JP2019026746A - Water repellent composition - Google Patents

Abstract

To provide a water repellent composition which does not use a fluorine-containing monomer, especially a fluoroalkyl group-containing monomer.SOLUTION: The water repellent composition contains: (1) a polymer comprising a repeating unit derived from (a) a nitrogen-containing monomer represented by formula CH=C(-R)-C(=O)-Y-Z(-Y-R)[where Ris a C7-40 hydrocarbon group; Ris a hydrogen atom or a methyl group; Yis -O- or -NH-; Yis -O-C(=O)-NH- or -NH-C(=O)-NH-; Z is a divalent or trivalent C1-5 hydrocarbon group; and n is 1 or 2] in an amount of 30-100 wt.% based on the polymer; and (2) a liquid medium.SELECTED DRAWING: None

Description

  The present invention relates to a water repellent composition.

Conventionally, a fluorine-containing water and oil repellent containing a fluorine compound is known. This water / oil repellent exhibits good water / oil repellency when treated on a substrate such as a textile product.
From recent research results [EPA report "PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS" (http://www.epa.gov/opptintr/pfoa/pfoara.pdf)] Concerns about the environmental impact of PFOA (perfluorooctanoic acid), a type of fluoroalkyl compound, have become apparent, and on April 14, 2003, EPA (US Environmental Protection Agency) will strengthen scientific research on PFOA Announced.
Meanwhile, Federal Register (FR Vol.68, No.73 / April 16, 2003 [FRL-2303-8], http://www.epa.gov/opptintr/pfoa/pfoafr.pdf) and EPA Environmental News FOR RELEASE : MONDAY APRIL 14, 2003 EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID (http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf) and EPA OPPT FACT SHEET April 14, 2003 (http: // www. epa.gov/opptintr/pfoa/pfoafacts.pdf) publishes that telomers can produce PFOA by degradation or metabolism (telomers mean long chain fluoroalkyl groups). We also announced that telomers are used in many products such as foam, water- and oil-repellent and antifouling foams, care products, cleaning products, carpets, textiles, paper and leather. Yes. There is concern about the accumulation of fluorine-containing compounds in the environment.

JP 2006-328624 A is a water repellent comprising a non-fluorine polymer containing a (meth) acrylic acid ester having 12 or more carbon atoms in the ester moiety as a monomer unit, the (meth) acrylic acid ester Discloses a water repellent that is 80 to 100% by mass with respect to the total amount of monomer units constituting the non-fluorine polymer.
However, this water repellent is inferior in water repellency.

  WO2015 / 076347 discloses a surface treatment agent comprising a non-fluorine polymer comprising a long-chain (meth) acrylate ester monomer and an amidoamine surfactant, and WO2015 / 080026 describes a single amount of a long-chain (meth) acrylate ester And a surface treatment agent comprising a (meth) acrylate monomer having a cyclic hydrocarbon group. In these surface treatment agents, no fluoroalkyl group-containing monomer is used.

JP 2006-328624 WO2015 / 076347 WO2015 / 080026

  An object of the present invention is to provide a water repellent composition that gives excellent water repellency and does not use a fluoroalkyl group-containing monomer, preferably a fluorine-containing monomer.

The present invention
(1) (a) 30-100% by weight of polymer, formula:
formula:
^{_{CH 2 = C (-R 2)}} -C (= O) -Y 1 -Z (-Y 2 -R 1) n
[Wherein R ¹ is a hydrocarbon group having 7 to 40 carbon atoms,
R ² is a hydrogen atom or a methyl group,
Y ¹ is —O— or —NH—;
Y ² is —O—C (═O) —NH— or —NH—C (═O) —NH—,
Z is a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms,
n is 1 or 2. ]
The polymer which has a repeating unit derived from the nitrogen-containing monomer shown by these.
According to one aspect, the present invention provides:
(1) (a) 30-100% by weight of polymer, formula:
formula:
^{_{CH 2 = C (-R 2)}} -C (= O) -Y 1 -Z (-Y 2 -R 1) n
[Wherein R ¹ is a hydrocarbon group having 7 to 40 carbon atoms,
R ² is a hydrogen atom or a methyl group,
Y ¹ is —O— or —NH—;
Y ² is —O—C (═O) —NH— or —NH—C (═O) —NH—,
Z is a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms,
n is 1 or 2. ]
A polymer having a repeating unit derived from a nitrogen-containing monomer represented by the formula (2) and (2) a water repellent composition comprising a liquid medium.

Since the water repellent composition of the present invention does not use a fluoroalkyl group-containing monomer, there is no concern about accumulation of fluorine-containing compounds in the environment. The water repellent composition of the present invention gives excellent water repellency to a substrate.
The stability (emulsion stability) of the water repellent composition of the present invention is good. The water repellent composition of the present invention is excellent in water / oil repellency (particularly water repellency) durability (particularly washing durability). Furthermore, it is excellent in processing stability at the time of water repellent treatment.

  The water repellent composition comprises (1) a polymer and (2) a liquid medium. The water repellent composition may further contain (3) a surfactant.

(1) Polymer The polymer of the present invention is a polymer having no fluoroalkyl group. The polymer of the present invention is preferably a non-fluorine polymer having no fluorine atom.
In the present invention, the polymer is
(A) It has a repeating unit derived from a nitrogen-containing monomer.
The polymer is further derived from (b) a polymerizable monomer other than the nitrogen-containing monomer (a), preferably derived from a non-fluorine polymerizable monomer other than the monomer (a). You may have a unit.

The polymerizable monomer other than the monomer (a) may be a non-fluorine non-crosslinkable monomer or a non-fluorine crosslinkable monomer.
Non-fluorine non-crosslinkable monomers have the formula:
CH ₂ = CA-T
[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 represents a hydrogen atom, a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom), a linear or cyclic hydrocarbon group having 1 to 40 carbon atoms, or a linear or cyclic group having an ester bond. An organic group having 2 to 41 carbon atoms. ]
It may be a compound shown by these.

  Examples of the linear or cyclic hydrocarbon group having 1 to 40 carbon atoms include a linear or branched saturated or unsaturated (eg, ethylenically unsaturated) aliphatic hydrocarbon group having 1 to 40 carbon atoms, carbon number 4 to 40 saturated or unsaturated (for example, ethylenically unsaturated) cycloaliphatic groups, C6 to C40 aromatic hydrocarbon groups, and C7 to C40 araliphatic hydrocarbon groups.

  Examples of the linear or cyclic organic group having 2 to 41 carbon atoms having an ester bond are -C (= O) -OQ and -OC (= O) -Q (where Q is 1 to 40 carbon atoms). A linear or branched saturated or unsaturated (eg ethylenically unsaturated) aliphatic hydrocarbon group, a saturated or unsaturated (eg ethylenically unsaturated) cyclic aliphatic group having 4 to 40 carbon atoms, carbon An aromatic hydrocarbon group having 6 to 40 carbon atoms and an araliphatic hydrocarbon group having 7 to 40 carbon atoms).

  The non-fluorine crosslinkable monomer is as described later.

Examples of polymerizable monomers other than the monomer (a) are as follows.
(B) an acrylate ester monomer,
(C) a non-fluorine crosslinkable monomer,
(D) a halogenated olefin, and (e) a silicone macromer having a polymerizable group.
The polymer may have a fluorine atom, but preferably does not have a fluorine atom. That is, the polymer is preferably a non-fluorine polymer, and all the monomers are preferably non-fluorine monomers.

(A) Nitrogen-containing monomer The nitrogen-containing monomer has the formula:
^{_{CH 2 = C (-R 2)}} -C (= O) -Y 1 -Z (-Y 2 -R 1) n
[Wherein R ¹ is a hydrocarbon group having 7 to 40 carbon atoms,
R ² is a hydrogen atom or a methyl group,
Y ¹ is —O— or —NH—;
Y ² is —O—C (═O) —NH— or —NH—C (═O) —NH—,
Z is a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms,
n is 1 or 2. ]
It is a compound shown by these.

The nitrogen-containing monomer does not have a fluoroalkyl group.
The nitrogen-containing monomer is (meth) acrylate or (meth) acrylamide having a urethane group or a urea group.

R ¹ is preferably a linear or branched hydrocarbon group. R ¹ is preferably an alkyl group. The number of carbon atoms of R ¹ is preferably 12 to 30, particularly 16 to 24 or 18 to 24.

Z may be a divalent or trivalent alkane group, for example, an alkylene group (a divalent alkylene group). The number of carbon atoms in Z is preferably 2 to 4, particularly 2. Specific examples of Z are divalent alkane _{group, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH ₂ CH ₂ CH ₂ — Examples of the trivalent alkane group include —CH ₂ CH═, —CH ₂ (CH—) CH ₂ —, and —CH ₂ CH ₂ (CH—) CH ₂ —.

The nitrogen-containing monomer can be produced by reacting hydroxyalkyl (meth) acrylate or hydroxyalkyl (meth) acrylamide with a long-chain alkyl isocyanate. Examples of the long-chain alkyl isocyanate include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, and behenyl isocyanate.
Alternatively, the nitrogen-containing monomer can also be produced by reacting a (meth) acrylate having an isocyanate group in the side chain, such as 2-methacryloyloxyethyl methacrylate, with a long-chain alkylamine or a long-chain alkyl alcohol. Examples of the long chain alkylamine include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of the long-chain alkyl alcohol include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

Specific examples of the nitrogen-containing monomer are as follows.

［上記式中、ｎは７〜４０の数であり、ｍは１〜５の数である。］

[In the above formula, n is a number from 7 to 40, and m is a number from 1 to 5. ]

(B) acrylate ester monomer polymer may have the repeating units derived from other acrylate ester monomer.
Examples of other acrylate ester monomers are as follows.
(B1) an acrylate ester monomer having an aliphatic hydrocarbon group, and (b2) an acrylate ester monomer having a cyclic hydrocarbon group. The polymer comprises a monomer (b1) and a monomer (b2). It may have repeating units derived from at least one monomer selected from the group.

(B1) aliphatic hydrocarbon radical acrylate ester monomer polymer having may have repeating units derived from an aliphatic hydrocarbon group containing acrylate ester monomer. The aliphatic hydrocarbon group-containing acrylate ester monomer is a (meth) acrylate ester (that is, acrylate or methacrylate).
A preferred example of an aliphatic hydrocarbon group-containing acrylate ester monomer has the formula:
^{_{CH 2 = CA 11 -C (=}} O) -O-A 12
[In the formula, A ¹¹ represents a hydrogen atom or a methyl group;
A ¹² is a linear or branched aliphatic hydrocarbon group having 1 to 40 carbon atoms. ]
It is a compound shown by these.

The aliphatic hydrocarbon group-containing acrylate ester monomer does not have a fluoroalkyl group. The aliphatic hydrocarbon group-containing acrylate ester monomer may contain a fluorine atom, but preferably does not contain a fluorine atom.
A ¹² is a linear or branched hydrocarbon group. The linear or branched hydrocarbon group may in particular be a linear hydrocarbon group. The linear or branched hydrocarbon group has 1 to 40 carbon atoms, preferably 18 to 40 carbon atoms. The linear or branched hydrocarbon group preferably has 18 to 28 carbon atoms, particularly 18 or 22, and is generally a saturated aliphatic hydrocarbon group, particularly preferably an alkyl group.
Specific examples of the aliphatic hydrocarbon group-containing acrylate ester monomer include lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate.
The presence of the aliphatic hydrocarbon group-containing acrylate ester makes the texture more flexible.

(B2) a cyclic acrylate ester monomer polymer having a hydrocarbon group may have a repeating unit derived from a cyclic hydrocarbon group containing acrylate ester monomer.
Cyclic hydrocarbon group-containing acrylate ester monomer
formula:
^{_{CH 2 = CA 21 -C (=}} O) -O-A 22
[Wherein A ²¹ is a hydrogen atom, a methyl group, a halogen, a linear or branched alkyl group having 2 to 21 carbon atoms, or a CFX ¹ X ² group (where X ¹ and X ² are a hydrogen atom, Fluorine atom, chlorine atom, bromine atom or iodine atom), cyano group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl Group,
A ²² is a cyclic hydrocarbon-containing group having 4 to 40 carbon atoms. ]
It is preferable that it is a compound shown by these.
The cyclic hydrocarbon group-containing acrylate ester monomer is preferably a monomer whose homopolymer has a high glass transition point (for example, 50 ° C. or higher, particularly 80 ° C. or higher).

  The cyclic hydrocarbon group-containing acrylate ester monomer does not have a fluoroalkyl group. The cyclic hydrocarbon group-containing acrylate ester monomer may contain a fluorine atom, but preferably does not contain a fluorine atom.

Examples of A ²¹ are a hydrogen atom, a methyl group, Cl, Br, I, F, CN, and CF ₃ . A ²¹ is preferably a chlorine atom.
A ²² is a cyclic hydrocarbon group which may have a chain group (for example, a linear or branched hydrocarbon group). Examples of the cyclic hydrocarbon group include saturated or unsaturated monocyclic groups, polycyclic groups, and bridged cyclic groups. The cyclic hydrocarbon group is preferably saturated. Carbon number of a cyclic hydrocarbon group is 4-40, and it is preferable that it is 6-20. 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 araliphatic group having 7 to 20 carbon atoms. The number of carbon atoms of the cyclic hydrocarbon group is particularly preferably 15 or less, for example 12 or less. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group. Specific examples of the cyclic hydrocarbon group are a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, and a dicyclopentenyl group.

As a specific example of the cyclic hydrocarbon group-containing acrylate ester monomer,
Cyclohexyl acrylate, t-butyl cyclohexyl acrylate, benzyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate; and cyclohexyl methacrylate, t-butyl cyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, dicyclopentanyl Examples include methacrylate and dicyclopentenyl methacrylate.
The presence of the cyclic hydrocarbon group-containing acrylate ester monomer can improve processing stability and improve water repellency.

(C) a non-fluorinated crosslinking monomer polymer may have the repeating units derived from fluorine-free crosslinkable monomer.
A non-fluorine crosslinkable monomer is a monomer which does not contain a fluorine atom. The non-fluorine crosslinkable monomer may be a compound having at least two reactive groups and / or olefinic carbon-carbon double bonds (preferably (meth) acrylate groups) and not containing fluorine. The non-fluorine crosslinkable monomer is a compound having at least two olefinic carbon-carbon double bonds (preferably a (meth) acrylate group), or at least one olefinic carbon-carbon double bond and at least one It may be a compound having a reactive group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, and the like.

  The non-fluorine crosslinkable monomer may be mono (meth) acrylate, di (meth) acrylate or mono (meth) acrylamide having a reactive group. Alternatively, the non-fluorine crosslinkable monomer may be di (meth) acrylate.

One example of a non-fluorine crosslinkable monomer is a vinyl monomer having a hydroxyl group.
Non-fluorine crosslinkable monomers include, for example, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2, 3 -Dihydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth) acrylate 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc. , It is not limited thereto.

  The presence of the non-fluorine crosslinkable monomer increases the washing durability imparted by the polymer.

(D) The halogenated olefin monomer copolymer may have a repeating unit derived from a halogenated olefin monomer.
The halogenated olefin monomer preferably does not have a fluorine atom.
The halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. The halogenated olefin monomer 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 monomer are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide. Vinyl chloride is preferred because of high water repellency (particularly durability of water repellency).
The presence of the halogenated olefin increases the washing durability provided by the polymer.

(E) The silicone macromer copolymer having a polymerizable group may have a repeating unit derived from a silicone macromer having a polymerizable group.

[式中、Ｒは、同一または異なって、炭素数１〜12の炭化水素基であり、
Ｘは、重合性官能基を有する基であり、
ｍは、５〜２００の数である。］
で示される化合物であることが好ましい。 The polymerizable group is generally a radical polymerizable group. A silicone macromer having a polymerizable group has the formula:

Wherein R is the same or different and is a hydrocarbon group having 1 to 12 carbon atoms,
X is a group having a polymerizable functional group,
m is a number from 5 to 200. ]
It is preferable that it is a compound shown by these.

It is preferable that 50 mol% or more of the total R groups are methyl groups. The hydrocarbon group may be substituted.
The X group (group containing a polymerizable functional group) is preferably formed by a polymerizable functional group and an alkylene group (the alkylene group preferably has 1 to 10 carbon atoms). Examples of the polymerizable group are (meth) acryloyl group, styryl group, allyl group, vinylbenzyl group, vinyl ether group, vinylalkylsilyl group, vinylketone group and isopropenyl group. (Meth) acryloyl groups, that is, acryloyl groups and methacryloyl groups are preferred. A silicone macromer having a methacryloyl group (that is, a methacryl-modified silicone macromer) is more preferable. A silicone macromer having a methacryloyl group only at one end (a methacryl-modified silicone macromer at one end) is particularly preferable.

Specific examples of the silicone macromer are as follows.

[上記式において、ｍは５〜２００の数である。]

[In the above formula, m is a number from 5 to 200. ]

  The number average molecular weight of the silicone macromer is generally 1,000 to 100,000, for example 2,000 to 50,000. The number average molecular weight is measured by gel permeation chromatography (polystyrene conversion).

  Silicone macromers can be produced by known methods. As the production method, for example, a method in which a living polymer is obtained by anionic polymerization of cyclic siloxane using lithium trialkylsilanolate as an initiator, and a silicone macromer is obtained by further reacting γ-methacryloxypropyldimethylmonochlorosilane, or The method of obtaining a silicone macromer as a condensate of terminal silanol group containing silicone and an organosilicon compound is mentioned.

  By using a silicone macromer, the resistance to chalk mark, texture and water repellency are increased.

(F) Other monomers (f) other than the monomer monomers (a) to (d), for example, non-fluorine non-crosslinkable monomers may be used.
Examples of other monomers include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate , And vinyl alkyl ethers. Other monomers are not limited to these examples.

  In the present specification, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acrylamide” means acrylamide or methacrylamide.

  Each of the monomers (a) to (f) may be a single species or a mixture of two or more species.

The amount of monomer (a) may be 30% by weight or more, preferably 40 parts by weight or more, particularly 50 parts by weight or more based on the polymer. The amount of the monomer (a) may be 95 parts by weight or less, for example 80 parts by weight or less, or 75 parts by weight or less, or 70 parts by weight or less based on the polymer.
In the polymer, with respect to 100 parts by weight of the monomer (a),
The amount of the repeating unit (b) is 0 to 200 parts by weight, preferably 1 to 100 parts by weight,
The amount of the repeating unit (c) is 0 to 50 parts by weight, preferably 1 to 10 parts by weight,
The amount of the repeating unit (d) is 0 to 100 parts by weight, preferably 1 to 60 parts by weight,
The amount of the repeating unit (e) is 0 to 70 parts by weight, preferably 1 to 15 parts by weight,
The amount of the repeating unit (f) may be 0 to 100 parts by weight, preferably 1 to 30 parts by weight.
In the polymer, the amount of each of the monomer (b1) and the monomer (b2) is 0 to 150 parts by weight, preferably 1 to 100 parts by weight with respect to 100 parts by weight of the monomer (a). For example, it may be 2-50.

  The number average molecular weight (Mn) of the polymer may generally be 1000 to 1000000, for example 5000 to 500000, in particular 3000 to 200000. The number average molecular weight (Mn) of the polymer is generally measured by GPC (gel permeation chromatography).

In the present invention, a monomer is polymerized to obtain a water repellent composition in which the polymer is dispersed or dissolved in a liquid medium.
The monomers used in the present invention are as follows.
Monomer (a),
Monomer (a) + (b),
Monomer (a) + (b) + (c),
Monomer (a) + (b) + (d), or Monomer (a) + (b) + (c) + (d).
In addition to the above, one or both of monomer (e) and monomer (f) may be used. The monomer (b) may be at least one of the monomer (b1) and the monomer (b2).

(2) The liquid medium water repellent composition contains a liquid medium. The liquid medium is an organic solvent, or water, an organic solvent, or a mixture of water and an organic solvent.
The water repellent composition is generally a solution or dispersion. The solution is a solution in which a polymer is dissolved in an organic solvent. The dispersion is an aqueous dispersion in which a polymer is dispersed in an aqueous medium (water or a mixture of water and an organic solvent).
Examples of the organic solvent include esters (for example, esters having 2 to 30 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (for example, ketones having 2 to 30 carbon atoms, specifically methyl ethyl ketone and diisobutyl). Ketone), alcohol (for example, alcohol having 1 to 30 carbon atoms, specifically isopropyl alcohol), aromatic solvent (for example, toluene and xylene), petroleum solvent (for example, alkane having 5 to 10 carbon atoms, Specifically, naphtha and kerosene).
The liquid medium may be water alone or a mixture of water and a (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% by weight or more) with respect to the liquid medium. The liquid medium is preferably water alone.

(3) When the surfactant water repellent composition is an aqueous dispersion, it preferably contains a surfactant.
In the water repellent composition of the present invention, the surfactant includes a nonionic surfactant. Furthermore, the surfactant preferably contains one or more surfactants selected from a cationic surfactant, an anionic surfactant, and an amphoteric surfactant. It is preferable to use a combination of a nonionic surfactant and a cationic surfactant.

(3-1) Nonionic surfactant Examples of the nonionic surfactant include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides.
Examples of the ether are compounds having an oxyalkylene group (preferably a polyoxyethylene group).
Examples of esters are alcohol and fatty acid esters. Examples of the alcohol are 1 to 6 valent (particularly 2 to 5 valent) alcohols having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, in particular 5 to 30 carbon atoms.
An example of the ester ether is a compound obtained by adding an alkylene oxide (particularly, ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of the alcohol are 1 to 6 (especially 2 to 5) carbon atoms having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, in particular 5 to 30 carbon atoms.

Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or dialkanolamino. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, in particular 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 a divalent to pentavalent alcohol having 3 to 30 carbon atoms.
The amine oxide may be an oxide of an amine (secondary amine or preferably tertiary amine) (for example having 5 to 50 carbon atoms).

The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The alkylene group in the oxyalkylene group preferably has 2 to 10 carbon atoms. 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 ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides, and is preferably a nonionic surfactant having an oxyalkylene group.

Nonionic surfactants are alkylene oxide adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, linear and / or branched fatty acids (saturated and / or unsaturated). Polyalkylene glycol ester, polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), alkylene oxide adduct of acetylene glycol, and the like. Among these, the structures of the alkylene oxide addition moiety and the polyalkylene glycol moiety are polyoxyethylene (POE) or polyoxypropylene (POP) or POE / POP copolymer (random copolymer or block copolymer) Is preferred).
The nonionic surfactant preferably has a structure that does not contain an aromatic group because of environmental problems (biodegradability, environmental hormones, etc.).

Nonionic surfactants have the formula:
^{_{R 1 O- (CH 2 CH 2}} O) p - (R 2 O) q -R 3
[Wherein R ¹ is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an acyl group,
Each of R ² is independently the same or different and is an alkylene group having 3 or more carbon atoms (for example, 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 of 2 or more,
q is 0 or a number of 1 or more. ]
It may be a compound shown by these.

R ¹ preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. Preferable specific examples of R ¹ include a lauryl group, a tridecyl group, and an oleyl group.
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 (for example, 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 which an oxypropylene chain is preferable.

Specific examples of the nonionic surfactant, ethylene oxide and hexyl phenol, isooctanoate butylphenol, hexadecanol, oleic acid, alkane _(C 12 _{-C 16)} thiol, sorbitan mono fatty acid _(C 7 _{-C 19)} or alkyl Condensation products with (C ₁₂ -C ₁₈ ) amine and the like are included.

The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example 30 to 75% by weight, in particular 40 to 70% by weight, based on 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.
The nonionic surfactant may be one kind alone, or a mixture of two or more kinds.

(3-2) Cationic surfactant The cationic surfactant is preferably a compound having no amide group.

  The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene addition type ammonium salt. Specific examples of the cationic surfactant include, but are not limited to, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt type surfactants such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, Quaternary ammonium salt type surfactants such as alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like can be mentioned.

Preferred examples of the cationic surfactant are:
^{R 21 -N + (-R 22)} (- R 23) (- R 24) X -
[Wherein R ²¹ , R ²² , R ²³ and R ²⁴ represent a hydrocarbon group having 1 to 30 carbon atoms,
X is an anionic group. ]
It is a compound of this.
Specific examples of R ²¹ , R ²² , R ²³ and —R ²⁴ are alkyl groups (eg, methyl group, butyl group, stearyl group, palmityl group). Specific examples of X are halogen (for example, chlorine) and acid (for example, hydrochloric acid, acetic acid).
The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 30 carbon atoms).

The cationic surfactant is preferably an ammonium salt. The cationic surfactant has the formula:
R ¹ _p -N ⁺ R ² _q X ⁻
[Wherein R ¹ is a linear and / or branched aliphatic (saturated and / or unsaturated) group of C12 or more (for example, C _{12 to} C ₅₀ ),
R ² is H or an alkyl group of C1-4, benzyl group, polyoxyethylene group (number of oxyethylene groups, for example, 1 (particularly 2, especially 3) to 50)
(CH ₃ and C ₂ H ₅ are particularly preferred),
X is a halogen atom (e.g.,), fatty bases C ₁ -C _4,
p is 1 or 2, q is 2 or 3, and p + q = 4. ]
It may be an ammonium salt represented by R ¹ may have 12 to 50 carbon atoms, for example 12 to 30 carbon atoms.

  Specific examples of the cationic surfactant include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl) trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyl Di (hydropolyoxyethylene) ammonium chloride, benzyldodecyl di (hydropolyoxyethylene) ammonium chloride, N- [2- (diethylamino) ethyl] oleamide hydrochloride are included.

  Examples of amphoteric surfactants include alanines, imidazolinium betaines, amide betaines, betaine acetate, and the like. Specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethylhydroxyethyl imidazolinium betaine, lauryl dimethyl. Examples include aminoacetic acid betaine and fatty acid amidopropyldimethylaminoacetic acid betaine.

Each of the nonionic surfactant, the cationic surfactant, and the amphoteric surfactant may be one kind or a combination of two or more.
The amount of the cationic surfactant may be 5% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more based on the total amount of the surfactant. The weight ratio of the nonionic surfactant to the cationic surfactant is preferably 95: 5 to 20:80, more preferably 85:15 to 40:60.
The amount of the cationic surfactant may be 0.05 to 10 parts by weight, for example, 0.1 to 8 parts by weight with respect to 100 parts by weight of the polymer. The total amount of the surfactant may be 0.1 to 20 parts by weight, for example, 0.2 to 10 parts by weight with respect to 100 parts by weight of the polymer.

(4) Additive The water repellent composition of the present invention contains (4) an additive in addition to the fluoropolymer (1) and the liquid medium (2) and, if necessary, (3) a surfactant. Also good.
Examples of the additive (4) are other water repellents, oil repellents, drying rate adjusting agents, cross-linking agents, film-forming aids, compatibilizing agents, surfactants, antifreezing agents, viscosity adjusting agents, UV absorbers. , Antioxidants, pH adjusting agents, antifoaming agents, texture adjusting agents, slipperiness adjusting agents, antistatic agents, hydrophilic agents, antibacterial agents, antiseptics, insecticides, fragrances, flame retardants, and the like.
The additive (4) may be a fluoropolymer.

  The water repellent composition of the present invention may contain only the non-fluorine polymer as a polymer (active ingredient), but may contain a fluorinated polymer in addition to the non-fluorine polymer. Good. In general, in a water repellent composition (particularly, an aqueous emulsion), particles formed of a non-fluorine polymer and particles formed of a fluoropolymer exist separately. That is, it is preferable to mix the non-fluorine polymer and the fluoropolymer after separately producing the non-fluoropolymer and the fluoropolymer. Generally, a non-fluoropolymer emulsion (especially an aqueous emulsion) and a fluoropolymer emulsion (especially an aqueous emulsion) are prepared separately, and then the non-fluoropolymer emulsion and the fluoropolymer emulsion are mixed. It is preferable.

The fluorine-containing polymer is a polymer having a repeating unit derived from a fluorine-containing monomer. The fluorine-containing monomer has the general formula:
CH ₂ = C (−X) −C (= O) −Y−Z−Rf
[Wherein, X represents 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 (where X ¹ and X ² is 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;
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,
—CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ is an alkyl group having 1 to 4 carbon atoms) or
-CH ₂ CH (OZ ¹ ) CH ₂ -group (where 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 (where m is 1 to 10, n is 0 to 10, is there),
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. ]
An acrylate ester or acrylamide represented by
The number of carbon atoms in the Rf group is preferably 1-6, in particular 4-6, especially 6.

The fluorine-containing polymer is a repeating polymer derived from at least one non-fluorine monomer selected from the group consisting of halogenated olefin monomers, non-fluorine non-crosslinkable monomers and non-fluorine crosslinkable monomers. You may have a unit.
The halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. Specific examples of halogenated olefin monomers are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide.

Preferred non-fluorine non-crosslinkable monomers have the formula:
CH ₂ = CA-T
[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 linear or cyclic hydrocarbon group having 1 to 20 carbon atoms, or a linear or cyclic organic group having 1 to 20 carbon atoms having an ester bond. ]
It is a compound shown by these. Specific examples of non-fluorine non-crosslinkable monomers include alkyl (meth) acrylate esters, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) Acrylate, methoxypolypropylene glycol (meth) acrylate, and vinyl alkyl ether are included.

  The non-fluorine crosslinkable monomer has a compound having at least two carbon-carbon double bonds (for example, (meth) acrylic group), or has at least one carbon-carbon double bond and at least one reactive group. It may be a compound.

The weight ratio of the non-fluorine polymer to the fluoropolymer in the water repellent composition may be 100: 0 to 10:90, such as 90:10 to 20:80, preferably 80:20 to 30:70. .
Each of the non-fluorine polymer and the fluorine-containing polymer may be a single polymer, or may be a combination of two or more polymers.
When a combination of a non-fluorinated polymer and a fluorinated polymer is used, performance (particularly water repellency) equivalent to or better than when only a fluorinated polymer is used is obtained.

The polymer in the present invention (a polymer having no fluoroalkyl group, particularly a non-fluorine polymer, and a fluorine-containing polymer, particularly a copolymer having a fluoroalkyl group) can be produced by any ordinary polymerization method. The reaction conditions can also be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization. Emulsion polymerization is preferred.
If the water repellent composition of the present invention is an aqueous emulsion, the method for producing the polymer is not limited. For example, a water-based emulsion can be obtained by producing a polymer by solution polymerization and then removing the solvent and adding a surfactant and water.

  In solution polymerization, a method in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, is heated and stirred in the range of 30 to 120 ° C. for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like. Can be 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 with respect to 100 parts by weight of the monomer.

  The organic solvent is inactive to the monomer and dissolves them. For example, an ester (for example, an ester having 2 to 30 carbon atoms, specifically, ethyl acetate or butyl acetate), a ketone (for example, carbon It may be a ketone having 2 to 30 (specifically, methyl ethyl ketone, diisobutyl ketone) or an alcohol (for example, an alcohol having 1 to 30 carbon atoms, specifically, isopropyl alcohol). 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, Examples include diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in the range of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight with respect to 100 parts by weight of the total amount of monomers.

  Emulsion polymerization employs a method in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after substitution with nitrogen, the mixture is stirred and polymerized in the range of 50 to 80 ° C. for 1 to 10 hours. Polymerization initiators include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azo Water-soluble materials such as bisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide Oil-soluble ones such as t-butyl peroxypivalate and diisopropyl peroxydicarbonate are used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

  In order to obtain a polymer aqueous dispersion with excellent storage stability, the monomer is polymerized by submerging the monomer into water using an emulsifier that can impart strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. It is desirable. As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and the emulsifier is used in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomer. Preference is given to using anionic and / or nonionic and / or cationic emulsifiers. When the monomers are not completely compatible with each other, it is preferable to add a compatibilizing agent such as a water-soluble organic solvent or a low molecular weight monomer that is sufficiently compatible with these monomers. By adding a compatibilizing agent, it is possible to improve emulsifying properties and copolymerization properties.

  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 and the like, and 1 to 50 parts by weight with respect to 100 parts by weight of water. For example, you may use in the range of 10-40 weight part. Examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., and 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of monomers, For example, you may use in the range of 10-40 weight part.

  In the polymerization, a chain transfer agent may be used. Depending on the amount of chain transfer agent used, the molecular weight of the polymer can be varied. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (for example, having 1 to 30 carbon atoms)), inorganic salts such as sodium hypophosphite and sodium bisulfite. Etc. You may use the usage-amount of a chain transfer agent in 0.01-10 weight part with respect to 100 weight part of total amounts of a monomer, for example, 0.1-5 weight part.

The water repellent composition of the present invention may be in the form of a solution, an emulsion (particularly an aqueous dispersion) or an aerosol, but is preferably a solution or an aqueous dispersion. The water repellent composition comprises a polymer (the active ingredient of the water repellent composition) and a medium (particularly 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, in particular 10 to 80% by weight, based on the water repellent composition.
In the water repellent composition, the concentration of the polymer may be 0.01 to 95% by weight, for example 5 to 50% by weight.

  The water repellent composition of the present invention can be used as an external treatment agent (surface treatment agent) or an internal treatment agent.

  When the water repellent composition of the present invention is an external treatment agent, it can be applied to an object to be treated by a conventionally known method. Usually, the water repellent composition is dispersed in an organic solvent or water, diluted, and attached to the surface of an object to be treated by a known method such as dip coating, spray coating or foam coating, and then dried. Is taken. If necessary, curing may be carried out by applying together with a suitable crosslinking agent (for example, blocked isocyanate). Furthermore, 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 can be added to the water repellent composition of the present invention. The concentration of the polymer in the treatment liquid brought into contact with the substrate may be 0.01 to 10% by weight (particularly in the case of dip coating), for example 0.05 to 10% by weight.

  Examples of the object to be treated with the treating agent composition (water repellent composition) of the present invention include textile products, stone materials, filters (for example, electrostatic filters), dust masks, and fuel cell components (for example, gas diffusion). Electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, plasters and the like. Various examples can be given as textile products. For example, natural animal and vegetable fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, glass fibers, and carbon fibers , Inorganic fibers such as asbestos fibers, or mixed fibers thereof.

The fiber product may be in the form of a fiber, cloth or the like.
The water repellent composition of the present invention can also be used as an internal release agent or an external release agent.

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

  Alternatively, the polymer may be applied to the textile by a cleaning method, such as a laundry application or a dry cleaning method.

  The textile products to be treated are typically fabrics, which include woven, knitted and non-woven fabrics, fabrics and carpets in clothing form, but fibers or yarns or intermediate fiber products (eg sliver or It may be a roving yarn). The textile product material may be natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or rheocell), or synthetic fibers (such as polyester, polyamide or acrylic fibers), or May be a mixture of fibers, such as a mixture of natural and synthetic fibers. The textile product is preferably a carpet.

Alternatively, the fibrous base material may be leather. In order to make the production polymer hydrophobic and oleophobic, aqueous solutions or aqueous emulsifications at various stages of leather processing, for example during the wet processing of leather or during the finishing of leather You may apply it to leather from things.
Alternatively, the fibrous substrate may be paper. The production polymer may be applied to preformed paper or may be applied at various stages of papermaking, for example during the drying period of the paper.

  “Treatment” means that a treatment agent is applied to an object to be treated by dipping, spraying, coating, or the like. By the treatment, the polymer which is an active ingredient of the treatment agent penetrates into the treatment object and / or adheres to the surface of the treatment object.

When the water repellent composition is an internal treatment agent, it can impart water repellency to the resin by adding it to the resin, for example, a thermoplastic resin. A water repellent composition can be used when producing a molded article of a resin.
The liquid medium is removed from the liquid (solution or dispersion) containing the polymer to obtain the polymer. For example, a polymer can be obtained by reprecipitating a polymer dispersion (aqueous dispersion or organic solvent dispersion) with water or an organic solvent and then drying.

For example, a molded body can be produced by a production method having a step of mixing a resin and a polymer to obtain a resin composition and a step of molding the resin composition. It is preferable to produce a molded article by melt-kneading using an extruder or the like.
In general, the thermoplastic resin and the polymer are compatible in the molten state. The kneading can be performed by a conventionally known method such as a single screw extruder, a twin screw extruder, or a roll. The resin composition thus obtained is molded by extrusion molding, injection molding, compression molding, blow molding, pressing or the like. The resin composition is molded into molded bodies having various shapes. The obtained molded body may be further heat-treated in an oven, a drying furnace or the like after the molding process. The molded article may be a single layer or a multilayer of 2 to 10 layers, for example, 3 to 5 layers.

  The molded body can be used for applications in which a thermoplastic resin is used, particularly for applications in which it is preferable to have excellent wiping resistance against dirt and excellent scratch resistance. Applications of molded products include automobiles (exterior parts and interior parts) (for example, bumpers, instrumental panels, door trims), home appliances (for example, washing machines and refrigerators) (for example, housings, doors in refrigerators, trays) , Vegetable compartment containers), various cases, buildings (interior and parts) (eg handrails, wallpaper, desks, chairs, toilet seats and toilet seat force bars, bathtubs), electronic devices (eg smartphone housings), drains Pipes, tableware, flooring, gasoline tanks, fuel hoses, OA equipment. Among these, automobile interior parts, home appliance interior parts, and buildings are more preferable.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.
In the following, parts or% or ratio represents parts by weight or weight% or weight ratio unless otherwise specified.
The test procedure is as follows.

Water Repellency Test A treatment liquid having a solid content concentration of 1.5% was prepared, and the cloth was immersed in this test solution, passed through a mangle, and the water repellency was evaluated with a test cloth heat-treated at 160 ° C. for 2 minutes. The water repellency of the treated fabric was evaluated according to the spray method of JIS-L-1092 (AATCC-22). As shown in the table below, the water-repellent No. Is represented by The larger the score, the better the water repellency.

Gum-up rate test The polymer dispersion is diluted with hard water B (hardness 16: calcium chloride 1.9425 g, magnesium chloride 0.3975 g, sodium sulfate 4.63 g / water 10 L) so that the solid concentration is 5% by weight. Prepare 1000g and put in a pad that can be adjusted to 40 ° C. A mungle is continuously treated with a polyester cloth having a width of 20 cm and a length of 80 cm as a ring so that it can be continuously treated at a mangle pressure of 0.4 MPa for 1 hour. The gum up rate is determined by the following formula.

(Gum-up amount to mangle) = (weight before treatment of polyester cloth + solid weight of diluted solution before treatment) − (weight after treatment of polyester fabric + solid weight of diluted solution after treatment)

(Gum-up rate) = 100 X (Amount of gum-up to mangle) / (Weight of diluted solution solids before treatment)

  When the gum-up rate is less than 4%, the gum-up is suppressed (processing stability is good).

Synthesis example 1
[Synthesis of C18UA (stearyl group-containing urethane acrylate)]

A 1 L four-necked flask is charged with 80.2 g of hydroxyethyl acrylate, 100 g of ethyl acetate, 0.03 g of tertiary butylcatechol, and 0.03 g of dibutyltin dilaurate. A stir bar, a thermometer and a reflux tube are set, 201.4 g of octadecyl isocyanate is dissolved in 100 g of ethyl acetate, and charged into a dropping funnel. A dropping funnel is set in a flask and heated to 70 ° C. The ethyl acetate solution of octadecyl isocyanate is gradually added dropwise from the dropping funnel over about 30 minutes while paying attention to heat generation. After completion of the dropwise addition, the reaction is continued for about 2 hours. After confirming that the isocyanate peak disappeared by infrared spectroscopy (IR), the reaction was terminated. The reaction product was reprecipitated in methanol, washed with methanol, and dried under reduced pressure to obtain a white powder. The reaction product was identified as C18UA by ¹ H-NMR.
From the differential scanning calorimeter (DSC), the melting point of the compound was about 73 ° C.

（ｎ＝１８） Synthesis example 2
[Synthesis of C18ureaMA (stearyl group-containing urea methacrylate)]

(N = 18)

Stearylamine 200 g, ethyl acetate 100 g, and tertiary butyl catechol 0.03 g are charged into a 1 L four-necked flask. A stir bar, a thermometer and a reflux tube are set, and 2-methacryloyloxyethyl isocyanate (CAS. No: 30673-80-7) is dissolved in 100 g of ethyl acetate and charged into a dropping funnel. The dropping funnel is set in the flask, and an ethyl acetate solution of 2-methacryloyloxyethyl isocyanate is gradually added dropwise from the dropping funnel over about 30 minutes while paying attention to heat generation. After completion of the dropwise addition, the reaction is continued for about 2 hours. After confirming that the isocyanate peak disappeared by infrared spectroscopy (IR), the reaction was terminated. The reaction product was reprecipitated in methanol, washed with methanol, and dried under reduced pressure to obtain a white powder. The reaction product was identified as C18ureaMA by ¹ H-NMR. From the differential scanning calorimeter (DSC), the melting point of the compound was about 91 ° C.

Synthesis example 3
[Synthesis of C18X2UMA (stearyl group-containing (2-chain type) urethane methacrylate)]

A 1 L four-necked flask is charged with 55.3 g of glycerol methacrylate, 100 g of ethyl acetate, 0.03 g of tertiary butylcatechol, and 0.03 g of dibutyltin dilaurate. A stir bar, a thermometer and a reflux tube are set, 201.4 g of octadecyl isocyanate is dissolved in 100 g of ethyl acetate, and charged into a dropping funnel. A dropping funnel is set in a flask and heated to 70 ° C. The ethyl acetate solution of octadecyl isocyanate is gradually added dropwise from the dropping funnel over about 30 minutes while paying attention to heat generation. After completion of the dropwise addition, the reaction is continued for about 2 hours. After confirming that the isocyanate peak disappeared by infrared spectroscopy (IR), the reaction was terminated. The reaction product was reprecipitated in methanol, washed with methanol, and dried under reduced pressure to obtain a white powder. The reaction product was identified as C18X2UMA by ¹ H-NMR. From a differential scanning calorimeter (DSC), the melting point of the compound was about 81 ° C.

Production Example 1
A 200 cc four-necked flask equipped with a nitrogen introduction tube, a thermometer, a stirring rod, and a reflux tube was charged with 40 g of C18UA, 0.04 g of lauryl mercaptan, and 56 g of toluene, and stirred at room temperature for 30 minutes under a nitrogen stream. Thereafter, a solution obtained by dissolving 0.4 g of AIBN (azobisisobutyronitrile) in 4 g of toluene was added, the temperature was raised to 80 ° C., and a polymerization reaction was performed for 8 hours. After obtaining the polymer, toluene was further added to prepare a toluene solution 1 having a solid content concentration of 20%.

Production Examples 2-8
Polymerization was carried out in the same manner as in Production Example 1 with the composition shown in Table 1 to obtain a polymer, and then diluted with toluene to prepare toluene solutions 2 to 8 having a solid content concentration of 20%.

Comparative production example 1
Polymerization was carried out in the same manner as in Production Example 1 with the composition shown in Table 1 to obtain a polymer, and then diluted with toluene to prepare a toluene solution having a solid content concentration of 20%.

Production Example 9
Tripropylene glycol 17g, C18UA 59g, N-methylol acrylamide 1g, pure water 136g, dimethyl dioctadecyl ammonium chloride 0.6g, sorbitan monooleate 1g, polyoxyethylene tridecyl ether 2g, polyoxyethylene lauryl ether 2.4 g was charged, heated to 80 ° C., stirred with a homomixer for 1 minute at 2000 rpm, and then emulsified and dispersed with ultrasound for 15 minutes. The emulsified dispersion was transferred to a 500 cc four-necked flask equipped with a nitrogen introduction tube, a thermometer, a stirrer, and a reflux tube. After purging with nitrogen, 0.1 g of lauryl mercaptan was added and stirred, and then 2,2-azobis (2- Amidinopropane) dihydrochloride (0.6 g) was added, the temperature was raised at 60 ° C., and the mixture was reacted for 4 hours to obtain an aqueous dispersion of a polymer. Thereafter, pure water was added to prepare an aqueous dispersion 9 having a solid content concentration of 20%.

Production Examples 10-12
Polymerization was carried out in the same manner as in Production Example 9 with the composition shown in Table 2 to obtain a polymer, and then diluted with pure water to prepare aqueous dispersions 10 to 12 having a solid content concentration of 20%.

Production Example 13
Tripropylene glycol 30 g, C18UA 40 g, stearyl acrylate 39 g, N-methylol acrylamide 1 g, pure water 180 g, trimethyloctadecyl ammonium chloride 2 g, sorbitan monooleate 2 g, polyoxyethylene tridecyl ether 2.5 g, polyoxy in a 500 ml polycontainer Ethylene lauryl ether (3.5 g) was charged, heated to 80 ° C., stirred with a homomixer for 1 minute at 2000 rpm, and then emulsified and dispersed with ultrasound for 15 minutes. The emulsified dispersion was transferred to a 500 ml autoclave, purged with nitrogen, and charged with 0.2 g of lauryl mercaptan and 20 g of vinyl chloride. Further, 1 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added, heated at 60 ° C. and reacted for 4 hours to obtain an aqueous dispersion of polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion 13 having a solid concentration of 20%.

Production Examples 14-15
Polymerization was carried out in the same manner as in Production Example 13 with the composition shown in Table 2, to obtain a polymer, and then diluted with pure water to prepare aqueous dispersions 14 to 15 having a solid content concentration of 20%.

Comparative Production Examples 2-3
Polymerization was carried out with the composition shown in Table 2 in the same manner as in Production Example 13 to obtain a polymer, which was further diluted with pure water to prepare an aqueous dispersion having a solid content concentration of 20%.

The meanings of the abbreviations are as follows.

Test example 1
The toluene solution 1 having a solid content concentration of 20% prepared in Production Example 1 was further diluted with toluene to prepare a treatment liquid having a solid content concentration of 1.5%. A polyester cloth (gray) and nylon cloth (black) were immersed in this treatment solution, and then lightly centrifuged for about 10 seconds. The wet pickup was about 65% (polyester cloth) and about 40% (nylon cloth). This treated cloth was passed through a pin tenter at 170 ° C. for 1 minute, dried and cured. The treated cloth was dried overnight at room temperature, and then passed through a pin tenter at 170 ° C. for 1 minute, followed by heat treatment. The test fabric thus treated was evaluated for water repellency by a water repellency test according to the spray method of JIS L-1092. Table 3 shows the results of water repellency.

Test Examples 2-8
Each toluene solution 2-8 having a solid content concentration of 20% prepared in Production Examples 2-8 was diluted with toluene in the same manner as in Test Example 1 (solid content concentration 1.5%), and the fabric was treated in the same manner as in Test Example 1. Then, a water repellency test was conducted. The results are shown in Table 3.

Comparative Test Example 1
The toluene solution with a solid content concentration of 20% prepared in Comparative Production Example 1 was diluted with toluene so that the solid content concentration became 1.5% as in Test Example 1, and the cloth was treated in the same manner as in Test Example 1. A water repellency test was conducted. The results are shown in Table 3.

Comparative Test Example 4
A solid paraffin wax having a melting point of about 75 ° C. was diluted with toluene to a solid content concentration of 1.5%, and the cloth was treated in the same manner as in Test Example 1 to conduct a water repellency test. The results are shown in Table 3.

Test Example 9
The aqueous dispersion 9 having a solid content concentration of 20% prepared in Production Example 9 was further diluted with tap water to prepare a treatment liquid having a solid content concentration of 1.5%. A polyester cloth (gray) and nylon cloth (black) were immersed in this treatment solution, and then squeezed with a mangle. The wet pickup was about 55% (polyester cloth) and about 35% (nylon cloth). This treated cloth was passed through a pin tenter at 170 ° C. for 1 minute, dried and cured. The test fabric thus treated was evaluated for water repellency by a water repellency test according to the spray method of JIS L-1092. Table 4 shows the water repellency results.
In addition, Table 4 shows the water repellency evaluation results of test cloths washed 10 times according to JIS L-0217 103 and then dried with a tumbler (60 ° C. for 30 minutes).

Test Examples 10-12
The aqueous dispersions 10 to 12 having a solid concentration of 20% prepared in Production Examples 10 to 12 were diluted with tap water so that the solid concentration was 1.5% in the same manner as in Test Example 9 to prepare a treatment liquid. . Using this treatment liquid, a fabric was treated in the same manner as in Test Example 9 to perform a water repellency test. The results are shown in Table 4.

Comparative Test Examples 2-3
The aqueous dispersion with a solid content concentration of 20% prepared in Comparative Production Examples 2-3 was diluted with tap water so that the solid content concentration was 1.5% in the same manner as in Test Example 9 to prepare a treatment liquid. Using this treatment liquid, a fabric was treated in the same manner as in Test Example 9 to perform a water repellency test. The results are shown in Table 4.

Measurement of Gum-up Rate Table 4 shows the results of measuring the gum-up rate for Production Examples 9 to 11 and 13 to 14 and Comparative Production Examples 2 and 3.

  The water repellent composition of the present invention can be used as an external treatment agent (surface treatment agent) or an internal treatment agent. The treatment agent of the present invention can be suitably used for substrates such as textiles and masonry, and imparts excellent water repellency to the substrate.

Claims (12)

(1) (a) 30-100% by weight of polymer, formula:
formula:
^{_{CH 2 = C (-R 2)}} -C (= O) -Y 1 -Z (-Y 2 -R 1) n
[Wherein R ¹ is a hydrocarbon group having 7 to 40 carbon atoms,
R ² is a hydrogen atom or a methyl group,
Y ¹ is —O— or —NH—;
Y ² is —O—C (═O) —NH— or —NH—C (═O) —NH—,
Z is a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms,
n is 1 or 2. ]
A water repellent composition comprising a polymer having a repeating unit derived from a nitrogen-containing monomer represented by the formula (2) and (2) a liquid medium. The water repellent composition according to claim 1, wherein in the monomer (a), R ¹ is an alkyl group, and Z is a divalent or trivalent linear or branched alkane group. The polymer (1) further has a repeating unit derived from a polymerizable monomer other than the monomer (a),
The polymerizable monomer other than the monomer (a) has the formula:
CH ₂ = CA-T
[Wherein A is a hydrogen atom, a methyl group, a chlorine atom, a bromine atom or an iodine atom,
T is a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a linear or cyclic hydrocarbon group having 1 to 40 carbon atoms, or a linear or cyclic organic group having 2 to 41 carbon atoms having an ester bond. . ]
The water repellent composition according to claim 1, which is a compound represented by the formula: A polymerizable monomer other than the monomer (a) is
(B) an acrylate ester monomer,
The water repellent composition according to claim 3, which is at least one selected from the group consisting of (c) a non-fluorine crosslinkable monomer and (d) a halogenated olefin. The other acrylate ester monomer (b)
The repellent property according to claim 4, which is at least one selected from the group consisting of (b1) an acrylate ester monomer having an aliphatic hydrocarbon group, and (b2) an acrylate ester monomer having a cyclic hydrocarbon group. Liquid medication composition.   The non-fluorine crosslinkable monomer (c) is a compound having at least two ethylenically unsaturated double bonds, or a compound having at least one ethylenically unsaturated double bond and at least one reactive group. Item 5. A water repellent composition according to Item 4.   The water repellent composition according to claim 4, wherein the halogenated olefin monomer (d) is at least one selected from the group consisting of vinyl chloride and vinylidene chloride.   In the polymer, the amount of the repeating unit (b) is 0 to 200 parts by weight and the amount of the repeating unit (c) is 0 to 50 parts by weight with respect to 100 parts by weight of the monomer (a). The water repellent composition according to any one of claims 4 to 7, wherein the amount of the unit (d) is 0 to 100 parts by weight. The water repellent composition is a solution and the liquid medium (2) is an organic solvent, or the water repellent composition is an aqueous dispersion, and the liquid medium (2) is water, an organic solvent or water and an organic solvent. The water repellent composition according to claim 1, which is a mixture of solvents.   The water repellent composition according to any one of claims 1 to 9, which is an external treatment agent or an internal treatment agent.   The method of processing a base material which consists of processing a base material with the water repellent composition in any one of Claims 1-10.   A fiber product is treated with the water repellent composition according to any one of claims 1 to 10, wherein the polymer permeates the inside of the object to be treated or adheres to the surface of the object to be treated. Manufacturing method of textile products.