JP2000160132A - Stain prevention and super water repellent functional materials - Google Patents

Abstract

(57) [Summary] An object of the present invention is to provide a pollution-preventing and super-water-repellent functional material having water-repellent / oil-repellent, water-repellent and antifouling properties. Furthermore, by performing surface treatment, impregnation treatment, and internal treatment (blend) of a plastic film, a plastic molded product, glass, ceramic, metal, paper, fiber, and the like using the functional material of the present invention, excellent prevention is obtained. An object of the present invention is to provide a molding material having stain and water repellency. SOLUTION: This is an oligomer or a polymer compound having a structure comprising a vinyl ether and / or vinyl ester grafted with silicone represented by the following general formula 1 and tri- or tetrafluoroethylene, or a polymer compound. And a super-water-repellent functional material and the above-mentioned oligomer or polymer compound. [Formula 1]

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic solvent-soluble stainproof and water-repellent functional material. Further, the present invention is used for surface treatment of plastic film, plastic molded body, glass, ceramic, metal, paper, fiber and the like, and impregnation treatment of the functional material. The present invention relates to a molding material excellent in anti-staining property and water repellency which contains a functional material on the surface or inside of a molded article, a binder or the like.

[0002]

2. Description of the Related Art Conventionally, various studies have been made on functional improvement of water repellency, oil repellency, antifouling property, and the like on the surface of inorganic materials such as glass, ceramics, and metals using various surface treatment agents.
The method is to improve the water repellency of the surface of the base material, prevent dirt components from approaching the surface of the substrate, and paint on the substrate surface a substance having a low surface energy, such as a silicone resin, a polyester resin, a fluororesin, etc. To increase the contact angle of the substrate surface with water to make the surface water-repellent, making it difficult to adhere, and to provide antistatic properties in the substrate or on the substrate surface, reduce the surface potential, and reduce static electricity. There is a method to prevent contamination by water. In summary, it can be said that this is a method of preventing the adhesion of dirt on the surface of the base material or providing physical properties that facilitate the removal of the dirt attached.

[0003] The types of drug systems imparting physical properties as described above can be broadly classified into fluorine systems, silicone (polysiloxane) systems, composites thereof, and hybrid systems. Among them, the most common one is a composite or hybrid drug of fluorine and silicone (polysiloxane).

Specifically, examples of the fluorine-based agent include a water-repellent paint in which a fluoroalkyl group-containing radically polymerized monomer is dispersed in a thermosetting matrix resin disclosed in JP-A-7-102187. Issues such as low compatibility with the resin, low durability, and low antifouling properties are considered.

[0005] As a silicone-based agent, Japanese Patent Publication 4-10
No. 3668 has proposed a plastic product mixed with a silicone resin. However, the compatibility and the water repellency of the silicone resin with other resins are not sufficient either.
In No. 828, there is also a method of treating the surface with an organosiloxane solution in the presence of an inorganic acid or organic acid catalyst.However, the need for an acid catalyst and the problem of incomplete polysiloxane structure due to hydrolysis-condensation of alkoxysilyl groups are mentioned. Can be JP 7-
In No. 90185, there is a stain-resistant treatment agent in which a silicone resin, a general-purpose resin, and an antibacterial agent are blended. However, microorganisms such as bacteria and fungi have excellent water repellency or water drainage because water is an essential nutrient for their growth. There is no problem if.

As a drug system obtained by compounding / hybridizing a fluorine-based and silicone (polysiloxane) -based compound, a water-repellent, oil-repellent, and antifouling agent using a perfluorooxyalkylene group-containing silane compound disclosed in JP-A-7-53919 is disclosed. There is known a technique for obtaining a water-repellent surface by treating the surface of an inorganic substrate with a material or a silane coupling agent containing a perfluoro group described in JP-A-58-172245. However, an acid catalyst for hydrolyzing and condensing the silane coupling agent is required, and thus there is a disadvantage that crosslinking is not caused unless heating is sufficient, and the durability is low.

[0007] Silane compounds and siloxane compounds containing a fluorine-containing organic group such as a perfluoroalkyl group have been conventionally used for surface treatment agents such as metals, glasses and ceramics.
Widely studied and used as water and oil repellents. However, these compounds generally provide a cured film by a dehydration condensation reaction of only the silicon-bonded alkoxy group, and are inferior in curability and durability on the substrate surface such as abrasion resistance. There was a problem. In addition, many of the fluorine-containing compounds used as the reaction reagents have a problem that the production cost is high.

In addition to the water- and oil-repellent and antifouling agents based on the above-mentioned functional compounds, it can be said that a fluorine-containing resin-based agent is also attracting attention. Polytetrafluoroethylene (hereinafter, PT
Fluorine-based polymers such as FE) are variously used due to their excellent water repellency. However, PTFT is low in moldability and resin strength (too rigid), and has poor adhesion to substrates and low solvent solubility due to low surface energy, and compatibility with other resins. It was bad. In addition, there is a problem of expensive materials.

As an improvement thereof, Japanese Patent Application Laid-Open No.
In some cases, such as No. 25, a fluoroethylene monomer and a vinyl ester monomer are copolymerized to form a surface modifier and a water / oil repellent. This is a solvent-soluble fluoropolymer obtained by copolymerizing a fluoroolefin and a hydrocarbon monomer such as vinyl ether or vinyl ester.
However, it is an inexpensive one. However, since it is copolymerized with other general-purpose resin monomers, its water repellency and oil repellency are low, and its main application is a protective coating for architectural and civil engineering structures requiring weather resistance and durability.

[0010] Furthermore, it can be said that this is a functional material which has solved the problems of the water-sliding material studied at Yamagata University in recent years. Specifically, the water-sliding material developed and proposed at Yamagata University is a hydroxyl-containing fluorine-containing polymer (that is, it is composed of hydroxyl-containing vinyl ether or vinyl ester, or both, and monochlorotrifluoro. A functional material obtained by grafting by reacting various silicone compounds having a carboxyl group, a halogen group, a hydroxyl group, or an epoxy group at one end with a hydroxyl group of an ethylene copolymer) in the presence of various acid catalysts. Although it has been reported, contamination prevention, super water repellency and the like have not been sufficiently satisfactory for practical use.

[0011]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above problems, and has drawbacks of PTFE (polytetrafluoroethylene copolymer) resin, such as moldability,
With low-strength, low-fluorocarbon olefin, which is an inexpensive fluororesin with improved low adhesion, solvent solubility derived from low surface energy, and low compatibility with other resins. Fluoropolymers obtained by copolymerizing hydrocarbon monomers such as vinyl ethers and vinyl esters,
It is an object of the present invention to provide a pollution-preventing and super-water-repellent functional material having water-repellent / oil-repellent, water-repellent, and antifouling properties. Furthermore, by performing surface treatment, impregnation treatment, and internal treatment (blend) of a plastic film, a plastic molded product, glass, ceramic, metal, paper, fiber, and the like using the functional material of the present invention, excellent prevention is obtained. An object of the present invention is to provide a molding material having stain and water repellency.

[0012]

Means for Solving the Problems The inventors of the present invention have studied to solve the above-mentioned problems, and as a result, have found that base materials derived from low moldability, low strength, and low surface energy, which are disadvantages of fluorine-containing resins, can be said. Inexpensive fluorine-containing resin with improved low adhesion and solvent solubility, and low compatibility with other resins,
In other words, a fluoropolymer obtained by copolymerizing fluoroethylene and a hydrocarbon monomer such as vinyl ether or vinyl ester, has an epoxy group at one end with silicone having excellent water repellency, oil repellency, low abrasion, lubricity, and antistatic properties. The present invention has led to the invention of a functional polymer obtained by cross-linking the above-mentioned compounds with dicarboxylic anhydrides and grafting.

Further, the present invention is particularly directed to a silicone modified with an epoxy group at one end, and the present inventors' anti-fouling and super-water-repellent functional material is characterized in that the hydroxyl group of the above-mentioned fluorine-containing resin is substituted with an anhydrous dicarboxylic acid. It can be said that this is a functional material obtained by reacting an acid to convert a hydroxyl group into a carboxyl group, and performing a ring-opening addition reaction between the carboxyl group and an epoxy group of one-terminal epoxy-modified silicone, thereby grafting.

More specifically, the present inventors consider that low reactivity of both functional groups is a problem in an addition reaction between a hydroxyl group and an epoxy group, and that the reactivity with both functional groups is high. Measures were taken to add a divalent crosslinking agent. That is, an addition reaction of a hydroxyl group and a dicarboxylic anhydride having a very high reactivity is carried out to introduce a dicarboxylic acid monoester group, followed by a ring-opening addition reaction of an epoxy group also having a high reactivity with a carboxyl group to obtain a fluorine-containing compound. The resin was grafted with silicone. By this means, the rate of grafting of the silicone to the fluorine-containing resin was improved, and the problem of resin degradation due to the addition of a strong acid catalyst was solved. Also, by changing the type of dicarboxylic anhydrides used as the divalent crosslinking agent, it is possible to further improve the antifouling property, water repellency and oil repellency.

The above object is achieved by the present invention described below. That is, the invention of claim 1 is based on the following general formula 1,
An oligomer or a polymer compound having a structure composed of a vinyl ether or / and a vinyl ester grafted with silicone and tri- or tetrafluoroethylene as shown in 2 above, which is a pollution-preventing and super-water-repellent functional material. .

[0016]

[Formula 13](Where x, z, and n are integers of 1 or more, and y is 0 or more
X is a fluorine atom or a chlorine atom, and Z is a direct bond.
Or an alkyl chain having 1 or more carbon atoms, or an oxygen atom,
Or an alkyl chain containing one or more carbon atoms containing an oxygen atom.
Then R₁Is an alkyl chain having 1 or more carbon atoms, or a saturated carbon
A ring or an aromatic group such as a phenyl group, R₆Has 1 or more carbon atoms
Alkyl group, or saturated carbocycle, or phenyl group
Aromatic group, R _TwoIs an alkyl chain having 2 to 8 carbon atoms,
Saturated carbocycle such as xyl group or aromatic such as phenyl group
A group, m is an integer of 1 or more;_ThreeIs hydrogen or 1 or more carbon atoms
A saturated carbocyclic ring bonded to the carbon in Z
May be formed. R_FourIs an alkyl group having 1 or more carbon atoms,
R_FiveRepresents an alkyl chain having 1 or more carbon atoms. )

[0017]

[Formula 14] (Where x ′, z ′ and n ′ are integers of 1 or more, y ′
Is an integer of 0 or more; X is a fluorine atom or a chlorine atom;
Represents a direct bond, an alkyl chain having 1 or more carbon atoms, or an oxygen atom, or an alkyl chain having 1 or more carbon atoms containing an oxygen atom, and R ₁ ′ represents an alkyl chain having 1 or more carbon atoms, or a saturated carbocyclic ring, or An aromatic group such as a phenyl group, R ₆ ′ is an alkyl group having 1 or more carbon atoms, or a saturated carbocyclic ring or an aromatic group such as a phenyl group, and R ₂ is an alkyl group having 2 to 8 carbon atoms, a cyclohexyl group, etc. A saturated carbocyclic ring or an aromatic group such as a phenyl group; m is an integer of 1 or more; R ₃ is hydrogen or an alkyl group having 1 or more carbon atoms; May be. R ₄ represents an alkyl group having 1 or more carbon atoms, and R ₅ represents an alkyl chain having 1 or more carbon atoms. )

According to a second aspect of the present invention, there is provided the contamination-preventing and super-water-repellent functional material according to the first aspect, wherein the hydroxyl-containing vinyl ether represented by the following general formula 3 and an oligomer or polymer having a tri- or tetrafluoroethylene structure: Or, or a hydroxyl group-containing vinyl ether and vinyl ester represented by the following general formula 4, and an oligomer or polymer having a tri- or tetrafluoroethylene structure, and a dicarboxylic anhydride represented by the following general formula 5,
The addition reaction is carried out in the presence of a basic catalyst, and a hydroxyl group-containing vinyl ether represented by the following general formula 6 and an oligomer having a tri- or tetrafluoroethylene structure, or a dibasic acid monoester of a polymer, or a compound represented by the following general formula 7 Hydroxyl-containing vinyl ethers and vinyl esters, and oligomers having a tri- or tetrafluoroethylene structure, or dibasic monoesters of polymers, and the carboxyl groups thereof, and then one-terminal epoxy-modified silicone represented by the following general formula 8: Oligomers having a structure comprising a vinyl ether or / and a vinyl ester grafted with silicone represented by the following general formulas 9 and 10 obtained by a ring-opening addition reaction of an epoxy group and tri- or tetrafluoroethylene, or It is a polymer compound Is the.

[0019]

Embedded image General formula 3 (Where x, z, and n are integers of 1 or more, y is an integer of 0 or more, X is a hydrogen atom or a chlorine atom, R ₁ is an alkyl chain having 1 or more carbon atoms, or a saturated carbocycle, or an aromatic group such as a phenyl group, R ₆ represents hydrogen, or C 1 or more alkyl groups atoms or a saturated carbocycle or an aromatic group such as a phenyl group.)

[0020]

[Formula 16] (Where x ′, z ′ and n ′ are integers of 1 or more, y ′
Is an integer of 0 or more; X is a hydrogen atom or a chlorine atom;
₁ 'is an alkyl chain having 1 or more carbon atoms, or a saturated carbocyclic ring,
Or an aromatic group such as a phenyl group, and R ₆ ′ is an alkyl group having 1 or more carbon atoms, or a saturated carbocyclic ring, or an aromatic group such as a phenyl group.

[0021]

[Formula 17] (Wherein, R ₂ represents an alkyl chain having 2 to 8 carbon atoms, a saturated carbocyclic ring such as a cyclohexyl group, or an aromatic group such as a phenyl group)

[0022]

Embedded image General formula 6 (Where x, z, and n are integers of 1 or more, y is an integer of 0 or more, X is a fluorine atom or a chlorine atom, R ₁ is an alkyl chain having 1 or more carbon atoms, or a saturated carbocycle, or An aromatic group such as a phenyl group, R ₆ is an alkyl group having 1 or more carbon atoms,
Or saturated carbocyclic or aromatic group such as a phenyl group, R ₂
Represents an alkyl chain having 2 to 8 carbon atoms, a saturated carbon ring such as a cyclohexyl group, or an aromatic group such as a phenyl group.

[0023]

Embedded image General formula 7 (Where x ′, z ′, and n ′ are integers of 1 or more, and y ′ is
An integer greater than or equal to 0, X is a fluorine atom or a chlorine atom,
R ₁ 'is an alkyl group having a prime number of 1 or more, or a saturated carbocyclic ring,
Or an aromatic group such as a phenyl group, R ₆ ′ is an alkyl group having 1 or more carbon atoms, or a saturated carbocyclic ring or an aromatic group such as a phenyl group, and R ₂ is an alkyl chain having 2 to 8 carbon atoms, a cyclohexyl group. Represents a saturated carbocyclic ring such as phenyl or an aromatic group such as phenyl)

[0024]

Embedded image General formula 8 (Wherein, m is an integer of 1 or more, R ₃ is hydrogen, or represents a number 1 or more alkyl group having a carbon may .R ₄ also form a saturated carbon ring bound to the carbon in the Z is An alkyl group having 1 or more carbon atoms, R ₅ represents an alkyl chain having 1 or more carbon atoms,
Represents a direct bond, an alkyl chain having 1 or more carbon atoms, or an oxygen atom, or an alkyl chain having 1 or more carbon atoms containing an oxygen atom.)

[0025]

Embedded image General formula 9(Where x, z, and n are integers of 1 or more, and y is 0 or more
X is a fluorine atom or a chlorine atom, and Z is a direct bond.
Or an alkyl chain having 1 or more carbon atoms, or an oxygen atom,
Or an alkyl chain containing one or more carbon atoms containing an oxygen atom.
Then R₁Is an alkyl chain having 1 or more carbon atoms, or a saturated carbon
A ring or an aromatic group such as a phenyl group, R₆Has 1 or more carbon atoms
Alkyl group, or saturated carbocycle, or phenyl group
Aromatic group, R _TwoIs an alkyl chain having 2 to 8 carbon atoms,
Saturated carbocycle such as xyl group or aromatic such as phenyl group
A group, m is an integer of 1 or more;_ThreeIs hydrogen or 1 or more carbon atoms
A saturated carbocyclic ring bonded to the carbon in Z
May be formed. R_FourIs an alkyl group having 1 or more carbon atoms,
R_FiveRepresents an alkyl chain having 1 or more carbon atoms. )

[0026]

Embedded image General formula 10 (Where x ′, z ′ and n ′ are integers of 1 or more, y ′
Is an integer of 0 or more; X is a fluorine atom or a chlorine atom;
Represents a direct bond, an alkyl chain having 1 or more carbon atoms, or an oxygen atom, or an alkyl chain having 1 or more carbon atoms containing an oxygen atom, and R1 'represents an alkyl chain having 1 or more carbon atoms, a saturated carbocyclic ring, or phenyl. aromatic groups such as, R6 'is alkyl group having 1 or more carbon atoms, or a saturated carbon ring, or an aromatic group such as a phenyl group, R ₂ is an alkyl chain of 2 to 8 carbon atoms, saturated carbon atoms such as cyclohexyl group A ring or an aromatic group such as a phenyl group; m is an integer of 1 or more; R ₃ is hydrogen or an alkyl group having 1 or more carbon atoms; good. R ₄ represents an alkyl group having 1 or more carbon atoms, and R ₅ represents an alkyl chain having 1 or more carbon atoms. )

The invention according to claim 3 is characterized by the following general formulas 1 and 2
It is excellent in contamination prevention and super water repellency characterized by containing an oligomer or a polymer compound having a structure composed of a vinyl ether or / and a vinyl ester grafted with silicone and tri- or tetrafluoroethylene as shown in (1). It is a molding material.

[0028]

Embedded image General formula 1(Where x, z, and n are integers of 1 or more, and y is 0 or more
X is a fluorine atom or a chlorine atom, and Z is a direct bond.
Or an alkyl chain having 1 or more carbon atoms, or an oxygen atom,
Or an alkyl chain containing one or more carbon atoms containing an oxygen atom.
Then R₁Is an alkyl chain having 1 or more carbon atoms, or a saturated carbon
A ring or an aromatic group such as a phenyl group, R₆Has 1 or more carbon atoms
Alkyl group, or saturated carbocycle, or phenyl group
Aromatic group, R _TwoIs an alkyl chain having 2 to 8 carbon atoms,
Saturated carbocycle such as xyl group or aromatic such as phenyl group
A group, m is an integer of 1 or more;_ThreeIs hydrogen or 1 or more carbon atoms
A saturated carbocyclic ring bonded to the carbon in Z
May be formed. R_FourIs an alkyl group having 1 or more carbon atoms,
R_FiveRepresents an alkyl chain having 1 or more carbon atoms. )

[0029]

Formula 2 (Where x ′, z ′ and n ′ are integers of 1 or more, y ′
Is an integer of 0 or more; X is a fluorine atom or a chlorine atom;
Represents a direct bond, an alkyl chain having 1 or more carbon atoms, or an oxygen atom, or an alkyl chain having 1 or more carbon atoms containing an oxygen atom, and R ₁ ′ represents an alkyl chain having 1 or more carbon atoms, or a saturated carbocyclic ring, or An aromatic group such as a phenyl group, R ₆ ′ is an alkyl group having 1 or more carbon atoms, or a saturated carbocyclic ring or an aromatic group such as a phenyl group, and R ₂ is an alkyl group having 2 to 8 carbon atoms, a cyclohexyl group, etc. A saturated carbocyclic ring or an aromatic group such as a phenyl group; m is an integer of 1 or more; R ₃ is hydrogen or an alkyl group having 1 or more carbon atoms; May be. R ₄ represents an alkyl group having 1 or more carbon atoms, and R ₅ represents an alkyl chain having 1 or more carbon atoms. )

The invention according to claim 4 provides the molding material according to any one of claims 1 to 3, which is excellent in the prevention of contamination and water repellency.
The hydroxyl group present in the vinyl ether or / and vinyl ester grafted with silicone and tri- or tetrafluoroethylene shown in the above, or a hydroxyl group present in the polymer reacts with a crosslinking agent capable of reacting with the hydroxyl group. , The oligomer or the polymer is cured to form a three-dimensional crosslinked structure.

[0031]

Embodiments of the present invention will be described below in more detail. The antifouling, super-water-repellent functional material of the present invention has a surface energy as a method for preventing the adhesion of dirt on the substrate surface considered from the antifouling property or for imparting physical properties for easily removing the adhering dirt. The contact angle of water on the substrate surface is increased by hybridizing a fluorine-containing resin with a small water contact angle and a water-repellent, oil-repellent, and antistatic (static) anti-static silicone resin having both slipperiness and lubricity. In addition, there is an effect that the surface of the base material is made super-water repellent to make it stain-resistant by improving the water drop.

The antifouling and super-water-repellent functional material of the present invention has the drawbacks of conventional polytetrafluoroethylene copolymers in terms of moldability, low resin strength and low surface energy. Low cost of improved adhesion to base material and low solvent solubility, and low compatibility with other resins by copolymerizing vinyl ether or vinyl ester with hydroxyl group with fluoroethylene Since such a fluorine-containing resin is used as a trunk polymer, it is excellent in weather resistance, durability and solvent solubility, and can be blended with other resins.

The fluororesin having a low surface energy is as follows:
Although generally excellent in water-repellent effect, the interaction with water molecules is strong due to the strong polarization action of fluorine atoms, and it is inferior in dropping water drops, so when applied as an antifouling treatment agent for various window glasses, etc. Water droplets do not fall and remain in a polka dot shape on the glass surface, thereby causing dust and oil in the air to adhere and contaminate, and also lead to the propagation of microorganisms such as bacteria and fungi. Also, 0 ° C
Under the following environment, water droplets freeze and cause various problems such as poor view of various window glasses and icing on the roof of a house. On the other hand, a silicone polymer (polysiloxane) prevents static electricity and the like, prevents dust and dirt, and has water repellency and oil repellency excellent in slipperiness. Therefore, the functional material obtained by grafting the fluorine-containing resin and silicone of the present invention by a chemical reaction with a divalent crosslinking agent has a high water repellency-imparting effect and an effect of improving the dropping property of water droplets or oil droplets. Excellent water repellency, oil repellency and antifouling properties can be imparted to the surface.

Accordingly, the functional material of the present invention can be used for a variety of conventional resin molded products in order to impart lubricity, water repellency and oil repellency to silicone resin as a lubricant. There is no problem such as bleed-out to a typical surface, and there is no addition of an acid catalyst and a curing step required for a silane compound having a hydrolyzable group, so that the operation can be said to be simple.

Further, the functional material of the present invention is a fluorinated polymer having a hydroxyl group (that is, it is a copolymer of a vinyl ether or a vinyl ester having a hydroxyl group, or a combination thereof with tri- or tetrafluoroethylene. The hydroxyl group of the polymer is reacted with a dicarboxylic anhydride in the presence of a base catalyst to convert the hydroxyl group into a carboxyl group, and the carboxyl group is subjected to a ring-opening addition reaction with the epoxy group of the one-terminal epoxy-modified silicone to carry out grafting. Thereby, the grafting ratio of silicone can be increased without using a strong acid catalyst.

The present inventors consider that low reactivity of both functional groups is a problem in the addition reaction between a hydroxyl group and an epoxy group, and add a divalent crosslinking agent having high reactivity with both functional groups. Take steps. That is, an addition reaction of a hydroxyl group and a dicarboxylic anhydride having a very high reactivity is carried out to introduce a dicarboxylic acid monoester group, followed by a ring-opening addition reaction of an epoxy group also having a high reactivity with a carboxyl group to obtain a fluorine-containing compound. The resin was grafted with silicone. By this means, the rate of grafting of the silicone to the fluorine-containing resin was improved, and the problem of resin degradation due to the addition of a strong acid catalyst was solved. Also, by changing the type of dicarboxylic anhydrides used as the divalent crosslinking agent, it is possible to further improve the antifouling property, water repellency and oil repellency.

The dicarboxylic anhydrides used as the divalent crosslinking agent include saturated aliphatic dicarboxylic anhydrides such as succinic anhydride, phthalic anhydride, 1,8-naphthalenedicarboxylic anhydride, and 2,3-naphthalenedicarboxylic anhydride. Examples thereof include aromatic dicarboxylic anhydrides such as acid anhydrides and saturated aliphatic ring dicarboxylic anhydrides such as 1,2-cyclohexanedicarboxylic anhydride, each of which has water repellency and a reaction solvent depending on the structure of its main chain. Since they have different solubilities, they should be used in consideration of them.

Tertiary amines are preferred as the base catalyst added in the addition reaction between the hydroxyl group of the hydroxyl group-containing fluororesin and the dicarboxylic anhydride. Specific examples include N, N-dimethylbenzylamine, pyridine, pyrazine, triethylamine, trimethylamine and the like. These base catalysts are desirably used in consideration of the physical properties such as the base dissociation constant (Kb) and the boiling point.

The antifouling and super-water-repellent functional material of the present invention can be diluted with various solvents to adjust the concentration, and can be coated and impregnated by an appropriate method to form a film. Further, the trunk polymer of the functional material of the present invention has a polyvinyl ether or polyvinyl ester unit, is excellent in compatibility with other resins, and the functional material of the present invention is transparent, so that the functional polymer of the other resin Various molding methods by blending with
For example, extrusion molding, injection molding, injection molding, blow molding, sheet molding, etc. are possible, and the film or molded product has excellent antifouling properties, water repellency, oil repellency, water drop, oil drop, weather resistance, durability Properties, abrasion resistance, and the like.

The solvent for the functional material of the present invention is not particularly limited as long as it dissolves the functional material of the present invention. Ketones such as acetone and methyl ethyl ketone, alcohols such as t-butyl alcohol, Examples thereof include esters such as ethyl acetate and butyl acetate, and aromatic hydrocarbons such as toluene and xylene.

The functional material of the present invention does not require a curing operation as in the case of a silane compound having a hydrolyzable group, and has water repellency, oil repellency, solvent resistance, chemical resistance, stain resistance,
It is possible to impart a characteristic property to a fluorine-containing coating such as weather resistance and to form a coating excellent in properties such as adhesion to various substrates and strength. However, in order to improve the adhesion to the substrate, a curing agent may be added. As the curing agent, polyisocyanates or oximes, lactams,
Examples thereof include those blocked with alcohols and the like, polyfunctional epoxides, amino resins such as melanin, benzoguanamine and urea. In addition, the functional material of the present invention may contain additives such as an agent for preventing deterioration and discoloration due to ultraviolet rays and a light stabilizer in addition to the curing agent.

Examples of the surface coating method of the functional material of the present invention include ordinary roll coating, doctor blade coating, knife edge coating, curtain coating, gravure coating, reverse coating, kiss coating, and bar coating. Known means and methods such as a coating method, spray coating, and brush coating are used. After coating, it is also possible to subsequently bake the coating film under predetermined conditions in consideration of the heat resistance of the base material. After forming the coating film, the surface may be polished. As the impregnation method, impregnation may be performed by a wet web method or a dry web method, and the amount of adhesion may be controlled by a squeezing roll.
In this case, the substrate is made of paper or fiber that is a porous body that can be impregnated.

The substrate to which the functional material of the present invention can be applied is not particularly limited, and the shape of the substrate is not limited to a flat surface, and may have a curved surface over the entire surface or partially.
For example, glass plates such as automotive glass, marine glass, aircraft glass, glass for various devices, ceramics such as concrete, metal plates such as copper, iron, stainless steel, aluminum, etc., Japanese paper, fine paper, and art Paper, coated paper, pure white roll paper, birchment paper, kraft paper,
Further, papers for cardboard use, synthetic resin films such as polyester resin, polycarbonate resin, polystyrene resin, and acrylic resin, and fibers such as cloth, natural fiber, and synthetic fiber can be used.

The functional material of the present invention has excellent adhesion to various metals, glass, resin, paper, concrete, etc. and has good weather resistance and durability. Since the aesthetic appearance can be maintained for a long period of time and the transparency is high, it is possible to prevent the weather resistance deterioration of the material without changing the appearance of the base material.

Next, the present invention will be described more specifically based on examples of the present invention, but the present invention is not limited to the materials described in the examples. As a commercial product, Lumiflon manufactured by Asahi Glass Co., Ltd. was used as a copolymer of hydroxyl group-containing vinyl ether, vinyl ester, or both, and fluoroethylene, which is the trunk polymer of the functional material of the present invention.

[0046]

<Example 1> Lumiflon LF600 (manufactured by Asahi Glass Co., Ltd., hydroxyl value of solid content 5) was placed in a 300 ml three-necked flask.
6, NV = 50 wt% toluene / xylene = 1/1 solution), 20 g corresponding to a solid content of about 10 mmol in hydroxyl value, 1.48 g (about 10 mmol) of equimolar phthalic anhydride, and 20 g of toluene as a diluting solvent N 2 as a base catalyst in the mixed solution of
0.5 g of N-dimethylbenzylamine (about 3 mmo)
l) The mixture was added and reacted in an oil bath at about 100 ° C. for about 30 minutes while stirring with a stirrer. One end-terminal epoxy-modified silicone having an equimolar concentration to Lumiflon LF600 (Chisso Corporation, trade name: FM-0511, molecular weight = about 10) was added to the reaction solution.
10) (about 10 mmol), and add about 100
The reaction was carried out at a temperature of about 2 hours with stirring with a stirrer.

Comparative Example 1 As Comparative Example 1, Lumiflon LF600, which is a raw material of the functional material of the present invention, was used as it was. The solid concentration was unified as it was in Example 1 and Comparative Examples 2 to 4 as it was.

Comparative Example 2 A 300 ml three-necked flask was charged with Lumiflon LF600 (manufactured by Asahi Glass Co., Ltd., solid content hydroxyl value: 5).
6, NV = 50 wt% toluene / xylene = 1/1 solution) and 20 g corresponding to a solid content of about 10 mmol in a hydroxyl value, and an equimolar concentration of one-terminal epoxy-modified silicone (manufactured by Chisso Corporation)
Product name: FM-0511, molecular weight = about 1000) 10g (about 10mm
ol) and 20 g of a diluting solvent toluene, and a catalytic amount of methanesulfonic acid of 0.5 g (about 5 mmol) was added as an acid catalyst, and the mixture was reacted in an oil bath at about 100 ° C. for about 2 hours while stirring with a stirrer. Was.

Comparative Example 3 The same operation as in Example 1 was performed, except that no catalyst was added.

Comparative Example 4 In Comparative Example 2, a catalyst amount of antimony trichloride, a Lewis acid, was 0.5 g (about 2 m) as an acid catalyst.
mol)), the same procedure as in Comparative Example 2 was performed.

<Test Example 1> [Observation Results of Graft Polymerization Reaction Solution State]
The results of observing the states of the graft polymerization reaction solutions of Example 1 and Comparative Examples 2 to 4 are shown in Table 1 below.

[0052]

[Table 1]

From the above results, the contamination-preventing and super-water-repellent functional material of the present invention can be obtained by observing the state of the synthesized product.
No gel was generated, and the reaction solution was transparent, indicating that the reaction was very mild.

<Test Example 2> [Evaluation of water drop and oil drop property of graft polymerization product] (Method of preparing sample for evaluating water drop and oil drop angle)
Among the Comparative Examples 1 to 4, the reaction solution or the reagent of Example 1, Comparative Example 1, and Comparative Example 2 having no gelled substance was used as the reaction solution, or the reagent was a polyisocyanate (Nippon Polyurethane Co., Ltd.).
Was added to the glass plate by a dipping method, dried at room temperature, and the solvent was removed. (Evaluation Method of Water Drop and Oil Drop Angle) As described above, three pieces of water (distilled water) were placed at predetermined positions on the coating formed on the glass plate.
0 mg and 25 mg of oil (Nissin Oil Co., Ltd., corn oil) were dropped, and the water or oil droplets were allowed to stand once, and then the other end was kept in contact with one end of the glass plate on the table. Lift up at speed. The angle at which the water droplet or oil droplet started to move from the position at the time of dropping was read as the water drop or oil drop angle. Further, in order to examine the durability and chemical resistance of the formed film, a film which was washed with a predetermined amount of acetone and then dried at room temperature was also evaluated. Table 2 shows the evaluation results.

[0055]

[Table 2]

From the results in Table 2, it can be seen from the results of the water-drop angle and oil-drop angle before washing with acetone that the fluorine-containing resin of Comparative Example 1 was not grafted with the silicone according to the present invention. It was found that there was a very high water- and oil-dropping property as compared with Also, from the result after acetone washing,
In the case of Comparative Example 2 in which the silicone was not grafted by crosslinking with dicarboxylic anhydride as in the present invention, both the water drop angle and the oil drop angle were reduced, and the silicone that did not undergo the grafting reaction was washed away with acetone. it is conceivable that. On the other hand, in Example 1 in which the hydroxyl group-containing fluororesin and the one-terminal epoxy-modified silicone were grafted with the dicarboxylic anhydride of the present invention, the water drop angle and oil drop angle were not reduced by acetone washing, and the durability was extremely high. It was found to have chemical resistance.

[0057]

The contamination-preventing and super-water-repellent functional material of the present invention comprises a copolymer of a vinyl ether or / and a vinyl ester having a hydroxyl group and tri- or tetrafluoroethylene as a trunk polymer, and a one-terminal epoxy-modified silicone. Is a functional material grafted with dicarboxylic anhydride as a divalent cross-linking agent. Solvent solubility, moldability, and resin strength, which were issues of conventional polytetrafluoroethylene (abbreviated as PTFE) Too rigid) and improved compatibility with other resins.

Further, according to the present invention, while maintaining the above-mentioned characteristics of the trunk polymer and the water repellency, durability and weather resistance peculiar to the fluorine-containing resin, the water repellency, oil repellency, water repellency, oil repellency, slip property peculiar to silicone are maintained. A functional material having properties such as antistatic properties and antistatic (static) antistatic properties was obtained.

As a measure for improving the low addition reactivity between the hydroxyl group of the hydroxyl group-containing fluororesin and the epoxy group of the one-terminal epoxy-modified silicone, dicarboxylic anhydrides which are liable to react with the hydroxyl group are added and reacted. By performing ring-opening addition of an epoxy group which easily reacts with a carboxyl group of the acid monoester, a pollution-preventing and super-water-repellent functional material having an improved silicone grafting rate under mild conditions was obtained.

Therefore, the contamination-preventing and super-water-repellent functional material of the present invention has excellent adhesion to the substrate surface and high transparency, durability and weather resistance, as well as water repellency, oil repellency, water repellency,
A film with excellent surface properties such as oil-removing property and stain resistance can be formed.Prevention of the contamination of the present invention on the surface and inside of buildings, various window glasses, home appliances, kitchen appliances, in-bath appliances, paper and textiles, etc. A molding material containing a super-water-repellent functional material can be provided. As a result, it is possible to prevent contamination of a product to which dirt is likely to adhere due to various causes, and to maintain a maintenance-free and clean state for a long time.

Also, since it has good compatibility with other resins, it can be blended with various resins, and can be molded by various molding methods or as a binder resin.
It is possible to provide a molding material containing the contamination-preventing and super-water-repellent functional material of the present invention on the surface or inside. As a result, it has become possible to develop a variety of applications having a variety of pollution prevention and super water repellency functions.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C09K 3/18 104 C09K 3/18 104 F term (reference) 4H020 BA36 4J031 AA14 AA16 AA17 AA59 AB01 AC03 AD01 AF10 AF12 AF30 CA06 CD09 CD26 4J100 AC22P AC26P AC30P AE09Q AE09R AE10Q AG08R BA03Q BA16H BC43Q BC43R CA05 CA31 FA03 HA61 HC28

Claims (4)

[Claims] 1. A silicone represented by the following general formulas 1 and 2
Grafted vinyl ether and / or vinyl ester
Structure consisting of toluene and tri- or tetrafluoroethylene
Oligomer or polymer compound having
A material for preventing pollution and super-water-repellent, characterized by: [Formula 1](Where x, z, and n are integers of 1 or more, and y is 0 or more
X is a fluorine atom or a chlorine atom, and Z is a direct bond.
Or an alkyl chain having 1 or more carbon atoms, or an oxygen atom,
Or an alkyl chain containing one or more carbon atoms containing an oxygen atom.
Then R₁Is an alkyl chain having 1 or more carbon atoms, or a saturated carbon
A ring or an aromatic group such as a phenyl group, R₆Has 1 or more carbon atoms
Alkyl group, or saturated carbocycle, or phenyl group
Aromatic group, R _TwoIs an alkyl chain having 2 to 8 carbon atoms,
Saturated carbocycle such as xyl group or aromatic such as phenyl group
A group, m is an integer of 1 or more;_ThreeIs hydrogen or 1 or more carbon atoms
A saturated carbocyclic ring bonded to the carbon in Z
May be formed. R_FourIs an alkyl group having 1 or more carbon atoms,
R_FiveRepresents an alkyl chain having 1 or more carbon atoms. ## STR2 ## Formula 2(Where x ', z' and n 'are integers of 1 or more, y'
Is an integer of 0 or more; X is a fluorine atom or a chlorine atom;
Is a direct bond, an alkyl chain having 1 or more carbon atoms, or an acid
C1 or more alkyl containing an atom or oxygen
Denotes a chain and R₁'Is an alkyl chain having 1 or more carbon atoms, or
A saturated carbocycle or an aromatic group such as a phenyl group, R₆′ Is charcoal
An alkyl group with a prime number of 1 or more, or a saturated carbocyclic or
An aromatic group such as a nyl group, R_TwoIs alkyl having 2 to 8 carbon atoms
Chain, saturated carbocycle such as cyclohexyl group, or phenyl group
An aromatic group such as m, m is an integer of 1 or more;_ThreeIs hydrogen or charcoal
Represents an alkyl group having a prime number of 1 or more, and is bonded to a carbon in Z
A saturated carbocycle may be formed. R_FourIs an atom having 1 or more carbon atoms.
Alkyl group, R_FiveRepresents an alkyl chain having 1 or more carbon atoms. ) 2. A hydroxyl group-containing vinyl ether represented by the following general formula 3 and tri, or an oligomer or a polymer having a tetrafluoroethylene structure, or a hydroxyl group-containing vinyl ether and a vinyl ester represented by the following general formula 4, and tri, or An oligomer or polymer having a tetrafluoroethylene structure is subjected to an addition reaction with a dicarboxylic anhydride represented by the following general formula 5 in the presence of a basic catalyst, and a hydroxyl group-containing vinyl ether represented by the following general formula 6 and tri, or Oligomers having a tetrafluoroethylene structure, or dibasic acid monoesters of polymers, or hydroxyl-containing vinyl ethers and vinyl esters represented by general formula 7, and tri- or oligomers having a tetrafluoroethylene structure, or dibasic polymers Acid monoe And a carboxyl group is grafted with the silicone represented by the following general formulas 9 and 10 obtained by ring-opening addition reaction of the carboxyl group and the epoxy group of the one-terminal epoxy-modified silicone represented by the following general formula 8 2. The pollution control and super water repellent material according to claim 1, wherein the material is an oligomer or a polymer compound having a structure composed of a modified vinyl ether and / or vinyl ester and tri- or tetrafluoroethylene. [Formula 3] (Where x, z, and n are integers of 1 or more, y is an integer of 0 or more, X is a hydrogen atom or a chlorine atom, R ₁ is an alkyl chain having 1 or more carbon atoms, or a saturated carbocycle, Or R ₆ represents hydrogen, an alkyl group having 1 or more carbon atoms, a saturated carbocyclic ring, or an aromatic group such as a phenyl group. (Where x ′, z ′ and n ′ are integers of 1 or more, y ′
Is an integer of 0 or more; X is a hydrogen atom or a chlorine atom;
₁ 'is an alkyl chain having 1 or more carbon atoms, or a saturated carbocyclic ring,
Or an aromatic group such as a phenyl group, and R ₆ ′ is an alkyl group having 1 or more carbon atoms, or a saturated carbocyclic ring, or an aromatic group such as a phenyl group. (Wherein, R ₂ represents an alkyl chain having 2 to 8 carbon atoms, a saturated carbocycle such as a cyclohexyl group, or an aromatic group such as a phenyl group). (Where x, z, and n are integers of 1 or more, y is an integer of 0 or more, X is a fluorine atom or a chlorine atom, R ₁ is an alkyl chain having 1 or more carbon atoms, or a saturated carbocycle, or An aromatic group such as a phenyl group, R ₆ is an alkyl group having 1 or more carbon atoms,
Or saturated carbocyclic or aromatic group such as a phenyl group, R ₂
Represents an alkyl chain having 2 to 8 carbon atoms, a saturated carbocyclic ring such as a cyclohexyl group, or an aromatic group such as a phenyl group. (Where x ′, z ′, and n ′ are integers of 1 or more, and y ′ is
An integer greater than or equal to 0, X is a fluorine atom or a chlorine atom,
R ₁ 'is an alkyl group having a prime number of 1 or more, or a saturated carbocyclic ring,
Or an aromatic group such as a phenyl group, R ₆ ′ is an alkyl group having 1 or more carbon atoms, or a saturated carbocyclic ring or an aromatic group such as a phenyl group, and R ₂ is an alkyl chain having 2 to 8 carbon atoms, a cyclohexyl group. Represents a saturated carbocyclic ring such as phenyl group or an aromatic group such as phenyl group. (Wherein, m is an integer of 1 or more, R ₃ is hydrogen, or represents a number 1 or more alkyl group having a carbon may .R ₄ also form a saturated carbon ring bound to the carbon in the Z is An alkyl group having 1 or more carbon atoms, R ₅ represents an alkyl chain having 1 or more carbon atoms,
Represents a direct bond, an alkyl chain having 1 or more carbon atoms, an oxygen atom, or an alkyl chain having 1 or more carbon atoms containing an oxygen atom. (Where x, z, and n are integers of 1 or more, y is an integer of 0 or more, X is a fluorine atom or a chlorine atom, Z is a direct bond, an alkyl chain having 1 or more carbon atoms, or an oxygen atom ,
Or an alkyl chain having 1 or more carbon atoms containing an oxygen atom, is an alkyl chain having 1 or more carbon atoms, or a saturated carbocyclic ring,
Or an aromatic group such as a phenyl group, R ₆ is an alkyl group having 1 or more carbon atoms, or a saturated carbocycle, or an aromatic group such as a phenyl group, and R ₂ is an alkyl chain having 2 to 8 carbon atoms, such as a cyclohexyl group. A saturated carbocyclic ring or an aromatic group such as a phenyl group, m
Represents an integer of 1 or more, and R ₃ represents hydrogen or an alkyl group having 1 or more carbon atoms, and may combine with carbon in Z to form a saturated carbocyclic ring. R ₄ represents an alkyl group having 1 or more carbon atoms, and R ₅ represents an alkyl chain having 1 or more carbon atoms. ## STR10 ## Formula 10 (Where x ′, z ′ and n ′ are integers of 1 or more, y ′
Is an integer of 0 or more; X is a fluorine atom or a chlorine atom;
Represents a direct bond, an alkyl chain having 1 or more carbon atoms, or an oxygen atom, or an alkyl chain having 1 or more carbon atoms containing an oxygen atom, and R ₁ ′ represents an alkyl chain having 1 or more carbon atoms, or a saturated carbocyclic ring, or An aromatic group such as a phenyl group, R ₆ ′ is an alkyl group having 1 or more carbon atoms, or a saturated carbocyclic ring or an aromatic group such as a phenyl group, and R ₂ is an alkyl group having 2 to 8 carbon atoms, a cyclohexyl group, etc. A saturated carbocyclic ring or an aromatic group such as a phenyl group; m is an integer of 1 or more; R ₃ is hydrogen or an alkyl group having 1 or more carbon atoms; May be. R ₄ represents an alkyl group having 1 or more carbon atoms, and R ₅ represents an alkyl chain having 1 or more carbon atoms. ) 3. A silicone represented by the following general formulas 1 and 2
Grafted vinyl ether and / or vinyl ester
Structure consisting of toluene and tri- or tetrafluoroethylene
Containing an oligomer or polymer compound having
Molding with excellent contamination prevention and water repellency characterized by having
material. [Formula 11](Where x, z, and n are integers of 1 or more, and y is 0 or more
X is a fluorine atom or a chlorine atom, and Z is a direct bond.
Or an alkyl chain having 1 or more carbon atoms, or an oxygen atom,
Or an alkyl chain containing one or more carbon atoms containing an oxygen atom.
Then R₁Is an alkyl chain having 1 or more carbon atoms, or a saturated carbon
A ring or an aromatic group such as a phenyl group, R₆Has 1 or more carbon atoms
Alkyl group, or saturated carbocycle, or phenyl group
Aromatic group, R _TwoIs an alkyl chain having 2 to 8 carbon atoms,
Saturated carbocycle such as xyl group or aromatic such as phenyl group
A group, m is an integer of 1 or more;_ThreeIs hydrogen or 1 or more carbon atoms
A saturated carbocyclic ring bonded to the carbon in Z
May be formed. R_FourIs an alkyl group having 1 or more carbon atoms,
R_FiveRepresents an alkyl chain having 1 or more carbon atoms. ## STR12 ## Formula 2(Where x ', z' and n 'are integers of 1 or more, y'
Is an integer of 0 or more; X is a fluorine atom or a chlorine atom;
Is a direct bond, an alkyl chain having 1 or more carbon atoms, or an acid
C1 or more alkyl containing an atom or oxygen
Denotes a chain and R₁'Is an alkyl chain having 1 or more carbon atoms, or
A saturated carbocycle or an aromatic group such as a phenyl group, R₆′ Is charcoal
An alkyl group with a prime number of 1 or more, or a saturated carbocyclic or
An aromatic group such as a nyl group, R_TwoIs alkyl having 2 to 8 carbon atoms
Chain, saturated carbocycle such as cyclohexyl group, or phenyl group
An aromatic group such as m, m is an integer of 1 or more;_ThreeIs hydrogen or charcoal
Represents an alkyl group having a prime number of 1 or more, and is bonded to a carbon in Z
A saturated carbocycle may be formed. R_FourIs an atom having 1 or more carbon atoms.
Alkyl group, R_FiveRepresents an alkyl chain having 1 or more carbon atoms. ) 4. The method according to claim 1, wherein
Oligomers having a structure comprising a vinyl ether or / and a vinyl ester grafted with silicone and tri- or tetrafluoroethylene shown in 9 and 10;
Alternatively, a hydroxyl group present in the polymer and a crosslinking agent capable of reacting with the hydroxyl group react with each other to form a three-dimensional crosslinked structure obtained by curing the oligomer or the polymer. 3. The molding material according to any one of 3), which is excellent in prevention of contamination and water repellency.