JPS58110555A - Fluorine-containing compound, its preparation and its use - Google Patents

Abstract

NEW MATERIAL:The compound of formulaI[Rf is 4-20C perfluoroalkyl; X is group of CH2CH(A) (A is methyl or ethyl), CmH2m (m is 1-4) or SO2N(R<1>) ClH2l (l is 1-4; R<1> is H or lower alkyl); Y is bivalent organic group]. USE:Water and oil repellent and surface tack eliminator. It has excellent water and oil repellency, and useful as a filmforming material for the surface of various solid materials and a surface tack eliminator such as a mold release agent. PROCESS:The compound of formulaIcan be prepared by reacting the diisocyanate compound of formula OCNYNCO with a fluorine-containing alcohol of formula RfXOH, and reacting the resultant compound of formula II with water.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel fluorine-containing urethane compound, particularly a fluorine-containing urethane compound containing a perfluoroalkyl group as a side chain, a method for producing a core compound, and a method for producing a core compound, which uses a skeleton compound as an active ingredient. The present invention relates to a water and oil repellent and a non-adhesive agent containing the compound as an active ingredient.

In general, uretashi compounds containing a barfluoroal+ru group 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. 3897227 and JP-A-54-7400). 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 inventor has developed a fluorine-containing urethane compound of this type that has water and oil repellency superior to conventional compounds, and has completed the present invention.

The fluorine-containing urethane compound of the present invention has the general formula [wherein R
f is a bar fluo DJ'JIjjitS with 4 to 20 carbon atoms.
and X is -CM2CM(A)-1-C, In2--
y, ti -502N(R”)CtH2t-t
. Ah mef J14 or ethyl group, m and tFil-
The integer of 4 and R1 represent a single hydrogen atom or a lower alkyl group. Moreover, Y represents a divalent organic group. ] 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 comprises a diisocyanate compound (2) represented by the general formula 0CNYNCO and a diisocyanate compound (2) represented by the general formula RfXOH
A compound represented by the general formula RfXOcNHYNCO is obtained by reacting the fluorine-containing alcohol (3) represented by
To produce 4), use the following reaction formula A), then this compound (4)
The compound (1) of the present invention is produced by reacting the compound (1) with water (reaction formula B below).

1 (JCNYNCO+ RfXDH→RfXOCNHYN
CO−・・−・−A+21 131 +
41tfil 14) (1) [In each formula, Rf%X and Y are the same as above. ]Reaction formula AF
As the diisocyanate compound (2) used in /C, a wide variety of known compounds can be used. Further, as the fluorine-containing alcohol (3), a wide range of known ones can be used, such as CF3CCF2), 502N-(C2H5
)CH2CH20H%CF3CCF2), CH2CH
20H.

can be mentioned. 1 Here, ru represents an integer from 3 to 19. The number of carbon atoms in part 410 is 4 to 20, and the number of carbon atoms is 5 to 16.

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 1. halogenated hydrocarbons such as l, 1-tric00 ethane, tric00 ethylene, tric00 methane, tric00 trifluoroethane, aromatic hydrocarbons such as beshizene and toluene, hegyu sashimi, hezuri υ, etc. saturated hydrocarbons, ethers such as ethylene glycol diethyl ether, ethylene glycol diethyl ether, and diethylene glycol dimethyl ether, and ketones such as acetoxy, methyl ethyl ketone, and -methyl isobutyl ketone. In order to carry out the reaction smoothly, those that dissolve water, ie, ethers and ketones, are preferred. In addition, catalysts that can be used in this reaction include a wide range of catalysts used in general urethane or polyurethane synthesis reactions (reaction between isocyanate groups and hydroxyl groups), such as triethylamine, triethylene amine, octanoic acid Examples include stannous. The amount of catalyst used is usually 0.5 to 5 tJL for (2),
It is about %. The usage ratio of (2) and (3) is not particularly limited, but usually (3) is 0.8 compared to (2).
About 1.27 mol, preferably equimolar, is used. The reaction temperature is room temperature to 100°C, preferably 40 to 100°C.

The reaction time is usually about 1 to 3 hours. In addition, this reaction is
It is desirable to conduct the reaction under anhydrous conditions in order to suppress undesirable side reactions.

The reaction of compound (4) of Reaction Formula B with water is preferably carried out 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 Q after the reaction of reaction formula A is completed. In this case, compound (4) can also be isolated and reacted with its water removal. The amount of water to be added is usually 0.0% per mole of compound (4).
The amount is about 4 to 0.66 mol, preferably 0.5 mol. The reaction time is usually about 2 to 5 hours.

This reaction is shown in the reaction formula B above, and the compound +411
el and water react to produce 1111 moles of an amino compound, and then the amino compound t61 mV and 1 mole of compound (4) remaining in the reaction system react to form the compound (1) of the present invention. is generated.

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 use of its low surface energy, especially as a water and oil repellent. Useful as a non-adhesive agent.

Water and oil repellents are books that lower the critical angular surface tension on the surface of solid objects to give them the property of repelling aqueous and oil-based substances. The oily substances include kerosene, heavy oil, gasoline, liquid rosefish, pitch, asphalt, cottonseed oil, rapeseed oil, whale oil, and other animal and vegetable mineral oils and fats.

This is a book that uses non-adhesive agents to lower the critical surface tension of the surface of the target object to prevent adhesive substances from adhering to the target object. This includes tenku agents and the like. Mold release agents are used to improve mold release by spraying or coating molds, wooden molds, etc. during the molding process of synthetic resins, etc., but generally they are used to improve internal release. It also includes resins called molds that are mixed with a mold release agent to improve mold release. Processing agents and back surface treatment agents for release paper include those that are coated on the back side of adhesive tape, etc. to prevent permanent adhesion and facilitate unwinding, as well as labels, patches, etc. This includes those used in the production of release paper used in the production of release paper, films, and release paper used in plywood molding processes. Furthermore, an anti-slip agent is used as a processing agent to prevent sheets, films, etc. from sagging when they 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 agent or a non-adhesive agent, K uses the compound of the present invention as a seventone, methyl ethyl ketone, ethyl acetate, dimethyl formamide, methyl chloroform, tric 00 ethylene, tric 00 trifluoro, etc. 0 etashi, tetrachrome 0! ; Prepared by dissolving the compound of the present invention in an organic solvent such as fluoroethane or a mixture of two or more, or diluting the compound of the present invention produced by reacting in the solvent with the above-mentioned solvent as necessary. do.

A near-aryl type product can also be prepared by adding a propellant such as 5000 difluoromethane, 7000 trifluoromethane, or dimethyl ether to such a solvent solution and filling it into a suitable container. First, 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.

Surfactants used for emulsification and dispersion include Kuma Ioshi type,
Both non-ionic type and cationic type can be used, and there are no particular limitations.

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.
Examples include porous articles such as wood, leather, fur, felt asbestos, and brick, and articles having smooth surfaces such as metal, tiles, plastics, and various painted surfaces. Fiber fabrics include natural fibers of animal and plant origin such as cotton, hemp, wool, and silk, various synthetic fibers such as boriatridine, polyester, polyvinyl acetal, polyacrylic nitrile, polyvinyl chloride, polypyrene, and rayon. , semi-synthetic fibers such as acetate, glass fibers, inorganic fibers such as asbestos fibers, or 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 the article can be applied to most of the articles that can be treated with the above-mentioned water and oil repellents.

The non-adhesive material of the present invention includes synthetic or natural resins such as polyurethane resin, Evo medium resin, phenol resin, vinyl chloride resin, acrylic resin, natural rubber, Ri00zurin 1M, and fluororubber. , synthetic or natural rubber, etc. Examples of industrial applications of non-adhesive agents include molds, wooden molds, plastic molds, paper molds, etc. used in the 5-stick and 1-m molding industries as so-called mold release agents, as well as paper, TOF, It can be applied to the back side treatment of adhesives such as cloth, plastic films, and metal foils, as well as to the production of labels, stickers, and release paper for wax products coated with adhesive in advance.

Regarding the concentration of the compound of the present invention in the water and oil repellent, the concentration of the compound of the present invention is usually about 0.01 to 30% by weight, and preferably about 0.1 to 2.0% by weight. . If the concentration of the solution is too low, it will be insufficient to impart water and oil repellency, 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 0.01 wt.
The amount below is sufficient, but if a particularly long service life is required with one application of the release agent, 0.05 to 30% by weight, preferably 0.1 to 10% by weight is appropriate. When used as a back surface treatment agent or an anti-oxidation 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 added at a concentration of 0.05 to
Appropriately, it is used by adding about 10% by weight and about 0.1 to 3% by weight to f\f.

The method of applying the water and oil repellent agent and the non-adhesive agent containing the compound of the present invention as an active ingredient varies depending on the type of object to be treated, the purpose of use, the preparation form of the water and oil repellent agent and the non-adhesive agent, etc. Just choose the appropriate one. In the case of an aqueous milk extract 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, coating, etc. and dried, and if necessary, cow-nearing may be performed. In addition, in the case of a near-reel type, all that is required is to spray the material onto the object to be treated and dry it.

Next, the present invention will be explained in more detail with reference to Examples. still,
In the examples, "part" and "%" are used unless otherwise specified.
"Parts by weight" and "% by weight" are shown.

In addition, water and oil repellency is indicated by the following scale. That is, water repellency is expressed as water repellency determined by the spray method of JIS L-1005, and oil repellency is expressed as determined by AATCC118-1972.
It was measured by the method of

Example 1 A 500 cr, four-hole flask equipped with a dropping tube with an isobaric tube, a thermometer, a nitrogen blowing tube and a vacuum stirring device is set on a silico oil bath.

2.4-) lylene diisocyanate 17.4 F (
0.1 mole) and 200 f of methyl ethyl ketone were introduced into the flask, and stirring was started while blowing nitrogen through the blow tube. After 15 minutes, the nitrogen blowing was stopped, the blowing tube was replaced with a cooling tube, and then the liquid temperature was brought to 75°C and the solution was dropped over 45 minutes. After dropping, stir for 30 minutes and add water to 0.9F (
0.05 tl) was added and stirring was continued for an additional 3 hours. The reaction solution was evaporated, the methyl ethyl ketone solvent was distilled off using a liter of water, and the residue was dried under vacuum to obtain 64f of a white solid with a melting point of 85°C. As a result of analysis by gas chromatography and infrared absorption spectroscopy, the selectivity for target product (1) was 98%.

The yield based on the raw material 2,4-tolylene diisocyanate was 9,591.

'pExample 2 4.4'-diphenylmetasidiisocyanate 2551
．． In the same manner as in Example 1 using 4f (0.1 tl), a white solid, a target product with a melting point of 90 to 91°C, and a yield a96' based on the raw material 4,4'-diphenylmetasidiisocyanate were obtained. It was n.

Example 3 Using 18.8F and '3H7 C3F0.502NCR2CM20H58.5f, the target product 69f as a pale yellow solid with a melting point of 91 to 93°C was obtained in ethylene glycol dimethyl ether in the same manner as in Example 1. Ta. (2) Selection Based on the head office's 95 ml, the yield was 93 ml based on the medium silylene diisocyanate used as the raw material.

Example 4 4.4'-Disilmethane diisocyanate 2
In the same manner as in Example 1 using 6.2f and C8F17CM2CM20H46,4F, a white solid, melting point I'l
The selectivity for l was 96 h, and the yield based on the raw material 4'-disylmethane diisocyanate was 94 h.

Example 5 1% by weight of the compound (1) synthesized in Example 1 was added to a mixed solvent of Tric00, Trif00, ethane and acetone in a volume ratio of I/1.
Make a dissolved solution and add cotton/polyester = 35 to this solution.
/65 blend fabric was dipped and the adhesion rate of the liquid was 100 by mandling.
% and dry at 100°C for 3 minutes. When the water repellency and oil repellency of this treated fabric was measured, the water repellency was 10.
The score was 0 points and the oil repellency score was 6 points.

Example 6 Compound (1) synthesized in Example 2 was mixed with KO008% by weight of a mixed solvent of Triku00Triff00etashi and acetone I/1 volume ratio.
350 parts of dissolved solution and 101991 parts of dichlorodiflu
Fill an air seal can with 00 parts to prepare an air seal for compound (1). This near reel is sprayed onto a raised polyester fabric used as a material for heating carpets to the extent that the entire surface is slightly moistened. After drying this cloth for 30 minutes at room temperature, it was washed with 30/70vo of isozylene alcohol/water.
A drop of the l ratio mixture was placed on a surface and held for more than 3 minutes. The oil repellency was 7 points.

Example 7 Example 1 part of the compound (1) synthesized just now is dissolved in a mixed solution of 90 parts of Trifluoro, 90 parts of Trifluoro, and 99 parts of acetate. This solution was applied to a copper mold for molding a disc having a concave portion of 40 cm in diameter and 2 cm 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 to the surface in the same manner.

100 parts of Epicoat #828 (manufactured by Shell Chemical Co., Ltd.) and 10 parts of triethylenetetramine as fJ type Eboshi resin.
Mix well and pour into each of the above-mentioned molds, and make a nozzle in the center to make it easier to take out the molded product after hardening. After leaving it at room temperature for 2 hours, heat it at 100℃ for 1 hour to harden it, then pull the caltrop to remove the molded product (disc) from the mold, and judge the mold release performance by the feeling in your hand according to the following criteria. do.

1 Mold Performance Criterion 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 by applying force.

l...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 compound ■ was 5, whereas the mold release performance of both A and B was 2. (above)

Claims (1)

[Claims] ('jj - General formula [wherein, Rf represents a perfluoro alkyl group having 4 to 20 carbon atoms, and X represents -CH2CH(A)-1-CmH2F
ll- or -502N(R1)CtH2t-. A
represents a methyl group or an ethyl group. The integers of m and zht~4 and R1 represent a hydrogen atom or a lower alkyl group. Mahy
indicates a divalent organic group. ] A fluorine-containing tantan compound represented by (2) General formula 0CNYNCOC In the formula, Y represents a divalent organic group. ] and a diisocyanate compound represented by the general formula RfXOHC, where Rf represents a perfluor'
-cmB2- or -502N CR')CtH2t-
shows. A is a methyl group or an ethyl group, 10,000 and t are 1 to 4
The integer R1 represents a hydrogen atom or a lower alkyl group. ]
Reaction of 1 with a fluorine-containing alcohol represented by the general formula Rf) cOCNHYNCO [wherein,
Rf. X and Y are the same as above. ] [wherein Rf%X and Y are the same as above. ] A method for producing a fluorine-containing urethane compound. ■ General formula - [In the formula, Rf represents a perfluoroalkyl group having 4 to 20 carbon atoms, and X is -CH2CHCA)-1-CmH2t
a- or -5o2N(R')C1H2 indicates -. -A
is a methyl group or an ethyl group, an integer from 1 to 40, R
1 represents a hydrogen atom or a lower alkyl group. Moreover, Y represents a divalent organic group. ] A water and oil repellent agent containing a fluorine-containing urethane compound represented by the following as an active ingredient. (41 general formula [wherein, Rf represents a bar 741074 and 714 having 4 to 20 carbon atoms, X ti -CI2CHCA)-1-C
□H2, l- or -5O2N(R1)CtH2t-. A is a methyl group or an ethyl group, m and t are integers of 1 to 4, and BL is a hydrogen atom or a lower alkyl group. Moreover, Y represents a divalent organic group. ] A non-adhesive agent containing a fluorine-containing urethane compound represented by the following as an active ingredient.