JP2021187952A - Surface treatment agent - Google Patents

Abstract

To provide a surface treatment agent (especially a water repellent) which provides a substrate such as fibers with excellent liquid repellency (especially, excellent water repellency).SOLUTION: Provided is a polymer having a repeating unit formed from a cholesteryl group-containing monomer (a) present in an amount of 20 to 100 weight % relative to the polymer, where the cholesteryl group-containing monomer (a) has a (meth)acryloyloxy group (H2C=CH-C(=O)-O- or H2C=C(CH3)-C(=O)-O-) and a cholesteryl group. The polymer may have a repeating unit formed from at least one monomer selected from the group consisting of (b) a (meth)acrylate monomer having a C1-40 linear or cyclic hydrocarbon group which is an alcohol residue, (c) a cross-linkable monomer, (d) a halogenated olefin monomer, and (e) a polydimethylsiloxane having a (meth)acryloyl group at one terminal.SELECTED DRAWING: None

Description

The present disclosure relates to a surface treatment agent containing a liquid repellent polymer which is a non-fluorine polymer. Specifically, the surface treatment agents of the present disclosure provide excellent liquid repellency, particularly water repellency, to textile products (eg, carpets), paper, non-woven fabrics, stones, electrostatic filters, dust masks, and fuel cell parts. Can be granted.

Conventionally, a fluorine-containing water-repellent oil-repellent agent containing a fluorine compound is known. This water- and oil-repellent agent exhibits good water- and oil-repellent properties when treated on a substrate such as a textile product. Since there is a concern that fluorine-containing compounds may accumulate in the environment, non-fluorine-based repellents have been proposed in recent years. Examples of the non-fluorine-based repellent are poly (meth) acrylate-based polymers and waxes having a long-chain alkyl group, urethane compounds containing a long-chain alkyl group, silicone compounds, and mixtures thereof.
It cannot be said that the conventional non-fluorine repellent has sufficient water repellency, and there is a demand for a non-fluorine repellent having higher performance water repellency.

Patent Document 1 (Japanese Unexamined Patent Publication No. 2003-082286) discloses a latex polymer having a strongly hydrophobic repeating unit (formed from cholesteryl acrylate or the like).

Japanese Unexamined Patent Publication No. 2003-082286

One object of the present disclosure is to provide a surface treatment agent that does not use a fluorine-containing monomer, particularly a fluoroalkyl group-containing monomer.
Another object of the present disclosure is to provide a surface treatment agent (particularly a water repellent) that imparts excellent liquid repellency (particularly, excellent water repellency) to a substrate such as a fiber.
Another object of the present disclosure is to provide a surface treatment agent having excellent processing stability.

The present disclosure relates to a polymer having a (meth) acrylate having a cholesteryl group as an essential constituent unit.
The polymer of the present disclosure is a liquid-repellent polymer that imparts liquid-repellent properties, particularly a water-repellent polymer.
Furthermore, the present disclosure relates to a liquid repellent composition comprising a liquid repellent polymer and a liquid medium.

The preferred embodiments of the present disclosure are as follows.

Aspect 1:
A polymer having a repeating unit formed of 20 to 100% by weight of a cholesteryl group-containing monomer (a) with respect to the polymer.
The cholesteryl group-containing monomer (a) is a (meth) acryloyloxy group (H ₂ C = CH-C (= O) -O- or H ₂ C = C (CH ₃ ) -C (= O) -O. -) And a polymer that is a monomer having a cholesteryl group.

Aspect 2:
An embodiment in which the polymer further has a repeating unit formed from at least one or more of the following monomers (b), (c), (d) and (e) in addition to the monomer (a). The polymer according to 1.
(B) A (meth) acrylate monomer having a chain or cyclic hydrocarbon group having 1 to 40 carbon atoms in an alcohol residue,
(C) Crosslinkable monomer,
(D) Halogenated olefin monomer,
(E) Polydimethylsiloxane having a (meth) acryloyl group at one end

Aspect 3:
The cholesteryl group-containing monomer (a) has the formula:
H ₂ C = C (-X) -C (= O) -O-Y ^1- Y ^2- Chol
[In the formula, X is a hydrogen atom, a methyl group or a chlorine atom,
Y ¹ is a direct bond or a divalent hydrocarbon group having 1 to 10 carbon atoms.
Y ² is a direct bond or a group composed of at least one selected from -O-, -C (= O)-, -S (= O) _{2- or -NH-.}
Chol is a cholesteryl group. ]
It is a compound indicated by
The hydrocarbon group-containing (meth) acrylate monomer (b) has the formula:
CH ₂ = CA ¹ COOA ²
[In the formula, A ¹ is a halogen atom other than a hydrogen atom, a methyl group, or a fluorine atom (for example, a chlorine atom, a bromine atom, and an iodine atom).
A ² is a chain or cyclic hydrocarbon group having 1 to 40 carbon atoms. ]
It is a compound indicated by
The crosslinkable monomer (c) has a compound having at least two ethylenically unsaturated carbon-carbon double bonds, or at least one ethylenically unsaturated carbon-carbon double bond and at least one reactive group. It is a compound
The halogenated olefin monomer (d) is a chlorinated olefin having 2 to 20 carbon atoms.
The polysiloxane monomer (e) has an average formula:
_{(R 2 SiO) a (RR} F 'SiO) b
[In the formula, a is 2 to 4000,
b is 1 to 10 and
Each R is an independent, monovalent organic group,
Alternatively, each R is a hydrocarbon group having 1 to 30 carbon atoms.
Alternatively, each R is a monovalent alkyl group having 1 to 12 carbon atoms.
Alternatively, each R is a methyl group;
Each R ^F'is R ^V (where R ^V is the formula: -R ¹ -CH = CH ₂ (where R ¹ is a divalent hydrocarbon group having at least two carbon atoms)). It is the group shown.),
^RA ( ^RA is the formula: -R ¹ -NH-C (= O) -CQ = CH ₂ (in the formula, R ¹ is a divalent hydrocarbon group having at least two carbon atoms, Q is hydrogen. A group represented by an atom or a methyl group.), Or R ^MA (R ^MA is the formula: -R ¹ -OC (= O) -CQ = CH ₂ (in the formula, R ¹ is at least A divalent hydrocarbon group having two carbon atoms, Q is a hydrogen atom or a methyl group)). ]
The polymer according to aspect 1 or 2, which is a compound represented by.

Aspect 4:
The cholesteryl group-containing monomer (a) is at least one compound selected from the group consisting of cholesteryl (meth) acrylate or cholesteryl urethane (meth) acrylate.
The hydrocarbon group-containing (meth) acrylate monomer (b) is at least one compound selected from the group consisting of stearyl (meth) acrylate, behenyl (meth) acrylate and isobornyl (meth) acrylate.
The crosslinkable monomer (c) is
Diacetone acrylamide, (meth) acrylamide, N-methylol acrylamide, 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) acrylate, butadiene, isoprene, chloroprene and glycidyl (meth) acrylate.
The halogenated olefin monomer (d) is at least one compound selected from the group consisting of vinyl chloride and vinylidene chloride.
The polysiloxane monomer (e) has an average formula:
_{(R 2 SiO) a (RR} F 'SiO) b
[In the formula, a is 2 to 4000,
b is 1 to 10 and
Each R is a methyl group,
Each R ^{F 'is} R ^MA (R ^MA has the ^{formula: -R 1 -OC (= O)} -CQ = CH 2 ( wherein, R ¹ is a divalent hydrocarbon having at least 2 carbon atoms A group, Q is a hydrogen atom or a methyl group.) Is a group represented by). ]
The polymer according to any one of aspects 1 to 3, which is a compound represented by.

Aspect 5:
For the polymer
The amount of the monomer (a) (repeating unit formed from) is 20 to 100% by weight.
The amount of the monomer (b) (repeating unit formed from) is 0 to 80% by weight.
The amount of the monomer (c) (repeating unit formed from) is 0 to 20% by weight.
The amount of the monomer (d) (repeating unit formed from) is 0 to 70% by weight.
The polymer according to any one of embodiments 1 to 4, wherein the amount of the monomer (e) (repeating unit formed from) is 0 to 80% by weight.
Aspect 6:
(1) A surface treatment agent comprising the polymer according to any one of aspects 1 to 5 and (2) a liquid medium.

Aspect 7:
The surface treatment agent according to embodiment 6, wherein the liquid medium (2) is an organic solvent, or is water, an organic solvent, or a mixture of water and an organic solvent.
Aspect 8:
(I) The surface treatment agent is a solution in which the polymer is dissolved in an organic solvent, or (ii) the surface treatment agent is such that the polymer is dispersed in water or a mixture of water and an organic solvent. The surface treatment agent according to Aspect 6 or 7, wherein the surface treatment agent is an aqueous dispersion and the surface treatment agent comprises (3) a surfactant containing a nonionic surfactant.
Aspect 9:
The surface treatment agent according to any one of aspects 6 to 8, wherein the surface treatment agent is a water repellent agent, an oil repellent agent, an antifouling agent, a stain remover, a release agent or a mold release agent.

Aspect 10:
Aspects 6-9, comprising a step of polymerizing a monomer containing a cholesteryl group-containing monomer (a) in the presence of a liquid medium to obtain a dispersion or solution of the liquid-repellent polymer (1). A method for producing the surface treatment agent according to any one.
Aspect 11:
A method for producing a treated substrate, which comprises applying the surface treatment agent according to any one of aspects 6 to 9 to the substrate.
Aspect 12:
A base material to which the polymer according to any one of aspects 1 to 5 is attached.

The surface treatment agent of the present disclosure does not cause sedimentation of particles, and the polymer does not adhere to the roll to cause stains on the fabric.
According to the present disclosure, excellent water repellency, oil repellency, stain resistance and stain removal property, particularly excellent water repellency, can be obtained. Water repellency, oil repellency, stain resistance and stain removal are excellent in durability (for example, washing durability).
According to the present disclosure, the texture of the base material is good, and even if the base material is treated at a low temperature, good performance can be exhibited.
Further, it is excellent in processing stability during polymer treatment.

The surface treatment agent contains a liquid-repellent polymer as an active ingredient. In the present specification, the liquid-repellent polymer may be simply referred to as a "polymer".

The surface treatment agent is
It contains (1) a liquid-repellent polymer and (2) a liquid medium.
The surface treatment agent may further contain (3) a surfactant and (4) at least one component selected from the group consisting of other components.

The liquid-repellent polymer (1) is a non-fluorine polymer. The monomer constituting the liquid-repellent polymer (1) does not contain a fluorine atom, that is, it is non-fluorine.

The liquid-repellent polymer (1) is
(A) It has a repeating unit formed from a cholesteryl group-containing monomer.
The liquid-repellent polymer (1) is further added.
(B) Hydrocarbon group-containing (meth) acrylate monomer,
(C) Crosslinkable monomer,
It may have a repeating unit formed from at least one monomer selected from the group consisting of (d) a halogenated olefin monomer and (e) a polysiloxane monomer.
The liquid-repellent polymer (1) is repeatedly formed from monomers other than (f) monomers (a) to (e) in addition to the monomers (a) to (e). It may have a unit.

(A) Cholesteryl group-containing monomer The cholesteryl group-containing monomer (a) is a (meth) acryloyloxy group (H ₂ C = CH-C (= O) -O- or H ₂ C = C (CH _3). ) -C (= O) -O-) and a monomer having a cholesteryl group.
The cholesteryl group-containing monomer (a) has the formula:
H ₂ C = C (-X) -C (= O) -O-Y ^1- Y ^2- Chol
[In the formula, X is a hydrogen atom, a methyl group or a chlorine atom,
Y ¹ is a direct bond or a divalent hydrocarbon group having 1 to 10 carbon atoms.
Y ² is a direct bond or a group composed of at least one selected from -O-, -C (= O)-, -S (= O) _{2- or -NH-.}
Chol is a cholesteryl group. ]
It is preferably a compound represented by.

Although X is a hydrogen atom, a methyl group or a chlorine atom, it is preferably a hydrogen atom because of its good liquid repellency and processing stability.

Y ¹ is a direct bond or a divalent hydrocarbon group having 1 to 10 carbon atoms. The number of carbon atoms of the divalent hydrocarbon group is preferably an integer of 1 to 5, particularly 2 or 4.

Y ² is a direct bond or a group formed by at least one of -O-, -C (= O)-, -S (= O) _{2- or -NH-.}
As ^{specific examples of Y 2} , -C (= O)-, -C (= O) -NH-, -C (= O) -O-, -NH-C (= O) -O-, -NH- C (= O)-, -NH-C (= O) -NH-, -NH-C ₆ H _6- , -NH-S (= O) _2- , or -S (= O) _2- NH- Can be mentioned.

Preferred examples of -Y ¹ -Y ^2- are direct bond,-(CH ₂ ) _m -NH-C (= O) -O-,-(CH ₂ ) _m- NH-S (= O) ₂ −, Or − (CH ₂ ) _m −S (= O) ₂ −NH− [m is 1 to 10. ]. It is particularly preferable that -Y ¹ -Y ^2- is a direct bond _{or-(CH 2} ) _m- NH-C (= O) -O-.

Chol is a cholesteryl group. The cholesteryl group includes not only a strict cholesteryl group but also a derivative of the cholesteryl group, for example, a dehydrocholesteryl group.

で示され、コレステリルウレタンアクリレートは、式；

で示される。 Preferred specific examples of the cholesteryl group-containing monomer (a) are cholesteryl (meth) acrylate or cholesteryl urethane (meth) acrylate. Cholesteryl methacrylate is expressed in the formula:

Indicated by, cholesteryl urethane acrylate is the formula;

Indicated by.

(B) Hydrocarbon Group-Containing (Meta) Acrylate Monomer The hydrocarbon group-containing (meth) acrylate monomer (b) is a chain or cyclic hydrocarbon group having 1 to 40 carbon atoms in the alcohol residue. It is a (meth) acrylate monomer having. The hydrocarbon group-containing (meth) acrylate monomer (b) is a (meth) acrylate ester having a chain or cyclic hydrocarbon group having 1 to 40 carbon atoms.
The hydrocarbon group-containing (meth) acrylate monomer (b) has the formula:
CH ₂ = CA ¹ COOA ²
[In the formula, A ¹ is a halogen atom other than a hydrogen atom, a methyl group, or a fluorine atom (for example, a chlorine atom, a bromine atom, and an iodine atom).
A ² is a chain or cyclic hydrocarbon group having 1 to 40 carbon atoms. ]
It may be a compound indicated by.
The number of carbon atoms of the hydrogen water group is preferably 4 to 30, for example, 5 to 26, particularly preferably 6 to 22.

Chain hydrocarbon groups are linear or branched hydrocarbon groups that are saturated or unsaturated. The chain hydrocarbon group is preferably a linear saturated hydrocarbon group. The chain hydrocarbon group is preferably an alkyl group. The number of carbon atoms is 7 to 40, preferably 11 to 27, and particularly preferably 15 to 23.
Specific examples of chain hydrocarbon groups _{are alkyl groups represented by C n} H _{2n + 1} (n is 7-40), such as lauryl, stearyl and behenyl.

The cyclic hydrocarbon group may be a saturated or unsaturated monocyclic group, a polycyclic group, a bridging ring group, or the like. The cyclic hydrocarbon group is preferably saturated. The cyclic hydrocarbon group preferably has 4 to 20 carbon atoms. Examples of the hydrocarbon group of the ring 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 of the cyclic hydrocarbon group is particularly preferably 15 or less, for example, 10 or less. It is preferred that the carbon atom in the ring of the cyclic hydrocarbon group is directly attached to the ester group in the (meth) acrylate group. 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, a dicyclopentenyl group, and an 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, and dicyclopentanyl (meth). Acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2- Examples thereof include ethyl-2-adamantyl (meth) acrylate.

By having the repeating unit formed from the hydrocarbon group-containing (meth) acrylate monomer (b), the liquid repellency (particularly water repellency), the film-forming property, and the texture are enhanced.

(C) Crosslinkable monomer The crosslinkable monomer (c) is a monomer containing no fluorine atom. The non-fluorine crosslinkable monomer (A4) may be a fluorine-free compound having at least two reactive groups and / or an ethylenically unsaturated carbon-carbon double bond. The crosslinkable monomer (c) has a compound having at least two ethylenically unsaturated carbon-carbon double bonds, or at least one ethylenically unsaturated carbon-carbon double bond and at least one reactive group. It may be a compound. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, and the like.

Examples of the crosslinkable monomer (c) include diacetone acrylamide, (meth) acrylamide, N-methylol acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and 3-chloro-2-hydroxypropyl ( Meta) acrylate, 2-acetoacetoxyethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, butadiene, isoprene, chloroprene, glycidyl (meth) acrylate, 2 -[(3,5-dimethylpyrazolyl) carboxyamino] ethyl methacrylate and the like are exemplified, but the present invention is not limited thereto.

Having a repeating unit formed from the crosslinkable monomer (c) enhances the washing durability of liquid repellency, particularly water repellency.

(D) Halogenated olefin monomer The halogenated olefin monomer (d) may be a halogenated olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. .. The halogenated olefin monomer (d) is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms and having 1 to 5 chlorine atoms. Preferred specific examples of the halogenated olefin monomer (d) are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide and vinylidene halides such as vinylidene chloride, vinylidene bromide and vinylidene iodide.
Having a repeating unit formed from the crosslinkable monomer (d) enhances the washing durability of liquid repellency, particularly water repellency.

(E) Polysiloxane monomer The polysiloxane monomer (e) is an organopolysiloxane having an olefinic double bond. The polysiloxane monomer may be a vinyl-functional organopolysiloxane, a (meth) acrylamide-functional organopolysiloxane, and / or a (meth) acrylate-functional organopolysiloxane.

Various organopolysiloxanes are widely known in the art and _{are often represented by the general formula R n} SiO _{(4-n) / 2} , in which case the organopolysiloxane is an arbitrary number of "M". (Unifunctional) siroxy unit (R ₃ SiO _0.5 ), "D" (bifunctional) siroxy unit (R ₂ SiO), "T" (trifunctional) siroxy unit (RSiO _1.5 ), Alternatively, it may contain a "Q" syloxy unit (SiO ₂ ) (in the formula, R is an independent, monovalent organic group). These syroxy units can be combined in various ways to form cyclic, linear or branched structures. The chemistry and physical properties of the resulting polymer structure can vary. For example, the organopolysiloxane can be a volatile or low viscosity liquid, a high viscosity liquid / gum, an elastomer or rubber, and a resin. R is independently a monovalent organic group, or R is a hydrocarbon group having 1 to 30 carbon atoms, or R is an alkyl group having 1 to 30 carbon atoms, or R. Is a methyl group.

In a useful polysiloxane monomer (e), _{at least one of the R groups in the formula R n} SiO _{(4-n) / 2} is a vinyl group, a (meth) acrylamide group or a (meth) acrylate. A vinyl group, a (meth) acrylamide group or a (meth) acrylate functional group can be present at any siloxy unit having an R substituent. That is, the vinyl functional group, the (meth) acrylamide functional group or the (meth) acrylate functional group can be present in any M unit, D unit or T unit. Typically, a vinyl group, a (meth) acrylamide group or a (meth) acrylate group is present as an R substituent in the D syroxy unit.

Vinyl-functional organic groups are represented by R ^V in the formula herein, where R ^V is the formula: -R ¹ -CH = CH ₂ (where R ¹ is divalent with at least two carbon atoms. It is exemplified by the group represented by). For R ¹ , the hydrocarbon may have 2 to 10 carbon atoms, especially 2 to 6. An example of a carbon atom vinyl functional organic group is as follows;
-CH = CH ₂ , -CH ₂ CH ₂ CH ₂ -CH = CH ₂ , -CH ₂ CHCH ₃ -CH = CH ₂ , -CH ₂ CH ₂ CH ₂ CH ₂ -CH = CH ₂ , -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -CH = CH ₂ , -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -CH = CH ₂ . Typically, the vinyl functional group is -CH = CH ₂ .

The (meth) acrylamide functional organic group is represented by ^RA in the formula herein, where ^RA is the formula: -R ¹ -NH-C (= O) -CQ = CH ₂ (in the formula, R ¹ is , A divalent hydrocarbon group having at least two carbon atoms, where Q is a hydrogen atom or a methyl group). For R ¹ , the hydrocarbon may have 2 to 10 carbon atoms, especially 2 to 6. An example of a (meth) acrylamide functional group is:
-CH ₂ CH ₂ CH ₂ -NH-C (= O) -CH = CH ₂ , -CH ₂ CH ₂ CH ₂ -NH-C (= O) -C (CH ₃ ) = CH ₂ , -CH ₂ CHCH ₃ -NH-C (= O) -CH = CH ₂ , -CH ₂ CHCH ₃ -NH-C (= O) -C (CH ₃ ) = CH ₂ , -CH ₂ CH ₂ CH ₂ CH ₂ -NH- C (= O) -C (CH ₃ ) = CH ₂ , -CH ₂ CH ₂ CH ₂ CH ₂ -NH-C (= O) -C (CH ₃ ) = CH ₂ . Typically, the (meth) acrylamide functional group is -CH ₂ CH ₂ CH ₂ -NH-C (= O) -C (CH ₃ ) = CH ₂ .

The (meth) acrylate functional organic group is represented by R ^MA in the formula herein, where R ^MA is the formula: -R ¹ -OC (= O) -CQ = CH ₂ (in the formula, R ¹ is It is exemplified by a divalent hydrocarbon group having at least two carbon atoms, where Q is a hydrogen atom or a methyl group). For R ¹ , the hydrocarbon may have 2 to 10 carbon atoms, especially 2 to 6. An example of a (meth) acrylate functional group is:
-CH ₂ CH ₂ CH ₂ -OC (= O) -CH = CH ₂ , -CH ₂ CH ₂ CH ₂ -OC (= O) -C (CH ₃ ) = CH ₂ ,
-CH ₂ CHCH3-OC (= O)-CH = CH ₂ , -CH ₂ CHCH3-OC (= O) -C (CH ₃ ) = CH ₂ ,
-CH ₂ CH ₂ CH ₂ CH ₂ -OC (= O) -C (CH ₃ ) = CH ₂ , -CH ₂ CH ₂ CH ₂ CH ₂ -OC (= O) -C (CH3) = CH ₂ . Typically, the (meth) acrylate functional group is -CH ₂ CH ₂ CH ₂ -OC (= O) -C (CH3) = CH ₂ .

In a preferred embodiment, the polysiloxane monomer (e) has a syroxy unit having the following average formula:
_{(R 2 SiO) a (RR} F 'SiO) b
[In the formula, a is 2 to 4000,
b is 1 to 10 and
Each R is an independent, monovalent organic group,
Alternatively, each R is a hydrocarbon group having 1 to 30 carbon atoms.
Alternatively, each R is a monovalent alkyl group having 1 to 12 carbon atoms.
Alternatively, each R is a methyl group;
Each R ^F'is R ^V (where R ^V is the formula: -R ¹ -CH = CH ₂ (where R ¹ is a divalent hydrocarbon group having at least two carbon atoms)). It is the group shown.),
^RA ( ^RA is the formula: -R ¹ -NH-C (= O) -CQ = CH ₂ (in the formula, R ¹ is a divalent hydrocarbon group having at least two carbon atoms, Q is hydrogen. A group represented by an atom or a methyl group.), Or R ^MA (R ^MA is the formula: -R ¹ -OC (= O) -CQ = CH ₂ (in the formula, R ¹ is at least A divalent hydrocarbon group having two carbon atoms, Q is a hydrogen atom or a methyl group)).
a may be 5 to 400. b is preferably 1 or 2, especially 1.
It is particularly preferable that each R is a methyl group.

The polysiloxane monomer (e) may be terminally hydrogen atom (which is a silanol group in the terminal siloxy unit of the terpolymer) or is an alkyl group having 1 to 30 carbon atoms. It may be (this is the alkoxy group in the terminal siloxy unit of the terpolymer). When an alkyl group is used, the alkyl group may be a linear alkyl or a branched alkyl having 1 to 30 carbon atoms, or the alkyl group may have 4 to 20 (or 8 to 20) carbon atoms. It may be a long-chain alkyl group of (eg, stearyl). Alternatively, the organopolysiloxane may have a trimethylsilyl group at the end.

Having a repeating unit formed from the polysiloxane monomer (e) enhances liquid repellency, especially water repellency. It also has the effect of giving the base material a flexible texture.

(F) Other Monomers Preferred examples of the other monomer (f) include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and methoxypolyethylene. Includes glycol (meth) acrylates, methoxypolypropylene glycol (meth) acrylates, and vinyl alkyl ethers. The other monomer (f) is not limited to these examples.
It is preferable that the monomer (f) is not present in the polymer.

Each of the monomers (a), (b), (c), (d), (e) and (f) may be one kind or a combination of two or more kinds.

Preferred combinations of monomers in the polymer are as follows.
Monomer (a),
Monomer (a) + (b),
Monomer (a) + (b) + (c), and monomer (a) + (b) + (c) + (e).
In the above combination, it is preferable to further contain the halogenated olefin monomer (d).

The amount of the monomer (a) (repeating unit formed from) is 20 to 100% by weight, preferably 30 to 98% by weight, for example 35 to 95% by weight, particularly 40 to 90% by weight, based on the polymer. May be%.
In the polymer, with respect to 100 parts by weight of the monomer (a) (repeating unit formed from).
The amount of the monomer (b) (repeating unit formed from) is 500 parts by weight or less, for example 0.1 to 300 parts by weight, particularly 1 to 200 parts by weight.
The amount of the monomer (c) (repeating unit formed from) is 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 monomer (d) (repeating unit formed from) is 500 parts by weight or less, for example 0.1 to 300 parts by weight, particularly 1 to 200 parts by weight.
The amount of the monomer (e) (repeating unit formed from) is 500 parts by weight or less, for example, 0.1 to 300 parts by weight, particularly 1 to 200 parts by weight.
The amount of the monomer (f) (repeating unit formed from) may be 500 parts by weight or less, for example 0.1 to 300 parts by weight, particularly 1 to 200 parts by weight.

Alternatively, for the polymer
The amount of the monomer (a) (repeating unit formed from) is 20-100% by weight, preferably 25-98% by weight, for example 30-95% by weight, particularly 35-90% by weight.
The amount of the monomer (b) (repeating unit formed from) is 0 to 80% by weight, for example 0.1 to 70% by weight, particularly 1 to 60% by weight.
The amount of the monomer (c) (repeating unit formed from) is 0 to 20% by weight, for example 0.1 to 10% by weight, particularly 0.5 to 5% by weight.
The amount of the monomer (d) (repeating unit formed from) is 0 to 70% by weight, for example 0.1 to 50% by weight, particularly 1 to 40% by weight.
The amount of the monomer (e) (repeating unit formed from) is 0 to 80% by weight, for example 0.1 to 70% by weight, particularly 1 to 60% by weight.
The amount of the monomer (f) (repeating unit formed from) may be 0 to 80% by weight, for example 0.1 to 70% by weight, particularly 1 to 60% by weight.
Alternatively, for the polymer,
The amount of the monomer (a) (repeating unit formed from) is preferably 25-98% by weight, for example 30-95% by weight, particularly 35-90% by weight.
The amount of the monomer (b) (repeating unit formed from) is 5 to 70% by weight, for example 10 to 65% by weight, particularly 15 to 60% by weight.
The amount of the monomer (c) (repeating unit formed from) is 0.1 to 10% by weight, for example 0.2 to 8% by weight, particularly 0.5 to 5% by weight.
The amount of the monomer (d) (repeating unit formed from) is 0 to 50% by weight, for example 0.1 to 40% by weight, particularly 1 to 30% by weight.
The amount of the monomer (e) (repeating unit formed from) is 0 to 10% by weight, for example 0.1 to 15% by weight, particularly 1 to 10% by weight.
The amount of the monomer (f) (repeating unit formed from) may be 0 to 10% by weight, particularly 0% by weight.

The number average molecular weight (Mn) of the liquid-repellent polymer may be generally 1000 to 10000, for example 2000 to 500000, particularly 3000 to 20000. The number average molecular weight (Mn) of the liquid-repellent polymer is generally measured by GPC (gel permeation chromatography).

(2) Liquid medium The surface treatment agent contains a liquid medium. The liquid medium is an organic solvent or is water, an organic solvent or a mixture of water and an organic solvent.
The surface treatment agent is generally a solution or a dispersion. The solution is a solution in which the polymer is dissolved in an organic solvent. The dispersion is an aqueous dispersion in which the polymer is dispersed in an aqueous medium (water or a mixture of water and an organic solvent).

Examples of organic solvents are esters (eg, esters with 2-40 carbon atoms, specifically ethyl acetate, butyl acetate), ketones (eg, ketones with 2-40 carbon atoms, specifically methyl ethyl ketone, diisobutyl). Ketones), alcohols (eg, alcohols with 1-40 carbon atoms, specifically isopropyl alcohols), aromatic solvents (eg, toluene and xylene), petroleum-based solvents (eg, alkanes with 5-10 carbon atoms, etc.). Specifically, it is a solvent, kerosene).
The liquid medium may be water alone or a mixture of water and a (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) Surfactant When the surface treatment agent (water repellent composition) is an aqueous dispersion, it is preferable to contain a surfactant.
In the surface treatment agent, the surfactant includes a nonionic surfactant. Further, 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.
Each of the nonionic surfactant, the cationic surfactant, and the amphoteric surfactant may be one kind or a combination of two or more.
The total amount of the surfactant may be 0.1 to 20 parts by weight, for example 0.2 to 10 parts by weight, based on 100 parts by weight of the polymer (or monomer).
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 amount of the cationic surfactant may be 0.05 to 10 parts by weight, for example, 0.1 to 8 parts by weight, based on 100 parts by weight of the polymer. The weight ratio of the nonionic surfactant to the cationic surfactant may be preferably 95: 5 to 20:80, more preferably 85: 15 to 40:60.

(4) Other components The surface treatment agent may contain at least one of a non-fluorine water-repellent compound and an additive as other components other than the liquid-repellent polymer, the liquid medium and the surfactant.
(E1) Non-Fluorine Water-Repellent Compound The surface treatment agent may contain a water-repellent compound (non-fluorine water-repellent compound) that does not contain a fluorine atom.
The non-fluorine water repellent compound may be a non-fluorine acrylate polymer, a saturated or unsaturated hydrocarbon compound, or a silicone-based compound.

The non-fluorinated acrylate polymer is a homopolymer composed of one kind of non-fluorinated acrylate monomer, a copolymer composed of at least two kinds of non-fluorinated acrylate monomers, or at least one kind of non-fluorinated polymer. It is a copolymer composed of an acrylate monomer and at least one other non-fluorine monomer (ethylenically unsaturated compound, for example, ethylene or vinyl-based monomer).
The non-fluorine acrylate monomer constituting the non-fluorine acrylate polymer has the formula:
CH ₂ = CA-T
[In the formula, A is a halogen atom other than a hydrogen atom, a methyl group, or 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 40 carbon atoms, or a chain or cyclic organic group having 1 to 41 carbon atoms having an ester bond. ]
It is a compound indicated by.

Examples of chain or cyclic hydrocarbon groups with 1 to 40 carbon atoms are linear or branched aliphatic hydrocarbon groups with 1 to 40 carbon atoms, cyclic aliphatic group with 4 to 40 carbon atoms, and 6 to 40 carbon atoms. It is an aromatic hydrocarbon group having 40 carbon atoms and an aromatic aliphatic hydrocarbon group having 7 to 40 carbon atoms.

Examples of chain or cyclic organic groups with 1-41 carbon atoms with ester bonds are -C (= O) -OQ and -OC (= O) -Q (where Q is 1-40 carbon atoms). Linear or branched aliphatic hydrocarbon group, cyclic aliphatic group having 4 to 40 carbon atoms, aromatic hydrocarbon group having 6 to 40 carbon atoms, aromatic aliphatic hydrocarbon group having 7 to 40 carbon atoms). ..

Examples of non-fluorinated acrylate monomers include, for example, alkyl (meth) acrylates, polyethylene glycol (meth) acrylates, polypropylene glycol (meth) acrylates, methoxypolyethylene glycol (meth) acrylates, methoxypolypropylene glycol (meth) acrylates. Is done.

The non-fluorine acrylate monomer is preferably an alkyl (meth) acrylate ester. The number of carbon atoms in the alkyl group may be 1-40, for example 6-40 (eg 10-30). Specific examples of the non-fluorinated 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 liquid-repellent polymer.

The saturated or unsaturated hydrocarbon compound is preferably a saturated hydrocarbon. In saturated or unsaturated hydrocarbon compounds, the number of carbon atoms may be 15 or more, preferably 20 to 300, for example 25 to 100. Specific examples of saturated or unsaturated hydrocarbon compounds include paraffin.
Silicone compounds are generally used as water repellents. The silicone-based 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 liquid-repellent polymer.

(E2) Additive The surface treatment agent may contain an additive.
Examples of additives are silicon-containing compounds, waxes, acrylic emulsions and the like. Other examples of additives include drying rate regulators, cross-linking agents, film-forming aids, compatibilizers, surfactants, antifreeze agents, viscosity regulators, UV absorbers, antioxidants, pH regulators, defoamers. Foaming agents, texture regulators, slipperiness regulators, antistatic agents, hydrophilic agents, antibacterial agents, preservatives, insect repellents, fragrances, flame retardants, etc.

The liquid-repellent polymer in the present disclosure can be produced by any of ordinary polymerization methods, and the conditions of the polymerization reaction can be arbitrarily selected. Examples of such a polymerization method include solution polymerization, suspension polymerization, and emulsion polymerization.

In solution polymerization, a method of dissolving a monomer in an organic solvent in the presence of a polymerization initiator, substituting with nitrogen, and then heating and stirring in the range of 30 to 120 ° C. for 1 to 10 hours is adopted. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butylperoxypivalate, diisopropylperoxydicarbonate 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 inert to the monomer and dissolves them, for example, an ester (for example, an ester having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (for example, carbon). It may be a ketone having the number of 2 to 40, specifically, a methyl ethyl ketone or a diisobutyl ketone), or an alcohol (for example, an alcohol having 1 to 40 carbon atoms, specifically, an 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, and the like. Examples thereof include diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichlorethylene, 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, based on 100 parts by weight of the monomer in total.

In emulsion polymerization, a method is adopted in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, substituted with nitrogen, and then stirred in the range of 50 to 80 ° C. for 1 to 10 hours for polymerization. The polymerization initiators are benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexylhydro peroxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine-dihydrochloride, and peroxide. Water-soluble substances such as sodium oxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypi Oil-soluble substances such as valet and diisopropylperoxydicarbonate 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 standing stability, a monomer is atomized into fine particles and polymerized using an emulsifying device such as a high-pressure homogenizer or an ultrasonic homogenizer that can impart strong crushing energy. Is desirable. Further, as the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and they are used in the range of 0.5 to 20 parts by weight with respect to 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 completely compatible, it is preferable to add a compatibilizer that is sufficiently compatible with these monomers, for example, a water-soluble organic solvent or a low molecular weight monomer. It is possible to improve emulsifying property and copolymerizability by adding a compatibilizer.

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, it may be used in the range of 10 to 40 parts by weight. Examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate and the like, and 1 to 50 parts by weight, based on 100 parts by weight of the total amount of the monomer. For example, it may be used in the range of 10 to 40 parts by weight.

A chain transfer agent may be used in the polymerization. The molecular weight of the polymer can be changed according to the amount of the chain transfer agent used. Examples of chain transfer agents are mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, thioglycerol (particularly alkyl mercaptan (eg, 1-40 carbon atoms)), inorganic salts such as sodium hypophosphite, sodium bisulfite. And so on. The amount of the chain transfer agent 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 surface treatment agent may be in the form of a solution, an emulsion (particularly an aqueous dispersion) or an aerosol, but is preferably an aqueous dispersion. The surface treatment agent comprises a polymer (active ingredient of the surface treatment agent) and a medium (particularly a liquid medium, such as an organic solvent and / or water). The amount of the medium may be, for example, 5-99.9% by weight, particularly 10-80% by weight, based on the treating agent.
In the surface treatment agent, the concentration of the polymer may be 0.01 to 95% by weight, 0.1 to 60% by weight, for example, 5 to 50% by weight.

The surface treatment agent can be used as a water repellent agent, an oil repellent agent, an antifouling agent, a stain remover, a release agent and a mold release agent.

The surface treatment agent can be applied to the object to be treated by a conventionally known method. Usually, a method is adopted in which the treatment agent is dispersed in an organic solvent or water, diluted, and adhered to the surface of the object to be treated by a known method such as dip coating, spray coating, foam coating and the like, and dried. .. If necessary, it may be applied together with a suitable cross-linking agent (for example, blocked isocyanate) for curing. Further, 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 surface treatment agent and use them in combination. The concentration of the liquid-repellent polymer in the treatment liquid to be 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.

Objects to be treated with a surface treatment agent (eg, water and oil repellent) include textile products, stones, filters (eg, electrostatic filters), dust masks, fuel cell parts (eg, gas diffusion electrodes and gas). Diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, coated surfaces, and plasters. Various examples can be given as textile products. For example, animal and vegetable natural 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 textile product may be in any form such as fiber or cloth.

The treatment agent can impart the desired peelability to the surface of the base material. Therefore, the surface of the base material can be easily peeled off from another surface (another surface on the base material or a surface on another base material).
Examples of substrates to which the treatment agent is applied are textile products (eg, non-woven fabrics and woven fabrics), paper, stone, leather, resin, glass, metal and the like. The equipment is preferably cloth or paper.
The treatment agent can be stripped between similar substrates (eg, cloth to cloth, paper to paper), or between different substrates (eg, cloth to resin, cloth to metal, paper to cloth, paper to glass). Used for peeling. The treatment agent can be used in the production of adhesive sheets, protective materials for adhesive surfaces of adhesive tapes, release films, release papers, sticky notes, and the like.

The surface treatment agent can also be used as an internal mold release agent or an external mold release agent.

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

Alternatively, the liquid-repellent polymer may be applied to the textile product by a cleaning method, for example, may be applied to the textile product by a washing application or a dry cleaning method.

The textile products to be processed are typically fabrics, which include textiles, knitted fabrics and non-woven fabrics, fabrics and carpets in the form of clothing, but textiles or yarns or intermediate textile products (eg, sliver or Coarse yarn, etc.) may be used. The textile material may be a natural fiber (eg, cotton or wool), a synthetic fiber (eg, biscorayon or leocell), or a synthetic fiber (eg, polyester, polyamide or acrylic fiber), or , A mixture of fibers (eg, a mixture of natural and synthetic fibers, etc.). The liquid-repellent polymers of the present disclosure are particularly effective in making cellulosic fibers (eg, cotton or rayon) oleophobic and oil-repellent. Also, the methods of the present disclosure generally make textile products hydrophobic and water repellent.

Alternatively, the fibrous substrate may be leather. The liquid-repellent polymer can be used in various stages of leather processing to make the leather hydrophobic and oleophobic, eg, during the wet processing of the leather, or during the finishing of the leather. It may be applied to leather from an aqueous emulsion.
Alternatively, the fibrous substrate may be paper. The liquid repellent 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 applying the treatment agent to the object to be treated by dipping, spraying, coating or the like. During the treatment, the polymer, which is the active ingredient of the treatment agent, penetrates into the inside of the object to be treated and / or adheres to the surface of the object to be treated.

Hereinafter, the present disclosure will be described in detail with reference to examples, but the present disclosure is not limited to these examples.
In the following, parts or% or ratios represent parts by weight or% by weight or ratios by weight unless otherwise specified.
The test procedure is as follows.

<Water repellency>
A treatment solution is prepared, the cloth is dipped in this test solution, passed through a mangle, and the water repellency is evaluated with the heat-treated test cloth. The water repellency of the treated cloth was evaluated according to the spray method of JIS-L-1092 (AATCC-22). As shown in the table below, the water repellent No. Represented by. The higher the score, the better the water repellency.

<Gum up rate>
Prepare 1000 g of a diluted solution of the polymer dispersion 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 content concentration becomes 5% by weight. , Put it in a pad that can control the temperature to 40 ° C. A polyester cloth having a width of 20 cm and a length of 80 cm is looped around the mangle so that continuous treatment can be performed, and continuous treatment is performed at a mangle pressure of 0.4 MPa for 1 hour. The gum-up rate is calculated by the following formula.
(Amount of gum up to mangle) = (Weight before treatment of polyester cloth + Weight of solid content of diluted solution before treatment)-(Weight of polyester cloth after treatment + Weight of solid content of diluted solution after treatment)
(Gum-up rate) = 100 X (Gum-up amount to mangle) / (Weight of diluted solution solid before treatment)
When the gum-up rate is less than 4%, the gum-up is suppressed (processing stability is good).

The meanings of the abbreviations are as follows.

Synthesis Example 1: Synthesis of cholesteryl acrylate (CLA) 40 g of cholesterol, 100 g of toluene, 0.005 g of tertiary butylcatechol and 10.78 g of triethylamine were charged into a 200 cc four-necked flask. A stirring rod, a thermometer, a reflux tube, and a dropping funnel were set. 9.457 g of acrylic acid chloride was charged into the dropping funnel. Acrylic acid chloride was gradually added dropwise from the dropping funnel at room temperature over about 20 minutes, paying attention to heat generation. After completion of the dropping, the reaction was further carried out at room temperature for about 3 hours. As the reaction progresses, the triethylamine salt of hydrochloric acid precipitates. It was confirmed by infrared spectroscopy (IR) that the peak derived from the hydroxyl group had disappeared, and the reaction was terminated. Further, 50 g of pure water was added and the mixture was stirred for 20 minutes, and then the contents were transferred to a separating funnel. After allowing to stand for 1 hour, the aqueous layer part was taken out. After newly adding 50 g of pure water and shaking well, the mixture was allowed to stand again and the aqueous layer portion was taken out (washing with water). After repeating this washing with water again, the oil layer (toluene solution) was detolueneized with an evaporator to obtain a reaction product. The reaction was identified as cholesteryl acrylate by 1 NMR.

Synthesis Example 2: Synthesis of cholesteryl urethane acrylate (CLUA) 40 g of cholesterol, 70 g of toluene, 0.005 g of tertiary butylcatechol, and 0.005 g of dibutyltin dilaurate were charged into a 200 cc four-necked flask. A stirring rod, a thermometer, a reflux tube, and a dropping funnel were set. The dropping funnel was charged with 14.453 g of 2-acryloyloxyethyl isocyanate (CH ₂ = CH-COO-CH ₂ CH _2- NCO) and 30 g of toluene. The temperature is raised to 75 ° C, and _{a toluene solution of 2-acryloyloxyethyl isocyanate (CH 2} = CH-COO-CH ₂ CH _2- NCO) is gradually added from the dropping funnel over about 20 minutes, paying attention to heat generation. Dropped. After completion of the dropping, the temperature was raised to 80 ° C., and the reaction was further carried out for about 3 hours. It was confirmed by infrared spectroscopy (IR) that the peak derived from isocyanate had disappeared, and the reaction was terminated. The contents were taken out, put into a large amount of methanol, the precipitate was filtered, washed again with methanol, and then dried under reduced pressure. The reaction was identified by 1 H-NMR as cholesteryl urethane acrylate.

<Manufacturing of polymer solution>
Production Example 1
15 g of CLA and 80 g of toluene were charged in a 200 cc four-necked flask equipped with a nitrogen introduction tube, a thermometer, a stirring rod, and a reflux tube, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. Then, 0.4 g of a solution in which 0.4 g of AIBN (azobisisobutyronitrile) was dissolved was added to 5.0 g of toluene, the temperature was raised to 80 ° C., and the polymerization reaction was carried out for 12 hours. After the polymerization, toluene was further added to prepare a toluene solution having a solid content concentration of 10%.

Production Examples 2-4
Polymerization was carried out in the same manner as in Production Example 1 with the composition shown in Table 1, and after the polymerization, the mixture was diluted with toluene to prepare a toluene solution having a solid content concentration of 10%.

Comparative manufacturing example 1
Polymerization was carried out in the same manner as in Production Example 1 with the composition shown in Table 1, and after the polymerization, the mixture was diluted with toluene to prepare a toluene solution having a solid content concentration of 10%.

<Manufacturing of aqueous polymer dispersion>
Production Example 5
Tripropylene glycol 17g, CLA 30g, stearyl acrylate 29g, N-methylolacrylamide 1g, pure water 136g, dimethyldioctadecylammonium chloride 0.6g, sorbitan monopalmitate 1g, polyoxyethylene tridecyl ether 2g, poly in a 500ml plastic container 2.4 g of oxyethylene lauryl ether was charged, heated to 80 ° C., stirred with a homomixer at 2000 rpm for 1 minute, and then emulsified and dispersed with ultrasonic waves for 15 minutes. The emulsified dispersion was transferred to a 500 cc four-necked flask equipped with a nitrogen introduction tube, a thermometer, a stirring rod and a reflux tube, and after nitrogen substitution, 0.1 g of lauryl mercaptan was charged and stirred, and then 2,2-azobis (2-). Amidinopropane) 2 hydrochloride (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 the polymer. Then, pure water was added to prepare an aqueous dispersion having a solid content concentration of 20%.

Production Example 6
Polymerization was carried out in the same manner as in Production Example 5 with the composition shown in Table 2, and after the polymerization, the mixture was further diluted with pure water to prepare an aqueous dispersion having a solid content concentration of 20%.

Production example 7
Tripropylene glycol 30g, CLA 40g, stearyl acrylate 39g, diacetone acrylamide 1g, pure water 180g, trimethyloctadecylammonium chloride 2g, sorbitan monopalmitate 2g, polyoxyethylene tridecyl ether 2.5g, polyoxyethylene in a 500ml plastic container 3.5 g of lauryl ether was charged, heated to 80 ° C., stirred with a homomixer at 2000 rpm for 1 minute, and then emulsified and dispersed with ultrasonic waves for 15 minutes. The emulsified dispersion was transferred to a 500 ml autoclave, and after nitrogen substitution, 0.2 g of lauryl mercaptan and 20 g of vinyl chloride were charged. Further, 1 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C. for 4 hours to obtain an aqueous dispersion of the polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion having a solid content concentration of 20%.

Production Examples 8 to 10
Polymerization was carried out in the same manner as in Production Example 13 with the composition shown in Table 2, and after the polymerization, the mixture was further diluted with pure water to prepare an aqueous dispersion having a solid content concentration of 20%.

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

Test Example 1
The toluene solution 1 having a solid content concentration of 10% prepared in Production Example 1 was further diluted with toluene to prepare a treatment solution having a solid content concentration of 1.5%. After immersing the polyester cloth (gray) and nylon cloth (black) in this treatment liquid, the mixture was lightly centrifugally dehydrated for about 10 seconds. Wet pickups were about 65% (polyester cloth) and about 40% (nylon cloth). The treated cloth was dried overnight at room temperature and then passed through a pin tenter at 170 ° C. for 1 minute for heat treatment. The test cloth treated in this manner was evaluated for water repellency by a water repellency test by a spray method of JIS L-1092. The results are shown in Table 3.

Test Examples 2-4
Each toluene solution 2 to 4 having a solid content concentration of 10% prepared in Production Examples 2 to 4 is diluted with toluene in the same manner as in Test Example 1 (solid content concentration 1.5%), and the cloth is treated in the same manner as in Test Example 1. Then, a water repellency test was performed. The results are shown in Table 3.

Comparative test example 1
The toluene solution having a solid content concentration of 10% prepared in Comparative Production Example 1 was diluted with toluene so that the solid content concentration was 1.5% in the same manner as in Test Example 1, and the cloth was treated in the same manner as in Test Example 1. A water repellency test was performed. The results are shown in Table 3.

Comparative test example 2
Solid paraffin wax having a melting point of about 75 ° C. is diluted with toluene so that the solid content concentration becomes 1.5%.
The cloth was treated in the same manner as in Test Example 1 to perform a water repellency test. The results are shown in Table 3.

Test Example 5
The aqueous dispersion 5 having a solid content concentration of 20% prepared in Production Example 5 was further diluted with tap water to prepare a treatment liquid having a solid content concentration of 1.5%. A polyester cloth (gray) and a nylon cloth (black) were dipped in this treatment liquid, and then squeezed with a mangle. Wet pickups were about 55% (polyester cloth) and about 35% (nylon cloth). The treated cloth was passed through a pin tenter at 170 ° C. for 1 minute, dried and cured. The test cloth treated in this manner was evaluated for water repellency by a water repellency test by a spray method of JIS L-1092. The results of water repellency are shown in Table 4.
Table 4 also shows the evaluation results of the water repellency of the test cloth dried in a tumbler (60 ° C. for 30 minutes) after washing 10 times according to JIS L-0217 103. The results of measuring the gum-up rate are also shown in Table 4.

Test Examples 6-10
The aqueous dispersion having a solid content concentration of 20% prepared in Production Examples 6 to 10 was diluted with tap water so that the solid content concentration became 1.5% in the same manner as in Test Example 5, to prepare a treatment liquid. A cloth was treated with this treatment liquid in the same manner as in Test Example 5 to perform a water repellency test. The results are shown in Table 4. The results of measuring the gum-up rate are also shown in Table 4.

Comparative test examples 3-4
The aqueous dispersion having a solid content concentration of 20% prepared in Comparative Production Examples 2 to 3 was diluted with tap water so that the solid content concentration became 1.5% in the same manner as in Test Example 5, to prepare a treatment liquid. A cloth was treated with this treatment liquid in the same manner as in Test Example 5 to perform a water repellency test. The results are shown in Table 4. The results of measuring the gum-up rate are also shown in Table 4.

Since the melting point of the side chain microcrystals derived from the (urethane) acrylate-based polymer having a cholesteryl group of the present disclosure is higher than that of the conventional for example stearyllate-based polymer, it is presumed that gum-up is suppressed. Will be done. The melting points of each monomer are as follows.

The surface treatment agent of the present disclosure can be used as a water repellent, an oil repellent, an antifouling agent, a stain remover, a release agent and a mold release agent.

Claims (12)

A polymer having a repeating unit formed of 20 to 100% by weight of a cholesteryl group-containing monomer (a) with respect to the polymer.
The cholesteryl group-containing monomer (a) is a (meth) acryloyloxy group (H ₂ C = CH-C (= O) -O- or H ₂ C = C (CH ₃ ) -C (= O) -O. -) And a polymer that is a monomer having a cholesteryl group. Claims that the polymer further has a repeating unit formed from at least one or more of the following monomers (b), (c), (d) and (e) in addition to the monomer (a). Item 1. The polymer according to Item 1.
(B) A (meth) acrylate monomer having a chain or cyclic hydrocarbon group having 1 to 40 carbon atoms in an alcohol residue,
(C) Crosslinkable monomer,
(D) Halogenated olefin monomer,
(E) Polydimethylsiloxane having a (meth) acryloyl group at one end The cholesteryl group-containing monomer (a) has the formula:
H ₂ C = C (-X) -C (= O) -O-Y ^1- Y ^2- Chol
[In the formula, X is a hydrogen atom, a methyl group or a chlorine atom,
Y ¹ is a direct bond or a divalent hydrocarbon group having 1 to 10 carbon atoms.
Y ² is a direct bond or a group composed of at least one selected from -O-, -C (= O)-, -S (= O) _{2- or -NH-.}
Chol is a cholesteryl group. ]
It is a compound indicated by
The hydrocarbon group-containing (meth) acrylate monomer (b) has the formula:
CH ₂ = CA ¹ COOA ²
[In the formula, A ¹ is a halogen atom other than a hydrogen atom, a methyl group, or a fluorine atom (for example, a chlorine atom, a bromine atom, and an iodine atom).
A ² is a chain or cyclic hydrocarbon group having 1 to 40 carbon atoms. ]
It is a compound indicated by
The crosslinkable monomer (c) has a compound having at least two ethylenically unsaturated carbon-carbon double bonds, or at least one ethylenically unsaturated carbon-carbon double bond and at least one reactive group. It is a compound
The halogenated olefin monomer (d) is a chlorinated olefin having 2 to 20 carbon atoms.
The polysiloxane monomer (e) has an average formula:
_{(R 2 SiO) a (RR} F 'SiO) b
[In the formula, a is 2 to 4000,
b is 1 to 10 and
Each R is an independent, monovalent organic group,
Alternatively, each R is a hydrocarbon group having 1 to 30 carbon atoms.
Alternatively, each R is a monovalent alkyl group having 1 to 12 carbon atoms.
Alternatively, each R is a methyl group;
Each R ^F'is R ^V (where R ^V is the formula: -R ¹ -CH = CH ₂ (where R ¹ is a divalent hydrocarbon group having at least two carbon atoms)). It is the group shown.),
^RA ( ^RA is the formula: -R ¹ -NH-C (= O) -CQ = CH ₂ (in the formula, R ¹ is a divalent hydrocarbon group having at least two carbon atoms, Q is hydrogen. A group represented by an atom or a methyl group.), Or R ^MA (R ^MA is the formula: -R ¹ -OC (= O) -CQ = CH ₂ (in the formula, R ¹ is at least A divalent hydrocarbon group having two carbon atoms, Q is a hydrogen atom or a methyl group)). ]
The polymer according to claim 1 or 2, which is a compound represented by. The cholesteryl group-containing monomer (a) is at least one compound selected from the group consisting of cholesteryl (meth) acrylate or cholesteryl urethane (meth) acrylate.
The hydrocarbon group-containing (meth) acrylate monomer (b) is at least one compound selected from the group consisting of stearyl (meth) acrylate, behenyl (meth) acrylate and isobornyl (meth) acrylate.
The crosslinkable monomer (c) is
Diacetone acrylamide, (meth) acrylamide, N-methylol acrylamide, 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) acrylate, butadiene, isoprene, chloroprene and glycidyl (meth) acrylate.
The halogenated olefin monomer (d) is at least one compound selected from the group consisting of vinyl chloride and vinylidene chloride.
The polysiloxane monomer (e) has an average formula:
_{(R 2 SiO) a (RR} F 'SiO) b
[In the formula, a is 2 to 4000,
b is 1 to 10 and
Each R is a methyl group,
Each R ^{F 'is} R ^MA (R ^MA has the ^{formula: -R 1 -OC (= O)} -CQ = CH 2 ( wherein, R ¹ is a divalent hydrocarbon having at least 2 carbon atoms A group, Q is a hydrogen atom or a methyl group.) Is a group represented by). ]
The polymer according to any one of claims 1 to 3, which is a compound represented by. For the polymer
The amount of the monomer (a) (repeating unit formed from) is 20 to 100% by weight.
The amount of the monomer (b) (repeating unit formed from) is 0 to 80% by weight.
The amount of the monomer (c) (repeating unit formed from) is 0 to 20% by weight.
The amount of the monomer (d) (repeating unit formed from) is 0 to 70% by weight.
The polymer according to any one of claims 1 to 4, wherein the amount of the monomer (e) (repeating unit formed from) is 0 to 80% by weight. (1) A surface treatment agent comprising the polymer according to any one of claims 1 to 5 and (2) a liquid medium. The surface treatment agent according to claim 6, wherein the liquid medium (2) is an organic solvent, or is water, an organic solvent, or a mixture of water and an organic solvent. (I) The surface treatment agent is a solution in which the polymer is dissolved in an organic solvent, or (ii) the surface treatment agent is such that the polymer is dispersed in water or a mixture of water and an organic solvent. The surface treatment agent according to claim 6 or 7, wherein the surface treatment agent is an aqueous dispersion and the surface treatment agent comprises (3) a surfactant containing a nonionic surfactant. The surface treatment agent according to any one of claims 6 to 8, wherein the surface treatment agent is a water repellent agent, an oil repellent agent, an antifouling agent, a stain remover, a release agent or a mold release agent. Claims 6 to 9 include a step of polymerizing a monomer containing a cholesteryl group-containing monomer (a) in the presence of a liquid medium to obtain a dispersion or solution of the liquid-repellent polymer (1). The method for producing the surface treatment agent according to any one of the above. A method for producing a treated substrate, which comprises applying the surface treatment agent according to any one of claims 6 to 9 to the substrate. A base material to which the polymer according to any one of claims 1 to 5 is attached.