JPH107742A - Fluorosilicone functionalizing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a functionalizing agent by using, as the essential ingredient, a specific fluorosilicone oligomer to thereby utilize its characteristics that it has both a high oil repellency and a high hydrophilicity. SOLUTION: This agent contains a fluorosilicone oligomer represented by the formula [wherein RF is (CF2 )n F or CF(CF3 )O(CF2 CF(CF3 )O)m C3 F7 (wherein n is an integer of 1-15; and m is 0-6); R1 is a lower alkyl or lower alkoxy; R2 is a lower alkyl; and x and y are each natural numnber]. Pref. RF is C3 F7 , C6 F13 , C7 F15 , or CF(CF3 )O(CF2 CF(CF3 )O)m C3 F7 (wherein m is 0, 1, or 2). The agent is used for a fiber-treating agnet, a paper-treating agent, a glass surface modifier, a resin surface modifier, etc. The mol.wt. of the oligomer, through not specifically limited, is pref. 1,000-15,000 when the coupling effect is required.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a function-imparting agent containing a novel fluorosilicone oligomer.

[0002]

2. Description of the Related Art It is known that a compound having a fluoroalkyl group in an organic compound has water / oil repellency and various physiological activities. In particular, fluorosilicone oligomers having a fluoroalkyl group introduced into polysiloxanes have excellent water and oil repellency, antifouling properties, surface tension lowering properties, heat resistance, cold resistance, oil resistance, chemical resistance, electrical insulation properties, Since it has a wide range of properties such as mold release properties, various compounds have been proposed (for example, JP-A-2-219829 or JP-A-2-219830). It is very useful, for example, as a water / oil repellency / fouling resistance imparting agent, and an adhesion improving agent for a resist for a semiconductor device. Further, a silicone oligomer in which a fluoroalkyl group has been introduced into a methacrylic group-containing organosilicon compound has been proposed in JP-A-4-342704.

[0003] In addition, polymers and oligomers obtained by copolymerizing a compound such as vinylidene chloride or vinyl chloride which can be copolymerized with a polymerizable compound containing a fluoroalkyl group have been known. It is widely used in the form of emulsion preparations, for example, as a water / oil repellent agent for fibers, a water / oil repellent agent for paper, or a water / oil repellent surface treatment agent for glass. However, these fluoroalkyl group-containing copolymers tend to precipitate due to various factors when used as an emulsion preparation, and thus have drawbacks such as poor mechanical stability and long-term storage stability of the emulsion. In addition, these fluoroalkyl group-containing copolymers have poor compatibility with general organic solvents and resins used industrially, so that their use is restricted. In addition, glass surface treatment agents such as automotive window glass, glass plates, glass containers, glass utensils, eyeglass lenses, and other glass products cause airborne fine dust, oil particles, and any other dirt to adhere to their surfaces. In order to solve the problem that the glass surface is contaminated or water droplets such as raindrops are attached and the view of the window glass is hindered, and the transparency of the glass is impaired, various methods have conventionally been used. A method has been proposed. For example, a method of imparting water / oil repellency to a glass surface by using a mixture of a polyfluoroalkyl group-containing silane compound and an alkoxysilane compound or an organohalosilane compound as described in JP-A-58-122797, -3017
42. A method for obtaining a short-time water-repellent effect with a water-repellent containing an amino-modified silicone oil and a surfactant in water and / or a water-soluble organic solvent as described in JP-A-7-29
1667, a method has been proposed in which a glass surface is treated with a combination of an amino-modified polysiloxane, formic acid, and a lower alcohol to impart water repellency. In addition, there is also a method of forming a uniform water film by spraying a solution mainly composed of a surfactant onto a window glass surface of a car in a rainy weather and moving a car wiper to temporarily secure a view. .

[0004] In addition, regarding the surface modification of resins, it has been widely practiced to add a coloring agent, a tactile sensation improving agent, a matting agent, etc. to an elastomer dissolved in a solvent and apply it to the surface of a resin molded product. I have. For the purpose of imparting antifouling properties, water / oil repellency, high wettability and the like to the polyester resin surface, JP-A-59-1
Japanese Patent No. 40280 proposes a modification method using a fluoroalkyl group-containing silicone, but has a drawback that adhesion to a polyester surface is insufficient and water / oil repellency is reduced. To solve this problem, Japanese Patent Application Laid-Open No. 5-254
No. 57 proposes using a component selected from the group consisting of a fluorosilicone oligomer, a hydrolyzate thereof, a hydrolyzed condensate thereof and a mixture thereof as a modifier. As described above, various fluorine compounds have been proposed for various uses and purposes, but a fluorosilicone oligomer containing a morpholino group as shown in the present invention and its novel properties and usefulness Little is known about.

[0005]

All of the conventional fluorosilicone oligomers have a certain degree of water and oil repellency, but fluorosilicone oligomers which have high oil repellency and also exhibit hydrophilicity under hydrophilic conditions are known. It was industrially demanded. It has both oil repellency and hydrophilicity, and a fiber treatment agent that gives a soil release function that makes it easier to remove stains on textiles, a paper treatment agent that gives oil repellency to paper, and antifouling properties on the glass surface. It is an object of the present invention to provide an agent for modifying various materials, such as a glass surface modifier that imparts a function of preventing the formation of water droplets or water droplets, or a resin surface modifier, and the like. For this purpose, amphiphilic fluorosilicone oligomers having a fluoroalkyl group as a hydrophobic end and a polyoxyethylene unit as a hydrophilic part have been studied as silane coupling agents. High hydrophilicity has not been obtained (H. Sawada et al., J. Jpn. Oil Ch.
em. Soc., 43, P65 (1994)).

An object of the present invention is to provide a fluorosilicone oligomer having both high oil repellency and hydrophilic property, that is, a novel fluorosilicone oligomer having a fluoroalkyl group and a hydrophilic morpholino group introduced into vinyl siloxane. To provide a function-imparting agent.

[0007]

According to the present invention, as a means for solving the above-mentioned problems, there is provided a function-imparting agent characterized by containing a fluorosilicone oligomer represented by the following general formula (A). Is done.

Embedded image Wherein the _{R F - (CF 2) n} F (n = 1~15 integer) or _{-CF (CF 3) O (CF} 2 CF (CF 3) O) m C 3 F
₇ (m = 0 to 6), R ₁ represents a lower alkyl group or a lower alkoxy group, R ₂ represents a lower alkyl group, x,
y indicates a natural number.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The fluorosilicone oligomer according to the present invention is a fluorosilicone oligomer represented by the general formula (A), wherein R _F in the formula A is — (CF ₂ ) _n F (n = 1 to 1).
5 integer) or _{-CF (CF 3) O (CF} 2 CF (CF
₃ ) O) _m C ₃ F ₇ (m = 0 to 6), x, y
Indicates a natural number. R _F is - when (CF _{2) n} F, it is difficult to manufacture if the number of carbon atoms is 16 or more. In addition, R _F is −
CF where the _{(CF 3) O (CF 2} CF (CF 3) O) represented by _m C ₃ F _7, when specifically enumerated, formula (B), (
C), (D), (E), (F), (G), and (H). R _F is _{-CF (CF 3) O (CF} 2 CF (CF 3) O)
When represented by _m C ₃ F ₇ , if the number of m is 7 or more, the solubility in a solvent is reduced, so that production is difficult.

[0009]

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Embedded image R ₁ in the formula A is suitably a lower alkyl group having 1 to 5 carbon atoms or a lower alkoxy group having 1 to 5 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group, a methoxy group,
An ethoxy group and an n-propoxy group are preferred, and a methoxy group is particularly preferred. Similarly, R ₂ is suitably a lower alkyl group having 1 to 5 carbon atoms, preferably a methyl group, an ethyl group and an n-propyl group, particularly preferably a methyl group. The proportion of each segment represented by x and y in Formula A varies depending on the type and structure of each segment, but is generally arbitrary. A preferable ratio of each segment can be determined based on a ratio of oil repellency and hydrophilicity that the obtained oligomer shows as a result. Further, the number average molecular weight of the fluorosilicone oligomer in the present invention is not particularly limited,
When the coupling effect is required, it is preferably in the range of 1,000 to 15,000. Further, the fluorosilicone oligomer represented by the general formula A in the present invention may contain, in an arbitrary ratio, one having a fluoroalkyl group R _F introduced only at one terminal. The production of the fluorosilicone oligomer in the present invention is possible by reacting a specific fluoroalkanoyl peroxide with methoxyvinylsilanes and acroylmorpholine.

The fluoroalkanoyl peroxide used for producing the fluorosilicone oligomer in the present invention is
It is represented by the following general formula (I).

Embedded imageIn formula I, R_FIs-(CF_Two)_n F (n is an integer from 1 to 15)
Or -CF (CF_Three) O (CF_Two CF (CF_Three) O)_mC_Three 
F₇(m is an integer of 0 to 6). R in formula I_FBut-
(CF_Two)_n When F has 16 or more carbon atoms, the formula I
R in_FIs -CF (CF_Three) O (CF_Two CF (CF_Three) O)_m
C_Three F₇ The peroxide peroxide when m is 7 or more when represented by
Luoroalkanoyl is soluble in the reaction solvent
It is difficult to use because of poor properties. R in formula I_FIs-(C
F_Two)_n When F is a perfluoropropyl group,
Fluorohexyl and perfluoroheptyl are preferred.
Can be mentioned. In addition, R in the formula I_FIs -CF (
CF_Three) O (CF_Two CF (CF _Three) O)_mC_Three F₇ Represented by
Sometimes, fluoroalkanoyl peroxide is converted to
Fluoro-2-methyl-3-oxahexanoyl, peroxide
Diperfluoro-2,5-dimethyl-3,6-dioxa
Nonanoyl and diperfluoro-2,5,8-peroxide
Limethyl-3,6,9-trioxadodecinoyl is preferred.
It can be mentioned.

The alkoxyvinylsilanes used in the present invention are represented by CH ₂ ＣＨCH—Si R ₁ (OR ₂ ) ₂ . Here, R ₁ is a lower alkyl group having 1 to 5 carbon atoms or a lower alkoxy group having 1 to 5 carbon atoms, and methyl, ethyl, n-propyl, methoxy, ethoxy and n-
A propoxy group is preferred, and R ₂ is suitably a lower alkyl group having 1 to 5 carbon atoms, preferably a methyl group, an ethyl group and an n-propyl group. From the viewpoint of reactivity and availability, trimethoxyvinylsilane is particularly preferred as the alkoxyvinylsilane. In the present invention, when reacting fluoroalkanoyl peroxide with alkoxyvinylsilanes and acroylmorpholine, the molar ratio of each charge is preferably in the range of 1: 1: 1 to 1:10:10, and particularly preferably. 1: 1: 1-1 to 1: 5: 5. When the charged molar ratios of the alkoxyvinylsilanes and acroylmorpholine are less than 1 and more than 10, respectively, the yield of the desired fluorosilicone oligomer is undesirably reduced. The fluorosilicone oligomer for this purpose can be obtained by a one-step reaction in which fluoroalkanoyl peroxide, alkoxyvinylsilanes and acroylmorpholine are mixed and reacted. Further, the reaction can be carried out at normal pressure. The reaction temperature is preferably −20 to 150 ° C., but 0 to 100 ° C.
Is particularly preferable in consideration of economy and the like. -20 ° C
Below, a long reaction time is required, and at 150 ° C. or higher, the pressure during the reaction is undesirably high. The reaction time can be, for example, about 10 hours when the reaction temperature is 20 ° C., and about 5 hours when the reaction temperature is 50 ° C., and preferably 3 to 10 hours industrially. As the solvent for performing the reaction, a halogenated aliphatic solvent can be widely used, and AK-225 can be used.
(1,1-dichloro-2,2,3,3,3-pentafluoropropane: 1,3-dichloro-1,2,2,3,3
-Pentafluoropropane = 1: 1.35 manufactured by Asahi Glass Co., Ltd.), chloroform, methylene chloride, bis (trifluoromethyl) benzene, benzotrifluoride,
Hexafluorobenzene and the like can be used.
The concentration of the fluoroalkanoyl peroxide in the reaction solvent is desirably 0.5 to 30% by weight. The product obtained by the production method of the present invention can be purified by a known purification method such as a reprecipitation method, distillation, or gel permeation chromatography (GPC).

The fiber treating agent of the present invention can be used by dissolving the fluorosilicone oligomer according to the present invention in a solvent as it is, imparting high oil repellency to the fiber product and imparting a hydrophilic property to the fiber product surface under hydrophilic conditions. , A fiber treatment agent having a soil release function that makes it easier to remove stains on fiber products. When dissolved in a solvent, the solvent is preferably dissolved in water, methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, chloroform, ethyl acetate, dichloromethane, benzene, toluene, m-xylene, acetone or the like. Among these, it is more preferable to use the compound by dissolving it in tetrahydrofuran, dimethylsulfoxide, dimethylformamide or the like having higher solubility. When used directly after dissolving in a solvent, the fibers can be treated by a method such as padding or dipping. In this case, the amount of the fluorosilicone oligomer according to the present invention attached to the textile is 0.1 to 10%, more preferably 0.2 to 3%, based on the weight of the textile, in consideration of economy, effects, and the like. It is preferred that

The fiber treating agent of the present invention may be used in combination with an elastomer generally used for coating or laminating as shown below, in addition to using the fluorosilicone oligomer of the present invention alone. Thereby, durable water and oil repellency and antifouling property can be obtained. The organic resin component of the elastomer is not particularly limited, and known resin compositions conventionally used for fiber processing, for example, general-purpose resins such as urethane resins and acrylic resins, fluorine resins, polyester resins, vinyl chloride resins, and chlorinated resins A sulfonated polyethylene resin, a polymer substance containing silicone as a main component, and the like can be used, and two or more of these can be used in combination. Further, the organic resin composition may be dissolved or dispersed in an organic solvent. The mixing ratio of the fluorosilicone oligomer to the organic resin component according to the present invention cannot be specified unconditionally because the amount of the processing liquid that can be attached to the fiber varies greatly depending on the processing method. The amount is adjusted so as to be in the range of 0.01 to 15 parts by weight. More preferably 0.05 to 10
It is blended so as to be in the range of parts by weight. When the blending amount is 0.
When the amount is less than 01 parts by weight, the effects of water / oil repellency and stain resistance cannot be obtained. On the other hand, if the amount exceeds 15 parts by weight, no further increase in the contact angle of oil or water is recognized, and the performance of the base resin may be impaired. In the present invention, the above-mentioned polyurethane is used in a form dissolved in a solvent. When the polyurethane is formed into a film by wet coagulation, it is appropriate to dissolve it in water or a water-soluble water-miscible solvent that can be extracted with a water-miscible solvent. For example, N, N-dimethylformamide, dimethylsulfone Silicide, tetrahydrofuran, tetramethylurea, N, N-dimethylacetamide, dioxane, butylcarbinol and the like can be used alone or in combination. In this case, acetone or methyl ethyl ketone may be added to the extent that the polyurethane does not solidify. When polyurethane is used for dry coating such as heating and drying directly after coating, in addition to the above solvents, toluene, xylene, ethyl acetate,
Solvents such as butyl acetate and isopropyl alcohol can be added as long as the polyurethane does not solidify. In the present invention, the compounding of the fluorosilicone oligomer with the polyurethane can be mixed when the polyurethane elastomer is dissolved in the solvent.

When the organic resin used in the fiber treating agent of the present invention is an acrylic resin, any commonly used acrylic copolymer can be used, but a functional group having an active hydrogen such as a hydroxyl group can be used. A group-containing acrylic copolymer can be more preferably used. As the acrylic copolymer, for example, an ethylenically unsaturated monomer copolymer containing a hydroxyl group or a carboxyl group can be used. As an example, an ethylenically unsaturated monomer having no hydroxyl group and no carboxyl group represented by the following formula (J) can be used. And a combination of a monomer and an ethylenically unsaturated monomer having a hydroxyl group or a carboxyl group represented by the following formula (K).

Embedded image [In formula J, R ₃ is hydrogen or an alkyl group having 1 to 2 carbon atoms, R ₄ is an alkyl group, an allyl group, a halogen-substituted alkyl group, a halogen-substituted allyl group, a nitrile group, or an alkoxycarbonyl having 2 to 24 carbon atoms. Shows a group]

Embedded image [In the formula K, R ₅ represents a hydrogen, an alkyl group or a carboxyalkyl group, R ₆ represents a hydrogen or a carboxyl group, R ₇ represents a hydrogen or a hydroxyalkyl group, and n represents 0 or a natural number.] Examples of the ethylenically unsaturated monomer having no hydroxyl group and no carboxyl group include acrylonitrile, alkyl acrylates such as methyl acrylate and butyl acrylate, alkyl methacrylates such as ethyl methacrylate and butyl acrylate, and styrene. Examples of the ethylenically unsaturated monomer having a hydroxyl group or a carboxyl group represented by the above) include ethylenically unsaturated acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid, 2-hydroxyethyl acrylate and hydroxypropyl. Hydroxyl such as acrylate Hydroxy acrylate, hydroxyalkyl methacrylate such as 2-hydroxyethyl methacrylate and hydroxypropyl methacrylate, 3-chloro-2-hydroxyalkyl methacrylate, and the like can be used. Each of the monomers represented by the formula (J) or (K) can be used in combination of two or more. In the present invention, the blending of the fluorosilicone oligomer into the above-mentioned acrylic resin is performed by mixing an acrylic copolymer and a crosslinking agent with ketones such as methyl ethyl ketone, aromatic hydrocarbons such as xylene and toluene, and esters such as ethyl acetate and butyl acetate. Or a solution in an organic solvent such as a halogenated hydrocarbon such as trichloroethylene. Examples of the cross-linking agent include amino-resin-based cross-linking agents such as methylolated amino resins obtained by the reaction of an aldehyde with an amino component such as melamine, urea, benzoguanamine, acetoguanamine, steroganamin, spiroguanamine, dicyandiamide, and toluylene-2,4-. Aromatic, aliphatic, and cycloaliphatic isocyanates such as diisocyanate, toluylene-2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, xylene diisocyanate, 1,5-naphthylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Crosslinking agents can be used.

The organic resin component used in the fiber treating agent of the present invention may be a high molecular substance containing silicone as a main component.
A product obtained by a dehydrocondensation reaction, a dealcoholization condensation reaction or an addition reaction of a silicone prepolymer having a hydrogen, an alkyl group or a hydroxyl group at a terminal by the following reaction formula can be used. Dehydrocondensation reaction type

Embedded image Alcohol-free condensation reaction type

Embedded image Addition reaction type

Embedded image In the present invention, the mixing of the fluorosilicone oligomer with the polymer substance containing the silicone prepolymer as a main component is performed by using a catalyst containing the silicone prepolymer and a metal such as platinum, zinc, and tin as an aromatic compound such as benzene, toluene, and xylene. It is performed by mixing with a solution of a group hydrocarbon or a halogenated hydrocarbon such as trichloroethylene or tetrachloroethylene alone or in a mixed solvent. When the mixed solution is processed into a fiber product, a silica-based reinforcing filler, a flame retardant, a moisture permeability improving agent, a coloring agent, and the like can be added as necessary.

In addition, as the organic resin used in the fiber treating agent of the present invention, a polymer mainly composed of vinyl chloride, a simple substance or a copolymer of chlorsulfonated polyethylene, or a mixture thereof can be used. The addition of the fluorosilicone oligomer to these organic resin components is carried out by mixing these organic resin components with a solution obtained by dissolving the same in a solvent or by kneading these organic resin components with an inorganic filler, a colorant or a plasticizer. It is performed by such a method. In the fiber treating agent of the present invention, the method of blending the fluorosilicone oligomer into the organic resin component is not particularly limited, since it may be uniformly dissolved or dispersed in the organic resin component. In addition to the mixing using a stirring blade and a motor, the mixing can be performed by a mixing method that applies a shearing force, such as a high-speed stirring / dispersing device, a bead mill, or a ball mill.

In addition, when a commercially available coating treatment agent containing an organic resin for fiber processing which is dissolved or dispersed in a solvent is used, the fluorosilicone oligomer according to the present invention can be mixed and added. Further, the fiber treating agent of the present invention may contain a preservative, a stabilizer, a coloring agent,
An H adjuster may be added. The method of applying a fiber treating agent combined with this elastomer to a fiber base fabric is as follows.
It may be performed by a usual coating method such as a floating knife coater, knife over roll coater, reverse roll coater, gravure coater, rotary screen, kiss roll coater and the like. The method for wet coagulation film formation, the method for drying after coating, and the like may be conventionally performed in the same manner as in the case of processing using respective organic resin components. Also, it can be coated on release paper, transferred to a fiber base cloth, and laminated. In this method of use, the fluorosilicone oligomer according to the present invention is dispersed in the resin component until the resin component such as an elastomer is dried or cured, but when the resin component is dried or cured, the fluorosilicone oligomer according to the present invention is dispersed. The fluoroalkyl group of the silicone oligomer moves and orients to the surface of the resin component due to the affinity of fluorine. This imparts functions such as water repellency, oil repellency, and stain resistance to the fiber. The fiber base fabric for processing the fiber processing agent of the present invention covers a wide range of materials such as chemical fibers such as nylon and polyester, natural fibers such as cotton and wool, and blends thereof.

Next, by using the paper treating agent of the present invention, it is possible to impart oil repellency, stain resistance and the like to the surface of the paper. In this case, the paper can be processed by an arbitrary method according to the material of the paper and the dosage form of the preparation. That is, the fluorosilicone oligomer according to the present invention can be used by dissolving it in a solvent as it is, and high oil repellency and stain resistance can be imparted to paper products. As a solvent for dissolving the fluorosilicone oligomer, water, methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, chloroform, ethyl acetate, dichloromethane, benzene, toluene, m-xylene, acetone, etc. can be used. Among these, it is more preferable to use the compound by dissolving it in tetrahydrofuran, dimethylsulfoxide, dimethylformamide or the like having higher solubility. The paper treating agent of the present invention can be used in combination with other water repellents, oil repellents, anti-slip agents, surface strength improvers, sizing agents, flame retardants, and the like, if necessary. As other water repellents and oil repellents, paraffin wax and synthetic products generally used for water repellency of paper can be used, and by using together with the fluorosilicone oligomer related to the present invention, water repellency and oil repellency can be improved. It is possible to improve the water resistance of the fluorosilicone oligomer according to the present invention. Examples of the water repellent include water-soluble or emulsion-based polyethylene wax, paraffin wax or a metal salt thereof, silicone-based wax, fluorine-based resin emulsion, silicone-based resin emulsion, alkylethylene urea, N-methylol fatty acid amide, or the like alone or Can be mixed and used. Examples of anti-slip agents include styrene-acrylic and styrene-maleic acid-based emulsion preparations and colloidal silica. Examples of surface strength improvers include starch, oxidized starch and modified products thereof,
Examples include carboxymethylcellulose, polyvinyl alcohol, polyacrylamide, and derivatives and modified products thereof.

The processing agent for paper of the present invention is prepared by adjusting the processing liquid so that the concentration of the fluorosilicone oligomer according to the present invention is 0.5 to 2%, and immersing the base paper in a tab size or the like. After being applied to the surface of paper by an external addition method such as calendar coating, coating using an off-machine coater or on-machine coater, or spray coating, 90 to 150 ° C.
Can be processed by drying for 1 to 20 minutes. Further, an internal addition method in which paper is made by adding to and mixing with pulp is also possible. Paper products treated with the paper treating agent of the present invention are used for packaging paper such as paperboard, hamburger, fried chicken and the like used for containers such as butter and chocolate, as well as kraft paper, liners, and corrugated cardboard. Widely available. Next, the glass surface treating agent of the present invention has high oil repellency and antifouling properties, and prevents contamination of the glass surface due to adhesion of fine dust and oil particles in the atmosphere and other dirt, In a hydrophilic environment, the glass surface is made hydrophilic to inhibit the formation of water droplets, form a uniform water film, and secure the view of an automobile window glass or the like.

After treating the glass surface with the glass surface treating agent of the present invention, the fluorosilicone oligomer according to the present invention is characterized in that the —Si—O—R group (R is a lower alkyl group) in the molecule contains water. The glass surface is hydrolyzed to cause cross-linking and silanol groups (-Si-O
H) and strongly adheres to the glass surface. After adhering to the glass surface, the fluorinated fluoroalkyl group (-R
_{While F} ) is oriented on the surface to exhibit fluorine-derived functions such as oil repellency, antifouling property, and antifogging property, when the glass surface becomes a hydrophilic environment, the fluorosilicone oligomer molecule according to the present invention is used. The morpholino group inside is inverted by the flip-flop effect and is replaced with a fluoroalkyl group to orientate on the glass surface to exhibit hydrophilicity.

The glass surface treating agent of the present invention contains fluorosilicone oligomer at a concentration of 0.5 to 30% by weight, more preferably 1 to 15% by weight, in consideration of economy, workability and film thickness. Dilute to use. Solvents used for dilution are methanol, ethanol, tetrahydrofuran,
Dimethyl sulfoxide, dimethylformamide, chloroform, dichloromethane, dichloroethane, ethyl acetate, benzene, toluene, m-xylene, acetone and the like can be used, among which tetrahydrofuran, dimethyl sulfoxide, dimethyl, dimethyl, which have higher solubility. More preferably, it is dissolved in formamide or the like. Further, the glass surface treating agent of the present invention may be, if necessary, fine particles of various metal oxides such as silica, alumina, zirconium oxide and titanium dioxide, coloring agents such as dyes and pigments, and conductive materials such as tin oxide and zinc oxide. A property imparting agent or the like can be added. The glass surface treatment agent of the present invention can be any treatment method depending on the shape of the glass substrate to be treated, for example, dipping, spraying, brushing, roll coating, etc., and further printing such as flexographic printing and screen printing. You can also choose the method. After treatment on a glass substrate, 10% at 100% relative humidity
Performing a heat treatment for 20 minutes or more at a temperature of 0 ° C. or more
The glass surface treatment agent according to the present invention is preferable for firmly adhering to the glass surface. Further, by previously polishing and cleaning the surface of the glass substrate to be treated using an abrasive such as cerium oxide or alumina, the adhesiveness to the glass surface can be further improved. Examples of glass products to be treated with the glass surface treating agent of the present invention include windowpanes and mirrors for transport machines such as trains, buses, trucks, passenger cars, ships, and aircraft, windowpanes for buildings, glass sheets for roofs and glass sheets for partitions. , Other mirrors, glasses, glass containers, glassware, glass parts of furniture, glass fibers such as glass wool, and the like.

Next, the resin surface treating agent containing the fluorosilicone oligomer of the present invention is used for surface treatment of various resin products to impart antifouling property, water and oil repellency, heat resistance, chemical resistance and the like. be able to. The resin surface treatment agent of the present invention can be used by dissolving the fluorosilicone oligomer according to the present invention in water or a solvent, but can improve water resistance, solvent resistance, abrasion resistance, and adhesion. Therefore, it is preferable to use in combination with a synthetic resin component serving as a binder component. Conventionally used elastomers can be used as the organic resin composition for the binder. The organic resin component of the elastomer is not particularly limited, and a known resin composition generally used conventionally, for example, a general-purpose resin such as a urethane resin and an acrylic resin, an acrylic urethane resin, a silicone-modified urethane resin, and a chloride resin Synthetic resins such as vinyl resin, epoxy resin, polyolefin-based resin, fluororesin, and polyester resin can be used, and two or more of these can be used in combination. In addition, this organic resin composition has not only a role as a binder, but also a tactile sensation improving effect and gloss control,
It may be used for a function such as heat resistance or chemical resistance. The organic resin composition may be one dissolved or dispersed in an organic solvent, and the fluorosilicone oligomer of the present invention may be dissolved in a compatible organic solvent and mixed. The organic solvents used are methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, chloroform,
Ethyl acetate, dichloromethane, benzene, toluene, m
-Xylene, acetone and the like are preferable, and among these, tetrahydrofuran, dimethylsulfoxide, dimethylformamide and the like having higher solubility are more preferable.

The physical properties and the like of the organic resin component of the resin surface treating agent of the present invention are not particularly limited. However, when a resin product is treated with the resin surface treating agent of the present invention and then vacuum-formed,
100% modulus value of organic resin component is 80kgf / c
m ² or less is desirable. If the 100% modulus exceeds 80 kgf / cm ² , it is not preferable because the elongation following property of the skin coating layer decreases during molding such as vacuum molding. The resin surface treatment agent of the present invention adjusts the color tone, if necessary, of beads such as acrylic resin or urethane resin, natural powder such as collagen or cellulose, or urea formalin resin powder for imparting a suede feel or the like. And dyes, antioxidants such as alkylphenols, alkylenebisphenols or alkylphenol thioethers, and ultraviolet absorbers such as phenylsalicylate, 2-hydroxyphenylbenzotriazole, 2-hydroxybenzophenone or 2-hydroxy-4-methoxybenzophenone , Stabilizers, plasticizers and the like can be added in required amounts. When used in combination with an organic resin composition, the mixing ratio of the fluorosilicone oligomer according to the present invention with the organic resin composition is such that the amount of the processing liquid that can be adhered to the substrate by the method using a resin surface treatment agent is Although it cannot be specified unequivocally because it is greatly different, the fluorosilicone oligomer according to the present invention is preferably 0.01 to 15 parts by weight, more preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the solid content of the organic resin component.
Add parts by weight.

Also, a commercially available resin surface treating agent in which an organic resin component is dissolved or dispersed in a solvent, for example, used for surface treatment of PVC leather, PVC sheet, polyolefin resin sheet, PVC wallpaper, synthetic leather or artificial leather. It is also possible to add and mix the fluorosilicone oligomer according to the present invention when using the surface treatment agent to be used. The resin surface treating agent of the present invention can be surface-treated on a wide range of resin products by known coating methods such as brush coating, spray coating, roll coating, gravure coating, knife coating, and dip coating. If necessary, a primer such as chlorinated polypropylene can be used as a primer before applying the resin surface treating agent of the present invention. Examples of resin products treated with the resin surface treating agent of the present invention include olefin resins, ABS resins, and AS resins used for home appliances, vehicle interior parts, stationery, furniture, other household goods, and the like.
Resin, resin molded products molded with vinyl chloride resin or urethane resin, various films made of olefin resin, polyester resin, vinyl chloride resin or urethane resin, vehicle interior materials and furniture, shoes, bags, stationery, etc. And leather artificial leather and synthetic leather used for apparel, shoes, bags, vehicle interior materials, furniture, stationery, and the like.

[0025]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. (Synthesis example 1) 2.13 g of diperfluorobutyryl peroxide
(5 mmol) with AK-225 (1,1-dichloro-
2,2,3,3,3-pentafluoropropane: 1,3
-Dichloro-1,2,2,3,3-pentafluoropropane = 1: 1.35 (manufactured by Asahi Glass Co., Ltd.) and dissolved in 21 g of trimethoxyvinylsilane (2.22 g (15 mmo)).
l) and 2.12 g of acryloylmorpholine (15 mmol
l) was added to the mixture dissolved in AK-22562g, and the mixture was stirred at 45 ° C under a nitrogen stream for 3 hours. After the completion of the reaction, the concentrate from which the reaction solvent was removed was purified by a reprecipitation method using AK-225 and hexane, and then the solvent was removed, followed by vacuum drying to obtain 3.1 g of a purified product. This purified product is
When analyzed by R, ¹ H-NMR and ¹⁹ F-NMR, it was a fluorosilicone oligomer having a compound represented by the following structural formula (L) as a constitutional unit. Table 1 shows the analysis results. Table 2 shows the ratio between x and y in the formula K obtained from the ¹ H-NMR measurement results.

[0026]

Embedded image

[Table 1]

(Synthesis Example 2) Diperfluorobutyryl peroxide (5 mmol) was converted to diperfluoroheptyl peroxide (5 mmol).
The reaction was carried out in the same manner as in Synthesis Example 1 except that 1 (3.63 g) was used, to obtain 3.3 g of a fluorosilicone oligomer having a compound represented by the following structural formula (M) as a structural unit.

Embedded image

(Synthesis Example 3) 5 mmol of diperfluorobutyryl peroxide was added to 5 mmol of diperfluorooctyl peroxide.
1 (4.13 g), the reaction was carried out in the same manner as in Synthesis Example 1 except that the reaction solvent AK-225 was replaced with the same amount of benzotrifluoride, to give a compound represented by the following structural formula (N). 3.1 g of a fluorosilicone oligomer serving as a structural unit was obtained.

Embedded image

(Synthesis Example 4) 5 mmol of diperfluorobutyryl peroxide was added to diperfluoro-2-methyl-3 peroxide.
- oxa except that instead of hexanoyl 5 mmol (3.29 g), the reaction was carried out in the same manner as in Synthesis Example 1, compound R _F is represented by _{-CF (CF 3) OC 3 F} 7 in the general formula (A) 1. A fluorosilicone oligomer having a structural unit of
8 g were obtained. The number average molecular weight of this product is shown in Table 2. Table 2 shows the ratio between x and y in the formula K obtained from the ¹ H-NMR measurement results.

Synthesis Example 5 Diperfluoro-2-peroxide
The reaction was carried out in the same manner as in Synthesis Example 4 except that 5 mmol of methyl-3-oxahexanoyl was replaced with 5 mmol (4.95 g) of diperfluoro-2,5-dimethyl-3,6-dioxanonanolyl peroxide. 2.4 g of a fluorosilicone oligomer having a compound represented by the general formula (A) in which R _F was represented by —CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) C ₃ F ₇ was obtained. The number average molecular weight of this product is shown in Table 2. Table 2 shows the ratio between x and y in the formula K obtained from the ¹ H-NMR measurement results.

(Synthesis Example 6) Diperfluoro-2-peroxide
5 mmol of methyl-3-oxahexanoyl was converted to diperfluoro-2,5,8-trimethyl-3,6,9-peroxide.
To 6 mmol (7.93 g) of trioxadodecinoyl,
18 mmol of 15 mmol of trimethoxyvinylsilane
(2.67 g), acryloyl morpholine 15 mmo
The reaction was carried out in the same manner as in Synthesis Example 4 except that l was changed to 18 mmol (2.54 g), respectively, and
The R _F is _{-CF (CF 3) O (CF} 2 CF (CF 3) O) 2 C
₃ was obtained fluorosilicone oligomer 3.7g of a constitutional unit of a compound represented by F _7. The number average molecular weight of this product is shown in Table 2. Table 2 shows the ratio between x and y in the formula K obtained from the ¹ H-NMR measurement results.

[0032]

[Table 2]

Example 1 Fiber treatment agent Butyl acrylate, ethyl acrylate, acrylonitrile and 2-hydroxy methacrylate were copolymerized at a weight ratio of 60: 28: 10: 2, respectively, and dissolved in toluene. Solid content 22%, viscosity 40,00
A solution A of 0 cps was prepared. To 100 parts by weight of this solution A, 1 part by weight of the fluorosilicone oligomer of Synthesis Example 1 dissolved in 10 parts by weight of dimethylformamide was added and mixed to prepare a fiber treating agent solution B. Separately, n-
Butanol: xylene = 3: 2 (weight ratio) mixed solution of amino resin-based crosslinking agent 2,4,6-tri (N-methoxymethyl, N-methyl) amino-1,3,5-triazine
A 0% solution C and a 50% solution D of a cross-linking catalyst alkylbenzenesulfonic acid were prepared with isopropyl alcohol.
Solutions B, C, D and toluene were each added in a weight ratio of 10%.
Coating 1 by mixing at a ratio of 0: 1: 0.4: 15
The liquid was prepared and calendered (condition: 170 ° C., pressure: 30 kg / cm) in advance at a rate of 50 g / m ² in a nylon plain woven fabric (warp: 120 yarns of 70 denier yarn / inch,
Weft: 90 yarns / inch of 70 denier yarn) using a floating knife coater. After application, 110
C., dried at 160.degree. C. for 1 minute to obtain an acrylic resin-based processed cloth.

(Example 2) Fiber treatment agent An acrylic resin-based resin was prepared in the same manner as in Example 1 except that the fluorosilicone oligomer of Synthesis Example 1 in Example 1 was replaced with the fluorosilicone oligomer of Synthesis Example 4. A work cloth was obtained.

(Comparative Example 1) Fiber treatment agent A solution E was prepared by adding 10 parts by weight of toluene to 100 parts by weight of the solution A of Example 1. The solution B in the preparation of the coating solution 1 of Example 1 was replaced with the solution E instead of the solution E.
Was prepared in the same manner as in Example 1 except that was prepared.

(Effect Example 1) The water repellency and oil repellency of the processed cloth and the untreated calender-treated cloth obtained in Examples 1 and 2 and Comparative Example 1 were evaluated. The results are shown in Table 4. Each evaluation method is shown below. Water repellency: Performed based on JIS L-1092 (92) spray test method. The water repellency was represented by the following water repellency score of 50 to 100 points. 50 points: the whole surface was wet. 70 points: Half of the surface wet, usually small individual wets penetrating the cloth. 80 points: Small individual droplet-like wetness on the surface. 90 points: those that do not wet the surface but have small water droplets attached. 100 points: No wet or water droplets adhered to the surface. Oil repellency: A few drops of the test solution shown in Table 3 were placed at two places on the test-treated paper and discriminated by the permeation state after 30 seconds (AAT)
CC-TM118-1966).

[0037]

[Table 3]

[0038]

[Table 4]

Example 3 Fiber treatment agent A polybutylene obtained by polycondensation of 1,4-butanediol and adipic acid was placed in a 300 cc flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. 40.0 g of adipate, 9.0 g of diphenylmethane-4,4'-diisocyanate and the antioxidant Irganox 1
010 (manufactured by Ciba Geigy) and 20.0 g of dimethylformamide were charged, and the mixture was reacted for 1 hour while maintaining the solution temperature at 60 ° C. while stirring under a nitrogen stream.

After cooling to 40 ° C., ethylene glycol
A mixed solution of 0 g and 5.0 g of dimethylformamide was evenly dropped over about 1 hour. The reaction temperature was further raised to 80 ° C., and 25.0 g of toluene was added every time the solution viscosity increased.
Stirring was continued for 10 hours while adding in portions. n-
0.1 g of butanol is added to 20.0 g of dimethylformamide
And 2 g of the fluorosilicone oligomer of Synthesis Example 1 was diluted with 15.0 g of dimethylformamide and added, and the stirring was stopped to remove the fiber treating agent solution. F was obtained. In 100 parts by weight of solution F, isocyanate-based crosslinking agent Coronate L
3.5 parts by weight (manufactured by Nippon Polyurethane Industry Co., Ltd.) and 20 parts by weight of methyl ethyl ketone were added to prepare a coating liquid. This coating liquid was applied to a polyester plain woven cloth (290 deniers / 30 denier yarns for both warp and weft yarns) previously calendered (conditions: 170 ° C., pressure 30 kg / cm) using a floating knife coater. After application, dry at 120 ° C for 2 minutes,
Heating was performed at 0 ° C. for 1 minute to obtain a urethane resin-based processed cloth.

Example 4, Effect Example 2 Fiber treatment agent The fluorosilicone oligomer of Synthesis Example 1 was dissolved in tetrahydrofuran to prepare a 1% dilution. A cotton cloth after refining was immersed in this solution for 1 minute (drawing ratio: 80%), and then air-dried in a fume hood. Using a dropper, add 0.5% of salad oil to each of the processed cloth and the cotton cloth before processing.
Each cloth was allowed to stand for one week in a constant temperature and humidity room at 20 ° C. and a relative humidity of 65%, and then each cloth was JIS L-0217.
After washing according to (103 method), the degree of oil stain was compared. As a result, the cloth treated with the fluorosilicone oligomer of Synthesis Example 1 lost traces of salad oil without any trace, whereas the stain of salad oil of untreated cotton cloth remained clearly, and the fiber of the present invention The soil release function of the treatment agent was confirmed.

(Example 5, Effect Example 3) Glass surface treating agent The fluorosilicone oligomer prepared in Synthesis Examples 1 and 4 to 6 was used as a tetrahydrofuran solution, 1N acetic acid was added, and the solution was previously washed with a detergent and acetone. By immersing the slide glass, a coating film of the fluorosilicone oligomer of Examples 1 and 4 to 6 was formed on the glass surface. The contact angles of dodecane and water on the surface of the coating film of this glass were measured using a contact angle meter CA-DT · A manufactured by Kyowa Interface Science Co., Ltd. The results are shown in Table 5. The contact angle of water was measured over time after placing water on the coating film surface.

Further, the antifouling property of the glass surface was evaluated in terms of the fingerprint removing property by the following method. That is, fingerprints were attached to the surface of the treated glass, and wiping operation was performed 20 times with a dried cotton cloth. The evaluation was performed according to the following three criteria. A: Fingerprint stains and oil stains do not remain. B: Fingerprints disappear, but some oil stains remain. C: Fingerprint remains, and oil stains remain clearly. The glass treated with the glass surface treating agent of the present invention exhibited excellent oil repellency on the glass surface as is apparent from the contact angles of dodecane in Table 3. On the other hand, the contact angle of water decreased with the passage of time and became 0 after 30 minutes, and the initial high water repellency turned hydrophilic. Further, the glass treated with the glass surface treating agent of the present invention exhibited high antifouling properties.

[0044]

[Table 5]

(Example 6) Paper treating agent Each of the fluorosilicone oligomers of Synthesis Examples 1 and 4 to 6 was dissolved in tetrahydrofuran at 1% to prepare a paper treating agent. Then, this solution was impregnated into a non-size kraft paper (basis weight 70 g / m ² ) with a size press machine at an impregnation rate of 9%.
After impregnating with 0%, it was dried at 100 ° C. for 30 seconds.
After leaving the treated paper in a constant temperature and humidity room at 20 ° C. and a relative humidity of 65% overnight, the oil repellency was evaluated. Oil repellency evaluation,
The following method was used, and the results are shown in Table 6. Oil repellency evaluation method: A few drops of the test solution shown in Table 3 above were placed on two places on the test paper, and discrimination was made based on the permeation state after 30 seconds (AATCC-TM118-1966).

[0046]

[Table 6]

Example 7 Resin Surface Treatment Agent The fluorosilicone oligomers of Synthesis Examples 1 and 6 were each dissolved in tetrahydrofuran at a concentration of 1%. A polyethylene terephthalate film previously immersed in methanol for 2 hours and degreased in this solution
After immersion for 100 minutes, it was dried by heating at 100 ° C. for 10 minutes. The contact angles of the treated film with water and dodecane were measured and are summarized in Table 7. As a comparative control, the contact angles of water and dodecane of the polyethylene terephthalate film subjected to only the degreasing treatment were measured.

[0048]

[Table 7]

Example 8 Resin surface treating agent N, N-dimethylformamide / methyl ethyl ketone =
A polyether type polyurethane resin having a 100% modulus of 30 kgf / cm ² and an elongation of 800% was dissolved in a 30/70 (% by weight) mixed solvent at a concentration of 16.5% by weight. To 100 parts of this solution, 10 parts of a solution obtained by dissolving the fluorosilicone oligomer of Synthesis Example 2 in 3.3% by weight of N, N-dimethylformamide was added to prepare a resin surface treating agent. Using a gravure coater (120 mesh), the resin surface treatment agent was applied twice to a 0.5 mm thick vinyl chloride sheet kneaded and colored with a white pigment.
After drying at 80 ° C. for 30 seconds, a surface-treated vinyl chloride sheet was produced.

(Example 9) Resin surface treating agent The same operation as in Example 8 was performed, except that the fluorosilicone oligomer of Synthesis Example 2 in Example 8 was replaced with the fluorosilicone oligomer of Synthesis Example 5, to obtain a surface-treated vinyl chloride sheet. Was prepared.

Comparative Example 2 Resin Surface Treatment Agent The polyether type polyurethane resin used in Example 8 was mixed with N, N-dimethylformamide / methyl ethyl ketone = 30/70 (% by weight) in a mixed solvent at 15.0% by weight. At a concentration of. This is a gravure coater (1
20 mesh), and applied twice to a 0.5 mm thick vinyl chloride sheet kneaded and colored with white pigment.
It dried at 30 degreeC for 30 second, and produced the surface-treated vinyl chloride sheet.

(Effect Example 4) The antifouling properties of the surface-treated PVC sheets produced in Examples 8 and 9 and Comparative Example 2 were evaluated by the following method, and the results are summarized in Table 8. Antifouling evaluation: On a treated PVC sheet, black oil-based ink pen (manufactured by Magic Ink Co., Ltd., large type), black ballpoint pen (Zebra Co., No. 5000), red crayon (Sakura Crepas Co., Ltd.) 1c with black water-based felt-tip pen (P520, S520) and coffee liquid
An m-width line was drawn. After standing at room temperature for 24 hours, the black oil-based ink pen, black ball-point pen and red crayon were wiped with a cloth soaked with ethanol, and the black aqueous felt-tip pen and coffee liquid were wiped with a cloth soaked with a neutral detergent diluted with water. went. The degree of dirt after the wiping operation was evaluated on the following five levels. Stain resistance index 5: Stain can be completely removed. ４ 4: Slight traces of dirt remain. ３3: Dirt can be removed to some extent, but remains clearly. 〃2: Dirt can be slightly removed. １ ： 1: Dirt can hardly be removed.

[0053]

[Table 8]

[0054]

The fluorosilicone oligomer according to the present invention is a novel compound, which exhibits high oil repellency in a hydrophobic environment, but changes from water repellency to hydrophilic over a short time in a hydrophilic environment. Has features. In addition, it has hydrophilic properties in addition to a wide range of properties such as excellent oil repellency, surface tension lowering property, heat resistance, cold resistance, oil resistance, chemical resistance, and mold release properties similar to conventional fluorosilicone oligomers. ing. For this reason, the fiber treating agent of the present invention has a soil release function that makes it easy to remove stains on textiles, in addition to oil repellency and the like, and the paper treating agent of the present invention has high oil repellency, Glass surface treatment agent is oil repellent,
In addition to antifouling properties and antifogging properties, it shows hydrophilicity under hydrophilic conditions, and has an effect such as securing a view of an automobile window glass. Further, the resin surface modifier of the present invention imparts water / oil repellency and antifouling property to the resin surface.

Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C09D 143/04 PGL C09D 143/04 PGL C09K 3/00 112 C09K 3/00 112F 3/18 104 3/18 104 D06M 13/50 D06M 13/50 15/643 15/643 // C08J 5/08 C08J 5/08 7/04 7/04 S

Claims (5)

[Claims] 1. A function-imparting agent comprising a fluorosilicone oligomer represented by the following general formula (1). Embedded image Wherein the _{R F - (CF 2) n} F, or, -CF (CF
_{3) O (CF 2 CF (} CF 3) O) m C 3 F 7 ( wherein, n 1
An integer of 1 to 15, m represents 0 to 6, R ₁ represents a lower alkyl group or a lower alkoxy group, R ₂ represents a lower alkyl group, and x and y represent natural numbers.] 2. The functionalizing agent according to claim 1, which is a fiber treating agent or a paper treating agent. 3. The function-imparting agent according to claim 1, which is a glass surface modifier. 4. The functionalizing agent according to claim 1, which is a resin surface treating agent. 5. The method according to claim 1, wherein R _F is C ₃ F ₇ , C ₆ F ₁₃ , C ₇ F ₁₅
Or _{-CF (CF 3) O (CF} 2 CF (CF 3) O) m
The function-imparting agent according to claim 1, wherein C ₃ F ₇ (m = 0, 1, 2).