TW517076B - Fluoropolymer coating composition and coated article - Google Patents

Abstract

This invention provides a fluoropolymer coating composition which is applicable thickly and capable of forming a coating film excellent in wearing resistance, corrosion resistance, nontackiness, and whiteness; and an article top-coated with the composition. The composition comprises fine particles of a fluoropolymer, a polyether resin in an amount of 0.1 to 300 wt.% of an oxidation catalyst, and a liquid carrier; in which the polyether resin is represented by the general formula (I): R1-Y1-(A-B)-R1 [where R1 represents hydrogen or alkyl group of 1-20 carbon atoms; Y1 represents an oxygen atom or an ether, ester, ester or thionyl group; A represents an epoxy residue having 3 or more carbon atoms (provided that the molecular weight of the epoxy moiety is 1x10<SP>3</SP> to 1x10<SP>4</SP>); and B represents an ester, thionyl, or phosphate group (provided that the segment in the parentheses represents a residue obtained by alternating copolymerization) and has a decomposition/vaporization temperature not higher than the decomposition temperature of the fluoropolymer].

Description

517076 V. Description of the invention (1) Technical field The present invention relates to a coating composition and a coating σ of a fluoropolymer. BACKGROUND OF THE INVENTION The conventional milk 13 coating composition is added with an anionic interface and a tongue agent as film-forming aids, but it is easy to cause pinholes due to easy foaming and film-forming properties. Poor and difficult to apply thickly, it will cause problems such as poor abrasion resistance, good corrosion resistance, poor health, and non-dryness. An object of the present invention is to provide a coating composition of a fluoropolymer and a coated article coated with the composition. The coating composition can be thickly coated and the coating film envied has excellent abrasion resistance and resistance. Corrosive and non-adhesive properties, especially those obtained by blending a specific polyether resin in a latex state. DISCLOSURE OF THE INVENTION The present invention relates to a coating composition of a fluoropolymer, which is an aeropolymer fine particle, an ether-based resin, an oxidation catalyst, and a liquid based on a weight basis of the fine particle of 0.1 to 300% by weight. A coating composition of a fluoropolymer composed of a carrier, the polyether resin has the general formula (I): R3'Y1- (AB) -R1 (I) [wherein R1 is the same or different hydrogen atom Or an alkyl group having a carbon number of 20, γι is an oxygen atom, an ether group, an ester group, a urea ester group, or a thionyl group, and A is an alkylene oxide residue having a carbon number of 3 or more (however, the molecular weight of the alkylene oxide portion 1 X 1 〇3 ~ 1 X i 〇 4), B is a resin represented by urea ester group, thionyl group or phosphate group (however, the brackets are the residues obtained by alternating copolymerization)], The decomposition gasification temperature is lower than the decomposition temperature of the fluoropolymer. In addition, the present invention relates to a coating layer coated with the aforementioned fluoropolymer.

517076 V. Description of the invention (2) The coated article of the compound is coated with a coating film. 4 Meng Fu, and the mouthpieces form at least 30 // in thick melting moon dagger, ΐ: Ming Γ ′ by using a specific polyether tree in the form of latex ′. 4. Add an oxidation catalyst to obtain a thick fluoropolymer coating combination. The specific polyether resin is described by the general formula (丨) ·· R1-Υ1-(AB) —Ri (I) grease. It does not have ethylene oxide residues, so it has hydrophobicity and temperature-induced interfacial activity, and the decomposition and gasification of the aforementioned resin ^ The decomposition temperature of the fluoropolymer used by Qiming is low (ie, low-temperature decomposability). Resin. Based on the consideration of hydrophobicity, the aforementioned R1 is preferably an alkyl group having 1 to 20 carbon atoms with the same or different hydrogen atoms. Based on the consideration of thermal decomposability, the aforementioned γι is preferably the same or different ether group, urea ester group or thionyl group. Fourth, in consideration of hydrophobicity and water dispersibility, the aforementioned A is preferably an oxane residue having a carbon number of 3 4 and the molecular weight of the alkylene oxide portion obtained by polymerization is i X 1 03 ~ 1 X 1 〇4 . Based on the ease of manufacture, the aforementioned B is preferably a urea ester group, a thionyl group, or a phosphate group. The brackets of the general formula (I) are preferably residues obtained by alternating copolymerization. The polyether resin represented by the above general formula (I) has hydrophobicity and water dispersion, and is suitable for use in consideration of stability and workability. The use form is latex, and it is easy to uniformly disperse the fluoropolymer particles because it is in a latex state. 517076 2. Description of the invention (3) Specific examples of the resin represented by the general formula (I), for example, when the aforementioned B is an adenyl group, ^

(1) 〇H- [(-CH2CH (CH3) 〇-) n-CONH-r-NHCO-] m-〇H

[Where m is an integer from 1 to loo, n is an integer from 10 to 200, and CONH-Ji -NHC0 is, for example, methylbenzyl diisocyanate (TDI) based urea ester residue, hexamethylene diisocyanate (HMDI) based urea ester Residues, isophorone diisocyanate (IpDI) based urea ester residues, dimethylbenzene diisocyanate (XD I) based urea ester residues, diphenylmethane diisocyanate (MD I) based urea ester residues, etc.] (2) C17H35C00-[(-CH2CH (CH3) 0〇n-C0NH-J1-NHC0-] ^ 0c ^ H35 (where m'n'J1 is the same as above) etc. as an example 'and based on thermal decomposition For consideration, the structure of (丨) is better. Also, when the aforementioned B is a thionyl group, it can be enumerated.

(3) H〇-[(CH2CH (CH3) 〇—) n—j2-] _ 〇H (where 'm, n are the same as above, J2 represents = s = 〇); (4) C17H35C0O-[(- CH2CH (CH3) 0-) n-J2-] n-C02C17H35 (where m, n, and J2 are the same as above) and the like, and the structure of (3) is preferred based on the consideration of thermal decomposition properties. In addition, when Ke said β is a phosphate group,

(5) H〇-[(CH2CH (CH3) 〇-) n_J3_] B_〇H (where m and n are the same as above, and π represents the residue of phosphoric acid); (6) C17H35COO-[(-CH2CH ( CH3) 〇-) n-j3-] m-C02C17H35 (where m, n, and J3 are the same as above) and the like, and the structure of (5) is preferred based on the consideration of thermal decomposition properties. 517076 V. Description of the invention (4) Base. Also in the foregoing specific examples, [] are residues obtained by alternating copolymerization. In the present invention, the fluoropolymer is a homopolymer of an early ethylene-based unsaturated hydrocarbon monomer completely substituted by a fluorine atom and a chlorine atom. Examples of the copolymer composed of the polymer, or the homopolymer and the aforementioned homopolymer of the copolymer include polytetrafluoroethylene (PTFE). The aforementioned copolymers can be exemplified by tetra-ethylene ethene (PFA) (but the carbon number of the alkyl group is 5), 7%, 7%, 7%, and 4 random ethylene-hexafluoro bridges. For example, fluorene polymer (FEP), etc., and based on the consideration of non-adhesive properties, heat resistance, and PFA are preferred. The numerical average molecular weight of the aforementioned fluoropolymer is 2 x iOLi χ 丨 07, and It is preferably 2x105 to 8x106. When the numerical average molecular weight is less than 2x0〇4, the coating film obtained tends to be brittle; when the numerical average molecular weight exceeds 1 X 107, there are particles because the melt viscosity is too high. The tendency to not fuse with each other. For example, the numerical average molecular weight of PTFE can be determined by "J〇urnal 〇; f

Applied Polymer Science ", Vol. 17, pages 3253 to 3257 (1933 years). Also, 'The numerical average molecular weight of FEP can be determined according to the method described in ASTM D_2116'. By measuring the melt flow rate (MFR), the melt dryness (MV) can be obtained according to formula (1), and then calculated according to formula (2) Numerical average molecular weight (Μη).

517076

Formula (1): MV =! LX working pressure (kggmm 2) X pinhole radius (mm) 8 X MFi? X pinhole length (Formula (2): * ϊίίΓ = 34 「娜 V162X10'13 ene furnace ^ ί polymerization The fine particles of the substance may be, for example, fine particles obtained by an emulsification polymerization fluorine method, and the average particle diameter is 0 · 〇1 ～ 丨 〇〇 #, and 0 · 1 ~ 5 // m is preferable. When When the particle size is less than 〇 · 〇1 # m, the properties of the composite film tend to deteriorate, and when the particle size is more than 丨 00, it tends to be a spray gun. It is also used for base coating. In the present invention, the aforementioned emulsion polymerization can be used. The fine particles of the fluoropolymer ^ dispersed in the night or obtained from &amp; water pure liquid ^ final micro and standing particles, but based on the consideration of the stability of the electrical repulsion of the particles, the use of = dispersed liquid is more Based on the consideration of the formation of the coating film, the solid content / degree is 20 to 80% by weight, and more preferably 40 to 70% by weight. In the present invention, based on the consideration that the coating can be further thickened, in addition to using the aforementioned ^ &amp; Water 丨 Polyurethane-free and non-surface active polymer__Resin, can be used together with the following hydrophilic polyether high Molecular surfactants. The polyether polymer surfactants are described by the general formula (丨 丨): R-Y- (Ca-Db-) c —γ —r (II) [where fc, R is hydrogen Atom or carbon number 20 alkyl group, Y is an oxygen atom, ether ^^ group: ^ gadolinyl, thionyl or phosphate group, C is ethylene oxide residue ^: ,,,% oxypropane Residues, &amp; is an integer from 30 to 2000, b is an integer from 20 to 500, and c is an integer from 1 to 10 (but

517076 V. Description of the invention (6)-(ca-Db-) c- is the residue obtained by alternating copolymerization or random copolymerization)]; General formula (III): RY-Ca-Db-Cd-YR (III) (where R, Y, C, D and b are the same as above, a and d are integers totaling 30 to 2000); General formula (IV): RY-Da-Cb-Dd-YR (IV) (In the formula, R, Y, C, and D are the same as described above, a and d are integers totaling from 20 to 5000, and b is an integer ranging from 30 to 2000); General formula (V): Z [-Y -(Ca-Db-) c — Y—R] e (V) [wherein 'Z is a polyvalent aliphatic saturated hydrocarbon group having an inverse number of 1 to 5, and r is a carbon atom with a carbon number of 20, Y is an oxygen atom, an ether group, an ester group, a urea group, a thionyl group or a phosphono group, C is an ethylene oxide residue, D is a propylene oxide residue, and a is an integer from 30 to 2000. , B is an integer of 20 ~ 500, c is 敕 ^ e is an integer of 1 ~ 4 (but a-(Ca-Db-) c- is a residue obtained by alternating copolymerization or messy copolymerization)]; VI): z [-Y_ca-Db-Cd ~ Y —R] e (VI) (where Z, R, Y, c, and D and the phase d represented by the general formula (v) are a total of 30 ~ Integer of 2000, e is an integer of i ~ 4); or, port type ( VII):

Page 10 517076 V. Description of the invention (7) z [-Y-Da-cb-Dd-YR] e (VII) (wherein z, R, Y, C &amp; D and the general formula (v) represent It is an integer of 20 ~ 500 in total, b is an integer of 30 ~ 200◦, and e is a fluorene-based polymer surfactant represented by or = of these L types =, since these have ethylene oxide residues, It is hydrophilic. In formula (1), when R is an alkyl group, it is better based on the consideration of thermal decomposition properties. Based on considerations of thermal decomposition, γ is oxygen: ί :, two ο: ί numbers are based on increasing considerations, ‘= * g, for smoothness considerations, C is an integer of 5 or better. The carbon number ti '/ two in the case where' tR is an alkyl group 'is based on the consideration of thermal decomposition properties. Based on the consideration of thermal decomposition, Y is an oxygen atom or ⑼ 二: With? For the consideration of film formation and thermal decomposition of Jiajiϊ, a is an integer: m is based on the consideration of withering, and b is an integer of 30 ~ 120 is a better soil; film formation and thermal decomposition are considered. d is 2 0 ~ 3 0 0 When the carbon number is 1 ~ 18 oxygen and the alkyl is an alkyl group, its ether group or r may be considered based on the thermal decomposability ί Based on the consideration of thermal decomposability, Y is an oxygen atom, 15 to 60 Zhi Yue 敕 1 \ # 父 佳. Based on the considerations of thickening and thermal decomposability, a is better. Its ^ father is good; based on the film formation considerations, b is an integer of 40 ~ 600 is better. Soil; consideration of viscosity increasing and thermal decomposability, which is an integer of 15 to 60, preferably 2 or 3 based on considerations of drilling increase and thermal decomposability, when the carbon number of Z is R , Based on the viscosity and thermal decomposition

517076 V. Description of the invention (8) Considering that its carbon number is 1 ~ · | s ^ atom or mystery or ° f for consideration of thermal decomposition, ¥ is the amount of oxygen, a is the soil of 40 ~ 600. ^ Based on In terms of film properties and thermal decomposability, an integer of 30 ~ 120 is / good for the car parent; based on the consideration of increasing the weight, Dagger is the age of Dugan for the car. Based on the consideration of smoothness, C is an integer of 1 ~ 5 :; the consideration of the decomposability when roasting, ... the preferred carbon number is based on the value of 18, and the scale is based on the consideration of thermal decomposition Or vinegar is two ί. ΪFor the consideration of thermal decomposition, Y is an oxygen atom or an integer of 20 ~ 300 = 杳 t 4 for the consideration of film formation and thermal decomposition, &amp; is the number Λ such as Du is good, based on the consideration of viscosity increase , B is 30 ~ 120 = 敫 number ^ 2. Based on the consideration of film formation and thermal decomposability, d is 20 ~ 3 00. The normal formula is based on the consideration of decomposability during baking, and e is preferably 1. The number 2 or ~ is considered to be more compatible with pyrolysis *, and the carbon of z Π: ^ is the burning base, based on the consideration of thermal decomposability, its ether American envy is better. Based on the consideration of thermal decomposability, it is more preferable that Y is an oxygen atom or 15 to 306. Based on the considerations of thickening and thermal decomposition properties, a is preferably a number of perch * / * ^. Based on the consideration of film-forming properties, b is an integer Λ ^^ of 40 to 6 0 0. Based on the consideration of film formation and thermal decomposability, d is the whole of 15 ~ 60 ", based on the consideration of decomposability during baking, e is better.:, Polyether is toward the molecular interface The active agent has the function of thickening and film formation ^^^^ Such as the hydrophilic polymer surfactant with a propylene oxide moiety as the lipophilic group and an ethylene oxide moiety, and can be obtained from 2 50 Μ, μ ^ decomposes in the temperature range up to the melting temperature of the gas polymer; and can form alternating copolymers (such as in the general formula (II) or (V)

Page 12 517076

V. Description of the invention (9) When a = b = l), block copolymer (for example, general formula (III), (IV), (VI) or (VII)), messy copolymer (for example, general formula (II) (V)) and other forms, but based on the consideration of easy viscosity increase, the best condition is to use at least one type of block copolymer manufactured by the general formula (II 丨). The average molecular weight of the ethylene glycol portion of these polyether polymer surfactants is 1xio3 to 2X105, preferably 2X103 to 8xi04, and 8X103 to 5X104. The average weight of the propylene oxide portion is $ 10. Good X103 ~ 3X104 'is preferably 2.5 * 103 ~ 3x104, and more preferably 3x is 2X104. 1 When the total molecular weight of the aforementioned ethylene oxide residues is less than 丨 χ ', it is easy to cause phase separation and make it impossible to divide evenly. Table, month and month, when the preparation exceeds 2 υ 1 05, it is easy to excessively thicken and make it impossible. Spraying. When the weight-average molecular weight of the aforementioned product / χ roast is less than 2 X 103, it is easy to produce the clothing and milk to cause vertical flow of the coating, and the vertical flow part is easy to cause when baking, and when it exceeds 3 XI 04, it is easy to cause thickening and make it difficult to apply. Cracking; Polyether-based polymer interfacial activity represented by general formula (11) Examples include N &lt; Specific examples

(7) a messy polymer represented by H0 (CH2CH20) a (CH (CH3) CH20) bH (where a is 3 0 0 and b is 75); (8) C17H35C00 (CH2CH20) a (CH (CH3) CH20) bC0017H3: (wherein a is 3 0 0 and b is 7 5) The structure of (7) is preferred based on the consideration of thermal decomposability. The specific examples of the polyether system represented by the general formula (I I I) of the polymer surfactant are listed below.

Page 13 517076 V. Description of the invention (ίο) (9) H0 (CH2CH20) a (CH (CH3) CH20) b (CH2CH20) dH (where a and d add up to 364 and b equals 69); (10) Block polymer represented by C17H35C00 (CH2CH20) a (CH (CH3) CH20) bCH2CH20) dC0C17H35 (wherein a and d are 300 and b is 60); etc. as an example; The structure of (9) is better. Specific examples of the polyether polymer surfactant represented by the general formula (IV) include (11) H0 (CH (CH3) CH20) a (CH2CH20) b (CH (CH3) CH20) dH (where, a The total with d is 64 and b is 350); (12) C17H35C00 (CH (CH3) CH20) a (CH2CH20) b (CH (CH3) CH20) dC0C17H35 (where a and d are 60 and b is 310) Representative block polymers; etc. as examples, but based on the consideration of thermal decomposability, the structure of 11) is preferred ° The polyether polymer surfactant represented by the general formula (V) # ^ can be listed

(13) CH2-0-(-CH2CH20) a (CH (CH3) CH20) bH

I

CH-〇-(-CH2CH20) a (CH (CH3) CH20) bH

Messy polymer represented by I CH2-0-(-CH2CH20) a (CH (CH3) CH20) bH (where a is 300 and b is 75); (14) CH2-0-(-CH2CH20) a ( CH (CH3) CH20) bC0C17H35 CH-0-(-CH2CH20) a (CH (CH3) CH20) bC0C17H35

Page 14 517076 V. Description of the invention (11)

I CH2-0-(-CH2CH20) a (CH (CH3) CH20) bC0C17H; 35 (where a is 300 and b is 75) is a messy polymer; etc. as an example, but based on consideration of thermal decomposability The structure of (1 3) is preferred. Specific examples of the polyether-based polymer surfactant represented by the general formula (V I)

(15) CH2-0-(-CH2CH20) a (CH (CH3) CH20) b (CH2CH20) dH

I

CH-0-(-CH2CH20) a (CH (CH3) CH20) b (CH2CH20) dH

I

CH2 ~ 0- (~ CH2CH20) a (CH (CH3) CH20) b (CH2CH20) dH (where a and d add up to 364 and b is 69); (16) CH2-0 ~ (-CH2CH20) a ( CH (CH3) CH20) b (CH2CH90) dC0C17H35

I CH-0-(-CH2CH20) a (CH (CH3) CH20) b (CH2CH90) dC0C17H35

A block polymer represented by I CH2-0-(-CH2CH20) a (CH (CH3) CH20) b (CH2CH20) dC0C17H35 (where a and d add up to 300 and b is 60); etc. are examples, but Based on the consideration of thermal decomposability, the structure of (1 5) is preferred. Specific examples of the polyether polymer surfactant represented by the general formula (V I I) include

(17) CH2-〇-((CH (CH3) CH20) a (CH2CH20) b (CH (CH3) CH20) dH

I

CH-0-(-CH (CH3) CH20) a (CH2CH20) b (CH (CH3) CH20) dH

517076 V. Description of the invention (12)

I CH2-0-(-CH (CH3) CH20) a (CH2CH20) b (CH (CH3) CH20) dH (where 3 and (1 are 64 in total and b is 350); (17) CH2-0- (-CH (CH3) CH20) a (CH2CH20) b (CH (CH3) CH20) dC0C17H35

I CH ^ 0-(-CH (CH3) CH20) a (CH2CH20) b (CH (CH3) CH20) dC0C17H35 CH 「0-(-CH (CH3) CH20) a (CH2CH20) b (CH (CH3) CH20) Block polymer represented by dC0C17H35 (where a and d are 60 in total, and b is 310); etc. as an example '; however, based on the consideration of thermal decomposability, the structure of (丨 7) is better. Based on easy viscosity increase In consideration, in the present invention, if a polyether polymer surfactant represented by the general formulae (丨 j) to (1 \) is used alone, it is better to use the general formula (III). Also, if 2 In the case of more than one type, although various combinations in the general formulae (II) to (IV) are possible, based on the considerations of thickening, flatness, and typicality, it is preferable to use the combination of (Π) and (111). Based on the consideration of 2 decomposability, the preferred combination of the specific examples at this time is, for example, the combination of (Ό and (9) or (10), the combination with (9) or (10), etc.) in the foregoing specific examples. Also, the present invention Among them, when the ether-based polymer surfactants represented by the general formulae (v) to (VII) are used alone, the formula (VI) is preferred because of the tendency to increase viscosity. If two or more kinds are used At the time, the various combinations in the general formulas k (V) ~ (VII) though Both can be, but based on the consideration of viscosity and property, it is better to use the combination of (V) and (VI). Based on the heat and the consideration of 'the best combination of specific examples at this time is, for example, the aforementioned specific examples (13) a combination of (15) or (16), (14) and (15) or (16), etc.

517076 V. Description of the invention (13) It is preferable to combine the aforementioned general formula (I)-using a polybond-based resin represented by the aforementioned general formula (I I). ', Qiao molecular surfactant is a liquid carrier compared to the present invention, can be a mixture of alcohols such as propanol, isopropanol; water ^ 7 1 water and methanol, ethanol, ethylene glycol, glycerol and other polyvalent Alcohol mixtures = alcohols, diethylene glycol, tris; amine mixtures such as water and diethylamine, triethylamine, ethanol ^ 7 and propionate, etc., · water and tetrahydrofuran, etc. = ethanolamine, Triethanolamine stops the condensation of the aforementioned fluoropolymer fine particles, and this compound is taken as an example. Based on the combination of anti-and amines is preferred.膜 For the consideration of membrane properties, water and water are used as the oxidation catalyst. Take the temperature above the melting point of the fluoropolymer for the part of the latex coating film resin latex or the above interface activity :; two; = polyether so it should have a perfect white coating film produced 2 / knife Deterioration residues are particularly noticeable in the case of thick coating. color. This problem remains in the hair: it is fast enough to completely decompose and remove the material of the discoloration source, and an oxidation catalyst is added to it. use. Reactive type and catalyst type. In the present invention, both of them can be made. For example, ‘ammonium nitrate, calcium nitrate, sodium nitrate, sodium nitrite, and other metal nitrates or nitrites; sodium acetate, etc. Based on the study of catalyst activity during high-temperature sintering of fluororesin coatings Ⅰ "Among the catalysts, calcium nitrate, sodium nitrosate, and sodium acetate with high heat resistance of the catalyst itself are preferred. Catalyst-type oxidation catalysts For example, column I, nickel nitrate, nickel sulfate, chlorination, page 17 517076, description of the invention (14) _ Shengbu juice-Er A, chemical bromide, vinegar k 钸, caprylic acid 钸 and other phosphonium salts 4. The above lice catalysts Among them, ^ Sour acid, octanoic acid, and stone acid are better. ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, 1 ~ 10 times ", hair

Λ $% is more preferable, and 0.05 to 2% by weight is more preferable. If the amount is too high, the discoloration source will remain. If it is too long, it has a long life, corrosion resistance, and diarrhea, and has a poor effect on the resistance of the coating film &quot; still corrosion resistance and resistance to dyeing. It can be added in the form of powder or liquid such as organic solvent. Exhausted in water, such as group: material = two medium (weight t; within the range that affects the physical properties of the composition, such as Dijiaguang: the same below) can be used for the following, for example, 曱 茇, body. Mica particles can be added to the liquid carrier m composed of non-polar solvents such as aromatics ~ C11, and mica particles coated with pigments can be added in advance. These fillers are good. Ranran, but based on the consideration of aesthetics, the size of the mica is 10 ~ 100, and 15 ~ 50 V &quot; 1 is better. The particle's wear resistance is less than 10_. Poor sexual coupling, Qi: 5 is good, it is easy to cause the reduction of non-adhesiveness. For example, "field": Mica particles coated with Ti3 with pigments can be listed, and the pigments such as T: Ή03 are coated on the aforementioned mica particles by sintering. The method of money is to use titanium, zirconium, molybdenum, zinc, antimony, tin, iron, nickel 517076 as the example of metal grate. V. Description of Invention (15) For example, based on the consideration that it is not easy to record, 10 ~ 100 // m, Less than 10 Clams are better to see mistakes, when the size is more than; 00 Brightness and abrasion resistance are deteriorated. This hair has a tendency to reduce non-bumping properties. Silicone oil and other defoamers. A Base fiber "emulsified cobalt temple desiccant, such as bulking agent 'C9 ~ C11 aromatic hydrocarbons, _A Junji: pigments such as ethylene polymerized titanium, red iron oxide, carbon black, etc .: agent: smoothing agent, oxygen can be, The method of adding the amount is the weight of the aforementioned fluoropolymer ^ is preferably less than 35%, or ^ + less than 50% of the standard, which is more likely to cause non-adhesive liquid when it exceeds 50%. ° Add ammonia water as needed Or mono-, di-, tri-ethanolamine and other specific polyether resins and the amount used above are 0.1% of the aforementioned aeropolymer microparticle surfactants, the effect will not be shown. The amount used is less than 4 intense. Ca n’t be read. When the film is read 300%, it will shrink when baked and become a filler. 0.2 to 20% of the toilet, preferably 0.2% by weight of the total weight of the product, and the wear resistance of the coating film is 2 to 1 () /. If the amount used is less than the deterioration of adhesion, it is said to be poor If it is more than 20%, it is easy to cause non-cardiac hair === coating; Second thing: B component concentration * If it is more than 80%, it is easy to cause spraying. °° Easily form a coating film. Related to the production of the present invention The method of applying the polymer coating composition can be described on page 19 of 517076. V. Description of the invention (16) The following method is given as an example. An aqueous dispersion of fluoropolymer fine particles (solid content 60% concentrated) 90 ~ 110 05〜1 98 部 ， The aforementioned polyfluorene was added to the container with% container, and the filler was sequentially added under stirring. 〇. 丨 ～ 丨 〇8 System polymer interface activity ♦ 0.5 ~ 198 parts of ether, 2 ~ 22 parts of liquid carrier, 1 0.05 ~ 10 parts added if necessary 'Stir at 5 ~ 30 ° C for 10 ~ 40 minutes until uniform 2 The fluoropolymer coating composition of the present invention is obtained ^ ~ ^ The composition of the present invention can be coated on a seed substrate by using a general method, for example, by sandblasting first After roughening the surface of metal, enamel, ceramics, etc., use a primer coating mixture (Daikin Industries (Stock Site, Polyflon Enamel EK-1 909BKN) for primer coating. The fluoropolymer in the coated composition (340 to 415. Bake for 10 to 30 minutes. The temperature of the fused polymer film at this time is more than 3 0 # m, and the% limit, When it exceeds 70 // m, the residues of the above-mentioned specific ether ethers and the polymer surfactant with an upper limit will remain in the coating film / the polyether properties will decrease sharply, so the film thickness is 30 ~ 70 " m is better. The non-adhesive composition of the present invention is suitable for use in metal conditioning appliances and pans, but the composition of the present invention is also suitable for use in ## 二 &gt; especially suitable for frying other products. Examples include glass or baking temperature.物 ％ &amp; 衣 ϋσ. For example, bearings, valves, electric wires, metal foils, two tubes of furnaces, textures, inner layers, soleplates, bread molds, electric cookers, handles & bottoms of ships, ovens, electric stoves, ice trays,

517076

Snow shovel, plow, chute, conveyor belt, roller, knife, awl-like tool, kitchen knife, funnel, and semiconductor tool) and molds are examples. The fluoropolymer coating composition (1) of the present invention is used in molds, molds, saws, files and other industrial containers (the following examples are particularly exemplified. (A) fine particles of a fluoropolymer (B) general formula (I) The content of the representative polyether-based resin is 0.30% by weight of (A). (30)% (C) oxidation catalyst ° (D) liquid carrier. This composition can be thickly coated. Forms a coating film with excellent abrasion resistance, anti-corrosion resistance, industrial strength, and whiteness, and can maintain excellent quality over a long period of time. The coating of sheet soil is preferably: The fine particles (B) of the polyether resin represented by the general formula (I) have a content of 0.1 to 30Q% (C) of the oxidation catalyst (D) as a weight basis of the (A1) liquid carrier: combination The material can be further-thickly coated, which can form a coating film with excellent abrasion resistance and resistance &gt; Coating with excellent whiteness'. The top of the composition: If the compound can maintain excellent quality for a longer period of time. More preferably: ( A2) Particles of PTFE, PFA and / or FEP

517076 V. Description of the invention (18) (B 1) Polyether resin represented by general formula (I) whose content is 0.1 to 30% by weight of (A2) (C) oxidation catalyst (especially phosphonium salt) (D) Liquid carrier This composition can form a coating film with more excellent gloss, corrosion resistance and whiteness, and the coated article top-coated with the composition can maintain excellent quality for a longer period of time. (2) (A) Fluoropolymer fine particles (B) Polyether resin represented by general formula (I), the content of which is 0.1 to 300% by weight of (A) (C) General formula (II) to ( VII) at least one polyether polymer surfactant, the content of which is 0.1 to 300% by weight of (A) (D) oxidation catalyst (E) liquid carrier. This composition may Thick coating can form a coating film with excellent abrasion resistance, corrosion resistance, whiteness, and non-adhesiveness. The coated article coated with the composition can maintain excellent quality for a long period of time. Preferably: (A 1) Tetrafluoroethylene polymer fine particles (B) Polyether resin represented by general formula (I), the content of which is 0.1 to 300% by weight of (A1) (C 1) The content of the polyether-based polymer surfactant represented by formula (II) is 0.1 to 300% by weight based on (A1)

Page 22 517076 V. Description of the invention (19)

(D) Oxidation catalyst (E) Liquid carrier This composition can be further improved: the coated articles coated with the composition can be coated for a longer period of time: (A2) PTFE, PFA and / or The fine particles of FEP (B1) in the general formula (I) are polyether resins in which R1 is a hydrogen atom, and the content thereof is (β) 1 to 30 ()% by weight based on (A) (C2) in the general formula (Π), r is Polyether polymer surfactant with hydrogen atom 'content is ο.υοο% by weight based on (A) (D 1) oxidation catalyst (especially sulfonium salt) (Ε) liquid carrier, the composition may be Further thick coating can form a coating film excellent in gloss, corrosion resistance, and whiteness, and a coated article top-coated with the composition can maintain excellent quality for a longer period of time. °° Next, the present invention will be described more specifically using examples, but the present invention is not limited to these examples. &quot; Example 1 The following ingredients were mixed in the order described. · (L) Aqueous PTFE dispersion (Poiy fion dispersion D-1 manufactured by Daikin Industries Co., Ltd., 60% solids aqueous dispersion (polyethylene oxide containing 6% as a dispersion stabilizer for pTFE) Alkyl phenol ether (EO = 10)) 150 parts (2) Polyether resin latex (manufactured by Sanyo Chemical Industry Co., Ltd.)

Page 23 517076 V. Description of the invention (20)

Permaline UA-2 0 0, emulsifier-free latex that combines polytetramethylene glycol by urea ester group to combine polytetramethylene glycol, solid content 30%) 6.0 part (3) 25% ten 3。 6 parts of sodium bisulfate aqueous solution (4) xylene 1, 1, 6 (5) oxidation catalyst (10 wt% sodium nitrite aqueous solution) 9. 0 parts (6) deionized water 7.0 parts A coating property test was performed on the obtained composition. The test was performed according to the following method. Physical properties of paint Viscosity: It was measured using a B-type rotational viscometer (No. 2 rotor) and rotating the rotor at 60 rpm for 2 minutes (temperature: 25 ° C). The results are shown in Table 1. Next, a sand-blasted aluminum frying pan was first coated with a dry primer mixture having a thickness of 15 // m (a Daikin Industry Co., Ltd. p0iyflon Wanqi EKK-1 909BKN (containing polymer醯 amine 醯 imine), and then spray the composition of the present invention obtained by mixing the components (1) to (6) above (the film thickness after baking is' bake at 380 ° C for 15 minutes (quick (Dry) to obtain a coating article using the composition of the present invention as a top coating with a total film thickness of 50 // m, and subject the coating article to physical properties of the coating film as described below. : Spraying on the non-sandblasted aluminum plate, drying (air-drying, quick-drying) under the aforementioned baking conditions, using an electromagnetic film thickness meter to determine.

Page 517076

Degree of discoloration: Use A to rate C for non-discolored persons. Visually observe the coating film obtained by the above (air-drying) method. The color of the color changer is set to B, and the value of the serious color change is evaluated to the value of L. Spray on the aluminum plate without sandblasting, and use the above-mentioned baking conditions for baking. A color computer (Model SM-7 manufactured by §4 Testing Machine (Co., Ltd.)) was used to evaluate the color tone at a thickness of 30 # m. [A larger value indicates higher whiteness. The results are shown in Table 1. Examples 2 to 7 and Comparative Example 8 Using the paint having the composition shown in Table 1, the same adjustment as in Example 丨 was performed, and the same evaluation as in Example 1 was performed. The results are shown in Table 1. In Table 1, the polyether resin (I) latex, each polyether polymer surfactant (11), (π I), (VI), a ground substrate, and Ti 02 coated mica are as follows: The person. Polyether resin (I) latex: Permarin UA-200 (manufactured by Niyo Kasei Industries, Ltd.). Poly-series polymer surfactant (I I): Ethylene oxide-propylene oxide mess copolymer (NEWOLE 75H-90 0 00, 20% aqueous solution manufactured by Sanyo Chemical Industry Co., Ltd.). In formula (II), R is Η, γ is an oxygen atom, a is 300, b is 75, and c is 1. Poly-series polymer surfactant (I I I): Ethylene oxide-propylene oxide mess copolymer (NEWPOLE PE128, 20% aqueous solution manufactured by Sanyo Chemical Industry Co., Ltd.). In formula (III), R is

Page 25 517076 V. Description of the invention (22) Η, Y is an oxygen atom, a is 182, b is 69, and d is 128. Polyether-based polymer surfactant (V I): Ethylene oxide fired propylene oxide fired copolymer (NEWPOLE V-10-C, 20% aqueous solution manufactured by Sanyo Chemical Industry Co., Ltd.). In the formula (VI), ^^ Η, Y is an oxygen atom, a is 182, b is 69, d is 128, and Z is a trivalent aliphatic saturated hydrocarbon compound. Grinding the base material: A mixture of 55 parts of deionized water and 45 parts of oxidized blue using a ball mill.

Ti02 coated mica: those with an average particle size of 3 0 // m.

Page 26 517076 V. Description of the invention (23) | SS W Leru c4 ^ ram 4 ^ v ~ s 3 3 Dust-repellent viscosity (cP) (House) ΐ 爹 杀 PTFE aqueous dispersion polyether resin φ latex Polyether-based Polymer Surfactant (II) Polyether-based Polymer Surfactant (II) Polyether-based Polymer Surfactant (VI) Twelve Xuan Shu G tear 25% aqueous solution 'P stupid deionized water grinding grade ΤΑ coated mica acid ibW〇% 7jc initial solution (_ («ί» ^ K (^ 1 to u \ o 150 6 3.6 1.6 7.0 subacid sodium 9.0 a ^, t〇4 ^ to 〆LO K) K) Lh o 150 6 &quot; 3.6 1.6 7.0 Zinc acid decoration 9.0 K) ^ tO ^ ^ K) 00 o 150 6 3.6 1.6 7.〇0.7 6.5 Nitric acid decoration 9.0 Lk) Ul s. ^ 〇K) ^ ^ ^ U) o 150 6 13.5 3.6 1.6 16.3 Rhenium nitrate 9.0 Private M, Private LO 4 ^ Lk) g '150 6 13.5 3.6 1.6 16.3 Nitrate 9.0 s. ON (0〆0 00 U) ►— * o 150 6 13.5 3.6 1.6 16.3 Rhenium nitrate 9.0 〇 \ ^ s. Vt O 00 K &gt; g 150 6 13.5 — 3.6 1.6 16.3 0.7 6.5 Rhenium nitrate 9.0 LO K) 4 ^ Lk) ^ J 〇〇Ul K) U \ o — one — '' 1 ^ ^ 1 · '^ ^-1 Comparative Example φ. / -S K) 4 ^ OQJ so &lt; J bo oo o Os 〇 一一 LO ~; &quot; * _ U… ^ bb 1, '^ ^ K) OJ ^ Ul OO LO 【J to 〇UJ | 150 6 13.5: (ii 3.6 1.6 16.3 K) / -s 4 ^ ^ ^ 0 ^ 00 0 U) g 1 150 6, 13.5 3.6 1.6 16.3 — private to &lt; -N · &lt;! ^ J LO 〇0 o 150 6 13.5 3.6 1.6 16.3-! Ln 00 ϋ, K) o — One LO one `` '^ b ON' '' '^ On 6 ® 5; K) h— * o 〇N 〇— — L〇; — • γ α, bs ·', '^ ^ ^ mo 150 3.6 1.6 6 Samarium nitrate 9.0 oo 11 ·! Page 27 517076 Jade and description of the invention (24) It can be seen from the results in Table 1 that the composition of the present invention formed by adding the general formula (1) to a resin and an oxidation catalyst is ineffective. Specific aggregation can greatly suppress discoloration. 'Not only thick coating, but also, when a single molecular surfactant is used in combination with the general formula (!!) ~ (Γ I t), the boundary film can be cracked, and the specific polymer of π is large and mass-produced. Better characteristics. (I, especially when it is quick-drying) 2 Industrial utilization k From the above results, it can be seen that the fluorine band of the present invention is thickly coated and can form abrasion resistance and color resistance. The coating composition can change color The coating film is dispersed in the coating due to the excellent non-adhesiveness and excellent workability and safety of the surface-coated resin latex using the aforementioned T. Therefore, it has excellent film-forming effects. In addition, since the covering article can be uniformly maintained, it can maintain excellent whiteness for a long period of time, and the layer is coated with the composition, the degree, and the quality.

Claims (1)

/ / • A coating combination of a fluoropolymer may be 7, Douban &amp;, based on the weight of the microparticles, A /, is a fluoropolymer microparticle oxidation catalyst; and the liquid carrier is equal to 1 and weighs 8% by weight. "Poly I-based tree" The polyether-based resin is of the general formula ⑴. The chaotic hydrate coating combination RI'y1 '(AB) -ri ⑴ [In the gas, R1 is the same or different hydrogen & oxygen atom, κ ,, n, or a carbon atom having 1 to 20 carbon atoms, "is the epoxy residue 2 r / day soil or thionyl, and A is 3 or more carbon atoms 103: 2 The molecular weight of the obtained epoxy sintered part is a resin represented by alternating mound-artificial ester group, thionyl group or phosphate group (however, the residue obtained in parentheses)], and the decomposition pore temperature of the resin is polymerized than that of the plate. The decomposition temperature of the substance is low. Person &amp; 2. t ΐPlease apply the coating group π of the fluoropolymer described in item 1 of the patent scope, which has 0.1 to 300% by weight of the aforementioned fluoropolymer fine particles. General formula (11): 丨 -Y- (Ca-Db-) c — Y —R II / R is a hydrogen atom or an alkyl group having a carbon number of 20, γ is an oxygen atom, an ether S, and a group: # 腺§Substantial, thionyl, or scale Group, C is ethylene oxide residue, such as% oxypropylene residue, a is an integer from 30 to 2000, b is an integer from 20 to 500, c is an integer from 1 to 10 (but,-(Ca-Db -) c-: Residues obtained by ΐ, polymerization or messy copolymerization); General formula (III): ... &quot; -Ca-Vc ~ (III) <In the formula, R, Y, r η i, 0 and 1 ) The same as above, a and d are a total of 30 ~ 2 000 Page 29 517076 VI. The integer of the patent application range); General formula (IV): RY-Da-Cb-Dd-YR (IV) a and d are integers totaling 20 ~ 500 (where R, Y, C And D is the same number as the above, 'b is an integer of 30 to 2000); General formula (V): z [—Y — (ca-Db-) c —Y — R] e (V) nicotyl, R is hydrogen Atom or alkyl group, urea ester group, and D group are propylene oxide residues, and C is an integer of 1 to 10,. In the formula, 'Z is a polyvalent aliphatic saturated carbon group having 1 to 5 carbon atoms, and γ is an oxygen atom, an ether group, a pyrrolyl group, or a phosphate group, and c is an ethylene oxide residue, &amp; Is an integer from 30 to 2000, b is an integer from 20 to 500, e is an integer from 1 to 4 (but,-(Ca-Db-) c- is a residue obtained by alternating copolymerization or messy copolymerization)]; General formula (VI): Z [-Y-Ca-Db-cd-YR] e (VI) (where Z, R, γ, c, D, and b are represented by general formula (v) — and d is an integer from 30 to 2000 in total, and e is an integer from 1 to 4); or the same as' a General formula (VI I): ^ Z [-Y-Da-Cb-Dd-YR] e (VII) (formula In the formula, Z, R, Y, C &amp; D are the same as those represented by the general formula (v), which is an integer of 20 to 500 in total, and e is an integer of 1 to 4). Take molecular surfactant or 2 These are the surfactants. Congratulations 3. The coating of fluoropolymer as described in item 1 or 2 of the scope of patent application Page 30 517076 6. Scope of Patent Application Composition, in which II polymer is a tetraethylene ethylene polymer. 4. The coating composition of a fluoropolymer as described in item 3 of the scope of the patent application, wherein the tetrafluoroethylene-based polymer is polytetrafluoroethylene, tetrafluoroethylene-perfluoro Scale) copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer, or two or more of the foregoing. 5. The fluoropolymer coating composition according to item 1 or 2 of the scope of the patent application, wherein (1) more mica particles, pigment-coated mica particles, metal flakes, or two or more of the foregoing substances are added. (2) and the tetragas ethylene polymer is polytetrafluoroethylene, tetrafluoroethylene-perfluoro (fired ethylene glycol ether) copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer or 2 More than one of the foregoing substances; based on the total amount of the component (1) and the component (2), the component (2) is 80 to 99.8% by weight, and the component (1) is 20 to 0.2% by weight . 6. The fluoropolymer coating composition according to item 1 or 2 of the scope of the patent application, wherein the liquid carrier is water. 0 (Π〜10 重量 ％ ° 7. The coating and composition of a fluoropolymer as described in item 1 or 2 of the scope of the patent application, wherein the addition amount of the oxidation catalyst is 0. 0 (Π ~ 10% by weight ° 8. The fluoropolymer coating composition according to item 1 or 2 of the scope of patent application, wherein the oxidation catalyst is added in the form of powder. 9. The fluorine according to item 1 or 2 of the scope of patent application Polymer coating composition, wherein the oxidation catalyst is ammonium nitrate, calcium nitrate, sodium nitrate, aluminum nitrate, sodium nitrite, sodium acetate, nickel nitrate, nickel sulfate, nickel chloride, acetic acid Page 517076 Page 32