JPH01313582A - Water and oil repellent, and water-and oil-repellent composition - Google Patents

Abstract

PURPOSE:To enable spraying on the surface of an object and melt compounding with plastics to impart persistent water and oil repellency by using as water and oil repellent an ester that is solid at ordinary temperatures and is obtained through a reaction of a monohydric alcohol and/or a diol with a carboxylated fluorine compound. CONSTITUTION:This water and oil repellent comprises an ester that is solid at ordinary temperatures and is prepared by reacting a monohydric alcohol and/or a diol with a compound having perfluoroalkyl groups and one carboxyl group. This ester can be applied alone to the surface of an object by, e.g., casting, it can be melt compounded with a high-molecular compound, or it can be mixed with a high-molecular compound and a solvent to form a composition. As the monohydric alcohol, a 6C or higher, especially 12C or higher, monohydric alcohol is preferably used to give an ester that is solid at ordinary temperatures. It is desirable that the number of carbon atoms of the perfluoroalkyl groups of the carboxylated fluorine compound is 4 or more, especially 7 or 8.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a water/oil repellent agent that imparts water/oil repellency to various products such as plastics, glass, fibers, etc., and a composition containing the same.

(Prior technology) Plastic molded bodies; glass products such as mirrors; textile products such as clothing and umbrellas may require water and oil repellency, and various turbid water and oil repellents have been developed. ing. ↑
Most water and oil repellents are fluorine-containing compounds. For example, Jikai I, 8-192852 and Japanese Patent Application Laid-open No. 58
Publication No. 152830 discloses a new fluorine-containing monomer for synthesizing a fluorine-containing polymer that can be used as a water/oil repellent agent.

The above-mentioned JP-A-58-192852 discloses a vinyl ester compound having a perfluoroalkyl group in its side chain.

And, in the above-mentioned Japanese Patent Application Laid-open No. 58-152830, δ-
Fluoro-α,β-unsaturated aliphatic compounds are disclosed.

An example of a fluorine-containing polymer that can be used as a water/oil repellent is perfluoroalkylethyl acrylate.

Examples include polymers obtained by copolymerizing perfluoroalkyl methacrylate with various monomers. For example, in JP-A-57-180680.

A polymer is disclosed in which a backbone segment made of a copolymer containing a diene yarn binder and a technical segment having a blocked polyfluoroalkyl group (for example, polyfluoroalkyl acrylate) are bonded. JP-A-61-2
Publication No. 09286 discloses a copolymer of a vinyl monomer containing a polyfluoroalkyl group and a vinyl monomer containing a polyfluoroalkoxysilyl group. Many various compositions containing such fluorine-containing polymers are also known. for example.

JP-A-58-147483 discloses a composition containing a polyfluoroalkyl group-containing silane compound, a silane coupling agent, and colloidal silica for the purpose of imparting water and oil repellency to a glass surface. There is. JP-A-58-104978 discloses compositions containing various fluoropolymers, chlorinated solvents, and propellants as aerosol-type water- and oil-repellent compositions intended to be applied to the surface of textile products. Disclosed. In addition, JP-A-5
9-219380 discloses a water- and oil-repellent emulsion containing a (co)polymer containing a fluorine-containing vinyl monomer.

The fluorine-containing polymer obtained by polymerizing the above-mentioned monomer, the above-mentioned 10-water/1-oil polymer, or the above composition can be applied to the surface of textile products, glass, various molded articles, etc. by coating or spraying. For example, when imparting salt water and oil repellency to the surface of plastic molded objects.

If a water/oil repellent agent can be mixed with a plastic material and molded by injection molding or extrusion molding, the above-mentioned coating and spraying steps will be unnecessary, and productivity will be improved. However, all of the above-mentioned water and oil repellents (polymers or compositions) have drawbacks such as poor affinity with plastic materials and bleeding on the surface of the molded product after molding.

(Problem to be solved by the invention) The present invention solves the above-mentioned conventional drawbacks.

Its purpose is to be able to impart salt water and oil repellency to the surface of objects requiring it by means such as coating or spraying.

The object of the present invention is to provide a water/oil repellent that can be mixed with materials such as plastics and melt-molded, and a composition containing the same.

(Means for Solving the Problems) The salt water/oil repellent of the present invention is an ester of a monohydric alcohol and/or diol and a compound having a perfluoroalkyl group and one carboxyl group, and is solid at room temperature. It consists of an ester with a shape.

The I8 water/oil repellent composition of the present invention contains the above-mentioned solid ester and polymer compound.

The ↑6 water/oil repellent composition of the present invention includes the above solid ester,
Contains a polymer compound and a solvent.

The monohydric alcohol used to prepare the ester, which is the water/oil repellent agent of the present invention, is not particularly limited, but in order for the obtained ester to become solid at room temperature, it usually has 2 or more carbon atoms, preferably 6 or more. 12 or more monohydric alcohols are used. Examples include hexanol, octatool, decanol, undecanol, dodecanol,
Tridecanol, tetradecanol, pentadecanol.

Saturated alcohols such as hexadecanol, heptadecanol, octadecanol (stearyl alcohol), nonadecanol, eicosanol, heneicosanol;
and 1-deken-10-ol, 2-deken-10-
ol, 3-undeken-1-ol, 2-bentadeken-5-ol, 3-hebutadeken-1-ol, 5-
Nonadeken-1-ol, l,4-eicosadiene-8
-All.

There are unsaturated alcohols such as 3,10.15-heneicosatrien-1-ol. Among these, stearyl alcohol is particularly preferably used.

The diol is not particularly limited either, but as in the case of monohydric alcohols, a compound is selected such that the resulting ester becomes solid at room temperature. Examples thereof include olefin diols such as polyethylene diol and polypropylene diol, ethylene glycol diols such as polyethylene glycol and polypropylene glycol, and ester diols such as polyethylene terephthalate diol.

As a compound having a perfluoroalkyl group and one carboxyl group (hereinafter referred to as a carboxyl group-containing fluorine compound), a perfluoroalkyl group (CfiF
Compounds in which carbon number (n) of Z, -1) is 4 or more are advantageously used, and compounds in which n is 7 or 8 are particularly preferred.

The above compounds include the following compounds:
C-F2. , -1-CH2C1l□-COOII.

CIIF2fi, + -C1h-COOH, CI, F2
L1, -C11□CH25CII2CH2-COOH
.

C, IF, L□+-CIIzSCHzCtl□-COO
II, Cl1Fzfi and +-CHzCHzSCHz-C
OOII.

C-hfi-+-(Cllz)*-COOH, Cf1h
n-+-(CH2)4-C0OH.

CIIFz, 1. +-(CHz)s-COOtl, C
llF211, +-(C1l□), -COOH.

C, Fz--+-5NIICthC1lz-COOH,
C,F2--1-5NHCH2-COOH.

One equivalent of these compounds is reacted with the hydroxyl group of the monohydric alcohol and/or diol.

The polymer compound contained in the water- and oil-repellent composition of the present invention may be a thermoplastic resin or a thermosetting resin. Thermoplastic resins include polyvinyl alcohol,
Polyvinyl butyral, polyethylene, polypropylene, polyvinyl chloride.

Examples include polystyrene, polymethyl methacrylate polycarbonate, acrylonitrile-styrene copolymer, and acrylonitrile-butadiene-styrene copolymer.

Thermosetting resins include epoxy resin, urethane resin,
Examples include melamine resin, phenol resin, silicone resin, imide resin, allyl resin, and unsaturated polyester.

The solvent contained in the water-repellent/oil-repellent composition of the present invention is mainly used to apply the composition to a water-repellent/oil-repellent composition for painting or spraying.
When used as an oil-based material, it is contained in the two compositions and is used to dissolve the above-mentioned ester and polymer compound (including an uncured thermosetting resin). Such solvents.

It is not particularly limited as long as it can dissolve esters and polymeric compounds. Solvents include ethyl acetate, propyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and benzene.

Toluene, ethylbenzene, xylene, cyclohexane, etc. are used.

The ester that is the I9 water/ta oil agent of the present invention can be obtained by reacting the monohydric alcohol and/or diol with the carboxyl group-containing fluorine compound in a conventional manner. The monohydric alcohol, diol and carboxyl group-containing fluorine compound are selected so that the resulting ester is solid at room temperature. for example,
The above monohydric alcohol and/or diol and the carboxyl group-containing fluorine compound are dissolved in a suitable solvent with a boiling point of 60°C or higher, and a catalyst is added thereto.
The ester is obtained by heating at C for 5-10 hours. Examples of the solvent include ethyl acetate, propyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, and ethylbenzene.

Xylene, cyclohexane, etc. are used. As the catalyst, used are acids commonly used in esterification reactions, such as inorganic acids such as concentrated sulfuric acid and concentrated hydrochloric acid; or organic acids such as trifluoroacetic acid and difluoroacetic acid. The above reaction temperature and reaction time are based on the monohydric alcohol used,
Since it varies depending on the type of diol and carboxyl group-containing fluorine compound, etc., select conditions that have high esterification efficiency and do not cause decomposition or side reactions of raw materials and products.
Set as appropriate. Since the obtained ester is solid at room temperature, for example, when it is applied to the surface of a molded object as a water/oil repellent, or when it is mixed with a plastic material and molded, it is stably attached to the surface of the molded object. exist. For example, one example is this.

When an ester is prepared by selecting a compound with a small number of carbon atoms as the monohydric alcohol and/or diol, the resulting ester becomes liquid. Liquid ester does not stably exist on the surface of the molded product and is easily removed, resulting in poor sustainability of water repellency and electro-oil functions.

The above ester can be applied as it is, for example, to the surface of a glass or plastic molded body by a method such as casting, and used as a water/oil repellent. Furthermore, water repellent 1 containing the above-mentioned water repellent 1 oil agent and a polymer compound is added.
8 oily compositions can be prepared. Such a composition includes, for example, the above-mentioned polymer compound "IyJ" (thermoplastic resin or uncured thermosetting resin) and the above-mentioned ester. This composition is heated and melted, and then extrusion molding or injection molding is performed. A plastic molded product having salt water and oil repellency can be obtained by molding by such methods.For compositions containing a polymer compound, the ester to be used may be selected depending on the type of the polymer compound, taking into account its affinity, etc. In the composition, the ester is selected from C6Fzn in the composition.
The ++ content is preferably 0.5% by weight or more, more preferably 1 to 10% by weight. In addition, in the case of a masterbatch composition, the above ester is CnF! It is preferable that the n+1 content is 15 to 80% by weight.

Still another salt water/oil repellent composition of the present invention contains the above solvent in addition to the above ester and polymer compound. Such a composition is suitable for glass.

It is used for the purpose of applying water- and oil-repellent coatings to the surfaces of various molded objects and textile products such as plastics, metals, and ceramics by means such as coating, casting, and spraying. What type of solvent?

It is appropriately selected depending on the type of ester and polymer compound contained. For example, a coating composition is prepared that includes a thermoplastic resin or an uncured thermosetting resin and a solvent capable of dissolving it.

The blending ratio of the polymer compound and ester is based on the composition containing the above-mentioned polymer compound and ester, and an appropriate amount of solvent is blended therein depending on the purpose.

The ester used in the present invention has a perfluoroalkyl group that has excellent water and oil repellency, so it has excellent salt water and oil repellency, and since it is an ester type, it has excellent compatibility with various resins. The composition of the present invention containing this ester and a polymer compound can be molded by, for example, extrusion molding or injection molding, and the molded product obtained has excellent water and oil repellency. In this way, water repellency and 80% water repellency can be achieved without the need for coating or other processes.
A molded article having oiliness is obtained, and the properties of the polymer compound serving as the base material do not change. Since processes such as coating are omitted, molded bodies can be produced at low cost. Furthermore, the composition of the present invention containing a solvent is used as a water- and oil-repellent composition for painting, and the resulting coating film has excellent water- and oil-repellency. It also has excellent adhesion between the coating film and the surface being coated.

(Example) The invention will be explained below with reference to examples.

Preparation of ester (A): CaF+7-CHzCHz-
Cool (fluorine compound containing carboxyl group) 23.7
5 g (0.05 mol) and 1 stearyl alcohol
3.5 g (0.05 mol) was dissolved in toluene 300, and 0.49 g (0.005 mol) of concentrated sulfuric acid was added thereto. This was reacted at 80'C for 6 hours with stirring. After the reaction is complete.

Water was added to this, and extraction was performed using a water/toluene system. Separate the toluene phase and remove the solvent after drying.

Drying was performed under reduced pressure at 60°C for 2 hours. 20.3 g of ester were obtained. As a result of elemental analysis of the produced ester, C:H was 8.0:1°0 (theoretical value 8.2:1.0).
)Met.

(B) Performance evaluation of ester: The ester obtained in section (A) was dissolved in toluene, and a film was formed by casting. Water and n-octane droplets are brought into contact with the surface, and the contact angle is measured using a contact angle measuring device CA-D.
(manufactured by Kyowa Interface Science). The results are shown in Table 1.

(C) Performance evaluation of ester-containing composition: The ester obtained in section (A) was mixed with various base resins [polystyrene (manufactured by Denki Kagaku Kogyo Co., Ltd., Denka Styrol 1/MW-1]).

Polyethylene (manufactured by Asahi Kasei Co., Ltd., Santic Toro 454)
Or polypropylene (manufactured by Mitsubishi Yuka Co., Ltd., Mitsubishi Polypro B
C05C)] at a ratio of 55% by weight, and a sheet was formed by injection molding.

Water and n-octane droplets were brought into contact with the surface of each sheet, and the contact angle was measured using the same measuring device as in section (A). The results are shown in Table 2.

(D) Performance evaluation of ester-containing compositions: various base resins [
Polystyrene (manufactured by Denki Kagaku Kogyo Co., Ltd., Denka Styrol M
(A
The ester obtained in section ) was blended at a ratio of 5% by weight, and this was dissolved in toluene. This solution was cast and dried to form a film with a thickness of 30 μm. A droplet of water and n-octane is brought into contact with the surface, and the contact angle is
It was measured using the same measuring device as in section A). The results are shown in Table 3.

Practical Lesson Itsu L: "-CsF l as a carboxyl group-containing fluorine compound?
-CIl□CH25CH, CIh-C00I! 26.
Example 1 except that 75 g (0.05 mol) was used.
-1 is the same. The yield and performance of the obtained ester are shown in Table 11, Table 2 and Table 3. Example 1 described below
The results of Nos. 3 to 1-6 are also shown in Table 1, Table 2, and Table 3.

CIIF+ as a fluorine compound containing two main carboxyl groups? −
C1hC1l□5C)l, -COOH26,05g (
The procedure is the same as in Example 1-1 except that 0.05 mol) was used.

14.9g of eicosa alcohol (as monohydric alcohol)
The procedure is the same as in Example 1-1 except that 0.05 mol) was used.

IL attached 221 CsF+q-C as a carboxyl group-containing fluorine compound
112CIl□S CII t CIt□-COO11
26.75 g (0.05 mol) and 14.9 g (0.05 mol) of eicosa alcohol as monohydric alcohol.
The procedure was the same as in Example 1-1 except that mol) was used.

cap+7- as a carboxylic group-containing fluorine compound
The procedure was the same as in Example 1-1 except that 26.05 g (0.05 mol) of C1hCIhSCHz-COOH and 14.9 g (0.05 mol) of eicosa alcohol were used as the monohydric alcohol.

3.0g of propyl alcohol as a monohydric alcohol (
When the same procedure as in Example 1-1 was carried out using 0.05 mol), a semi-solid ester was obtained.

Since this ester has a low melting point, it was not possible to measure the contact angle using a film made only of this ester. This ester was mixed with various base resins in the same manner as in Example 1-1 and (C) at a concentration of 5%, and a sheet was formed in the same manner, and the contact angles of water and low-octane droplets were measured. The results are shown in Table 2. Furthermore, Example 1-1
As in Section (D), various base resins and esters were mixed, a film was formed by casting, and the contact angles of water and n-octane droplets were measured. The results are shown in Table 3.

The resin used as the base material in Example 1-1 (C) was individually molded into a sheet shape by injection molding, and water and n- The contact angle of octane droplets was measured. The results are shown in Table 2. Further, only the resin used as the base material in Example 1-1 (D) was cast to form a film according to Example 1-1 (D), and the contact angle of water and n-octane droplets was was measured. The results are shown in Table 3.

(Left below) Preparation of ester (A): CaF+t-CHzCHz-
COOH (fluorine compound containing carboxyl group) 4.7
5g (0.01 mol) and polyethylene diol (manufactured by Mitsubishi Kasei ■, Polytail HA, Mw = 2230) 1
1.15 g (0,005 mol) was added to xylene 150 and heated to 100"C to dissolve it. To this solution was added 0.1 g (0,001 mol) of concentrated sulfuric acid, and
The reaction was allowed to proceed for 8 hours while stirring at o'c. After cooling, water and toluene were added, and extraction was performed using a water/toluene system. Separate the organic phase.

After drying, the solvent was removed and drying was performed under reduced pressure at 60°C for 2 hours. 14.2 g of ester were obtained.

(B) Performance evaluation of ester 2 The ester obtained in Example (^) was dissolved in toluene and a film was formed by casting. Water and n-octane droplets were brought into contact with the surface, respectively, and the contact angle was measured using a contact angle measuring device CA-D (manufactured by Kyowa Kaimen Kagaku Co., Ltd.). The results are shown in Table 4.

(C) Two performance evaluation examples of ester-containing compositions (8)
The ester obtained in Section 1 is mixed with various base resins [polystyrene (
Denka Styrol MW-1, manufactured by Denki Kagaku Kogyo Co., Ltd.), polyethylene (Santic M-6545, manufactured by Asahi Kasei Co., Ltd.), or polypropylene (manufactured by Mitsubishi Yuka Co., Ltd.).

Mitsubishi Polypro BCO5C)] was blended at a ratio of 55% by weight, and after kneading, hot pressing was performed at 200°C for 10 minutes to obtain a sheet-shaped molded product. Water and n-octane droplets were brought into contact with the surface of each sheet, and the contact angle was measured using the same measuring device as in Example (8). The results are shown in Table 5.

(D) Performance evaluation of ester-containing compositions: various base resins [
Polystyrene (manufactured by Denki Kagaku Kogyo Co., Ltd., Denka Styrol M
LI), polymethyl methacrylate (manufactured by Kyowa Gas Chemical Co., Ltd.), polycarbonate (manufactured by Kijin Kasei Co., Ltd., Panlite L-
1250)] was blended with the ester obtained in Section (8) of this Example at a ratio of 5% by weight, and dissolved in toluene. This solution was cast and dried to form a 30 μm thick film. Water and n-octane droplets were brought into contact with the surface, and the contact angle was measured using the same measuring device as in Example (A). The results are shown in Table 6.

Jitsuki Itsu Kameji” 2 C3Fll-C as a carboxyl group-containing fluorine compound
H2CHzsclI. CIl□-COOH5.35g
(0.01 mol) was used.

The same as Example 2-1 except that the reaction time was 6 hours. Table 4 shows the yield and performance of the obtained ester.
2 Shown in Tables 5 and 6. Examples 2-3 to 2-6 described below
The results are also shown in Table 42, Table 5 and Table 6.

Jitsushin Ie: "-CaF I as a carboxyl group-containing fluorine compound?
-CII□Cl12SCH2-COOH5,21g (
The procedure was the same as in Example 2-1 except that 0.01 mol) was used and the second reaction time was 6 hours.

Real new skin λ: Polyethylene glycol (Mw=300
0) Same as Example 2-1 except that 15 g (0,005 mol) was used.

CIIFI□- as a fluorine compound containing carboxyl group
CH2C112SCII□CHz-COOt(5,35
g (0,01 mol), and polyethylene glycol (Mw=3000) as diol 15 g (0,
The procedure was the same as in Example 2-1 except that 0.005 mol) was used and the reaction time was 6 hours.

CaF+y-C as a carboxyl group-containing fluorine compound
I12CH,5CH2-COOI (5,21g (0
Example 2 except that 15 g (0,005 mol) of polyethylene glycol (Mw=3000) was used as the diol and the reaction time was 6 hours.
-1 is the same.

diethylene glycol 0.53g (0,
When the same procedure as in Example 2-1 was carried out using 0.005 mol), a semi-solid ester was obtained. Since this ester has a low melting point, it was not possible to measure the contact angle using a film made only of this ester. This ester was mixed with various base resins at a concentration of 5% as in Example 2-1 and (C), and a sheet was formed in the same manner to measure the contact angle of water and n-octane droplets. did. The results are shown in Table 5. Further, in the same manner as in Example 2-1 (D), various base resins and esters were mixed, a film was formed by casting, and the contact angles of water and n-octane droplets were measured. The results are shown in Table 6. For comparison,
The results of Comparative Example 1-2 using only the base resin are shown in Tables 2 and 3.

(The following is a blank space) (Effect of the invention) According to the present invention, it is possible to impart water repellency and oil repellency to the surface of an object requiring it by means such as coating or spraying, and Provided are water and oil repellents that can be melt-molded by mixing with materials such as, and compositions containing the same. Especially when a composition containing this water/oil repellent and a polymer compound is used.

A molded article with excellent T6 water/oil repellency and stain prevention performance can be obtained at low cost through a Lee process such as extrusion molding.

that's all

Claims (1)

[Claims] 1. A water/oil repellent agent which is an ester of a monohydric alcohol and/or diol and a compound having a perfluoroalkyl group and one carboxyl group, which is solid at room temperature. . 2. A water- and oil-repellent composition containing the solid ester and polymer compound according to claim 1. 3. A water- and oil-repellent composition containing the solid ester according to claim 1, a polymer compound, and a solvent.