JPH01263161A - Fluorine-containing coating agent and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title coating agent to be used for imparting the surface of substrate with water- and oil-repellency, antifouling nature, nontackiness, lubricity, etc., by reaction between a fluorine-contg. alcohol and an alkyl titan ate. CONSTITUTION:The objective coating agent of the formula (n is 1-4) can be obtained by reaction under normal pressure pref. at 100-200 deg.C between (A) a fluorine-contg. alcohol of the formula RfOH (Rf is 4-16C fluorine-contg. alkyl) (e.g., 1H,1H-heptafluoro-1-butanol) and (B) an alkyltitanate of the formula Ti(OR)4 (R is H or 1-10C alkyl) (e.g., tetramethyl titanate) followed by reaction under a reduced pressure of 10-200Torr.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a compound used to impart water and oil repellency, stain resistance, non-adhesiveness, lubricity, etc. to the surface of an inorganic or organic material base material. Regarding fluorine coating agent.

[Prior Art] Conventionally, coating agents have been used to form a coating on the surface of a substrate and provide various properties such as protection, cosmetic properties, smoothness, and insulation to the substrate. Many types of 6 have been put into practical use, but for the purpose of imparting water and oil repellency, stain resistance, non-adhesiveness, lubricity, etc. to the surface of inorganic or right-hand materials, fluorine compounds unique to fluorine compounds are used. A method of forming a fluororesin film that takes advantage of its low surface energy properties and a method of applying fluorine-containing oil have been adopted.

[Problem to be solved by the invention] However, fluororesins have poor adhesion to inorganic materials such as metals, glass, and cement, various plastics, and organic materials such as wood, making it difficult to form coatings on the surfaces of these substrates. In order to form, texture is applied to the surface of the base material,
Requires special preprocessing such as creating an anchor effect.

In addition, although the method of applying fluorine-containing oil initially shows good properties, over time the oil detaches from the surface of the substrate and loses its effectiveness, resulting in poor coating due to small phenomena due to the historically low surface energy. It may metastasize and adhere to areas other than its intended purpose, causing unexpected damage.

In addition, two-component type fluorine-containing polymers whose main ingredient is a fluorine-containing polymer having a 1q hydroxyl group by copolymerizing a fluoroolefin and a hydroxyalkyl vinyl ether, and which use polyvalent isocyanate or methylol melamine as a curing agent. A coating agent has been proposed (Japanese Unexamined Patent Publication No. 57-3417). Although this coating agent forms an excellent film, it still does not have sufficient adhesion to various substrates and is a two-component type, making it difficult to use. There is room for improvement.

Therefore, in view of the above circumstances, the present invention provides a fluorine-containing coating agent that can form a fluorine-containing coating film having good adhesion to inorganic and organic materials and excellent properties, and that can be liquefied. The purpose is to provide a manufacturing method.

[Means for Solving the Problems] As a result of extensive studies, the present inventors found that titanium-containing fluoroalkyl compounds have good adhesion to many types of substrates, and are based on the low surface energy characteristic of fluorine compounds. The present invention was completed by discovering that it can be used as a liquid-type coating agent while retaining its properties.

Of course, the active ingredient of the present invention has the general formula [I] (R'O) n T l (OR) 4-n [I
[In the formula, R1 represents a fluorine-containing alkyl group having 4 to 16 carbon atoms, R represents hydrogen or an alkyl group having 1 to 10 carbon atoms, and n represents an integer of 1 to 4. The present invention relates to a fluorine-containing coating agent, which is a fluorine-containing alkyl compound containing titanium represented by formula 1, and a method for producing the same.

The coating agent which is a fluorine-containing alkyl compound containing titanium according to the present invention includes not only the individual compounds represented by -drinking amount [i] but also a mixture of the individual compounds shown by -drinking amount [I], That is, substituents Rf and R1 Onibi n
It is also intended to include mixtures of compounds that fall within the above definition.

Furthermore, in general formula [i] representing a single compound,
When there are two or more substituents Rf containing r1 pieces and substituents containing (4-n) pieces, the plurality of substituents may be the same or different.

In the substituent Rf representing a fluorine-containing alkyl group having 4 to 16 carbon atoms in general formula [I], the ratio of fluorine atoms to hydrogen atoms is preferably at least 3:1 or more. When this ratio is 3:1 or less, the low surface energy characteristic peculiar to the fluorine-containing alkyl group becomes weak even if the number of carbon atoms is within the above range.

Note that when the number of carbon atoms in the substituent Rf is less than 4, the low surface energy property is also weak, and when the number of -5 carbon atoms exceeds 16, it is difficult to obtain raw materials.

The alkyl group R and the fluorine-containing alkyl group include linear and branched ones.

- In the drink price [I], n is arbitrary within the range of 1 to 4, but desirably has a structure where n=3 or n=2.

However, it is not necessary that the number one of n is an integer, and n=
It may be a decimal number of 1 to 4 (ie, a mixture of [)-1, 2, 3, 4 compounds).

- According to the present invention, the titanium-containing fluorine-containing alkyl compound represented by drinking price [I] has the general formula [I[] Rf OH[II] [wherein Ri is a fluorine-containing compound having 4 to 16 carbon atoms] Represents an aryl group. ] A fluorine-containing alcohol represented by the general formula [111]% formula% [ ] [wherein 1 or hydrogen or an alkyl group having 1 to 10 carbon atoms is represented. '] It can be produced by reacting an alkyl titanate represented by:

The alkyl titanates of the raw material compound represented by the general formula [111] used in the reaction include tetramethyl titanate (C=1>, tetraethyl titanate (C=2), tetraisopropyrutitanate (C=3), Tetrapropyl titanate (C=3), tetramethyl titanate-1~
(C=4>, tetraisobutyl titanate (C=4),
Tetrapendel titanate (C=5>, tetraethyl titanate (C=6), tetraethyl titanate (C=7>, tetraocdyl titanate-1-(C=8), tetranonyl titanate (C=9>, detradecyl) Examples include titanium (C=10>), which can be used alone or in a mixture. Tetraisopropyl titanate and tetrabutyl titanate are particularly preferred.

These titanates are known compounds and can be obtained commercially or can be produced by methods known per se.

The other raw material, the fluorine-containing alcohol represented by the general formula [I], is not particularly limited as long as it has 4 to 16 carbon atoms and the ratio of fluorine atoms to hydrogen atoms is at least 3:1 or more. However, conventionally known compounds can be used, such as those listed below.

That is, 11-1.1H-heptafluoro-1-butanol C3
F7 CH20H1 1171 tol-pentadecaful;)1] -'l-octatool
C7F15CH20H.

1F1.11-1, 91-1-hexadecaflu A rho-1-nonanol l-1c8F16CH
20H1I H,11-1,21-1,2H-perfluoro-1-heptatool C5F11CH2
CH20 1.117 IH, 2H, 2H-perful,
4-1-71 Ktanol 06F13C1-
1,2CH201-1,11-1,11-1,21-1
,28-perfluoro-1-decanol C
3F1□CH, 2CH20H.

1 to 1. IH,2H,2H-perfluoro-1-te1~
Radecanol 012F25CH2CH20H1I
H, 11-1,211,2 days-perfluoro-1-hexadecanol c14F29c+-t2 ct-
+20H1 and other fluorocarbon alcohols, each of which can be used alone or in the form of a mixture.

Next, a method for producing the fluorine-containing coating agent represented by the general formula [I] will be specifically explained.

The fluorine-containing alkyl alcohol Rf OH and the alkyl titanate rr (OR)4 used in the reaction have a molar ratio of 1.
By setting 2.3.4, mono-substituted, di-substituted, tri-substituted, and tetra-substituted products of the fluorine-containing alkoxy group RfO can be obtained, respectively.

This upper ratio can be arbitrarily selected between 1 and 4, and in this case, the reaction product is a mixture of the above substituents.
Therefore, depending on the use of the coating agent, it may be preferable.

The reaction is usually preferably carried out in a solvent-free system at normal pressure and at reduced pressure in the later stages of the reaction, but it is also possible to carry out the reaction in a pressurized system and use a solvent.

As a solvent, general organic solvents may be used, but chlorinated fluorohydrocarbon solvents such as trifluorotrichloroethane (Freon 113), difluorote 1 to lachlorethane (Freon 1), etc.
12), Pencitriflu Fanglite, etc. are more preferable.

The reaction temperature is preferably between 100 and 200°C.

If the temperature is below 100°C, the reaction will be slow, and if it is above 200°C, the product may decompose or develop a blue color, which is not preferred.

As the substitution reaction progresses, the corresponding alkyl alkyl is distilled out, but in order to complete the desired reaction, 10T
It is preferable to terminate the reaction after distilling off a predetermined amount of alkyl alcohol by reducing the pressure to 200 Torr orr.

The reaction time is not particularly limited, but it is usually preferably carried out for 30 minutes to 10 hours. Especially in the late stage of the reaction, 1Q
Even under reduced pressure conditions of less than l-orr or more than 10 orr, if the reaction time is long, fluorine-containing alkyl alcohol with a high melting point will distill out in addition to norkyl alkyl, so the piping in the system will be In some cases, it may cause a seizure.

This is not preferable because it not only results in the loss of expensive fluorine-containing alkyl alkyl but also leads to a decrease in the performance of the resulting reaction product.

The properties of the reaction product vary depending on the type of raw materials used, and it is a colorless to pale yellow viscous liquid or solid at room temperature, but it should be handled as a solution by heating it or dissolving it in a chlorofluorohydrocarbon solvent. I can do it.

The fluorine-containing coating agent of the present invention is usually used as a solution or emulsion diluted with a solvent.

As a solvent, 1 helifluorotricholtan (Freon 113), difluorotetrachloroethane (Freon 11),
2) Preferably, a fluorine-based solvent such as pencitrifluΔlide, a chlorinated solvent such as trichlorethylene, or a mixture thereof. Among them, fluorinated solvents such as 1 to fluorotrichloroethane (Freon 113) are particularly preferred because they have a high solubility in the present coating agent. Furthermore, additives such as surfactants and leveling agents can be added to the solution depending on the intended use.

As the base material for the coating, inorganic materials such as metals, metal oxides, glass, carbon, and graphite, and organic materials such as plastics, fibers, wood grains, and paper can be used.

]-Ting methods include brush coating method, spray method, roll coating method, dip coating method, and spin-rolling method.
15 general coating methods such as the method 15 can be used.

The film can be formed at room temperature, but it may be performed under different temperature conditions in order to adjust the formation rate.

The thickness of the coating film depends on the concentration of the fluorine-containing agent in the solvent during dipping, the dipping temperature, the pulling rate at the dip, and the spin code. It can be arbitrarily changed depending on the rotation speed, etc., and can be selected depending on the purpose of use, and it is possible to form a film with a thickness of several angstroms to several tens of microns.

The m degree of the fluorine-containing compound in the solvent during coating is preferably in the range of 0.1 to 50%.

In this range, the culm film thickness becomes thicker when the concentration of the fluorine-containing compound is high.

When the m degree is less than 0.1% by weight, the film thickness is thin and the water and oil repellency decreases, and when it is more than 50% by weight, the water and oil repellency does not improve despite the film thickness, and the surface uniformity deteriorates. , it is undesirable because it has disadvantages such as easy peeling.

From a practical point of view considering economic efficiency-b, it is especially 0.2 to 1.
The active ingredient is the titanium-containing fluorine-containing alkyl compound of the present invention, which is preferably in the range of 0%.Although the mechanism of action of the adhesion development in the titanium-ting agent is not necessarily clear, the hydroxyl group on the surface of the base material and the titanium alkoxy This is presumed to be due to the group reacting with the presence of a trace amount of water to form a strong bond.

[Applications] The coating agent according to the present invention can be used for various applications in the following fields that utilize the low surface energy properties of fluorine compounds.

Fields in which water and oil repellency is utilized: It provides water and oil repellency and stain resistance to a variety of substrates, and can be applied to fibrous, porous and continuous surfaces.

Examples include woven clothing, furniture, hangings, rugs, paper bags, cardboard containers, trunks, hunt bags, shoes, jackets, wood and asbestos wallboards, bricks, concrete.
There are tiles on the floor and walls.

It can also be used to treat surfaces such as crow, stone, wood, plaster, wallpaper and wallboard, as well as painted or unpainted metal such as appliances and car bodies.

Fields that take advantage of the low ameability of the surface: Gold R of iron, stainless steel, aluminum, duralumin, etc.
It has good adhesion to substrates and takes advantage of its low surface adhesion properties, so it can be used as a mold release agent for plastics, as an anti-icing agent for airplanes, and as an anti-seizure agent for frying pans.

Fields where surface lubricity is used Magnetic tape (for audio, video, and digital audio It is useful as a surface solid lubricant for magnetic recording materials such as floppy disks, hard disks, etc.

[Effects of the Invention] As explained above, the fluorine-containing coating agent of the present invention can be applied to metal materials such as nickel, aluminum, copper, iron, and stainless steel, IaU-free coatings such as glass and ceramics, polyethylene, polypropylene, and chloride. A film with good adhesion can be formed on the surface of a wide variety of substrates, such as plastics such as vinyl, wood, cloth, etc., and the low surface energy properties of fluorine-containing alkyl groups on the surface of these substrates. That is, it is useful for applications that impart water and oil repellency, antifouling properties, non-stick properties, lubricity, etc. Furthermore, the method for producing a fluorine-containing coating agent of the present invention is an economical method in which the molar ratio of fluorine-containing alkyl alcohol and alkyl titanate can be arbitrarily selected depending on the application.

[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples and Test Examples, but the present invention is not limited to the following examples.

Note that parts and percentages are based on weight unless otherwise specified.

Example 1 Te 1 to Love Chill Titanium 1 (OC4Hg)
417.0 parts and IH, 11-1, 21-1, 28 perfur Δ]-1-decanol C8F17CH2CH20
9.6 parts of 11B (3 times the amount of titanate) was placed in a 200-inch Karasu distillation pot equipped with a stirrer, thermometer, temperature-controlled condenser, and distillate receiver, and heated in an oil bath to give 16 parts.
After reacting at 0'C under normal pressure for 1 hour, 4.0 parts of butanol was distilled out.

Next, the pressure was reduced to 20 Torr, and the temperature was increased to 160°C.
By reacting for a period of time, an additional 6.0 parts of butanol was distilled out, yielding 72.5 parts of a viscous yellow-brown reaction product in the kettle.

This reaction product was analyzed by NMR and mass spectrometry. NMR spectrum δ(D Drn )1.0
The molar ratio of C3F17CH2CH20/C4to190 bonded to li was determined from the peak mass ratio of (methyl of butoxy group) and 2.5 (2-methylene of fluorinated alkoxy group) (Example 2 below) The same applies to 4.

> 3.09 / 0.91.

This means that the average luminosity of the fluorine-containing titanate molecules is 3.
This shows that it has 0.9 moles of fluorinated alkoxy groups and 0.9 FE of alkoxy groups, and the results of mass spectrometry show that in addition to 3-substituted fluorinated alkoxy groups, there are also small amounts of 1-4@substituted fluorinated alkoxy groups. It was confirmed that the mixture contained

In addition, TiO2 produced by hydrolyzing a predetermined amount of the product
The l-i content was determined by firing to a constant weight and found to be 3.22% (theoretical (Fj 3.17%)).

Example 2 23.8 parts of tetrabutyl titanate-1 and I H,1)-
1°2H,2H-perfluoro-1-decanol65.
The reaction was carried out in the same manner as in Example 1 except that 0 part (2 times the mole of titanate) was used. 10.4 parts of distilled butanol and 76.4 parts of a pale yellow viscous reaction product were added to 1 q.
Ta. Analysis of this reaction product in the same manner as in Example 1 revealed that CF CI-I Cl-10/
The molar ratio of C4)-190 was 2/2, and the Ti content was 4.33% (theoretical value 4.27%).

Example 3 Tetrabutyl Digitane (~8.51 parts and I H, 11-
1゜21-1,2)-1-Perfle 1''-1-decanol 46.5 parts (4 parts total for titanate)
The reaction was carried out in the same manner as in Example 1 except that t! was used. 7.2
2 parts distilled butanol and 45.15 parts reaction product to 1 q.

This reaction product was a 1-bar color solid at a temperature of 100 m, and when analyzed using the same method as in Example 1, it was found that CB1-117cH2Cl-120/C4+1 bonded to Ti.
90(1)-[le ratio is 3.7/0.3, l-i
The content was 2.56% (theoretical value 2.52%).

Example 4 1 to 34.0 parts of Detolabudil Ditane and IH,1)-
1゜217 21-1-Perfluoreo[1-1-Decanol 46.4 parts (1 times mole relative to titanate) was used in the same manner as in Example 1, and 7.5 parts of the reaction mixture was distilled off. The reaction product of butanol and 70.1 parts is a light yellow viscous liquid, 8jq.

The results of compositional analysis of this reaction product show that 08F, □C)-12CH20/C4t-1g O bonded to Ti
The coefficient ratio was 0.99/3.01, and the titanium content was 6.58% (theoretical value 6.56%).

Example 5 Tetraisopropyl titanate Ti (Oi-031-1□) 49 was used instead of tetrabutyl titanate in Example 1.
．． Using 4 parts, 1F1.11-1゜2 i-1, 2H-
46.4 parts of perfluoro-1-decanol and 150'C
5.65 parts at normal pressure and 0.1 parts at reduced pressure
There was distillation of 8 parts of isopropanol, yielding 50.24 parts of a viscous yellow-brown reaction product.

This was a pale yellow slurry at room temperature.

Test Example 1 Fluorine-containing alkyl titanate [CF
CH' cHO) King 18 17 2 2
3.09 (QC41-+9) 9.91 was dissolved in Triflo-Machi-Rikuma-Raethane to prepare a 10% solution.

Next, using this solution, a glass substrate and a nickel-plated aluminum substrate were coated by the dip method.

After drying at room temperature for a day and night, the following tests "9'A-C" were conducted. The results are shown in Table 1.

A. Water repellency and oil repellency test The contact angles with respect to pure water and [)-hexylidecane were measured using [contact angle h], and the water repellency and oil repellency were evaluated, respectively.

B. Adhesion f [test goban [1 (ri [1 skirt)] test method (JISDO20
2>, make 11 cuts of 1M in the coating film reaching the object
Attach them orthogonally at intervals to make 100 goban stitches. Adhesiveness was evaluated based on the number of squares [1] remaining on the surface of the base material when Cellotape was adhered to these goblets and peeled off.

C0 Hardness Test Using the pencil hardness test method (JIS K5400), the coating film was scratched with a pencil, and the hardness of the coating film was evaluated based on the hardness of the pencil at which scratches began.

Test Example 2 The same treatment as in Test Example 1 was performed except that the fluorine-containing alkyl titanate obtained in Example 5 was used in Test Example 1. The results are shown in Table 1.

Test Examples 3 to 4 In Test Example 1, 1q of fluorine-containing alkyl titanium-1 to Example 2 was added (C8F17CH2CH20) 2
T! (QC41''9) 2 (Test Example 3) and (C8F1□0H20>3. obtained in Example 3).
7-I-i (QCH) In place of (Test Example 4), the properties shown in Table 2 were obtained as a result of conducting the same process on a chive-plated aluminum substrate.

Test Examples 5 to 11 In Test Example 1, the concentration of the coating composition in the solvent trichlorotrifluoroethane was 60% and 50%, respectively.
%, 25%, 5%, 1%, 0.2%, and 0.02% in the same manner as in Test Example 1, N 1-Al1! The physical properties of the film when coated on a substrate are shown in Table 3 together with the physical properties of Test Example 1.

Claims (1)

[Claims] 1) General formula (R_fO)_nTi(OR)_4_-_n[I][
In the formula, R_f represents a fluorine-containing alkyl group having 4 to 16 carbon atoms, R represents hydrogen or an alkyl group having 1 to 10 carbon atoms, and n represents an integer or decimal number of 1 to 4. ] A fluorine-containing coating agent containing at least one butane-containing fluorine-containing alkyl compound as an active ingredient. 2) The fluorine-containing alkyl compound of general formula [I] is 0.1
Claim 1, which is a solution containing ~50% by weight
The fluorine-containing coating agent described in section. 3) General formula R_fOH[II] [In the formula, R_f represents a fluorine-containing alkyl group having 4 to 16 carbon atoms. ] A fluorine-containing alcohol represented by the general formula Ti(OR)_4[III] [wherein R represents hydrogen or an alkyl group having 1 to 10 carbon atoms. ] The general formula (R_fO)_nTi(OR)_4_-_n[I][
In the formula, R_f and R have the same meanings as above, and n represents an integer of 1 to 4. ] A method for producing a fluorine-containing coating agent. 4) The manufacturing method according to claim 3, wherein the reaction is carried out at a temperature of 100 to 200°C and under normal pressure, and then the reaction is carried out under reduced pressure of 10 to 200 Torr.