JPS6232186B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel fluorine-containing urethane compound, particularly a fluorine-containing urethane compound containing a perfluoroalkyl group as a side chain, a method for producing the compound, a water and oil repellent containing the compound as an active ingredient, and a method for making the compound effective. It relates to a non-adhesive agent as a component. In general, urethane compounds containing perfluoroalkyl groups are known as water and oil repellents with abrasion resistance, and have been put to practical use as water and oil repellents for carpets (U.S. Pat. No. 3,896,035, U.S. Pat. No. 3,897,227). and Japanese Unexamined Patent Publication No. 54-74000). However, conventional fluorine-containing urethane compounds have insufficient water repellency when treated on cloth surfaces, and are unsatisfactory for use as water and oil repellents. The present inventors have developed a fluorine-containing urethane compound of this type that has superior water and oil repellency compared to conventional compounds, and has completed the present invention. The fluorine-containing urethane compound of the present invention has the general formula [In the formula, Rf represents a perfluoroalkyl group having 4 to 20 carbon atoms, and X is -CH ₂ CH(A)-, -C _n H
_2n - or -SO ₂ N (R ¹ ) C _l H _2l -. A is a methyl group or an ethyl group, m and l are integers of 1 to 4,
R ¹ represents a hydrogen atom or a lower alkyl group. Also, Y is

【formula】

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【formula】

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[Formula] is shown. ] It is a substance that exhibits good water and oil repellency and is useful as a material for forming films on the surfaces of various solid substances. The compound of the present invention is also useful as a non-adhesive agent such as a mold release agent during molding. The compounds of the present invention are all novel compounds that have not been described in any literature, and can be easily synthesized, for example, by the method described below. That is, the compound of the present invention is a diisocyanate compound (2) represented by the general formula OCNYNCO and a diisocyanate compound (2) represented by the general formula OCNYNCO.
By reacting with a fluorine-containing alcohol (3) represented by RfXOH, the general formula

The compound (1) of the present invention is produced by producing a compound (4) represented by the formula (reaction formula A below), and then reacting this compound (4) with water (the following reaction B). [In each formula, Rf, X and Y are the same as above. ]Diisocyanate compound used in reaction formula A
As for (2),

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【formula】

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[Formula] or

Use with [expression]. Further, as the fluorine-containing alcohol (3), a wide variety of known ones can be used, such as CF ₃ (CF ₂ ) _o SO ₂ N
_- ( _C2H5 ) _{CH2CH2OH , CF3}
( _CF2 ) _{o CH2CH2OH ,}

【formula】

[Formula] etc. can be mentioned. Here, n represents an integer of 3 to 19. The perfluoroalkyl group has 4 to 20 carbon atoms, preferably 5 to 16 carbon atoms. The reaction between the diisocyanate compound (2) of Reaction Formula A and the fluorine-containing alcohol (3) is carried out in the presence or absence of a catalyst, usually in an organic solvent inert to isocyanate groups. Examples of the organic solvent include halogenated hydrocarbons such as 1,1,1-trichloroethane, trichloroethylene, trichloromethane, and trichlorotrifluoroethane, aromatic hydrocarbons such as benzene and toluene, hexane,
Examples include saturated hydrocarbons such as heptane, ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diethylene glycol dimethyl ether, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. In order to carry out this process smoothly, water-soluble substances, ie, ethers and ketones, are preferable. In addition, as a catalyst that can be used in this reaction, a wide range of catalysts used in general urethane or polyurethane synthesis reactions (reaction of isocyanate groups and hydroxyl groups) can be used, such as triethylamine, triethylenediamine, mono-octanoic acid, etc. Examples include tin. The amount of catalyst used is usually about 0.5 to 5 mol% based on (2). There is no particular limitation on the ratio of use of (2) and (3), but usually
(3) is used in an amount of about 0.8 to 12 moles, preferably in equal moles. Reaction temperature is room temperature to 100℃, preferably 40 to 100℃
It is. The reaction time is usually about 1 to 3 hours.
Note that this reaction is desirably carried out under anhydrous conditions in order to suppress undesirable side reactions. It is desirable that the reaction between compound (4) of Reaction Formula B and water is continued under the same conditions without isolating the compound (4) produced after the reaction of Reaction Formula A is completed. This is usually carried out by adding a predetermined amount of water after the reaction of reaction formula A is completed. In this case, compound (4) can also be isolated and then reacted with water. The amount of water added is usually about 0.4 to 0.6 mol, preferably 0.5 mol, per 1 mol of compound (4). Reaction time is usually 2-5
It takes about an hour. In this reaction, as shown in reaction formula B, the compound
(4) 1 mol and 1 mol of water react to form an amino compound (5) 1
Then, 1 mole of amino compound (5) reacts with 1 mole of compound (4) remaining in the reaction system to produce compound (1) of the present invention. The compound of the present invention can be used for various purposes in the form of an organic solvent solution or an aqueous emulsion, but since it has a perfluoroalkyl group, its low surface energy can be used to make it particularly suitable for water and oil repellents and non-adhesive agents. It is useful as Water and oil repellents are agents that lower the critical surface tension of the surface of a solid object and give it the property of repelling aqueous and oil-based substances. Oily substances include animal and vegetable mineral oils and fats such as kerosene, heavy oil, gasoline, liquid paraffin, pitch, asphalt, cottonseed oil, rapeseed oil, and whale oil. Non-adhesive agents are those that reduce the critical surface tension of the surface of the target object and prevent adhesive substances from adhering to the target object, and include so-called mold release agents, back treatment agents,
Includes processing agents for release paper, anti-blocking agents, etc. Mold release agents are sprayed or applied onto metal molds, wooden molds, and other molds during the molding process for rubber, synthetic resin, etc. to improve mold release, but they are generally referred to as internal mold release. It also includes resins in which a mold release agent is mixed with the resin to improve release from the mold. For release paper processing agents and back surface treatment agents,
Used to coat the back of cellophane tape, adhesive tape, etc. to permanently prevent adhesion and make unwinding easier, and for the production of release paper for labels, patches, etc., and for film and plywood molding processes. This includes those used in the production of release paper. The anti-blocking agent is used as a processing agent to prevent blocking when sheets, films, etc. are held in close contact with each other for a long period of time. In order to put the compound of the present invention into practical use as a water and oil repellent or a non-adhesive agent, the compound of the present invention may be used in acetone, methyl ethyl ketone, ethyl acetate, dimethyl formamide, methyl chloroform, trichloroethylene, trichlorotrifluoroethane, tetrachlorodifluoroethane, etc. The compound of the present invention is prepared by dissolving the compound in one or a mixture of two or more organic solvents, or by diluting the resulting compound of the present invention by reacting in the solvent with the above-mentioned solvent, if necessary. An aerosol type solution can also be prepared by adding a propellant such as dichlorodifluoromethane, monochlorotrifluoromethane, or dimethyl ether to such a solvent solution and filling it into a suitable vessel. Furthermore, an aqueous emulsion can be prepared by emulsifying and dispersing the compound of the present invention in an aqueous medium using various additives and a suitable surfactant. The surfactant used for emulsification and dispersion may be anionic, nonionic, or cationic, and is not particularly limited. Articles that can be treated with water and oil repellents containing the compound of the present invention as an active ingredient are not particularly limited, and various examples can be mentioned. For example, it is particularly useful for textile fabrics, paper, etc., as well as porous articles such as wood, leather, blankets, felt, asbestos, brick, etc., and articles with smooth surfaces such as metals, tiles, plastics, various painted surfaces, etc. can be mentioned. Fiber fabrics include natural fibers of animal and plant origin such as cotton, linen, wool, and silk;
Various synthetic fibers such as polyamide, polyester, polyvinyl acetal, polyacrylonitrile, polyvinyl chloride, polypropylene, rayon,
Examples include semi-synthetic fibers such as acetate, glass fibers, inorganic fibers such as asbestos fibers, and woven fabrics of mixed fibers thereof. There are no particular limitations on the articles that can be treated with the non-adhesive agent containing the compound of the present invention as an active ingredient, and most of the articles that can be treated with the above-mentioned water and oil repellents can be applied.
Substances that can be used as the non-adhesive of the present invention include polyurethane resins, epoxy resins, phenol resins, vinyl chloride resins, acrylic resins, natural rubber,
Examples include synthetic or natural resins such as chloroprene rubber and fluorocarbon rubber, and synthetic or natural rubber. Examples of industrial applications of non-adhesive agents include metal molds, wooden molds, plastic molds, paper molds, etc. used in the plastic and rubber molding industry as so-called mold release agents, as well as paper, cellophane, cloth, and plastic films. It can be applied to the back side treatment of adhesive tapes such as metal foils, and the production of release paper for labels, stickers, and patches coated with adhesive in advance. The concentration of the compound of the present invention in the water and oil repellent is not particularly limited, but is usually about 0.01 to 30% by weight, particularly preferably about 0.1 to 2.0% by weight. If the concentration of the solution is too low, imparting water and oil repellency will be insufficient, and if the concentration is too high, it will be economically disadvantageous. The concentration of the compound of the present invention in the non-adhesive agent is as follows: When used as a mold release agent, when the purpose is only one mold release,
0.01% by weight or less is sufficient, but if a long service life is required with one application of mold release agent, 0.05 to 30%
% by weight, preferably from 0.1 to 10% by weight, is suitable. When used as a backside treatment agent or antiblocking agent, it can be used in approximately the same amount. When used as an internal mold release agent, the compounds of the present invention may be present in amounts of 0.05 to 10% by weight relative to the control resin;
In particular, it is appropriate to add about 0.1 to 3% by weight. The method of applying the water and oil repellent and non-adhesive agent containing the compound of the present invention as an active ingredient depends on the type of object to be treated, the purpose of use, the preparation form of the water and oil repellent agent and non-adhesive agent, etc. Just choose something. In the case of an aqueous emulsion or a solvent solution type, it may be applied to the surface of the object to be treated by a known method such as spraying, dipping, or coating and then dried, and curing may be performed if necessary. In addition, in the case of an aerosol type, it is sufficient to simply spray the object onto the object to be treated and dry it. Next, the present invention will be explained in more detail with reference to Examples. In the examples, "parts" and "%" indicate "parts by weight" and "% by weight" unless otherwise specified.
In addition, water and oil repellency is indicated by the following scale. That is,
Water repellency was expressed as water repellency determined by the spray method of JIS L-1005, and oil repellency was measured by the method of AATCC118-1972. Example 1 A 500 c.c. four-necked flask equipped with a dropping funnel with an isobaric tube, a thermometer, a nitrogen blowing tube, and a vacuum stirring device is set on a silicone oil bath. 2,
17.4 g (0.1 mol) of 4-tolylene diisocyanate and 200 g of methyl ethyl ketone were introduced into the flask, and stirring was started while blowing nitrogen through the blow tube. After 15 minutes, stop the nitrogen blowing, replace the blowing tube with the cooling tube, and maintain the liquid temperature at 75°C. From the dropping funnel under a dry nitrogen atmosphere

[Formula] 51.4g (0.1 mol) was added dropwise over 45 minutes. After dropping, stir for 30 minutes, add 0.9 g (0.05 mol) of water, and
Stirring was continued for an hour. The reaction solution was taken, the solvent methyl ethyl ketone was distilled off using an evaporator, and the residue was vacuum dried to obtain 64 g of a white solid with a melting point of 85°C. As a result of analysis by gas chromatography and infrared absorption spectrum, the target substance The selection rate for () was 98%. The yield was 95% based on the raw material 2,4-tolylene diisocyanate. Example 2 4,4'-diphenylmethane diisocyanate 25
g (0.1 mol) and

[Formula] 51.4g (0.1 mol) was used in the same manner as in Example 1 to obtain the desired product as a white solid with a melting point of 90 to 91°C. Obtained 70g. The selectivity of 4, which is the raw material, is 97%.
The yield was 96% based on 4'-diphenylmethane diisocyanate. Example 3 18.8g xylylene diisocyanate and

[Formula] Using 58.5 g, the desired product was obtained as a pale yellow solid with a melting point of 91 to 93°C in ethylene glycol dimethyl ether in the same manner as in Example 1. Obtained 69g. The selectivity was 95%, and the yield based on xylylene diisocyanate, the raw material, was 93%. Example _{4 A} white solid with _a melting _point of 111 to
113℃ target 65g was obtained. The selectivity was 96%, and the yield based on the raw material 4,4'-dicyclohexylmethane diisocyanate was 94%. Example 5 Compound synthesized in Example 1, 2, 3 or 4,
, or 1% by weight dissolved in a mixed solvent of trichlorotrifluoroethane and acetone at a volume ratio of 1/1, respectively. A cotton/polyester blend cloth of 35/65 was dipped in this solution, and the liquid was attached using a mangle. Squeeze to 100% and dry at 100℃ for 3 minutes. The water repellency and oil repellency of these treated fabrics were measured and were as shown in Table 1.

[Table] Example 6 Fill an aerosol can with 350 parts of a solution of 0.8% by weight of the compound synthesized in Example 2 dissolved in a mixed solvent of trichlorotrifluoroethane and acetone in a 1/1 volume ratio and 100 parts of dichlorodifluoromethane to prepare the compound. Make an aerosol of This aerosol is sprayed onto a raised polyester fabric used as a material for a heating carpet to the extent that the entire surface is slightly moistened. After drying this cloth at room temperature for 30 minutes,
A drop of a 30/70 uol mixture of isopropyl alcohol/water was placed on the surface and held for more than 3 minutes. The oil repellency was 7 points. Example 7 Compound synthesized in Example 1, 2, 3 or 4,
, or are dissolved in a mixture of 90 parts of trichlorotrifluoroethane and 9 parts of acetone. This solution was brushed onto a steel mold for forming a disc having a concave portion of 40 mm in diameter and 2 mm in thickness and air-dried. For comparison, commercially available mold release agents A (silicon type) and B (oil/fat wax type) were each diluted with toluene to a concentration of 1% and applied with a brush in the same manner. As a curable epoxy resin, 100 parts of Epicoat #828 (manufactured by Ciel Chemical Co., Ltd.) and 10 parts of triethylenetetramine were mixed well and injected into each of the molds, and the central part was placed to make it easier to take out the molded product after hardening. Put up a pin for it. After leaving it at room temperature for 2 hours, heat it at 100℃ for 1 hour to harden it, then pull the pin to remove the molded product (disk) from the mold, and judge the mold release performance by the feeling in your hand according to the following criteria. do. Mold release performance criteria 5: The molded product can be removed from the mold with almost no force applied. 4...It can be removed by applying light force. 3...It can be removed by applying a little force. 2...Difficult to remove even if force is applied. 1...The molded product adheres to the mold and cannot be removed at all even if force is applied. As a result, the mold release performance of each compound was as shown in Table 2.

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Claims (1)

[Claims] 1. General formula [In the formula, Rf represents a perfluoroalkyl group having 4 to 20 carbon atoms, and X is -CH ₂ CH(A)-, -C _n H
_2n - or -SO ₂ N (R ¹ ) C _l H _2l -. A represents a methyl group or an ethyl group. m and l are integers of 1 to 4, and R ₁ represents a hydrogen atom or a lower alkyl group. Further, Y represents [Formula] [Formula] [Formula] [Formula] [Formula] [Formula]. ] A fluorine-containing urethane compound represented by: 2 General formula OCNYNCO [wherein Y represents [formula] [formula] [formula] [formula] [formula] [formula]. ] and a diisocyanate compound represented by the general formula RfXOH [wherein, Rf represents a perfluoroalkyl group having 4 to 20 carbon atoms, and X represents -CH ₂ CH(A)
--, --C _n H _2n -- or --SO ₂ N(R ¹ )C _l H _2l --. A is a methyl group or an ethyl group, m and l are 1-
The integer of 4 and R ¹ represent a hydrogen atom or a lower alkyl group. ] is reacted with a fluorine-containing alcohol represented by the general formula [Formula] [where Rf, X and Y are the same as above. A compound represented by the general formula [Formula] [wherein Rf, ] A method for producing a fluorine-containing urethane compound. 3 General formula [In the formula, Rf represents a perfluoroalkyl group having 4 to 20 carbon atoms, and X is -CH ₂ CH(A)-, -C _n H
_2n - or -SO ₂ N (R ¹ ) C _l H _2l -. A is a methyl group or an ethyl group, m and l are integers of 1 to 4,
R ¹ represents a hydrogen atom or a lower alkyl group. Further, Y represents [Formula] [Formula] [Formula] [Formula] [Formula] [Formula]. ] A water and oil repellent agent containing a fluorine-containing urethane compound represented by the following as an active ingredient. 4 General formula [In the formula, Rf represents a perfluoroalkyl group having 4 to 20 carbon atoms, and X is -CH ₂ CH(A)-, -C _n H
_2n - or -SO ₂ N (R ¹ ) C _l H _2l -. A is a methyl group or an ethyl group, m and l are integers of 1 to 4,
R ¹ represents a hydrogen atom or a lower alkyl group. Further, Y represents [Formula] [Formula] [Formula] [Formula] [Formula] [Formula]. ] A non-adhesive agent containing a fluorine-containing urethane compound represented by the following as an active ingredient.