JPH05163284A - Metallic compound containing fluorinated carbon chain and fluorine-containing surface modifying agent - Google Patents

Abstract

PURPOSE:To provide the subject compound effective for imparting the surface of an inorganic material with not only water and oil repellency but also excellent rustproofing effect and useful as a fluorine-containing surface modifying agent. CONSTITUTION:The compound of formula I {M is Ti, Zr or Al; R is 1-4C alkyl; X is 1-30C alkyl or alkoxy; R1 and R2 are H or 1-30C alkyl; Y is CO or CHR' (R' is same as R1); Z is group of formula II or formula III [Rf and Rf' are 1-30C fluoroalkyl; Q and Q' are (CH2)K ((k) is 1-30) or single bond]; when M is Ti or Zr, (a) is 4 and (m) and (n) are 1 or 2 (m+n<=3), and when M is Al, (a) is 3 and (m) and (n) are l}. The compound of formula I can be produced e.g. by reacting a compound of formula H(OR)2 with a compound of formula IV and a compound of formula Z-H in a solvent (e.g. heptane, benzene or methyl acetate) preferably at 60-130 deg.C for 30 min to 2hr.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface modifier which imparts a characteristic property of fluorocarbon to an inorganic surface and has an excellent rust preventive effect.

[0002]

2. Description of the Related Art Conventionally, surface modifiers (or surfactants)
As the hydrocarbon group, a hydrocarbon group having a long hydrocarbon chain as a hydrophobic group and a fluorine group having a long fluorocarbon chain are known. Fluorine-based surface modifiers (1) greatly reduce the surface tension of water, (2) exhibit high surface activity at low concentrations, and (3) heat resistance and chemical resistance, compared with those of hydrocarbon type. (4) It has excellent properties such as (4) showing surface activity even in organic solvents and having water and oil repellency, but it has a drawback that it is weakly bound to an inorganic surface and is peeled off by an organic solvent. .. On the other hand, the hydrocarbon-based surface modifier binds to the inorganic surface via a covalent bond and imparts properties such as water repellency, but it cannot impart oil repellency.

Examples of the fluorocarbon-based surface modifiers include titanate-based surface modifiers described in JP-A-60-254119 and JP-A-61-297478, and JP-A-2-2.
Aluminate-based surface modifiers such as 58885, JP-A-64
No. 33164 and the zirconate-based surface modifiers of JP-A-2-258886 are known. The inorganic substances treated with these surface modifiers show not only water repellency but also oil repellency. However, the rust preventive effect on materials that are extremely susceptible to oxidation, such as rare earth magnetic materials, has not been satisfactory.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a surface modifier which imparts an excellent rust preventive effect.

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that the above objects can be achieved by a certain kind of fluorocarbon chain-containing metal compound. They have found the present invention and completed the present invention. That is,
The present invention relates to a fluorocarbon chain-containing metal compound represented by the following general formula (I).

[Chemical 4] In the formula, M is Ti, Zr or Al, and R is 1 carbon atom.
~ 4 alkyl group, X is an alkyl group or an alkoxy group having 1 to 30 carbon atoms, R1 and R2 may be the same or different, but a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, Y represents -CO- or -CHR'- (wherein R'is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms), and Z is represented by the following general formulas (a) to (f). The group

[Chemical 5] [In the group, Rf and Rf ′ may be the same or different, but a fluoroalkyl group having 1 to 30 carbon atoms is represented by Q
And Q ′ may be the same or different,
(CH2) k- (wherein K is an integer of 1 to 30) or a single bond. ] When M is Ti or Zr, a is 4, m,
n represents 1 or 2 (however, m + n ≦ 3), and when M is Al, a represents 3 and m = n = 1.

The present invention also relates to an alkoxy metal compound represented by the following general formula (II)
Fluorocarbon chain-containing metal compound (where M is T) obtained by reacting s molar equivalent of the compound represented by I) with t molar equivalent of the fluorocarbon chain-containing compound represented by the general formula (IV).
In the case of i or Zr, s and t are 0.1 to 3.4, (s +
t ≦ 3.5), and when M is Al, s and t are 0.1
˜2.4, (s + t ≦ 2.5). And at least one of the above). M (OR) a (II)

[Chemical 6] Z-H (IV) In the formula, M, R, a, X, R1, R2, Y and Z are the same as in the general formula (I).

Examples of the alkoxy metal compound (II) which is a raw material of the fluorocarbon chain-containing metal compound of the present invention include tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium, tetramethoxy zirconium and tetraethoxy. Zirconium, tetraisopropoxy zirconium, tetrabutoxy zirconium, trimethoxy aluminum, triethoxy aluminum, triisopropoxy aluminum,
Tributoxyaluminum and the like can be mentioned, and from the viewpoint of reactivity and economical efficiency, tetraisopropoxytitanium, tetrabutoxytitanium, tetraisopropoxyzirconium, tetrabutoxyzirconium, triisopropoxyaluminum and tributoxyaluminum are preferable.

Examples of the compound represented by the general formula (III) include β-ketocarboxylic acid derivatives, β-hydroxyketone derivatives, malonic acid monoester derivatives and β-hydroxycarboxylic acid ester derivatives. Such compounds include acetoacetic acid, 4-hydroxy-2-butanone, 4-hydroxy-2-hexanone, 4-hydroxy-2-octanone, 4-hydroxy-2-decanone, 5-hydroxy-3-hexanone, 5-hydroxy-3-octanone, 5-hydroxy-3-decanone, ethyl malonate, propyl malonate, butyl malonate, hexyl malonate, decyl malonate, lauryl malonate,
Stearyl malonate, ethyl methyl malonate, ethyl ethyl malonate, methyl 3-hydroxybutanoate, ethyl 3-hydroxybutanoate, propyl 3-hydroxybutanoate, butyl 3-hydroxybutanoate, hexyl 3-hydroxybutanoate, 3 -Decyl hydroxybutanoate, 3
Examples thereof include lauryl hydroxybutanoate, stearyl 3-hydroxybutanoate, methyl heptanoate, and methyl hexanoate. Among them, β-hydroxyketone derivatives having no ester by-product are preferable.

Further, as the compound represented by the general formula (IV), fluoroalkylcarboxylic acid, di (fluoroalkyl) pyrophosphate ester, di (fluoroalkyl) phosphate ester, fluoroalkylsulfonic acid or fluoroalkyl alcohol and the like can be mentioned. Can be mentioned.

The fluoroalkyl represented by Rf may be either straight chain or branched chain, for example, C
F3, C2F5, C3F7, C4F9, C5F11, C6F13, C7
F15, C8F17, C8F16H, C9F19, C9F18H, C10
F21, C10F20H, C11F23, C11F22H, C12F25,
C12F24H, C13F27, C13F26H, C14F29, C14F
28H, C15F31, C15F30H, C16F33, C16F32H,
C17F35, C17F34H, C18F37, C18F36H and the like can be mentioned, but among them, C7 from the viewpoint of effect and economical efficiency.
F15, C7F14H, C8F17, C8F16H, C9F19, C9
F18H, C10F21 and C10F20H are preferred. If a spacer Q is present, CH2, C2H4, C3H6, C4
H8, C5H10, C6H12, C7H14, C8H16, C9H18,
C10H20 etc. can be mentioned, but among them C2H4, C4
H8 and C6H12 are preferred.

Specific examples of the compound of the general formula (IV) include C4F9CO2H, C5F11CO2H and C6F13CO2.
H, C7F15CO2H, C8F17CO2H, C9F19CO2
H, C10F21CO2H, di (1H, 1H, 2H, 2H-
Perfluorohexyl) pyrophosphate, di (1H, 1H,
2H, 2H-perfluorooctyl) pyrophosphate, di (1H, 1H, 2H, 2H-perfluorodecyl) pyrophosphate, di (1H, 1H, 2H, 2H-perfluorododecyl) pyrophosphate, di (1H, 1H , 2H, 2H-perfluorohexyl) phosphoric acid, di (1H, 1H, 2H,
2H-perfluorooctyl) phosphoric acid, di (1H, 1
H, 2H, 2H-perfluorodecyl) phosphoric acid, di (1
H, 1H, 2H, 2H-perfluorododecyl) phosphoric acid, C4F9SO3H, C5F11SO3H, C6F13SO3
H, C7F15SO3H, C8F17SO3H, C9F19SO3
H, C10F21SO3H, C4F9 (CH2) 2OH, C6F11
3 (CH2) 2OH, C8F17 (CH2) 2OH, C10F21
(CH2) 2OH and the like can be mentioned.

Next, a method for producing the fluorocarbon chain-containing metal compound of the present invention will be described. The reaction of the alkoxy metal compound represented by the general formula (II) with the compound represented by the general formula (III) and the fluorocarbon chain-containing compound represented by the general formula (IV) is carried out without a solvent or in a solvent. You can

Examples of the solvent include aliphatic hydrocarbons such as heptane, hexane and octane, aromatic hydrocarbons such as benzene, toluene and xylene, methyl acetate and ethyl acetate.
Esters such as butyl acetate, ethers such as diethyl ether and diisopropyl ether, and alcohols such as methanol, ethanol and isopropanol are used.

When an alkoxytitanium compound or an alkoxyzirconium compound is used as a raw material, the addition ratio of the compound represented by the general formula (III) and the fluorocarbon chain-containing compound (IV) to the compound is 0.1 to 3.4, respectively. It is in the range of molar equivalents. However, the total molar equivalent of the two compounds (III, IV) is 3.5 or less. When an alkoxyaluminum compound is used as a raw material, the compound represented by the general formula (III) and the fluorocarbon chain-containing compound (I
The addition ratio of V) is in the range of 0.1 to 2.4 molar equivalents. However, the total molar equivalent of the two compounds (III, IV) is 2.5 or less.

The reaction temperature is from room temperature to 150 ° C, preferably 60 to 130 ° C. If it is lower than room temperature, the reaction is slow and not practical, and if it exceeds 150 ° C., decomposition, coloring, etc. occur, which is not preferable. The reaction time varies depending on the conditions such as the raw materials and the reaction temperature and cannot be determined unconditionally, but is usually 15
Minutes to 24 hours, preferably 30 minutes to 2 hours. The fluorocarbon chain-containing metal compound of the present invention is a highly viscous liquid obtained by concentrating the reaction solution obtained as described above,
Obtained as a wax or powdery material.

In using the surface modifier of the present invention for an inorganic substance, the substance obtained by the above method may be used as it is, but the reaction product before distilling off the alcohol or the solvent is used as it is. May be. Further, it may be used in combination with a conventionally known surface modifier. The addition amount of the surface modifier used in the present invention varies depending on the type of the inorganic substance, the specific surface area and the amount of water bound to the surface, but in the case of the inorganic filler, it is 0. 05-20% by weight, preferably 0.2-
It is 10% by weight. As the surface treatment method, (1) the present modifier is added as it is to the filler, and a Henschel mixer is used.
A method of co-milling using a mill such as a ball mill or atomizer colloid mill, (2) toluene, xylene, benzene, hexane, cyclohexane, methyl ethyl ketone, acetone, acetonitrile, carbon tetrachloride, chloroform, methylene chloride, trichloroethylene, diethyl ether, A method of adding a filler to a suitable organic solvent such as tetrahydrofuran with stirring, and removing the solvent after stirring and mixing,
(3) A method in which the present modifier is directly added to the mixture of the organic medium and the filler, and the mixture is mixed with a hot roll or the like can be mentioned.

Examples of inorganic substances to be applied include rare earth magnetic powders such as samarium cobalt, neodymium iron cobalt and zirconium cobalt for the purpose of rust prevention, but they are used for ordinary surface treatment, that is, imparting water and oil repellency. MO ・ Fe2O3 (M is Ba, Sr, Ca, M
g, Zn, Pb) or other ferrite magnetic powder, iron, zinc, copper, silver, metal such as nickel, tungsten, molybdenum, rhenium, niobium, tantalum, lead, tungsten trioxide, aluminum oxide, Metal oxides such as lanthanum oxide, cadmium oxide, chromium oxide, yttrium oxide, titanium oxide, copper oxide, cuprous oxide, lead oxide, zinc oxide, gadolinium oxide, iron sesquioxide, ferric tetroxide, and gamma ferric oxide Substances, lead carbonate, strontium carbonate, calcium carbonate, barium carbonate and other metal carbonates,
In addition to metal hydroxides such as aluminum hydroxide, magnesium hydroxide, chromium hydroxide, nickel hydroxide, etc., chromium lead, navy blue, ultramarine blue, cobalt blue, chromium phosphate, zinc phosphate,
Pigment of cyanamide lead, calcium leadate, basic silicochromate, carbon pigment, yellow lead, cadmium yellow, zinc yellow, navels yellow, rhodamine, benzidine yellow, talc, kaolin, silica, bentonite, glass, tungsten carbide, para Ammonium tungstate, asbestos,
Silicon Carbide, Acetylene Black, Graphite, Carbon Black, Barium Titanate, Cadmium Sulfide,
It may be applied to barium sulfate, carbon fluoride, graphite fluoride, granular ammonium salt, litharge, zirconate titanate, ammonium dihydrogen phosphate, ethylenediamine tartrate and the like. In addition, phthalocyanine blue, Hansa Yellow, Litol red, phthalocyanine green, quinacridone red,
It can be applied to organic substances such as organic pigments such as aniline black. Further, the shape of these inorganic substances is not limited to powder and granules, and includes all shapes such as rod-like, plate-like, linear, lump-like and cotton-like.

Also, when the surface modifier of the present invention is used in a resin, there is no problem at all, polyolefin such as polyethylene and polypropylene, chlorinated polyolefin such as chlorinated polyethylene, natural rubber, ethylene-propylene copolymer rubber, Rubber such as butyl rubber, butadiene rubber, isoprene rubber, nitrile rubber, chloroprene rubber, nylon 12, nylon 46, nylon 11, nylon 6,
It can be used for polyamide such as nylon 66, PPS, ethylene-vinyl acetate copolymer, styrene-acrylic copolymer, polyester, epoxy resin and the like.

Next, the contents of the present invention will be described in detail with reference to examples. It should be noted that the following examples do not limit the scope of the present invention, but are intended to more clearly illustrate the characteristics of the present invention.

Synthesis Example The raw materials shown in Table 1 were heated and mixed at 100 ° C. in the absence of a solvent to remove the produced low boiling point alcohol to prepare a surface modifier. The product was confirmed to have no OH absorption in the infrared absorption spectrum.

[0021]

[Table 1]

Test Example The compounds obtained in the synthesis examples, stearic acid and stearylamine were used as surface modifiers and evaluated as follows. 1 part by weight of the surface modifier is dissolved in 40 parts of toluene, and Nd2Fe14B powder (GM Magnequench MQ)
P-B) 100 parts by weight were mixed and stirred at room temperature for 10 minutes, then toluene was distilled off under reduced pressure at 60 ° C and dried under reduced pressure at 85 ° C to obtain a treated powder. 90% relative humidity,
An oxidation resistance test was conducted at 80 ° C. for 1,000 hours. Further, 0.2 g of this treated powder was molded by an IR tableting machine, and the contact angle with water and liquid paraffin was measured to evaluate the water and oil repellency. (Table 2).

[0023]

[Table 2]

[0024]

As described above, it can be seen that the surface modifier using the compound of the present invention not only imparts water and oil repellency to the surface of the inorganic substance, but also imparts an excellent rust preventive effect.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C09K 3/00 112 A 9049-4H 3/18 102 8318-4H

Claims (2)

[Claims] 1. A fluorocarbon chain-containing metal compound represented by the following general formula (I). [Chemical 1] In the formula, M is Ti, Zr or Al, and R is 1 carbon atom.
~ 4 alkyl group, X is an alkyl group or an alkoxy group having 1 to 30 carbon atoms, R1 and R2 may be the same or different, but a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, Y represents -CO- or -CHR'- (wherein R'is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms), and Z is represented by the following general formulas (a) to (f). A group represented by [In the group, Rf and Rf ′ may be the same or different, but a fluoroalkyl group having 1 to 30 carbon atoms is represented by Q
And Q ′ may be the same or different,
(CH2) k- (wherein K is an integer of 1 to 30) or a single bond. ] When M is Ti or Zr, a is 4, m,
n represents 1 or 2 (however, m + n ≦ 3), and when M is Al, a represents 3 and m = n = 1. 2. A s molar equivalent of a compound represented by the general formula (III) and a fluorocarbon chain represented by the general formula (IV) with respect to an alkoxy metal compound represented by the following general formula (II). Fluorocarbon chain-containing metal compound obtained by reacting compound t molar equivalent (provided that M is Ti or Zr, s and t are 0.1 to 3.4 (s + t ≦ 3.5), and Is Al, s and t are 0.1 to 2.4, (s +
t ≦ 2.5). ) A fluorine-based surface modifier containing at least one of M (OR) a (II) embedded image Z-H (IV) In the formula, M, R, a, X, R1, R2, Y and Z are the same as in the general formula (I).