JP3150838B2 - One-part curable fluorine-containing resin compound, production method thereof, coating agent and coating method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to various films, coatings,
The present invention relates to a one-part curable fluorine-containing resin compound for providing a coating agent (paint) capable of imparting excellent surface properties to other resin molded articles and inorganic surfaces, a coating agent having the resin compound, and a coating method.

[0002]

2. Description of the Related Art Conventionally, the surfaces of various films, coatings, and other various resin molded products have been required to be excellent in stain resistance, water resistance, abrasion resistance, adhesion resistance, and the like. Some require a low surface friction coefficient.

[0003] In order to meet such demands, a method of adding a lubricant such as silicone oil, wax or fatty acid which gives lubricity and water repellency to various resin molded articles, or a silicone or fluorine functional resin is used. A coating method and the like have been performed. According to this method, a certain purpose can be achieved, but the lubricant added to the molded product bleeds out to the surface of the molded product with time, causing various problems. It is limited by the amount added, and the desired performance cannot be sufficiently exhibited. As a method for solving the above-mentioned disadvantages, a method using a resin having a low coefficient of friction as a resin itself, for example, a silicone-modified resin or a fluorine-modified resin has been proposed.

[0004]

[Problems to be solved by the invention]
Since these resins are thermosetting resins using various curing agents from the viewpoint of durability, there is a problem that a heating step for curing is required at the time of film formation, and the film formation step is complicated. . Further, although the formed films have a high melting point, if the curing reaction is insufficient, problems due to poor curing such as solvent resistance, adhesion to a substrate, and heat resistance tend to occur. Therefore, an object of the present invention is to simplify the process of forming a film,
Another object of the present invention is to provide a fluorine-containing resin compound which provides a one-part curable coating agent capable of forming a film having excellent performance.

[0005]

The above object is achieved by the present invention described below. That is, the present invention relates to an organic polyisocyanate.
Through urethane bond and / or urea bond to annate residue
The fluorine-containing compound and the silane coupling agent
A fluorine-containing resin compound, wherein the fluorine-containing compound is one molecule
Hydroxyl group, epoxy group, amino group and carboxy
Reactive organic functional groups and the other molecular chain terminal perfluoroalkyl groups which react with isocyanate groups selected from the Le group
Is a chain compound having a silane coupling agent
Bond to the Si atom represented by the general formula (1) or (2)
Lower alkoxy group and isocyanate group at the molecular chain end
A compound having a reactive organic functional group that reacts with
The fluorine compound and the silane coupling agent are
Of all reactive organic functional groups and organic polyisocyanates
Reacts with the isocyanate group to form
One-part curable fluorine resin compound , which has no free isocyanate group and has a hydrolyzable silyl group, which is bonded to a polyisocyanate residue , and
And the above-mentioned organic polyisocyanate and the above-mentioned fluorine-containing compound
Product and a silane coupling agent with an organic polyisocyanate
The total amount of isocyanate groups in
The total amount of reactive organic functional groups in the coupling
The reaction is carried out so as to have an equivalent amount.
Does not have a cyanate group and has a hydrolyzable silyl group
Of a one-part curable fluorine resin compound, characterized in that
It is a production method, a coating agent containing the resin compound as a film-forming component, and a method for coating a substrate using the coating agent. (R ¹ is a lower alkyl group, R ² is a lower alkyl group or a lower alkyl group.
X is a divalent organic group, and a
It has an atom such as O, N or S as a linking group.
You may. (M is an integer of 0 to 3 and n is 3-m) (Y is a group capable of reacting with an isocyanate group, and R ¹ ,
R ² , X, m and n are as defined above . )

[0006]

The reaction product of a fluorine-containing compound having a reactive organic functional group and a perfluoroalkyl group, a silane coupling agent having a reactive organic functional group, and an organic polyisocyanate is used as a film forming component of the coating agent. By doing so, since the film-forming component has a hydrolyzable silyl group, it is crosslinked by moisture or moisture in the air, so that one-part curing of the film composed of the coating agent becomes possible, and the process of forming the film is significantly simplified. Be transformed into Further, due to the hydrolyzable silyl group present in the film-forming component, the adhesion of the film to the substrate surface is improved, and a film having excellent various properties is formed.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments. Preferred examples of the fluorine-containing compound having a reactive organic functional group and a perfluoroalkyl group used in the present invention include the following compounds.

(1) Alcohol type

(2) Epoxy type The above epoxy compound can be used by reacting it with a polyol, polyamide, polycarboxylic acid or the like so as to have a terminal active hydrogen.

(3) Amine type

(4) Carboxylic acid type

(5) One-end diol type

The fluorine-containing compounds having a reactive organic functional group listed above are examples of preferred compounds used in the present invention, and the present invention is not limited to these exemplified compounds. Therefore, not only the compounds exemplified above, but also other compounds that are currently commercially available and easily obtainable from the market can be used in the present invention.

Examples of the silane coupling agent having a reactive organic functional group used in the present invention include the following compounds. (1) A silane coupling agent having at least one free isocyanate group.

[0015]

(R ¹ is a lower alkyl group, R ² is a lower alkyl group or a lower alkoxy group, X is a divalent organic group, and preferably a C ₀ -C ₅₀ aliphatic, aromatic or aliphatic aromatic group. Group, and these groups may have each atom such as O, N or S as a linking group therein.
(M is an integer of 0 to 3 and n is 3-m)

Preferred specific examples of the silane coupling agent having a free isocyanate group are as follows.

(2) A silane coupling agent having a reactive organic functional group other than a free isocyanate group includes a compound represented by the following general formula.

(Y is, for example, an amino group, an epoxy group,
Groups which are capable of reacting with an isocyanate group such as a hydroxyl group and a thiol group, particularly preferably an amino group, a thiol group and a hydroxyl group. R ¹ , R ² , X, m and n are as defined above. Preferred specific examples of the silane coupling agent having a reactive organic functional group are as follows.

[0020]

The silane coupling agents listed above are examples of preferred compounds used in the present invention,
The present invention is not limited to these examples. Therefore, not only the above-listed compounds but also other compounds that are currently commercially available and easily available from the market can be used in the present invention.

As the organic polyisocyanate to be reacted with the fluorine-containing compound and the silane coupling agent used in the present invention, any known organic polyisocyanate can be used. 4-diisocyanate 4-methoxy-1,3-phenylene diisocyanate 4-isopropyl-1,3-phenylene diisocyanate 4-chloro-1,3-phenylene diisocyanate 4-butoxy-1,3-phenylene diisocyanate 2,4-diisocyanate-diphenyl ether Methylene diisocyanate 4,4-methylenebis (phenyl isocyanate) judylene diisocyanate 1,5-naphthalenedi isocyanate 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-methylene bis (cyclohexyl isocyanate) 1,5-tetrahydronaphthalene And diisocyanates.

Further, adducts of these organic polyisocyanates with other compounds, such as those having the following structural formulas, are not limited thereto.

[0024]

[0025]

[0026]

[0027]

Urethane prepolymers obtained by reacting these organic polyisocyanates with low molecular weight polyols or polyamines to form terminal isocyanates can also be used in the present invention. The resin compound according to the present invention comprises a fluorine-containing compound having a reactive organic functional group as described above, a silane coupling agent having a reactive organic functional group, and an organic polyisocyanate as described above. Total amount and isocyanate group
The total amount is approximately equal to the molar ratio (mol) in the absence or presence of an organic solvent in the presence or absence of a conventional urethane catalyst.
~ 150 ° C, preferably about 10 ~ 20 ° C
It can be easily obtained by reacting for 4 hours.

When the resin compound according to the present invention is used as a film-forming component of a coating agent, the compound can be used alone. However, in order to improve coating suitability to a substrate and film formability, etc. Conventionally known various resins can be mixed and used. As these various resins, acrylic resin, polyurethane resin, polyester resin, polybutadiene resin, silicone resin, melamine resin, phenol resin, polyvinyl chloride resin, cellulose resin, epoxy resin, polyvinyl butyral resin, alkyd resin, modified cellulose resin, Fluorine resin or polyamide resin can be used. Further, resins obtained by modifying various resins with a silicone compound or a fluorine compound can also be used. When these various resins are used in combination, the amount of the resin used is about 0.1% by weight to 100% by weight based on the solids fraction of the resin compound according to the present invention.

The coating agent according to the present invention comprises the above-mentioned fluorine-containing resin compound according to the present invention and a solvent as essential components.
The amount of the solvent used is preferably in a range where the total solid content of the coating agent is 5 to 50% by weight. The solvent for the coating agent used in the present invention is a solvent used in a usual coating agent, for example, methyl ethyl ketone, methyl-n-propyl ketone, methyl isobutyl ketone, diethyl ketone, methyl formate, ethyl formate, Propyl formate, methyl acetate, ethyl acetate, butyl acetate, acetone, cyclohexane, tetrahydrofuran, dioxane, methanol, ethanol, isopropyl alcohol, butanol, toluene, xylene, dimethylformamide, dimethyl sulfoxide, perchlorethylene,
Trichloroethylene, methyl cellosolve, butyl cellosolve, cellosolve acetate and the like can be mentioned. Further, the coating agent according to the present invention may include an extender pigment, an organic pigment, an inorganic pigment, a plasticizer, an ultraviolet absorber, an antistatic agent, a leveling agent, and the like, as necessary, similarly to other general coating agents. I can do it. The method for producing a coating agent according to the present invention may be exactly the same as the method for producing a coating agent of the prior art, and is not particularly limited.

The coating agent according to the present invention is cured by causing a hydrolytic silyl group in a film-forming component to undergo a cross-linking reaction, that is, a self-condensation of silanol, by being brought into contact with moisture, water or steam in the air. No special heating equipment or treatment is required for curing.

In the present invention, in order to promote the silanol self-condensation, it is preferable to add a catalyst to the coating agent. As such catalysts, alkyl titanates, tin octylates, carboxylate salts such as dibutyltin dilaurate, amino salts such as dibutylamine-2-ethylhexoate, and other acidic and basic catalysts are generally preferred. . The use amount thereof is preferably in the range of 0.0001% by weight to 10% by weight of the resin compound as the film forming component. In addition, some hydrolyzable silyl groups improve the adhesion of the coating to the substrate by interacting with the interface of the substrate surface, and the perfluoroalkyl group part is oriented on the surface of the coating. According to the coating agent of the present invention, a surface property having excellent properties such as heat resistance, slipperiness, water repellency, and chemical resistance can be imparted to the substrate surface.

[0033]

Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following description, “parts” or “%” is based on weight unless otherwise specified. Example 1 Adduct of hexamethylene diisocyanate with water [Duranate 24A-100, manufactured by Asahi Kasei Corporation, NCO% =
23.5%] 150 parts and ethyl acetate 100 parts at 80 ° C
While stirring well, a fluorine-containing compound having a terminal hydroxyl group having the above structure (hydroxyl value: 119 KOHmg /
g) 65 parts were gradually added dropwise and reacted for 4 hours.

Thereafter, the mixture was cooled to 40 ° C. and, while stirring well, 3-aminopropyltriethoxysilane 1
The reaction product (1) was obtained by gradually dropping 53 parts and reacting. The reaction product obtained was (1), according to the infrared absorption spectrum not observed absorption by free isocyanate groups 2,270Cm ^-1, also, -CF the 1,190Cm ^-1
_It showed an absorption band based on the ₂ -group. Finally, ethyl acetate was added to obtain a solution (A) of the resin compound of the present invention having a solid content of 50%.

Embodiment 2 1 mole of trimethylolpropane and 3 moles of toluene
Adduct with 2,4-diisocyanate (Coronate L,
200 parts of NCO% = 13.0%, solid content 75%, manufactured by Nippon Polyurethane Co., Ltd.) and 100 parts of ethyl acetate are stirred well at 80 ° C., and the fluorine-containing one-terminal hydroxyl group having the above structure is added therein. Compound (hydroxyl value: 110 KOHmg /
g) 53 parts were slowly dropped to react.

Thereafter, the mixture was cooled to 40 ° C. and stirred well.
Into this, 132 parts of N-phenyl-γ-aminopropyltrimethoxysilane was gradually added dropwise and reacted to obtain a reaction product (2). According to the infrared absorption spectrum of the obtained reaction product (2), no absorption due to a free isocyanate group was observed at 2,270 cm ^-1 , and 1,190 cm
It showed an absorption band based on the group - -CF ₂ ^-1. Finally, ethyl acetate was added to obtain a solution (B) of the resin compound of the present invention having a solid content of 50%.

Embodiment 3 While thoroughly stirring 79 parts of isophorone diisocyanate and 50 parts of ethyl acetate at 80 ° C., a fluorine-containing compound having the above structure (hydroxyl value: 110 KOHmg /
g) 100 parts were gradually added, and then reacted at 90 ° C. for 5 hours. Next, the mixture was cooled to 40 ° C., and 68 parts of 3-aminopropyltriethoxysilane was gradually added dropwise thereto with sufficient stirring to cause a reaction to obtain a reaction product (3).

The obtained reaction product (3), according to the infrared absorption spectrum not observed absorption by free isocyanate groups 2,270Cm ^-1, also, -CF ₂ to 1,190Cm ^-1 -Showed an absorption band based on the group. Finally, ethyl acetate was added to obtain a solution (C) of the resin compound of the present invention having a solid content of 50%.

Example 4 100 parts of the solution (A) of the resin compound of Example 1, 300 parts of methyl ethyl ketone, 0.5 part of water and 0.1 part of tin octylate.
01 parts were mixed and stirred well to obtain a coating agent of the present invention. Example 5 100 parts of the solution (B) of the resin compound of Example 2, 300 parts of methyl ethyl ketone, 0.5 part of water and 0.1 part of tin octylate.
01 parts were mixed and stirred well to obtain a coating agent of the present invention. Example 6 100 parts of the solution (C) of the resin compound of Example 3, 300 parts of methyl ethyl ketone, 0.5 part of water and 0.1 part of tin octylate.
01 parts were mixed and stirred well to obtain a coating agent of the present invention.

Comparative Example 1 100 parts of a solution (solid content: 50%) of a fluorine-based silane coupling agent represented by the following structural formula, methyl ethyl ketone 3
00 parts, 0.5 part of water and 0.01 part of tin octylate were mixed and stirred well to obtain a coating agent for a comparative test.

Evaluation as coating agent The coating agent prepared in each of Examples 4 to 6 and Comparative Example 1 was coated on one surface of a polyurethane belt for precision conveyance (manufactured by Nippon Siegling Co., Ltd.) to a thickness of 2 to 3 μm after drying. Was applied. However, drying is natural drying (23 ° C, humidity 4
6%), and after standing for 3 days, the following various physical properties were measured for the formed film. The results are shown in Table 1 below.

Adhesion : Evaluated by performing a cross-cut cellophane tape peel test (cross-cut method, 1 mm square cross-cut). Rubbing test : rubbing 10 times with a cloth impregnated with xylene,
The state of the coating was observed. Abrasion resistance ; Taber abrasion test (conditions: wear wheel CS-1)
Abrasion resistance test was performed (1,000 times) at 0, 1 kg of load and 70 rpm. Water repellency : The contact angle of a coated surface with a water drop was measured. Oil repellency : measured according to AATCC method 118-1966.

[0043]

[Table 1] * 1: Uncoated belt * 2: Scuffing As shown in Table 1 above, the coating agent of Comparative Example 1 is excellent in water repellency and oil repellency, but has no film-forming property, and therefore has an adhesive property, a rubbing property and Poor wear resistance.

Evaluation as Coating Agent for Glass The four types of coating agents prepared in Examples 4 to 6 and Comparative Example 1 were each impregnated into a cloth and thinly applied to an automobile windshield (Toyota, Corolla SE). Natural drying (2
(3 ° C., humidity: 48%) for 2 days, and the following properties were measured for the formed film. The results are shown in Table 2 below. Running test : The vehicle was run while water was sprayed on the surface of the windshield, and the initial speed at which attached water droplets were flipped off was measured. Rubbing test : Sprinkle water on the surface of the windshield and wipe off the water with a wiper.
The same operation was repeated, and the movement of the wiper and the water was observed.

[0045]

[Table 2]

Evaluation silica when applied to hydrophobic treatment of silica [Aerosil 300, manufactured by Nippon Aerosil Co., Ltd.]
While stirring in a Hensyl mixer (rotational speed: 1880 rpm), the respective solutions of Examples 1 to 3 and Comparative Example 1 were sprayed uniformly, and after high-speed stirring at 115 ° C. for 30 minutes, 130 ° C.
For 10 hours to obtain four types of resin silica. still,
The treatment ratio was silica / treatment agent (pure fraction ratio) = 100/15. Using these resin silicas, four types of water-repellent coating agents having the following formulations were prepared. Example 7 Dialomer FF-5201 [Silicone / Fluorine copolymer resin manufactured by Dainichi Seika Kogyo Co., Ltd.] (40%) 100 parts Silica treated with the resin of Example 1 16 parts (40HPR) The dispersion (solid content) 15%) of 100 parts of a polyisocyanate (Coronate XH, manufactured by Nippon Polyurethane Co., Ltd.) was added to 3 parts of a crosslinking agent to obtain a water-repellent coating agent of the present invention. The dispersion was performed by a sand mill.

Example 8 The water-repellent coating agent of the present invention was prepared in the same manner as in Example 7 except that the silica treated with the resin of Example 2 was used in the same amount in place of the resin-treated silica in Example 7. And Example 9 A water-repellent coating agent of the present invention was prepared in the same manner as in Example 7 except that the same amount of silica treated with the resin of Example 3 was used instead of the resin-treated silica in Example 7. Comparative Example 2 The water-repellent coating agent of the present invention was prepared in the same manner as in Example 7 except that the same amount of silica treated with the resin of Comparative Example 1 was used instead of the resin-treated silica in Example 7.

Each of the above water-repellent coating agents was applied to a steel plate on which an epoxy resin primer was baked after the zinc phosphate treatment so that the film thickness after drying was 20 μm, and baked at 130 ° C. for 5 minutes to prepare a coated plate. . The following various physical properties were measured for each of the obtained coated plates. The results are shown in Table 3 below. Adhesion ; cross-cut cellophane tape peel test (cross cut method,
(1 mm square). DuPont impact : According to DuPont impact tester, under conditions of 1/2 inch, falling weight 500g and falling weight height 50cm,
An impact was applied from the back side of the film, cellophane tape was attached to the impacted portion, and the film was quickly peeled off, and the remaining state of the film was evaluated. Water repellency : The contact angle of a coated surface with a water drop was measured.

[0049]

[Table 3] As shown in Table 3 above, when the resin compound according to the present invention was applied to the hydrophobic treatment of silica, a film excellent in adhesion, impact strength and water repellency was formed. In the case of (1), the formed coating film had low adhesiveness, and the coating film was peeled off even by Dupont impact.

[0050]

According to the present invention, there is provided a fluorine-containing resin compound which can be crosslinked by moisture or moisture in the air and is useful as a film forming component of a coating agent capable of one-part curing. Therefore, the coating agent containing the fluorine-containing resin compound according to the present invention can simplify the film forming step. In addition, since the fluorine-containing resin compound according to the present invention has a hydrolyzable silyl group and a fluorine-containing segment excellent in reactivity, the coating agent containing the resin has excellent adhesion to a substrate. With water repellency, stain resistance,
A film having excellent surface properties such as abrasion resistance and adhesion resistance can be formed. Therefore, according to the present invention, it is possible to provide a binder for magnetic recording or thermal recording, a back coat agent, a releasable treatment agent, a treatment agent for inorganic surfaces such as glass, various overcoat agents, a hard coat agent, and the like.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Katsumi Kuriyama 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Inside Dainippon Chemical Industry Co., Ltd. (56) References JP-A-2-286761 (JP, A) ( 58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 18/38 C09D 175/04

Claims (4)

(57) [Claims] 1. An organic polyisocyanate residue comprising urethane
And / or a fluorinated compound through a urea bond.
A fluorine-containing resin compound with a run coupling agent
Therefore, the fluorine-containing compound has a hydroxyl group and an epoxy group at one molecular chain terminal.
Isocyanate selected from amino group, amino group and carboxyl group
Reactive organic functional groups that react with annate groups and the other molecular chain
A chain compound having a perfluoroalkyl group at the terminal
The silane coupling agent is represented by the following general formula (1) or
Lower alkoxy group bonded to Si atom shown in (2)
And reactive organic compounds that react with isocyanate groups at molecular chain terminals
A compound having a functional group, such as a fluorine-containing compound and silane
The coupling agents each have a reactive organic functional group
All isocyanate groups of organic polyisocyanate
React to form the above bond to form an organic polyisocyanate
A one-part curable fluororesin compound, having no free isocyanate group and having a hydrolyzable silyl group , bonded to a residue . (R ¹ is a lower alkyl group, R ² is a lower alkyl group or a lower alkyl group.
X is a divalent organic group, and a
It has an atom such as O, N or S as a linking group.
You may. (M is an integer of 0 to 3 and n is 3-m) (Y is a group capable of reacting with an isocyanate group, and R ¹ ,
R ² , X, m and n are as defined above. ) 2. A hydroxyl group at one end of a molecular chain, epoxy
Groups, isocyanurate selected from amino and mosquito carboxyl group
A reactive organic functional group that reacts with the
Chain-containing fluorinated compounds having a perfluoroalkyl group at the terminal
And a Si atom represented by the following general formula (3) or (4)
Between Lower Alkoxy Group and Isocyanate Group Attached to Titanium
A silane coupling agent having a reactive organic functional group
An organic polyisocyanate, an organic polyisocyanate
And the total amount of isocyanate groups of the above fluorine-containing compound and
Reacts with the isocyanate group of the silane coupling agent
The total amount of reactive organic functional groups must be equal to each other in moles.
Having a free isocyanate group characterized by
One-part curable without hydrolyzable silyl group
A method for producing a fluororesin compound. (R ¹ is a lower alkyl group, R ² is a lower alkyl group or a lower alkyl group.
X is a divalent organic group, and a
It has an atom such as O, N or S as a linking group.
You may. (M is an integer of 0 to 3 and n is 3-m) (Y is a group capable of reacting with an isocyanate group. R ¹ ,
R ² , X, m and n are as defined above. ) Also according to claim 1 as wherein film-forming component
A coating agent comprising a resin compound obtained by the method of claim 2 . 4. A method for coating a substrate, wherein the coating agent according to claim 3 is applied to an arbitrary substrate surface, and dried and cured, wherein moisture is used as a curing agent.