JP2794037B2 - Fluorine-containing arylguanamine derivatives and uses thereof - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel fluorine-containing arylguanamine derivative useful as a polymerizable monomer, a raw material of various fluorine-containing compound derivatives, and the use thereof.

[Conventional technology]

Conventionally, as a guanamine compound having a fluorine-containing substituent, (Wherein, m represents an integer selected from 1 to 15), Etc. are known.

However, the former known compound is produced only using a fluorinated fatty acid ester and a biguanide as raw materials,
That the production of the raw material requires a complicated process, that the raw material is difficult to handle due to poor stability, that the yield in the production of the former known compound is unfavorable, and that steps such as purification and separation are complicated; Are very poor reactivity of the amino group in the compound, useful various fluorine-containing compound derivatives provided by reacting the amino group,
The latter known compound has defects such as that the production of a fluorine-containing resin is significantly restricted, and the latter known compound generates many by-products during the production, and furthermore, its purification and separation are difficult, and the fluorine-containing substitution in the known compound is difficult. The group is easily separated by hydrolysis, heat, light, or the like, and has a defect such as difficulty in maintaining an intended function for a long period of time.
There were significant technical and economic restrictions on production and use.

The present inventor has conducted extensive research to overcome the above-mentioned deficiencies in guanamine compounds having a fluorine-containing substituent. As a result, the production is simple, and an active amino acid showing remarkably excellent reactivity with compounds having various functional groups. Very good surface because it has a group, and there is almost no elimination of fluorine-containing substituents by hydrolysis, heat, light, etc., it can maintain its function for a long time, and it has a long-chain perfluoroalkyl group. Has properties, etc., rubber material, release agent, water / oil repellent, optical material, gas separation membrane material, resist material, antifouling paint, weather resistant paint, paper processing agent, fiber treatment agent, heat resistant resin, interface A novel fluorinated arylguanamine having an extremely wide range of applications and utility represented by the following formula, which can provide a fluorinated polymer, fluorinated compound, or fluorinated composition useful as an activator or the like. Provided the thing (Japanese Patent Application No. 1-2463
No. 37).

(Wherein, n represents an integer selected from 1 to 14) [Problem to be Solved by the Invention] The present invention provides an excellent novel compound which is a derivative of such a useful novel fluorine-containing arylguanamine compound, It is intended to provide its use.

[Means for solving the problem]

The present inventors have conducted intensive studies on such useful derivatives of the fluorine-containing arylguanamine compound, and as a result, have obtained an active hydroxyl group which is easy to produce, has extremely excellent reactivity with compounds having various functional groups, and has a hydrolytic property. There is almost no elimination of fluorine-containing substituents due to decomposition, heat, light, etc., and the function can be maintained for a long time. Rubber materials, release agents, water / oil repellents, optical materials, gas separation film materials, resist materials, Antifouling paint, weather resistant paint, paper processing agent, fiber treatment agent, heat resistant resin,
Fluorinated polymers, fluorinated compounds, such as surfactants,
The present invention has been accomplished by finding a novel fluorine-containing arylguanamine derivative capable of providing a fluorine-containing composition and the like.

That is, the present invention provides: (Wherein, n represents an integer selected from 1 to 14) At least one methylol obtained by reacting a fluorinated arylguanamine compound represented by the following formula with at least one selected from formaldehydes: A water- and oil-repellent agent for fibers, comprising as a component at least one selected from the group consisting of a fluorine-containing arylguanamine derivative having a group and (2) the fluorine-containing arylguanamine derivative described in (1). .

In the fluorine-containing arylguanamine compound (II) according to the present invention, n is an integer selected from 1 to 14, but is preferably an odd number from the viewpoint of easy availability of raw materials, and n is an integer of 3 or more. In particular, the surface properties such as antifouling property, water / oil repellency, lubricity, and non-adhesiveness are excellent and particularly useful.

Specific examples of such a fluorine-containing arylguanamine compound (II) include 2,4-diamino-6- (4-pentafluoroethylphenyl) -s-triazine and 2,4-diamino-6- (4-heptafur Orthopropylphenyl) -s
-Triazine, 2,4-diamino-6- (4-nonafluorobutylphenyl) -s-triazine, 2,4-diamino-6- (4-undecafluoropentylphenyl) -s
-Triazine, 2,4-diamino-6- (4-tridecafluorohexylphenyl) -s-triazine, 2,4-diamino-6- (4-pentadecafluoroheptylphenyl) -s-triazine, 4-diamino-6- (4-heptadecafluorooctylphenyl) -s-triazine, 2,4-diamino-6- (4-nonadecafluorononylphenyl) -s-triazine, 2,4-diamino- 6-
(4-Henicosafluorodecylphenyl) -s-triazine, 2,4-diamino-6- (4-pentacosafluorodecylphenyl) -s-triazine, 2,4-diamino-6- (4-no Nacosafluorotetradecylphenyl) -s-triazine, 2,4-diamino-6- (4-hentriacontafluoropentadecylphenyl) -s-
Examples include triazine, but are not limited to these compounds.

Such a fluorinated arylguanamine compound (II) is represented by the general formula: (Wherein, n represents an integer selected from 1 to 14), and a fluorinated nitrile and dicyandiamide are mixed with a non-aqueous solvent such as an alcohol, an amine, a carboxylic acid amide, a sulfolane, or a sulfoxide. In the presence of a basic compound such as an amine, an alkali metal hydroxide or an alkali metal alcoholate, the reaction can be carried out at a temperature of usually 80 ° C to 150 ° C.

The above-mentioned fluorinated nitrile (III) is, for example, 1
-Perfluoroalkyl iodides, bromides, chlorides, etc.
It can be obtained by reacting 4-halogen-substituted benzonitrile and metallic copper in an aprotic polar solvent.

Examples of such formaldehydes include formaldehyde, formalin, paraform, hexamethylenetetramine, methylhemiformal, butylhemiformal, formaldehyde sodium bisulfite adduct, and the like. It is not limited to compounds.

In addition, such a reaction is preferably carried out in a solvent, optionally in the presence of a basic compound, under conditions of pH 7.0 to 13.0, more preferably pH 7.5 to 11.0.

Such solvents include, for example, water, methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, dodecyl alcohol, allyl alcohol, propargyl alcohol , Benzyl alcohol, cyclohexanol, ethylene glycol, 1,4-butanediol, glycene, 1,2,6-hexanetriol, 2-methoxyethanol, 2-ethoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, full Furyl alcohol, tetrahydrofurfuryl alcohol,
Diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, 1-ethoxy-
Compounds having a hydroxyl group such as 2-propanol, dipropylene glycol, diacetone alcohol, 2,2,2-trifluoroethanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, ethyl acetate, butyl acetate, and acetic acid Esters such as benzyl, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, crown ether, ethers such as anisole, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, Examples thereof include carboxylic acid amides such as N-methylpyrrolidone, sulfolane such as sulfolane, sulfoxides such as dimethyl sulfoxide, and water and alcohols are particularly preferable. These solvents may be used alone or in a mixed system of two or more kinds such as a mixed solvent of water and alcohol, and may be appropriately selected in some cases.

Examples of such basic compounds include lithium hydroxide, potassium hydroxide, alkali metal hydroxides such as sodium hydroxide, magnesium hydroxide, alkaline earth metal hydroxides such as barium hydroxide, potassium carbonate, and carbonate. Alkali metal carbonates such as sodium, potassium ethylate,
Alkali metal alcoholates such as sodium methylate and sodium ethylate, 1,8-diazabicyclo [5.4.0]
Undecene-7, triethylenediamine, piperidine,
Examples thereof include amines such as ammonia and the like, and particularly preferred are alkali metal hydroxides, alkali metal carbonates and alkali metal alcoholates, and these may be used alone or in combination of two or more. Further, the amount of the compound to be added can be appropriately selected in some cases.

Further, when the reaction is carried out at a temperature of usually 30 ° C. or higher, preferably 40 ° C. or higher, the reaction proceeds rapidly and smoothly, and the desired derivative can be obtained in high yield. However, as the reaction temperature increases, the amount of by-products increases.
Reaction temperatures of less than or equal to ° C are preferred.

The reaction system is not particularly limited, but the reaction can be carried out under normal pressure or in a closed container under spontaneously generated pressure, and further under pressure, and can be appropriately selected in some cases.

The novel fluorinated arylguanamine derivative according to the present invention has at least one methylol group, has extremely excellent reactivity with compounds having various functional groups, resins and the like, and has various fluorinated compound derivatives, polymerizable monomers It is useful as a raw material of, for example, alcohols, carboxylic acids, isocyanates, and can be provided with compounds and resins which are difficult to obtain from known compounds by reacting with epoxies. Further, acrylic resins, epoxy resins, urethane resins , Aminoalkyd resin, phenolic resin, fluororesin, vinyl resin, etc. various polymer chain extenders, crosslinking agents,
It can be used as an excellent surface modifier such as a hardening agent or the like, or a water-repellent agent such as a synthetic fiber such as polyester fiber or acrylic acid fiber, or a natural fiber such as cotton or wool, but is not limited thereto. It is not something to be done.

As described above, the fluorinated arylguanamine derivative is excellent in polymerizability with various compounds and resins, and such polymerization is performed by any polymerization such as solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, and interfacial polymerization. It may be in a form, and can be appropriately selected in some cases.

In the novel fluorinated arylguanamine derivative according to the present invention, the hydroxyl group of the derivative shows excellent reactivity with compounds having various functional groups, and the fluorinated substituent of the derivative has chemical and physical properties. Is very stable, and the elimination of the fluorinated substituent by hydrolysis, heat, light, etc. hardly occurs, so that the desired function can be maintained for a long time, and the novel fluorinated arylguanamine of the present invention can be maintained. Derivatives are extremely useful because they can provide various fluorine-containing polymers, fluorine-containing compounds, and fluorine-containing compositions having excellent functionality that are difficult to obtain with known compounds.

Further, the fluorine-containing aryl guanamine derivative according to the present invention, using the above specific compound, a solvent, a reaction aid,
By appropriately selecting the pH, the reaction temperature, and the like, the production is simple, the desired target derivative can be obtained in a high yield, and it is technically and economically excellent and extremely practical.

Such a novel fluorine-containing arylguanamine derivative is
Alcohols, carboxylic acids, excellent reactivity with various compounds such as isocyanates, and also excellent in polymerizability with various resins, can be used as derivative raw materials, resin raw materials, rubber materials, film blocking prevention, Additives to resin, lubricating additive, release agent, wax such as car wax, back surface treatment agent for tape, non-adhesive for carry for electrostatic printing, improvement in printing durability of letterpress printing as reduction of friction coefficient of resin Agents, oil repellents for cameras, machines, etc., water repellents, oil repellents, optical materials, gas separation membrane materials, resist materials, home appliances, automobiles and other antifouling paints, anticorrosion paints, weather resistant paints, anti-icing paints, Anti-freezing paint, moisture-proof insulation of printed circuit boards, moisture-proofing agent for electric parts and circuit boards, etc., as a means of improving moisture-proof properties of semiconductor resin, prevention of bleeding of packaging paper, prevention of contamination of recording paper and labels, non-adhesiveness of release paper Grant, etc. Paper processing agents, antifouling processing for interior products such as curtains, sofas, wall cloths, carpets, etc., fiber processing agents such as fiber moisture permeation prevention processing, sweat absorption processing, SR processing, leather processing agents, heat resistant resins, corrosion inhibitors And a fluorine-containing polymer, a fluorine-containing compound, and a fluorine-containing composition, which are extremely useful as surfactants, insecticides, fungicides, medicines and the like.

〔Example〕

Next, the present invention will be described in detail with reference examples, examples and application examples. However, these Reference Examples, Examples, and Application Examples do not limit the scope of the present invention.

Reference Example 1 4-nona-fluorobenzyl butyl benzonitrile _{[C 4 F 9 C 6 H 6} CN ]
Production of: In a 500 ml flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and N ₂ blowing tube, 34.4 g (0.15 mol) of 4-iodobenzonitrile, 25.4 g (0.40 mol) of copper powder, and dimethyl sulfoxide Add 200 ml and stir. Then, the mixture was gradually heated under a nitrogen atmosphere, and 58.8 g (0.17 mol) of 1-iodoperfluorobutane was maintained while maintaining the internal temperature at 110 ° C.
Is added by a dropping funnel, and the dropping is completed in one hour. After the addition is completed, the internal temperature is further raised to 130 ° C., and
Allowed to react for hours. The reaction mixture was poured into 500 ml of distilled water, extracted with ether, and the ether obtained by removing the extracted portion was dried under reduced pressure. Next, this was recrystallized with toluene to obtain 40.0 g of 4-nonafluorobutylbenzonitrile (white crystals, melting point: 51.0 to 54.0).
° C). The results of elemental analysis, infrared absorption spectrum analysis, mass spectrum analysis, and ¹ H nuclear magnetic resonance absorption spectrum analysis of the target product are shown below.

Elemental analysis CHNF measurement: 41.2% 1.3% 4.4% 53.0% Calculated: 41.14% 1.26% 4.36% 53.24% Infrared absorption spectrum analysis (KBr method) Absorption based on benzene ring CH and skeleton 3.2μ, 3.3 μ, 6.1 μ, 6.6 μ, 11.7 μ Absorption based on nitrile group 4.5 μ Absorption based on CF 7.3 μ to 9.0 μ (broad absorption) Mass spectrum analysis (m / z): 321 (M ⁺ ), 302, 152 ¹ H nuclear magnetic resonance absorption spectrum analysis (internal standard: TMS, solvent: d ₆ -DMSO) Absorption based on benzene ring CH δ value 7.91 to 7.94 ppm (2H) δ value 8.10 to 8.13 ppm (2H) Reference example 24 4-tridecafluorohexyl benzonitrile [C ₆ F ₁₃ C
₆ H ₄ CN] Preparation of stirrer, a thermometer, a reflux condenser, a dropping funnel, a 500ml flask equipped with a N ₂ blow pipe, 4-bromo-benzonitrile 30.9 g (0.17 mol), copper powder 22.9 g (0.36 Mol) and 200 ml of dimethyl sulfoxide, and the mixture is stirred. Then, the mixture is gradually heated under a nitrogen atmosphere, and while maintaining the internal temperature at 110 ° C., 66.9 g (0.15 mol) of 1-iodoperfluorohexane is added through a dropping funnel, and the dropwise addition is completed in one hour. After completion of the addition, the internal temperature was further raised to 130 ° C., and the mixture was reacted for 5 hours while stirring. The reaction mixture was poured into 500 ml of distilled water, extracted with ether, and the ether obtained by removing the extracted portion was dried under reduced pressure. Next, this was recrystallized with a toluene-methanol solvent system to obtain 57.5 g of 4-tridecafluorohexylbenzonitrile (white crystals, melting point: 63.0 to 64.5 ° C). The results of elemental analysis, infrared absorption spectrum analysis, mass spectrum analysis, and ¹ H nuclear magnetic resonance absorption spectrum analysis of the target product are shown below.

Elemental analysis CHNF measurement: 37.1% 0.9% 3.3% 58.8% Calculated: 37.07% 0.96% 3.33% 58.64% Infrared absorption spectrum analysis (KBr method) Absorption based on benzene ring CH and skeleton 3.2μ, 3.3 μ, 6.1μ, 6.6μ, 11.8μ Absorption based on nitrile group 4.5μ Absorption based on CF 7.3μ ~ 8.9μ (broad absorption) Mass spectrum analysis (m / z): 421 (M ⁺ ), 402, 152 ¹ H nuclear magnetic resonance absorption spectrum analysis (internal standard: TMS, solvent: d ₆ -DMSO) Absorption based on benzene ring CH δ value 7.92 to 7.95 ppm (2H) δ value 8.12 to 8.15 ppm (2H) Reference example 34-Heptadecafluorooctylbenzonitrile [C ₈ F
Production of ₁₇ C ₆ H ₄ CN]: 50 equipped with a stirrer, thermometer, reflux condenser and N ₂ blowing tube
In a 0 ml flask, 27.3 g of 4-bromobenzonitrile (0.15
Mol), 25.4 g (0.40 mol) of copper powder, 92.8 g (0.17 mol) of 1-iodoperfluorooctane, and 200 ml of N, N-dimethylformamide, and gradually heated under a nitrogen atmosphere to lower the internal temperature. The mixture was stirred for 1 hour while maintaining the temperature at 110 ° C. Thereafter, the internal temperature was raised to 120 ° C., and the mixture was reacted for 5 hours with stirring. Pour the reaction mixture into 500 ml of distilled water,
Extraction was carried out with ether, and the solid content obtained by removing the ether of this extract was dried under reduced pressure. Next, this was recrystallized from methanol to give 57.9 g of 4-heptadecafluorooctylbenzonitrile (white crystals, melting point of 93.0 to
94.5 ° C). The results of elemental analysis, infrared absorption spectrum analysis, mass spectrum analysis, and ¹ H nuclear magnetic resonance absorption spectrum analysis of the target product are shown below.

Elemental analysis CHNF measurement: 34.7% 0.7% 2.7% 61.8% Calculated: 34.57% 0.77% 2.69% 61.97% Infrared absorption spectrum analysis (KBr method) Absorption based on benzene ring CH and skeleton 3.2μ, 3.3 μ, 6.1 μ, 6.6 μ, 11.6 μ Absorption based on nitrile group 4.5 μ Absorption based on CF 7.3 μm to 8.9 μ (wide absorption) Mass spectrum analysis (m / z): 521 (M ⁺ ), 502, 152 ¹ H nuclear magnetic resonance absorption spectrum analysis (internal standard: TMS, solvent: d ₆ -DMSO) Absorption based on benzene ring CH δ value 7.90 to 7.93 ppm (2H) δ value 8.10 to 8.13 ppm (2H) Reference example 4 4-heptacosafluorodecylbenzonitrile [C ₁₂ F
Production of ₂₅ C ₆ H ₄ CN]: 1-iodoperfluorooctane 9 in Reference Example 3
Reference Example 3 except that 126.8 g (0.17 mol) of 1-iodoperfluorodecane was used instead of 2.8 g (0.17 mol).
Reaction and treatment were carried out in the same manner as described above to obtain a solid content. Next, this was recrystallized from methanol to give 4-pentacosafluorodecylbenzonitrile (white crystals, melting point: 10%).
7-111 ° C). The results of elemental analysis, infrared absorption spectrum analysis, mass spectrum analysis, and ¹ H nuclear magnetic resonance absorption spectrum analysis of the target product are shown below.

Elemental analysis CHNF measured value: 31.6% 0.5% 2.0% 66.0% Calculated value: 31.64% 0.56% 1.94% 65.86% Infrared absorption spectrum analysis (KBr method) Absorption based on benzene ring CH and skeleton 3.2μ, 3.3 μ, 6.1 μ, 6.6 μ, 11.8 μ Absorption based on nitrile group 4.5 μ Absorption based on CF 7.3 μ to 8.9 μ (wide absorption) Mass spectrum analysis (m / z): 721 (M ⁺ ), 702, 152 ¹ H nuclear magnetic resonance absorption spectrum analysis (internal standard: TMS, solvent: d ₆ -DMSO) Absorption based on benzene ring CH δ value 7.91 to 7.94 ppm (2H) δ value 8.11 to 8.14 ppm (2H) Reference example 5 2,4-diamino-6- (4-nona fluoride behenate chill phenyl) -s-triazine _{[C 4 F 9 C 6 H 4} -C 3 N 3 (NH 2) 2 ] preparation of a stirrer, thermometer In a 500 ml flask equipped with a reflux condenser, 32.1 g (0.1 mol) of 4-nonafluorobutylbenzonitrile obtained by the method of Reference Example 1 was added. Amide
12.6 g (0.15 mol), caustic potash 0.6 g, methyl cellosolve 2
Then, the mixture was reacted at a temperature of 120 to 125 ° C. for 10 hours while stirring. After removing methyl cellosolve from the reaction mixture under reduced pressure, the solid was washed with water and dried under reduced pressure. Next, this was recrystallized in a toluene-methanol solvent system to obtain 37.3 g of 2,4-diamino-6- (4-nonafluorobutylphenyl) -s-triazine (white crystal, melting point: 217.
0-219.5 ° C). The results of elemental analysis, infrared absorption spectrum analysis, mass spectrum analysis, and ¹ H nuclear magnetic resonance absorption spectrum analysis of the target product are shown below.

Elemental analysis C H N F Found: 38.5% 2.0% 17.3% 42.1% Calculated: 38.53% 1.99% 17.28% 42.20% IR absorption spectrum analysis absorbing 2.9μ based on (KBr method) NH ₂ group, a 3.0μ benzene ring based absorption 6.3μ C-F based on the absorption 7.3Myu～8.9Myu (broad absorption) based on the triazine ring absorption 12.2μ mass spectrometry (m / z): 405 ( M +), 386,236 1 H nuclear magnetic resonance Spectral analysis (internal standard: TMS, solvent: d ₆ -DMSO) Absorption δ value based on NH ₂ group 6.88 ppm (4H, singlet) Absorption value based on benzene ring CH δ value 7.80 to 7.83 ppm (2H) δ value 8.43~8.46ppm (2H) reference example 6 2,4-diamino-6- (4-dec-fluoride-hexyl phenyl) -s-triazine _{[C 6 F 13 C 6 H 4} -C 3 N 3 (NH 2)
₂ ] Production: Instead of 32.1 g (0.1 mol) of 4-nonafluorobutylbenzonitrile in Reference Example 5, 4-tridecafluorohexylbenzonitrile 4 obtained by the method of Reference Example 2 was used.
The reaction and treatment were carried out in the same manner as in Reference Example 5 except that 2.1 g (0.1 mol) was used, and a solid content was obtained. Next, this was recrystallized in a toluene-methanol solvent system to give 2,4-
Diamino-6- (4-tridecafluorohexylphenyl) -s-triazine (white crystal, melting point 222.5-223.5
° C). The results of elemental analysis, infrared absorption spectrum analysis, mass spectrum analysis, and ¹ H nuclear magnetic resonance absorption spectrum analysis of the target product are shown below.

Elemental analysis CHNF measurement value: 35.7% 1.5% 13.9% 48.7% Calculated value: 35.66% 1.60% 13.86% 48.88% Infrared absorption spectrum analysis (KBr method) Absorption based on NH ₂ group 2.9μ, 3.0μ based absorption 6.3μ C-F based on the absorption 7.3Myu～9.0Myu (broad absorption) based on the triazine ring absorption 12.2μ mass spectrometry (m / z): 505 ( M +), 486,236 1 H nuclear magnetic resonance Spectral analysis (internal standard substance: TMS, solvent: d ₆ -DMSO) Absorption δ value based on NH ₂ group 6.90 ppm (4H, singlet) Absorption value based on benzene ring CH δ value 7.81 to 7.84 ppm (2H) δ value 8.43~8.46ppm (2H) reference example 7 2,4-diamino-6- (4-heptadecafluoro-fluorobenzyl octylphenyl) -s-triazine _{[C 8 F 17 C 6 H 4} -C 3 N 3 (NH 2) _2] preparation of instead, towards the reference example 3 4-nona-fluorobenzyl butyl benzonitrile 32.1g in reference example 5 (0.1 mol) 4 heptadecaethylene fluorosilicone octyl benzonitrile obtained in
Except for using 52.1 g (0.1 mol), the reaction and treatment were carried out in the same manner as in Reference Example 5 to obtain a solid content. Next, this was recrystallized from methanol to give 2,4-diamino-6-
(4-Heptadecafluorooctylphenyl) -s-triazine (white crystal, melting point: 222.0-223.0 ° C.) was obtained. The results of elemental analysis, infrared absorption spectrum analysis, mass spectrum analysis, and ¹ H nuclear magnetic resonance absorption spectrum analysis of the target product are shown below.

Elemental analysis CHNF measured value: 33.8% 1.3% 11.6% 53.5% Calculated value: 33.74% 1.33% 11.57% 53.36% Infrared absorption spectrum analysis (KBr method) Absorption based on NH ₂ group 2.9μ, 3.0μ based absorption 6.3μ C-F based on the absorption 7.3Myu～8.8Myu (broad absorption) based on the triazine ring absorption 12.2μ mass spectrometry (m / z): 605 ( M +), 586,236 1 H nuclear magnetic resonance Spectral analysis (internal standard: TMS, solvent: d ₆ -DMSO) Absorption δ value based on NH ₂ group 6.88 ppm (4H, singlet) Absorption value based on benzene ring CH δ value 7.79 to 7.82 ppm (2H) δ value 8.43~8.46ppm (2H) reference example 8 2,4-diamino-6- (4-hepta Kosa fluorosilicone dodecylphenyl) -s-triazine _{[C 12 F 25 C 6 H 4} -C 3 N 3 (NH 2) _2] preparation of instead, towards the reference example 4 4-nona-fluorobenzyl butyl benzonitrile 32.1g in reference example 5 (0.1 mol) 4- penta Kosa fluorosilicone dodecyl benzonitrile obtained in
The reaction and treatment were carried out in the same manner as in Reference Example 5 except that 72.1 g (0.1 mol) was used, and a solid content was obtained. Next, this was recrystallized from ethyl acetate to give 2,4-diamino-6-
(4-Pentacosafluorodecylphenyl) -s-triazine (white crystals, melting point 212.0-215.0 ° C.) was obtained. The results of elemental analysis, infrared absorption spectrum analysis, mass spectrum analysis, and ¹ H nuclear magnetic resonance absorption spectrum analysis of the target product are shown below.

Elemental analysis C H N F Found: 31.3% 0.9% 8.7% 58.8% Calculated: 31.32% 1.00% 8.70% 58.98% infrared absorption spectrum analysis absorbing 2.9μ based on (KBr method) NH ₂ group, a 3.0μ benzene ring based absorption 6.3μ C-F based on the absorption 7.3Myu～8.9Myu (broad absorption) based on the triazine ring absorption 12.2μ mass spectrometry (m / z): 805 ( M +), 786,236 1 H nuclear magnetic resonance Spectral analysis (internal standard: TMS, solvent: d ₆ -DMSO) Absorption δ value based on NH ₂ group 6.89 ppm (4H, singlet) Absorption value based on benzene ring CH δ value 7.81 to 7.84 ppm (2H) δ value 8.43 to 8.46 ppm (2H) Example 1 Production of N-methylol compound of 2,4-diamino-6- (4-nonafluorobutylphenyl) -s-triazine: 2,2 obtained by the method of Reference Example 5 4-diamino-6- (4
-Nonafluorobutylphenyl) -s-triazine 20.3
g (0.05 mol), 9.7 g of 37% formalin (formaldehyde 0.12 mol) adjusted to pH 10.0 with 10% aqueous potassium hydroxide solution
Was added. The mixture was heated with stirring at a temperature of 70-75 ° C for 20 minutes. This reaction mixture was a clear liquid, and as a result of analysis, it was found that 2.1 mol of formaldehyde was methylol-bonded to 1 mol of 2,4-diamino-6- (4-nonafluorobutylphenyl) -s-triazine. there were.

Example 2 Production of N-methylolated product of 2,4-diamino-6- (4-tridecafluorohexylphenyl) -s-triazine: 2,4-diamino-6- (obtained by the method of Reference Example 6 4
-Tridecafluorohexylphenyl) -s-triazine (25.3 g, 0.05 mol) in 10% aqueous potassium hydroxide solution to pH10.5
40.6 g of 37% formalin (formaldehyde 0.5
0 mol) was added. The mixture was heated with stirring at a temperature of 75-80 ° C for 1 hour. The reaction mixture was a clear liquid, and as a result of analysis, 2,4-diamino-6- (4
(Tridecafluorohexylphenyl) -s-triazine (1 mole) and formaldehyde (4.0 mole) bonded to methylol.

Example 3 Production of N-methylol compound of 2,4-diamino-6- (4-nonafluorobutylphenyl) -s-triazine: 2,4-diamino-6 (obtained by the method of Reference Example 5 4
-Nonafluorobutylphenyl) -s-triazine 20.3
To 1 g (0.05 mol), 18.7 g (0.23 mol of formaldehyde) of 37% formalin adjusted to pH 10.5 with a 10% aqueous sodium hydroxide solution was added. The mixture was heated with stirring at a temperature of 70-75 ° C for 30 minutes. The reaction mixture was a clear liquid, and as a result of analysis, 2,4-diamino-6- (4-
Nonafluorobutylphenyl) -s-triazine (1 mol) was combined with 3.7 mol of formaldehyde by methylol bond.

Example 4 Production of N-methylolated product of 2,4-diamino-6- (4-tridecafluorohexylphenyl) -s-triazine: 2,4-diamino-6- (obtained by the method of Reference Example 6 4
-Tridecafluorohexylphenyl) -s-triazine (25.3 g, 0.05 mol) in 10% aqueous sodium hydroxide solution at pH 10.
16.2 g of 37% formalin adjusted to 0 (formaldehyde 0.
2 mol) was added. The mixture was heated with stirring at a temperature of 70-75 ° C for 30 minutes. The reaction mixture was a clear liquid, and as a result of analysis, 2,4-diamino-6- (4
(Tridecafluorohexylphenyl) -s-triazine (1 mol) was combined with 3.6 mol of formaldehyde by methylol bond.

Example 5 Production of N-methylol compound of 2,4-diamino-6- (4-heptadecafluorooctylphenyl) -s-triazine: 2,4-diamino-6 obtained by the method of Reference Example 7 (4
-Heptadecafluorooctylphenyl) -s-triazine (30.3 g, 0.05 mol) was added to a 10% aqueous solution of sodium hydroxide at pH1.
20.3 g of 37% formalin adjusted to 1.0 (formaldehyde
0.25 mol). This mixture is heated at 60-65 ° C for 1 hour.
Heat with stirring for hours. The reaction mixture was a liquid separated into two layers, which was dehydrated under reduced pressure to obtain a viscous liquid. As a result of analyzing this, 2,4-diamino-6-
3.6 mol of formaldehyde was bonded to methylol with respect to 1 mol of (4-heptadecafluorooctylphenyl) -s-triazine.

Example 6 Production of N-methylol compound of 2,4-diamino-6- (4-pentacosafluorodecylphenyl) -s-triazine: 2,4-diamino-6 obtained by the method of Reference Example 8. (4
-Pentacosafluorodecylphenyl) -s-triazine (40.3 g, 0.05 mol) in 10% aqueous sodium hydroxide solution at pH 1
21.9 g of 37% formalin adjusted to 0.0 (formaldehyde
0.27 mol) was added. This mixture is heated at 75-80 ° C for 1 hour.
Heat with stirring for hours. The reaction mixture was a liquid separated into two layers, which was dehydrated under reduced pressure to obtain a viscous liquid. As a result of analyzing this, 2,4-diamino-6-
One mole of (4-pentacosafluorodecylphenyl) -s-triazine had 3.5 moles of formaldehyde bonded to methylol.

As shown in Examples 1 to 6, these novel fluorinated arylguanamine compounds and formaldehyde source undergo methylolation reaction very easily under mild conditions, and N- is very useful as various derivatives and resin intermediates. It is intended to provide a methylol-fluorinated arylguanamine derivative.

Example 7 Polymerization of N-methylol fluorinated aryl guanamine derivative and water repellency test of the resin: Using the N-methylol fluorinated aryl guanamine derivative obtained in Examples 3 to 6, water-ethanol (weight ratio)
30/70) to prepare a 5% by weight solution. to this,
As a catalyst, 30% by weight of ammonium chloride (based on the solid content of the derivative) was added. Using this solution, 1% by weight (based on the weight of the cloth) of the derivative was applied to a cotton cloth, and then the treated cotton cloth was dried and cured at 140 ° C. for 5 minutes. Table 1 shows the results of a water repellency test performed using this hardened cotton cloth.

As shown in Table 1, this novel N-methylol fluorine-containing arylguanamine derivative exhibited extremely excellent water repellency, and the derivative had extremely excellent properties.

The water repellency test was performed in accordance with JIS L 1005 (spray method).

Example 8 Polymerization of N-methylolated product of 2,4-diamino-6- (4-tridecafluorohexylphenyl) -s-triazine and stability test of fluorine-containing substituent: obtained by the method of Example 4. 2,4-diamino-6- (4
-Tridecafluorohexylphenyl) -s-triazine (5.0 g) was dissolved in iso-propyl alcohol (10 ml), p-toluenesulfonic acid (0.025 g) was added as a curing catalyst, and applied to a galvanized steel sheet. −2
Heat curing was performed under the condition of 0 minutes.

Using this painted steel sheet, wet resistance test (temperature 50 ℃, humidity
98%, 500 hours). No blistering, discoloration, etc. were observed on the surface of the coating film of the test steel sheet. Further, the coating film was peeled off, and elemental analysis was performed. .

As described above, this novel N-methylol fluorine-containing arylguanamine derivative is excellent in polymerizability, and the fluorine-containing substituent of the derivative is hard to be released by heat, water, etc., and has extremely excellent properties. Met.

Application Example 1 Production of N-methoxymethylated 2,4-diamino-6- (4-tridecafluorohexylphenyl) -s-triazine: 2,4-diamino-6 obtained by the method of Example 4. (4
-Tridecafluorohexylphenyl) -s-triazine 10.0 g of N-methylol compound (3.6 mol bond of formaldehyde to 1 mol of triazine)
Dehydration was performed under reduced pressure, and 50 ml of methanol was added thereto. The mixture was adjusted to pH 2.0 with 20% nitric acid,
Heated at 0-45 ° C for 1 hour. After adjusting the pH of the reaction mixture to 7.5 with a 10% aqueous solution of potassium hydroxide, methanol and water were removed under reduced pressure, and the solid content was filtered to obtain a viscous liquid. As a result of analyzing this, 2,4-diamino-6- (4-
3.1 equivalents of N-methoxymethyl groups were bonded to 1 mol of (tridecafluorohexylphenyl) -s-triazine.

As described above, this novel N-methylol fluorine-containing arylguanamine derivative easily undergoes an alkyl etherification reaction under mild conditions with an alcohol, and has extremely excellent reactivity. It provides an N-alkyl etherified product of the derivative which is extremely useful as a compound.

[Effects of the Invention] The novel fluorinated arylguanamine derivative having at least one methylol group according to the present invention has an active methylol group, and thus can be used with a compound having various functional groups, a polymer, etc. It has excellent reactivity, stability of the fluorinated substituent, excellent durability, can maintain the function for a long time, and has extremely excellent surface properties due to a long-chain perfluoroalkyl group. It can provide hard-to-obtain compounds, resins, etc., is useful for a very wide range of uses, and is an industrially excellent invention.

Claims (3)

(57) [Claims] (1) General formula (Wherein, n represents an integer selected from 1 to 14) At least one methylol obtained by reacting a fluorinated arylguanamine compound represented by the following formula with at least one selected from formaldehydes: A fluorine-containing arylguanamine derivative having a group. 2. The at least one formaldehyde according to claim 1, wherein the formaldehyde is at least one selected from formaldehyde, formalin, paraform, hexamethylenetetramine, methylhemiformal, and butylhemiformal. A fluorine-containing arylguanamine derivative having a methylol group. 3. A water / oil repellent for fibers comprising at least one selected from the fluorine-containing arylguanamine derivatives according to claim 1.