaminoethylamine, diethanolpropylamine And the like.

As an example of the film forming component of the present invention, the film forming component when a polyisocyanate compound having three isocyanate groups is used as the polyisocyanate compound can be represented by the following general formula (2).

  The film-forming component of the present invention may be produced in a solvent or without a solvent, but industrially, a solution obtained by producing in an organic solvent can be used as a coating composition as it is. Therefore, it is advantageous. As the solvent, any of an organic solvent inert to the reaction raw material and the product can be used, and preferable examples thereof are methyl ethyl ketone, methyl-n-propyl ketone, methyl isobutyl ketone, diethyl ketone, methyl formate, formic acid. Examples include ethyl, propyl formate, methyl acetate, ethyl acetate, butyl acetate, acetone, cyclohexanone, tetrahydrofuran, dioxane, toluene, xylene, dimethylformamide, dimethyl sulfoxide, perchloroethylene, trichloroethylene, methyl cellosolve, butyl cellosolve, cellosolve acetate, etc. .

The film-forming component obtained as described above has a perfluoroalkyl group and at least two active hydrogen-containing groups in the same molecule. By reacting the film-forming component with a crosslinking agent or a curing agent, A strong coating film can be formed. Various crosslinking agents or curing agents that can be used can be used, but polyisocyanates are preferred, and non-yellowing discoloration isocyanates such as hexamethylene diisocyanate and isophorone diisocyanate and their adducts are particularly useful. These block bodies can also be suitably used. These crosslinking agents or curing agents may be added to the coating composition of the present invention from the beginning, but are preferably added when the coating composition is used. The amount of the crosslinking agent or curing agent used is preferably such that the ratio of NCO / OH (or NH ₂ ) = 1.0 to 1.5 with respect to the active hydrogen-containing group of the film forming component.

  The film-forming component used in the present invention can be produced without using a catalyst or the like, but the reaction can be promoted and produced by using a known catalyst regardless of metal or amine.

  The film-forming component obtained as described above may be used in a blend with other resins. In this case, as the resin to be blended, polyurethane elastomer, polyester elastomer, polyamide elastomer, styrene elastomer (SBS, SEBS) , Maleic acid-modified SEBS, etc.), olefin elastomers (EPR, EPDM, etc.), styrene resins (PS, HIPS, AS, ABS, AES, etc.), chlorine resins (PVC, chlorine polyethylene, etc.), olefin resins ( PE, PP, EVA, etc.), ester resins, amide resins and the like.

  The amount of the other resin added when the film-forming component is blended with another resin is preferably on a mass basis as a ratio of the film-forming component of the present invention in the total solid content in the paint. It is 5 to 95%, particularly preferably 30 to 70%.

The coating composition of the present invention essentially comprises the above film-forming component and a solvent that dissolves the film-forming component. Examples of the solvent that dissolves the film-forming component include the above-mentioned solvents that can be used in the production of the film-forming component. Although the density | concentration in the coating composition of the film forming component of this invention is not specifically limited, Preferably it is about 10-50 mass%. If the concentration is too low, it is difficult to form a coating film having a sufficient thickness, and if the concentration is too high, the coating suitability may be insufficient. The coating composition of the present invention contains a crosslinking agent or a curing agent in addition to the above essential components, a colorant, an antioxidant (such as a hindered phenol, phosphite, and thioether), a light stabilizer (hindered amine). Etc.), ultraviolet absorbers (benzophenone series, benzotriazole series etc.), gas discoloration stabilizers (hydrazine series etc.), hydrolysis inhibitors (carbodiimide etc.), metal deactivators and the like.
As the matting agent, organic fine particles, inorganic fine particles and other additives can be appropriately used. Examples of the organic fine particles and inorganic fine particles include silica components, silicone resin fine particles, fluororesin fine particles, acrylic resin fine particles, urethane resin fine particles, and polyethylene resin fine particles.

  The coating composition of the present invention has water repellency, oil repellency, antifouling function, abrasion resistance, impact resistance, hydrolysis resistance, light resistance, heat resistance, yellowing resistance, cold resistance, non-tackiness, Because it can form a coating film with excellent solvent resistance, chemical resistance, mechanical strength, flexibility, and adhesion, it can be used for vehicle paints, building material paints, electronic material paints, and pollution prevention. It is useful as paints for sports goods such as films and sheets, wallpaper materials, artificial leather, synthetic leather, textile treatment agents, inks, golf balls, and various molded products.

EXAMPLES Next, although an Example , a reference example, and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to these Examples. In the following examples, “parts” and “%” are based on mass unless otherwise specified.

Reference example 1
In a reaction vessel equipped with a stirrer, 100 parts of Duranate P301-75E (Asahi Kasei Chemicals Polyisocyanate, NCO content 12.5%, non-volatile content 75%), 47.1 parts of 2- (perfluorooctyl) ethanol, dibutyltin dilaurate 0.005 part, 74.4 parts of ethyl acetate and 49.4 parts of dimethylformamide were added and reacted for 5 hours while stirring at a reaction temperature of 80 ° C. After measuring the isocyanate group concentration in the reaction solution (measuring method: JIS K-1603) and confirming that the reaction between polyisocyanate and 2- (perfluorooctyl) ethanol has completely proceeded, trimethylolpropane 26. 6 parts were added and reacted at a temperature of 80 ° C. for 2 hours.

All of the isocyanate groups to confirm that lost by the reaction by infrared absorption spectrum measurement was obtained paint composition (A-1). When the molecular weight of the film-forming component in the obtained coating composition was measured, it was a number average molecular weight of 1,510. When the hydroxyl value was measured in a state where the solvent in the composition was completely volatilized and removed, 153.0 mg KOH / g. In addition, molecular weight is a polystyrene conversion value (GPC apparatus: Tosoh Co., Ltd. HPLC8020, column: TSKgel G2000H _XL ) by GPC measurement, and the hydroxyl value measurement was measured according to JIS-K0070.

  To 100 parts of the resulting coating composition (A-1), 37 parts of Duranate 21S-75E (Asahi Kasei Chemicals polyisocyanate, non-volatile content 75%, NCO content 15.5%) was added as a curing agent. The coating composition (B-1) was obtained by adjusting the solid content to 20%. This was coated on a polyethylene terephthalate (hereinafter referred to as PET) film so that the dried film had a thickness of 10 μm, dried in an oven at 120 ° C. for 5 minutes, and then left in a 50 ° C. oven for 48 hours to be completely cured. The coating film (C-1) was created.

Example 2
In a reaction vessel equipped with a stirrer, 100 parts of Duranate P301-75E (Asahi Kasei Chemicals polyisocyanate, NCO content 12.5%, non-volatile content 75%), 44.8 parts of 2- (perfluorooctyl) ethanol, one end type Carbinol-modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., average molecular weight 2,700) 13.2 parts, 0.005 part of dibutyltin dilaurate, 79.8 parts of ethyl acetate and 54.8 parts of dimethylformamide were added at 80 ° C. The reaction was allowed to proceed for 5 hours with stirring at the reaction temperature. Next, 26.6 parts of trimethylolpropane was added and reacted at 80 ° C. for 2 hours to obtain a coating composition (A-2) of the present invention. Incidentally, progress of the reaction was ascertained in the same manner as in Reference Example 1, in the same manner as in Reference Example 1, where the molecular weight and hydroxyl value of the resulting film-forming component was measured, the number average molecular weight of 2,200, a hydroxyl value Was 142.0 mgKOH / g.

  To 100 parts of the resulting coating composition (A-2), 35 parts of Duranate 21S-75E (Asahi Kasei Chemicals polyisocyanate, NCO content 15.5%) is added as a curing agent, and the total solid content is 20% with ethyl acetate. Thus, a coating composition (B-2) was obtained. This was coated on a PET film so that the dry film had a thickness of 10 μm, dried in an oven at 120 ° C. for 5 minutes, and then allowed to stand in a 50 ° C. oven for 48 hours to be completely cured. )created.

Example 3
In a reaction vessel equipped with a stirrer, Duranate 24A-100 (polyisocyanate manufactured by Asahi Kasei Chemicals Corporation, NCO content 23.1%, nonvolatile content 100%) 100 parts, 2- (perfluorooctyl) ethanol 78.4 parts, one-end type Carbinol-modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., average molecular weight 2,700) 49.0 parts, 0.005 part of dibutyltin dilaurate, 194.3 parts of ethyl acetate and 194.3 parts of dimethylformamide were added at 80 ° C. The reaction was allowed to proceed for 5 hours with stirring at the reaction temperature. Next, 161.2 parts of polyoxypropylene triamine (manufactured by Sun Techno Chemical Co., Ltd., average molecular weight 440) was added and reacted at 80 ° C. for 30 minutes to obtain a coating composition (A-3) of the present invention. Incidentally, progress of the reaction was ascertained in the same manner as in Reference Example 1, in the same manner as in Reference Example 1, the number-average molecular weight 2,740 was measured molecular weight of the film forming component, by titration with hydrochloric acid while in solution all The amine equivalent was measured and found to be 0.94 meq / g.

  To 100 parts of the resulting coating composition (A-3), 42 parts of Duranate 17B-60PX (block isocyanate manufactured by Asahi Kasei Chemicals Co., Ltd., effective NCO content 9.5%) is added as a curing agent, and the total solid content is 20 with ethyl acetate. % To obtain a coating composition (B-3). This was coated on a PET film so that the dry film had a thickness of 10 μm and left in an oven at 130 ° C. for 90 minutes to prepare a coating film (C-3).

Reference example 4
167 parts of Resamine ME-3612LP (a polyurethane resin solution manufactured by Dainichi Seika Kogyo Co., Ltd., non-volatile content: 30%) with 100 parts of the coating composition (A-1) obtained in Reference Example 1, Duranate as a curing agent 24 A-100 (Asahi Kasei Chemicals polyisocyanate, NCO content 23.5%) 24 parts was added, and the total solid content was adjusted to 20% with DMF to obtain a coating composition (B-4). This was coated on a PET film so that the dry film had a thickness of 10 μm, and left in an oven at 130 ° C. for 90 minutes to prepare a coating film (C-4).

Comparative Example 1
100 parts of Rezamin ME-3612LP (polyurethane resin solution manufactured by Dainichi Seika Kogyo Co., Ltd., nonvolatile content 30%), Duranate 24A-100 (polyisocyanate manufactured by Asahi Kasei Chemicals Co., Ltd., NCO content 23.5%) as a curing agent 20 Part was added and the coating composition (B-5) was created. This was coated on a PET film so that the dry film had a thickness of 10 μm, dried in an oven at 120 ° C. for 5 minutes, then left in a 50 ° C. oven for 48 hours to completely cure, and the coating film (C-5 )created.

Comparative Example 2
Resamine ME-3612LP (polyurethane resin solution manufactured by Dainichi Seika Kogyo Co., Ltd., 30% nonvolatile content) in 200 parts fluoroolefin-vinyl ether resin solution (solid content 60%, hydroxyl value 24 mgKOH / g, manufactured by Asahi Glass) 7.8 parts of Duranate 24A-100 (Asahi Kasei Chemicals Polyisocyanate, NCO content 23.5%) was added as a curing agent to prepare a coating composition (B-6). This was coated on a PET film so that the dried film had a thickness of 10 μm, dried in an oven at 120 ° C. for 5 minutes, then left in a 50 ° C. oven for 48 hours to completely cure, and the coating film (C-6 )created.

Comparative Example 3
Add 100 parts of polycarbonate diol having a molecular weight of 2,000, 12.5 parts of 1,4-butanediol and 20 parts of both-end carbinol-modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., average molecular weight 3,200) to obtain a solid content. Dimethylformamide was added and dissolved uniformly so as to be 35%. 4,4′-methylenebis (phenylisocyanate) was added in an amount such that the NCO / OH group was 1.0 and reacted at a temperature of 80 ° C. until a predetermined viscosity was reached. The obtained solution was applied onto a PET film so that the dry film had a thickness of 10 μm and dried in an oven at 120 ° C. for 5 minutes to prepare a coating film (C-7).

Table 1 shows the results obtained by measuring the surface characteristics of the coating films (C-1 to C-7) prepared in Examples 2 and 3, Reference Examples 1 and 4 and Comparative Examples 1 to 3. Moreover, the test of each item was done with the following method.

<Contact angle>
Measurement was carried out at 20 ° C. using a contact angle meter CA-A type manufactured by Kyowa Interface Science Co., Ltd. <Glossy>
Using a digital variable angle gloss meter UGV-5D manufactured by Suga Test Instruments Co., Ltd., the gloss value at 60 ° -60 ° (incident angle-light receiving angle) was measured.

<Contamination resistance>
Each contaminant was dropped on the coating film and allowed to stand at room temperature (20 ° C.) for 18 hours. The contaminant was rubbed off with a dry cloth, and the surface contamination was visually determined.
Judgment criteria A: No trace is left (no force is required for wiping).
○: No trace remains (a little force is required when wiping).
Δ: A trace remains.
X: A trace remains completely.
Contaminant Coffee: Made by dissolving 10 g of Nescafe Gold Blend in 100 ml of water.
Soy sauce: Kikkoman Uses deep mouth soy sauce.
Water-based pen: PILOT black oil-based pen: Magic ink 500

  As described above, the coating composition of the present invention exhibits water and oil repellency due to the surface characteristics of the Rf group, and exhibits superior stain resistance compared to conventional polyurethane coatings. Furthermore, the coating composition of the present invention can be produced by a simple method and is very useful industrially.

Claims (9)

A fluorine-containing compound having an active hydrogen-containing group and a perfluoroalkyl group;
Polyisocyanate,
A coating composition containing, as a film-forming component, a reaction product with a compound having an active hydrogen-containing group,
The coating composition, wherein the film-forming component is a compound represented by the following general formula (1):
General formula (1)

[In the formula, a, b, c and d each represent a number in the range of 1 to 10 (where b × c = 2.0 or more,
Rf represents a perfluoroalkyl group,
X is an alkylene group of C ₁ -C _6, arylene group,

Y represents —O—, —NR ₀ — (R ₀ represents H or an alkyl group having 1 to 6 carbon atoms),
Z represents an active hydrogen-containing group,
R ₁ represents a polyisocyanate residue,
R ₂ and R ₃ represent an organic group,
W represents an organic group which may have a Si atom as a bonding group therein, but does not represent a group —R ₂ — (R ₃ —Z) _b or Rf—X—Y—. . The coating composition according to claim 1, wherein the fluorine-containing compound is at least one selected from the following compound group.

The coating composition according to claim 1 or 2 , wherein the polyisocyanate is at least one selected from the following compound group.

Wherein the general formula Z comprises an active hydrogen-containing group represented by (1) the group _{-R 2 - (R 3 -Z)} b comprises a compound having an active hydrogen-containing group, a reactive residue of an isocyanate group ,
Compound having the active hydrogen-containing group, glycols, polyhydric alcohols, dibasic acids and glycols and polyester polyols obtained from lactones system obtained by a lactone compound by ring-opening polymerization in glycols and polyols Polyester polyols, polycarbonate polyols, polyether polyols, silicone polyols having a siloxane bond in the molecule, aliphatic diamine compounds, aliphatic polyvalent amines, aromatic diamine compounds, alicyclic diamine compounds, polyamine compounds, The coating composition according to any one of claims 1 to 3, wherein the coating composition is selected from the group consisting of amino alcohols.   The coating composition according to claim 1, wherein the film-forming component has a number average molecular weight of 500 to 20,000.   The coating composition according to claim 1, wherein the film-forming component contains 3 to 80% by mass of fluorine introduced from the Rf group of the fluorine-containing compound having an active hydrogen-containing group.   The coating composition according to claim 1, wherein the film-forming component contains 1 to 75% by mass of a polysiloxane segment derived from a polysiloxane compound having at least one active hydrogen-containing group.   Furthermore, the coating composition of Claim 1 containing a hardening | curing agent. The coating composition according to claim 8 , wherein the curing agent is a polyisocyanate.