JP2003327650A - Coating composition containing polyurethane having tertiary amino group-bearing polyurethane chain skeleton and fluoroalkyl side chain group - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyurethane-based coating composition which imparts water repellency, oil repellency and stainproof properties. <P>SOLUTION: This fluorine-containing polyurethane composition is mainly composed of a comb-shaped polyurethane polymer and an organic solvent, which polyurethane polymer has a recurring unit represented by formula A [wherein R<SP>1</SP>is CH<SB>2</SB>(CF<SB>2</SB>)<SB>a</SB>F, CH<SB>2</SB>(CF<SB>2</SB>)<SB>b</SB>H, CH<SB>2</SB>CH<SB>2</SB>(CF<SB>2</SB>)<SB>c</SB>F, CH<SB>2</SB>CH<SB>2</SB>(CF<SB>2</SB>)<SB>d</SB>CF(CF<SB>3</SB>)<SB>2</SB>, CH<SB>2</SB>CH(OH)CH<SB>2</SB>(CF<SB>2</SB>)<SB>e</SB>F or CH<SB>2</SB>CH(OH)CH<SB>2</SB>(CF<SB>2</SB>)<SB>f</SB>CF(CF<SB>3</SB>)<SB>2</SB>; (a) is 1 or 2; (b) is 2,4, 6 or 8; (c) is 4, 6 or 8; (d) is 2, 4 or 6; (e) is 4, 6 or 8; (f) is 2, 4 or 6; R<SP>2</SP>is a group selected from general formulae B to E and (CH<SB>2</SB>)<SB>6</SB>; and (n) is 5-50] and is synthesized from a diethanolamine compound bearing a tertiary amino group and a diisocyanate. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an inorganic material such as a stone material having a repeating unit represented by the general formula A,
And a comb-shaped polyurethane polymer having a tertiary amino group effectively acting as an adsorption point for a metal material in the polyurethane main chain, and a side chain having a fluorinated alkyl group at the N of the amino group is introduced, and an organic solvent, particularly Acetone, acetate,
And a fluorine-based polyurethane composition containing at least one organic solvent selected from the group consisting of tetrahydrofuran. In particular, it has a repeating unit represented by the general formula A, which has good adhesiveness to the above materials, good solubility in organic solvents, and can improve water repellency, oil repellency, antifouling property, etc. of the surface to be treated. The present invention relates to a coating composition using a fluorinated polyurethane.

[0002]

2. Description of the Related Art Conventionally, as a polymeric material using a fluorinated alkyl group as a functional group for imparting a function of improving water repellency, oil repellency, antifouling property, etc., an acrylic or methacrylic monomer has been used. Polymers such as acrylic polymers synthesized using the functional group-introduced are mainly known. However, the above-mentioned acrylic polymers have a disadvantage in that it is necessary to use a fluorine-based solvent or to form an emulsion type in order to form a coating agent. Further, due to the structure of the polymer, there is a disadvantage that the affinity for an inorganic material such as a metal is small and the adhesiveness to the surface to be treated such as a metal is not sufficient.

Under these circumstances, the present inventor has found that the raw materials for producing polyurethanes and polyesters, especially the above polymers, have water repellency,
As a part of a compound group which is a diol compound which is expected to impart properties such as oil repellency and which is easy to synthesize, Compound 1 having the following structure is proposed (Japanese Patent Laid-Open Publication No. 20-29200).
No. 01-64243. Hereinafter referred to as Document 1. ).

[0004]

[Chemical 4]

As R ² in the compound 1, CH ₂ C _m F _{2m + 1} , CH ₂ CH ₂ C _m F
_{2m + 1} (where m is in the range of 1 to 10) is proposed. However, no specific example is presented. In addition, when the polymer compound is synthesized using the above-mentioned diol as a raw material for polyurethane, the affinity of the polymer compound for a solvent and the adhesiveness to an inorganic material such as a metal material when used as a coating material are not mentioned at all. Absent.

On the other hand, Japanese Patent Laid-Open No. 2001-329038
(Published November 27, 2001, referred to as Reference 2 below)
In addition, using dialkanolamines as a raw material for polyurethane synthesis, as specific examples, diethanolaminopropylamine, isophorone diisocyanate, and 2-
A diol obtained from (perfluorodecyl) ethanol is described. Using the diol as Example 9, polyurethane is synthesized using dimethylformamide as a solvent, a film is prepared from the solution, and its surface characteristics are measured. The contact angle with water was 112 °, the contact angle with dodecane was 71 °, and the adhesiveness of the film formed on the polyester film [peeling force was 19.6.
(N / m)] is reported. However, these compounds have a urea bond in the side chain and are different in side chain structure from the polyurethane of the present invention which does not have such a bond. Therefore, it cannot be said to be sufficient in improving the solubility in an organic solvent and the adhesiveness when coated with an inorganic material such as steel. Further, the tertiary amine compound of the present invention is obtained in a nearly stoichiometric manner by Michael addition of diethanolamine and acrylic ester,
It has an advantage that raw materials are easily available.

[0007]

The problem of the present invention is that the function of the fluorinated alkyl group is sufficiently exerted, the raw materials are easily synthesized, and the coating film formed is soluble in a general-purpose solvent. It is an object of the present invention to design a polyurethane-based polymer compound having excellent adhesiveness to a surface to be treated, thereby providing a fluorine-based polyurethane composition that can be easily handled. Therefore,
The following tertiary amine is newly synthesized, a polyurethane compound is synthesized by reacting this with a diisocyanate, and the solubility of the polyurethane compound in various organic solvents,
And, when the adhesiveness with the metal surface was examined, it was found that it was soluble in low boiling point solvents such as acetone and ethyl acetate, and that the composition with the solvent was useful as a coating agent for stones and metals. The above-mentioned subject was able to be solved.

[0008]

The present invention has the general formula A
A fluorine-based polyurethane composition having a repeating unit represented by, having a tertiary amino group in the main chain, and having a comb-shaped polyurethane polymer synthesized from diethanolamines and diisocyanates and an organic solvent as main components Yes,
Preferably, the organic solvent is at least one selected from the group consisting of acetone, acetic acid ester, and tetrahydrofuran, and more preferably, the fluorine-based polyurethane composition, more preferably polyurethane is a repeating unit of the compound B. The above-mentioned fluorine-based polyurethane composition is characterized by having

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail. A. The diethanolamines represented by the following compound 2 for synthesizing the polyurethane used in the present invention are synthesized by applying the Michael addition reaction proposed by the present inventor in Document 1.

[0010]

[Chemical 5]

[0011] In the compounds 2, ^{R 1} is the same as ^{R 1} in the general formula A.

[0012]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not construed to be limited to these examples. About measuring equipment. Measurement of weight average molecular weight: Tosoh GPC HLC-8
Using a 120 type, dimethylformamide containing 0.01 M lithium bromide was measured as a solvent to obtain a molecular weight in terms of standard polystyrene. Infrared absorption spectrum: FT-720 manufactured by Horiba, Ltd. was used. NMR spectrum; JNM EX manufactured by JEOL Datum
-270 type was used. Measurement of water repellency and oil repellency: The contact angle is measured by a contact angle measuring instrument GI type manufactured by Elma Optical Co., Ltd. Water repellency was evaluated from the contact angle with water, and oil repellency was evaluated from the contact angles with n-hexadecane and diiodomethane.

Example 1 Synthesis of compound C.

[0014]

[Chemical 6]

The Michael addition reaction of equimolar perfluorodecylethyl acrylate and diethanolamine is
The mixture is heated in dioxane at 50 ° C. for 24 hours to synthesize the corresponding diol. Using the synthesized diol as it is, 105 mol% of isophorone diisocyanate was added to the diol, this was dissolved in dioxane, dibutyltin dilaurate (5 mol% to the diol) was added as a catalyst, and the addition reaction was performed while heating under reflux. Was carried out for 24 hours. Thereafter, ethanol was added to this solution to block the isocyanate at the terminal (E ₂ ) to synthesize the polyurethane of the compound C. The average molecular weight of the obtained polyurethane was 1.38 × 10 ⁴ . By adjusting the mol% of diisocyanate with respect to the diol of the polymerization conditions, n can be in the range of 5 to 50 which is preferable for synthesizing the coating composition.

The infrared spectrum is shown in FIG. This figure
From 1714 cm^-1, 1518 cm ^-1, 1214 cm
^-1Has absorption due to urethane bond, and 700 to 8
00 cm^-1The absorption due to the C—F bond was confirmed. N
The MR spectrum is shown in FIG. 0.8-1.4ppm
There is a peak of isophorone unit, at 4 to 4.5 ppm
-CH of ester group of diol unit_TwoCH_Two(CF_Two)
CF_Three-CH in_TwoCH_Two-Proton peak is
Was seen. From the above, the polyuretase having the above-mentioned molecular structure
It was confirmed that the synthesis of

Solubility of the synthesized polyurethane. As the solvent for dissolving the polyurethane, acetone, methyl ethyl ketone, ethyl acetate, dioxane, tetrahydrofuran, dimethylformamide, chloroform and the like were confirmed. It was not completely dissolved in alcohol such as methanol and ethanol. Solubility in low boiling point solvents such as acetone, methyl ethyl ketone, and ethyl acetate is advantageous in that when used as a coating agent, there is no problem of residual solvent in the coating film.

Water repellency and oil repellency of the coated thin film. As the coating composition, the polyurethane obtained by the above-mentioned polyurethane synthesis was added to dioxane at 5%.
The dissolved solution was used. The thin film for measurement was formed by immersing a slide glass in the solution and then air-drying. 1. Results of measurement of water repellency: The contact angle of the thin film with water was 107.5 °, which was as high as that of the fluoropolymer. Measurement result of oil repellency; contact angle to n-hexadecane is 70.5 °, and contact angle to diiodomethane is 8
It was 1.9 °. In the case of n-hexadecane, slidability was observed.

[0019]

As described above, the polyurethane of the present invention is efficiently synthesized, and the obtained polyurethane is soluble in a solvent having a low boiling point such as acetone or ethyl acetate. The combination brings about the excellent effect of obtaining a useful coating composition. Further, it can be expected to improve the adhesiveness to an inorganic material such as metal.

[Brief description of drawings]

FIG. 1 Infrared spectrum of Example 1

FIG. 2 NMR spectrum of Example 1

Claims (3)

[Claims] 1. A fluoropolyurethane composition comprising a comb-shaped polyurethane polymer synthesized from diethanolamines and diisocyanates having a tertiary amino group having a repeating unit represented by the general formula A and an organic solvent as main components. object. [Chemical 1] However, R ¹ is CH ₂ (CF ₂ ) _a F, CH ₂ (C
_{F 2) b H, CH 2} CH 2 (CF 2) C F, CH 2 CH
_{2 (CF 2) d CF (} CF 3) 2, CH 2 CH (OH)
CH ₂ (CF ₂ ) _e F or CH ₂ CH (OH) CH
₂ (CF ₂ ) _f CF (CF ₃ ) ₂ , a is 1 or 2, b is 2, 4, 6 or 8, c is 4, 6 or 8, d
Is 2, 4 or 6, e is 4, 6 or 8 and f is 2, 4 or 6. R ² is a group selected from the following group 1 and n is 5 to 50. [Chemical 2] 2. The fluorine-based polyurethane composition according to claim 1, wherein the organic solvent is at least one selected from the group consisting of acetone, acetic acid ester, and tetrahydrofuran. 3. The fluorine-based polyurethane composition according to claim 1, wherein the polyurethane has a repeating unit of the following compound B. [Chemical 3]