KR101228627B1 - Aqueous polymer dispersion composition and water-repellent oil-repellent agent - Google Patents

Abstract

Even if the usage-amount of Rf containing resin is drastically reduced, the water-dispersible water and oil repellent composition which can exhibit high water / oil repellency and its durability is obtained. A water and oil repellent composition is provided, comprising a polymer (A) and a polymer (B), and wherein the polymer (A) and the polymer (B) are not present in the same particle. Polymer (A): The addition polymer containing the polymer unit of the following polymerizable monomer (a), and the following polymerizable monomer (b) or (c). Polymer (B): The addition polymer which does not contain the polymer unit of a polymerizable monomer (a), and contains a polymerizable monomer (c) or a polymerizable monomer (y). Polymerizable monomer (a): (meth) acrylate which has a polyfluoroalkyl group, or the acrylate in which the (alpha) position was substituted by halogen. Polymerizable monomer (b) and (c): The acrylate which has an alkyl group and the (alpha) position which does not have a polyfluoroalkyl group is halogen-substituted. Polymerizable monomer (y): The polymerizable monomer which the halogen atom couple | bonded with the carbon atom which forms unsaturated double bond.

Description

Aqueous polymer dispersion composition and water / oil repellent agent {AQUEOUS POLYMER DISPERSION COMPOSITION AND WATER-REPELLENT OIL-REPELLENT AGENT}

An object of the present invention is to provide a water and oil repellent composition (particularly a water and water repellent composition) capable of imparting excellent water / oil repellency (particularly water repellency) and durability to articles such as fibers even if the amount of the fluorine-containing monomer is reduced. do.

Conventionally, polymers or copolymers of polymerizable monomers containing fluoroalkyl, or compounds containing fluoroalkyl are treated with fiber products or the like as organic solvent solutions or aqueous dispersions to impart water and oil repellency on their surfaces. The technique is known.

Attempts have been made to copolymerize monomers having an adhesive group together with fluoroalkyl-containing polymerizable monomers for the purpose of improving the durability of water and oil repellency for washing or dry cleaning. In addition, attempts have been made to blend a polymer not containing fluoroalkyl and a polymer containing fluoroalkyl to create an economically excellent water and oil repellent composition (Patent Documents 1 to 2).

Moreover, using the polymerizable monomer which has a specific structure as a polymer and a copolymer which can be added without reducing antifouling performance, durability, etc. is proposed (patent document 3).

Recently, it has been disclosed that a resin composition having a surface having improved surface properties such as water and oil repellency and its retention properties by mixing two kinds of polymers having different fluoroalkyl group-containing polymers with a polymer not containing a fluoroalkyl group is disclosed. There is (patent document 4).

Furthermore, it is disclosed that the slip resistance is improved by mixing a polymer having at least one homopolymer or copolymer of a hydrocarbon-based polymerizable compound and having a glass transition point of 50 ° C or higher (Patent Document 5), and a fluoroalkyl-containing polymer and a fluoro The liquid repellent for carpets which mixes the polymer which does not contain a low alkyl, and all have a glass transition point or melting point of 45 degreeC or more is disclosed (patent document 6).

Japanese Patent Publication No. 38-22487 Japanese Patent Publication No. 41-8579 Japanese Patent Publication No. 49-42878 Japanese Patent Publication No. 06-228241 Japanese Patent Laid-Open No. 61-264081 United States Patent US4043964

In the conventional water and oil repellent agent, a monomer having an adhesive group is copolymerized with a fluoroalkyl-containing polymerizable monomer for the purpose of improving the durability of the water and oil repellent property for washing, dry cleaning, or the like. Attempts have been made to blend polymers and polymers with high film strength. However, high water / oil repellency can be achieved by introducing a large amount of fluorinated monomers, but this results in a lack of durability. On the contrary, sufficient durability can be provided by introducing a large amount of monomer having an adhesive group, but the water / oil repellency is insufficient. Moreover, in order to express sufficient water / oil repellency, it is necessary to introduce a large amount of fluorine monomer, and since the fluorine monomer is very expensive, cost was high.

Even if the usage-amount of a fluorine monomer is reduced, the processing agent which showed high water-oil-oil repellency and excellent also in the durability of water-oil repellency was desired.

MEANS TO SOLVE THE PROBLEM In order to solve the said problem, the present inventors earnestly examined for the purpose of providing the water- and oil-repellent composition which exhibits high water / oil repellency, and also excellent durability, even if the usage-amount of a fluorine monomer is reduced. As a result, a polymer having a polymer unit having a specific chemical structure and a polymer having a polymer unit derived from a monomer containing a fluoroalkyl group can also have a significant water / oil repellency and durability by mixing in an aqueous dispersion, and the above object can be achieved. It discovered that there existed and came to complete this invention.

That is, this invention provides the water-dispersible water-repellent oil-repellent composition containing an aqueous medium, the following polymer (A), and the following polymer (B).

Polymer (A): a polymer containing a fluoroalkyl group,

Polymer (B): A polymer containing a halogen atom in the main chain.

The term "containing a halogen atom in the main chain" means that a halogen atom is directly bonded to a carbon atom constituting the main chain of the polymer.

According to the present invention, a water-dispersible water / oil repellent composition obtained by mixing a polymer (B) having a polymer unit having a specific chemical structure and a polymer (A) having a polymer unit derived from a monomer comprising a fluoroalkyl is significantly water-repellent. Oily and durable. For this reason, the present invention can provide a water and oil repellent agent that reduces costs by reducing the amount of fluorine monomer used, exhibits high water and oil repellency, and is also excellent in durability.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention provides the water- and oil-repellent composition comprising the following polymer (A) and the following polymer (B), and wherein the polymer (A) and the polymer (B) are not present in the same particle. In general, particles comprising polymer (A) and particles comprising polymer (B) are present separately in the aqueous dispersion.

Polymer (A): The polymer unit (preferably 50 weight% or more) of the following polymerizable monomer (a), and the polymer unit (at least one of the following polymerizable monomer (b) or polymerizable monomer (c) (preferably). A polymer comprising up to 50% by weight (including 0% by weight but preferably 1% by weight or more).

Polymer (B): The polymer which does not contain the polymer unit of a polymerizable monomer (a), and contains at least one of a polymerizable monomer (y) or a polymerizable monomer (c).

Polymerizable monomer (a): (meth) acrylate which has a polyfluoroalkyl group, or the acrylate in which the (alpha) position was substituted by halogen.

Polymerizable monomer (b): (meth) acrylate which has an alkyl group and does not have a polyfluoroalkyl group.

Polymerizable monomer (c): The acrylate which has the alkyl group and halogen-substituted in the (alpha) position which does not have a polyfluoroalkyl group.

Polymerizable monomer (y): Polymerizable monomers other than the polymerizable monomers (a), (b) and (c), and polymerizable monomers in which a halogen atom is bonded to a carbon atom forming an unsaturated double bond.

The present invention also provides an article processed using the water / oil repellent composition.

In this specification, acrylic acid and methacrylic acid are named generically (meth) acrylic acid. The same applies to notation such as (meth) acrylate. Moreover, a polyfluoroalkyl group is described as Rf group.

The polymer (A) is 50% by weight or less (0% by weight) of 50% by weight or more of the polymerized unit of the polymerizable monomer (a), and at least one polymerized unit of the polymerizable monomer (b) or the polymerizable monomer (c). And (y) in which a halogen atom is bonded to a carbon atom forming an unsaturated double bond (x), including polymerizable monomers (x) other than the polymerizable monomers (a) and (b), if necessary. Or a polymerized unit of a polymerizable monomer (z)) having a reactive group, and the total of the polymerized unit of the polymerizable monomer (a) and the polymerized unit of the polymerizable monomer (b) and the polymerizable monomer (c) is 50% by weight. It is preferable that it is addition polymer which is more than%. That is, the polymer (A) does not need to contain the polymer unit of a polymerizable monomer (b) or (c).

The polymerizable monomer (a) is a (meth) acrylate having an Rf group or an acrylate in which the α position is halogen-substituted (hereinafter referred to as monomer (a) or an Rf group-containing monomer). The (meth) acrylate having an Rf group or the acrylates in which the α-position is halogen-substituted refers to a compound in which the Rf group is present in an alcohol residue portion of (meth) acrylic acid or an α-substituted acrylic acid ester.

Rf group is group in which two or more of the hydrogen atoms of the alkyl group were substituted by the fluorine atom. As for carbon number of Rf group, 2-20 are preferable, Especially 4-16, Especially 4-6 are preferable. When carbon number is less than 2, water repellency tends to fall, and when it is more than 20, monomer (a) turns into solid at normal temperature, and its sublimability also tends to become difficult to handle.

In addition, the Rf group may contain a halogen atom other than the fluorine atom. As another halogen atom, a chlorine atom is preferable. In addition, an etheric oxygen atom or a thioether sulfur atom may be inserted between the carbon-carbon bonds in the Rf group. Examples of the structure of the terminal portion of the Rf group include CF ₃ CF _2- , (CF ₃ ) ₂ CF-, CHF _2- , CH ₂ F-, CClF _2- , and CF ₃ CF _2- .

The Rf group is a group in which two or more hydrogen atoms in the saturated alkyl group are substituted with fluorine atoms. The ratio of the fluorine atoms in the Rf group is preferably a case where (the number of fluorine atoms in the Rf group) / (the number of fluorine atoms in the Rf group + the number of hydrogen atoms in the Rf group) are 40% or more, particularly in the case of 60% or more Is preferred. In addition, one part or all of the hydrogen atom may be substituted by the chlorine atom in Rf group.

The Rf group preferably has a straight or branched structure, and particularly preferably a straight chain structure. In the case of a branched structure, it is preferable that the branched portion is present near the terminal of the Rf group. In addition, it is preferable that a branch part is a short chain whose carbon number is about 1-4. Moreover, preferable carbon number of a Rf group is 1-12.

Particularly preferred as an Rf group is an Rf group containing a perfluoroalkyl group or a perfluoroalkyl group moiety when the proportion of the above fluorine atoms is substantially 100%. The perfluoroalkyl group is preferably a straight chain structure. As a linear perfluoroalkyl group, it is preferable to represent with C _m F _{2m + 1-} [where m is an integer of 2-20].

Specific examples of the Rf group are given below. In addition, in the following examples, the group of structural isomers is included in the other group of the structure which has the same molecular formula. C ₄ F _9- [F (CF ₂ ) _4- , (CF ₃ ) ₂ CFCF _2- , (CF ₃ ) ₃ C-], C ₅ F _11- [F (CF ₂ ) _5- , (CF ₃ ) ₃ CCF ₂ -etc.], C ₆ F _13- [F (CF ₂ ) ₆ -etc.], C ₇ F _15- , C ₈ H _17- , C ₉ F _19- , C ₁₀ F _21- , Cl (CF ₂ ) _t- , H (CF ₂ ) _t- (t is an integer from 2 to 20), (CF ₃ ) ₂ CF (CF ₂ ) _y- (y is an integer from 1 to 17), and the like.

In the Rf group-containing monomer, the Rf group and the polymerizable unsaturated group are bonded directly or indirectly through a bonding group, and are preferably bonded indirectly. As a coupling group, it is a bivalent or more coupling group, and the bonding group containing an alkylene group, ester group, an amide group, an amino group, a urethane group, an ether group, a phenyleneoxy group, a sulfonyl group, or these structures is preferable. Known or well-known compounds are employ | adopted for these Rf group containing monomers, and can be easily synthesize | combined from Rf group containing alcohol, Rf group containing carboxylic acid, or Rf group containing sulfonic acid.

Among these, as the Rf group-containing monomer in the present invention, a compound having a structure in which one of the Rf groups is linked via a polymerizable unsaturated group and a divalent bonding group is preferable. For example, Rf group containing acrylate, Rf group containing methacrylate, Rf group containing styrene, Rf group containing vinyl ester, Rf group containing fumarate, etc. are preferable.

Moreover, as a Rf group containing monomer in this invention, the (meth) acrylate containing an Rf group or the acrylate in which the (alpha) position was chlorinated are especially preferable at the point of general use.

Preferred Rf group-containing monomers can be represented by the following formulas.

[Wherein, Rf represents a fluoroalkyl group, Q ¹ represents a divalent organic group, and X ¹ represents a monovalent organic group containing a polymerizable unsaturated group.]

Q ¹ represents a divalent organic group, and-(CH ₂ ) _{n + p} -,-(CH ₂ ) _n C (O) ONH (CH ₂ ) _p -,-(CH ₂ ) _n CONH (CH ₂ ) _p -,-(CH ₂ ) _n SO ₂ NH (CH ₂ ) _p -,-(CH ₂ ) _n NHC (O) NH (CH ₂ ) _p -and the like are preferable. However, n and p represent the integer of 0 or 1 or more, and n + p is an integer of 2-22. Among these, as Q ¹ , — (CH ₂ ) _{n + p} −, — (CH ₂ ) _n C (O) ONH (CH ₂ ) _p −, — (CH ₂ ) _n SO ₂ NH (CH ₂ ) _p − In addition, p is an integer of 2 or more, and n + p is preferably 2 to 6, and particularly,-(CH ₂ ) _{n + p} -when n + p is 2 to 6, ie, dimethylene group or more. Preference is given to hexamethylene groups.

X <^1> represents the monovalent organic group containing a polymerizable unsaturated group, and the residue of an olefin, the residue of vinyl ether, the residue of vinyl ester, the residue of (meth) acrylate, the residue of styrene, etc. are preferable. . As the residue of olefins, -CR ¹ = CH ₂ or -OCH ₂ -φ-CR ¹ = CH ₂ is preferable, and as residues of (meth) acrylates, -OC (O) CR ¹ = CH ₂ , vinyl ethers Residues of -OCR ¹ = CH ₂ , vinyl ester residues of -C (O) OCR ¹ = CH ₂ , and styrene residues of -φ-CH = CH ₂ or -O-φ-CH = CH ₂ . desirable. However, R ¹ is a hydrogen atom, a straight or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a CFX ¹ X ² group (wherein X ¹ and X ² are hydrogen atoms) , Fluorine atom, chlorine atom, bromine atom or iodine atom), cyano group, linear or branched fluoroalkyl having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl group, φ is phenyl It's Rengi. Among these, as X ¹ , residues of (meth) acrylates are preferable, and in particular, -OC (O) CR ¹ = CH ₂ when R ¹ is a hydrogen atom or a methyl group or a chlorine atom, that is, an acryloxy group or meta A krilloxy group or the (alpha)-chloro acryloxy group is preferable. Examples of the Rf group-containing monomer include (meth) acrylates particularly from the viewpoints of polymerizability with other monomers, flexibility of the film formed on the fiber, adhesion to a substrate, solubility in a solvent, and ease of emulsion polymerization. Is preferred.

Rf group containing monomer can use 1 type (s) or 2 or more types.

Examples of the Rf group-containing monomer may be those of the following general formula.

[Wherein X is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a CFX ¹ X ² group (wherein X ¹ and X ² are Hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom), cyano group, linear or branched fluoroalkyl having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl group; Y is -O- or -NH-; Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group, a CH (R ¹ ) SO ₂ -group (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms) or -CH ₂ CCH (OZ ¹ ) CH ₂ -group (wherein Z ¹ is a hydrogen atom or an acetyl group) or-(CH ₂ ) _m -SO _2- (CH ₂ ) _n -group or-(CH ₂ ) _m -S- ( CH ₂ ) _n -group (wherein m is 1 to 10 and n is 0 to 10), and Rf is a linear or branched fluoroalkyl group having 1 to 21 carbon atoms.

As a specific example of an Rf group containing monomer, the following can be illustrated, for example, It is not limited to these.

[Wherein, Rf is C1-C21, especially 1-6 fluoroalkyl.]

The Rf group-containing monomer may be a mixture of two or more kinds. The amount of the Rf group-containing monomer may be 50 to 100% by weight, for example, 50 to 90% by weight based on the polymer (A).

The polymerizable monomer (b) is a (meth) acrylate having an alkyl group and not having a Rf group (hereinafter referred to as monomer (b)). (Meth) acrylate which has an alkyl group means the compound in which an alkyl group exists in the alcohol residue part of a (meth) acrylic acid ester. As an alkyl group, a C2 or more, for example, 2-30 alkyl group (cyclic and chain alkyl group), especially a linear alkyl group is preferable.

As a specific example of monomer (b), ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Isodecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, etc. are preferable. It can be heard. The monomer (b) may have two or more kinds of polymerizable monomers having an alkyl group and not having an Rf group.

The polymerizable monomer (c) is an acrylate (hereinafter referred to as monomer (c)) in which the α-position having an alkyl group and no Rf group is halogen-substituted. The acrylate in which the α-position having an alkyl group is halogen-substituted is a acrylate ester in which the α-position of the acrylate ester is halogen-substituted, and refers to a compound in which the alkyl group is present in the alcohol residue portion. As an alkyl group, a C2 or more, for example, 2-30 alkyl group (cyclic and chain alkyl group), especially a linear alkyl group is preferable.

Specific examples of the monomer (c) include ethyl α-chloroacrylate, n-butyl α-chloroacrylate, isobutyl α-chloroacrylate, t-butyl α-chloroacrylate and 2-ethylhexyl α-chloroacrylate Isodecyl α-chloroacrylate, cetyl α-chloroacrylate, stearyl α-chloroacrylate, behenyl α-chloroacrylate, lauryl α-chloroacrylate, cyclohexyl α-chloroacrylate, and the like. It can be heard. The monomer (c) may have two or more kinds of polymerizable monomers having an alkyl group and not having an Rf group.

In the polymer (A), when the polymerized unit of the monomer (b) or the monomer (c) is included, the weight ratio of the polymerized unit of the monomer (a) / (polymerized unit of the monomer (b) + monomer (c)) is 1 or more is preferable.

The polymer (A) is a polymerizable monomer (x) other than the polymerizable monomers (a), (b) and (c) (for example, in which a halogen atom is bonded to a carbon atom forming an unsaturated double bond) ( y) or a polymerized unit of a polymerizable monomer (z) having a reactive group, and further comprising a total of the polymerized unit of the polymerizable monomer (a) and the polymerized unit of the polymerizable monomer (b) and the polymerizable monomer (c). It is preferable that it is an addition polymer which is 70 weight% or more with respect to the polymer.

It is preferable that the ratio of the polymerized unit of the monomer (a) in a polymer (A) is 50 weight% or more, for example, 50-90 weight%, especially 60-80 weight% with respect to a polymer. It is preferable that the ratio of the polymerized unit of the monomer (b) in a polymer (A) is 50 weight% or less with respect to a polymer, for example, 1-40 weight%, especially 3-30 weight%. The proportion of the polymerized unit of the monomer (c) in the polymer (A) is 50% by weight or less, for example, 0 to 40% by weight, especially 0 to 30% by weight, especially 1 to 10% by weight, based on the polymer. Is preferably.

The sum total of the polymerization unit of monomer (a), the polymerization unit of monomer (b), the polymerization unit of monomer (c), and the polymerization unit of monomer (x) is 90 weight% or more with respect to polymer (A), for example It is preferable that it is 95 to 100 weight%.

As for the ratio of the polymerized unit of a monomer (x), 70 weight% or less, for example, 0-40 weight% or less, especially 1-30 weight% are preferable with respect to a polymer (A).

Monomer (x), especially monomer (y), should just be a compound which does not contain a fluorine atom. As monomer (x), the copolymerizable monomer which has a benzene ring may be sufficient. In this case, (meth) acrylates having a benzene ring are preferable. The benzene ring may have a substituent (for example, a C1-C10 alkyl group or an alkoxy group, or a halogen atom). As (meth) acrylate which has a benzene ring, the compound which the methyl group, the methoxy group, the chlorine atom, etc. couple | bonded with phenyl (meth) acrylate, benzyl (meth) acrylate, or these benzene rings is preferable.

Moreover, ethylene, styrene, etc. may be sufficient.

As the monomer (y) in which a halogen atom is bonded to a carbon atom forming an unsaturated double bond in the monomer (x), a repeating unit in which a halogen atom is directly bonded to a carbon atom constituting the main chain exists. Such a repeating unit can be derived from the monomer in which a halogen atom is directly bonded to the carbon atom which forms a carbon-carbon double bond (it calls it "the main chain monomer which has a halogen atom" in this specification). Examples of halogen atoms are fluorine, chlorine, bromine, and iodine.

Examples of the main chain monomer having a halogen atom (that is, monomer (y)) include vinylidene halides such as vinyl chloride and vinyl fluoride, vinylidene halides such as vinylidene chloride and vinylidene fluoride, chlorotrifluoroethylene, and a hydrocarbon group. -Chloro (meth) acrylate, and the like. (Alpha) -chloro (meth) acrylate which has a hydrocarbon group is contained in monomer (c), and it does not correspond to monomer (y). As the monomer (y), vinyl chloride and vinylidene chloride are preferable. The main chain monomer having a halogen atom may be one kind or a combination of two or more kinds.

It is preferable that the quantity of the polymerized unit of monomer (y) is 40 weight% or less with respect to a polymer (A), for example, 0-30 weight%, especially 1-25 weight%.

As a polymerizable monomer (z) which has a reactive group, superposition | polymerization, such as an epoxy group, a halogen atom, a hydroxyl group, an amide group, an amino group, an imino group, an alkoxy silyl group, an N-methylol group, an N-alkyloxyalkyl group, a blocked isocyanato group, etc. You may contain reactive groups other than a sex unsaturated bond. As the reactive group-containing polymerizable monomer (z), for example, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-methyl All (meth) acrylamide, diacetone (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide , N-butoxymethyl (meth) acrylamide, γ-trimethoxysilylpropyl (meth) acrylate, glycidyl (meth) acrylate, and the like are preferable.

As the hydroxyl group-containing (meth) acrylate, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono ( Preferred are meth) acrylate, poly (oxyethylene / oxypropylene) glycol mono (meth) acrylate, glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, and the like.

As a copolymerizable monomer which has a blocked isocyanato group, the block product of the reaction product obtained by making hydroxyl-containing (meth) acrylate and polyisocyanate react at the ratio of at least 1 isocyanate group, hydroxyl-containing (meth) acrylate, and at least Preferred are reaction products obtained by reacting a polyisocyanate derivative having one blocked isocyanate group and at least one free isocyanate group.

As polyisocyanate, Aliphatic polyisocyanate, such as hexamethylene diisocyanate and lysine diisocyanate, or isophorone diisocyanate, 4,4'- dicyclohexyl methane diisocyanate, cyclohexylene diisocyanate, bis (isocyanate methyl) cyclohexane, etc. And alicyclic polyisocyanate, and their nurate-modified product, prepolymer-modified product, biuret-modified product and the like, and aliphatic diisocyanate or alicyclic diisocyanate are preferable.

Examples of the blocking agent for obtaining a blocked isocyanato group include oximes, alkyl ketooximes, phenols, β-diketones, malonic esters, lactams and alkanols. As a specific example of a blocking agent, cyclohexane oxime, methyl ethyl keto oxime, phenol, cresol, acetylacetone, diethyl malonate, isopropanol, t-butanol, epsilon caprolactam, maleimide, sodium bisulfite, etc. are mentioned. . Cyclohexane oxime, methyl ethyl keto oxime, etc. are preferable.

It is preferable that the quantity of the polymerization unit of the monomer (z) in a polymer (A) is 10 weight% or less, for example, 0.1-8 weight% with respect to a polymer (A).

It is preferable that the quantity of the polymerization unit of the monomer (x) except the monomer (y) and the monomer (z) is 30 weight% or less, for example, 0-10 weight% with respect to a polymer (A).

As a polymerization method of obtaining a polymer (A), when superposing | polymerizing by an emulsion polymerization method or a dispersion polymerization method, the method of superposing | polymerizing the said polymerizable monomer by adding a polymerization initiator in presence of an emulsifier and a polymerization medium can be illustrated. have. It does not specifically limit as an emulsifier, One or more types of well-known or well-known emulsifiers of nonionic, cationic, anionic, and amphoteric types can be employed. As for the quantity of an emulsifier, 0.5-20 weight part is preferable with respect to 100 weight part of polymerizable monomers, Especially about 1-10 weight part is preferable at the point of water-oil repellency and stability of a dispersion liquid.

As a polymerization medium, it is a medium containing water, and you may contain an organic solvent as needed. As the organic solvent, water-soluble organic solvents are preferable, and organic solvents such as esters, ketones, and ethers (alcohols) are preferable. As the ester organic solvent, ethyl acetate, butyl acetate, diethyl succinate, and the like are preferred. As the ketone organic solvent, methyl ethyl ketone, methyl isobutyl ketone, acetone, and the like are preferable, and ether (alcohol) As an organic solvent, diethylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, glycol, these monomethyl ether, dimethyl ether, diethyl ether, etc. are preferable. Among these, as the organic solvent, an ether solvent (alcohol) organic solvent is preferable from the viewpoint of low flammability. The ratio of water and an organic solvent is not specifically limited, Any ratio may be sufficient. The amount of the organic solvent may be 100 parts by weight or less, for example, 1 to 10 parts by weight with respect to 100 parts by weight of water. The amount of the polymerization medium may be 0.5 to 100 parts by weight, for example, 1 to 20 parts by weight, based on 1 part by weight of the polymerizable monomer.

As a polymerization initiator, a water-soluble or oil-soluble polymerization initiator is preferable, and general-purpose initiators, such as a persulfate type, an azo type, a peroxide type, and a redox type, can be used according to polymerization temperature. Although polymerization temperature is not specifically limited, 20 to 150 degreeC is preferable.

In addition, in the polymerization reaction of a 1st polymer, you may contain a chain transfer agent in order to control molecular weight. As a chain transfer agent, mercaptans can be used preferably.

In the polymerization reaction, a mixture composed of the polymerizable monomer, water, and an emulsifier may be pre-dispersed beforehand by a homomixer or a high pressure emulsifier or the like as a preliminary step for starting the polymerization.

It is preferable that the polymer (A) (1st polymer) synthesize | combined by the said method exists as microparticles | fine-particles in a medium. It is preferable that the particle diameter of the microparticles | fine-particles of a polymer (A) is 0.001-1 micrometer, for example, 0.01-0.5 micrometer. If it is this range, in order to obtain a stable dispersion liquid, the quantity of an emulsifier will be minimum, high water / oil repellent performance, and polymer microparticles will exist stably in a medium. When it exceeds 0.5 micrometer, there exists a possibility of settling in the case of long-term storage. The particle diameter can be measured by a dynamic light scattering device, an electron microscope, or the like. When superposing | polymerizing in presence of an emulsifier by the normal method of emulsion polymerization, an average particle diameter is normally contained in said preferable range.

The polymer (B) does not contain the polymer unit of a polymerizable monomer (a), and the sum total of at least one polymer unit of a polymerizable monomer (c) and a polymerizable monomer (y) contains 10 weight% or more, and superposes | polymerizes, It is preferable that it is an addition polymer containing the polymerization unit of the polymerizable monomer (z) which has a polymerizable monomer or reactive group except polymer (y) among the polymerizable monomer (b) or the polymerizable monomer (x).

The polymer (B) may be a weight that does not contain a fluorine atom.

Monomers (a), (b), (c), (x), (y) and (z) in the polymer (B) are monomers (a), (b) and () in the polymer (A). c), (x), (y) and (z). In the polymer (B), the monomer (a) does not exist.

Monomers (b), (c), (x), (y) and (z) in the polymer (B) are monomers (b), (c), (x) and () in the polymer (A). y) and (z) may be same or different. In addition, you may use each of monomer (b), (c), (x), (y), and (z) in 2 or more types.

In the polymer (B), at least one of the monomer (c) or the monomer (y) is present.

In the polymer (B), the amount of the monomer (b) (relative to the polymer) is 90% by weight or less, for example, 5 to 80% by weight, in particular 10 to 70% by weight, in particular 30 to 65% by weight, monomer The amount of (c) is, for example, 0 to 8% by weight, in particular 0.5 to 5% by weight, the amount of monomer (y) is at least 20% by weight, for example 25 to 85% by weight, in particular 30 to 80% by weight. Is preferably. The total amount of the monomer (c) and the monomer (y) is 10% by weight or more, for example 20 to 90% by weight, particularly preferably 30 to 80% by weight. The amount of monomer (x) excluding monomer (y) and monomer (z) is 40% by weight or less, for example 0-30% by weight, in particular 0-20% by weight, and the amount of monomer (z) is 10% by weight or less For example, it is preferable that it is 0.1 to 8 weight%.

As a polymerization method of obtaining a polymer (B), emulsion polymerization, suspension polymerization, etc. are preferable similarly to the polymerization method of obtaining a polymer (A), and emulsion polymerization is especially preferable. By emulsion polymerization etc., the polymer (B) is obtained by disperse | distributing as particle | grains in an aqueous solvent (also called a dispersion).

It is preferable to perform emulsion polymerization using a polymerization initiator. As a polymerization initiator, a peroxide or an azo compound is preferable, and an azo compound is especially preferable. As an example of an azo-type compound, the oil-soluble polymerization initiator demonstrated in the polymer (A), 2,2'- azobis (2-methylpropionamidine) hydrochloride, 2,2'- azobis [2- (2-imidazoline Water-soluble polymerization initiators, such as the 2-yl) propane] hydrochloride and 2,2'- azobis [2- (2-imidazolin-2-yl) propane] sulfate hydrate, are mentioned preferably.

Moreover, you may add a chain transfer agent at the time of a polymerization reaction in order to control the molecular weight of the polymer (B) obtained. As a chain transfer agent, the chain transfer agent quoted in description of a polymer (A) can be used preferably.

In the dispersion of a polymer (B), an emulsifier may exist. As an emulsifier, the nonionic emulsifier, cationic emulsifier, anionic emulsifier, or amphoteric emulsifier described in the polymer (A) is preferable.

Emulsifiers may be used alone or in combination of two or more. When using together emulsifiers with different ionicity, the combination of a nonionic emulsifier and a cationic emulsifier, or a nonionic emulsifier and an amphoteric emulsifier is preferable. The amount of the emulsifier is preferably 1 to 20 parts by weight based on 100 parts by weight of the polymer (B).

The average particle diameter of the polymer (B) is preferably 0.001 to 1 µm, particularly 0.03 to 0.5 µm. When the average particle diameter is less than 0.03 µm, in order to obtain a stable dispersion, a large amount of an emulsifier or a self-emulsifiable polymerizable monomer may be required, and the water repellency may decrease. Moreover, when it exceeds 0.5 micrometer, there exists a possibility that a particle may settle.

In the water / oil repellent composition of the present invention, the polymer (A) and the polymer (B) do not exist in the same particle, and each form particles separately. In order to obtain the polymer (A) and the polymer (B), the water- and oil-repellent composition of the present invention is polymerized separately for each of the polymers, and separately forms particles to obtain a dispersion, and then the respective dispersions are mixed. It is preferable to prepare.

In the water / oil repellent composition, the weight ratio of the polymer (A) and the polymer (B) is preferably (A) / (B) = 40/60 to 90/10, particularly preferably 50/50 to 80/20. If the ratio of a polymer (A) or a polymer (B) exists in said range, it will be excellent in water / oil repellency and durability of water / oil repellency. In addition, the polymer concentration (solid content concentration) in the water / oil repellent composition is preferably 0.1 to 50% by weight.

Each of the polymer (A) and the polymer (B) may use two or more kinds of polymers.

In the water / oil repellent composition of the present invention, in order to express various physical properties in articles such as textile products, polymers other than the polymer (A) or the polymer (B), water repellents, oil repellents, catalysts for promoting crosslinking, as necessary. You may mix | blend a tactile modifier, an antistatic agent, a penetrant, an insect repellent, a flame retardant, an anti-wrinkle shrinkage inhibitor, a dye stabilizer, a pH adjuster, etc.

The water / oil repellent composition of the present invention is applied to an article by diluting to an arbitrary concentration according to the purpose, use, and the like. As a water-repellent processing method to an article, arbitrary methods are employ | adopted according to the kind of article, the manufacturing form of a composition, etc. For example, the method of adhering to the surface of an article and drying by coating processing methods, such as immersion or application | coating, is employ | adopted. Moreover, you may apply with a suitable crosslinking agent and heat-process if needed.

As a water-repellent processing method to an article, the method of immersing an article in the water / oil repellent composition containing a polymer (A) and a polymer (B) is preferable. In addition, after the article is immersed in the composition containing the polymer (B) and not containing the polymer (A), the water repellent processing method of immersing the composition containing the polymer (A) and not containing the polymer (B) is also equivalent. It is preferable because an effect is obtained.

The article (substrate or to-be-processed article) to be treated using the water / oil repellent composition (treatment agent) of the present invention is not particularly limited and, in addition to textile products, stones, filters (for example, electrostatic filters), dustproof masks, glass, Paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, coated surfaces, plasters and the like. Fibers, fiber fabrics, fiber knits and the like are preferred. Examples of the fibers include animal and animal natural fibers such as cotton, hemp, wool and silk, polyamides, polyesters, synthetic fibers such as polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene, and semisynthetic fibers such as rayon and acetate. And inorganic fibers such as glass fibers and carbon fibers, or mixed fibers thereof. The article processed using the water / oil repellent composition of the present invention has excellent water repellency and is excellent in durability.

In this invention, a to-be-processed article is processed with a processing agent. "Treatment" means applying a processing agent to a to-be-processed object by immersion, spraying, application | coating, etc. By treatment, the fluorine-containing polymer, which is an active ingredient of the treatment agent, penetrates into the interior of the workpiece and / or adheres to the surface of the workpiece.

<Examples>

An Example and a comparative example are shown to the following, and this invention is demonstrated in more detail.

In the following,% and parts means% by weight and parts by weight, unless otherwise specified.

The characteristic was measured as follows.

Water repellent Oil repellent

In the case of treating the T / C cloth, the polymer dispersion is diluted with water so that the solid concentration is 30% by weight, and diluted with water so that the concentration of the 30% by weight dispersion is 3.2% to prepare a treatment liquid. T / C cloth (twill, 200 g / m 2, undyed cloth) was immersed in the treatment liquid, squeezed at 4 kg / cm 2, 4 m / min with mangle, and heat treated at 170 ° C. for 1 minute, followed by Evaluate water and oil repellency. Likewise, the treatment liquid is prepared by diluting with water such that the concentration of the 30 wt% dispersion is 4.8%. In the case of treating the cotton cloth, a cotton cloth (twill, 160 g / m 2, undyed cloth) is immersed in the treatment liquid, squeezed at 4 kg / cm 2, 4 m / min with mangle, and heat treated at 170 ° C. for 2 minutes, followed by treatment cloth To evaluate the water and oil repellency of the. Likewise, the treatment liquid is prepared by diluting with water such that the concentration of the 30 wt% dispersion is 4.8%. When treating a polyester cloth, a polyester cloth (microfiber navy) is immersed in the treatment liquid, squeezed at 4 kg / cm 2 and 4 m / min with mangle, and heat treated at 170 ° C. for 2 minutes, and then the water and oil repellency of the treated cloth is Evaluate. Water repellency is shown with the water repellency number (refer Table 1 below) by the spray method of AATCC-21. Oil repellency was dropped by dropping the test solution shown in Table 2 on the test cloth by AATCC-118 on the test cloth, and observed the penetration state after 30 seconds. do. In the case of the same grade, it is evaluated as + when the water and oil repellency is higher, and-when the water repellency is higher.

Water repellent Oil-repellent  Laundry durability

According to JIS L-0217-103 method, it is 25 minutes (5 minutes X HL, 5 times consecutively) washing with washing liquid of 40 degrees Celsius, 3 minutes of dehydration, 2 minutes of rinsing, 3 minutes of rinsing, 2 minutes of rinsing, 3 minutes of dehydration, Tumbler drying is performed and subsequent water / oil repellency is evaluated (HL-5).

Average particle diameter

The average particle diameter of the dispersed particles is measured using a laser light scattering method (Fiber-Optics Particle Analyzer FPAR-1000 manufactured by Otsuka Denshi Co., Ltd.).

Hereinafter, n-butyl acrylate is n-BA, N-methylol acrylamide is N-MAM, 3-chloro-2-hydroxypropyl methacrylate is TM, lauryl mercaptan is L-SH, n-butyl Methacrylate is n-BMA, t-butyl methacrylate is t-BMA, stearyl acrylate is StA, lauryl acrylate is LA, vinyl chloride is VCl, 3,3,4,4,5,5, 6,6,7,7,8,8,8-tridecafluorooctylmethacrylate is 13FMA, 2,2,3,3,4,4,5,5,6,6,7,7,8 , 8,9,9,9-heptadecafluoro-nonylacrylate was described as 17FA.

As the emulsifier, C2ABT was used for dicured tallow alkyldimethylammonium chloride, PP-40R for sorbitan monopalmitate, K220 for polyethylene glycol lauryl ether, and BO50 for polyoxyethylene oleyl ether.

In addition, tripropylene glycol was described as TPG, and 2,2'- azobis (2-amidinopropane) dihydrochloride was NC-32W.

Synthesis Example 1

In a 500 mL container, as polymerizable monomers, n-BA (63.11 g), N-MAM (1.26 g), TM (0.63 g), L-SH (0.9 g), emulsifier C2ABT (0.91 g) and PP- 40R (1.22g), K220 (5.25g), BO50 (1.3g), water (103.4g) and TPG (18.62g) were added, pre-dispersed with a homomixer, and then cooled using an ultrasonic emulsifier for 5 minutes. The treatment gave an emulsion of the monomer mixture.

The emulsion was placed in a 500 mL separable flask equipped with a cooling tube, a nitrogen introduction tube, and a thermometer, and after nitrogen substitution, NC-32W (0.38 g), which is an initiator, was dissolved in water (4 g) and added thereto, followed by 60 ° C. After heating up, the mixture was polymerized for 3 hours to obtain a dispersion of non-fluorinated polymer particles having a solid content of 35.3% and an average particle diameter of 0.109 µm (207.1 g).

Synthesis Examples 2 to 16

In the same manner as in Synthesis Example 1, the monomer mixture shown in Table 3 was emulsified, and when VCl was used as the monomer, a 500 mL stainless steel autoclave was used. Otherwise, 500 mL with a cooling tube, a nitrogen introduction tube, and a thermometer. It put in the separable flask of and superposed | polymerized, and obtained various non-fluorine polymer particles.

Examples 1-6, Comparative Examples 1-6

The dispersion liquid mixture which blended the dispersion liquid which diluted the polymer particle dispersion liquid obtained by the synthesis examples 1-16 with water so that solid content concentration might be 30 weight%, by the mixing ratio shown in Tables 7-10 was obtained.

Test Examples 1 to 6

The water- and oil-repellent property was evaluated about the polymer particle dispersion liquid obtained in said Examples 1-6.

The evaluation results are shown in Table 11.

Comparative Test Examples 1 to 6

The water- and oil-repellent property was evaluated about the polymer particle dispersion liquid obtained by said Comparative Examples 1-6.

The evaluation results are shown in Table 12.

Comparative Test Examples 7 to 10

The water- and oil-repellent property was evaluated about the polymer particle dispersion liquid obtained by the said synthesis examples 13-16.

The evaluation results are shown in Table 13.

Test Examples 7 to 8 and Comparative Test Examples 11 to 12

The water- and oil-repellent wash | cleaning durability was evaluated about the various dough which processed the resin aqueous dispersion liquid shown in Table 14, Table 15 by the method shown by the test example 1.

The evaluation results are shown in Tables 14 to 15.

Claims (16)

A water dispersion type water and oil repellent composition comprising an aqueous medium, the following polymer (A), and the following polymer (B).
Polymer (A): A polymer containing a polyfluoroalkyl group
Polymer (B): A polymer containing halogen atoms other than fluorine atoms in the main chain and not containing fluorine atoms The water-dispersible water and oil repellent composition according to claim 1, wherein the polymer (B) contains at least one of acrylate, vinyl chloride or vinylidene chloride having a halogen-substituted alkyl group in the α-position as a polymer unit. The polymer (B) according to claim 2, wherein the polymer (B) is a polymer containing 10 to 100% by weight of at least one polymerized unit of acrylate, vinyl chloride and vinylidene chloride having a halogen-substituted alkyl group other than the fluorine atom. Water dispersion type water and oil repellent composition. The water-dispersible oil and oil repellent composition according to any one of claims 1 to 3, wherein the polymer (A) is a polymer comprising a polymer unit derived from a polyfluoroalkyl group-containing monomer. The water-dispersible oil and oil repellent composition according to claim 4, wherein the polymer (A) is a polymer containing 50 to 100% by weight of polymerized units derived from a polyfluoroalkyl group-containing monomer. 4. The polyfluoroalkyl group of claim 1, wherein the polyfluoroalkyl group is of the formula C _m F _{2m + 1-} , wherein m is an integer from 2 to 20, or (CF ₃ ) ₂ CF (CF ₂ CF ₂ ) _n- (wherein n is an integer of 0 to 10) water-dispersible water- and oil-repellent composition. The water-dispersible water and oil repellent composition according to claim 5, wherein the polyfluoroalkyl group-containing monomer is represented by the formula (1).
&Lt; Formula 1 >

[In the formula 1, Rf is an alkyl group polyfluoroalkyl, Q ¹ is an organic divalent group, X ¹ represents a monovalent organic group containing a polymerizable unsaturated group.] The water-dispersible oil and oil repellent composition according to claim 5, wherein the polyfluoroalkyl group-containing monomer is a compound represented by the formula (2).
(2)

In Formula 2, X is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a CFX ¹ X ² group (wherein X ¹ and X ² are Hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom), cyano group, linear or branched fluoroalkyl having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl group;
Y is -O- or -NH-;
Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group, or a -CH ₂ CH ₂ N (R ¹ ) SO ₂ -group (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms) ) Or -CH ₂ CH (OZ ¹ ) CH ₂ -group (wherein Z ¹ is a hydrogen atom or an acetyl group) or-(CH ₂ ) _m -SO _2- (CH ₂ ) _n -group or-(CH ₂ ) _m -S- (CH ₂ ) _n -group, with m being 1 to 10 and n being 0 to 10,
Rf is a linear or branched polyfluoroalkyl group having 1 to 21 carbon atoms.] The water-dispersible water and oil repellent composition according to claim 5, wherein the polymer (A) comprises 10 to 50% by weight of monomers other than the polyfluoroalkyl group-containing monomers. The water-dispersible water and oil repellent composition according to claim 9, wherein the other monomer is a monomer mixture containing at least one of vinyl chloride or vinylidene chloride. The water dispersion type water and oil repellent composition according to any one of claims 1 to 3, wherein the polymer (A) has a particle diameter of 0.001 to 1 µm. The water-dispersible water and oil repellent composition according to any one of claims 1 to 3, wherein the polymer (B) has a particle diameter of 0.001 to 1 µm. The polymer (A) according to any one of claims 1 to 3, wherein the polymerized unit of the polymerizable monomer (a) and the polymerizable monomer (b) or at least one of the polymerizable monomer (c) are polymerized. A water-dispersible water and oil repellent composition which is a polymer comprising a unit.
Polymerizable monomer (a): (meth) acrylate having a polyfluoroalkyl group or acrylates in which the α-position is halogen-substituted
Polymerizable monomer (b): (meth) acrylate which has an alkyl group and does not have a polyfluoroalkyl group
Polymerizable monomer (c): an acrylate having an alkyl group and a halogen-substituted α-position having no polyfluoroalkyl group The polymer (B) does not contain the polymer unit of the following polymerizable monomer (a), and is in the following polymerizable monomer (y) and the following polymerizable monomer (c) in any one of Claims 1-3. A water-dispersible water and oil repellent composition which is a polymer comprising at least one side.
Polymerizable monomer (a): (meth) acrylate having a polyfluoroalkyl group or acrylates in which the α-position is halogen-substituted
Polymerizable monomer (b): (meth) acrylate which has an alkyl group and does not have a polyfluoroalkyl group
Polymerizable monomer (c): α-position having an alkyl group and no polyfluoroalkyl group is a halogen-substituted acrylate other than a fluorine atom
Polymerizable monomer (y): Polymerizable monomers other than the polymerizable monomers (a), (b) and (c), and polymerizable monomers in which halogen atoms other than fluorine atoms are bonded to carbon atoms forming unsaturated double bonds. The method of treating a base material with the water / oil repellent composition of any one of Claims 1-3. The processing base material obtained by the processing method of Claim 15.