WO2022176290A1 - Water- and oil-repellent composition, fiber treating agent, fiber treatment method, processed fiber product and coating agent - Google Patents

Abstract

A water- and oil-repellent composition that comprises copolymer (A) containing no structural unit having a siloxane bond, copolymer (B) containing a structural unit having a siloxane bond, a polyether-modified polydimethylsiloxane and an aqueous medium, wherein: copolymer (A) contains a structural unit derived from a compound having an ethylenically unsaturated bond and an ester bond and having no carboxy group and a structural unit derived from a compound having an ethylenically unsaturated bond and a carboxy group; and copolymer (B) contains a structural unit derived from a compound having an ethylenically unsaturated bond and an ester bond and having no carboxy group, a structural unit derived from a compound having an ethylenically unsaturated bond and a carboxy group, and a structural unit derived from a polydimethylsiloxane having an ethylenically unsaturated bond.

Description

Water and oil repellent composition, fiber treatment agent, fiber treatment method, fiber processed product and coating agent

TECHNICAL FIELD The present invention relates to a water and oil repellent composition, a fiber treatment agent, a method for treating fibers, a processed fiber product, and a coating agent.
This application claims priority based on Japanese Patent Application No. 2021-023556 filed in Japan on February 17, 2021, the content of which is incorporated herein.

Conventionally, as a method of imparting water and oil repellency to substrates such as fibers and paper, water and oil repellent treatment using a water and oil repellent composition has been performed. Some water and oil repellent compositions contain a compound having a perfluoroalkyl group with 8 or more carbon atoms.

However, compounds containing perfluoroalkyl groups with 8 or more carbon atoms may generate perfluorooctanoic acid (hereinafter sometimes abbreviated as "PFOA") by decomposition or metabolism. There is Perfluorooctanoic acid is required by the US Environmental Protection Agency to reduce production. Therefore, a water and oil repellent composition containing a compound containing a perfluoroalkyl group with a short carbon chain has been proposed.

For example, Patent Document 1 discloses a pyrazole-blocked hydrophobic polyisocyanate aqueous dispersion containing a pyrazole-blocked hydrophobic polyisocyanate and a nonionic surfactant, and a water-repellent liquid having a perfluoroalkyl group having 6 or less carbon atoms. A water and oil repellent composition is described that includes an oil repellent component.

Patent Document 2 discloses a fluoropolymer having a structural unit having a polyfluoroalkyl group having 1 to 6 carbon atoms, a fluoropolymer having a structural unit based on a fluoroolefin, and an aqueous medium. A water and oil repellent composition is described.

Furthermore, in recent years, it has been considered to reduce the use of compounds containing perfluoroalkyl groups with short carbon chains. Therefore, water and oil repellent compositions containing no fluorine compounds have been proposed.

For example, in Patent Document 3, a copolymer (A) containing a structural unit based on an ethylenically unsaturated carboxylic acid ester monomer and a structural unit based on an ethylenically unsaturated carboxylic acid monomer is prepared in an aqueous medium. An oil repellent composition is described comprising an aqueous emulsion dispersed in (B) and a polyether-modified polydimethylsiloxane (C).

Patent Document 4 describes a silicone obtained by polymerizing a (meth)acrylate having a quaternary ammonium group, a (meth)acrylic-modified silicone oil at both ends, and a monomer containing a nonionic hydrophobic ethylenically unsaturated monomer. - Textile treatment oil repellents containing acrylic copolymers are described.

JP 2012-031285 A WO2012/020806 WO2018/163911 JP 2016-102272 A

However, conventional water and oil repellent compositions that do not contain fluorine-based compounds sometimes cannot impart sufficient oil and water repellency to substrates.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a water and oil repellent composition capable of imparting high oil repellency and water repellency to a substrate.
Another object of the present invention is to provide a fiber treatment agent, a paper treatment agent and a coating agent capable of imparting high oil repellency and water repellency to substrates.

In order to solve the above problems, the inventors have made extensive studies. As a result, a copolymer having a structural unit derived from a compound having an ethylenically unsaturated bond and a carboxy group, and a copolymer having a structural unit derived from a compound having an ethylenically unsaturated bond and a carboxy group and an ethylenically unsaturated bond The present inventors have found that a water- and oil-repellent composition containing a copolymer having a structural unit derived from polydimethylsiloxane can be provided, and have completed the present invention.
That is, the present invention relates to the following matters.

A first aspect of the present invention provides the following water and oil repellent composition.
[1] A copolymer (A) containing no structural unit having a siloxane bond, a copolymer (B) containing a structural unit having a siloxane bond, a polyether-modified polydimethylsiloxane (C), and an aqueous medium ( D) and
The copolymer (A) is
a structural unit (a1) derived from a compound having an ethylenically unsaturated bond and an ester bond and having no carboxyl group;
and a structural unit (a2) derived from a compound having an ethylenically unsaturated bond and a carboxy group,
The copolymer (B) is
a structural unit (b1) derived from a compound having an ethylenically unsaturated bond and an ester bond and having no carboxyl group;
a structural unit (b2) derived from a compound having an ethylenically unsaturated bond and a carboxy group;
A water and oil repellent composition having a structural unit (b3) derived from polydimethylsiloxane having an ethylenically unsaturated bond and represented by the following formula (1).

（式（１）において、Ｒ^１は水素原子又はメチル基を示す；Ｒ^２はエーテル結合を含んでもよい炭素原子数１～６の２価脂肪族基を示す；Ｒ^３は炭素原子数１～３０の脂肪族基、芳香族基、または水酸基を示す；ｈは０、１、２のいずれかである；ｊは０～５００の整数を示す。）

(In formula (1), R ¹ represents a hydrogen atom or a methyl group; R ² represents a divalent aliphatic group having 1 to 6 carbon atoms which may contain an ether bond; R ³ represents a C 1 to 30 aliphatic, aromatic, or hydroxyl groups; h is 0, 1, or 2; j is an integer from 0 to 500.)

The water and oil repellent composition of the first aspect of the present invention preferably has the characteristics described in [2] to [11] below. It is also preferable to arbitrarily combine two or more of the features described in [2] to [11] below.
[2] The water/oil repellent composition according to [1], wherein the structural unit (a1) and the structural unit (b1) are structural units derived from a compound having a (meth)acryloyl group.
[3] The water/oil repellent composition according to [1] or [2], wherein the structural unit (a2) and the structural unit (b2) are structural units derived from (meth)acrylic acid.

[4] The water repellent according to any one of [1] to [3], wherein the mass ratio of the copolymer (A) and the copolymer (B) is 10/90 or more and 90/10 or less. Oil composition.
[5] The water/oil repellent composition according to any one of [1] to [4], wherein the copolymer (A) contains 0.10% by mass or more and 20% by mass or less of the structural unit (a2). .

[6] The water and oil repellent composition according to any one of [1] to [5], wherein the copolymer (B) contains 0.10% by mass or more and 20% by mass or less of the structural unit (b2). .
[7] The water/oil repellent composition according to any one of [1] to [6], wherein the copolymer (B) contains 3.0% by mass or more and 50% by mass or less of the structural unit (b3). .

[8] The water/oil repellent composition according to any one of [1] to [7], wherein the polyether-modified polydimethylsiloxane (C) has a hydroxyl group at the end of the polyether chain.
[9] Contain 0.10 parts by mass or more and 20 parts by mass or less of the polyether-modified polydimethylsiloxane (C) with respect to a total of 100 parts by mass of the copolymer (A) and the copolymer (B) The water and oil repellent composition according to any one of [1] to [8].

[10] The water/oil repellent composition according to any one of [1] to [9], further comprising a surfactant (E).
[11] The water/oil repellent composition according to [10], wherein the surfactant (E) is an anionic surfactant.

A second aspect of the present invention provides the following fiber treatment agent.
[12] A fiber treatment agent comprising the water/oil repellent composition according to any one of [1] to [11].
A third aspect of the present invention provides the following fiber treatment method.
[13] A method for treating fibers using the fiber treatment agent of [12].
A fourth aspect of the present invention provides the following coating agent.
[14] A coating agent comprising the water and oil repellent composition according to any one of [1] to [11].
A fifth aspect of the present invention provides the following fiber processed product.
[15] A processed fiber product in which the solid content contained in the fiber treatment agent according to [12] adheres to the fiber.

The water and oil repellent composition of the present invention can impart high oil repellency and water repellency to substrates.
In addition, since the fiber treatment agent, paper treatment agent and coating agent of the present invention contain the water and oil repellent composition of the present invention, they can impart high oil repellency and water repellency to substrates.

The water and oil repellent composition, fiber treatment agent, paper treatment agent and coating agent of the present invention are described in detail below. In addition, this invention is not limited only to embodiment shown below. The configuration described below can be modified as appropriate without departing from the scope of the present invention. For example, the present invention is not limited only to the following examples, and additions, omissions, substitutions of numbers, amounts, ratios, compositions, types, positions, materials, configurations, etc. or can be changed.

In the following description, "monomer" means a compound having a radically polymerizable ethylenically unsaturated bond. "Ethylenically unsaturated bond" means a double bond between carbon atoms, excluding carbon atoms that form an aromatic ring. In the following description, unless otherwise specified, the term "ethylenically unsaturated bond" means an ethylenically unsaturated bond having radical polymerizability.
"(Meth)acryl" means "acryl" or "methacryl". "(Meth)acrylate" means "acrylate" or "methacrylate".

“Non-volatile matter” means a component having a boiling point of 130° C. or higher at 1 atmosphere (1013 hPa) among components contained in the composition or the like.
"Active ingredient" means an ingredient in a mixture that falls under a category when used as a mixture, such as a solution. For example, an active ingredient in a propylene glycol 1-monomethyl ether solution of polyether-modified polydimethylsiloxane refers to all compounds contained in the solution and corresponding to polyether-modified polydimethylsiloxane.

The number average molecular weight and weight average molecular weight are polystyrene equivalent values measured using gel permeation chromatography (GPC).

In a polymer of a compound having an ethylenically unsaturated bond, a structural unit derived from a compound having an ethylenically unsaturated bond is the chemical structure of the portion other than the ethylenically unsaturated bond of the compound and the structure of the polymer. It is assumed that the chemical structure of the portion other than the portion corresponding to the ethylenically unsaturated bond of the unit is the same. For example, a structural unit derived from methyl acrylate has a structure represented by —CH ₂ CH(COOCH ₃ )— in a polymer.

However, unless otherwise specified, if the polymer has an ionic functional group such as a carboxyl group and has a structural unit derived from a compound having an ethylenically unsaturated bond, part of the functional group is a structural unit derived from the same compound, whether ion-exchanged or not. For example, in a polymer, not only the structure represented by -CH ₂ -C(CH ₃ )(COOH)- but also the structural unit represented by -CH ₂ -C(CH ₃ )(COONa)- A structural unit derived from an acid.

In the following description, the compound from which the structural unit of the polymer is derived refers to a compound that has a corresponding relationship with the structural unit, and corresponds to the monomer used in the actual production process of the polymer. No need.

After the polymerization, the chemical structure of the monomer used and the ethylenically unsaturated bond of the resulting polymer are changed by chemically reacting the portion other than the chain portion corresponding to the ethylenically unsaturated bond of the polymer. When the chemical structure of a portion other than the corresponding portion does not match, the structural unit possessed by the polymer is based on the chemical structure after the above-described chemical reaction after polymerization. For example, when vinyl acetate is polymerized and then the resulting polymer is saponified, the chemical structure of the polymer obtained by saponification is the standard. Therefore, the saponified structural unit is not a structural unit derived from vinyl acetate, but a structural unit derived from vinyl alcohol.

<1. Water and oil repellent composition>
The water and oil repellent composition of the present embodiment comprises a copolymer (A) that does not contain a structural unit having a siloxane bond (-Si-O-Si-) and a copolymer (A) that contains a structural unit having a siloxane bond ( B), polyether-modified polydimethylsiloxane (C), and an aqueous medium (D). The water/oil repellent composition of the present embodiment may further contain other components such as a surfactant (E), if necessary. The water and oil repellent composition of the present embodiment may not contain a compound having a perfluoroalkyl group with 8 or more carbon atoms. The water and oil repellent composition of this embodiment may not contain a fluorine-containing compound.

In the water and oil repellent composition of the present embodiment, the copolymer (A) and copolymer (B) preferably form an emulsion in the aqueous medium (D). Here, even if the copolymer (A) and the copolymer (B) are solid, they form an emulsion as long as they are dispersed in the aqueous medium (D). That is, the copolymer (A) and the copolymer (B) may form liquid particles or may form solid particles.

[1-1. Copolymer (A)]
Copolymer (A) does not contain a structural unit having a siloxane bond. The copolymer (A) has a structural unit (a1) derived from a compound having an ethylenically unsaturated bond and an ester bond and having no carboxyl group (hereinafter sometimes abbreviated as "structural unit (a1)" ) and a structural unit (a2) derived from a compound having an ethylenically unsaturated bond and a carboxy group (hereinafter sometimes abbreviated as “structural unit (a2)”). The copolymer (A) preferably consists of the structural unit (a1) and the structural unit (a2) except for the terminal structure.
The copolymer (A) imparts good oil repellency to the base material to which the water and oil repellent composition of the present embodiment is applied.

[1-1-1. structural unit (a1)]
By having the structural unit (a1) in the copolymer (A), it is possible to impart high oil repellency to the substrate and to obtain a highly stable water and oil repellent composition. The structural unit (a1) may consist of one kind of structure, or may contain two or more kinds of structures.
The type and content of the compound from which the structural unit (a1) is derived may be appropriately determined, for example, in order to adjust the glass transition point Tg of the copolymer (A). Specifically, when the glass transition point of the copolymer (A) is to be lowered, a large amount of a homopolymer having a low glass transition point should be included as the compound from which the structural unit (a1) is derived. When the glass transition point of the copolymer (A) is to be increased, a large amount of the homopolymer having a high glass transition point should be included as the compound from which the structural unit (a1) is derived.

The structural unit (a1) is preferably a structural unit derived from a compound having a (meth)acryloyl group, more preferably a structural unit derived from a (meth)acrylic acid alkyl ester.
When the compound from which the structural unit (a1) is derived is a (meth)acrylic acid alkyl ester, the portion other than the (meth)acryloyloxy group has from 1 to 8 carbon atoms in the hydrocarbon structure (meth) More preferably, it is an acrylic acid alkyl ester. The number of carbon atoms is preferably 2 or more and 7 or less, more preferably 3 or more and 6 or less, and even more preferably 4 or more and 5 or less. This is because the texture of the substrate treated with the water and oil repellent composition according to the present embodiment can be easily adjusted.

Examples of (meth)acrylic acid alkyl esters having 1 to 8 carbon atoms in the hydrocarbon structure other than the (meth)acryloyloxy group include methyl (meth)acrylate, ethyl (meth)acrylate, allyl ( meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (Meth)acrylate, dimethylhexyl (meth)acrylate, and octyl (meth)acrylate.

When the water and oil repellent composition of the present embodiment is contained in a paper treatment agent used for paper treatment or a fiber treatment agent used for treatment of fibers, the compound from which the structural unit (a1) is derived is the above compound. Among them, one or more selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate is particularly preferred.

The compound from which the structural unit (a1) is derived contains a (meth)acrylic acid alkyl ester having a chain hydrocarbon structure with 9 or more carbon atoms as the hydrocarbon structure of the portion other than the (meth)acryloyloxy group. You can stay. In this case, it is possible to obtain a water and oil repellent composition that imparts better water repellency to a substrate while maintaining oil repellency.

When the structural unit (a1) is a structural unit derived from a hydrocarbon having an ethylenically unsaturated bond, it is preferably an aromatic vinyl compound. Examples of aromatic vinyl compounds include styrene, α-methylstyrene, p-methylstyrene and the like.

[1-1-2. structural unit (a2)]
When the copolymer (A) has the structural unit (a2), it becomes a water and oil repellent composition capable of imparting high oil repellency to a substrate. The structural unit (a2) may consist of one kind of structure, or may contain two or more kinds of structures.
The compound from which the structural unit (a2) is derived may be any compound having an ethylenically unsaturated bond and a carboxy group. Examples of compounds from which the structural unit (a2) is derived include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, citraconic acid, maleic acid, maleic anhydride, and fumaric acid. The compound from which the structural unit (a2) is derived preferably contains either one or both of acrylic acid and methacrylic acid, more preferably one or both of acrylic acid and methacrylic acid. Structural unit (a2) may or may not contain an ester bond.

[1-1-3. Content of each structural unit in copolymer (A)]
The content of the structural unit (a1) in the copolymer (A) is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, 85% by mass or more is particularly preferable. This is because a water and oil repellent composition having good stability can be obtained.
The content of the structural unit (a1) in the copolymer (A) is preferably 99% by mass or less, more preferably 98% by mass or less, in order to easily secure the content of the structural unit (a2). is more preferably 97% by mass or less, and particularly preferably 96% by mass or less. The content of the structural unit (a1) in the copolymer (A) is optionally, for example, 30% by mass to 99% by mass, 40% by mass to 60% by mass, or 60% by mass to 70% by mass. Or, 70% to 80% by mass, 88% to 99% by mass, 90% to 98% by mass, 93% to 97% by mass, or 94% to 96% by mass. .

When the compound from which the structural unit (a1) is derived is a (meth)acrylic acid alkyl ester in which the number of carbon atoms in the hydrocarbon structure of the portion other than the (meth)acryloyloxy group is 1 or more and 8 or less, the copolymer The content of the structural unit (a1) in (A) is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more. This is because the texture of the base material treated with the water and oil repellent composition according to the present embodiment can be easily adjusted.
When the compound from which the structural unit (a1) is derived is a (meth)acrylic acid alkyl ester in which the number of carbon atoms in the hydrocarbon structure of the portion other than the (meth)acryloyloxy group is 1 or more and 8 or less, the copolymer The content of the structural unit (a1) in (A) is preferably 99% by mass or less, more preferably 98% by mass or less, so that the content of the structural unit (a2) can be easily secured. .

The content of the structural unit (a2) in the copolymer (A) is preferably 0.10% by mass or more, more preferably 0.50% by mass or more, and 1.0% by mass or more. It is more preferable that the content is 1.8% by mass or more, and it is particularly preferable that the content is 1.8% by mass or more. This is because the water and oil repellent composition can impart better oil repellency to the substrate.
The content of the structural unit (a2) in the copolymer (A) is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5.0% by mass or less. It is preferably 3.0% by mass or less, and particularly preferably 3.0% by mass or less. This is because a low-cost water and oil repellent composition can be obtained. In addition, since it becomes easier to ensure the content of the structural unit (a1), it becomes easier to ensure good water repellency in the substrate treated with the water and oil repellent composition. The content of the structural unit (a2) in the copolymer (A) is optionally, for example, 0.10% by mass to 20.0% by mass, 0.30% by mass to 15.0% by mass, or , 0.50% to 8.0% by mass, 0.8% to 7.0% by mass, 1.0% to 6.0% by mass, or 1.2% to 4.0% by mass %, or 1.5 mass % to 3.5 mass %.

The copolymer (A) may contain structural units other than the structural unit (a1) and the structural unit (a2). However, the copolymer (A) preferably contains a total of 50% by mass or more of the structural unit (a1) and the structural unit (a2), more preferably 70% by mass or more, and may contain 90% by mass or more. More preferably, it is particularly preferable to contain 95% by mass or more.

The copolymer (A) may contain the polymerization initiator used in the polymerization for producing the copolymer (A). The polymerization initiator can be arbitrarily selected, and examples thereof include persulfates, hydrogen peroxide, azo compounds, organic peroxides, and the like. The polymerization initiator may be included as a redox initiator that uses both the polymerization initiator and the reducing agent. Only one type of polymerization initiator may be contained, or two or more types may be contained.
The copolymer (A) may contain the chain transfer agent used during the polymerization for producing the copolymer (A). A chain transfer agent adjusts the molecular weight of the copolymer (A) produced by polymerization. Examples of chain transfer agents include, for example, mercaptans, thioglycolic acid and its esters, β-mercaptopropionic acid and its esters, and the like. Only one type of chain transfer agent may be contained, or two or more types may be contained. The amount of polymerization initiator and chain transfer agent can be selected arbitrarily. For example, the content of these compounds is 0.1 to 10.0% by mass, 0.5 to 5.0% by mass, or 1.0 to 3.0% by mass with respect to a total of 100% by mass of the monomers. Examples include 0% by mass, but are not limited to these examples.

[1-2. Copolymer (B)]
The copolymer (B) contains a structural unit (b1) derived from a compound having an ethylenically unsaturated bond and an ester bond and having no carboxy group (hereinafter sometimes abbreviated as "structural unit (b1)"). ), a structural unit (b2) derived from a compound having an ethylenically unsaturated bond and a carboxy group (hereinafter sometimes abbreviated as “structural unit (b2)”), and formula (1) described later represented by a structural unit (b3) derived from polydimethylsiloxane having an ethylenically unsaturated bond (hereinafter sometimes abbreviated as "structural unit (b3)").
Structural unit (b1) and structural unit (b2) in the present embodiment do not contain a structural unit having a siloxane bond.
The copolymer (B) preferably consists of the structural unit (b1), the structural unit (b2) and the structural unit (b3) except for the terminal structure.
The copolymer (B) imparts oil repellency and good water repellency to the base material to which the water and oil repellent composition of the present embodiment is adhered.

[1-2-1. structural unit (b1) and structural unit (b2)]
The required structure, preferred structure, and specific examples of the structural unit (b1) are the same as those of the structural unit (a1). In the water and oil repellent composition of the present embodiment, the structural unit (a1) of the copolymer (A) and the structural unit (b1) of the copolymer (B) may be the same, can be different.
The required structure, preferred structure, and specific examples of the structural unit (b2) are the same as those of the structural unit (a2). In the water and oil repellent composition of the present embodiment, the structural unit (a2) of the copolymer (A) and the structural unit (b2) of the copolymer (B) may be the same, can be different.

[1-2-2. structural unit (b3)]
Structural unit (b3) is a structural unit derived from polydimethylsiloxane having an ethylenically unsaturated bond represented by the following formula (1), and is a portion forming a polysiloxane side chain in copolymer (B). be. By having the structural unit (b3) in the copolymer (B), a water and oil repellent composition that can impart high water repellency to a substrate can be obtained. The structural unit (b3) may consist of one kind of structure, or may contain two or more kinds of structures.

（式（１）において、Ｒ^１は水素原子又はメチル基を示す；Ｒ^２はエーテル結合を含んでもよい炭素原子数１～６の２価脂肪族基を示す；Ｒ^３は炭素原子数１～３０の脂肪族基、芳香族基、または水酸基を示す；ｈは０、１、２のいずれかである；ｊは０～５００の整数を示す。）

(In formula (1), R ¹ represents a hydrogen atom or a methyl group; R ² represents a divalent aliphatic group having 1 to 6 carbon atoms which may contain an ether bond; R ³ represents a C 1 to 30 aliphatic, aromatic, or hydroxyl groups; h is 0, 1, or 2; j is an integer from 0 to 500.)

R ¹ in formula (1) represents a hydrogen atom or a methyl group.
R ² in formula (1) is a C 1-6 divalent aliphatic group which may contain an ether bond. The number of carbon atoms in R ² is preferably 1-4, and may be 1-4 or 2-3 as necessary. This is because, according to the number of atoms, the water and oil repellent composition can impart high oil repellency to the substrate. R ² is more preferably a hydrocarbon chain, more preferably a straight hydrocarbon chain. This is because the water and oil repellent composition can impart high water repellency to the substrate.

R ³ in formula (1) is an aliphatic group having 1 to 30 carbon atoms, an aromatic group, or a hydroxyl group. R ³ is preferably an aliphatic group having 1 to 30 carbon atoms, more preferably an aliphatic group having 2 to 18 carbon atoms, and more preferably an aliphatic group having 2 to 10 carbon atoms. is more preferred, and an aliphatic group having 2 to 6 carbon atoms is particularly preferred. For example, the number of carbon atoms may be 3-5 or 2-4. More preferably ^, R3 is a hydrocarbon chain, more preferably a straight hydrocarbon chain. This is because the water and oil repellent composition can impart high water repellency to the substrate.

j in formula (1) is an integer of 0 to 500, and since the number average molecular weight of the compound represented by formula (1) is in a preferred range, it is preferably an integer of 1 to 400, and an integer of 10 to 300 is more preferable. For example, j may be an integer ranging from 1-200, 1-150, 1-80, 1-30, 1-10, or 1-5. The compound from which the structural unit (b3) is derived may be only one of the compounds represented by formula (1), or may contain two or more.

The number average molecular weight of the compound represented by formula (1) is preferably 300 or more, more preferably 1,000 or more, still more preferably 3,000 or more, and 7,000 or more. It is particularly preferred to have This is because better water repellency can be obtained in the substrate treated with the water and oil repellent composition. The number average molecular weight of the compound represented by formula (1) is preferably 40,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less. This is because the copolymerizability of the compound represented by the formula (1) is improved during the polymerization for producing the copolymer (B).

[1-2-3. Content of each structural unit in copolymer (B)]
The content of the structural unit (b1) in the copolymer (B) is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, It is particularly preferred that the content is 70% by mass or more. This is because a water and oil repellent composition having good stability can be obtained.
The content of the structural unit (b1) in the copolymer (B) is preferably 96% by mass or less in order to easily ensure the content of the structural unit (b2) and the structural unit (b3). It is more preferably 90% by mass or less, more preferably 90% by mass or less. The content of the structural unit (b1) in the copolymer (B) is, for example, 30% by mass to 96% by mass, 45% by mass to 95% by mass, 55% by mass to 94% by mass, or 60% by mass. It may be up to 85 mass %, or 65 mass % to 80 mass %.

When the compound from which the structural unit (b1) is derived is a (meth)acrylic acid alkyl ester in which the number of carbon atoms in the hydrocarbon structure of the portion other than the (meth)acryloyloxy group is 1 or more and 8 or less, the copolymer The content of the structural unit (b1) in (B) is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more. This is because the texture of the base material treated with the water and oil repellent composition according to the present embodiment can be easily adjusted.
When the compound from which the structural unit (b1) is derived is a (meth)acrylic acid alkyl ester in which the number of carbon atoms in the hydrocarbon structure of the portion other than the (meth)acryloyloxy group is 1 or more and 8 or less, the copolymer The content of the structural unit (b1) in (B) is preferably 96% by mass or less, more preferably 93% by mass or less, in order to easily ensure the content of the structural unit (b2) and the structural unit (b3). is more preferable.

The content of the structural unit (b2) in the copolymer (B) is preferably 0.10% by mass or more, more preferably 0.50% by mass or more, and 0.85% by mass or more. It is more preferable that the content is 1.8% by mass or more, and it is particularly preferable that the content is 1.8% by mass or more. This is because the water and oil repellent composition can impart better oil repellency to the substrate.
The content of the structural unit (b2) in the copolymer (B) is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5.0% by mass or less. It is preferably 3.0% by mass or less, and particularly preferably 3.0% by mass or less. This is because a low-cost water and oil repellent composition can be obtained. In addition, since the contents of the structural unit (b1) and the structural unit (b3) are easily ensured, it is easy to ensure good water repellency in the substrate treated with the water and oil repellent composition. The content of the structural unit (b2) in the copolymer (B) is, for example, 0.10% by mass to 20.0% by mass, 0.30% by mass to 15.0% by mass, or 0.7% by mass. % to 10.0% by mass, 1.0% to 8.0% by mass, 1.2% to 6.0% by mass, or 1.5% to 3.0% by mass good.

The content of the structural unit (b3) in the copolymer (B) is preferably 3.0% by mass or more, more preferably 5.0% by mass or more, and 7.0% by mass or more. It is even more preferable to have This is because the water and oil repellent composition can impart better water repellency to the substrate. The content of the structural unit (b3) in the copolymer (B) is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 15% by mass or less. This is because the contents of the structural unit (b1) and the structural unit (b2) can be easily ensured, and the texture of the substrate treated with the water and oil repellent composition can be maintained well. The content of the structural unit (b3) in the copolymer (B) is, for example, 3.0% by mass to 50.0% by mass, 4.0% by mass to 47.0% by mass, or 5.0% by mass. % to 45.0 mass%, 6.0 mass% to 43 mass%, 8.0 mass% to 40.0 mass%, 10.0 mass% to 25.0 mass%, or 15.0 mass% % to 20.0% by mass.

The copolymer (B) may contain structural units other than the structural unit (b1), the structural unit (b2), and the structural unit (b3). However, the copolymer (B) preferably contains a total of 50% by mass or more of the structural unit (b1), the structural unit (b2), and the structural unit (b3), more preferably 70% by mass or more, More preferably 90% by mass or more, particularly preferably 95% by mass or more.

In the present embodiment, the content of the structural unit (b3) in the total amount of the copolymer (A) and the copolymer (B) is preferably 1.5% by mass or more, and 2.5% by mass. It is more preferably 3.5% by mass or more, and more preferably 3.5% by mass or more. This is because the water and oil repellent composition can impart better water repellency to the substrate.
7. The content of the structural unit (b3) in the total amount of the copolymer (A) and the copolymer (B) is preferably 30% by mass or less, more preferably 15% by mass or less. It is more preferably 5% by mass or less. This is because the contents of the structural units (a1), (a2), (b1) and (b2) can be easily ensured, and the resulting water and oil repellent composition can impart better water repellency and oil repellency to the substrate. For example, the content of the structural unit (b3) in the total amount is 1.5% by mass or more and 30% by mass or less, 2.0% by mass or more and 25% by mass or less, or 3.0% by mass or more and 20% by mass or less. , 4.0% by mass or more and 15% by mass or less, or 5.0% by mass or more and 10% by mass or less, or the like.

The copolymer (B) may contain the polymerization initiator used in the polymerization for producing the copolymer (B). Examples of the polymerization initiator include the same ones that may be contained in the copolymer (A). In the water and oil repellent composition of the present embodiment, when the copolymer (A) and the copolymer (B) contain a polymerization initiator, the polymerization initiator contained in the copolymer (A) and the polymerization initiator contained in the copolymer (B) may be the same or different.
The copolymer (B) may contain the chain transfer agent used during the polymerization for producing the copolymer (B). Examples of the chain transfer agent include those that may be contained in the copolymer (A). In the water and oil repellent composition of the present embodiment, when the copolymer (A) and the copolymer (B) contain a chain transfer agent, the chain transfer agent contained in the copolymer (A) and the chain transfer agent contained in the copolymer (B) may be the same or different.

[1-3. Compounding ratio of copolymer (A) and copolymer (B)]
In the water and oil repellent composition according to the present embodiment, the value of the blending ratio based on the mass of the copolymer (A) and the copolymer (B) (mass of copolymer (A) / copolymer (B ) is preferably 10/90 or more, more preferably 20/80 or more. This is because the water and oil repellent composition can impart better oil repellency to the substrate. In the water and oil repellent composition according to the present embodiment, the blending ratio based on the mass of the copolymer (A) and the copolymer (B) may be 30/70 or more, or 40/60. or more.
In the water and oil repellent composition according to the present embodiment, the blending ratio based on the mass of the copolymer (A) and the copolymer (B) is preferably 90/10 or less, more preferably 80/20. It is more preferably 70/30 or less, particularly preferably 60/40 or less. This is because the water and oil repellent composition can impart better water repellency to the substrate.

[1-4. Polyether-modified polydimethylsiloxane (C)]
Polyether-modified polydimethylsiloxane (C) is a compound in which some or all of the hydrogen atoms of the methyl groups of polydimethylsiloxane are replaced with polyether chains. That is, the polyether-modified polydimethylsiloxane is a graft copolymer having a polysiloxane main chain and polyether side chains. The polyether-modified polydimethylsiloxane (C) preferably has a solubility in 100 g of the aqueous medium (D) at 20° C. of 1.0 g/100 g or more, more preferably 3.0 g/100 g or more. , but not limited to this. The polyether-modified polydimethylsiloxane (C) imparts good water repellency and oil repellency to the substrate to which the water and oil repellent composition of the present embodiment is applied.

The polyether-modified polydimethylsiloxane (C) preferably has at least one of an alkoxy group and a hydroxyl group at the end of the polyether chain, and more preferably has a hydroxyl group at the end of the polyether chain. preferable. When the polyether-modified polydimethylsiloxane (C) has a hydroxyl group at the end of the polyether chain, it becomes a water and oil repellent composition capable of imparting better oil repellency to a substrate. For example, the type and number of polyether chains to be added can be arbitrarily selected. For example, the position and number of polyether chains bonded to Si of polydimethylsiloxane can be arbitrarily selected. Examples of polyether chains include, but are not limited to, -(C ₁ H ₂ O) _x (C ₂ H ₄ O) _y (C ₃ H ₆ O) _z R and the like. Each of x, y, and z is an integer of 0 or 1 or more, and not all of them are 0 at the same time. R is preferably either an alkyl group having 1 to 10 carbon atoms or hydrogen. Each of x, y, and z may be, for example, 0 to 300, 0 to 100, 0 to 50, 0 to 20, or 0 to 10. The number and arrangement of methylene oxide, ethylene oxide and propylene oxide in the polyether chain can be arbitrarily selected, and they may be arranged continuously, alternately or randomly.
Commercially available examples of compositions containing polyether-modified polydimethylsiloxane (C) having hydroxyl groups at the ends of polyether chains include BYK SILCLEAN 3720 manufactured by BYK, TEGO (registered trademark) Protect 5100N manufactured by Evonik, and Shin-Etsu. Examples include KP-109 manufactured by Silicone Co., Ltd.

The weight average molecular weight of the polyether-modified polydimethylsiloxane (C) is preferably 1,000 or more, more preferably 5,000 or more, even more preferably 7,000 or more. This is because the water and oil repellent composition can impart better oil repellency to the substrate.
The weight average molecular weight of the polyether-modified polydimethylsiloxane (C) is preferably 50,000 or less, more preferably 30,000 or less, even more preferably 14,000 or less. This is because the water and oil repellent composition can impart better water repellency to the substrate.

The content of the polyether-modified polydimethylsiloxane (C) is preferably 0.10 parts by mass or more with respect to a total of 100 parts by mass of the copolymer (A) and the copolymer (B). It is more preferably 0.20 parts by mass or more, still more preferably 0.50 parts by mass or more, and particularly preferably 0.90 parts by mass or more. This is because the water and oil repellent composition can impart better oil repellency to the substrate.
The content of the polyether-modified polydimethylsiloxane (C) is preferably 20 parts by mass or less with respect to a total of 100 parts by mass of the copolymer (A) and the copolymer (B), and 10 parts by mass. is more preferably 7.0 parts by mass or less, particularly preferably 3.5 parts by mass or less, and most preferably 1.5 parts by mass or less. This is to improve the texture of the fiber or paper treated with the water and oil repellent composition. The content of the polyether-modified polydimethylsiloxane (C) is, for example, 0.10 parts by mass or more and 5.0 parts by mass or less, or 0.20 parts by mass or more and 3.0 parts by mass or less, or 0.30 parts by mass. It may be 2.0 parts by mass or more, or 0.40 parts by mass or more and 1.0 parts by mass or less.

[1-5. Aqueous medium (D)]
The aqueous medium (D) contains water as an essential component. The aqueous medium (D) may contain a hydrophilic solvent in addition to water. The content of water in the aqueous medium (D) can be arbitrarily selected, but is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 98% by mass or more, It may be 100% by mass.
Examples of hydrophilic solvents include alcohols such as methyl alcohol, ethanol, propylene glycol 1-monomethyl ether, n-propyl alcohol, isopropyl alcohol, t-butyl alcohol and benzyl alcohol, and nitrogen-containing organic solvents such as N-methylpyrrolidone. be done. Only one type of hydrophilic solvent may be contained, or two or more types may be contained.
The content of the hydrophilic solvent in the aqueous medium (D) is preferably 10% by mass or less, more preferably 5.0% by mass or less. This is because it is possible to suppress an increase in cost due to the use of a hydrophilic solvent.

The content of the aqueous medium (D) contained in the water and oil repellent composition is preferably determined so that the non-volatile content of the water and oil repellent composition is a desired value.
The non-volatile content of the water- and oil-repellent composition is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. This is because a water and oil repellent composition capable of efficiently imparting a water and oil repellent effect to a substrate can be obtained with a small amount of use.
The non-volatile content of the water- and oil-repellent composition is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less. This is because the water and oil repellent composition has good storage stability and can be easily applied uniformly to a substrate.
The content of the aqueous medium (D) contained in the water- and oil-repellent composition can be arbitrarily selected, for example, 3 to 95 mass%, 5 to 90 mass%, or 10 mass% or more. 80% by mass or less, 30% by mass or more and 70% by mass or less, 40% by mass or more and 60% by mass or less, and the like, but are not limited to these examples.

[1-6. Other ingredients]
The water and oil repellent composition of the present embodiment comprises a copolymer (A), a copolymer (B), a polyether-modified polydimethylsiloxane (C), an aqueous medium (D), and optionally Other ingredients may be included as required. Other components that can be contained in the water and oil repellent composition of the present embodiment include resins, cross-linking agents, thickeners, pH adjusters, film forming aids, plasticizers, preservatives, antifoaming agents, surfactants, agent (E) and the like. One or two or more of the other components may be contained depending on the specifications of the water and oil repellent composition as long as the object of the present invention can be achieved.

[1-6-1. Surfactant (E)]
As the surfactant (E), anionic surfactants, nonionic surfactants and cationic surfactants can be used, and commercially available products may be used. Surfactant (E) does not have an ethylenically unsaturated bond. In the present embodiment, the surfactant having an ethylenically unsaturated bond having radical polymerizability, the component added during the synthesis of the copolymer (A) becomes the structural unit of the copolymer (A). , the components added during the synthesis of the copolymer (B) become the structural units of the copolymer (B).

The anionic surfactant is preferably a sulfonate, more preferably an aromatic sulfonate, and even more preferably a linear alkylbenzene sulfonate. The number of carbon atoms in the linear alkyl group in the linear alkylbenzenesulfonate is preferably 3 or more, more preferably 6 or more, and even more preferably 8 or more. This is because the affinity of the anionic surfactant for the copolymer (A) and the copolymer (B) is increased. The number of carbon atoms in the linear alkyl group in the linear alkylbenzene sulfonate is preferably 50 or less, more preferably 30 or less, even more preferably 20 or less. This is because the affinity of the anionic surfactant for the aqueous medium (D) is improved.
The surfactant (E) preferably contains an anionic surfactant. This is because the water and oil repellent composition has high adhesion to the substrate.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polycyclic finyl ethers, polyoxyalkylene alkyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and the like.
Cationic surfactants include alkyltrimethylammonium chloride, ceyltrimethylammonium bromide, laurylpyridinium chloride and the like. As the cationic surfactant, it is preferable to use a hydrochloride of a compound having an ammonium group, and it is more preferable to use a quaternary ammonium chloride.

When the water and oil repellent composition of the present embodiment contains a surfactant (E), the content of the surfactant (E) with respect to a total of 100 parts by mass of the copolymer (A) and the copolymer (B) is , is preferably 0.15 parts by mass or more, more preferably 0.40 parts by mass or more, and even more preferably 0.90 parts by mass or more. This is because the copolymer (A) and the copolymer (B) can be stably dispersed in the water and oil repellent composition.
In the water and oil repellent composition of the present embodiment, the content of the surfactant (E) is 5.0 parts by mass or less with respect to a total of 100 parts by mass of the copolymer (A) and the copolymer (B). is preferably 3.0 parts by mass or less, and even more preferably 1.5 parts by mass or less. This is because the substrate adhesion of the coating layer obtained from the water and oil repellent composition can be maintained without impairing the water resistance.

The surfactant (E) contained in the water and oil repellent composition of the present embodiment is partially or wholly the surfactant and/or copolymer used during polymerization for producing the copolymer (A). It may be the surfactant used during the polymerization for producing coalescence (B). The surfactant used during the polymerization for producing the copolymer (A) and the surfactant used during the polymerization for producing the copolymer (B) may be different or the same. There may be.
Further, the surfactant (E) contained in the water and oil repellent composition of the present embodiment is partly or wholly added after the copolymer (A) and the copolymer (B) are produced. may be

<2. Method for producing a water and oil repellent composition>
The water and oil repellent composition of the present embodiment can be produced, for example, by the method shown below. The method for producing the water and oil repellent composition according to the present invention is not limited to the method described below.
First, a first polymerization step is performed to produce an aqueous emulsion (α) in which the copolymer (A) is dispersed in the aqueous medium (D). Further, a second polymerization step is performed to produce an aqueous emulsion (β) in which the copolymer (B) is dispersed in the aqueous medium (D). Thereafter, a mixing step of mixing the aqueous emulsion (α), the aqueous emulsion (β) and the polyether-modified polydimethylsiloxane (C) is performed. Through the steps described above, the water and oil repellent composition of the present embodiment is obtained.

[2-1-1. First polymerization step]
In the first polymerization step, a monomer containing a compound from which the structural unit (a1) is derived and a compound from which the structural unit (a2) is derived, a surfactant (E), an aqueous medium (D), and necessary It is preferable to mix a polymerization initiator and a chain transfer agent to be used according to the above conditions and carry out emulsion polymerization. As a result, a copolymer (A) is produced by copolymerizing a monomer containing a compound from which the structural unit (a1) is derived and a compound from which the structural unit (a2) is derived, and the surfactant ( An aqueous emulsion (α) containing E) is obtained in which the copolymer (A) is dispersed in the aqueous medium (D).
In the first polymerization step, emulsion polymerization can be carried out, for example, at a temperature of 30-85°C.

As in the example described here, when the chemical structure of the copolymer (A) obtained by polymerization is not changed (however, ion exchange may be performed), as a material for the aqueous emulsion (α) Each monomer used maintains its structure other than the ethylenically unsaturated bond even after polymerization (excluding ion exchange).

The amount of the aqueous medium (D) used as a material for the aqueous emulsion (α) is the sum of the compound derived from the structural unit (a1) and the compound derived from the structural unit (a2) (total monomer ) is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and even more preferably 100 parts by mass or more. The compound from which the structural unit (a1) is derived and the compound from which the structural unit (a2) is derived can be emulsified in the aqueous medium (D) for efficient emulsion polymerization, and the copolymer (A ) can be stably dispersed in the aqueous medium (D).

The amount of the aqueous medium (D) used as a material for the aqueous emulsion (α) is based on a total of 100 parts by mass of the compound from which the structural unit (a1) is derived and the compound from which the structural unit (a2) is derived. , preferably 400 parts by mass or less, more preferably 300 parts by mass or less, and even more preferably 200 parts by mass or less. By suppressing the amount of the excess aqueous medium (D), it is possible to improve productivity, suppress the increase in manufacturing and handling costs due to the miniaturization of manufacturing facilities and storage facilities, etc., and further suppress transportation costs. This is because

In the present embodiment, the amount of surfactant (E) used with respect to the total weight of the monomers used as the materials of the water-based emulsion (α) is 100 parts by mass of the copolymer (A) in the water-based emulsion (α). is the same as the content of the surfactant (E) for

The polymerization initiator described above is preferably used in the first polymerization step. In order to obtain an appropriate polymerization rate, the amount of the polymerization initiator used is the total of the compound derived from the structural unit (a1) and the compound derived from the structural unit (a2) (total of monomers) 100 It is preferably 0.01 to 1.0 parts by mass, more preferably 0.05 to 0.80 parts by mass, and preferably 0.1 to 0.5 parts by mass. More preferred.

In the first polymerization step, each component used as the material of the water-based emulsion (α) may be collectively charged and emulsion polymerized, or emulsion polymerization may be performed while continuously supplying each component. In the case of emulsion polymerization while continuously supplying each component, for example, the method shown below can be used.
First, a part of the aqueous medium (D) and a part of the surfactant (E) are mixed to obtain a mixture. A part of the polymerization initiator is mixed with the obtained mixture to obtain a polymerization initiator solution.
On the other hand, the compound from which the structural unit (a1) is derived, the compound from which the structural unit (a2) is derived, the remainder of the aqueous medium (D), and the remainder of the surfactant (E) are mixed and emulsified. Thus, a mixed emulsion is obtained.
Then, a method of emulsifying polymerization by stirring while continuously supplying the mixed emulsion and the remainder of the polymerization initiator into the polymerization initiator solution can be used.

[2-1-2. Second polymerization step]
In the second polymerization step, a monomer containing a compound from which the structural unit (b1) is derived, a compound from which the structural unit (b2) is derived, and a compound from which the structural unit (b3) is derived, and a surfactant ( E), an aqueous medium (D), a polymerization initiator used as necessary, and a chain transfer agent are preferably mixed to carry out emulsion polymerization. Thus, the copolymer (B) obtained by copolymerizing the compound from which the structural unit (b1) is derived, the compound from which the structural unit (b2) is derived, and the compound from which the structural unit (b3) is derived is generated to obtain an aqueous emulsion (β) in which the surfactant (E) is contained and the copolymer (B) is dispersed in the aqueous medium (D).

In the second polymerization step, emulsion polymerization can be carried out at a temperature of, for example, 30-85°C.
The second polymerization step may be performed after the first polymerization step, before the first polymerization step, or simultaneously with the first polymerization step.

As in the example described here, when the chemical structure of the copolymer (B) obtained by polymerization is not changed (however, ion exchange may be performed), as a material for the aqueous emulsion (β) Each monomer used maintains its structure other than the ethylenically unsaturated bond even after polymerization (excluding ion exchange).

The preferred amount of the aqueous medium (D) used as the material for the aqueous emulsion (β) (the preferred amount relative to the total amount of monomers) is the preferred amount of the aqueous medium (D) used as the material for the aqueous emulsion (α). are the same.

In the present embodiment, the amount of the surfactant (E) used relative to the total mass of the monomers used as the materials of the water-based emulsion (β) is 100 parts by mass of the copolymer (B) in the water-based emulsion (β). is the same as the content of the surfactant (E) for
Preferred usage of surfactant (E) used as a material for aqueous emulsion (β) (preferred usage relative to the total amount of monomers) is same as quantity.

In the second polymerization step, as in the first polymerization step, it is preferable to use the polymerization initiator described above. The amount of the polymerization initiator used (preferred amount used relative to the total amount of monomers) is the same as in the case of using the polymerization initiator in the first polymerization step.

In the second polymerization step, each component used as the material of the water-based emulsion (β) may be collectively charged and emulsion polymerized, or emulsion polymerization may be performed while continuously supplying each component. When the emulsion polymerization is carried out while continuously supplying each component, for example, the same method as that which can be used in the first polymerization step can be used.

[2-2. Mixing process]
In the mixing step, the aqueous emulsion (α) obtained in the first polymerization step, the aqueous emulsion (β) obtained in the second polymerization step, and the polyether-modified polydimethylsiloxane (C) are mixed.
As a mixing method, a known method can be used. For example, as a mixing method, a method of stirring for 5 minutes at a temperature of 23° C. and a number of revolutions of 500 rpm using Homo Disper Model 2.5 (manufactured by PRIMIX) can be mentioned.

In the method for producing a water and oil repellent composition of the present embodiment, the aqueous emulsion (α) is produced using the surfactant (E) in the first polymerization step, and the surfactant (E) is used in the second polymerization step. Although the case of producing the aqueous emulsion (β) using is described as an example, the timing of adding the surfactant (E) can be adjusted as appropriate depending on the purpose of using the surfactant (E). is.

Specifically, the surfactant (E) is used not only in the first polymerization step and the second polymerization step, but also after the first polymerization step and the second polymerization step and before the mixing step, if necessary. may be added to the aqueous emulsion (α) and/or the aqueous emulsion (β). In this case, the copolymer (A) can be more stably dispersed in the aqueous emulsion (α) and/or the copolymer (B) can be more stably dispersed in the aqueous emulsion (β). be able to.
Further, the surfactant (E) may be added together with the aqueous emulsion (α) and the aqueous emulsion (β) in the mixing step, if necessary, or the water and oil repellent composition obtained after the mixing step. may be further added to In this case, the copolymer (A) and the copolymer (B) can be stably dispersed in the water and oil repellent composition.

In the method for producing the water and oil repellent composition of the present embodiment, the case where the aqueous medium (D) is used as the material of the aqueous emulsion (α) and the aqueous emulsion (β) has been described as an example, but the aqueous medium (D ) may optionally be added to the aqueous emulsion (α) and/or the aqueous emulsion (β) after the first and second polymerization steps and before the mixing step.
Further, the aqueous medium (D) may optionally be added together with the aqueous emulsion (α) and the aqueous emulsion (β) in the mixing step, or may be added to the water/oil repellent composition obtained after the mixing step. Further may be added. Moreover, after the mixing step, a part of the aqueous medium (D) may be removed by concentrating the water and oil repellent composition using a known method, if necessary.

Since the water and oil repellent composition of the present embodiment contains the copolymer (A) and the copolymer (B), it can impart high water repellency and oil repellency to the substrate.
On the other hand, for example, in a water and oil repellent composition that does not contain the copolymer (A) but contains only the copolymer (B), the water and oil repellent composition of the present embodiment and the structural unit (b3) are included. If the ratios are the same, the oil repellency that can be imparted to the substrate is inferior. This is because, in the water and oil repellent composition containing only the copolymer (B), the structural unit (b3) in the copolymer (B) attracts oil, thereby lowering the oil repellency that can be imparted to the substrate. presumed to be because

<3. Application of Water and Oil Repellent Composition>
The water and oil repellent composition of the present embodiment can impart high oil repellency and water repellency to a substrate, and has good adsorptivity to the substrate. The water and oil repellent composition of the present embodiment can impart high oil repellency and water repellency to substrates such as fibers, paper, and glass. Therefore, preferred uses of the water and oil repellent composition of the present embodiment include materials for fiber treatment agents, paper treatment agents, and coating agents.

[3-1. Fiber treatment agent]
The fiber treatment agent of the present embodiment contains the water and oil repellent composition of the present embodiment, and may consist of only the water and oil repellent composition of the present embodiment. In addition to the composition, known and commonly used additives such as antifoaming agents, preservatives, pH adjusters, surfactants, cross-linking agents, antistatic agents, wetting agents, thickeners, pigments, etc. may be added according to the present invention. It may be appropriately selected and contained within a range that can achieve the purpose of.

The fiber treatment agent of this embodiment can impart high oil repellency and water repellency to fibers. As used herein, the term "fiber" means fibers and articles made from fibers. The fibers treated with the fiber treatment agent may be in any form such as staple fibers (fibers), linters, rovings, sliver, yarns, woven fabrics, knitted fabrics, non-woven fabrics, paper and the like. As used herein, fibers also include paper. Examples of fiber materials to be treated include cotton, flax, jute, hemp, ramie, regenerated fiber cellulose, cellulose fibers such as rayon, polyvinyl alcohol-based synthetic fibers, and pulp. The fiber treated with the fiber treatment agent preferably contains 30 mass % or more of the above material. The fiber treatment agent of the present embodiment can impart high oil repellency and water repellency to paper. The paper treated with the paper treatment agent is not particularly limited, but examples thereof include general-purpose paper using pulp cellulose.

In the water- and oil-repellent fibers treated with the fiber treatment agent of the present embodiment, the fiber treatment agent containing the water- and oil-repellent agent composition of the present embodiment is attached to the base fiber. The total amount of the water and oil repellent composition adhered to 100 parts by mass of the base fiber is preferably 1.0 parts by mass or more, more preferably 2.0 parts by mass or more. This is because the water repellency and oil repellency of the water and oil repellent fibers are improved. The amount of the water/oil repellent composition attached to 100 parts by mass of the fiber serving as the base material is preferably 20 parts by mass or less, more preferably 10 parts by mass or less. This is because, by attaching the fiber treatment agent to the fibers, it is possible to suppress deterioration of the texture and suppress an increase in the mass.

Examples of a method for treating fibers as a base material using the fiber treatment agent of the present embodiment, that is, a method for producing a processed fiber product using the fiber treatment agent include the following methods.
First, fibers as a base material are impregnated or coated with a fiber treatment agent. As a method of impregnation or coating, for example, methods such as dipping, spray coating and roll coating can be used. After the fibers are impregnated or coated with the fiber treatment agent, the amount of the fiber treatment agent adhered to the fibers is adjusted. A method for adjusting the adhesion amount includes a method of squeezing using a mangle roll or the like, but is not limited to this method. After the fibers are impregnated or coated with the fiber treatment agent, the fibers are preferably dried. The drying temperature of the fibers is preferably 80°C to 170°C, more preferably 90°C to 150°C.
The processed fiber product is obtained by impregnating or applying the fiber treatment agent of the present embodiment to the fiber and drying it. That is, the processed fiber product means a product in which the solid content (non-volatile content) contained in the fiber treatment agent adheres to the fiber.

[3-3. Coating agent〕
The coating agent of the present embodiment contains the water and oil repellent composition of the present embodiment, and may consist only of the water and oil repellent composition of the present embodiment. Known and commonly used additives such as antifoaming agents, preservatives, pH adjusters, surfactants, cross-linking agents, antistatic agents, wetting agents, thickeners, pigments, etc. It may be appropriately selected and contained within a range that does not impair the purpose of.

Examples of substrates to be coated with the coating agent of the present embodiment include glass, polyolefin resin, polyester resin, polycarbonate resin, acrylonitrile butadiene styrene copolymer (ABS resin), polystyrene resin, etc., or molding thereof. products (films, sheets, cups, etc.), metals, etc., but are not limited to these.

Examples of the method for treating the substrate using the coating agent of the present embodiment include the methods shown below.
First, a coating agent is applied to the substrate. Examples of the method of applying the coating agent to the base material include spraying, brush coating, roller coating, trowel coating, dipping, air knife, flow coating, bar coating, roll coating, gravure coating, and methods using an applicator.

It is preferable to dry the base material after applying the coating agent to the base material. The drying temperature for drying the substrate coated with the coating agent is preferably 80° C. or higher, more preferably 100° C. or higher. This is because the drying time can be shortened and high productivity can be obtained. The drying temperature for drying the base material coated with the coating agent is preferably 170° C. or lower, and more preferably 150° C. or higher. When the drying temperature is 170° C. or lower, deterioration of the water and oil repellent composition contained in the coating agent can be suppressed. The drying time is not particularly limited and can be determined according to the coating amount of the coating agent on the substrate.

EXAMPLES The present invention will now be described in more detail with reference to examples and comparative examples. In addition, the present invention is not limited only to the following examples.
<1. Production of aqueous emulsion (α-1)>
In a five-necked separable flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a reflux condenser, and a dropping funnel, 120 g of ion-exchanged water as an aqueous medium (D) and a surfactant (E) as 1 g of Newex R-25L was added, and the temperature was raised to 80° C. to form a mixed solution. The resulting mixed solution was kept at 80° C., and 10 g of a 3% by mass aqueous solution of potassium persulfate as a polymerization initiator was added to the mixed solution to prepare a polymerization initiator solution.

On the other hand, in a 1-liter beaker, the monomer (a1) and the monomer (a2) shown in Table 1 are placed in the ratio shown in Table 1, and 420 g of ion-exchanged water as an aqueous medium (D) and a surfactant ( E) was added with 18.2 g of Newlex R-25L and mixed with a homomixer to emulsify to obtain a mixed emulsion.

Then, while maintaining the temperature in the five-necked flask containing the polymerization initiator solution at 80° C., the mixed emulsion and the 3% by mass aqueous solution of potassium persulfate as the polymerization initiator were added to the polymerization initiator solution. 44 g of the mixture was continuously added dropwise from the funnel over 3 hours while stirring to carry out emulsion polymerization.
The temperature inside the five-necked flask was kept at 80° C. for 1 hour after the end of the dropwise addition while stirring the inside of the five-necked flask. After that, cooling of the five-necked flask was started, and the temperature inside the five-necked flask was cooled to 30°C. Through the above steps, an aqueous emulsion (α-1) containing the copolymer (A) was obtained.

<2. Production of Aqueous Emulsion (α-2), (β-1) to (β-5)>
The copolymer (A) was produced in the same manner as the aqueous emulsion (α-1) except that the monomers (a1) and (a2) shown in Table 1 were used in the proportions shown in Table 1. An aqueous emulsion (α-2) containing
Instead of the monomer (a1) and the monomer (a2) shown in Table 1, the monomers (b1), (b2), and (b3) shown in Table 1 were used in the proportions shown in Table 1. Aqueous emulsions (β-1) to (β-5) each containing copolymer (B) were obtained in the same manner as in the production of aqueous emulsion (α-1).

In Table 1, monomer (a1) or (b1) is a compound from which structural unit (a1) or (b1) is derived. The monomer (a2) or (b2) is a compound from which the structural unit (a2) or (b2) is derived. The monomer (b3) is a compound from which the structural unit (b3) is derived.

The materials used in Table 1 are as follows.
Monomer (b3); Polydimethylsiloxane having an ethylenically unsaturated bond (manufactured by JNC, Silaplane (registered trademark) FM-0725 (a compound represented by formula (1). R in formula (1) ¹ is a methyl group, R ² is -CH ₂ CH ₂ CH ₂ -, R ³ is an n-butyl group, h is 2, j is 125. The number average molecular weight (Mn) is 10,000.))
Surfactant (E): Newex R-25L (manufactured by NOF Corporation: straight-chain sodium alkylbenzene sulfonate (straight-chain alkyl group has 10 to 16 carbon atoms, anionic surfactant), 25% by mass aqueous solution)
Polymerization initiator; 3 mass% aqueous solution of potassium persulfate (KPS)

The numerical values shown in the columns of aqueous medium (D), surfactant (E), and polymerization initiator in Table 1 are aqueous emulsions (α-1), (α-2), and aqueous emulsions (β-1) to Total mass (sum of monomers) used for the synthesis of (β-5). Therefore, the numerical value of the aqueous medium (D) shown in Table 1 does not include the water contained in the surfactant (E) and the polymerization initiator.

<3. Preparation of Water and Oil Repellent Composition>
Aqueous emulsions (α-1) and (α-2) shown in Table 1, aqueous emulsions (β-1) to (β-5) shown in Table 1, and polyether-modified polydimethylsiloxane (C), Example 1 mixed in the ratio shown in Table 2 or Table 3 and containing the copolymer (A), the copolymer (B), and the polyether-modified polydimethylsiloxane (C) in the ratio shown in Table 2 or Table 3 Water and oil repellent compositions of Examples 1 to 12 and Comparative Examples 1 to 8 were obtained.

The numerical values shown in the column of copolymer (A) in Tables 2 and 3 are the water-based emulsions (α- 1) or (α-2), and the numerical value in parentheses is the mass of the copolymer (A) contained in the aqueous emulsion (α-1) or (α-2). The content of the copolymer (A) in the aqueous emulsion (α-1) or (α-2) accounts for the total amount of the monomer, surfactant, polymerization initiator, and aqueous medium in Table 1, It is the ratio of monomers.

The numerical values shown in the column of copolymer (B) in Tables 2 and 3 are the water-based emulsions (β- 1) to (β-5), and the numbers in parentheses are the masses of the copolymer (B) contained in the aqueous emulsions (β-1) to (β-5), respectively. The mass of the copolymer (B) in the aqueous emulsions (β-1) to (β-5) is the total amount of the monomer, surfactant, polymerization initiator, and aqueous medium in Table 1. is the proportion of the polymer.

The polyether-modified polydimethylsiloxane (C) used in Tables 2 and 3 is as follows.
BYK SILCLEAN 3720; polyether-modified polydimethylsiloxane having hydroxyl groups at the ends of polyether chains, weight average molecular weight (Mw) of 10,000, and solvent (methoxypropanol) other than the active ingredient. (manufactured by BYK)
TEGO (registered trademark) Protect 5100N; polyether-modified polydimethylsiloxane having a hydroxyl group at the end of the polyether chain, weight average molecular weight (Mw) of 10,000, solvent (water) except for active ingredients. (manufactured by Evonik)
KP-109; polyether-modified polydimethylsiloxane, weight average molecular weight (Mw) 10,000, solvent (propylene glycol monomethyl ether) other than the active ingredient. (manufactured by Shin-Etsu Silicone Co., Ltd.)

<4. Oil repellency evaluation>
Using the water and oil repellent compositions of Examples 1 to 12 and Comparative Examples 1 to 8 thus obtained, the following first test and second test were performed to evaluate the oil repellency. The results are shown in Tables 2 and 3.

[4-1. First test]
The water and oil repellent composition was diluted with ion-exchanged water to twice the mass basis. A square cotton cloth (cotton cloth No. 3) measuring 200 mm long and 200 mm wide was immersed in the diluted water and oil repellent composition. Thereafter, the cotton cloth was dried by heating at 130° C. for 5 minutes using an oven to obtain a test cloth. The test cloth was prepared so that the amount of the water and oil repellent composition components attached after drying was 20 parts by weight per 100 parts by weight of the cotton cloth.

0.03 ml of the test liquid was dropped on one side of the obtained test cloth and left to stand. After 1 minute, the state of the test liquid was visually observed and evaluated according to the following criteria.
In the first test, an oil repellent grade 1 test liquid (Nujol) specified in the oil repellency test of the AATCC 118 method was used as the test liquid, and an oil repellent grade 2 test liquid (Nujol/n-hexadecane) was used as the test liquid. = 65/35). Moreover, as the test cloth and the test liquid, those at 23° C. were used. The standing and visual observation of the test solution on the test cloth were performed in a constant temperature room at 23°C.

"Evaluation criteria"
Very Good: The test liquid retains the droplets.
Good: Spherical droplets of the test liquid collapse and the test liquid spreads on the test cloth, but does not soak into the test cloth.
Fairly good: The test liquid soaks into the test cloth within 30 seconds to 1 minute after the test liquid is allowed to stand.
Poor: The test liquid soaks into the test cloth within 30 seconds after the test liquid is allowed to stand still.

[4-2. Second test]
The water and oil repellent composition is applied to a glass plate as a substrate using an applicator so as to have a thickness of 150 μm (undried state), and is dried by heat treatment at 130° C. for 5 minutes using an oven. , a specimen (coating material) was obtained.
On the surface of the obtained test piece coated with the water and oil repellent composition, 2 μl of an oil repellent class 1 test liquid (Nujol) specified in the AATCC 118 method oil repellent test was gently placed, and after 10 seconds, the test liquid was applied. was measured by the θ/2 method using an automatic contact angle meter CA-VP type (manufactured by Kyowa Interface Science Co., Ltd.). A larger contact angle indicates better oil repellency.

<5. Water repellency evaluation>
Using the water and oil repellent compositions of Examples 1 to 12 and Comparative Examples 1 to 8, the water repellency test (spray test) described in JIS L 1092 (2009) Section 7.2 was performed. rice field. Evaluation criteria are as follows. The larger the class number, the better the water repellency. Tables 2 and 3 show the test results.

"Evaluation criteria"
Grade 1: Wetness over the entire surface.
Grade 2: Wetness over half the surface area, with small individual wettings penetrating the fabric.
Grade 3: Wetting area less than half the surface, showing small individual droplets of wetting on the surface. Grade 4: showing no wetting on the surface, but showing adhesion of small water droplets.
Grade 5: The surface is free from wetting and water droplets.

<6. Evaluation result>
[6-1. oil repellency]
As shown in Table 2, the substrates treated with the water and oil repellent compositions of Examples 1 to 12 penetrated both Nujol and Nujol/n-hexadecane = 65/35 test liquids. (first test), and the value of the contact angle to the droplet of the test liquid (Nujol) was also large (second test). From this, it was found that the water and oil repellent compositions of Examples 1 to 12 can impart high oil repellency to substrates.
In contrast, as shown in Table 3, the substrates treated with the water- and oil-repellent compositions of Comparative Examples 2 to 8 that do not contain the aqueous emulsion (α-1) (copolymer (A)) Nujol/n-hexadecane = 65/35 permeates easily into the material, and sufficient oil repellency cannot be imparted to the base material.

[6-2. water repellency]
As shown in Table 2, as a result of the water repellency test, the substrates treated with the water and oil repellent compositions of Examples 1 to 12 did not show extensive wettability. From this, it was found that the water and oil repellent compositions of Examples 1 to 12 can impart high water repellency to substrates.
On the other hand, as shown in Table 3, Comparative Example 1 containing no aqueous emulsions (β-1) to (β-5) (copolymer (B)), aqueous emulsion (α-1) (copolymer The substrates treated with the water and oil repellent compositions of Comparative Examples 3, 4, and 8, which did not contain (A)), showed wettability over half or more of the surface area as a result of the water repellency test. Therefore, the water and oil repellent compositions of Comparative Examples 1, 3, 4 and 8 could not impart sufficient water repellency to the substrate.
From the above, it was found that the water and oil repellent composition according to the present invention can impart high oil repellency and water repellency to substrates.

The present invention can provide a water and oil repellent composition that can impart high oil repellency and water repellency to substrates.

Claims (16)

a copolymer (A) that does not contain a structural unit having a siloxane bond;
a copolymer (B) containing a structural unit having a siloxane bond;
a polyether-modified polydimethylsiloxane (C);
and an aqueous medium (D),
The copolymer (A) is
a structural unit (a1) derived from a compound having an ethylenically unsaturated bond and an ester bond and having no carboxyl group;
and a structural unit (a2) derived from a compound having an ethylenically unsaturated bond and a carboxy group,
The copolymer (B) is
a structural unit (b1) derived from a compound having an ethylenically unsaturated bond and an ester bond and having no carboxyl group;
a structural unit (b2) derived from a compound having an ethylenically unsaturated bond and a carboxy group;
A water and oil repellent composition having a structural unit (b3) derived from polydimethylsiloxane having an ethylenically unsaturated bond and represented by the following formula (1).

(In Formula (1), R ¹ represents a hydrogen atom or a methyl group; R ² represents a divalent aliphatic group having 1 to 6 carbon atoms which may contain an ether bond; R ³ represents a C 1 to 30 of an aliphatic group, an aromatic group, or a hydroxyl group, h is any one of 0, 1, or 2, and j is an integer of 0 to 500.) The water and oil repellent composition according to claim 1, wherein the structural unit (a1) and the structural unit (b1) are structural units derived from a compound having a (meth)acryloyl group. The water and oil repellent composition according to claim 1 or claim 2, wherein the structural unit (a2) and the structural unit (b2) are structural units derived from (meth)acrylic acid. The water and oil repellent according to any one of claims 1 to 3, wherein the mass ratio of the copolymer (A) and the copolymer (B) is 10/90 or more and 90/10 or less. Composition. The water and oil repellent composition according to any one of claims 1 to 4, wherein the copolymer (A) contains 0.10% by mass or more and 20% by mass or less of the structural unit (a2). The water and oil repellent composition according to any one of claims 1 to 5, wherein the copolymer (B) contains 0.10% by mass or more and 20% by mass or less of the structural unit (b2). The water and oil repellent composition according to any one of claims 1 to 6, wherein the copolymer (B) contains 3.0% by mass or more and 50% by mass or less of the structural unit (b3). The water and oil repellent composition according to any one of claims 1 to 7, wherein the polyether-modified polydimethylsiloxane (C) has a hydroxyl group at the end of the polyether chain. The polyether-modified polydimethylsiloxane (C) is contained in an amount of 0.10 parts by mass or more and 20 parts by mass or less with respect to a total of 100 parts by mass of the copolymer (A) and the copolymer (B). The water and oil repellent composition according to any one of claims 1 to 8. The water and oil repellent composition according to any one of claims 1 to 9, further comprising a surfactant (E). The water and oil repellent composition according to claim 10, wherein the surfactant (E) is an anionic surfactant. A fiber treatment agent containing the water and oil repellent composition according to any one of claims 1 to 11. A fiber treatment method using the fiber treatment agent of claim 12. A coating agent containing the water and oil repellent composition according to any one of claims 1 to 11. A fiber processed product in which the solid content contained in the fiber treatment agent of claim 12 adheres to the fiber. The structural unit (a1) and the structural unit (b1) are at least one selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. is one,
The structural unit (a2) and the structural unit (b2) are at least one selected from the group consisting of acrylic acid and methacrylic acid,
The content of the structural unit (a1) in the copolymer (A) is 85% by mass or more and 99% by mass or less,
The content of the structural unit (a2) in the copolymer (A) is 0.5% by mass or more and 5.0% by mass or less,
The content of the structural unit (b1) in the copolymer (B) is 50% by mass or more and 93% by mass or less,
The content of the structural unit (b2) in the copolymer (B) is 0.5% by mass or more and 5.0% by mass or less,
The content of the structural unit (b3) in the copolymer (B) is 7.0% by mass or more and 50% by mass or less,
The content of the structural unit (b3) in the total amount of the copolymer (A) and the copolymer (B) is 1.5% by mass or more and 30% by mass or less,
The ratio represented by the mass of the copolymer (A)/the mass of the copolymer (B) is 10/90 to 90/10,
The water and oil repellent composition according to claim 1, wherein the polyether-modified polydimethylsiloxane (C) has a weight average molecular weight of 7,000 or more and 14,000 or less.