JPH02308873A - Coating composition - Google Patents

Abstract

PURPOSE:To provide the title composition capable of giving coating films of excellent in surface characteristics such as water-and-oil repellency and icingproofness, stability, durability, etc., containing a hydroxyl group contg. polymer and a curing agent comprising a specific methylol-modified fluorine- contg. guanamine condensate. CONSTITUTION:The objective composition containing (A) a hydroxyl group- contg. polymer and (B) a curing agent comprising a methylol-modified fluorine- contg. guanamine condensate prepared by condensation between (1) a fluorine- contg. guanamine compound of formula I (Rf is fluorine-contg. group), (2) another compound capable of condensation and (3) a formaldehyde. The Rf is pref. a fluorine-contg. group of formula II (R1 is CF3, C2F5, C4F9. etc.; R2 is F or CF3; R3 is methylene, ethylene. etc.; n is 1-7).

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a stain-proof, non-adhesive, water-repellent product which contains a specific fluorine-containing guanamine condensate and a polymer having a hydroxyl group as essential components. The present invention relates to a novel coating-forming composition that is useful for forming coating layers with excellent oiliness, mold releasability, etc. over a long period of time.

[Conventional technology]

Conventionally, coating compositions having a fluorine-containing substituent in the side chain include CH2=CHOC)+2(CF2)L-1cF3 (wherein l represents an integer selected from 1 to 12), or CH2= CHC00C112C)+2(CF2)ffi
Coating compositions made of polymers containing -ICF3 (where m is an integer selected from 1 to 12) as an essential structural unit are known.

However, it is difficult to obtain a general-purpose copolymer containing general-purpose monomers such as (meth)acrylic acid ester, styrene, acrylonitrile, etc. as a structural unit, and it is difficult to obtain a polymer containing the former known compound as an essential constituent unit. In addition, the fluorine-containing substituent group is easily separated by hydrolysis, heat, light, etc., and the polymer having the latter known compound as an essential constituent unit has defects such as significant restrictions on the polymer composition. Compositions containing polymers containing these known compounds as essential constituent units, which have defects such as difficulty in maintaining their functions over a long period of time, must be manufactured and used.
It was severely limited technically and economically.

[Problem to be solved by the invention]

As a result of intensive studies to overcome the above-mentioned defects in coating compositions having fluorine-containing substituents in their side chains, the inventors of the present invention have found that the fluorine-containing substituents are hardly removed by hydrolysis, heat, light, etc., and the coating composition maintains its functionality for a long period of time. Furthermore, coating layers can be easily formed using various polymers having hydroxyl groups, and there are extremely few restrictions on the production and composition of coating materials (
Anti-fouling paint, anti-corrosion paint, weather-resistant paint, anti-icing paint, snow-prevention coating for roofing materials, road signs, steel towers, electric wires, etc., moisture-proof coating, release coating for molding molds, etc. A new material that can provide extremely useful materials for floor desk applications such as dirt-lubricant coating materials, water-repellent and oil-repellent materials, optical materials, gas separation membrane materials, paper processing materials, fiber processing materials, rubber materials, resist materials, etc. The present invention was achieved by discovering a composition for forming a coating.

That is, the present invention provides a coating forming composition comprising a polymer having a hydroxyl group and a curing agent as essential components, wherein the curing agent is represented by the general formula (wherein Rf represents a fluorine-containing group). At least one kind selected from fluorine-containing guanamine compounds, or at least one kind chosen from among the above-mentioned fluorine-containing guanamine compounds and at least one kind selected from other co-condensable compounds from among formaldehydes. A coating forming composition characterized by containing as a component a methylolated fluorine-containing guanamine condensate obtained by condensation reaction with at least one selected one, and a polymer having a hydroxyl group and a curing agent as essential components. In the coating forming composition, the curing agent is
An etherified fluorine-containing guanamine condensate obtained by subjecting the methylolated fluorine-containing guanamine condensate described in the preceding section to an etherification reaction with at least one selected from aliphatic alcohols and alicyclic alcohols having 1 to 20 carbon atoms. A composition for forming a coating, which is characterized in that it contains a substance as a component.

As the polymer having a hydroxyl group according to the present invention, various polymers can be used as long as they have a hydroxyl group,
For example, hydroxyalkyl vinyl ether, hydroxyalkyl (meth)acrylate, allyl alcohol, methallyl alcohol, 4-hydroxy-1,1,2-)
Refluorobutene-1,6-hydroxy-1,1,2
, 3,3,4,4-heptafluoro-hexene-1 and other hydroxyl group-containing monomers as structural units, addition polymers or grafted polymers, vinyl carboxylates, allyl carboxylates, polyolefins, etc. Polymers containing as constituent units monomers having groups that can be converted to hydroxyl groups by hydrolysis, alcoholysis, oxidation, etc., with this part converted to hydroxyl groups, polybasic acids and polyhydric alcohols, or polybasic acids and polyhydric alcohols, or polybasic acids and polyhydric alcohols, or Polyester polymers with hydroxyl groups obtained by condensation polymerization of derivatives or ring-opening polymerization of lactones, polyhydric alcohols, epoxy condensation polymers with hydroxyl groups obtained by reacting phenols with epichlorohydrin, etc., ethylene oxide, propylene Polymers obtained by addition condensation of alkylene oxide polymers having hydroxyl groups having oxides etc. as essential constituent units, silicone resins having hydroxyl groups such as organosiloxanol, melamine, guanamines, ureas, phenols and formaldehydes. Phenol alkyd polymers obtained by co-condensation of polybasic acids, polyhydric alcohols, fatty acids, and phenol formaldehyde, etc., as well as polymers modified using isocyanates, ε-caprolactone, etc., or the above-mentioned polymers, etc. Combination etc. are useful, but
It is not limited to these.

Further, as such a polymer, a polymer containing a hydroxyl group in a primary or secondary form is preferable from the viewpoint of reaction during coating formation.

Furthermore, as polymers having such hydroxyl groups, hydroxyalkyl (
(meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylonitrile, (meth)acrylamide, Acrylic polymers having other constituent units such as styrene, p-methylstyrene, vinyl acetate, maleic anhydride, butadiene, and derivatives thereof, fluoroolefins, cyclohexyl vinyl ethers, alkyl vinyl ethers, and hydroxyalkyl vinyl ethers as essential constituent units. and 40 to 60 mol%, respectively, and 5
Fluorine-containing polymers, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride containing in proportions of ~45 mol%, 5-45 mol%, and 3-15 mol% , hymic anhydride, succinic anhydride, adipic acid, sebacic acid,
Polybasic acids such as azelaic acid, dodecanedicarboxylic acid, maleic anhydride, ethylene glycol, propylene glycol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, triethylene glycol, bisphenol dihydroxypropyl ether, cyclohexane dimetatool, glycerin , polyester polymers having hydroxyl groups obtained by polycondensation of polyhydric alcohols such as trimethylolethane and trimethylolpropane, or derivatives thereof, bisphenol A, etc.
Preferred are epoxy polymers having hydroxyl groups obtained by polycondensation of polyhydric phenol and epichlorohydrin, and the like.

Specific examples of such polymers having hydroxyl groups include Door Akron 600, Door Acron 700 (manufactured by Toa Paint ■), Magiklon-600 (manufactured by Kansai Paint ■), and Almatex 7.
4B-5M, 748-16AE, 781-26, 781-27, 7B2-5, 784, 762LV
55A, D104, D105, D151, 89
4-2 Acrylic resin (manufactured by Mitsui Toatsu Chemical Co., Ltd.), etc., Orester Q152, Orester Q161-45, Orester Q169 [
Polyester modified acrylic resin such as manufactured by Mitsui Toatsu Chemical Co., Ltd., Lumiflon LF100, Lumiflon LP200, Lumiflon LF302
, LF400 , LF554 , LF600
Fluorine-containing resin such as C manufactured by Asahi Glass, Belacolite N-6
601-60-5 [manufactured by Dainippon Ink & Chemicals ■] oil-modified polyester resin, Almatex p-645, same P
-646, P-647BS, HMP15, 11
MP25, HMP34 (manufactured by Mitsui Toatsu Chemical),
Veracolite N-6602-60-5, Veracolite M-6401
-50, M-6402-50, M-6003-60
, M-6005-60, M-6007-60, 4
8-312, 49-376, 46-169-5, M-6201-40-IM, M-6204-50-5
, M-6204-50-3 [Dainippon Ink Chemical Industry ■
], Dynapol R29, LH790, LH81
2. Oil-free polyester resin such as L I+ 821C manufactured by Dynamite Norpel, Aloblack 1F 10. Silicone-modified polyester resins such as 1711, 7323 (manufactured by Kuuchaku Arrow Kagaku ■), Epikote 1001, 1004, 1007, 1009,
1010, 0L55-B-40 (manufactured by Yuka Shell Epoxy Co., Ltd.), Araldite GY-6071, GY-60
84, epoxy resins such as cy-6097 (manufactured by Ciba Geigy), Epoky 8031 manufactured by Mitsui Toatsu Chemical Co., Ltd.), Evotote YD-017, YD-014, VD-01
1. Yo-128 (manufactured by Tobu Kasei), Epicron 40
50 (manufactured by Dainippon Ink & Chemicals), Eponix 1
10, Urethane-modified epoxy resin such as 3100 (manufactured by Dainippon Toyo ■), Plaxel G-101, Plaxel G-102
, ε-caprolactone modified epoxy resins such as G-401, G-701, G-702 (manufactured by Daicel Chemical Industries, Ltd.), Evokey 701) IV (manufactured by Mitsui Toatsu Chemical Industries, Ltd.)
Examples include polyester-modified epoxy resins such as
It is not limited to these.

In the fluorine-containing guanamine compound (1) according to the present invention, Rf is a fluorine-containing group, such as F, CF3-(CF2), 6-+- group (where m is 1 to
A perfluoroalkyl group represented by H-(ChCF2) (indicates an integer selected from 1 to 8), and ωH- represented by a - group (in the formula, ! represents an integer selected from 1 to 8) Perfluoroalkyl group, CF3CF2CF2
-0-(CF(CF3)CF20) p-+-CF(C
F3) - group (wherein p represents an integer selected from 1 to 30);
Fluoro-substituted phenyl group, CF3-(CFZ) , -C
A fluorine-containing alkoxy group represented by H2CII20- group (wherein S represents an integer selected from 1 to 15),
R1-(CFzCF (R2)) , -1-Ih- group [wherein, Rf is CF3, CzFs, Czh, (CF3)
, cp, C4F9, (Ch)zcF-0 group, R2 is F atom and/or CF3 group, R3
is one selected from methylene, ethylene, trimethylene, and propylene groups, and n is an integer selected from 1 to 7], but is limited only to these. isn't it.

Furthermore, such an Rf group is a fluorine-containing guanamine compound (1
), the amino group in the compound (1) has excellent reactivity and the condensate can be easily produced using the compound (1);
In the production of the fluorine-containing group, there are almost no by-products produced and the steps such as purification and separation are simple, and the production cost of the fluorine-containing base material is low and easy to obtain, and the fluorine-containing group is not separated by hydrolysis, heat, light, etc. General formula % formula %
) [In the formula, R1 is CF3, CzFs, CJq, (CF3)
2CF, C4F9, (Ch) One type selected from 2CF-0 group, R2 is F atom and/or CF3 group, R
A fluorine-containing group represented by 3 is one selected from methylene, ethylene, trimethylene, and propylene groups, and n is an integer selected from 1 to 7 is preferred. In the fluorine-containing group (It), Rf is CF3, C2
PS, C3F? , (CF3)2CF, CaFq, (C
F3) One type selected from zcF-0 groups, and R
2 is an F atom and/or a CF3 group, but from the viewpoint of reactivity during raw material production, R2 is particularly preferably an F atom, and furthermore, h
is one selected from methylene, ethylene, trimethylene, and propylene groups, and methylene and ethylene groups are particularly preferred from the viewpoint of raw materials and ease of production of the compound (I).

Further, when the number of carbon atoms bonded to the F atom is 3 or more, such an Rf group is particularly useful because of excellent surface properties such as antifouling properties, water/oil repellency, lubricity, and non-adhesiveness.

Specific examples of such fluorine-containing guanamine compounds (I) include 2,4-diamino-6-fluoro-S-triazine, 2,4-diamino-6-trifluoromethyl-S-)
Riazine, 2,4-diamino-6-berfluoroethyl-5-)riazine, 2,4-diamino-6-berfluoropropyl-8-triazine, 2,4-diamino-6-
Berfluorobutyl-8-triazine, 2,4-diamino-6-berfluoropentyl-8-triazine, 2.
4-diamino-6-berfluoroheptyl-5-triazine, 2,4-diamino-6-berfluorononyl-s
-') Riazine, 2,4-diamino-6-berfluorotridecyl-S-triazine, 2,4-diamino-6-
Verfluoropentadecyl-5-) riazine, 2.4-
Diamino-6-(ωH-berfluoroethyl)-8-triazine, 2,4-diamino-6-(ωH-berfluorobutyl)-S-)riazine, 2,4-diamino-6-
(ωH-perfluorohexyl)-S-) riazine, 2
,4-diamino-6-(ωH-berfluorooctyl)
-s-) riazine, 2.4-diamino-6-(ωH-berfluorodecyl)-S-triazine, 2.4-diamino-6-(ωH-berfluorododecyl)-S-triazine, 2, 4-Diamino-6-(ωH-berfluortetradecyl)-S-) riazine, 2,4-diamino-6
-(ωH-berfluorhexadecyl)-s-1-lyazine, 2,4-diamino-6-berfluoro-(1-methyl-2-oxapentyl)-s-)lyazine, 2.4
-diamino-6-perfluoro-(1,4-dimethyl-
2,5-dioxaoctyl)-s-) riazine, 2.4
-diamino-6-perfluoro-(1,4,7-)dimethyl-2,5,8-trioxaundecyl)-S-) riazine, 2,4-diamino-6-perfluoro-(1,
4,7,10-tetramethyl-2,5,8,11-tetraoxatetradecyl)-s-triazine, 2,4-diamino-6-(3-fluorophenyl)-8-triazine, 2.4 -diamino-6-(2,5-difluorophenyl)-5-triazine, 2,4-diamino-6-(3
-) trifluoromethylphenyl)-8-triazine, 2
．． 4-diamino-6-(3,3,3-trifluoropropoxy)-s-1-riazine, 2,4-diamino-6-
(s,3,4.j,4-pentafluorobutoxy)-S
-triazine, 2,4-diamino-6-(3,3,4,
4,5,5,6,6,6-nonafluorohexyloxy)-S-triazine, 2,4-diamino-6-(IH,
IH, 211, 2) 1-berfluorooctyloxy)
-8-triazine, 2,4-diamino-6-(IH,I
H,2H,2H-berfluorodecyloxy)-S-)
Riazine, 2,4-diamino-6-(IH, 111,2
H,2H-perfluorotetradecyloxy)-S-)
Riazine, 2,4-diamino-6-(IH, 18,21
4,211-berfluorhexadecyloxy)-s-
Triazine, 2,4-diamino-6-(2,2,2-)
(lifluoroethyl)-s-) liazine, 2,4-diamino-6-(2,2,3,3,3-pentafluoropropyl)-S-) riazine, 2,4-diamino-6-(IH
, LH-heptafluorobutyl)-s-triazine, 2
．． 4-Diamino-6-(111,111-nonafluoropentyl)-s-)'JT riazine, 4-diamino-6
-(18,n+-undecafluorohexyl)-S-)
Riazine, 2,4-diamino-6-(IH, 111-)
Ridecafluoroheptyl)-8-triazine, 2.4-
Diamino-6-(LH, LH-pentadecafluorooctyl)-s-triazine, 2,4-diamino-6-(I
H,18-hebutadecafluorononyl)-3-triazine, 2,4-diamino-6-(IH,18-nonadecafluorodecyl)-s-)riazine, 2,4-diamino-
6-(III, IH-heneicosafluorundecyl) -S-triazine, 2,4-diamino-6-(I
H,IH-pentacosafluorotridecyl)-S-triazine, 2.4-diamino-6-(II, l1l-nonacosafluoropentadecyl)-S-) liazine, 2.4
-diamino-6-(Ill,LH-)lydoriacontafluorheptadecyl)-S-)lyazine, 2,4-diamino-6-(3,3,3-)lifluoropropyl)-8
-triazine, 2,4-diamino-6-(3,3°4.
4.4-Pentafluorobutyl)-S-triazine, 2
．． 4-diamino-6-(3,3,4,4,5,5,5-
hebutafluoropentyl)-3-) riazine, 2.4-
Diamino-6-(3,3,4,4,5,5,6,6,6
-nonafluorohexyl)-8-triazine, 2.4-
Diamino-6-(IH,IH,2)1,28-undecafluoroheptyl 1s-)riazine, 2,4-diamino-6-(IH,IH,2H,2H-)lidecafluorooctyl)- 8-triazine, 2,4-diamino-6-(
IH, IH, 211,28-pentadecafluorononyl)-s-)') azine, 2,4-diamino-6-(
IH, LH, 211,2H-heptadecafluorodecyl)-5-) riazine, 2,4-diamino-6-(LH,
IH, 2H, 2H-nonadecafluorundecyl)-S
-) riazine, 2,4-diamino-6-(IH, IH,
2H,2H-heneicosafluorododecyl)-8-triazine, 2.4-diamino-6-(1)1. IH, 2
8,2H-tricosafluoro, lutrizosyl) -S-triazine, 2,4-diamino-6-(11(, IH, 2
8,2H-pentacosafluorotetradecyl)-3-triazine, 2,4-diamino-6-(IH,LH,28
, 211-hebutacosafluoropentadecyl)-s-triazine, 2,4-diamino-6-(LH, IH, 2H
, 2H-nonacosafluorohexadecyl)-8-triazine, 2,4-diamino-6-(IH, IH, 21(,
28-hentriacontafluorheptadecyl 15-)
Riazine, 2,4-diamino-6-(E, IH, 2H,
2H-) Lydoriacontafluorooctadecyl)-s-
) riazine, 2,4-diamino-6-(4,4,5,5
,5-pentafluoropentyl)-8-triazine, 2
,4-diamino-6-(4,4,5,5,6°6.7.
7.7-nonafluoroheptyl)-s-) riazine, 2
,4-diamino-6-(111,111,2H,2H,
3H,38-tridecafluorononyl)-3-)riazine, 2,4-diamino-6-(111,111,2H,
2H,3H,311-pentadecafluorodecyl)-s
-triazine, 2゜4-diamino-6-(LH, 111
,2H,2+1,3H,3+1-heptadecafluorundecyl)-3-triazine, 2,4-diamino-6-
(11(,LH,2H,28,3H,3H-nonadecafluorododecyl)-5-)lyazine, 2゜4-diamino-6-(111,IH,2H,28,31(,3H-nonaphtha) fluoroheptadecyl)-5-) riazine, 2.
4-diamino-6-(1-methyl-1l+, 2H,
2+1-heptadecafluorodecyl 1l-3-) riazine, 2,4-diamino-6-(1-()lifluoromethyl)-3,4,4,4-tetrafluorobutyl2 3
-triazine, 2,4-diamino-6-(5-()lifluoromethyl)-III, 18,214,2H-octafluorohexyl) -S-triazine, 2,4-diamino-6-C1-()lifluoromethyl) -LH,I
ll, 28.2H-dodecafluorooctyl)-s-triazine, 2.4-diamino-6-(9-D-lifluoromethyl)-1H,IH,28,2)1-hexadecafluorodecyl]-8- Triazine, 2,4-diamino-6
-(11-()lifluoromethyl) -1)1. Ill
, 2H,2H-eicosafluorododecyl]-s-triazine, 2,4-diamino-6-(15-(trifluoromethyl)-18,Ill, 2H,2+1-octacosafluorohexadecyl]-3- Triazine, 2,4-diamino-6-C4-()lifluoromethyl)-Ill,
1B-octafluoropentyl]-8-triazine, 2
．． 4-diamino-6-(6-()lifluoromethyl)-
Ill, LH-dodecafluorohebutyl]-3-triazine, 2,4-diamino-6-(8-(1-lifluoromethyl)-1H,LH-hexadecafluorononyl>S-)lyazine, 2.4- Diamino-6-[12-(
trifluoromethyl)-11(,II(-tetracosafluorotridecyl)-3-)riazine, 2,4-diamino-6-(4-()trifluoromethyl)-4,5,5,
5-tetrafluoropentyl-3-triazine, 2.
4-diamino-6-(8-()lifluoromethyl)-1
8,III, 2H,2H,3H,3H-dodecafluorononyl]-3-triazine, 2,4-diamino-6-(
2-(berfluorisopropoxy)-ethyl>S-)
Riazine, 2,4-diamino-6-(3,3,4,4-
Tetrafluoro-4-(berfluorisopropoxy)
-butyl]-3-triazine, 2,4-diamino-6-
(6-(berfluoroisopropoxy)-1)1.1)
1,214.2H-octafluorohexyl)-5-)
Riazine, 2,4-diamino-6-(8-(berfluoroisopropoxy)-1)1. IH,2H,2H-dodecafluorooctyl]-8-triazine, 2,4-diamino-6-(12-(berfluoroisopropoxy)
-1H,IH,28,2) 1-eicosafluorododecyl: l-3-) riazine, 2,4-diamino-6-[1
4-(berfluorisopropoxy)-LH,18,2
H,28-tetracosafluorotetradecyl)-S-)
Lyazine, 2,4-diamino-6-C1-(berfluoroisopropoxy)=IH,IH-dodecafluoroheptyl)-S-) Lyazine, 2,4-diamino-6-[1
1-(berfluorisopropoxy)-1H,IH-eicosafluorundecyl)-3-) riazine, 2,4
-diamino-6-(9-(berfluoroisopropoxy)-IH,111,2H,2+1.38.3H-dodecafluorononyl]-8-triazine,2,4-diamino-6-(1-( trifluoromethyl)-18,LH,2
H,2H-hexafluoropentylcy8-triazine, 2,4-cyamino-6-(3-()lifluoromethyl)-11LIB, 2H,2)1-octafluorohexyl)-3-)lyazine, 2. 4-diamino-6-[3-
(trifluoromethyl)-LH,IH,2H,2H-decafluoroheptyl)-5-) riazine, 2,4-diamino-6-[3,5-bis(trifluoromethyl)
-11L111.211.28-heptafluorohexyl-8-triazine, 2,4-diamino-6-[3
-(trifluoromethyl)-1H,LH,2H,21-
1-dodecafluorooctyl)-s-) riazine, 2.
4-diamino-6-[,3-D-lifluoromethyl]-4
-(berfluorisopropoxy)-trifluorobutyl) -S-triazine, 2,4-diamino-6-(3
,5-bis(trifluoromethyl)-11(,Il+
, 211,2H-undecafluorooctyl-8-triazine, 2,4-diamino-6-(3,5,7-1-
Lis(trifluoromethyl)-LH, IH, 2H, 2H
-decafluorooctyl)-s-) riazine, 2.4-
Diamino-6-[2,4-bis(trifluoromethyl)
-1H,LH-pentadecafluorononyl)-S-)
Riazine, 2゜4-diamino-6-(3,5-bis(trifluoromethyl)-6-(berfluoroisopropoxy)-18,IH,28,2H-hexafluorohexyl)-s-triazine, 2 ,4-diamino-6-(
'l-(trifluoromethyl)-LH,LH,28,2
11-hexadecafluorodecyl)-3-) riazine,
Examples include 2,4-diamino-6-(ICl3-bis(trifluoromethyl)-1H,IH,21(,2H-)licosafluorotetradecyl)-5-)riazine, but are limited to these compounds. It is not something that will be done.

In addition, other cocondensable compounds according to the present invention include, for example, guanamine compounds such as melamine, N-phenyl-melamine, 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, p
-Alkylphenols such as nonylphenol and m-ethylphenol, aniline, ammeline, etc. are useful;
Furthermore, melamine, benzoguanamine, urea, and phenol are preferred, but the compound is not limited to these compounds.

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 or acidic conditions. , under strong alkaline conditions at a temperature of 50~
Examples include a method of carrying out the reaction at 80°C, a method of carrying out the reaction at a temperature of 60 to 80°C under slightly acidic or alkaline conditions of pH 6 to 9, etc.
The desired methylolated fluorine-containing guanamine condensate can be obtained by adjusting ++ and carrying out the reaction, but the addition reaction of formaldehyde is usually slow under acidic conditions of pH 5 or lower, and under alkaline conditions of pH 810 or higher. This is not preferred because not only side reactions occur, but also a large amount of salt is contained in the intended condensate, which limits its use.

Note that such reactions are not limited to these methods.

Examples of such solvents include water, alcohols such as methanol, ethanol, butanol, 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 coating forming composition comprising a polymer having a hydroxyl group and a curing agent as essential components, wherein the curing agent has 1 to 20 carbon atoms in combination with the methylolated fluorine-containing guanamine condensate. Provided is a composition for forming a coating, which contains as a component an etherified fluorine-containing guanamine condensate obtained by subjecting at least one kind selected from aliphatic alcohols and alicyclic alcohols to an etherification reaction. It is something.

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 saturated aliphatic alcohols having 1 to 6 carbon atoms are also useful because of ease of production and reactivity of the fluorine-containing guanamine condensate. and cyclohexyl alcohol are particularly preferred.

Specific examples of such aliphatic alcohols and alicyclic alcohols having 1 to 20 carbon atoms include methanol, ethanol, n-propanol, and is.

-Propertool, allyl alcohol, n-butyl alcohol, 1so-butyl alcohol, tert-butyl alcohol, propagyl alcohol, neopentyl alcohol, n-hexyl alcohol, n-octyl alcohol, 2-ethyl-hexyl alcohol, n- Aliphatic alcohols such as nonyl alcohol, n-dodecyl alcohol, n-hexadecyl alcohol, n-octadecyl alcohol, n-eicosyl alcohol, cyclohexyl alcohol, cyclohexenyl alcohol, 4-methylcyclohexyl alcohol, 3-methylcyclohexyl alcohol , cyclohexylmethanol, 4-ethylcyclohexyl alcohol, 4-hexylcyclohexyl alcohol, 3,5-di-n-hexylcyclohexyl alcohol and the like, but are not limited to these.

In addition, as an etherification reaction between the methylolated fluorine-containing guanamine condensate and one type selected from aliphatic alcohols and alicyclic alcohols having 1 to 20 carbon atoms, the methylolated guanamine condensate obtained by separation may be performed. Using a fluorine-containing guanamine condensate or a methylolated fluorine-containing guanamine condensate having a moisture content of 20% or less and one kind selected from such aliphatic alcohols and alicyclic alcohols, under acidic conditions, preferably at a pt+ of 1.0 to 5.0, etherification in a solution or suspension at a reaction temperature of 30 to 80°C using an appropriate non-aqueous solvent or an excess of the above-mentioned aliphatic alcohol or alicyclic alcohol depending on the case. Examples include methods of carrying out the reaction, and the desired etherified fluorine-containing guanamine condensate can be obtained, but the method is not limited to these methods.

Furthermore, as the etherified fluorine-containing guanamine condensate according to the present invention, the above-mentioned fluorine-containing guanamine compound (1)
At least one selected from the monomethylolated product, dimethylolated product, trimethylolated product, and tetramethylolated product of An etherification reaction is carried out in a solution or suspension using at least one kind selected from alcohols and alicyclic alcohols under acidic conditions at a reaction temperature of 30 to 80°C, and a condensation reaction is carried out. The etherified fluorine-containing guanamine condensates obtained by the methods described above can also be used, but the invention is not limited to the etherified fluorine-containing guanamine condensates obtained by these methods.

In the coating forming composition according to the present invention, in addition to the curing agent containing the above-mentioned methylolated fluorine-containing guanamine condensate and/or etherified fluorine-containing guanamine condensate as a component, a commonly used curing agent is used as necessary. For example, melamine curing agents such as butoxylated methylmelamine, ethoxylated methylmelamine, methoxylated methylmelamine, epoxy-modified melamine, urea resin curing agents such as butoxylated methylurea, methoxylated methylurea, long chain Curing agents such as polybasic acid curing agents such as aliphatic dicarboxylic acids, aromatic polycarboxylic acids or their anhydrides, polyvalent isocyanates, and block polyvalent isocyanates are useful, and commercially available products include Cymil 300.
, 301, 303, 325, 370, 113
0-266J (manufactured by Mitsui Sui Anamitsu ■), Kneepan 20SR-60, 28-60 (manufactured by Mitsui Toatsu Chemical ■)
], Nikalak MV-3 Kano, Nikalak MV-30, Nikalak MX-
40, MX-485, MV-22, MS-15 (
Made by Three Phase Chemical ■], Sumimart 100C, Sumimart 55
, M-40S (manufactured by Jumin Kagaku ■), Regimin 745,
Examples include, but are not limited to, 747, 753, and 755 (manufactured by Monsanto ■). still,
One type or two or more types of such curing agents can be used, and the type and amount of the curing agent can also be selected as appropriate.

In the coating forming composition according to the present invention, the amount ratio of the polymer having a hydroxyl group to the curing agent containing the above-mentioned methylol compound fluorine-containing guanamine condensate and/or etherified fluorine-containing guanamine condensate as a component; The quantitative ratio of the polymer having the above-mentioned methylol-containing fluorine-containing guanamine condensate and/or the etherified fluorine-containing guanamine condensate can be appropriately selected depending on the composition, curing conditions, use, etc.

Further, in the coating forming composition according to the present invention, the coating layer is formed by curing by heating etc. in the absence of a catalyst,
Further, it can be obtained by appropriately selecting and adding a curing accelerator such as an acidic catalyst such as P-)luenesulfonic acid or dodecylbenzenesulfonic acid as needed and curing, but the method is not limited to these methods.

The composition for forming a coating according to the present invention may optionally contain a pigment, and such pigments may be inorganic pigments or organic pigments such as coloring pigments, extender pigments, and rust-preventing pigments, which are known per se, and are not particularly limited. For example, coloring pigments such as titanium dioxide, carbon black, graphite, black iron oxide, cadmium red, red iron oxide, cadmium yellow, strontium chromate, aluminum powder, alumina, phthalocyanine blue, quinacridone red, azo red, clay, talc, asbestos. , precipitated barium sulfate, extender pigments such as bentonite, chromate pigments, condensed phosphate pigments, molybdate pigments, borate pigments, and antirust pigments such as lead zinc oxide and magnesium oxide. , can be used alone or in combination of two or more.

In addition, in such a composition for forming a coating, an ultraviolet absorber,
By containing resin deterioration inhibitors such as light stabilizers and antioxidants, it is possible to prevent the coating layer from deteriorating over time due to ultraviolet rays.

Such ultraviolet absorbers absorb ultraviolet energy, are compatible with or uniformly dispersed in such compositions, and do not easily decompose and lose their effectiveness at baking temperatures during coating formation, etc. Any of them may be used, for example, benzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, etc. Hensiphenone UV absorber, 2-(2'-hydroxy-5''-methylphenyl)
Benzotriazole, 2-(2'-hydroxy-3゛,
5''-Diisoamylphenyl) benzotriazole and other hesitriazole UV absorbers, 4-tertbutylphenyl salicylate and other salicylic acid ester UV absorbers, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate There are diphenyl acrylate type UV absorbers such as, acetophenone type UV absorbers such as hydroxy-5-methoxy-acetophenone, oxalic acid anilide type UV absorbers, etc., and these can be used alone or in combination of two or more, and are commercially available. For example, Tinuvin 900, Tinuvin 328 (manufactured by Chino Geigy), Ubinul 400 (manufactured by BASF), Sand 3206 (manufactured by Sandbore), and the like.

In addition, such light stabilizers include, for example, tetrakis(2,
2,6,6-tetramethyl-4-piperidyl)-1,2
, 3,4-butanetetracarboxylate, bis(2,
2,,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-bentamethyl-4-
piperidyl) sebacate, 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butyl malonate bis(L2,2,6-bentamethyl-4-piperidyl), dimethyl-2-(4-hydroxy-2 ,2゜6.
Examples of the antioxidant include 4,4゛-6-tetramethyl-1-piperidyl) ethanol condensate, etc.
Methylenebis(2,6-di-tert-butylphenol), dilaurylthiodipropionate, tetrakis(3
-(3,5-di-tertbutyl-4-hydroxyphenol)-propionate], these can be used alone or in combination of two or more, and are preferably used in combination with the ultraviolet absorber.

In addition to the above-mentioned components, such coating forming compositions also contain various fillers and lubricants, such as fluorinated graphite, graphite,
molybdenum disulfide, metal soap, bellfluoro polymer,
Berfluoroalkyl group-containing compounds, silicone compounds, etc., plasticizers, such as dioctyl phthalate, tricresyl phosphate, dibutyl sebacate, etc., viscosity imparting agents, such as rosin, coumaron resin, ester gum, low molecular weight epoxy resin, polyoxy Anti-sagging agents such as tetramethylene glycol, flame retardants such as aluminum stearate, silica gel, surfactants and other additives may be used as appropriate.

The coating-forming compositions according to the invention may be applied using conventional methods, such as non-electrophoretic methods, ie dip coating, water coating and spray coating.

In general, such coating compositions may be used on any substrate, such as wood, metal, glass, cloth, leather, plastic, foam, and may be applied over a variety of primers. In the case of conductive substrates, for example metal substrates, they may be coated by electrodeposition.

The novel coating-forming composition according to the present invention is a composition comprising a polymer having a hydroxyl group and a curing agent as essential components, wherein the curing agent contains such a methylol compound having an active group, a fluorine-guanamine condensation compound, and a curing agent. Since it contains a fluorine-containing guanamine condensate and/or such an etherified fluorine-containing guanamine condensate, a fluorine-containing coating layer can be formed using various polymers having hydroxyl groups, and there are extremely few restrictions on the production and composition of the coating material. In addition, the fluorine-containing groups of the fluorine-containing guanamine condensate are hardly detached by hydrolysis, heat, light, etc. and can maintain their functions for a long period of time. We can provide a variety of coating materials, including rubber materials, anti-blocking coatings for films, friction thread count reducing materials for resins, lubricants, release coatings for molding molds, back treatment materials for tapes, and for electrostatic printing. Carry's non-adhesive coating materials, Toppan Printing's printing durability improving coating materials, ink-repellent coating materials, water-repellent and oil-repellent coating materials, optical materials, gas separation membrane materials, resist materials, home appliances, antifouling paints for automobiles, etc. Anti-corrosion paint, weather-resistant paint, anti-icing paint, anti-icing paint, snow prevention paint for roofing materials, road signs, steel towers, electric wires, etc., antifouling lubricant coating materials for sash, moisture-proof insulation for printed circuit boards, semiconductor resin coatings, etc. Moisture-proof covering materials for electrical parts, circuit boards, etc. to improve moisture-proof properties, paper processing materials such as preventing oil leakage from packaging paper, preventing contamination of recording paper and labels, and imparting non-adhesive properties to release paper, curtains, sofas - 1 Coating materials that are extremely useful for floor desk applications, such as antifouling treatment of interior products such as wall cloths and carpets, fiber processing materials such as moisture permeation prevention treatment, sweat absorption treatment, SR treatment, etc., leather treatment materials, heat-resistant resins, etc. can be provided.

〔Example〕

Next, the present invention will be explained in detail using examples.

However, the scope of the present invention is not limited to these examples.

Reference Example 1 Production of methylolated condensate of 2.4-diamino-6-(2,2,3,3,3-pentafluoropropyl)-s-triazine: 2.4-diamino-6-(2, 2,3,3,3-pentafluoropropyl)-s-) riazine 12.2 g (
0.05 mol) and 21.7 g of methyl hemiformal (
0.35 mol) and 40 g of methanol were added, the pH was adjusted to 7.5 with a 30% aqueous sodium hydroxide solution, and the mixture was reacted at a temperature of 70°C for 1.5 hours. This reaction mixture was a clear liquid, and as a result of analysis, it was found that 2,4-diamino-6-(2
It was a methylolated condensate of the compound in which 3.72 equivalents of methylol group and 0.14 equivalent of methylene group were bonded to 1 mole of S-triazine (2°3.3.3-pentafluoropropyl)-S-triazine.

Reference Example 2 Production of etherified condensate of 2.4-diamino-6-(2,2,3,3,3-pentafluoropropyl)-S-)riazine: 2,4 obtained in Reference Example 1 -diamino-6-(2゜2.
A solution of the methylolated condensate of 3,3.3-pentafluoropropyl)-8-triazine was adjusted to pH 1 with 30% sulfuric acid.
, 5, and the reaction was carried out at a temperature of 50°C for 1 hour.

This reaction mixture was a clear liquid, and as a result of its analysis, it was found that the total It was an etherified condensate of the compound in which 3.84 equivalents of formaldehyde bonds, 1.47 equivalents of methyl ether groups, 1.27 equivalents of methylol groups, and 1.10 equivalents of methylene groups were bonded.

Reference example 3 2.4-diamino-6-(18,LH,2H,2+1-
) Ridecafluorooctyl)-S=) Preparation of methylolated condensate of liazine: 2,4-diamino-6-(Ill, IH, 211,2H
-tridecafluorooctyl)-8-) riazine22.
9 g (0.05 mol) of methyl hemiformal 31.
Add 0 g (0.50 mol) and 40 g of methanol,
The pu was adjusted to 6.5 with a 30% caustic soda aqueous solution, and the mixture was reacted at a temperature of 75°C for 1 hour. This reaction mixture was a clear liquid, and as a result of analysis, it was found that 2,4-diamino-
3. methylol groups per mole of 6-(18°IH,2H,2H-)lidecafluorooctyl)-s-triazine.
It was a methylolated condensate of the compound to which 91 equivalents and 0.18 equivalents of methylene groups were bonded.

Reference example 4 2.4-diamino-6-(18,III, 2H,28-
Production of etherified condensate of tridecafluorooctyl)-S-triazine: 2,4-diamino-6-(IH,I
A methylolated condensate solution of H,2B,2H-tridecafluorooctyl)-3-triazine was adjusted to pH 4.0 with 30% sulfuric acid, and reacted at a temperature of 70°C for 1.5 hours. This reaction mixture was a clear liquid, and as a result of analysis, it was found that 2,4-diamino-6-(1B, IH).

Total formaldehyde bond amount: 3.8 g per mole of 2H,211-tridecafluorooctyl)-S-triazine
equivalent, methyl ether group 2.93 equivalent, methylol group 0
．． It was an etherified condensate of the compound to which 64 equivalents and 0.32 equivalents of methylene groups were bonded.

Reference example 5 2.4-diamino-6-(berfluoroheptyl)-8
-Production of etherified condensate of triazine = 24.0 g (0.05 mol) of 2.4-diamino-6-(berfluorheptyl)-5-triazine and 15.5 g (0.25 mol) of methyl hemiformal mole) and methanol 4
Add 0g and adjust the pH to 11.5 with 30% caustic soda aqueous solution.
The temperature was adjusted to 70°C and the reaction was carried out for 1 hour.

Next, this reaction solution was adjusted to pH 2.0 with concentrated nitric acid, and reacted at a temperature of 60°C for 1 hour. After cooling the reaction mixture, the PL+ was adjusted to 8.0 with a 30% aqueous sodium hydroxide solution, and the precipitate was removed by vacuum filtration to obtain a clear liquid.

As a result of analysis, the total amount of formaldehyde bonds was 3.62 equivalents per mole of 2,4-diamino-6-(berfluorheptyl)-S-)riazine, and 2 methyl ether groups.
．． 81 equivalents, methylol group 0.53 equivalents, methylene group 0
．． It was an etherified condensate of the compound in which 28 equivalents were bound.

Reference Example 6 Production of 2.4-diamino-6-(ωH-berfluorooctyl)-3-triazine and its etherified condensate: 500 mj! 27.5 g (0.2 mol) of biguanide basic hydrochloride and 300 mf of anhydrous methanol were added to the flask under a nitrogen atmosphere, followed by 1 ml of sodium methylate.
1.1 g (0,205 mol) was added, stirred, and refluxed for 5 hours. Next, while maintaining the internal temperature at 35°C to 50°C and stirring, ωH-methyl berfluoroperargonate [HCJ+aCOOCII:+:196.6g (0
, 21 mol) was gradually added. After the addition was completed, the temperature was gradually increased and the mixture was stirred under reflux for 30 hours. 500 ml of distilled water was added to this reaction mixture, and the precipitate was filtered and dried under reduced pressure. Next, this was recrystallized with ethyl acetate, and 2
．． 4-diamino-6-(ωH-berfluorooctyl)
76.5 g of -S-triazine (white crystals) was obtained.

Next, 24.0 g of 2,4-diamino-6-(berfluorheptyl)-8-triazine in Reference Example 5 (
0.05 mol), the above-mentioned 2,4-sheer 4
2=Mino-6-(ωH-berfluorooctyl)-8-triazine 25.6 g (0.05 mol) The reaction and adjustment were carried out in the same manner as in Reference Example 5, and a transparent liquid was obtained. I got it. As a result of analyzing this, 2,4-diamino-6
-(ωH-berfluorooctyl) -S-Triazine 3.5 g equivalent of total formaldehyde bonding amount per mol of triazine,
Methyl ether group 2.82 equivalents, methylol group 0.48
It was an etherified condensate of the compound to which 0.2 g equivalent of methylene group was bonded.

Reference Example 7 2.4-diamino-6-berfluoro-(1-methyl-
Production of etherified condensate of 2-oxapentyl)-8-triazine: 24.0 g (0,
Same as Reference Example 5 except that 19.8 g (0.05 mol) of 2.4-diamino-6-berfluoro-(1-methyl-2-oxapentyl)-3-triazine was used instead of 0.05 mol). Reaction and adjustment were carried out in the same manner to obtain a clear liquid. As a result of analyzing this, 2,4-diamino-
6-Verfluoro-(1-methyl-2-oxapentyl)-S-)Total formaldehyde bond amount per mole of riazine: 3.67 equivalents, methyl ether group 2.85 equivalent, methylol group 0.51 equivalent, methylene group 0 .31 equivalents were bound to the etherified condensate of the compound.

Reference example 8 2.4-diamino-6-(3,3,4,4,5,5,6
, 6,6-nonafluorohexyl)-5-) Preparation of etherified cocondensate of liazine and melamine: 2.4-diamino-6-(3,3,4,4,5,5,6
,6,6-nonafluorohexyl)-3-) riazine 1
7.9 g (0.05 mol) and 6.3 g melamine
(0.05 mol), 74.4 g (1.20 mol) of methyl hemiformal and 40 g of methanol
g was added thereto, the pH was adjusted to 8.0 with a 30% aqueous solution of caustic soda, and the mixture was reacted at a temperature of 70'C for 1.5 hours. Next, 3
The pl+ was adjusted to 4.5 with 0% sulfuric acid, and the reaction was carried out at a temperature of 70°C for 1.5 hours. This reaction mixture was a clear liquid, and the PU was adjusted to 7.5 with a 30% aqueous sodium hydroxide solution, excess formaldehyde, methanol and water were removed under reduced pressure, and n-butanol was added to dissolve it. As a result of analyzing this reaction product, the total amount of formaldehyde bonds was 4.83 equivalents and 3.22 equivalents of methyl ether groups per triazine nucleus! , methylol group 1.40 equivalents,
It was an etherified cocondensate to which 0.21 equivalents of methylene groups were bonded.

Reference example 9 2.4-diamino-6-(IH, 18,21-1,28
-Heptadecafluorodecyl)-3-) Production of etherified condensate of liazine: 2,4-diamino-6-(IH, IH
,28,211=)lidecafluorooctyl)-s-
Instead of 22.9 g (0.05 mol) of triazine, 2,4-diamino-6-(IH, 111,21(,
The reaction was carried out in the same manner as in Reference Example 3 except that 27.9 g (0.05 mol) of 211-heptadecafluorodecyl)-s-1-riazine was used to obtain a methylolated condensate.

Next, 2,4-diamino-6-(LH
, IH, 2H, 2) 1-) Ridekafluorookuchi JL/
) The reaction was carried out in the same manner as in Reference Example 4, except that the above methylolated condensate was used instead of the methylolated condensate solution of -3-triazine. Analysis of this reaction mixture revealed that 2,4-diamino-6-(IH, II+,
28,211-heptadecafluorodecyl) -total formaldehyde bond amount per 1 mole of triazine 3.9
It was an etherified condensate of the compound in which 1 equivalent of methyl ether group, 2.97 equivalents of methyl ether group, 0.61 equivalent of methylol group, and 0.33 equivalent of methylene group were bonded.

Reference Example 10 Production of a polymer containing 2-berfluorooctylethyl methacrylate as a constituent unit: A mixed solvent of 40 g of butyl acetate and 40 g of toluene was heated to reflux to produce 25 g of 2-berfluorooctylethyl methacrylate, 20 g of styrene, and n- 39 g of butyl methacrylate, 5 g of 2-hydroxyethyl methacrylate H, 1 g of acrylic acid, and 2 g of polymerization initiator 2.2''-azobisisobutyronitrile
A mixed solution consisting of the following was added dropwise over 3 hours and heated for further 2 hours to obtain a fluoropolymer solution with a non-volatile content of 55% and a polymerization average molecular weight of 14,000.

-46= Reference Example 11 Production of acrylic copolymer: Follow the same procedure as in Reference Example 10 except that 25 g of 2-ethylhexyl methacrylate was used instead of 25 g of 2-berfluorooctylethyl methacrylate in Reference Example 10. The reaction was carried out, and the non-volatile content was 55%, and the polymerization average molecular weight was 1.
4000 acrylic copolymer solution was obtained.

Example 1 Curability and water/oil repellency test of a resin composition comprising an acrylic resin and a methylolated fluorine-containing guanamine condensate: 2,4-diamino-6-(2
,2,3,3,3-pentafluoropropyl)-8-triazine methylolated fluorine-containing guanamine condensate 5g
(solid content) [n-butanol-methyl isobutyl ketone mixed solvent (weight ratio 50150)] was added to 30 g of acrylic resin Almatex D104J [manufactured by Mitsui Toatsu Chemicals, nonvolatile content 50% by weight]. The resin composition was prepared by stirring thoroughly with a mixer.Next, this resin composition was applied to a galvanized steel plate, and then 160'C-2
It was heated and cured for 0 minutes.

Using the coating film of the heat-treated coated steel plate, tests for hardenability and water and oil repellency were conducted.

As a comparative example, 16.3 g of amino resin "Niepan 20SR-60J [manufactured by Mitsui Toatsu Chemicals ■, non-volatile content 60% by weight] was used instead of the 50% solution of the methylolated fluorine-containing guanamine condensate, and the same conditions were used. Curing is performed at
The coating film was tested.

In the Examples and Comparative Examples, the curability test of the coating film was as follows:
After wiping the surface of the coating film 50 times with a cloth impregnated with Pheasant Roll, the condition of the coating film was visually observed and the following judgments were made.

◎: Almost no peeling of the paint film △: Slight peeling of the paint film ×: Much peeling of the paint film Also, the water and oil repellency test of the paint film
yne/cm). The smaller the surface tension value, the greater the water repellency or oil repellency.

Example 2 Curability and water/oil repellency test of a resin composition comprising an acrylic resin and a methylolated fluorine-containing guanamine condensate: 2,4-diamino-6-(I) obtained by the method of Reference Example 3
H, III, 2) A 50% by weight solution of 5 g (solid content) of a methylolated fluorine-containing guanamine condensate of 1,211-tridecafluorooctyl)-8-triazine (n-butanol-methyl isobutyl ketone mixed solvent (by weight) Ratio 501
50) ), acrylic resin [Almatex 785-
5J (manufactured by Mitsui Toatsu Chemical, non-volatile content 50% by weight) 3
0 g and stirred well with a mixer to prepare a resin composition. Next, this resin composition was applied to a galvanized steel plate, and then heated and cured at 160°C for 20 minutes.

Using the coating film of the heat-treated coated steel plate, tests for hardenability and water and oil repellency were conducted. (The test method is the same as in Example 1.) As a comparative example, instead of the 50% solution of the methylolated fluorine-containing guanamine condensate, amine resin "Niepan 20SR-60" (manufactured by Mitsui Toatsu Chemical Co., Ltd.) was used. Non-volatile content 60
Using 6.3 g (% by weight), curing was performed under the same conditions, and the coating film was tested.

Example 3 Curability and water/oil repellency test of resin composition comprising acrylic resin and etherified fluorine-containing guanamine condensate: 2,4-diamino-6-(1) 1°1 in Example 2
11.2H,2H-)lidecafluorooctyl>-s
-2,4-diamino-6-(11(,11(,21(,2
Resin preparation and coating film formation were carried out in the same manner as in Example 2, except that the etherified fluorine-containing guanamine condensate of 11-tridecafluorooctyl)-S-) riazine was used as 5 g (solid content).

Using the coating film of the heat-treated coated steel sheet, tests for hardenability and clear water oil repellency were conducted. (The test method is the same as in Example 1) In addition, a comparative example was conducted using the comparative test coating film in Example 2.

Example 4 Curability and water/oil repellency test of a resin composition comprising an epoxy resin and an etherified fluorine-containing guanamine condensate: 2,4-diamino-6-(ω
A 50% by weight solution of 5 g (solid content) of etherified fluorinated guanamine condensate of H-berfluorooctyl)-s-triazine (1so-butanol-butyl acetate mixed solvent (
Weight ratio 50150)), epoxy resin "Evokey 8"
03J CMitsui Toatsu Chemical ■, non-volatile content 40% by weight)
A resin composition was prepared by adding 37.5 g of the resin and stirring well with a mixer. Next, this resin composition was applied to a galvanized steel plate, and then heated and cured at 160°C for 20 minutes.

Using the coating film of the heat-treated coated steel plate, tests for hardenability and water and oil repellency were conducted. (The test method is the same as in Example 1.) As a comparative example, instead of the 50% solution of the etherified fluorine-containing guanamine condensate, amino resin "Niepan 203E-60J" (manufactured by Mitsui Toatsu Chemical Co., Ltd., non-volatile minute 6
0% by weight) was used to cure under the same conditions, and the coating film was tested.

52-Example 5 Curability and water/oil repellency test of a resin composition comprising a fluorine-containing resin and an etherified fluorine-containing guanamine condensate: 2,4-diamino-6-(bel) obtained by the method of Reference Example 5 50 of 4.8 g (solid content) of etherified fluorinated guanamine condensate of (fluoroheptyl)-5-triazine
The weight% solution [n-butanol-methyl isobutyl ketone mixed solvent (weight ratio 50150)] was added to the fluorine-containing resin "
Lumiflon LP200J (manufactured by Asahi Glass, non-volatile content 6)
0% by weight], 40 mg of p-toluenesulfonic acid was further added as a curing accelerator, and the mixture was thoroughly stirred with a mixer to prepare a resin composition.

Next, after applying this resin composition to a galvanized steel plate,
It was heated and cured at 0°C for 20 minutes.

Using the coating film of the heat-treated coated steel plate, hardenability and water repellency tests were conducted. (The test method is the same as in Example I.) As a comparative example, instead of the 50% solution of the etherified fluorine-containing guanamine condensate, an amino resin "Niepan 205E-60JC" manufactured by Mitsui Toatsu Chemical Co., Ltd., non-volatile Curing was carried out under the same conditions using 5.4 g (60% by weight),
The coating film was tested.

Example 6 Curability and water/oil repellency test of a resin composition comprising a polyester resin and an etherified fluorine-containing guanamine condensate; 2,4-diamino-6-perfluoro-(1- Methyl-2-oxapentyl)-3-
Etherified fluorine-containing guanamine condensate of triazine 5g
(solid content) 50% by weight solution (isopropyl alcohol-methyl cellosolve mixed solvent (weight ratio 50150))
, polyester resin "Almatex P646 J"
C, manufactured by Mitsui Toatsu Kagaku ■, non-volatile content: 60% by weight] was added to 25 g, and the resin composition was prepared by stirring well with a mixer. Next, after applying this resin composition to a galvanized steel plate, 1
It was heated and cured at 60'C for 20 minutes.

Using the coating film of the heat-treated coated steel plate, tests for hardenability and water and oil repellency were conducted. (The test method is the same as in Example 1.) As a comparative example, instead of the 50% solution of the etherified fluorine-containing guanamine condensate, amino resin "Niepan 203E-60J" (manufactured by Mitsui Toatsu Chemical Co., Ltd., non-volatile 60% by weight] 6.3 g was used to cure under the same conditions, and the coating film was tested.

Example 7 Curability and water loss resistance test of a resin composition comprising an alkyd resin, an etherified fluorine-containing guanamine condensate, and another curing agent: 2,4-diamino-6- obtained by the method of Reference Example 2 (2
,2,3,3,3-pentafluoropropyl) -s-
Etherified fluorine-containing guanamine condensate of triazine 18
g (solid content) 50% by weight solution (methanol solvent),
In addition to 30 g of alkyd resin "YURIX 210sJ [manufactured by Mitsui Toatsu Chemicals, non-volatile content 70%]", we added amino resin "Niepan 136J (manufactured by Mitsui Toatsu Chemicals, non-volatile content 70%), butylated urea-melamine cocondensation resin, non-volatile content 60%. weight%
), 6 g of a 50% by weight solution of p~toluenesulfonic acid (isopropanol solvent) was added, and the mixture was thoroughly stirred with a mixer to prepare a resin composition. Next, this resin composition was applied to a matte steel plate, and then cured at 25°C for 5 hours.

Using the coating film of the coated steel plate that had been treated in this manner, tests were conducted on hardenability and water and oil repellency. (The test method is the same as in Example 1.) As a comparative example, 15 g of the amino resin "Niepan 136J" was used instead of the 50% solution of the etherified fluorine-containing guanamine condensate, and curing was performed under the same conditions. , the coating film was tested.

Example 8 Curability and water loss resistance test of a resin composition comprising an acrylic resin and an etherified fluorine-containing guanamine cocondensate: 2,4-diamino-6-(2,2°3
．． 2 obtained by the method of Reference Example 8 instead of a 50% by weight solution of 5 g (solid content) of methylolated fluorinated guanamine condensate of 3.3-pentafluoropropyl)-s-t')7dine, 4-diamino-6-(3,3゜4.4,5,
5,6.6.6-nonafluorohexyl)-S-triazine and 50% by weight solution of 5 g (solid content) of etherified fluorine-containing guanamine cocondensate of melamine [n-butanol-methyl isobutyl ketone mixed solvent (weight ratio 50150
) Resin preparation and coating film creation were carried out in the same manner as in Example 1 except for the following.

Using the coating film of the heat-treated coated steel plate, tests for hardenability and water and oil repellency were conducted. (The test method is the same as in Example 1) In addition, a comparative example was conducted using the comparative test coating film in Example 1.

As shown in Examples 1 to 8, the coating forming composition according to the present invention can easily form a coating layer using various polymers having hydroxyl groups, and there are no restrictions on the production and composition of coating materials. (and the coating-forming layer has extremely excellent water and oil repellency, so it could provide a coating material useful for floor desks, making it an extremely useful coating-forming composition.

Example 9 Water and oil repellency retention test in a coating layer obtained from a resin composition containing a methylolated fluorine-containing guanamine condensate as a component: 2,4-diamino-6 obtained by the method of Reference Example 3 ~ to just - - (18,IH,2H,2H-)ridecafluorooctyl)-S-) A 50% by weight solution of 5 g (solid content) of a methylolated fluorine-containing guanamine condensate of riazine [n-butanol-methyl Isobutyl ketone mixed solvent (weight ratio 501
50) ) was added to 27.3 g of the acrylic copolymer solution (nonvolatile content 55% by weight) obtained by the method of Reference Example 11,
A resin composition was prepared by thoroughly stirring with a mixer. Next, after applying this resin composition to a satin steel plate,
It was heated and cured for 0 minutes.

Using the coating film of the heat-treated coated steel sheet, a hardening test and a water and oil repellency test were conducted before and after a weather 0-meter exposure test (1000 hours). (The test method is the same as in Example 1) Example 10 Water and oil repellency retention test in a coating layer obtained from a resin composition containing an etherified fluorine-containing guanamine condensate as a component: In Example 9 2,4-diamino-6-(Ill,
Ill, 21(,2H-)lidecafluorooctyl)-
Instead of 5 g (solid content) of the methylolated fluorine-containing guanamine condensate of s-triazine, 2,4-diamino-6-(Ill, LH, 2H, 2H
Resin preparation and coating film creation were carried out in the same manner as in Example 9, except that the etherified fluorinated guanamine condensate of (hebutadecafluorodecyl)-s-1-riazine was used as 5 g (solid content). Curability and water/oil repellency tests were conducted using the coating film of a heat-treated coated steel plate.

Comparative Example 7 Water and oil repellency retention test in a coating layer obtained from a resin composition containing a fluoropolymer having fluorine-containing methacrylate as a constituent unit: Fluoropolymer obtained by the method of Reference Example 10 To 27.3 g of the combined solution (non-volatile content 55% by weight), 16.3 g of amino resin Kneepan 2o'5E-6oJ (Mitsui Toatsu Chemical ■, non-volatile content 60% by weight) was added, and the resin was stirred well with a mixer. A composition was prepared.Next, this resin composition was applied to a matte steel plate, and then heated and cured at 160°C for 20 minutes.

Using the coating film of the heat-treated coated steel sheet, tests for hardenability and water and oil repellency were conducted in the same manner as in Example 9.

Comparative Example 8 Water and oil repellency retention test in a coating layer obtained from a resin composition containing an acrylic copolymer: Fluorine-containing polymer solution (non-volatile) obtained by the method of Reference Example 10 in Comparative Example 7 The resin was prepared in the same manner as in Comparative Example 7, except that 27.3 g of the acrylic copolymer solution (nonvolatile content 55% by weight) obtained by the method of Reference Example 11 was used instead of 27.3 g (55% by weight). Adjustments and coating were made.

The curability and water and oil repellency tests were conducted in the same manner as in Example 9 using the coating film of the heat-treated coated mesh board.

The test results for Examples 9 and 10, and Comparative Examples 7 and 8 are shown in Table 1.

As shown in Table 1, the coating forming layer obtained from the coating forming composition according to the present invention has extremely superior water and oil repellency compared to coating layers obtained from known coating compositions. In addition, the desired function could be maintained for a long period of time, and the coating forming composition could provide a coating material useful for floor desks.

Table 1 (Note 1) "Previous" refers to the measured value before the weather 0-meter test, 63-Example 11 Icing property in coating forming layer obtained from resin composition containing fluorine-containing guanamine condensate as a component Test: Using the coating film of the heat-treated coated steel plate obtained in Example 10, the icing shear fracture strength (kg/c+fl) was measured when frozen at -10°C for 2 hours using the test method described below. did.

As a comparative example, a test was conducted in the same manner as above using the coating film of the heat-treated coated steel sheet in Comparative Example 8.

As shown above, the coating forming layer obtained from the coating forming composition according to the present invention has significantly lower icing shear fracture strength than coating layers obtained from known coating compositions, and has anti-icing properties. was extremely excellent.

[Icing shear fracture strength test method]

As shown in FIG. 1, a stainless steel ring (inner diameter 25 +++ m) (2) was placed on the coating film (1) of the painted steel plate, and the ring was cooled for 1 hour in a constant temperature refrigerator (-10°C). Next, 2 g of deionized water kept at 5°C was poured into the ring (2) to form ice on the test coating, and immediately
Cool in C) for 2 hours. This cooled ring (2
) by a metal rod (3) driven by power? ii'
Shear fracture strength (kg) for peeling off ice (4) given J
/c+fl) was measured. The lower the strength, the lower the icing property.

Example 12 2.4-diamino-6-(111,LH,211,21
1-) Stability test of fluorine-containing substituent in etherified fluorine-containing guanamine condensate of Ridecafluorooctyl)-3-triazine: 2,4-diamino-6-(I
II, III, 2H, 2+1- 26
J (manufactured by Mitsui Toatsu Chemical, non-volatile content 50% by weight) 40
g, and stirred well with a mixer to prepare a resin composition. Next, this resin composition was applied to a galvanized steel plate, and then heated and cured at 150°C for 30 minutes.

Using this painted steel plate, 600
A time exposure test was conducted. The coating film of the test steel sheet was peeled off and elemental analysis was performed, and the result was that the F content was 8.2% (pre-test measurement value F content 8.3%).

As shown above, the fluorine-containing substituent of the coating forming layer obtained from the coating forming composition according to the present invention is difficult to be removed by ultraviolet rays, water, etc., and has extremely excellent stability and durability. The coating-forming composition was able to provide an extremely excellent coating material that could maintain its intended function over a long period of time.

[Effects of the Invention] Since the coating forming composition according to the present invention contains a methylolated and/or etherified fluorine-containing guanamine condensate as an essential component, The fluorine-containing coating layer can be easily formed, there are very few restrictions on the production and composition of the coating material, and the resulting coating layer has extremely excellent surface properties such as water and oil repellency and anti-icing properties. This fluorine-containing substituent has excellent stability and durability, and can provide a coating material that is difficult to obtain from known coating compositions.It is an extremely excellent invention that can be applied to the industrial field of floor desks.

[Brief explanation of drawings]

FIG. 1 illustrates a method for testing icing shear fracture strength on painted steel plates. (1): Paint film (2) stainless steel ring (3): metal rod (4): ice Patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (4)

[Claims] (1) In a coating forming composition containing a polymer having a hydroxyl group and a curing agent as essential components, the curing agent has a general formula ▲a mathematical formula, a chemical formula, a table, etc.▼(I) (in the formula, R_f represents a fluorine-containing group) or from among other compounds capable of co-condensation with at least one selected from the fluorine-containing guanamine compounds represented by 1. A coating-forming composition comprising, as a component, a methylolated fluorine-containing guanamine condensate obtained by subjecting at least one type of guanamine to a condensation reaction with at least one type selected from formaldehydes. (2) A coating forming composition comprising a polymer having a hydroxyl group and a curing agent as essential components, wherein the curing agent comprises the methylolated fluorine-containing guanamine condensate according to claim 1 and a carbon atom having 1 to 20 carbon atoms. 1. A composition for forming a coating, comprising as a component an etherified fluorine-containing guanamine condensate obtained by subjecting at least one selected from aliphatic alcohols and alicyclic alcohols to an etherification reaction. (3) The R_f group according to claim 1 has the general formula R_1-[CF_2CF(R_2)]_n_-_1-R
_3-(II) [wherein, R_1 is CF_3, C_2_5,
C_3F_7, (CF_3)_2CF, C_4F_9,
(CF_3)_2One type selected from CF-O group, R
_2 is an F atom and/or a CF_3 group, R_3 is one selected from methylene, ethylene, trimethylene, and propylene groups, and n is an integer selected from 1 to 7.]
A coating-forming composition characterized by having a fluorine-containing group represented by: (4) A composition for forming a coating, wherein the other cocondensable compound according to claim 1 is at least one selected from melamine, benzoguanamine, urea, and phenol.