Hydrophobic and oleophobic agent composition, fiber treatment agent, method for treating fiber, fiber processed product, and coating agent

Abstract

The present application provides a hydrophobic and oleophobic agent composition containing a copolymer (A) not containing a structural unit having a siloxane bond, a copolymer (B) containing a structural unit having a siloxane bond, a polyether-modified polydimethylsiloxane, and an aqueous medium; the copolymer (A) contains a structural unit derived from a compound having an ethylenic unsaturated bond and an ester bond and not having a carboxyl group, and a structural unit derived from a compound having an ethylenic unsaturated bond and a carboxyl group, and the copolymer (B) contains a structural unit derived from a compound having an ethylenic unsaturated bond and an ester bond and not having a carboxyl group, a structural unit derived from a compound having an ethylenic unsaturated bond and a carboxyl group, and a structural unit derived from a polydimethylsiloxane having an ethylenic unsaturated bond.

Description

TECHNICAL FIELD

[0001] The present application relates to a hydrophobic and oleophobic agent composition, a fiber treatment agent, a fiber treatment method, a fiber processed product, and a coating agent.

[0002] This application claims priority based on Japanese Patent Application No. 2021-023556 filed on February 17, 2021, the contents of which are incorporated herein. BACKGROUND

[0003] In the past, as a method of imparting hydrophobic and oleophobic properties to a base material such as a fiber, paper, or the like, hydrophobic and oleophobic treatment using a hydrophobic and oleophobic agent composition has been performed. As the hydrophobic and oleophobic agent composition, there is a composition containing a compound having a perfluoroalkyl group having 8 or more carbon atoms.

[0004] However, the compound containing a perfluoroalkyl group having 8 or more carbon atoms has a possibility of generating perfluoro-octanoic acid (hereinafter, sometimes referred to as “PFOA”) by decomposition or metabolism. Perfluoro-octanoic acid is required to be reduced in the amount of generation by the United States Environmental Protection Agency. Therefore, a hydrophobic and oleophobic agent composition containing a compound containing a perfluoroalkyl group having a shorter carbon chain has been proposed.

[0005] For example, Patent Literature 1 describes a hydrophobic and oleophobic agent composition containing a pyrazole-capped hydrophobic polyisocyanate aqueous dispersion containing a pyrazole-capped hydrophobic polyisocyanate and a nonionic surfactant, and a hydrophobic and oleophobic component having a perfluoroalkyl group having 6 or less carbon atoms.

[0006] Patent Literature 2 describes a hydrophobic and oleophobic agent composition containing: a fluorine-containing polymer containing a structural unit having a polyfluoroalkyl group having 1 to 6 carbon atoms; a fluorine-containing polymer having a structural unit based on a fluoroolefin; and an aqueous medium.

[0007] Further, in recent years, the application of a compound containing a perfluoroalkyl group having a shorter carbon chain has also been studied to be reduced. Therefore, a hydrophobic and oleophobic agent composition not containing a fluorine-based compound has been proposed.

[0008] For example, Patent Literature 3 describes an oleophobic agent composition containing an aqueous emulsion in which a copolymer (A) containing a structural unit based on an ethylenically unsaturated carboxylate monomer and a structural unit based on an ethylenically unsaturated carboxylic acid monomer is dispersed in an aqueous medium (B), and a polyether-modified polydimethylsiloxane (C).

[0009] Patent Literature 4 describes an oil-and-water repellent agent for fiber treatment, which contains a silicone-acrylic copolymer obtained by polymerizing monomers containing a (meth)acrylate having a quaternary ammonium group, a both-end (meth)acryl-modified silicone oil, and a nonionic hydrophobic ethylenically unsaturated monomer.

[0010] Prior Art Documents

[0011] Patent Literature

[0012] Patent Literature 1: Japanese Patent Application Laid-Open (JP-A) No. 2012-031285

[0013] Patent Literature 2: International Publication No. 2012 / 020806

[0014] Patent Literature 3: International Publication No. 2018 / 163911

[0015] Patent Literature 4: Japanese Patent Application Laid-Open (JP-A) No. 2016-102272 SUMMARY

[0016] PROBLEMS TO BE SOLVED BY THE INVENTION

[0017] However, the conventional hydrophobic and oleophobic agent composition not containing a fluorine-based compound sometimes fails to impart sufficient oil repellency and water repellency to a substrate.

[0018] The present application has been achieved in view of the above-described circumstances, and an object thereof is to provide a hydrophobic and oleophobic agent composition capable of imparting high oil repellency and water repellency to a substrate.

[0019] Further, an object of the present application 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 a substrate.

[0020] MEANS FOR SOLVING THE PROBLEMS

[0021] The present inventors have conducted intensive studies in order to solve the above-described problems. As a result, it has been found that a hydrophobic and oleophobic agent composition containing a copolymer containing a structural unit derived from a compound having an ethylenically unsaturated bond and a carboxyl group, and a copolymer containing a structural unit derived from a compound having an ethylenically unsaturated bond and a carboxyl group and a structural unit derived from a polydimethylsiloxane having an ethylenically unsaturated bond is sufficient, and thus the present application has been achieved.

[0022] That is, the present application relates to the following matters.

[0023] The first mode of the present application provides the following hydrophobic and oleophobic agent composition.

[0024] [1] A hydrophobic and oleophobic agent composition containing a copolymer (A) not containing 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),

[0025] The copolymer (A) contains:

[0026] a structural unit (al) derived from a compound having an ethylenic unsaturated bond and an ester bond and not having a carboxyl group, and

[0027] a structural unit (a2) derived from a compound having an ethylenic unsaturated bond and a carboxyl group;

[0028] The copolymer (B) contains:

[0029] a structural unit (bl) derived from a compound having an ethylenic unsaturated bond and an ester bond and not having a carboxyl group,

[0030] a structural unit (b2) derived from a compound having an ethylenic unsaturated bond and a carboxyl group, and

[0031] a structural unit (b3) derived from a polydimethylsiloxane having an ethylenic unsaturated bond represented by the following formula (1).

[0032]

[0033] (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 can contain an ether bond; R 3 represents an aliphatic group, an aromatic group, or a hydroxyl group having 1 to 30 carbon atoms; h is any one of 0, 1, and 2; j represents an integer of 0 to 500.)

[0034] The hydrophobic and oleophobic agent composition of the first aspect of the present application preferably has the features described in [2] to

[11] below. The features described in [2] to

[11] below are also preferably arbitrarily combined by two or more.

[0035] [2] The hydrophobic and oleophobic agent composition according to [1], the structural unit (al) and the structural unit (bl) being structural units derived from a compound having a (meth)acryloyl group.

[0036] [3] The hydrophobic and oleophobic agent composition according to [1] or [2], the structural unit (a2) and the structural unit (b2) being structural units derived from a (meth)acrylic acid.

[0037] [4] The hydrophobic and oleophobic agent composition according to any one of [1] to [3], wherein the mass ratio of the copolymer (A) to the copolymer (B) is 10 / 90 to 90 / 10.

[0038] [5] The hydrophobic and oleophobic agent composition according to any one of [1] to [4], wherein the copolymer (A) contains 0.10 mass% to 20 mass% of the structural unit (a2).

[0039] [6] The hydrophobic and oleophobic agent composition according to any one of [1] to [5], wherein the copolymer (B) contains 0.10 mass% to 20 mass% of the structural unit (b2).

[0040] [7] The hydrophobic and oleophobic agent composition according to any one of [1] to [6], wherein the copolymer (B) contains 3.0 mass% to 50 mass% of the structural unit (b3).

[0041] [8] The hydrophobic and oleophobic agent composition according to any one of [1] to [7], wherein the polyether-modified dimethylpolysiloxane (C) has a hydroxyl group at the terminal of a polyether chain.

[0042] [9] The hydrophobic and oleophobic agent composition according to any one of [1] to [8], wherein 0.10 parts by mass to 20 parts by mass of the polyether-modified dimethylpolysiloxane (C) is contained with respect to 100 parts by mass of the total of the copolymer (A) and the copolymer (B).

[0043]

[10] The hydrophobic and oleophobic agent composition according to any one of [1] to [9], further comprising a surfactant (E).

[0044]

[11] The hydrophobic and oleophobic agent composition according to

[10] , wherein the surfactant (E) is an anionic surfactant.

[0045] A second aspect of the present application provides the following fiber treatment agent.

[0046]

[12] A fiber treatment agent comprising the hydrophobic and oleophobic agent composition according to any one of [1] to

[11] .

[0047] A third aspect of the present application provides the following method for treating a fiber.

[0048]

[13] A method for treating a fiber using the fiber treatment agent of

[12] .

[0049] A fourth aspect of the present application provides the following coating agent.

[0050]

[14] A coating agent comprising the hydrophobic and oleophobic agent composition according to any one of [1] to

[11] .

[0051] A fifth aspect of the present application provides the following fiber-processed product.

[0052]

[15] A fiber-processed product in which a solid component contained in the fiber treatment agent of

[12] is attached to a fiber.

[0053] Effects of the Invention

[0054] The hydrophobic and oleophobic agent composition according to the present application can impart high oil repellency and water repellency to a substrate.

[0055] In addition, the fiber treatment agent, paper treatment agent, and coating agent of the present application contain the hydrophobic and oleophobic agent composition of the present application, and thus can impart high oil repellency and water repellency to a substrate. DETAILED DESCRIPTION

[0056] Hereinafter, the hydrophobic and oleophobic agent composition, fiber treatment agent, paper treatment agent, and coating agent of the present application will be described in detail. Note that the present application is not limited to the following examples. The configurations described below can be appropriately changed within the scope of the present application. For example, the present application is not limited to the following examples, and numbers, amounts, ratios, compositions, types, positions, materials, configurations, and the like can be added, omitted, replaced, changed, and the like within the scope of the present application.

[0057] In the following description, the term "monomer" refers to a compound having a radically polymerizable ethylenic unsaturated bond. The term "ethylenic unsaturated bond" refers to a double bond between carbon atoms other than carbon atoms forming an aromatic ring. Note that in the following description, the term "ethylenic unsaturated bond" refers to a radically polymerizable ethylenic unsaturated bond, unless otherwise specified.

[0058] "(Meth)acryl-" refers to "acryl-" or "methacryl-". "(Meth)acrylate" refers to "acrylate" or "methacrylate".

[0059] The term "non-volatile component" refers to a component contained in a composition or the like, having a boiling point of 130°C or higher at 1 atm (1013 hPa).

[0060] The term "effective component" refers to a component belonging to a certain category of components, in the case where components of the category are used in the form of a mixture such as a solution. For example, the term "effective component" in a propylene glycol 1-monomethyl ether solution of a polyether-modified polydimethylsiloxane refers to all compounds contained in the solution that belong to the polyether-modified polydimethylsiloxane.

[0061] The number average molecular weight and the weight average molecular weight are polystyrene conversion values measured by gel permeation chromatography (GPC).

[0062] In the polymer of a compound having an ethylenic unsaturated bond, the structural unit derived from the compound having an ethylenic unsaturated bond, the chemical structure of the portion other than the ethylenic unsaturated bond of the compound, and the chemical structure of the portion other than the portion corresponding to the ethylenic unsaturated bond of the structural unit in the polymer are the same. For example, the structural unit derived from methyl acrylate has a structure represented by -CH2CH(COOCH3)- in the polymer.

[0063] However, unless otherwise specified, in the case where the polymer contains a structural unit derived from a compound having an ionic functional group such as a carboxyl group and having an ethylenic unsaturated bond, a part of the functional group thereof is regarded as a structural unit derived from the same compound regardless of whether ion exchange is performed or not. For example, in the polymer, not only a structure represented by -CH2-C(CH3)(COOH)-, but also a structure represented by -CH2-C(CH3)(COONa)- is regarded as a structural unit derived from methacrylic acid.

[0064] In the following description, the compound which becomes the source of the structural unit possessed by the polymer means a compound in which a corresponding relationship exists between the compound and the structural unit, and does not need to coincide with the monomer used in the actual manufacturing process of the polymer.

[0065] In the case where the chemical structure of the monomer used and the chemical structure of the portion other than the portion corresponding to the ethylenic unsaturated bond of the obtained polymer are not the same due to chemical reaction or the like of the portion other than the chain-like portion corresponding to the ethylenic unsaturated bond of the polymer after polymerization, the structural unit possessed by the polymer is based on the chemical structure after the above chemical reaction or the like is performed after polymerization. For example, in the case where vinyl acetate is polymerized and then the obtained polymer is saponified, the chemical structure of the polymer obtained by saponification is based. Therefore, the saponified structural unit is not a structural unit derived from vinyl acetate, but a structural unit derived from vinyl alcohol.

[0066] <1. Hydrophobic and oleophobic agent composition>

[0067] The hydrophobic and oleophobic agent composition of the present embodiment contains a copolymer (A) not containing a structural unit having a siloxane bond (-Si-O-Si-), a copolymer (B) containing a structural unit having a siloxane bond, a polyether-modified polydimethylsiloxane (C), and an aqueous medium (D). The hydrophobic and oleophobic agent composition of the present embodiment can further contain other components such as a surfactant (E) as needed. The hydrophobic and oleophobic agent composition of the present embodiment can not contain a compound having a perfluoroalkyl group having 8 or more carbon atoms. The hydrophobic and oleophobic agent composition of the present embodiment can not contain a fluorine-containing compound.

[0068] In the hydrophobic and oleophobic agent composition of the present embodiment, the copolymer (A) and the copolymer (B) preferably form an emulsion in the aqueous medium (D). Here, the copolymer (A) and the copolymer (B) are considered to form an emulsion as long as they are dispersed in the aqueous medium (D) even if they are solids. That is, the copolymer (A) and the copolymer (B) can form liquid particles or solid particles.

[0069] [1-1. Copolymer (A)]

[0070] The copolymer (A) does not contain a structural unit having a siloxane bond. The copolymer (A) contains a structural unit (al) derived from a compound having an ethylenic unsaturated bond and an ester bond and not having a carboxyl group (hereinafter sometimes referred to simply as "structural unit (al)", and a structural unit (a2) derived from a compound having an ethylenic unsaturated bond and a carboxyl group (hereinafter sometimes referred to simply as "structural unit (a2)").

[0071] The copolymer (A) imparts good oleophobicity to a substrate on which the hydrophobic and oleophobic agent composition of the present embodiment is attached.

[0072] [1-1-1. Structural unit (al)]

[0073] Since the copolymer (A) contains the structural unit (al), it becomes a hydrophobic and oleophobic agent composition capable of imparting high oleophobicity to a substrate and having high stability. The structural unit (al) can be composed of one structure or can contain two or more structures.

[0074] The kind of the compound that becomes the source of the structural unit (al) and the content rate thereof can be appropriately determined, for example, in order to adjust the glass transition temperature Tg of the copolymer (A). Specifically, in the case of lowering the glass transition temperature of the copolymer (A), it is sufficient that a compound whose homopolymer has a low glass transition temperature be contained more as the compound that becomes the source of the structural unit (al). In the case of increasing the glass transition temperature of the copolymer (A), it is sufficient that a compound whose homopolymer has a high glass transition temperature be contained more as the compound that becomes the source of the structural unit (al).

[0075] The structural unit (al) is preferably a structural unit derived from a compound having a (meth)acryl group, and more preferably a structural unit derived from an alkyl (meth)acrylate.

[0076] In the case where the compound that is the source of the structural unit (a1) is an alkyl (meth)acrylate, it is further preferred that the alkyl (meth)acrylate having a hydrocarbon structure other than the (meth)acryloyloxy group has a carbon number of 1 to 8. The carbon number is preferably 2 to 7, more preferably 3 to 6, and further preferably 4 to 5. The reason for this is that the adjustment of the hand feeling of the substrate treated with the hydrophobic and oleophobic agent composition according to the present embodiment becomes easy.

[0077] Examples of the alkyl (meth)acrylate having a hydrocarbon structure other than the (meth)acryloyloxy group having a carbon number of 1 to 8 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.

[0078] In the case where the hydrophobic and oleophobic agent composition according to the present embodiment is included in a paper treatment agent for the treatment of paper or a fiber treatment agent for the treatment of fibers, among the above compounds, the compound that is the source of the structural unit (a1) is particularly preferably one or two or more selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0079] The compound that is the source of the structural unit (a1) can include an alkyl (meth)acrylate having a chain hydrocarbon structure having a carbon number of 9 or more as a hydrocarbon structure other than the (meth)acryloyloxy group. In this case, a hydrophobic and oleophobic agent composition that imparts a more excellent hydrophobic property to a substrate while maintaining the oleophobic property can be obtained.

[0080] In the case where the structural unit (a1) is a structural unit derived from a hydrocarbon having an ethylenic unsaturated bond, an aromatic vinyl compound is preferred. Examples of the aromatic vinyl compound include styrene, a-methylstyrene, p-methylstyrene, and the like.

[0081] [1-1-2. Structural Unit (a2)]

[0082] Since the copolymer (A) contains the structural unit (a2), a hydrophobic and oleophobic agent composition that imparts a high oleophobic property to a substrate can be obtained. The structural unit (a2) can be composed of one structure, or can include two or more structures.

[0083] The compound that is the source of the structural unit (a2) is only required to be a compound having an ethylenically unsaturated bond and a carboxyl group. As the compound that is the source of the structural unit (a2), for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, citraconic acid, maleic acid, maleic anhydride, fumaric acid, and the like can be given. The compound that is the source of the structural unit (a2) preferably contains either or both of acrylic acid or methacrylic acid, and more preferably is either or both of acrylic acid or methacrylic acid. The structural unit (a2) can or can not contain an ester bond.

[0084] [1-1-3. Content of each structural unit in the copolymer (A)]

[0085] 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, and particularly preferably 85% by mass or more. The reason for this is that a hydrophobic and oleophobic agent composition having good stability is obtained.

[0086] In order to easily ensure the content of the structural unit (a2), 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, further preferably 97% by mass or less, and particularly preferably 96% by mass or less. As needed, the content of the structural unit (a1) in the copolymer (A) can be, for example, 30% by mass to 99% by mass, 40% by mass to 60% by mass, 60% by mass to 70% by mass, 70% by mass to 80% by mass, 88% by mass to 99% by mass, 90% by mass to 98% by mass, 93% by mass to 97% by mass, or 94% by mass to 96% by mass.

[0087] In the case where the compound that is the source of the structural unit (a1) is an (meth)acrylic acid alkyl ester having a hydrocarbon structure other than the (meth)acryloyloxy group and having 1 to 8 carbon atoms, the content of the structural unit (a1) in the copolymer (A) is preferably 30% by mass or more, and more preferably 50% by mass or more, and further preferably 70% by mass or more. The reason for this is that adjustment of the hand feeling of a substrate treated with the hydrophobic and oleophobic agent composition according to the present embodiment becomes easy.

[0088] In the case where the compound that is the source of the structural unit (a1) is an (meth)acrylic acid alkyl ester having a hydrocarbon structure other than the (meth)acryloyloxy group and having 1 to 8 carbon atoms, in order to easily ensure the content of the structural unit (a2), the content of the structural unit (a1) in the copolymer (A) is preferably 99% by mass or less, and more preferably 98% by mass or less.

[0089] 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, further preferably 1.0% by mass or more, and particularly preferably 1.8% by mass or more. The reason for this is that a hydrophobic and oleophobic agent composition capable of imparting a more excellent oil repellency to a substrate is obtained.

[0090] 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, further preferably 5.0% by mass or less, and particularly preferably 3.0% by mass or less. The reason for this is that a low-cost hydrophobic and oleophobic agent composition is obtained. In addition, since the content of the structural unit (al) is easily ensured, excellent hydrophobicity in a substrate treated with the hydrophobic and oleophobic agent composition is easily ensured. The content of the structural unit (a2) in the copolymer (A) may, for example, be 0.10% by mass to 20.0% by mass, 0.30% by mass to 15.0% by mass, 0.50% by mass to 8.0% by mass, 0.8% by mass to 7.0% by mass, 1.0% by mass to 6.0% by mass, 1.2% by mass to 4.0% by mass, or 1.5% by mass to 3.5% by mass, as needed.

[0091] The copolymer (A) can include a structural unit other than the structural unit (al) and the structural unit (a2). However, the copolymer (A) preferably includes the structural unit (al) and the structural unit (a2) in a total of 50% by mass or more, more preferably includes the structural unit (al) and the structural unit (a2) in a total of 70% by mass or more, further preferably includes the structural unit (al) and the structural unit (a2) in a total of 90% by mass or more, and particularly preferably includes the structural unit (al) and the structural unit (a2) in a total of 95% by mass or more.

[0092] The copolymer (A) can include a polymerization initiator used at the time of polymerization for producing the copolymer (A). As the polymerization initiator, any of, for example, a persulfate, hydrogen peroxide, an azo compound, an organic peroxide, and the like can be arbitrarily selected. The polymerization initiator can also be included as a redox initiator in which the above-described polymerization initiator and a reducing agent are used in combination. Only one kind of polymerization initiator can be included, or two or more kinds of polymerization initiators can be included.

[0093] The copolymer (A) can contain a chain transfer agent used at the time of polymerization for producing the copolymer (A). The chain transfer agent is a substance that adjusts the molecular weight of the copolymer (A) produced by polymerization. As examples of the chain transfer agent, mention can be made of, for example, mercaptans, mercaptoacetic acid and esters thereof, β-mercaptopropionic acid and esters thereof, and the like. One kind of chain transfer agent can be contained alone, or two or more kinds of chain transfer agents can be contained. The amount of the polymerization initiator, the chain transfer agent can be arbitrarily selected. For example, the content of these compounds can be mentioned as 0.1 to 10.0 mass%, 0.5 to 5.0 mass%, 1.0 to 3.0 mass%, and the like, relative to 100 parts by mass of the total of the monomers, but is not limited to these examples alone.

[0094] 〔1-2. Copolymer (B)〕

[0095] The copolymer (B) contains a structural unit (bl) derived from a compound having an ethylenic unsaturated bond and an ester bond and not having a carboxyl group (hereinafter sometimes referred to simply as "structural unit (bl)", a structural unit (b2) derived from a compound having an ethylenic unsaturated bond and a carboxyl group (hereinafter sometimes referred to simply as "structural unit (b2)", and a structural unit (b3) derived from a polydimethylsiloxane having an ethylenic unsaturated bond represented by the following formula (1) (hereinafter sometimes referred to simply as "structural unit (b3)").

[0096] The structural unit (bl) and the structural unit (b2) in the present embodiment do not contain a structural unit having a siloxane bond.

[0097] The copolymer (B) preferably has a structure other than the terminal structure composed of the structural unit (bl), the structural unit (b2), and the structural unit (b3).

[0098] The copolymer (B) imparts oil repellency to a substrate to which the hydrophobic and oleophobic agent composition of the present embodiment is attached, and imparts good hydrophobicity.

[0099] [1-2-1. Structural unit (bl) and structural unit (b2)]

[0100] The structural unit (bl) and the structural unit (b2) in the present embodiment do not contain a structural unit having a siloxane bond.

[0101] The structural unit (bl) and the structural unit (b2) in the present embodiment do not contain a structural unit having a siloxane bond.

[0102] [1-2-2. Structural unit (b3)]

[0103] The structural unit (b3) is a structural unit derived from a polydimethylsiloxane having an ethylenically unsaturated bond represented by the following formula (1), and is a portion forming a polysiloxane side chain in the copolymer (B). Since the copolymer (B) contains the structural unit (b3), it becomes a hydrophobic and oleophobic agent composition capable of imparting high hydrophobicity to a substrate. The structural unit (b3) can be composed of one structure, or can contain two or more structures.

[0104]

[0105] (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 can contain an ether bond; R 3 represents an aliphatic group, an aromatic group, or a hydroxyl group having 1 to 30 carbon atoms; h is any one of 0, 1, and 2; j represents an integer of 0 to 500.)

[0106] R 1 in formula (1) represents a hydrogen atom or a methyl group.

[0107] R 2 in formula (1) is a divalent aliphatic group having 1 to 6 carbon atoms which can contain an ether bond. R 2 The number of carbon atoms of R 2 is preferably 1 to 4, and can be 1 to 4, 2 to 3, as needed. The reason for this is that, if the above number of atoms is adopted, it becomes a hydrophobic and oleophobic agent composition capable of imparting high oleophobicity to a substrate.

[0108] R 3 in formula (1) is an aliphatic group, an aromatic group, or a hydroxyl group having 1 to 30 carbon atoms. R 3 is preferably an aliphatic group having 1 to 30 carbon atoms, more preferably an aliphatic group having 2 to 18 carbon atoms, further preferably an aliphatic group having 2 to 10 carbon atoms, and particularly preferably an aliphatic group having 2 to 6 carbon atoms. For example, the above number of carbon atoms can be 3 to 5, 2 to 4. R 3 is more preferably a hydrocarbon chain, and further preferably a straight-chain hydrocarbon chain. The reason for this is that it becomes a hydrophobic and oleophobic agent composition capable of imparting high hydrophobicity to a substrate.

[0109] j in formula (1) is an integer of 0 to 500, and in order to make the number average molecular weight of the compound represented by formula (1) be within a preferable range, it is preferably an integer of 1 to 400, and further preferably an integer of 10 to 300. For example, j can also be an integer in the range of 1 to 200, 1 to 150, 1 to 80, 1 to 30, 1 to 10, or 1 to 5. The compound that becomes the source of the structural unit (b3) can be only one of the compounds represented by formula (1), or can include two or more of the compounds represented by formula (1).

[0110] The number average molecular weight of the compound represented by formula (1) is preferably 300 or greater, more preferably 1,000 or greater, further preferably 3,000 or greater, and particularly preferably 7,000 or greater. The reason for this is that more favorable hydrophobicity can be obtained in a substrate that has been treated with the hydrophobic and oleophobic agent 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 further preferably 15,000 or less. The reason for this is that the copolymerizability of the compound represented by formula (1) during polymerization for producing the copolymer (B) is improved.

[0111] [1-2-3. Content of each structural unit in the copolymer (B)]

[0112] The content of the structural unit (b1) in the copolymer (B) is preferably 30% by mass or greater, more preferably 40% by mass or greater, further preferably 50% by mass or greater, and particularly preferably 70% by mass or greater. The reason for this is that a hydrophobic and oleophobic agent composition having favorable stability is obtained.

[0113] In order to easily ensure the contents of the structural unit (b2) and the structural unit (b3), the content of the structural unit (b1) in the copolymer (B) is preferably 96% by mass or less, more preferably 93% by mass or less, and further preferably 90% by mass or less. The content of the structural unit (b1) in the copolymer (B) can be, for example, 30% by mass to 96% by mass, 45% by mass to 95% by mass, 55% by mass to 94% by mass, 60% by mass to 85% by mass, or 65% by mass to 80% by mass.

[0114] In the case where the compound that becomes the source of the structural unit (b1) is a (meth)acryl alkyl ester having a hydrocarbon structure with a carbon atom number of 1 to 8 other than a (meth)acryloyloxy group, the content of the structural unit (b1) in the copolymer (B) is preferably 30% by mass or greater, more preferably 50% by mass or greater, and further preferably 70% by mass or greater. The reason for this is that adjustment of the hand feeling of a substrate that has been treated with the hydrophobic and oleophobic agent composition according to the present embodiment becomes easy.

[0115] In the case where the compound that is the source of the structural unit (b1) is a (meth)acrylate having a hydrocarbon structure other than the (meth)acryloyloxy group and having a carbon number of 1 to 8, in order to easily ensure the content rates of the structural unit (b2) and the structural unit (b3), the content rate of the structural unit (b1) in the copolymer (B) is preferably 96% by mass or less, more preferably 93% by mass or less.

[0116] The content rate 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, further preferably 0.85% by mass or more, particularly preferably 1.8% by mass or more. The reason for this is that a hydrophobic and oleophobic agent composition that can impart a more excellent oil repellency to a substrate is obtained.

[0117] The content rate of the structural unit (b2) in the copolymer (B) is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5.0% by mass or less, particularly preferably 3.0% by mass or less. The reason for this is that a hydrophobic and oleophobic agent composition that is low in cost is obtained. In addition, since the content rates of the structural unit (b1) and the structural unit (b3) are easily ensured, an excellent hydrophobicity in a substrate that has been treated with the hydrophobic and oleophobic agent composition is easily ensured. The content rate of the structural unit (b2) in the copolymer (B) may be, for example, 0.10% by mass to 20.0% by mass, 0.30% by mass to 15.0% by mass, 0.7% by mass to 10.0% by mass, 1.0% by mass to 8.0% by mass, 1.2% by mass to 6.0% by mass, 1.5% by mass to 3.0% by mass.

[0118] The content rate 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, further preferably 7.0% by mass or more. The reason for this is that a hydrophobic and oleophobic agent composition that can impart a more excellent hydrophobicity to a substrate is obtained. The content rate of the structural unit (b3) in the copolymer (B) is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 15% by mass or less. The reason for this is that the content rates of the structural unit (b1) and the structural unit (b2) are easily ensured, and the hand feeling of a substrate that has been treated with the hydrophobic and oleophobic agent composition can be maintained. The content rate of the structural unit (b3) in the copolymer (B) may be, for example, 3.0% by mass to 50.0% by mass, 4.0% by mass to 47.0% by mass, 5.0% by mass to 45.0% by mass, 6.0% by mass to 43% by mass, 8.0% by mass to 40.0% by mass, 10.0% by mass to 25.0% by mass, 15.0% by mass to 20.0% by mass.

[0119] The copolymer (B) can also include a structural unit other than the structural unit (b1), the structural unit (b2), and the structural unit (b3). However, the copolymer (B) preferably includes the structural unit (b1), the structural unit (b2), and the structural unit (b3) in a total of 50% by mass or more, more preferably in a total of 70% by mass or more, further preferably in a total of 90% by mass or more, and particularly preferably in a total of 95% by mass or more.

[0120] In the present embodiment, the content ratio 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, more preferably 2.5% by mass or more, and further preferably 3.5% by mass or more. The reason for this is that a hydrophobic and oleophobic agent composition capable of imparting a more excellent hydrophobicity to a substrate is obtained.

[0121] The content ratio 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, and further preferably 7.5% by mass or less. The reason for this is that the content ratios of the structural units (a1), (a2), (b1), and (b2) are easily ensured, and a hydrophobic and oleophobic agent composition capable of imparting a more excellent hydrophobicity and oleophobicity to a substrate is obtained. For example, the content ratio of the structural unit (b3) in the above total amount can be 1.5% by mass to 30% by mass, 2.0% by mass to 25% by mass, 3.0% by mass to 20% by mass, 4.0% by mass to 15% by mass, 5.0% by mass to 10% by mass, or the like.

[0122] The copolymer (B) can include a polymerization initiator used at the time of polymerization for manufacturing the copolymer (B). As the polymerization initiator, the same polymerization initiators as those that can be included in the copolymer (A) can be cited. In the hydrophobic and oleophobic agent composition of the present embodiment, in the case where a polymerization initiator is included in the copolymer (A) and the copolymer (B), the polymerization initiator included in the copolymer (A) and the polymerization initiator included in the copolymer (B) can be the same or different.

[0123] The copolymer (B) can include a chain transfer agent used at the time of polymerization for manufacturing the copolymer (B). As the chain transfer agent, the same chain transfer agents as those that can be included in the copolymer (A) can be cited. In the hydrophobic and oleophobic agent composition of the present embodiment, in the case where a chain transfer agent is included in the copolymer (A) and the copolymer (B), the chain transfer agent included in the copolymer (A) and the chain transfer agent included in the copolymer (B) can be the same or different.

[0124] 〔1-3. Mixing ratio of copolymer (A) and copolymer (B)〕

[0125] In the hydrophobic and oleophobic agent composition according to the present embodiment, the value of the mixing ratio by mass of copolymer (A) and copolymer (B) (mass of copolymer (A) / mass of copolymer (B)) is preferably 10 / 90 or more, and more preferably 20 / 80 or more. The reason for this is that a hydrophobic and oleophobic agent composition capable of imparting more excellent oil repellency to a substrate is obtained. In the hydrophobic and oleophobic agent composition according to the present embodiment, the value of the mixing ratio by mass of copolymer (A) and copolymer (B) can also be 30 / 70 or more, or 40 / 60 or more.

[0126] In the hydrophobic and oleophobic agent composition according to the present embodiment, the value of the mixing ratio by mass of copolymer (A) and copolymer (B) is preferably 90 / 10 or less, more preferably 80 / 20 or less, further preferably 70 / 30 or less, and particularly preferably 60 / 40 or less. The reason for this is that a hydrophobic and oleophobic agent composition capable of imparting more excellent hydrophobicity to a substrate is obtained.

[0127] 〔1-4. Polyether-modified dimethylpolysiloxane (C)〕

[0128] The polyether-modified dimethylpolysiloxane (C) is a compound in which a part or all of the hydrogen atoms of the methyl groups of dimethylpolysiloxane are substituted with a polyether chain. That is, the polyether-modified dimethylpolysiloxane is a graft copolymer in which the main chain is polysiloxane and a polyether side chain is present. The solubility of the polyether-modified dimethylpolysiloxane (C) in 100 g of the aqueous medium (D) at 20°C is preferably 1.0 g / 100 g or more, and more preferably 3.0 g / 100 g or more, but is not limited thereto. The polyether-modified dimethylpolysiloxane (C) imparts excellent hydrophobicity and oil repellency to a substrate to which the hydrophobic and oleophobic agent composition according to the present embodiment is attached.

[0129] As the polyether-modified dimethylpolysiloxane (C), a polyether-modified dimethylpolysiloxane having at least either an alkoxy group or a hydroxyl group at the terminal of the polyether chain is preferable, and a polyether-modified dimethylpolysiloxane having a hydroxyl group at the terminal of the polyether chain is more preferable. In the case where the polyether-modified dimethylpolysiloxane (C) is a polyether-modified dimethylpolysiloxane having a hydroxyl group at the terminal of the polyether chain, a hydrophobic and oleophobic agent composition capable of imparting more excellent oil repellency to a substrate is obtained. The kind and the number of polyether chains can be arbitrarily selected, for example. The position and the number of the polyether chain bonded to Si of dimethylpolysiloxane can be arbitrarily selected, for example. As examples of the polyether chain, -(C1H2O) x (C2H4O) y (C3H6O) zR is not limited to this example. x, y, z are each an integer of 0 or more, and none of them are 0 at the same time. R is preferably either of an alkyl group having 1 to 10 carbon atoms and hydrogen. x, y, z can each be, for example, 0 to 300, 0 to 100, 0 to 50, 0 to 20, 0 to 10. The number of methylene oxide, oxymethylene, propylene oxide in the above polyether chain, and the arrangement method can be arbitrarily selected, and each can be arranged continuously, alternately, or randomly.

[0130] As examples of commercially available products of the composition containing the polyether-modified dimethylpolysiloxane (C) having a hydroxyl group at the terminal of the polyether chain, BYK SILCLEAN 3720 manufactured by BYK, TEGO (registered trademark) Protect 5100N manufactured by Evonik, KP-109 manufactured by Shin-Etsu Silicone, and the like can be given.

[0131] The weight average molecular weight of the polyether-modified dimethylpolysiloxane (C) is preferably 1,000 or more, more preferably 5,000 or more, and further preferably 7,000 or more. The reason is that it becomes a hydrophobic and oleophobic agent composition capable of imparting a more excellent hydrophobicity to a substrate.

[0132] The weight average molecular weight of the polyether-modified dimethylpolysiloxane (C) is preferably 50,000 or less, more preferably 30,000 or less, and further preferably 14,000 or less. The reason is that it becomes a hydrophobic and oleophobic agent composition capable of imparting a more excellent hydrophobicity to a substrate.

[0133] The content of the polyether-modified dimethylpolysiloxane (C) is preferably 0.10 parts by mass or more, more preferably 0.20 parts by mass or more, further preferably 0.50 parts by mass or more, and particularly preferably 0.90 parts by mass or more, with respect to 100 parts by mass of the total of the copolymer (A) and the copolymer (B). The reason is that it becomes a hydrophobic and oleophobic agent composition capable of imparting a more excellent hydrophobicity to a substrate.

[0134] The content of the polyether-modified dimethylpolysiloxane (C) is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, further 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, with respect to 100 parts by mass of the total of the copolymer (A) and the copolymer (B). The reason is that it makes the hand feeling of a fiber or paper treated with the hydrophobic and oleophobic agent composition good. The content of the above polyether-modified dimethylpolysiloxane (C) can be, for example, 0.10 parts by mass to 5.0 parts by mass, 0.20 parts by mass to 3.0 parts by mass, 0.30 parts by mass to 2.0 parts by mass, 0.40 parts by mass to 1.0 parts by mass, and the like.

[0135] 〔1-5. Aqueous medium (D)〕

[0136] The aqueous medium (D) contains water as an essential component. The aqueous medium (D) can also 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, and further preferably 98% by mass or more, and can also be 100% by mass.

[0137] As the hydrophilic solvent, there can be mentioned, for example, methanol, ethanol, propylene glycol 1-monomethyl ether, n-propanol, isopropanol, t-butanol, benzyl alcohol, and the like, alcohols, N-methylpyrrolidone, nitrogen-containing organic solvents, and the like. The hydrophilic solvent can be contained singly or in a combination of two or more.

[0138] The content of the hydrophilic solvent in the aqueous medium (D) is preferably 10% by mass or less, and more preferably 5.0% by mass or less. The reason for this is that it is possible to suppress an increase in cost resulting from the use of the hydrophilic solvent.

[0139] The content of the aqueous medium (D) contained in the hydrophobic and oleophobic composition is preferably determined in such a manner that the nonvolatile component concentration of the hydrophobic and oleophobic agent composition becomes a desired value.

[0140] The nonvolatile component concentration of the hydrophobic and oleophobic composition is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more. The reason for this is that it becomes a hydrophobic and oleophobic agent composition that can effectively impart a hydrophobic and oleophobic effect to a substrate with a small amount of use.

[0141] The nonvolatile component concentration of the hydrophobic and oleophobic composition is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less. The reason for this is that it becomes a hydrophobic and oleophobic agent composition that has good storage stability and is easily applied uniformly to a substrate.

[0142] The content of the aqueous medium (D) contained in the hydrophobic and oleophobic composition can be arbitrarily selected, and examples thereof include, for example, 3% by mass to 95% by mass, 5% by mass to 90% by mass, 10% by mass to 80% by mass, 30% by mass to 70% by mass, 40% by mass to 60% by mass, and the like, but is not limited to these examples.

[0143] 〔1-6. Other components〕

[0144] The hydrophobic and oleophobic agent composition of the present embodiment can contain other components in addition to the copolymer (A), the copolymer (B), the polyether-modified polydimethylsiloxane (C), and the aqueous medium (D), as needed. As the other components that can be contained in the hydrophobic and oleophobic agent composition of the present embodiment, resins, crosslinking agents, thickening agents, pH adjustors, film-forming aids, plasticizers, preservatives, antifoaming agents, surfactants (E), and the like can be given. Depending on the specifications of the hydrophobic and oleophobic agent composition, one or two or more other components can be contained within a range capable of achieving the object of the present application.

[0145] [1-6-1. Surfactant (E)]

[0146] As the surfactant (E), anionic surfactants, nonionic surfactants, cationic surfactants can be used, and commercially available products can also be used. The surfactant (E) does not have an ethylenically unsaturated bond. In the present embodiment, a surfactant having an ethylenically unsaturated bond having radical polymerizability becomes a structural unit of the copolymer (A) as a component added at the time of synthesis of the copolymer (A) and becomes a structural unit of the copolymer (B) as a component added at the time of synthesis of the copolymer (B).

[0147] The anionic surfactant is preferably a sulfonate, more preferably an aromatic sulfonate, and further preferably a linear alkylbenzene sulfonate. The number of carbon atoms of the linear alkyl group in the linear alkylbenzene sulfonate is preferably 3 or more, more preferably 6 or more, and further preferably 8 or more. The reason for this is that the affinity of the anionic surfactant to the copolymer (A) and the copolymer (B) becomes high. The number of carbon atoms of the linear alkyl group in the linear alkylbenzene sulfonate is preferably 50 or less, more preferably 30 or less, and further preferably 20 or less. The reason for this is that the affinity of the anionic surfactant to the aqueous medium (D) is improved.

[0148] As the surfactant (E), it is preferable to contain an anionic surfactant. The reason for this is that a hydrophobic and oleophobic agent composition having high adhesion to a substrate is obtained.

[0149] As the nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polycyclic phenyl ether, polyoxyalkylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and the like can be given.

[0150] As the cationic surfactant, alkyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, laurylpyridinium chloride, and the like can be given. As the cationic surfactant, it is preferable to use a hydrochloride of a compound having an ammonium group, and more preferably a quaternary ammonium chloride.

[0151] ​In the case where the hydrophobic and oleophobic agent composition of the present embodiment contains the surfactant (E), the content of the surfactant (E) is preferably 0.15 parts by mass or more, more preferably 0.40 parts by mass or more, and further preferably 0.90 parts by mass or more, relative to 100 parts by mass of the total of the copolymer (A) and the copolymer (B). The reason for this is that the copolymer (A) and the copolymer (B) can be stably dispersed in the hydrophobic and oleophobic agent composition.

[0152] In the hydrophobic and oleophobic agent composition of the present embodiment, the content of the surfactant (E) is preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, and further preferably 1.5 parts by mass or less, relative to 100 parts by mass of the total of the copolymer (A) and the copolymer (B). The reason for this is that the substrate adhesion of the coating obtained using the hydrophobic and oleophobic agent composition can be maintained without impairing water resistance.

[0153] A part or all of the surfactant (E) contained in the hydrophobic and oleophobic agent composition of the present embodiment can be a surfactant used at the time of polymerization for producing the copolymer (A) and / or a surfactant used at the time of polymerization for producing the copolymer (B). The surfactant used at the time of polymerization for producing the copolymer (A) and the surfactant used at the time of polymerization for producing the copolymer (B) can be different or the same.

[0154] In addition, a part or all of the surfactant (E) contained in the hydrophobic and oleophobic agent composition of the present embodiment can be added after the copolymer (A) and the copolymer (B) are produced.

[0155] <2. Method for producing hydrophobic and oleophobic agent composition>

[0156] The hydrophobic and oleophobic agent composition of the present embodiment can be produced, for example, by the method shown below. The method for producing the hydrophobic and oleophobic agent composition according to the present application is not limited to the method described below.

[0157] First, a first polymerization step is performed, that is, an aqueous emulsion (a) in which the copolymer (A) is dispersed in an aqueous medium (D) is produced. In addition, a second polymerization step is performed, that is, an aqueous emulsion (β) in which the copolymer (B) is dispersed in an aqueous medium (D) is produced. Then, a mixing step is performed, that is, the aqueous emulsion (a), the aqueous emulsion (β), and the polyether-modified polydimethylsiloxane (C) are mixed. By the above steps, the hydrophobic and oleophobic agent composition of the present embodiment can be obtained.

[0158] 〔2-1-1. First polymerization step〕

[0159] In the 1st polymerization step, it is preferable to mix and perform emulsion polymerization of the monomers including the compound that is a source of the structural unit (al) and the compound that is a source of the structural unit (a2), the surfactant (E), the aqueous medium (D), the polymerization initiator used as necessary, and the chain transfer agent. Thereby, the copolymer (A) that is copolymerized from the monomers including the compound that is a source of the structural unit (al) and the compound that is a source of the structural unit (a2) is generated, and the water-based emulsion (α) that includes the surfactant (E) and in which the copolymer (A) is dispersed in the aqueous medium (D) is obtained.

[0160] In the 1st polymerization step, emulsion polymerization can be performed at a temperature of, for example, 30 to 85°C.

[0161] As in the example described herein, each monomer used as a material of the water-based emulsion (α) maintains the structure other than the olefinic unsaturated bond (except for ion exchange) after polymerization without changing the chemical structure of the copolymer (A) obtained by polymerization (but ion exchange can be performed).

[0162] The use amount of the aqueous medium (D) used as a material of the water-based emulsion (α) is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and further preferably 100 parts by mass or more, with respect to 100 parts by mass of the total of the compound that is a source of the structural unit (al) and the compound that is a source of the structural unit (a2) (total of the monomers). The reason for this is that the compound that is a source of the structural unit (al) and the compound that is a source of the structural unit (a2) can be emulsified in the aqueous medium (D) and emulsion polymerization can be performed efficiently, and the copolymer (A) generated by emulsion polymerization can be stably dispersed in the aqueous medium (D).

[0163] The use amount of the aqueous medium (D) used as a material of the water-based emulsion (α) is preferably 400 parts by mass or less, more preferably 300 parts by mass or less, and further preferably 200 parts by mass or less, with respect to 100 parts by mass of the total of the compound that is a source of the structural unit (al) and the compound that is a source of the structural unit (a2). The reason for this is that by suppressing the amount of the remaining aqueous medium (D), productivity can be improved, the cost increase in manufacturing and operation can be suppressed by downsizing of manufacturing equipment and storage equipment and the like, and furthermore, transportation costs can also be suppressed.

[0164] In the present embodiment, the use amount of the surfactant (E) with respect to the total mass of the monomers used as a material of the water-based emulsion (α) is the same as the content of the surfactant (E) with respect to 100 parts by mass of the copolymer (A) in the water-based emulsion (α).

[0165] In the 1st polymerization step, the above-described polymerization initiator is preferably used. In order to set an appropriate polymerization rate, the amount of the polymerization initiator used is preferably 0.01 to 1.0 parts by mass, more preferably 0.05 to 0.80 parts by mass, and further preferably 0.1 to 0.5 parts by mass, with respect to 100 parts by mass of the total of the compound that is a source of the structural unit (al) and the compound that is a source of the structural unit (a2) (total of monomers).

[0166] In the 1st polymerization step, each component used as a material of the water-based emulsion (a) can be charged together and emulsion polymerization can be performed, or emulsion polymerization can be performed while each component is continuously supplied. In the case of performing emulsion polymerization while each component is continuously supplied, for example, the following method can be employed.

[0167] First, a part of the aqueous medium (D) and a part of the surfactant (E) are mixed to prepare a mixed solution. A part of the polymerization initiator is mixed to the obtained mixed solution to prepare a polymerization initiator solution.

[0168] On the other hand, the compound that is a source of the structural unit (al), the compound that is a source of the structural unit (a2), the remaining part of the aqueous medium (D), and the remaining part of the surfactant (E) are mixed and emulsified to prepare a mixed emulsion.

[0169] Then, a method of stirring while continuously supplying the mixed emulsion and the remaining part of the polymerization initiator to the polymerization initiator solution can be employed to perform emulsion polymerization.

[0170] 〔2-1-2. 2nd polymerization step〕

[0171] In the 2nd polymerization step, monomers including the compound that is a source of the structural unit (bl), the compound that is a source of the structural unit (b2), and the compound that is a source of the structural unit (b3), the surfactant (E), the aqueous medium (D), the polymerization initiator used as necessary, and the chain transfer agent are mixed and emulsion polymerization is performed. Thereby, the copolymer (B) copolymerized from the compound that is a source of the structural unit (bl), the compound that is a source of the structural unit (b2), and the compound that is a source of the structural unit (b3) is generated, and the water-based emulsion (β) including the surfactant (E) and in which the copolymer (B) is dispersed in the aqueous medium (D) can be obtained.

[0172] In the 2nd polymerization step, emulsion polymerization can be performed at a temperature of, for example, 30 to 85°C.

[0173] The 2nd polymerization step can be performed after the 1st polymerization step, can be performed before the 1st polymerization step, or can be performed simultaneously with the 1st polymerization step.

[0174] As in the example described herein, each monomer used as the material for the water-based emulsion (β) maintains the structure other than the olefinic unsaturated bond (except for ion exchange) after polymerization, without changing the chemical structure of the copolymer (B) obtained by polymerization (however, ion exchange can be performed).

[0175] The preferred use amount of the aqueous medium (D) used as the material for the water-based emulsion (β) (relative to the preferred use amount of the monomers) is the same as the preferred use amount of the aqueous medium (D) used as the material for the water-based emulsion (α).

[0176] In the present embodiment, the use amount of the surfactant (E) relative to the total mass of the monomers used as the material for the water-based emulsion (β) is the same as the content of the surfactant (E) relative to 100 parts by mass of the copolymer (B) in the water-based emulsion (β).

[0177] The preferred use amount of the surfactant (E) used as the material for the water-based emulsion (β) (relative to the preferred use amount of the monomers) is the same as the preferred use amount of the surfactant (E) used as the material for the water-based emulsion (α).

[0178] In the second polymerization step, as in the first polymerization step, the above-described polymerization initiator is preferably used. The use amount of the polymerization initiator (relative to the preferred use amount of the monomers) is the same as in the case where the polymerization initiator is used in the first polymerization step.

[0179] In the second polymerization step, each component used as the material for the water-based emulsion (β) can be charged together and emulsion polymerization can be performed, or emulsion polymerization can be performed while each component is continuously supplied. In the case where emulsion polymerization is performed while each component is continuously supplied, for example, the same method as the method that can be used in the first polymerization step can be employed.

[0180] 〔2-2. Mixing Step〕

[0181] In the mixing step, the water-based emulsion (α) obtained in the first polymerization step, the water-based emulsion (β) obtained in the second polymerization step, and the polyether-modified polydimethylsiloxane (C) are mixed.

[0182] As the mixing method, a known method can be employed. For example, as the mixing method, a method in which a homo-mixer Model 2.5 (manufactured by PRIMIX Co., Ltd.) is used, and stirring is performed at a temperature of 23°C and a rotation speed of 500 rpm for 5 minutes can be cited.

[0183] In the production method of the hydrophobic and oleophobic agent composition of the present embodiment, the case where the water-based emulsion (a) is produced using the surfactant (E) in the first polymerization step and the water-based emulsion (β) is produced using the surfactant (E) in the second polymerization step is exemplified, but the timing of adding the surfactant (E) can be appropriately adjusted according to the purpose of using the surfactant (E).

[0184] Specifically, the surfactant (E) can be added to the water-based emulsion (a) and / or the water-based emulsion (β) as needed 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. In this case, the copolymer (A) can be more stably dispersed in the water-based emulsion (a), and / or the copolymer (B) can be more stably dispersed in the water-based emulsion (β).

[0185] In addition, the surfactant (E) can be added together with the water-based emulsion (a) and the water-based emulsion (β) in the mixing step as needed, or can be further added to the hydrophobic and oleophobic agent composition obtained after the mixing step. In this case, the copolymer (A) and the copolymer (B) can be stably dispersed in the hydrophobic and oleophobic agent composition.

[0186] In the production method of the hydrophobic and oleophobic agent composition of the present embodiment, the case where the water-based emulsion (a) and the water-based emulsion (β) are produced using the water-based medium (D) is exemplified, but the water-based medium (D) can be added to the water-based emulsion (a) and / or the water-based emulsion (β) as needed after the first polymerization step and the second polymerization step and before the mixing step.

[0187] In addition, the water-based medium (D) can be added together with the water-based emulsion (a) and the water-based emulsion (β) in the mixing step as needed, or can be further added to the hydrophobic and oleophobic agent composition obtained after the mixing step. In addition, after the mixing step, the hydrophobic and oleophobic agent composition can be concentrated as needed by a known method, whereby a part of the water-based medium (D) is removed.

[0188] The hydrophobic and oleophobic agent composition of the present embodiment contains the copolymer (A) and the copolymer (B), and thus can impart high hydrophobicity and oleophobicity to a substrate.

[0189] On the other hand, for example, in a hydrophobic and oleophobic agent composition containing only the copolymer (B) without containing the copolymer (A), the oleophobicity imparted to a substrate is poor when the content ratio of the structural unit (b3) is the same as that of the hydrophobic and oleophobic agent composition of the present embodiment. It is inferred that the reason is that, in the hydrophobic and oleophobic agent composition containing only the copolymer (B), the structural unit (b3) in the copolymer (B) absorbs oil, and thus the oleophobicity imparted to a substrate decreases.

[0190] <3. Use of the hydrophobic and oleophobic agent composition>

[0191] The hydrophobic and oleophobic agent composition of the present embodiment can impart high oil repellency and water repellency to a substrate, and has good adsorptivity to the substrate. The hydrophobic and oleophobic agent composition of the present embodiment can impart high oil repellency and water repellency to a substrate such as a fiber, paper, or glass. Thus, as a suitable use of the hydrophobic and oleophobic agent composition of the present embodiment, a fiber treatment agent, a paper treatment agent, or a material for a coating agent can be given.

[0192] 〔3-1. Fiber treatment agent〕

[0193] The fiber treatment agent of the present embodiment is a fiber treatment agent containing the hydrophobic and oleophobic agent composition of the present embodiment, and can be made of only the hydrophobic and oleophobic agent composition of the present embodiment, or can contain, in addition to the hydrophobic and oleophobic agent composition, known and commonly used additives such as an antifoaming agent, a preservative, a pH adjustor, a surfactant, a crosslinking agent, an antistatic agent, a wetting agent, a thickening agent, a pigment, and the like, as needed, within a range that does not impair the object of the present invention.

[0194] The fiber treatment agent of the present embodiment can impart high oil repellency and water repellency to a fiber. In the present specification, the term "fiber" refers to a fiber and an article using a fiber as a raw material. The fiber treated with the fiber treatment agent can be in any form such as a short fiber (fiber), a linter, a roving, a sliver, a yarn, a woven fabric, a knitted fabric, a nonwoven fabric, paper, and the like. In the present specification, the fiber also includes paper. As a raw material of the fiber to be treated, cellulose fibers such as cotton, flax, jute, hemp, ramie, regenerated fiber cellulose, and rayon, polyvinyl alcohol-based synthetic fibers, and pulp can be given. The fiber treated with the fiber treatment agent preferably contains 30% by mass or more of the above-mentioned raw materials. The fiber treatment agent of the present embodiment can impart high oil repellency and water repellency to paper. As the paper to be treated with the paper treatment agent, there is no particular limitation, and a general paper using pulp cellulose can be given.

[0195] The hydrophobic and oleophobic fiber treated with the fiber treatment agent of the present embodiment has the fiber treatment agent containing the hydrophobic and oleophobic agent composition of the present embodiment attached to the fiber serving as a substrate. The total attached amount of the above-mentioned hydrophobic and oleophobic agent composition is preferably 1.0 parts by mass or more, and more preferably 2.0 parts by mass or more, relative to 100 parts by mass of the fiber serving as a substrate. The reason is that the water repellency and the oil repellency of the hydrophobic and oleophobic fiber are improved. The attached amount of the above-mentioned hydrophobic and oleophobic agent composition is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, relative to 100 parts by mass of the fiber serving as a substrate. The reason is that by having the fiber treatment agent attached to the fiber, the hand feeling can be inhibited from being deteriorated, and the mass increase can be inhibited.

[0196] As a method of treating a fiber as a substrate with the fiber treatment agent of the present embodiment, i.e., a method of producing a fiber product using the fiber treatment agent, for example, the following method can be mentioned.

[0197] First, the fiber treatment agent is impregnated or coated on a fiber as a substrate. As a method of impregnation or coating, for example, a method such as dipping, spraying, roll coating, etc. can be used. After the fiber treatment agent is impregnated or coated on the fiber, the amount of the fiber treatment agent adhered to the fiber is adjusted. As a method of adjusting the amount of adhesion, a method of passing through a nip roll, etc. can be mentioned, but is not limited thereto. It is preferable to dry the fiber after the fiber treatment agent is impregnated or coated on the fiber. The drying temperature of the fiber is preferably 80°C to 170°C, and more preferably 90°C to 150°C.

[0198] The fiber product is formed by impregnating or coating the fiber treatment agent of the present embodiment on a fiber and drying it. That is, the fiber product refers to an article in which the solid component (non-volatile component) contained in the fiber treatment agent is adhered to the fiber.

[0199] [3-3. Coating agent]

[0200] The coating agent of the present embodiment is a coating agent containing the hydrophobic and oleophobic agent composition of the present embodiment, and can be made of only the hydrophobic and oleophobic agent composition of the present embodiment, or can contain, in addition to the hydrophobic and oleophobic agent composition, known common additives such as an antifoaming agent, a preservative, a pH adjustor, a surfactant, a crosslinking agent, an antistatic agent, a wetting agent, a thickening agent, a pigment, etc. as necessary, without impairing the object of the present application.

[0201] As a substrate to be coated with the coating agent of the present embodiment, for example, glass, a polyolefin-based resin, a polyester-based resin, a polycarbonate-based resin, an acrylonitrile butadiene styrene copolymer (ABS resin), a polystyrene-based resin, etc. or a molded product (film, sheet, cup, etc.) thereof, a metal, etc. can be mentioned, but are not limited thereto.

[0202] As a method of treating the above-mentioned substrate with the coating agent of the present embodiment, for example, the following method can be mentioned.

[0203] First, the coating agent is coated on a substrate. As a method of coating the coating agent on the substrate, for example, a method such as spraying, brushing, roll coating, troweling, dipping, air-knife coating, flow coating, bar coating, roll coating, gravure coating, use of an applicator, etc. can be mentioned.

[0204] It is preferable to apply the coating agent to the substrate and then dry the substrate. 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 it shortens the drying time and achieves high productivity. The drying temperature for drying the substrate coated with the coating agent is preferably 170°C or lower, more preferably 150°C or higher. If the drying temperature is 170°C or lower, it is possible to suppress the deterioration of the hydrophobic and oleophobic agent composition contained in the coating agent. The drying time can be determined based on factors such as the amount of coating agent applied to the substrate, and is not particularly limited.

[0205] Example

[0206] The present invention will now be described in more detail using examples and comparative examples. It should be noted that the present invention is not limited to the following examples.

[0207] <1. Manufacturing of Aqueous Emulsion (α-1)>

[0208] In a five-necked separable flask equipped with a stirrer, thermometer, nitrogen inlet tube, reflux condenser, and dropping funnel, 120 g of ion-exchanged water as the aqueous medium (D) and 1 g of Newrex R-25L as the surfactant (E) were added. The mixture was heated to 80°C to prepare a solution. The resulting 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 prepare a polymerization initiator solution.

[0209] On the other hand, monomers (a1) and (a2) shown in Table 1 were placed into a 1-liter beaker in the proportions shown in Table 1, and 420g of ion-exchanged water as an aqueous medium (D) and 18.2g of Newrex R-25L as a surfactant (E) were added. The mixture was then emulsified using a homogenizer to produce a mixed emulsion.

[0210] Then, while maintaining the temperature of the five-necked flask containing the polymerization initiator solution at 80°C, the mixed emulsion and 44g of a 3% by mass aqueous solution of potassium persulfate as the polymerization initiator were continuously added dropwise from the funnel to the polymerization initiator solution over 3 hours, and the mixture was stirred to carry out emulsion polymerization.

[0211] One hour after the addition was completed, the temperature inside the five-necked flask was maintained at 80°C while stirring. Then, the flask was cooled to 30°C. Through the above process, an aqueous emulsion (α-1) containing copolymer (A) was obtained.

[0212] <2. Manufacturing of aqueous emulsions (α-2), (β-1) to (β-5)>

[0213] Using the monomers (al) and (a2) shown in Table 1 in the proportions shown in Table 1, and otherwise operating in the same manner as in the production of the water-based emulsion (α-1), a water-based emulsion (α-2) containing the copolymer (A) was obtained.

[0214] Instead of the monomers (al) and (a2) shown in Table 1, the monomers (bl), (b2), and (b3) shown in Table 1 were used in the proportions shown in Table 1, and otherwise operating in the same manner as in the production of the water-based emulsion (α-1), water-based emulsions (β-1) to (β-5) each containing the copolymer (B) were obtained.

[0215]

[0216] In Table 1, the monomer (al) or (bl) is a compound that is a source of the structural unit (al) or (bl). The monomer (a2) or (b2) is a compound that is a source of the structural unit (a2) or (b2). The monomer (b3) is a compound that is a source of the structural unit (b3).

[0217] The materials used in Table 1 are described below.

[0218] Monomer (b3); polydimethylsiloxane having an ethylenically unsaturated bond (manufactured by JNC Corporation, Silaplane (registered trademark) FM-0725 (is a compound represented by Formula (1). R 1 is a methyl group. R 2 is -CH2CH2CH2-. R 3 is a n-butyl group. h is 2. j is 125. The number average molecular weight (Mn) is 10,000.)

[0219] Surfactant (E); Neorexs R-25L (manufactured by NOF Corporation: sodium linear alkylbenzenesulfonate (the number of carbon atoms of the linear alkyl group is 10 to 16, an anionic surfactant), 25 mass% aqueous solution)

[0220] Polymerization initiator; 3 mass% aqueous solution of potassium persulfate (KPS)

[0221] The values shown in the columns of the aqueous medium (D), the surfactant (E), and the polymerization initiator in Table 1 are the total mass of the monomers (total of the monomers) used for the synthesis of the water-based emulsion (α-1), (α-2), and the water-based emulsions (β-1) to (β-5). Therefore, the values of the aqueous medium (D) shown in Table 1 do not include the water contained in the surfactant (E) and the polymerization initiator.

[0222] <3. Preparation of hydrophobic and oleophobic agent composition>

[0223] The water-based emulsion (α-1), (α-2) shown in Table 1, and the water-based emulsion (β-1) to (β-5) shown in Table 1, and the polyether-modified dimethylpolysiloxane (C) were mixed in the proportions shown in Table 2 or Table 3 to obtain the hydrophobic and oleophobic agent compositions of Examples 1 to 12, and Comparative Examples 1 to 8 containing the copolymer (A), the copolymer (B), and the polyether-modified dimethylpolysiloxane (C) in the proportions shown in Table 2 or Table 3.

[0224] The values shown in the column of copolymer (A) in Table 2 and Table 3 are the mass of the water-based emulsion (α-1) or (α-2) used in the hydrophobic and oleophobic agent compositions of Examples 1 to 12, and Comparative Examples 1 to 8, and the values in parentheses are the mass of the copolymer (A) contained in the water-based emulsion (α-1) or (α-2). The content of the copolymer (A) in the water-based emulsion (α-1) or (α-2) is the proportion of the monomer in the total amount of the monomer, the surfactant, the polymerization initiator, and the aqueous medium in Table 1.

[0225] The values shown in the column of copolymer (B) in Table 2 and Table 3 are the mass of the water-based emulsion (β-1) to (β-5) used in the hydrophobic and oleophobic agent compositions of Examples 1 to 12, and Comparative Examples 1 to 8, and the values in parentheses are the mass of the copolymer (B) contained in each of the water-based emulsion (β-1) to (β-5). The mass of the copolymer (B) in the water-based emulsion (β-1) to (β-5) is the proportion of the monomer in the total amount of the monomer, the surfactant, the polymerization initiator, and the aqueous medium in Table 1.

[0226]

[0227]

[0228] The polyether-modified dimethylpolysiloxane (C) used in Table 2 and Table 3 is described below.

[0229] BYK SILCLEAN 3720; polyether-modified dimethylpolysiloxane having a hydroxyl group at the end of a polyether chain, with a weight average molecular weight (Mw) of 10,000, and a solvent (methoxy propanol) other than the active ingredient.

[0230] (BYK Co., Ltd.)

[0231] TEGO (registered trademark) Protect 5100N; polyether-modified dimethylpolysiloxane having a hydroxyl group at the end of a polyether chain, with a weight average molecular weight (Mw) of 10,000, and a solvent (water) other than the active ingredient.

[0232] (Evonik Co., Ltd.)

[0233] KP-109; polyether-modified polydimethylsiloxane, weight average molecular weight (Mw) 10,000, solvent (propylene glycol monomethyl ether) except for the active ingredient. (Shin-Etsu Silicone Co., Ltd.)

[0234] <4. Evaluation of oil repellency>

[0235] Using the hydrophobic and oil-repellent agent compositions of Examples 1 to 12 and Comparative Examples 1 to 8 obtained as described above, the following indicated 1st Test and 2nd Test were performed, and the oil repellency was evaluated. The results thereof are shown in Tables 2 and 3.

[0236] 〔4-1. 1st Test〕

[0237] The hydrophobic and oil-repellent agent composition was diluted with ion exchange water to twice the mass basis. In the diluted hydrophobic and oil-repellent agent composition, a cotton cloth (Mingin 3) of a square shape of 200 mm in length and 200 mm in width was immersed. Then, using an oven, the cotton cloth was heated at 130°C for 5 minutes to dry, and a test cloth was prepared. The test cloth was prepared in such a manner that the attached amount of the hydrophobic and oil-repellent agent composition component after drying was 20 parts by mass with respect to 100 parts by mass of the cotton cloth.

[0238] To one side of the obtained test cloth, 0.03 ml of a test liquid was added dropwise, and left to stand, and the state of the test liquid after 1 minute was observed by visual observation, and evaluated according to the following criteria.

[0239] The 1st Test was performed for the case where the test liquid prescribed for oil repellency 1 in the oil repellency test using the AATCC 118 method (nujol) was used as the test liquid, and the case where the test liquid prescribed for oil repellency 2 (nujol / n-hexadecane = 65 / 35) was used as the test liquid. In addition, as the test cloth and the test liquid, a test cloth and a test liquid at 23°C were used. The standing of the test liquid on the test cloth and the visual observation were performed in a constant temperature room at 23°C.

[0240] “Evaluation Criteria”

[0241] Very good: the test liquid remained as a spherical drop.

[0242] Good: the spherical drop of the test liquid collapsed, and the test liquid spread on the test cloth, but did not penetrate into the test cloth.

[0243] Slightly good: the test liquid penetrated into the test cloth more than 30 seconds and within 1 minute after the standing of the test liquid.

[0244] Poor: the test liquid penetrated into the test cloth within 30 seconds after the standing of the test liquid.

[0245] 〔4-2. 2nd Test〕

[0246] The hydrophobic and oleophobic agent composition was applied to a glass plate as a substrate using an applicator so as to have a thickness of 150 μm (in a non-dried state), and dried using an oven at 130°C for 5 minutes to obtain a test body (coated material).

[0247] On the surface of the obtained test body on which the hydrophobic and oleophobic agent composition was applied, 2 μl of test liquid (white oil) of the oil-repellency 1st grade prescribed in the oil repellency test of AATCC 118 was gently placed, and the contact angle of the test liquid after 10 seconds was measured by the θ / 2 method using an automatic contact angle meter CA-VP type (Kosaka Laboratory Co., Ltd.). The greater the contact angle, the more excellent the oil repellency.

[0248] <5. Hydrophobicity Evaluation>

[0249] The hydrophobic and oleophobic agent compositions of Examples 1 to 12 and Comparative Examples 1 to 8 were subjected to the hydrophobicity test (spray test) described in JIS L 1092 (2009) 7.2. The evaluation criteria are described below. The greater the grade, the more excellent the hydrophobicity. The test results are shown in Tables 2 and 3.

[0250] "Evaluation Criteria"

[0251] 1st grade: The surface as a whole showed wetting.

[0252] 2nd grade: The surface showed wetting in more than half of the area, and showed a state in which a small amount of wetted permeated cloth was present.

[0253] 3rd grade: The wetted area was less than half of the surface, and the surface showed a state in which a small amount of water droplet-like wetting was present.

[0254] 4th grade: The surface did not show wetting, but showed the presence of small water droplets.

[0255] 5th grade: The surface did not show wetting and the presence of water droplets.

[0256] <6. Evaluation Results>

[0257] [6-1. Oil Repellency]

[0258] As shown in Table 2, the substrates treated with the hydrophobic and oleophobic agent compositions of Examples 1 to 12 were difficult to permeate with any of the test liquids (1st test), white oil, and white oil / n-hexadecane = 65 / 35, and the values of the contact angle of the droplets of the test liquid (white oil) were also large (2nd test). Thus, it was found that the hydrophobic and oleophobic agent compositions of Examples 1 to 12 were able to impart high oil repellency to the substrate.

[0259] On the other hand, as shown in Table 3, the substrates treated with the hydrophobic and oleophobic agent compositions of Comparative Examples 2 to 8 not containing the water-based emulsion (a-1) (copolymer (A)) were easily permeated with white oil / n-hexadecane = 65 / 35, and could not impart sufficient oleophobicity to the substrates.

[0260] 〔6-2. Hydrophobicity〕

[0261] As shown in Table 2, the results of the hydrophobicity test of the substrates treated with the hydrophobic and oleophobic agent compositions of Examples 1 to 12 were that wetting was not observed in a large area. It was thus known that the hydrophobic and oleophobic agent compositions of Examples 1 to 12 could impart high hydrophobicity to the substrates.

[0262] On the other hand, as shown in Table 3, the results of the hydrophobicity test of the substrates treated with the hydrophobic and oleophobic agent compositions of Comparative Example 1 not containing the water-based emulsion (β-1) to (β-5) (copolymer (B)), Comparative Examples 3, 4, 8 not containing the water-based emulsion (a-1) (copolymer (A)) were that wetting was shown in an area of more than half of the surface. Therefore, the hydrophobic and oleophobic agent compositions of Comparative Examples 1, 3, 4, 8 could not impart sufficient hydrophobicity to the substrates.

[0263] From the above, it was known that the hydrophobic and oleophobic agent composition according to the present application could impart high oleophobicity and hydrophobicity to the substrates.

[0264] Industrial applicability

[0265] The present application can provide a hydrophobic and oleophobic agent composition which can impart high oleophobicity and hydrophobicity to a substrate.

Claims

1. A hydrophobic and oleophobic agent composition, comprising: a copolymer (A) not containing 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) contains: a structural unit (al) derived from a compound having an ethylenic unsaturated bond and an ester bond and not having a carboxyl group, and a structural unit (a2) derived from a compound having an ethylenic unsaturated bond and a carboxyl group; the copolymer (B) contains: a structural unit (bl) derived from a compound having an ethylenic unsaturated bond and an ester bond and not having a carboxyl group, a structural unit (b2) derived from a compound having an ethylenic unsaturated bond and a carboxyl group, and a structural unit (b3) derived from a polydimethylsiloxane having an ethylenic unsaturated bond represented by the following formula (1); the mass ratio of the copolymer (A) to the copolymer (B) is 10 / 90 to 90 / 10, 0.10 parts by mass to 20 parts by mass of the polyether-modified polydimethylsiloxane (C) relative to 100 parts by mass of the total of the copolymer (A) and the copolymer (B).

2. The hydrophobic and oleophobic agent composition according to claim 1, the structural unit (al) and the structural unit (bl) being structural units derived from a compound having a (meth)acryl group.

3. The hydrophobic and oleophobic agent composition according to claim 1 or 2, the structural unit (a2) and the structural unit (b2) being structural units derived from a (meth)acrylic acid.

4. The hydrophobic and oleophobic agent composition according to claim 1 or 2, the copolymer (A) containing 0.10% by mass to 20% by mass of the structural unit (a2).

5. The hydrophobic and oleophobic agent composition according to claim 1 or 2, the copolymer (B) containing 0.10% by mass to 20% by mass of the structural unit (b2).

6. The hydrophobic and oleophobic agent composition according to claim 1 or 2, the copolymer (B) containing 3.0% by mass to 50% by mass of the structural unit (b3).

7. The hydrophobic and oleophobic agent composition according to claim 1 or 2, the polyether-modified polydimethylsiloxane (C) having a hydroxyl group at the terminal of a polyether chain.

8. The hydrophobic and oleophobic agent composition according to claim 1 or 2, further comprising a surfactant (E). 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 can include an ether linkage; R 3 represents an aliphatic group having 1 to 30 carbon atoms, an aromatic group, or a hydroxyl group; h is any one of 0, 1, and 2; j represents an integer of 0 to 500, 9. The hydrophobic and oleophobic agent composition according to claim 8, the surfactant (E) being an anionic surfactant.

10. The hydrophobic and oleophobic agent composition according to claim 1, the structural unit (al) and the structural unit (bl) being at least one selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, the structural unit (a2) and the structural unit (b2) being at least one selected from the group consisting of acrylic acid and methacrylic acid, the content of the structural unit (al) in the copolymer (A) being 85% by mass to 99% by mass, ​ ​ ​ ​ ​ ​ ​ ​ ​ the content of the structural unit (a2) in the copolymer (A) is 0.5 to 5.0 mass%, the content of the structural unit (b1) in the copolymer (B) is 50 to 93 mass%, the content of the structural unit (b2) in the copolymer (B) is 0.5 to 5.0 mass%, the content of the structural unit (b3) in the copolymer (B) is 7.0 to 50 mass%, the content of the structural unit (b3) in the total amount of the copolymer (A) and the copolymer (B) is 1.5 to 30 mass%, the weight average molecular weight of the polyether-modified polydimethylsiloxane (C) is 7,000 to 14,000.

11. A fiber treatment agent comprising the hydrophobic and oleophobic agent composition according to any one of claims 1 to 10.

12. A method for treating a fiber using the fiber treatment agent according to claim 11.

13. A coating agent comprising the hydrophobic and oleophobic agent composition according to any one of claims 1 to 10.

14. A fiber product in which a solid component contained in the fiber treatment agent according to claim 11 is attached to a fiber.

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