KR102170599B1 - Surface treatment agent - Google Patents

Abstract

It provides a surface treatment agent with improved processing stability, especially inspectionability, in water and oil repellent processing of fibers and the like. (A) a water and oil repellent polymer having a repeating unit derived from one or both of a fluorine-containing monomer (A1) having a fluoroalkyl group and a long-chain (meth)acrylate ester monomer (A2), (B) a polymeric surfactant, And (C) a liquid medium. It is preferable that the high molecular surfactant (B) is a quaternary ammonium salt polymer.

Description

Surface treatment agent

The present invention relates to a surface treatment agent containing a water and oil repellent polymer and a high molecular surfactant. Specifically, the present invention can impart excellent water repellency, oil repellency, and antifouling properties to fiber products (eg, carpets), paper, nonwoven fabrics, stone materials, electrostatic filters, dust masks, and components of fuel cells.

Conventionally, various fluorine-containing compounds have been proposed. The fluorine-containing compound has the advantage of excellent properties such as heat resistance, oxidation resistance, and weather resistance. Utilizing the characteristic that the free energy of the fluorine-containing compound is low, that is, it is difficult to adhere, the fluorine-containing compound is used, for example, as a water and oil repellent agent and an antifouling agent.

As a fluorine-containing compound usable as a water and oil repellent agent, a fluorine-containing polymer comprising a (meth)acrylate ester having a fluoroalkyl group as a constituent monomer can be mentioned. In the practical treatment of fibers of a surface treatment agent, it has been shown from the results of various studies so far that not a static contact angle, but a dynamic contact angle, particularly a receding contact angle, is important as its surface property. That is, although the advancing contact angle of water does not depend on the number of side chain carbon atoms of the fluoroalkyl group, the receding contact angle of water is shown to be significantly smaller at 7 or less compared to 8 or more carbon atoms in the side chain. Correspondingly, X-ray analysis shows that crystallization of the side chain occurs when the number of carbon atoms in the side chain is 7 or more. It is known that the practical water repellency correlates with the crystallinity of the side chain, and that the motility of the surface treatment agent molecule is an important factor in the expression of practical performance (for example, Takashige Maekawa, Fine Chemicals, Vol 23, No. 6). , P12 (1994)). For the above reasons, in a (meth)acrylate-based polymer having a short fluoroalkyl group with a side chain of 7 (especially 6 or less) or less, there is a problem that the practical performance cannot be satisfied as it is because the crystallinity of the side chain is low. there was.

Fluorine-containing surface treatment agents with excellent product stability have been proposed.

Japanese Patent Application Laid-Open No. Hei 9-118877 discloses a polymer (a) containing a polymerized unit of acrylate or methacrylate containing a polyfluoroalkyl group dispersed in an aqueous medium, and moisture containing a surfactant (b). In the acid-type water and oil repellent composition, the surfactant (b) comprises at least three of the following surfactant (c), the following surfactant (d), and the following surfactant (e) Disclosed is an excellent water dispersion type water and oil repellent composition.

Japanese Patent Application Laid-Open No. 9-125051 discloses an aqueous medium, a polymer (a) containing a polymerized unit of acrylate or methacrylate containing a polyfluoroalkyl group dispersed in the aqueous medium, and a surfactant (b). Disclosed is a water dispersion type water and oil repellent composition containing excellent stability.

Japanese Patent Laid-Open No. 2015-120984 discloses that at least one antimicrobial agent selected from metal oxides, pyridine compounds, and cationic polymers, and at least one compound selected from absorbents, nonionic softeners, and cationic softeners It discloses an imparted fiber product.

Conventional fluorine-containing water and oil repellent agents have insufficient processing stability in water and oil repellent processing.

Japanese Patent Application Laid-Open No. Hei 9-118877 Japanese Patent Laid-Open No. Hei 9-125051 Japanese Patent Laid-Open No. 2015-120984

One object of the present invention is to provide a surface treatment agent having improved processing stability, in particular, gum-up properties for water and oil repellent processing of fibers.

Another object of the present invention is to provide a surface treatment agent having excellent chemical stability (contaminant stability) and mechanical stability.

The present invention,

(A) a water and oil repellent polymer having a repeating unit derived from one or both of a fluorine-containing monomer (A1) having a fluoroalkyl group and a long-chain (meth)acrylate ester monomer (A2),

(B) a polymeric surfactant, and

(C) liquid medium

It provides a surface treatment agent comprising a.

The present invention, also

(I) In the presence of a liquid medium, a monomer comprising a fluorine-containing monomer (A1) having a fluoroalkyl group or a long-chain (meth)acrylate ester monomer (A2) is polymerized, and a fluorine-containing monomer having a fluoroalkyl group ( A1) or a step of obtaining an aqueous dispersion of a water and oil repellent polymer having a repeating unit derived from a long-chain (meth)acrylate ester monomer (A2), and

(Ii) A method for producing a surface treatment agent further comprising a step of adding a polymeric surfactant to an aqueous dispersion of a water- and oil-repellent polymer is provided.

The surface treatment agent of the present invention does not cause sedimentation of particles, so that the polymer adheres to the roll and does not cause cloth contamination.

Advantageous Effects of Invention According to the present invention, excellent water repellency, oil repellency, antifouling property and dirt-repellency, for example, excellent durability of water and oil repellency can be obtained.

The surface treatment agent of the present invention can be used as a water and oil repellent agent, an antifouling agent, and/or a soil releasing agent.

The surface treatment agent is generally an aqueous emulsion of a water and oil repellent polymer.

The surface treatment agent,

(A) a water and oil repellent polymer having repeating units derived from one or both of a fluorine-containing monomer (A1) or a long-chain (meth)acrylate ester monomer (A2) having a fluoroalkyl group,

(B) a polymeric surfactant, and

(C) liquid medium

It is made including.

The water and oil repellent polymer is a homopolymer having a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group or a long-chain (meth)acrylate ester monomer, a fluorine-containing monomer having a fluoroalkyl group, and a long-chain (meth)acrylate ester monomer A copolymer having a repeating unit derived from two or more monomers selected from, or a repeating unit derived from another polymerizable compound copolymerizable with a repeating unit derived from a fluorine-containing monomer or a long-chain (meth)acrylate ester monomer having a fluoroalkyl group It is a copolymer having.

The water and oil repellent polymer is a fluorine-containing polymer or a non-fluorine polymer. The fluorine-containing polymer is a polymer having repeating units derived from a fluorine-containing monomer having a fluoroalkyl group, and the non-fluorine polymer is a polymer having repeating units derived from a long-chain (meth)acrylate ester monomer.

In the present invention, the water and oil repellent polymer (A) is composed of only repeating units derived from (A1) a fluorine-containing monomer having a fluoroalkyl group and/or (A2) a repeating unit derived from a long-chain (meth)acrylate ester monomer. Can be done,

In addition to the repeating units (A1) and/or (A2),

One or both of (A3) a repeating unit derived from a non-fluorine non-crosslinkable monomer and (A4) a repeating unit derived from a non-fluorine non-crosslinkable monomer.

It is preferable to have.

The water and oil repellent polymer (A) has a repeating unit derived from one or both of (A1) a fluorine-containing monomer having a fluoroalkyl group and (A2) a long-chain (meth)acrylate ester monomer. That is, the water and oil repellent polymer (A) has one or both of (A1) a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group and (A2) a repeating unit derived from a long-chain (meth)acrylate ester monomer. .

(A1) Fluorine-containing monomer

The fluorine-containing monomer is generally a polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group or methacrylic acid group or an α-substituted acrylic acid group.

The fluorine-containing monomer has the formula:

[In the formula, X is a hydrogen atom, a monovalent organic group, or a halogen atom,

Y is -O- or -NH-,

Z is a direct bond or a divalent organic group,

Rf is a C1-C20 fluoroalkyl group]

It is preferable that it is a compound represented by.

Z is, for example, a linear or branched aliphatic group having 1 to 20 carbon atoms (especially an alkylene group), for example, represented by the formula -(CH ₂ ) _x- (wherein x is 1 to 10) A group, or a group represented by the formula -R ² (R ¹ )N-SO ₂ -or the formula- -R ² (R ¹ )N-CO- (in the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms, , R ² is a C 1 to C 10 linear alkylene group or a branched alkylene group), or the formula -CH ₂ CH(OR ³ )CH ₂ -(Ar-O) _p- (wherein R ³ is, A group represented by a hydrogen atom, or an acyl group having 1 to 10 carbon atoms (for example, formyl or acetyl, etc.), Ar is an arylene group having a substituent as necessary, p represents 0 or 1), or, A group represented by the formula -CH ₂ -Ar-(O) _q- (wherein Ar is an arylene group having a substituent as necessary, q is 0 or 1), -(CH ₂ ) _m -SO _2- (CH ₂ ) _n -group or -(CH ₂ ) _m -S-(CH ₂ ) _n -group (however, m is 1 to 10, n may be 0 to 10).

Specific examples of X are H, CH ₃ , Cl, Br, I, F, CN, and CF ₃ . It is preferable that X is a methyl group or a chlorine atom, and it is especially preferable that it is a chlorine atom.

The fluorine-containing monomer has the general formula:

[In the formula, 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, a CFX ¹ X ² group (however, X ¹ and X ² are, A hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, and ;

Y is -O- or -NH-;

Z is a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms, -CH ₂ CH ₂ N(R ¹ )SO ₂ -group (however, R ¹ is a C 1 to C 4 Is an alkyl group of),

^{_{-CH 2 CH (OZ 1) CH}} 2 - (Ph-O) p - group (where, Z ¹ is a hydrogen atom or an acetyl group, Ph is a phenylene group, p is 0 or 1), - (CH _{2) n} -Ph-O- group (however, Ph is a phenylene group, n is 0 to 10), -(CH ₂ ) _m -SO ₂ -(CH ₂ ) _n -group or -(CH ₂ ) _m -S-( CH ₂ ) _n -group (however, m is 1 to 10, n is 0 to 10),

Rf is a C 1 to C 20 linear or branched fluoroalkyl group]

It is preferably an acrylate ester or acrylamide represented by.

In the fluorine-containing monomer, it is preferable that the Rf group is a perfluoroalkyl group. The number of carbon atoms of the Rf group is preferably 1 to 12, for example 1 to 6, particularly 4 to 6, and particularly 6. Examples of Rf groups are -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF(CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF(CF ₃ ) ₂ , -C(CF ₃ ) ₃ , -(CF ₂ ) ₄ CF ₃ , -(CF ₂ ) ₂ CF(CF ₃ ) ₂ , -CF ₂ C(CF ₃ ) ₃ , -CF(CF ₃ )CF ₂ CF ₂ CF ₃ , -(CF ₂ ) ₅ CF ₃ , -(CF ₂ ) ₃ CF(CF ₃ ) ₂ , -(CF ₂ ) ₄ CF(CF ₃ ) ₂ , -C ₈ F ₁₇ etc.

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,

-CH ₂ CH ₂ N(R ¹ )SO ₂ -group (however, R ¹ is an alkyl group having 1 to 4 carbon atoms),

^{_{-CH 2 CH (OZ 1) CH}} 2 - (Ph-O) p - group (where, Z ¹ is a hydrogen atom or an acetyl group, Ph is a phenylene group, p is 0 or 1), - (CH _{2) n} -Ph-O- group (however, Ph is a phenylene group, n is 0 to 10), -(CH ₂ ) _m -SO ₂ -(CH ₂ ) _n -group or -(CH ₂ ) _m -S-( CH ₂ ) _n -group (however, m is 1 to 10, n is preferably 0 to 10). It is preferable that the aliphatic group is an alkylene group (particularly, the number of carbon atoms is 1 to 4, for example 1 or 2). The aromatic group or the cyclic aliphatic group may be substituted or unsubstituted. The S group or the SO ₂ group may be directly bonded to the Rf group.

As a specific example of a fluorine-containing monomer, although the following can be illustrated, for example, it is not limited to these.

[In the above formula, Rf is a fluoroalkyl group having 1 to 20 carbon atoms]

(A2) Long chain (meth)acrylate Ester monomer

The long chain (meth)acrylate ester monomer has the formula:

[In the formula, A ¹¹ is a hydrogen atom or a methyl group,

A ¹² is a C18 to C30 linear or branched hydrocarbon group]

It may be a compound represented by

The long-chain (meth)acrylate ester monomer does not have a fluoroalkyl group. Although the long-chain (meth)acrylate ester monomer may contain a fluorine atom, it is preferable that it does not contain a fluorine atom.

It is particularly preferable that A ¹¹ is a methyl group.

A ¹² is a linear or branched hydrocarbon group. A linear or branched hydrocarbon group may be particularly a linear hydrocarbon group. The linear or branched hydrocarbon group has 18 to 30 carbon atoms. The linear or branched hydrocarbon group preferably has 18 to 28 carbon atoms, particularly 18 or 22 carbon atoms, and is generally a saturated aliphatic hydrocarbon group, particularly preferably an alkyl group.

Preferred specific examples of the long-chain (meth)acrylate ester monomer are stearyl (meth)acrylate and behenyl (meth)acrylate. Stearyl (meth)acrylate is particularly preferred.

By the presence of the long-chain (meth)acrylate ester monomer, the water repellency, oil repellency, and texture imparted by the water and oil repellent polymer are enhanced.

(A3) Non-fluorine Non-crosslinking Monomer

The non-fluorine non-crosslinkable monomer (A3) is a monomer other than the long-chain (meth)acrylate ester monomer (A2). The non-fluorine non-crosslinkable monomer (A3) is a monomer that does not contain a fluorine atom. The non-fluorine non-crosslinkable monomer (A3) does not have a crosslinkable functional group. Unlike the crosslinkable monomer (A4), the non-fluorine non-crosslinkable monomer (A3) is non-crosslinkable. The non-fluorine non-crosslinkable monomer (A3) is preferably a non-fluorine monomer having a carbon-carbon double bond. The non-fluorine non-crosslinkable monomer (A3) is preferably a fluorine-free vinyl monomer. The non-fluorine non-crosslinkable monomer (A3) is generally a compound having one carbon-carbon double bond.

A preferred non-fluorine non-crosslinkable monomer (A3) is of the formula:

[In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom, and an iodine atom),

T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a chain or cyclic organic group having 1 to 31 carbon atoms having an ester bond]

It is a compound represented by.

Examples of the chain or cyclic hydrocarbon group having 1 to 30 carbon atoms include a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and 7 to 30 carbon atoms. It is an aromatic aliphatic hydrocarbon group of.

Examples of a chain or cyclic C1-C31 organic group having an ester bond include -C(=O)-OQ and -OC(=O)-Q (wherein Q is a straight chain or branched C1-C30 An aliphatic hydrocarbon group, a cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic aliphatic hydrocarbon group having 7 to 30 carbon atoms).

Preferred examples of the non-fluorine non-crosslinkable monomer (A3) include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) ) Acrylate, methoxypolypropylene glycol (meth)acrylate, and vinylalkyl ether. The non-fluorine non-crosslinkable monomer (A3) is not limited to these examples.

The non-fluorine non-crosslinkable monomer (A3) may be a (meth)acrylate ester having an alkyl group. The number of carbon atoms in the alkyl group may be 1 to 17. For example, the non-fluorine non-crosslinkable monomer (A3) has the general formula:

[In the formula, A ¹ is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (eg, a chlorine atom, a bromine atom, and an iodine atom),

A ² is an alkyl group represented by C _n H _{2n +1} (n=1 to 17)]

It may be an acrylate represented by.

The fluorine-containing monomer does not need to have a repeating unit derived from a (meth)acrylate ester having an alkyl group having 1 to 17 carbon atoms.

The non-fluorine non-crosslinkable monomer (A3) may be a (meth)acrylate monomer having a cyclic hydrocarbon group. The (meth)acrylate monomer having a cyclic hydrocarbon group is a compound having a (preferably monovalent) cyclic hydrocarbon group and a monovalent (meth)acrylate group. The monovalent cyclic hydrocarbon group and the monovalent (meth)acrylate group are directly bonded. As a cyclic hydrocarbon group, a saturated or unsaturated monocyclic group, a polycyclic group, a temporary exchange group, etc. are mentioned. It is preferable that the cyclic hydrocarbon group is saturated. It is preferable that carbon number of a cyclic hydrocarbon group is 4-20. Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an aromatic aliphatic group having 7 to 20 carbon atoms. The number of carbon atoms in the cyclic hydrocarbon group is particularly preferably 15 or less, for example 10 or less. It is preferable that the carbon atom in the ring of the cyclic hydrocarbon group is directly bonded to the ester group in the (meth)acrylate group. It is preferable that the cyclic hydrocarbon group is a saturated cyclic aliphatic group.

Specific examples of the cyclic hydrocarbon group are cyclohexyl group, t-butylcyclohexyl group, isobornyl group, dicyclopentanyl group, dicyclopentenyl group, and adamantyl group. The acrylate group is preferably an acrylate group or a methacrylate group, but a methacrylate group is particularly preferable. Specific examples of the monomer having a cyclic hydrocarbon group include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth) Acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adaman Tyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, etc. are mentioned.

The non-fluorine non-crosslinkable monomer (A3) may be a halogenated olefin. The halogenated olefin may be a halogenated olefin having 2 to 20 carbon atoms substituted with a 1 to 10 chlorine atom, a bromine atom or an iodine atom. The halogenated olefin (b) is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Preferred specific examples of the halogenated olefin (b) are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, and vinylidene iodide.

(A4) Non-fluorine Crosslinking Monomer

The water and oil repellent polymer may have a repeating unit derived from the non-fluorine crosslinkable monomer (A4). The non-fluorine crosslinkable monomer (A4) is a monomer containing no fluorine atom. The non-fluorine crosslinkable monomer (A4) may be a compound having at least two reactive groups and/or a carbon-carbon double bond and not containing fluorine. The non-fluorine crosslinkable monomer (A4) may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group. Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a block isocyanate group, an amino group, and a carboxyl group.

Examples of the non-fluorine crosslinkable monomer (A4) include diacetoneacrylamide, (meth)acrylamide, N-methylolacrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3 -Chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth) Although acrylate, butadiene, isoprene, chloroprene, glycidyl (meth)acrylate, etc. are illustrated, it is not limited to these.

By copolymerizing a non-fluorinated non-crosslinkable monomer (A3) and/or a non-fluorinated crosslinkable monomer (A4), such as water and oil repellency and stain resistance, and cleaning resistance, washing resistance, solubility in solvents, hardness, texture, etc. Various properties can be improved as needed.

The monomer may be polymerized in the presence of at least one compound selected from the group consisting of a block isocyanate compound and an organopolysiloxane compound. The amount of the block isocyanate compound (or organopolysiloxane compound) may be 0 to 100 parts by weight, for example 1 to 50 parts by weight, based on 100 parts by weight of the monomer.

By polymerizing the monomer in the presence of a block isocyanate compound, a polymer having a block isocyanate group is obtained. The blocked isocyanate compound is an isocyanate blocked by at least one type of blocking agent. Examples of blocking agents include oximes, phenols, alcohols, mercaptans, amides, imides, imidazoles, urea, amines, imines, pyrazoles, and active methylene compounds. Other examples of the blocking agent include pyridinols, thiophenols, diketones, and esters. The blocked isocyanate compound may be modified with a compound having a hydrophilic group.

A polymer having a siloxane group is obtained by polymerizing the monomer in the presence of an organopolysiloxane compound (eg, mercapto functional organopolysiloxane, vinyl functional organopolysiloxane). In one embodiment, the mercapto functional organopolysiloxane has a siloxy unit having the following average formula:

[In the formula, a is 0 to 4000, or 0 to 1000, or 0 to 400,

b is 1 to 1000, or 1 to 100, or 1 to 50,

c is 1 to 1000, or 1 to 100, or 1 to 50;

R is independently a monovalent organic group,

Or, R is a C1-C30 hydrocarbon,

Or, R is a C1-C12 monovalent alkyl group,

Or R is a methyl group;

R ^N is a monovalent amino functional organic group as defined above,

R ^S is a monovalent mercapto-functional organic group defined above]

Each amount of the fluorine-containing monomer (A1) and the long-chain (meth)acrylate ester monomer (A2) (or the sum of the monomer (A1) and the monomer (A2)) (however, the sum of the monomer (A1) and the monomer (A2)) Is 100% by weight or less) may be 30 to 100% by weight, preferably 32 to 98% by weight, for example 35 to 95% by weight, particularly 40 to 90% by weight, based on the water and oil repellent polymer.

In the water and oil repellent polymer, with respect to 100 parts by weight in total of the fluorine-containing monomer (A1) and the long-chain (meth)acrylate ester monomer (A2),

The amount of the non-fluorine non-crosslinkable monomer (A3) is 1000 parts by weight or less, for example 0.1 to 300 parts by weight, in particular 1 to 200 parts by weight,

The amount of the non-fluorine crosslinkable monomer (A4) may be 50 parts by weight or less, for example 30 parts by weight or less, particularly 0.1 to 20 parts by weight.

The amount of the non-fluorine non-crosslinkable monomer (A3) is 2 to 68% by weight, for example 5 to 65% by weight, based on the water and oil repellent polymer (or the total of the monomer (A1), the monomer (A2) and the monomer (A3)). %, particularly 10 to 60% by weight.

The number average molecular weight (Mn) of the water and oil repellent polymer may be generally 1000 to 1000000, for example 2000 to 500000, particularly 3000 to 200000. The number average molecular weight (Mn) of the water and oil repellent polymer is generally measured by GPC (gel permeation chromatography).

(2) Polymer type surfactant

The polymeric surfactant may be a surfactant for polymerization added before polymerization and/or a surfactant for addition after polymerization was completed. It is preferable that the polymeric surfactant is a surfactant for later addition.

The polymeric surfactant is preferably a cationic polymeric surfactant, particularly a quaternary ammonium salt polymer. In the polymeric surfactant, it is preferable that the nitrogen atom forms an imino group. In the polymeric surfactant, it is preferable that a nitrogen atom forms part of a main chain.

Polymeric surfactant, formula:

[In the formula, X is a halogen atom or a fatty acid base of C ₁ to C ₄ ,

Each Y is the same or different, and is a hydrocarbon group having 1 to 10 carbon atoms which may have a direct bond or a monovalent or divalent oxygen atom,

At least two Y may form a ring together with an adjacent nitrogen atom,

r is 1 or 2]

You may have a repeating unit represented by.

In X, specific examples of the halogen atom are a chlorine atom, a bromine atom, and an iodine atom. A fatty acid base is a group excluding a hydrogen atom from a fatty acid. It is preferable that a fatty acid is a C2-C20 fatty acid. Specific examples of fatty acids are acetic acid and butyric acid.

Y is preferably a C 1 to C 10 linear and/or branched aliphatic group (eg, an alkyl group or an alkylene group) which may have a monovalent or divalent oxygen atom. Examples of the aliphatic group which may have an oxygen atom are a hydroxyalkyl group or a hydroxyalkylene group (e.g., -CH ₂ CH(OH)CH ₂ -), or an oxyalkyl group or an oxyalkylene group (-OCH ₂ CH ₂ -)to be.

When r is 2, each of the eight Y groups may be the same or different.

Preferred polymeric surfactants are of the formula:

[In the formula, X is a halogen atom or a fatty acid base of C ₁ to C ₄ ,

Y ¹ , Y ² , Y ³ and Y ⁴ are a divalent aliphatic group having 1 to 10 carbon atoms which may have a direct bond or an oxygen atom,

Y ² and Y ³ may form a ring together with an adjacent nitrogen atom,

Z ¹ and Z ² are C 1 to C 10 linear and/or branched aliphatic groups,

r is 1 or 2,

n is a number of 2 or more]

It is a compound represented by.

In X, specific examples of the halogen atom are a chlorine atom, a bromine atom, and an iodine atom. A fatty acid base is a group excluding a hydrogen atom from a fatty acid. It is preferable that a fatty acid is a C2-C20 fatty acid. Specific examples of fatty acids are acetic acid and butyric acid.

It is preferable that Y ¹ , Y ² , Y ³ and Y ⁴ are a direct bond or an alkylene group having 1 to 10 carbon atoms. When Y ² and Y ³ form a ring together with an adjacent nitrogen atom, it is preferable that the formed ring is a 5- or 6-membered ring. Specific examples of the ring to be formed are an aziridine ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring. A pyrrolidine ring is preferred.

Specific examples of Z ¹ and Z ² are a methyl group and an ethyl group.

n may be a number of 5 to 10000, for example 10 to 1000.

It is preferable that the polymeric surfactant does not have either an oxyalkylene group or an OH group, and it is more preferable that it does not have (both) both an oxyalkylene group and an OH group.

Preferred specific examples of the polymeric surfactant are as follows.

Polydiallyldimethylammonium chloride,

Dimethylamine/Epichlorohydrin Copolymer

Poly[oxyethylene (dimethylimino) propylene (dimethylimino) ethylene dichloride],

Poly[oxyethylene(dimethylimino)ethylene(dimethylimino)ethylenedichloride].

It is preferable that the weight average molecular weight of the high molecular surfactant is 3,000 to 100,000, particularly 5,000 to 50,000. The weight average molecular weight can be measured by gel permeation chromatography (GPC) using polyethylene glycol as a standard substance.

The amount of the polymeric surfactant may be 0.01 to 10 parts by weight, for example 0.02 to 5 parts by weight, particularly 0.03 to 2 parts by weight, based on 100 parts by weight of the water and oil repellent polymer.

(3) liquid medium

The liquid medium may be an aqueous medium, that is, water alone, or a mixture of water and (water miscible) organic solvent. The amount of the organic solvent may be 30% by weight or less, for example, 10% by weight or less (preferably 0.1% or more) with respect to the liquid medium. As for the liquid medium, it is preferable that water is independent. The liquid medium may be only an organic solvent.

The amount of the liquid medium may be 30 to 99.1% by weight, particularly 50 to 99% by weight, based on the surface treatment agent.

(4) Surfactant for polymerization

In the present invention, it is generally preferred to polymerize the monomer in the presence of a polymerization surfactant.

In the present invention, the polymerization surfactant may be at least one selected from nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

(4-1) Nonionic surfactant

Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides.

An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are alcohols (eg, aliphatic alcohols) having 1 to hexavalent (especially 2 to 5) carbon atoms (especially 3 to 30 carbon atoms). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

An example of an ester ether is a compound obtained by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are alcohols (eg, aliphatic alcohols) having 1 to hexavalent (especially 2 to 5) carbon atoms (especially 3 to 30 carbon atoms). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

Examples of alkanolamides are compounds formed of fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or a dialkanolamide. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

The polyhydric alcohol may be an alcohol having 2 to 5 carbon atoms and 15 to 30 carbon atoms.

The amine oxide may be an oxide (eg, 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

It is preferable that the nonionic surfactant is a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). It is preferable that carbon number of the alkylene group in an oxyalkylene group is 2-10. In general, the number of oxyalkylene groups in the molecule of the nonionic surfactant is preferably 2 to 100.

The nonionic surfactant is selected from the group consisting of ether, ester, ester ether, alkanolamide, polyhydric alcohol and amine oxide, and is preferably a nonionic surfactant having an oxyalkylene group.

Nonionic surfactants are linear and/or branched aliphatic (saturated and/or unsaturated) alkylene oxide adducts, linear and/or branched fatty acid (saturated and/or unsaturated) polyalkylene glycols. An ester, a polyoxyethylene (POE)/polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, or the like may be used. Among these, the structure of the alkylene oxide addition portion and the polyalkylene glycol portion is preferably polyoxyethylene (POE) or polyoxypropylene (POP) or a POE/POP copolymer (random copolymer or block copolymer may be used). .

Further, the nonionic surfactant is preferably a structure that does not contain an aromatic group from environmental problems (biodegradability, environmental hormones, etc.).

Nonionic surfactants have the formula:

[In the formula, R ¹ is a C 1 to C 22 alkyl group or a C 2 to C 22 alkenyl group or acyl group,

Each of R ² is independently the same or different and is an alkylene group having 3 or more carbon atoms (eg, 3 to 10),

R ³ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms,

p is a number greater than or equal to 2,

q is a number greater than or equal to 0 or 1]

It may be a compound represented by

R ¹ is preferably 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. As a preferable specific example of R ¹ , a lauryl group, a tridecyl group, and an oleyl group are mentioned.

Examples of R ² are a propylene group and a butylene group.

In the nonionic surfactant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (eg, 5 to 200). That is, -(R ² O) _q -may form a polyoxyalkylene chain.

The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly, a polyoxyalkylene chain) in the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain. Among them, an oxypropylene chain is preferable.

Preferred nonionic surfactants are of the formula:

[In the formula, R ¹ and p have the same meaning as above]

It is a surfactant represented by.

Specific examples of nonionic surfactants,

[In the formula, p and q have the same meaning as above]

Etc.

Specific examples of the nonionic surfactant include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkane (C ₁₂ -C ₁₆ ) thiol, sorbitan mono fatty acid (C ₇ -C ₁₉ ) or alkyl (C ₁₂ -C ₁₈ ) Condensation products with amines and the like are included.

The proportion of the polyoxyethylene block may be 5 to 80% by weight, for example 30 to 75% by weight, in particular 40 to 70% by weight, relative to the molecular weight of the nonionic surfactant (copolymer).

The average molecular weight of the nonionic surfactant is generally 300 to 5,000, for example 500 to 3,000.

Nonionic surfactants may be used alone or in combination of two or more.

It is preferable that the nonionic surfactant is a combination of two or more. In a combination of two or more, the at least one nonionic surfactant is R ¹ O-(CH ₂ ), wherein the R ¹ group (and/or the R ³ group) is a branched alkyl group (eg, isotridecyl group). CH ₂ O) _p -(R ² O) _q -R ³ [particularly, R ¹ O-(CH ₂ CH ₂ O) _p -H] may be used. The amount of the nonionic surfactant in which the R ¹ group is a branched alkyl group may be 5 to 100 parts by weight, for example 8 to 50 parts by weight, particularly 10 to 40 parts by weight, based on the total 100 parts by weight of the nonionic surfactant. In a combination of two or more, the remaining nonionic surfactant, wherein the R ¹ group (and/or the R ³ group) is a (saturated and/or unsaturated) linear alkyl group (e.g., a lauryl group (n-ra) Uryl group)) R ¹ O-(CH ₂ CH ₂ O) _p -(R ² O) _q -R ³ [in particular, R ¹ O-(CH ₂ CH ₂ O) _p -H] do.

As a nonionic surfactant, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid Ester, polyoxyethylene glycerin fatty acid ester, polyglycerol fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkyl alkanolamide, acetylene glycol, oxyethylene adduct of acetylene glycol And polyethylene glycol polypropylene glycol block copolymers.

(4-2) cationic surfactant

It is preferable that the cationic surfactant is a compound which does not have an amide group.

Examples of cationic surfactants include amines, amine salts, quaternary ammonium salts, imidazoline and imidazolinium salts.

The cationic surfactant is preferably an amine salt, a quaternary ammonium salt, or an oxyethylene addition type ammonium salt. Specific examples of the cationic surfactant are not particularly limited, but amine salt-type surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives and imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, And quaternary ammonium salt-type surfactants such as pyridinium salts, alkyl isoquinolinium salts, benzethonium chloride, and the like.

Examples of cationic surfactants are:

[In the formula, each of R ²¹ , R ²² , R ²³ and R ²⁴ is independently the same or different, and a hydrogen atom or a hydrocarbon group having 1 to 50 carbon atoms,

X is an anionic group]

It is a compound of. The hydrocarbon group may have an oxygen atom, and may be, for example, an oxyalkylene such as a polyoxyalkylene group (the alkylene has 2 to 5 carbon atoms, for example). R ²¹ , R ²² , R ²³ and R ²⁴ are preferably a hydrocarbon group having 1 to 30 carbon atoms (eg, an aliphatic hydrocarbon, an aromatic hydrocarbon or an aromatic aliphatic hydrocarbon).

Specific examples of R ²¹ , R ²² , R ²³ and R ²⁴ include an alkyl group (e.g., a methyl group, a butyl group, a stearyl group, a palmityl group), an aryl group (e.g., a phenyl group), an aralkyl group (e.g. For example, it is a benzyl group (phenylmethyl group) and a phenethyl group (phenylethyl group)).

Specific examples of X are halogens (eg, chlorine), acids (eg, inorganic acids such as hydrochloric acid, organic acids such as acetic acid (especially fatty acids)).

It is particularly preferable that the cationic surfactant is a monoalkyltrimethylammonium salt (alkyl has 4 to 30 carbon atoms).

The cationic surfactant is preferably an ammonium salt, particularly a quaternary ammonium salt. Cationic surfactants have the formula:

[In the formula, each of R ³¹ is independently the same or different, and a C ₁₂ or more (eg, C ₁₂ to C ₅₀ ) linear and/or branched aliphatic (saturated and/or unsaturated) group,

Each of R ³² is independently the same or different, and H or a C1 to 4 alkyl group, a benzyl group, or a polyoxyethylene group (the number of oxyethylene groups, such as 1 (especially 2, particularly 3) to 50) ( CH ₃ , C ₂ H ₅ are particularly preferred),

X is a halogen atom (e.g., chlorine and bromine), C ₁ to C ₄ fatty acid base,

p is 1 or 2, q is 2 or 3, and p+q=4]

It may be an ammonium salt represented by. The number of carbon atoms of R ³¹ may be 12 to 50, for example 12 to 30.

Specific examples of the cationic surfactant include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, Methyl dodecyldi (hydropolyoxyethylene) ammonium chloride and benzyl dodecyldi (hydropolyoxyethylene) ammonium chloride are included.

(4-3) anionic surfactant

The anionic surfactant is preferably a salt of an organic acid (for example, a salt of an organic acid and an inorganic base or an amine).

Specific examples of the anionic surfactant include sodium lauryl sulfate, triethanolamine lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene nonylphenyl ether sulfate, triethanolamine polyoxyethylene lauryl ether sulfate, sodium cocoyl sarcosine, Sodium N-cocoylmethyltaurine, sodium polyoxyethylene palm alkyl ether sulfate, sodium dietherhexylsulfosuccinate, sodium α-olefin sulfonate, sodium lauryl phosphate, sodium polyoxyethylene lauryl ether phosphate, perfluoroalkylcarboxylate (Brand name UNIDAIN DS-101, 102 (made by Daikin Kogyo Co., Ltd.)), etc. are mentioned.

(4-4) amphoteric surfactant

Specific examples of the amphoteric surfactant include alanine, imidazolinium betaine, amide betaine, and betaine acetate. Specifically, lauryl betaine, stearyl betaine, lauryl carboxymethylhydroxy Ethyl imidazolium betaine, lauryl dimethyl amino acetate betaine, fatty acid amidopropyl dimethyl amino acetate betaine, and the like.

Each of a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant may be one or a combination of two or more.

The amount of the polymerization surfactant may be 0.05 to 20 parts by weight, for example 0.1 to 10 parts by weight, based on 100 parts by weight of the water and oil repellent polymer.

(5) other ingredients

The surface treatment agent may contain at least one of a non-fluorine water-repellent compound and an additive as other components other than a water-repellent polymer, a liquid medium, and a surfactant.

(5-1) Non-fluorine water repellent compound

The surface treatment agent may contain a water repellent compound that does not contain a fluorine atom (a non-fluorine water repellent compound).

The non-fluorine water-repellent compound may be a non-fluorine acrylate polymer, a saturated or unsaturated hydrocarbon compound, or a silicone compound.

The non-fluorine acrylate polymer is a homopolymer composed of one type of non-fluorine acrylate monomer, or a copolymer composed of at least two types of non-fluorine acrylate monomer, or at least one type of non-fluorine acrylate monomer and It is a copolymer composed of at least one other non-fluorinated monomer (ethylenically unsaturated compound, for example, ethylene, vinyl monomer).

The non-fluorine acrylate monomer constituting the non-fluorine acrylate polymer is of the formula:

[In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom, and an iodine atom),

T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a chain or cyclic organic group having 1 to 31 carbon atoms having an ester bond]

It is a compound represented by.

Examples of a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms include a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and a 7 to 30 carbon number. It is an aromatic aliphatic hydrocarbon group.

Examples of a chain or cyclic C1-C31 organic group having an ester bond include -C(=O)-OQ and -OC(=O)-Q (wherein Q is a straight chain or branched C1-C30 An aliphatic hydrocarbon group, a cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic aliphatic hydrocarbon group having 7 to 30 carbon atoms).

Examples of the non-fluorine acrylate monomer include, for example, alkyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, and methoxy polypropylene. Glycol (meth)acrylate is included.

It is preferable that the non-fluorine acrylate monomer is an alkyl (meth)acrylate ester. The number of carbon atoms in the alkyl group may be 1 to 30, or may be, for example, 6 to 30 (eg, 10 to 30). Specific examples of the non-fluorine acrylate monomer are lauryl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate.

The non-fluorine acrylate polymer can be produced by the same polymerization method as the water and oil repellent polymer.

The saturated or unsaturated hydrocarbon-based compound is preferably a saturated hydrocarbon. In a saturated or unsaturated hydrocarbon-based compound, the number of carbon atoms may be 15 or more, preferably 20 to 300, for example 25 to 100. Specific examples of the saturated or unsaturated hydrocarbon-based compound are paraffin.

Silicone compounds are generally used as water repellents. The silicone compound is not limited as long as it is a compound exhibiting water repellency.

The amount of the non-fluorine water-repellent compound may be 500 parts by weight or less, for example 5 to 200 parts by weight, particularly 5 to 100 parts by weight, based on 100 parts by weight of the water and oil repellent polymer.

(5-2) additive

The surface treatment agent may contain an additive.

Examples of additives are silicon-containing compounds, waxes, and acrylic emulsions. Other examples of additives include other fluorine-containing polymers, drying rate modifiers, crosslinking agents, film forming aids, compatibilizers, surfactants, antifreeze agents, viscosity modifiers, ultraviolet absorbers, antioxidants, pH modifiers, antifoaming agents, texture modifiers, slip modifiers, Antistatic agents, hydrophilic agents, antibacterial agents, preservatives, insect repellents, fragrances, and flame retardants.

The water-and-oil-repellent polymer and the non-fluorine polymer in the present invention can be produced by any of the usual polymerization methods, and the conditions of the polymerization reaction can also be arbitrarily selected. As such a polymerization method, solution polymerization, suspension polymerization, and emulsion polymerization are mentioned.

In solution polymerization, a method of dissolving a monomer in an organic solvent in the presence of a polymerization initiator and nitrogen substitution, followed by heating and stirring in a range of 30 to 120°C for 1 to 10 hours is employed. As a polymerization initiator, for example, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydica Lebonate, etc. are mentioned. The polymerization initiator is used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, based on 100 parts by weight of the monomer.

The organic solvent is inert to the monomer and dissolves them, and, for example, esters (e.g., esters having 2 to 30 carbon atoms, specifically ethyl acetate, butyl acetate), ketones (e.g., 2 to 30 carbon atoms) Ketone, specifically methyl ethyl ketone, diisobutyl ketone), alcohol (for example, alcohol having 1 to 30 carbon atoms, specifically isopropyl alcohol) may be used. Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone. , Methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodi Fluoroethane, trichlorotrifluoroethane, and the like. The organic solvent is used in a range of 10 to 2000 parts by weight, for example 50 to 1000 parts by weight, based on 100 parts by weight of the total monomers.

In emulsion polymerization, in the presence of a polymerization initiator and an emulsifier, a method of emulsifying a monomer in water and replacing it with nitrogen, followed by stirring at 50 to 80° C. for 1 to 10 hours to polymerize is employed. The polymerization initiator is benzoyl peroxide, lauroyl peroxide, t-butylperbenzoate, 1-hydroxycyclohexylhydro peroxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine-dihydrochloride, azobis Water-soluble ones such as isobutyronitrile, sodium peroxide, potassium persulfate, and ammonium persulfate, or azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t -Soluble things, such as butyl peroxy pivalate and diisopropyl peroxy dicarbonate, are used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the monomer.

In order to obtain an aqueous polymer dispersion having excellent standing stability, it is preferable to polymerize the monomer by micronizing it in water using an emulsifying device capable of imparting strong crushing energy such as a high pressure homogenizer or an ultrasonic homogenizer. In addition, various anionic, cationic or nonionic emulsifiers can be used as the emulsifier, and are used in the range of 0.5 to 20 parts by weight based on 100 parts by weight of the monomer. It is preferred to use anionic and/or nonionic and/or cationic emulsifiers. When the monomers are not compatible at all, it is preferable to add a compatibilizing agent sufficiently compatible with these monomers, for example, a water-soluble organic solvent or a monomer having a low molecular weight. By adding a compatibilizing agent, it is possible to improve emulsification and copolymerization.

Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc., and 1 to 50 parts by weight based on 100 parts by weight of water , For example, you may use in the range of 10 to 40 parts by weight. Further, examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, and the like, and from 1 to 100 parts by weight of the total amount of the monomer You may use it in a range of 50 parts by weight, for example, 10 to 40 parts by weight.

In polymerization, you may use a chain transfer agent. The molecular weight of the polymer can be changed according to the amount of the chain transfer agent used. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (especially (e.g., alkyl mercaptans having 1 to 30 carbon atoms), sodium hypophosphite, sodium hydrogen sulfite, etc.) Salt, etc. The amount of the chain transfer agent to be used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the monomers.

The treatment agent of the present invention may be in the form of a solution, an emulsion (particularly, an aqueous dispersion) or an aerosol, but is preferably an aqueous dispersion. The treatment agent contains a water-repellent polymer (active ingredient of a surface treatment agent) and a medium (especially a liquid medium, such as an organic solvent and/or water). The amount of the medium may be, for example, 5 to 99.9% by weight, particularly 10 to 80% by weight, based on the treatment agent.

In the treatment agent, the concentration of the water and oil repellent polymer may be 0.01 to 95% by weight, for example 5 to 50% by weight.

The treatment agent of the present invention can be applied to an object to be treated by a conventionally known method. In general, a method of dispersing the treatment agent in an organic solvent or water, diluting it, attaching it to the surface of the object to be treated, and drying it by a known method such as immersion coating, spray coating, bubble coating, or the like is employed. Further, if necessary, curing may be performed by applying together with an appropriate crosslinking agent (eg, block isocyanate). In addition, it is also possible to add an insect repellent, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent, and the like to the treatment agent of the present invention and use in combination. The concentration of the water- and oil-repellent polymer in the treatment liquid to be brought into contact with the substrate may be 0.01 to 10% by weight (especially in the case of immersion coating), for example, 0.05 to 10% by weight.

Examples of the object to be treated with the treatment agent of the present invention (e.g., water and oil repellent) include textile products, stone materials, filters (e.g., electrostatic filters), dust masks, and components of fuel cells (e.g., gas diffusion) Electrodes and gas diffusion support), glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plasters. As a textile product, various examples can be mentioned. For example, natural fibers of animal and vegetable origin such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic such as rayon and acetate Inorganic fibers such as fibers, glass fibers, carbon fibers, and asbestos fibers, or mixed fibers thereof.

The fiber product may be in any form of fiber or cloth.

The treatment agent of the present invention can also be used as an internal mold release agent or an external mold release agent.

The water and oil repellent polymer can be applied to fibrous substrates (eg, fibrous products, etc.) by any of the known methods for treating fibrous products with liquids. When the textile product is a cloth, the cloth may be immersed in a solution, or the solution may be adhered or sprayed onto the cloth. The treated fiber product is dried and preferably heated at, for example, 100° C. to 200° C. in order to develop oil repellency.

Alternatively, the water and oil repellent polymer may be applied to a fiber product by a cleaning method, or may be applied to a fiber product in, for example, a laundry application or a dry cleaning method.

The fibrous products to be treated are typically fabrics, which include fabrics, knitted and nonwoven fabrics, fabrics and carpets in the form of clothing, but fibrous or yarn or intermediate fibrous products (e.g., sliver or irradiated絲) etc.) may be sufficient. Fiber product materials are natural fibers (e.g., cotton or wool, etc.), chemical fibers (e.g., viscose rayon or rheocell, etc.), or synthetic fibers (e.g., polyester, polyamide or acrylic fibers, etc.) ) May be sufficient, or a mixture of fibers (for example, a mixture of natural fibers and synthetic fibers, etc.) may be used. The water and oil repellent polymer of the present invention is particularly effective in making cellulose fibers (eg, cotton or rayon) oleophobic and oil repellent. In addition, the method of the present invention generally renders the fiber product hydrophobic and water repellent.

Alternatively, the fibrous substrate may be leather. In order to make the leather hydrophobic and oleophobic, the water- and oil-repellent polymer may be applied to the leather as an aqueous solution or water-based emulsion at various stages of leather processing, for example, during the wet processing of the leather, or during the finishing period of the leather. do.

Alternatively, the fibrous substrate may be paper. The water and oil repellent polymer may be applied to paper formed in advance, or may be applied at various stages of paper making, for example, during the drying period of the paper.

"Treatment" means applying a treatment agent to an object to be treated by immersion, spraying, coating, or the like. By the treatment, the polymer, which is an active ingredient of the treatment agent, penetrates into the interior of the target object and/or adheres to the surface of the target object.

Example

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

In the following, parts or% or ratio represent parts by weight or% by weight or a weight ratio unless otherwise specified.

The procedure of the test is as follows.

Water repellency test

According to the spray method of JIS-L-1092 (AATCC-22), the water repellency of the treated cloth was evaluated. As shown in Table 1 described below, it is represented by water repellency No. The higher the score, the better the water repellency, and depending on the state, the median value (95, 85, 75), and the superiority and inferiority are given by +-

Checkability

The aqueous dispersion of the polymer is diluted with tap water so that the solid content concentration is 1.8% by weight, and a pad that can be adjusted to a temperature of 40°C is placed in a treatment bath, and a cotton cloth is rounded on a mangle roll to allow continuous treatment, and a pressure of 5.5kgf/ Continuous treatment was performed in cm 2. The appearance of the adhesion of the polymer to the mangle after 1 hour was observed, and the inspection property was judged according to the criteria in Table 2 below.

Manufacturing Example 1

In a 500mL autoclave, C ₆ F ₁₃ CH ₂ CH ₂ OCOC(CH ₃ )=CH ₂ (C6SFMA)=80g, stearyl acrylate=20g, pure water=200g, tripropylene glycol=30g, polyoxyethylene(POE)ole One ether = 3 g and polyoxyethylene (POE) isotridecyl ether = 7 g were added, and the mixture was emulsified and dispersed by ultrasonic waves at 60° C. for 15 minutes under stirring. After emulsification, after nitrogen substitution in the autoclave, 2,2-azobis(2-amidinopropane) dihydrochloride = 1 g was added and reacted at 60° C. for 3 hours to obtain an aqueous dispersion of a polymer. In addition, the solid content concentration in pure water was adjusted to 30%.

Manufacturing Example 2

In a 500mL autoclave, C ₆ F ₁₃ CH ₂ CH ₂ OCOC(CH ₃ )=CH ₂ (C6SFMA)=80g, stearyl acrylate=20g, pure water=200g, tripropylene glycol=30g, polyoxyethylene(POE)ole Il ether = 3 g, polyoxyethylene (POE) isotridecyl ether = 4 g, dioctadecyl dimethyl ammonium chloride (DOdDMAC) = 3 g were added, and emulsified and dispersed at 60° C. for 15 minutes by ultrasonic waves under stirring. After emulsification, after nitrogen substitution in the autoclave, 2,2-azobis(2-amidinopropane) dihydrochloride = 1 g was added and reacted at 60° C. for 3 hours to obtain an aqueous dispersion of a polymer. In addition, the solid content concentration in pure water was adjusted to 30%.

Manufacturing Example 3

In a 500 mL autoclave, C ₆ F ₁₃ CH ₂ CH ₂ OCOC(CH ₃ )=CH ₂ (C6SFMA)=60g, stearyl acrylate=10g, isobornyl methacrylate=10g, pure water=200g, tripropylene glycol= 30 g, polyoxyethylene (POE) oleyl ether = 3 g, and polyoxyethylene (POE) isotridecyl ether = 7 g were added, followed by emulsification and dispersion at 60° C. for 15 minutes by ultrasonic waves under stirring. After emulsification, after nitrogen substitution in the autoclave, vinyl chloride (VCM) = 20 g was press-fitted, 2,2-azobis (2-amidinopropane) dihydrochloride = 1 g was added, and reacted at 60° C. for 3 hours. An aqueous dispersion of the polymer was obtained. In addition, the solid content concentration in pure water was adjusted to 30%.

Manufacturing Example 4

In a 500mL autoclave, C ₆ F ₁₃ CH ₂ CH ₂ OCOC(Cl)=CH ₂ (C6SFCLA)=80g, stearyl acrylate=20g, pure water=200g, tripropylene glycol=30g, polyoxyethylene (POE)oleyl Ether = 3 g and polyoxyethylene (POE) isotridecyl ether = 7 g were added, followed by emulsification and dispersion by ultrasonic waves at 60° C. for 15 minutes under stirring. After emulsification, after nitrogen substitution in the autoclave, 2,2-azobis(2-amidinopropane) dihydrochloride = 1 g was added and reacted at 60° C. for 3 hours to obtain an aqueous dispersion of a polymer. In addition, the solid content concentration in pure water was adjusted to 30%.

Manufacturing Example 5

In a 500 mL autoclave, C ₆ F ₁₃ CH ₂ CH ₂ OCOC(Cl)=CH ₂ (C6SFCLA)=60 g, lauryl acrylate=20 g, isobornyl methacrylate=20 g, pure water=200 g, tripropylene glycol=30 g , Polyoxyethylene (POE) oleyl ether = 3 g, and polyoxyethylene (POE) isotridecyl ether = 7 g were added, followed by emulsification and dispersion at 60° C. for 15 minutes by ultrasonic waves under stirring. After emulsification, after nitrogen substitution in the autoclave, 2,2-azobis(2-amidinopropane) dihydrochloride = 1 g was added and reacted at 60° C. for 3 hours to obtain an aqueous dispersion of a polymer. In addition, the solid content concentration in pure water was adjusted to 30%.

Manufacturing Example 6

In a 500 mL autoclave, C ₆ F ₁₃ CH ₂ CH ₂ OCOC(Cl)=CH ₂ (C6SFCLA)=40g, lauryl acrylate=20g, isobornyl methacrylate=20g, pure water=200g, tripropylene glycol=30g , Polyoxyethylene (POE) oleyl ether = 3 g, and polyoxyethylene (POE) isotridecyl ether = 7 g were added, followed by emulsification and dispersion at 60° C. for 15 minutes by ultrasonic waves under stirring. After emulsification, after nitrogen substitution in the autoclave, vinyl chloride (VCM) = 20 g was press-fitted, 2,2-azobis (2-amidinopropane) dihydrochloride = 1 g was added, and reacted at 60° C. for 3 hours. An aqueous dispersion of the polymer was obtained. In addition, the solid content concentration in pure water was adjusted to 30%.

Manufacturing Example 7

Stearyl acrylate = 90 g, 2,3-dihydroxypropyl methacrylate = 10 g, pure water = 200 g, tripropylene glycol = 30 g, polyoxyethylene (POE) oleyl ether = 3 g, polyoxyethylene in a 500 mL autoclave (POE) Isotridecyl ether=7 g was put, and it emulsified and dispersed by ultrasonic wave at 60 degreeC for 15 minutes under stirring. After emulsification, after nitrogen substitution in the autoclave, 2,2-azobis(2-amidinopropane) dihydrochloride = 1 g was added and reacted at 60° C. for 3 hours to obtain an aqueous dispersion of a polymer. In addition, the solid content concentration in pure water was adjusted to 30%.

Manufacturing Example 8

Stearyl acrylate = 70 g, 2,3-dihydroxypropyl methacrylate = 10 g, pure water = 200 g, tripropylene glycol = 30 g, polyoxyethylene (POE) oleyl ether = 3 g, polyoxyethylene in a 500 mL autoclave (POE) Isotridecyl ether=7 g was put, and it emulsified and dispersed by ultrasonic wave at 60 degreeC for 15 minutes under stirring. After emulsification, after nitrogen substitution in the autoclave, 2,2-azobis(2-amidinopropane) dihydrochloride = 1 g was added, and after reacting at 60° C. for 1 hour, vinyl chloride = 20 g was press-fitted, and further The reaction was carried out for 2 hours to obtain an aqueous dispersion of a polymer. In addition, the solid content concentration in pure water was adjusted to 30%.

The composition for each preparation example is summarized in Table 3.

Example 1

To 100 parts of the polymerization dispersion (30%) prepared in Production Example 1, 0.1 part of a 30% aqueous solution of polydiallyldimethylammonium chloride (molecular weight 9000) (PDADMAC-9000) was mixed to prepare an aqueous dispersion. A test solution was prepared by diluting this dispersion with tap water so that the solid content concentration was 0.15% by weight, 0.30% by weight, and 0.60% by weight, and a polyester cloth was immersed in the test solution, then passed through a mangle, and at 160°C for 2 minutes. , Water repellency was evaluated with a heat-treated test cloth (low concentration water repellency). Further, the water repellency was similarly evaluated for the test solution diluted with tap water so that the solid content concentration of the dispersion was 0.60% by weight and the disperse dye was 0.006% by weight. Moreover, the inspectionability was evaluated.

Example 2

To 100 parts of the polymerization dispersion (30%) prepared in Preparation Example 1, 0.1 part of a 30% aqueous solution of polydiallyldimethylammonium chloride (molecular weight 30000) (PDADMAC-30000) was mixed to prepare an aqueous dispersion. It evaluated in the same manner as in 1.

Example 3

To 100 parts of the polymerization dispersion (30%) prepared in Production Example 1, 0.5 parts of a 30% aqueous solution of polydiallyldimethylammonium chloride (molecular weight 30000) (PDADMAC-30000) was mixed to prepare an aqueous dispersion. It evaluated in the same manner as in 1.

Example 4

To 100 parts of the polymerization dispersion (30%) prepared in Production Example 1, 0.1 part of a 30% aqueous solution of dimethylamine epichlorohydrin condensate (molecular weight 9000) (PDMAECH-9000) was mixed to prepare an aqueous dispersion. , Evaluation was performed in the same manner as in Example 1.

Examples 5 to 11

To 100 parts of the polymerization dispersion (30%) prepared in Preparation Examples 2 to 8, 0.1 part of a 30% aqueous solution of polydiallyldimethylammonium chloride (molecular weight 30000) (PDADMAC-30000) was mixed to prepare an aqueous dispersion, Evaluation was performed in the same manner as in Example 1.

Comparative Example 1

Nothing was added to the polymerization dispersion (30%) prepared in Production Example 1, and evaluation was performed in the same manner as in Example 1.

Comparative Example 2

To 100 parts of the polymerization dispersion (30%) prepared in Production Example 1, 0.1 part of a 30% aqueous solution of polyoxyethylene tallow alkylbenzyl ammonium chloride (TBzPOEC) was mixed to prepare an aqueous dispersion, and evaluated in the same manner as in Example 1. Was done.

Comparative Example 3

An aqueous dispersion was prepared in which 0.1 part of a 30% aqueous solution of lauryl dimethylamine oxide (LDMAO) was mixed with 100 parts of the polymerization dispersion (30%) prepared in Production Example 1, and evaluation was performed in the same manner as in Example 1. I did.

Comparative Example 4

An aqueous dispersion was prepared in which 0.1 part of a 30% aqueous solution of dimethylaminopropylamide stearate (StDMAPAD) was mixed with 100 parts of the polymerization dispersion (30%) prepared in Production Example 1, and evaluation was performed in the same manner as in Example 1. I did.

Comparative Examples 5 to 8

Production Example 1 was prepared and evaluated in the same manner as Comparative Examples 1 to 4 in place of Production Example 8.

The performance of each example is shown in Tables 4 and 5.

The surface treatment agent of the present invention can be used as, for example, a water and oil repellent agent, an antifouling agent, and a soil releasing agent.

Claims (14)

(A) a water and oil repellent polymer having a repeating unit derived from one or both of a fluorine-containing monomer (A1) having a fluoroalkyl group and a long-chain (meth)acrylate ester monomer (A2),
(B) a polymeric surfactant, and
(C) liquid medium
As a surface treatment agent containing,
Fluorine-containing monomer (A1) is the formula:

[In the formula, X is a hydrogen atom, CH ₃ , CN, CF ₃ or a halogen atom,
Y is -O- or -NH-,
Z is a direct bond, or
A linear or branched aliphatic group having 1 to 20 carbon atoms, or
Group represented by the formula -R ² (R ¹ )N-SO ₂ -or the formula -R ² (R ¹ )N-CO- (in the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms, and R ² is, A linear alkylene group or a branched alkylene group having 1 to 10 carbon atoms), or
Formula -CH ₂ CH(OR ³ )CH ₂ -(Ar-O) _p -(In the formula, R ³ is a hydrogen atom or an acyl group having 1 to 10 carbon atoms, Ar is an arylene group, p is 0 or 1 A group represented by), or
A group represented by the formula -CH ₂ -Ar-(O) _q- (wherein Ar is an arylene group, q is 0 or 1), or
-(CH ₂ ) _m -SO ₂ -(CH ₂ ) _n -group or -(CH ₂ ) _m -S-(CH ₂ ) _n -group (however, m is 1 to 10, n is 0 to 10) ego,
Rf is a C1-C20 fluoroalkyl group]
It is a compound represented by,
Long-chain (meth)acrylate ester monomer (A2) has the formula:

[In the formula, A ¹¹ is a hydrogen atom or a methyl group,
A ¹² is a C18 to C30 linear or branched hydrocarbon group]
It is a compound represented by,
Polymeric surfactant (B) is the formula:

[In the formula, X is a halogen atom or a fatty acid base of C ₁ to C ₄ ,
Each Y is the same or different, and is a hydrocarbon group having 1 to 10 carbon atoms which may have a direct bond or a monovalent or divalent oxygen atom,
At least two Y may form a ring together with an adjacent nitrogen atom,
r is 1 or 2]
It is a quaternary ammonium salt polymer having a repeating unit represented by,
The total amount of the fluorine-containing monomer (A1) and the long-chain (meth)acrylate ester monomer (A2) is 30 to 100% by weight based on the water and oil repellent polymer, and the amount of the high molecular surfactant (B) is the water and oil repellent polymer. (A) 0.01 to 10 parts by weight based on 100 parts by weight of the surface treatment agent. The method of claim 1,
In the fluorine-containing monomer (A1), X is CH ₃ or Cl, and Rf is a perfluoroalkyl group having 1 to 6 carbon atoms. The method of claim 1,
The water and oil repellent polymer is a water and oil repellent polymer having a repeating unit derived from a fluorine-containing monomer (A1) having a fluoroalkyl group and a long-chain (meth)acrylate ester monomer (A2), or
It is a water and oil repellent polymer having a repeating unit derived from a fluorine-containing monomer (A1) having a fluoroalkyl group, but not having a repeating unit derived from a long-chain (meth)acrylate ester monomer (A2), or
It is a water and oil repellent polymer having a repeating unit derived from a long-chain (meth)acrylate ester monomer (A2), but not having a repeating unit derived from a fluorine-containing monomer (A1) having a fluoroalkyl group,
The water and oil repellent polymer,
(A3) a repeating unit derived from a non-fluorine non-crosslinkable monomer and
(A4) Repeating unit derived from non-fluorine crosslinkable monomer
Have at least one more of,
The non-fluorine non-crosslinkable monomer (A3) has the general formula:

[In the formula, A ¹ is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom,
A ² is an alkyl group represented by C _n H _2n+1 (however, n=1 to 17).
Acrylate represented by,
(Meth)acrylate monomer having a cyclic hydrocarbon group to which a monovalent cyclic hydrocarbon group and a monovalent (meth)acrylate group are directly bonded, and
Halogenated olefins having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms
It is at least one compound selected from the group consisting of,
The surface treatment agent in which the non-fluorine crosslinkable monomer (A4) is a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group. The method according to any one of claims 1 to 3,
The polymeric surfactant (B) has the formula:

[In the formula, X is a halogen atom or a fatty acid base of C ₁ to C ₄ ,
Y ¹ , Y ² , Y ³ and Y ⁴ are a divalent aliphatic group having 1 to 10 carbon atoms which may have a direct bond or an oxygen atom,
Y ² and Y ³ may form a ring together with an adjacent nitrogen atom,
Z ¹ and Z ² are C 1 to C 10 linear and/or branched aliphatic groups,
r is 1 or 2,
n is a number of 2 or more]
A surface treatment agent which is a compound represented by. The method according to any one of claims 1 to 3,
A surface treatment agent having a weight average molecular weight of 3,000 to 100,000 of the high molecular surfactant (B). The method according to any one of claims 1 to 3,
The amount of the liquid medium (C) is 30 to 99.1% by weight based on the surface treatment agent, the surface treatment agent. The method of claim 3,
The sum of the fluorine-containing monomer (A1) and the long-chain (meth)acrylate ester monomer (A2) is 32 to 98% by weight based on the water and oil repellent polymer,
The amount of the non-fluorine non-crosslinkable monomer (A3) is 2 to 68% by weight based on the water and oil repellent polymer,
The amount of the non-fluorine crosslinkable monomer (A4) is 50 parts by weight or less with respect to 100 parts by weight in total of the fluorine-containing monomer (A1) and the long-chain (meth)acrylate ester monomer (A2). The method according to any one of claims 1 to 3,
The surface treatment agent is a water-and-oil-repellent agent, an antifouling agent, or a pollution desorbing agent. (I) In the presence of a liquid medium, a fluorine-containing monomer (A1) having a fluoroalkyl group and a monomer containing one or both of the long-chain (meth)acrylate ester monomer (A2) are polymerized to obtain a fluorine-containing monomer (A1) And a step of obtaining an aqueous dispersion of a water and oil repellent polymer having repeating units derived from one or both of the long-chain (meth)acrylate ester monomer (A2), and
(Ii) The process of adding a polymeric surfactant to the aqueous dispersion of the water and oil repellent polymer
A method for producing the surface treatment agent according to any one of claims 1 to 3, having a. A method for producing a treated substrate comprising applying the surface treatment agent according to any one of claims 1 to 3 to the substrate. delete delete delete delete