JPH03145476A - Fluorine-containing arylguanamine condensate - Google Patents

Abstract

NEW MATERIAL:Condensate of methylolated fluorine-containing arylguanamine. EXAMPLE:Methylolated condensate of 2,4-diamino-6-(4-nonafluorobutylphenyl)-s- triazine. USE:A polymerizable monomer useful as a raw material for various fluorine- containing compound derivatives. It has excellent reactivity and polymerizability to compounds, polymers, etc., having various functional groups and forms fluorine-containing substituent having excellent stability and durability. PREPARATION:The subject compound can be produced by the condensation reaction of a fluorine-containing arylguanamine compound of formula (n is 1-14) and other co-condensable compound (e.g. melamine) with formaldehydes.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel fluorine-containing arylguanamine condensate useful as a polymerizable monomer, a raw material for various fluororesins, and the like.

(Prior Art) Conventionally, as guanamine compounds having a fluorine-containing substituent, the following are known: (wherein m represents an integer selected from 1 to 15).

However, the former known compound is manufactured only using fluorine-containing fatty acid ester and biguanide as raw materials, but the manufacturing process of the raw materials requires complicated processes, and the stability of the raw materials is poor, making it difficult to handle. The yield in the production of known compounds is unfavorable, the steps such as purification and separation are complicated, and furthermore, the reactivity of the amino group in the compound is extremely poor, and various useful compounds that can be provided by reacting the amino group are The latter known compound has drawbacks such as significant limitations in the production of fluorine compound derivatives and fluorine-containing resins, and the fact that the latter produces many by-products during production and is difficult to purify and separate. These known compounds have defects such as the fact that the fluorine-containing substituent group is easily separated by hydrolysis, heat, light, etc., making it difficult to maintain the desired function over a long period of time. was subject to significant technical and economic limitations.

As a result of extensive research to overcome the above-mentioned defects in guanamine compounds having fluorine-containing substituents, the present inventors found that
It is easy to manufacture, has an active amino group that exhibits remarkable reactivity with compounds having various functional groups, and has almost no separation of fluorine-containing substituents by hydrolysis, heat, light, etc.
It can maintain its functionality over a long period of time, and because it has a long-chain perfluoroalkyl group, it has extremely excellent surface properties, making it useful for rubber materials, mold release agents, water and oil repellents, optical materials, etc.
Provides fluorine-containing polymers, fluorine-containing compounds, and fluorine-containing compositions useful as gas separation membrane materials, resist materials, antifouling paints, weather-resistant paints, paper processing agents, fiber treatment agents, heat-resistant resins, surfactants, etc. We have provided a novel fluorine-containing arylguanamine compound represented by the following formula, which has extremely useful uses and usefulness (Japanese Patent Application No. 1-2463).
No. 37〉.

(In the formula, n represents an integer selected from 1 to 14) [
Problems to be Solved by the Invention] An object of the present invention is to provide an excellent new fluorine-containing arylguanamine condensate that is a derivative of such a useful new fluorine-containing arylguanamine compound.

[Means to solve problems]

As a result of intensive studies on such useful derivatives of fluorine-containing arylguanamine compounds, the present inventors found that they are easy to produce, have active groups that exhibit remarkable reactivity with compounds having various functional groups, and have hydrated derivatives. There is almost no separation of fluorine-containing substituents due to decomposition, heat, light, etc., and functions can be maintained for a long period of time. Rubber materials, mold release agents, water and oil repellents, optical materials, gas separation membrane materials, resist materials, A novel fluorine-containing arylguanamine condensation product that can provide fluorine-containing polymers, fluorine-containing materials, etc. as antifouling paints, weather-resistant paints, paper processing agents, fiber treatment agents, heat-resistant resins, surfactants, etc. We discovered this and arrived at the present invention.

That is, the present invention provides at least one fluorine-containing arylguanamine compound represented by the general formula (in the formula, n is an integer selected from 1 to 14); A methylol compound fluorinated arylguana obtained by condensing at least one type selected from elementary arylguanamine compounds and at least one type selected from other cocondensable compounds with at least one type selected from formaldehydes. The methylol compound fluoroarylguanamine condensate described in (2) and (1) and at least one selected from aliphatic alcohols and alicyclic alcohols having 0 to 20 carbon atoms are combined into an ether. This is an etherified fluorine-containing arylguanamine condensate obtained by a chemical reaction.

Fluorine-containing arylguanamine compound (1) according to the present invention
), n is an integer selected from 1 to 14, but an odd number is preferable from the viewpoint of ease of obtaining raw materials, etc., and when n is an integer of 3 or more, it has good stain resistance and water repellency. It is particularly useful because of its excellent surface properties such as oiliness, lubricity, and non-adhesion.

Specific examples of the fluorine-containing arylguanamine compound (1) include 2,4-cyano-6-(4-pentafluoroethylphenyl)-S-)riazine, 2,4-diamino-6-(4- Hebutafluoropropylphenyl)-
s-triazine, 2,4-cyamino-6-(4-nonafluorobutylphenyl)-8-triazine, 2,4-cyamino-6-(4undecafluoropentylphenyl)
-s-triazine, 2,4-diamino-6-(4-tridecafluorohexylphenyl)-s-1-riazine,
24-diamino-6-(4-pentadecafluoroheptylphenyl)-3-triazine, 2,4-diamino-6
-(4-hebutadecafluorooctylphenyl)-S-
Triazine, 2.4-cya≧no 6-(4-nonadecafluorononylphenyl)-S-triazine, 2.4-cyamino-6-(4-heneicosafluorodecylphenyl)-S-)lyazine, 2 .4-cyamino-6-(4-pentacosafluorotetradecylphenyl)-S-)riazine, 2.4-cyamino-6-(4-nonacosafluorotetradecylphenyl)-S-triazine, 2. Examples include 4-diamino-6-(4-hentriacontafluoropentadecylphenyl)-S-)riazine, but are not limited to these compounds.

Such a fluorine-containing arylguanamine compound (1) is made by combining a fluorine-containing nitrile represented by the general formula (wherein n has the same meaning as above) and dicyandiamide with alcohols, amines, carboxylic acid amides, and sulfolanes. , in non-aqueous solvents such as sulfoxides, amines,
In the presence of basic compounds such as alkali metal hydroxides and alkali metal alcolades, usually at a temperature of 80″C to 150°C.
It can be obtained by carrying out the reaction at

In addition, the above-mentioned fluorine-containing nitriles (n) include, for example, l-berfluoroalkyl iodide, bromide, chloride, etc.
It can be obtained by reacting halogen-substituted benzonitrile and metallic copper in an aprotic polar solvent.

In addition, other cocondensable compounds according to the present invention include, for example, guanamine compounds such as melamine, N-phenylmelamine, benzoguanamine, acetoguanamine, and formoguanamine, urea, N-methylurea, N-ethylurea, and N-ethylurea. , alkyl urea such as N'-dimethylurea, thiourea, alkylthiourea such as N-methylthiourea, N-butylthiourea, phenol, p-methylphenol,
Alkylphenols such as p-nonylphenol and m-ethylphenol, aniline, ammeline, etc. are useful;
Furthermore, melakiran, penzoguan ξane, urea, and phenol are preferred, but the compounds are not limited to these.

Examples of formaldehydes according to the present invention include formaldehyde, formalin, paraform, hexamethylenetetramine, methyl hemiformal, butyl hemiformal, formaldehyde sodium bisulfite adduct, etc., but any formaldehyde sodium bisulfite adduct may be used as long as it acts as a formaldehyde source. , but is not limited to these compounds.

In addition, such a condensation reaction is carried out in advance by carrying out the reaction in a solvent at a temperature of 50 to 80°C under alkaline conditions, and then carrying out the reaction at a temperature of 60 to 80°C under weakly alkaline to acidic conditions; Temperature 50-8 under strong alkaline conditions
Examples include a method in which the reaction is carried out at 0°C, a method in which the reaction is carried out at a temperature of 60 to 80°C under slightly acidic or alkaline conditions of pH 6 to 9, and the reaction is carried out by adjusting the pH as necessary. The desired methylol-containing fluoroarylguanagon condensate can be obtained by carrying out this reaction.However, under acidic conditions with a pH of 5 or less, the formaldehyde (tjJO reaction) is slow, and under alkaline conditions with a pH of 10 or higher, This is undesirable because the purpose-built hardware contains a large amount of salt, which limits its use.However, such reactions are not limited to these methods.

Examples of such solvents include water, alcohols such as methanol, ethanol, butyl alcohol, and cyclohexanol, esters, ketones, ethers, and carboxylic acid amides, with water and alcohols being particularly preferred. .

Incidentally, these solvents may be used alone or in a mixed system of two or more such as a mixed solvent of water and alcohol, and can be appropriately selected depending on the case.

Furthermore, the present invention provides a methylolated fluorine-containing arylguanamine condensate obtained by etherifying at least [+] selected from aliphatic alcohols and alicyclic alcohols having 1 to 20 carbon atoms. The present invention provides a novel ether compound fluoroarylguana condensate.

Among such aliphatic alcohols and alicyclic alcohols having 1 to 20 carbon atoms, saturated aliphatic alcohols having linear or side chains having 1 to 20 carbon atoms, unsaturated aliphatic alcohols having branched chains Saturated alicyclic alcohols and unsaturated alicyclic alcohols are sometimes useful, and alcohols having 1 to 6 carbon atoms are also useful for ease of production, usefulness of the fluorine-containing arylguanamine condensate, reactivity, etc. Particular preference is given to saturated aliphatic alcohols and cyclohexanol.

Specific examples of such aliphatic alcohols and alicyclic alcohols having 1 to 20 carbon atoms include methanol, ethanol, n-propyl alcohol, 1so-propyl alcohol, allyl alcohol, n-butyl alcohol, 1so-butyl alcohol, tert-butyl alcohol, propargyl alcohol, neopentyl alcohol, n-hexyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, n-nonyl alcohol, n-dodecyl alcohol, n-hexadecyl alcohol, n-octadecyl alcohol, n- eicosyl alcohol, etc.) aliphatic alcohol, cyclohexanol,
Cyclohexenol, 4-methylcyclohexanol,
Examples include, but are not limited to, 3-methylcyclohexanol, cyclohexylcarbinol, 4-ethylcyclohexanol, 4-hexylcyclohexanol, 3,5-di-n-hexylcyclohexanol, and the like.

In addition, as an etherification reaction between such a methylolated fluorine-containing arylguanamine condensate and one type selected from aliphatic alcohols and alicyclic alcohols having 1 to 20 carbon atoms, a methylol compound obtained by separation may be performed. Using a fluorine arylguanamine condensate or a methylol compound fluorine arylguanamine condensate with a water content of 20% or less and one kind selected from such aliphatic alcohols and alicyclic alcohols, under acidic conditions, preferably p
At H1.0 to 5.0, at a reaction temperature of 30 to 80'C,
The etherification reaction of the present invention includes a method in which the etherification reaction is carried out in a solution or suspension using an excess of a non-aqueous solvent or the above-mentioned aliphatic alcohol or alicyclic alcohol as appropriate depending on the case. Although a fluorine-containing arylguanamine condensate can be obtained, the method is not limited to these methods.

The novel fluorine-containing arylguanamine condensate according to the present invention has an active methylol group and/or ether group, has excellent reactivity with compounds having various functional groups, resins, etc., and is suitable for various fluorine-containing compound derivatives. is useful as a raw material for polymerizable monomers, etc., and can be reacted with alcohols, carboxylic acids, isocyanates, and epoxies to provide compounds and resins that are difficult to obtain from known compounds, and can also be used as acrylic resins and epoxy resins. , chain extenders and crosslinking agents for various polymers such as urethane resins, alkyd resins, phenolic resins, fluororesins, vinyl resins, etc.
It can be used as an excellent surface modifier such as a water and oil repellent for fibers such as hardeners, synthetic fibers such as polyester fibers and acrylic acid fibers, and natural fibers such as cotton and wool, but is limited to these. It is not something that will be done.

As mentioned above, the fluorine-containing arylguanagon metal condensate has excellent polymerizability with various compounds and PI4 fats, but
Such polymerization may be in any form such as solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, interfacial polymerization, etc., and can be appropriately selected depending on the case.

In the novel fluorine-containing arylguanamine condensate according to the present invention, the active methylol group and/or ether group of the condensate exhibits excellent reactivity with compounds having various functional groups; The fluorine-containing substituents possessed by
Since the fluorine-containing substituent is hardly removed by heat, light, etc., the desired function can be maintained for a long period of time, and the novel fluorine-containing arylguanamine condensate of the present invention has functionality that is difficult to obtain with known compounds. Various excellent fluorine-containing polymers,
It is extremely useful as it can provide fluorine-containing and 11-carbon compounds.

Furthermore, the fluorine-containing arylguanamine condensate according to the present invention can be easily produced by using the above-mentioned specific compounds and resins, and by appropriately selecting the solvent, reaction aid, pH1 reaction temperature, etc. It is possible to obtain the desired condensate in high yield, is technically and economically superior, and is extremely practical.

Such novel fluorine-containing arylguanagon metal condensates have excellent reactivity with various compounds such as alcohols, carboxylic acids, and isocyanates, and also have excellent polymerizability with various resins, and can be used as raw materials for derivatives and resins. Can be used as additives to resins such as preventing blocking of rubber materials, films, and lowering the friction coefficient of resins, lubricating additives, mold release agents, waxes such as car wax, backing agents for tapes, and carriers for electrostatic printing. non-adhesive agents, printing durability improvers for Toppan Printing, oil repellents for cameras, machinery, etc., water and oil repellents, optical materials, gas separation membrane materials, resist materials, antifouling paints and anticorrosion for home appliances, automobiles, etc. Moisture-proofing paints, weather-resistant paints, anti-icing paints, anti-icing paints, moisture-proof insulation for printed circuit boards, moisture-proofing treatment agents for electrical parts, circuit boards, etc. to improve the moisture-proofing properties of semiconductor resins, extraction bleed prevention for packaging paper, and recording. Paper processing agents for preventing stains on paper and labels, imparting non-adhesiveness to release paper, anti-fouling treatment for interior products such as curtains, sofa-1 wall cloth, carpets, moisture permeation prevention treatment for fibers, sweat absorption treatment, SR treatment Fluorine-containing polymers that are extremely useful as textile processing agents, leather processing agents, heat-resistant resins, corrosion inhibitors, surfactants, insecticides, fungicides, medicines, etc.
It is possible to provide fluorine-containing string products.

(Example) Next, the present invention will be explained in detail using reference examples, working examples, and application examples.However, these reference examples, working examples, and application examples are intended to limit the scope of the present invention only to these. isn't it.

Reference example 1 4-nonafluorobutylbenzonitrile (CaFqCJ
<CN) Production: In a 500/nff1 flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and N2 blowing tube, 34.4 g (0.15 mol) of 4-iodohendinitrile and 2 copper powder were added.
5.4 g (0.40 mol), dimethyl sulfoxide 2
Add 00Id and stir. Next, the l-
58.8 g (0.17 mol) of iodoperfluorobutane was added using a dropping funnel, and the dropwise addition was completed in 1 hour. After the addition was completed, the internal temperature was further raised to 130°C, and the reaction was continued for 2 hours with stirring. This reaction mixture was mixed with 50 ml of distilled water.
The solid content obtained by removing the ether from the extracted bones was dried under reduced pressure.Next, this was recrystallized with toluene to obtain 40.0
g of 4-nonafluorobutylbenzonitrile (white crystals, melting point 51.0-54.0°C) was obtained. The results of elemental analysis, infrared absorption spectrum analysis, mass spectrum analysis, and +11 nuclear magnetic resonance absorption spectrum analysis of the target product are shown below.

Elemental analysis CHNF Measured value: 41.21 1.3$ 4.4%
53.0! Direct calculation: 41.14K 1.
261 4.361 53.24 Infrared absorption spectrum analysis (KBr method) Absorption based on benzene ring C-H and skeleton 3.2μ, 3.3μ, 6.1μ, 6.6μ, 11.7μ
Absorption based on nitrile group: 4.5 μ Absorption exposed to C-F: 7.3 μ to 9.0 μ (broad absorption) Mass spectrum analysis (m/z): 321 (M”), 302.15
2'I+ nuclear magnetic resonance absorption spectroscopy (internal standard Tt:TMs, solvent n d & -D gate So)
Absorption δ value based on benzene ring C-H 7.91 to 7.94 pp (2■) δ i direct
8.10~&, 13 pp+w (21υ Reference Example 2 4-tridecafluorohexylbenzonitrile (CiF
+3CJ4CN) Production: Stirrer, thermometer, reflux condenser, dropping funnel, N.

In a 500 flask equipped with a blow tube, 30.9 g (0.17 mol) of 4-bromobenzonitrile and 22 g of copper powder were added.
．． 9 g (0.36 mol), dimethyl sulfoxide 20
Add 1-iodoperfluorohexane and stir.Next, gradually heat under a nitrogen atmosphere and while maintaining the internal temperature at 110°C, add 66.9 g (0.15 mol) of 1-iodoperfluorohexane.
was added using a dropping funnel, and the addition was completed in 1 hour.

After the addition was completed, the internal temperature was further raised to 130°C, and the reaction was continued for 5 hours with stirring. This reaction mixture was mixed with distilled water.
The solid content obtained by removing the ether from the extracted bones was dried under reduced pressure. Next, this was recrystallized in a toluene-methanol solvent system, and 51.5 g of 4-tridecafluorohexylhendinitrile (white crystals, melting point 63.0-64.5°C) was obtained.
) was obtained. The results of elemental analysis, infrared absorption spectrum analysis, mass spectrum analysis, and 'H nuclear magnetic resonance absorption spectrum analysis of the target product are shown below.

Elemental analysis CHNF Measured value: 37.1χ 0.9X 3.3X
58.8! Calculated value: 37.07X 0.96X
3.33! 58.64X infrared absorption spectrum analysis (KBr method) Absorption based on benzene ring C-H and skeleton 3.2μ, 3.3μ, 6.1μ, 6.6μ, 11.8μ
Absorption based on nitrile group: 4.5 μ Absorption based on C-F: 7.3 μ to 8.9 μ (broad absorption) Mass spectrum analysis (m/z): 421 (M′″), 402.1
52'11 nuclear magnetic resonance absorption spectrum analysis (internal standard substance: TMS, solvent: d, -DMSO) Absorption based on benzene ring C-H δ1 7.92-7.95ρp偕(2H) δ value 8.1
2-8.15 ppm (2H) Reference Example 3 4-Hebutadecafluorooctylbenzonitrile (Cg
Production of F+tCJaCN): In a 500I11 flask equipped with a stirrer, thermometer, reflux condenser, and N2 blowing tube,
27.3 g of 4-promohenzonitrile (0,15
mol), copper) 25.4 g (0.40 mol),
92.8 g of 1-iodoperfluorooctane (0,1
7 mol), N,N-dimethylformad, and gradually raised the temperature in a nitrogen atmosphere to bring the indoor bath to 110 mol.
The mixture was stirred for 1 hour while maintaining the temperature at °C. After that, increase the internal temperature to 12
The temperature was raised to 0°C, and the reaction was allowed to proceed for 5 hours while stirring.

This reaction mixture was poured into 500ml of distilled water, extracted with ether, the extracted ether was removed, and the resulting solid content was dried under reduced pressure.Next, it was recrystallized with methanol. and 57.9 g of 4-hebutadecafluorooctylbenzonitrile (white crystals, melting point 93.0~
94.5°C) was obtained. The results of elemental analysis, infrared absorption spectrum analysis, mass spectrum analysis, and 'H nuclear magnetic resonance absorption spectrum analysis of the target product are shown below.

Elemental analysis CHNF ijllll constant (i: 34.7% 0.72
2.7! 61.8X calculated value: 34.57X
O,77χ 2.69X 61.97X Infrared absorption spectrum analysis (KBr method) Absorption based on Hensen ring C-H and skeleton 3.2μ, 3.3μ, 6.1μ, 6.6μ, 11.6μ
Absorption based on nitrile group: 4.5 μ Absorption based on C-F: 7.3 μ to 8.9 μ (broad absorption) Mass spectrum analysis (m/z): 521 (M”), 502.15
21H nuclear magnetic resonance absorption spectrum analysis (internal standard substance: TMS, solvent j d, -D SO) Absorption δ value based on benzene ring C-H 7.90-7.93 ppm (2B) δ value 8
．． 10-8.13 ppm (211) Reference Example 4 4-Pentacosafluorododecylbenzonitrile (C4
Production of FzsCJaCN): 1-iodoperfluorooctane 92 in Reference Example 3
．． The reaction and treatment were carried out in the same manner as in Reference Example 3, except that 126.8 g (0.17 mol) of ■-iodoperfluorododecane was used instead of 8 g (0.17 mol), and the solid content was reduced. Obtained. Next, this was recrystallized with methanol to obtain 4-pentacosafluorododecylbenzonitrile (white crystals, melting point 107~Ill''C). Elemental analysis, infrared absorption spectrum analysis, and mass of the target product. The results of the SW vector analysis and 'H nuclear magnetic resonance absorption spectrum analysis are shown below.

Elemental analysis CHNF Measured value: 31.6X 0.5$ 2.0$
66.0! Calculated value: 31.64X 0.56
X 1.94$ 65.86X Infrared absorption spectrum analysis (KBr method) Absorption based on benzene ring C-H and skeleton 3.2μ, 3.3μ, 6.1μ, 6.6μ, 11.8μ
Absorption based on nitrile group: 4.5 μ Absorption based on C-F: 7.3 μ to 8.9 μ (broad absorption) Mass spectrum analysis (m/z): 721 (Ma, 702.1
52+H nuclear magnetic resonance absorption spectroscopy (internal standard substance: TMS, solvent: d, -D?l5O)
Absorption δ value based on benzene ring C-H 7.91-7.94 ppm (2B) δ value 8
．． 11-8.14 ppm (211) Reference example 5 2.4-diamino-6-(4-nonafluorobutyl 7
, z = Le) -S -) Rear shift [CaFqChH
Production of s-CsNs(NHz)z): 32.1 g (0, 1 mol), dicyandiamide 12.6 g (0,15-i-l),
0.6 g of caustic potash and methyl cellosolve 200- were charged and reacted for 10 hours with stirring at a temperature of 120-125"C. After removing methyl cellosolve from the reaction mixture under reduced pressure, the solid content 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-cyano6-(4-nonafluorobutylphenyl)-S-triazine (white crystals, (melting point: 217.0-219.5°C).The results of elemental analysis, infrared absorption spectrum analysis, mass spectrum analysis, and 'H nuclear magnetic resonance absorption spectrum analysis of the target product are shown below.

Elemental analysis CHNF measurement value 7 38.5! 2.0χ 17.3!
42.1χ calculated value: 38.53X 1.99χ
17.28X 42.20! Infrared absorption spectrum analysis (KBr method) Absorption based on NO3 group 2.9μ, 3.0
Absorption based on μ benzene ring 6.3 μ Absorption based on C-F 7.3 μ to 8.9 μ (broad absorption) Absorption based on triazine ring 12.2 μ Mass spectrum analysis (m/z): 405 (M”), 386 ．．
236H nuclear magnetic resonance absorption spectrum analysis (internal standard substance: TMS, solvent: d, -IIMSO)
Absorption δ value based on NHz group 6.88 ppm (4H, singlet) Absorption δ value based on benzene ring C-H (straight 7.80-7.83 ppm (2H)
δ value 8.43-8.46ρpta (2H) Reference example 6 2.4-diamino-6-(4-tridecafluorohexylphenyl) -s -) riazine CC,F+zCJ4
Production of CcoL (NHz)z): Instead of 32.1 g (0.1 mol) of 4-nonafluorobutylbenzonitrile in Reference Example 5, Reference Example 2
The reaction and treatment were carried out in the same manner as in Reference Example 5, except that 42.1 g (0.1 mol) of 4-tridecafluorohexylbenzonitrile obtained by the method was used, and the solid content was obtained. This was recrystallized in a toluene-methanol solvent system to obtain 2,4-cyamino-6-(4-1ridecafluorohexylphenyl)-s-triazine (white crystals, melting point 222.5-223.5°C). ) was obtained. The results of elemental analysis, infrared absorption spectrum analysis, mass spectrum analysis, and 'H nuclear magnetic resonance absorption spectrum analysis of the target product are shown below.

Elemental analysis CHNF Measured value: 35. MaX 1.5$ 13.9X
48.7X calculated value: 35.66$ 1.60$
13.86$ 48.88'& Infrared absorption spectrum analysis (KBr method) Absorption based on NH2 group 2.9μ, 3
．． 0 μ Absorption based on benzene ring 6.3 μ Absorption based on C-F 7.3 μ to 9.0 μ (broad absorption) Absorption based on triazine ring 12.2 μ Mass spectrum analysis (m/z): 505 (M”), 486 ．．
236'11 nuclear magnetic resonance absorption spectroscopy (internal standard substance: TMS, solvent: di-DMSO) N
Absorption δ value based on To group 6.90 pps+ (4H, symblent)
Absorption δ value exposed to benzene ring C-H 7.81-7.84 ppm (2H) δ value 8
．． 43-8.46 ppm (28) Reference Example 7 2.4-diamino-6-(4-hebutadecafluorooctylphenyl)-S-) riazine (CsF + yca
Production of lla-CJs (NHz): Reference Example 5
4-nonafluorobutylbenzonitrile in 32.
Except that 52.1 g (0.1 mol) of 4-hebutadecafluorooctylbenzonitrile obtained by the method of Reference Example 3 was used instead of 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 with methanol, and 2.
4,-Diamino-6-(4-hebutadecafluorooctylphenyl) -S triazine (white crystals, melting point 222
．． 0-223.0°C). elemental analysis of the target object;
Infrared absorption spectroscopy, mass spectrometry, 'H
The results of nuclear magnetic resonance absorption spectrum analysis are shown below.

Elemental analysis CHNF measurement 4ri: 33.8z1.3! 11.6X
Calculated value: 33.74$ 1.332 11.57
% 53.362 Infrared absorption spectrum analysis (KBr
Method) Absorption based on Ni1□ group 2.9μ, 3.0μ Absorption based on benzene ring 6.3μ Absorption based on C-F 7.3μ to 8.8μ (broad absorption) Absorption based on triazine ring 12.2μ Mass spectrum Analysis (m/Z): 605 (M'), 586.23611
Nuclear magnetic resonance absorption spectroscopy (internal standard substance: TMS, solvent: d, -D gate 5o) N
ll! Absorption δ value based on group 6.88 pp+* (411°benzene ring C-
Absorption δ value based on H 7.79-7.82 pp Hinoki (2H) δ value 8.
43-8.46 ppm (2H)53.5χ singlet) Reference example 8 2.4-diamino-6-(4 pentacosafluorododecylphenyl)-S-) riazine (C+□hsc
Production of J4-CsNi (old N): 4 in Reference Example 5
-32.1 g of nonafluorobutylbenzonitrile (
4-pentacosafluorododecylbenzonitrile obtained by the method of Reference Example 4 instead of 72.0', 1 mol).
The reaction and treatment were carried out in the same manner as in Reference Example 5 except that 1 g (0.1 mol) was used to obtain a solid content. Next, this was recrystallized from ethyl acetate to produce 2,4-diamino-6-(4-pentacosafluorododecylphenyl).
-3-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 111 nuclear magnetic resonance absorption spectrum analysis of the target product are shown below.

Elemental analysis CHNF Measured value: 31.3χ 0.9$ 8.7$
58.8χ calculation (tj 31.32$ 1.OO
X 8.70! 58.98X infrared absorption spectrum analysis (KBr method) Absorption based on NH group 2.9μ, 3
．． 0 μ Absorption based on benzene ring 6.3 μ Absorption based on C-F 7.3 μ to 8.9 μ (broad absorption) Absorption exposed to triazine ring 12.2 μ Mass spectrum analysis (m/z): 805 (M'), 786 .2361■
Nuclear magnetic resonance absorption spectroscopy (internal standard substance: TMS, solvent: di-D 5O) N
Absorption δ value based on O3 group 6.89 pp+w (4H, singlet) Absorption δ value based on benzene ring C-H 7.81-7.84 ppm (2H) δi
8.43-8.46 ppm (2) 1) Example 1 Production of methylolated condensate of 2.4-diamino-6-(4-nonafluorobutylphenyl)-S-)riazine: of Reference Example 5 2,4-shea trillion no 6=(4
-nonafluorobutylphenyl)-S-triazine 20
．． 3 g (0.05 mol) of 37% formalin adjusted to pl (12°0) with 20% caustic potassium aqueous solution.
g (0.28 mol formaldehyde) was added. This mixture was reacted for 20 minutes at a temperature of 70°C. This reaction mixture was adjusted to pH 7.5 with 10% nitric acid, and after removing excess formaldehyde and water under reduced pressure, methanol was added to dissolve it. As a result of this analysis, the total amount of formaldehyde bound per triazine nucleus was 3.67.
It was a methylolated condensate of the compound in which 3.26 equivalents of methylol groups and 0.41 equivalents of dimethylene ether groups were bonded.

Example 2 Preparation of methylolated condensate of 2,4-cyano6-(4-tridecafluorohexylphenyl)-S-triazine: 2,4-cyano6- obtained by the method of Reference Example 6 (4
-Tridecafluorohexylphenyl)-s-) 25.3 g (0.05 mol) of riazine was adjusted to pH with sodium carbonate.
25.9 g of 37% formalin adjusted to 7.0 (0,
32 mol) was added. This mixture was heated to 65°C for 3 hours.
The reaction was allowed to proceed for 0 minutes. After removing excess formaldehyde and water from the reaction mixture under reduced pressure, methanol was added to dissolve it. As a result of analysis, it was found to be a methylolated condensate of the compound in which a total of 3.74 equivalents of formaldehyde bonds, 3.65 equivalents of methylol groups, and 0.0 g equivalent of methylene groups were bonded to one triazine nucleus.

Example 3 Preparation of methylolated condensate of 2,4-diamino-6-(4-hebutadecafluorooctylphenyl)-S-)riazine: 2,4-diamino-6-(4- Tridecafluorohexylphenyl)-S-) riazine25.
3 g (0.05 mol) of 2,4-cyamino-6-(4-heptadecafluorooctylphenyl)-S-) liazine obtained by the method of Reference Example 7, 30.3
The reaction and treatment were carried out in the same manner as in Example 2, except that g (0.05 mol) was used.

As a result of this analysis, the total formaldehyde bond amount was 3.73 equivalents per triazine nucleus, and the methylol group was 3.62 equivalents.
It was a methylolated condensate of the compound in which 0.11 equivalents of methylene groups were bonded.

- Example 4 Production of methylolated condensate of 2,4-diamino-6-(4-pentacosafluorododecylphenyl)-S-)riazine: 2,4-diamino-6-(4 -tridecafluorohexylphenyl)-S-) riazine25.
3 g (instead of 0.05 mol), 40.3 g of 2,4-diamino-6-(4pentacosafluorododecylphenyl)-S-)riazine obtained by the method of Reference Example 8
The reaction and treatment were carried out in the same manner as in Example 2 except for using (0.05 mol).

As a result of this analysis, the total formaldehyde bond amount was 3.67 equivalents per triazine nucleus, and the methylol group was 3.60 equivalents.
It was a methylolated condensate of the compound to which 0.07 equivalents of methylene groups were bonded.

Example 5 Preparation of etherified condensate of 2,4-diamino-6-(4-nonafluorobutylphenyl)-s-1-riazine: 2,4-diamino-6-(obtained in Example 1) A methanol solution of the methylolated condensate of '4-nonafluorobutylphenyl)-3-triazine log was purified with 20% nitric acid.
The temperature was adjusted to 4.0, and the reaction was carried out at a temperature of 60° C. for 1 hour.

This reaction mixture was a clear liquid, and analysis of this revealed that the total formaldehyde bond i for one triazine nucleus was
It was an etherified condensate of the compound in which 3.6 g equivalent, 1.83 equivalent of methyl ether group, 1.65 equivalent of methylol group, and 0.21 equivalent of methylene group were bonded.

Example 6 Preparation of etherified condensate of 2.4-cyamino-6-(4-tridecafluorohexylphenyl)-S-) riazine: 2,4-cyamino-6- obtained by the method of Example 2 (4
A methanol solution of a methylolated condensate of (tridecafluorohexylphenyl) S-triazine was adjusted to pus, s with 30% sulfuric acid, and reacted at a temperature of 70°C for 1 hour. This reaction mixture was a transparent liquid, and as a result of its analysis, the total amount of formaldehyde bonds per triazine nucleus was 3.73 equivalents, methyl ether group 1.78 equivalent, methylol group 1.82 equivalent, and methylene group 0. It was an etherified condensate of the compound in which 13 equivalents were bound.

Example 7 Production of etherified cocondensate of 2.4-diamino-6-(4-)lidecafluorohexylphenyl)-S-) liazine and melamine: 2,4-diamino obtained by the method of Reference Example 6 -6(4-
tridecafluorohexylphenyl) s-triazine 2
5.3 g (0.05 mol) and melamine 6.3
g (0.05 mol), 74.4 g (1.20 mol) of methyl hemiformal and 5 mol of methanol.
0g was added, adjusted to pl+8.0 with 30% caustic potassium aqueous solution, and reacted at a temperature of 75°C for 30 minutes.
After adjusting to puto with 30% sulfuric acid, 1 at a temperature of 70°C.
Allowed time to react. This reaction mixture was a clear liquid, and after adjusting the pH to 7.5 and removing excess formaldehyde, methanol and water under reduced pressure, n-butyl alcohol was added and dissolved. As a result of analyzing this, the total amount of formaldehyde bonds was 4.38 equivalents, 2.2 g equivalent of methyl ether group, 1.98 equivalent of methylol group, and 0.11 equivalent of methylene group were bonded to one triazine nucleus. It was a thing.

Application example 1 Polymerization of methylolated condensate of fluorine-containing arylguanamine and water repellency test of the resin: Using the methylolated condensate of fluorine-containing arylguanamine obtained in Examples 1 to 4, water-methanol (ffi amount A 5% by weight solution was prepared using a solvent with a ratio of 20/80).

To this was added 30 ft1% ammonium chloride (based on the solid content of the condensate) as a catalyst.

Using this solution, 1% by weight (based on the weight of the cloth) of the condensate was deposited on a cotton cloth, and then the treated cotton cloth was dried and cured at 140 DEG C. for 5 minutes. Table 1 shows the results of a water repellency test using this cured cotton fabric.

As shown in Table 1, this new methylol compound fluoroarylguanamine condensate exhibited very excellent water repellency, and the condensate had extremely excellent properties.

In addition, the water repellency test is based on JIS L 1005 (spray method)
The test was conducted in accordance with the .

Application example 2 Polymerization of methylolated condensate of 2.4-diamino-6-(4-)lidecafluorohexylphenyl)-S-) riazine and stability test of fluorine-containing substituent: Methylolated condensate of 2,4-cyagono-6-(4-tridecafluorohexylphenyl)-S-triazine5. Og to n-butyl alcohol 10
After dissolving it in Ii and adding 0.025 g of P-toluenesulfonic acid as a curing catalyst, and applying it to a galvanized steel plate,
It was heated and cured at 0°C for 20 minutes.

A moisture resistance test (temperature: 50°C, humidity: 98%, 500 hours) was conducted using this coated steel plate. No blisters, discoloration, etc. were observed on the surface of the coating film of the test steel sheet, and furthermore, as a result of peeling off the coating film and conducting elemental analysis, the F content was 42.2% (
The measured value before the test was F content of 143.1%).

As shown above, this new methylol compound fluoroarylguanane condensate has excellent polymerizability, and furthermore, the fluorine-containing substituents of the condensate are difficult to separate from due to heat, water, etc., and have extremely excellent properties. It was something.

Application example 3 Polymerizability of etherified condensate of 2.4-diamino-6-(4-)lidecafluorohexylphenyl)-s-triazine and stability test of fluorine-containing substituent: 2 obtained in Example 6 , 5-0 g of etherified condensate of 4-diamino-6-(4tridecafluorohexylphenyl)-S-triazine was dissolved in 101 d of 1so-propyl alcohol, and an acrylic resin (non-volatile content 50% by weight, solid content OH value 60) ) After applying this resin solution to a galvanized steel plate, it was heated at 150°C-30
It was heated and cured under the conditions of 10 minutes.

Using this coated steel plate, a moisture resistance test (temperature: 50° C., humidity: 98%, 500 hours) was conducted. No blisters, discoloration, etc. were observed on the surface of the coating film of the test steel plate, and as a result of peeling off the coating film and conducting elemental analysis, the F content was 7.8% (pre-test measurement (f F content 7.9 %)Met.

As shown above, this new etherified fluorine-containing arylguanamine condensate has excellent polymerizability, and furthermore, the fluorine-containing substituent of the condensate is difficult to separate from due to heat, water, etc., and has extremely excellent properties. It was something.

〔Effect of the invention〕

The novel methylol-containing fluorinated arylguanamine condensates and etherified fluorinated arylguanamine condensates according to the present invention can be combined with compounds, polymers, etc. having active methylol groups and/or ether groups and various functional groups. It has excellent reactivity and polymerizability, as well as stability and durability of fluorine-containing substituents, and can provide compounds and resins that are difficult to obtain from known compounds. It's an excellent invention.

Claims (5)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, n represents an integer selected from 1 to 14) A condensation reaction is carried out with at least one kind selected from formaldehydes together with one kind or at least one kind selected from such fluorine-containing arylguanamine compounds and at least one kind chosen from other co-condensable compounds. A methylolated fluorine-containing arylguanamine condensate obtained by (2) The other cocondensable compound according to claim 1 is
A methylolated fluorine-containing arylguanamine condensate characterized by being at least one selected from melamine, benzoguanamine, urea, and phenol. (3) A methylolated fluorine-containing arylguanamine, wherein the formaldehyde according to claim 1 is at least one selected from formaldehyde, formalin, paraform, hexamethylenetetramine, methyl hemiformal, and butyl hemiformal. condensate. (4) Etherification reaction of the methylolated fluorine-containing arylguanamine condensate according to claims 1, 2, and 3 with at least one selected from aliphatic alcohols and alicyclic alcohols having 1 to 20 carbon atoms. At least the etherified fluorine-containing arylguanamine condensate obtained. (5) At least one selected from the aliphatic alcohols and alicyclic alcohols having 1 to 20 carbon atoms according to claim 4 is a saturated aliphatic alcohol having 1 to 6 carbon atoms and cyclohexanol. An etherified fluorine-containing arylguanamine condensate characterized by being at least one selected from among these.