Water-repellent and oil-repellent compositions, fiber treatment agents, fiber treatment methods, fiber processed products, and coating agents

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 structural unit (a1) derived from a compound having an ethylenically unsaturated bond and an ester bond and having no amide bond and structural unit (a2) derived from a compound having an ethylenically unsaturated bond and an amide bond; and copolymer (B) contains structural unit (b1) derived from a compound having an ethylenically unsaturated bond and an ester bond and having no amide bond, structural unit (b2) derived from a compound having an ethylenically unsaturated bond and an amide bond, and structural unit (b3) derived from a polydimethylsiloxane having an ethylenically unsaturated bond.

Description

[Technical Field]

[0001] The present invention relates to a water-repellent and oil-repellent composition, a fiber treatment agent, a fiber treatment method, a fiber processed product, and a coating agent. This application claims priority based on Japanese Patent Application No. 2020-218523, filed in Japan on December 28, 2020, and the contents of that application are incorporated herein by reference. [Background technology]

[0002] Conventionally, a method for imparting water- and oil-repellent properties to substrates such as fibers and paper has been performed using water- and oil-repellent compositions. Some water- and oil-repellent compositions contain compounds having perfluoroalkyl groups with 8 or more carbon atoms.

[0003] However, compounds containing perfluoroalkyl groups with eight or more carbon atoms may produce perfluorooctanoic acid (hereinafter sometimes abbreviated as "PFOA") through decomposition or metabolism. The U.S. Environmental Protection Agency has requested that the amount of perfluorooctanoic acid produced be reduced. For this reason, water- and oil-repellent compositions containing compounds with short-chain perfluoroalkyl groups have been proposed.

[0004] For example, Patent Document 1 describes a water-repellent and oil-repellent composition comprising a pyrazole-block hydrophobic polyisocyanate aqueous dispersion containing a pyrazole-block hydrophobic polyisocyanate and a nonionic surfactant, and a water-repellent and oil-repellent component having a perfluoroalkyl group with 6 or fewer carbon atoms.

[0005] Patent Document 2 describes a water- and oil-repellent composition comprising a fluorine-containing polymer having a structural unit having a polyfluoroalkyl group with 1 to 6 carbon atoms, a fluorine-containing polymer having a structural unit based on a fluoroolefin, and an aqueous medium.

[0006] Furthermore, in recent years, there has been research into reducing the use of compounds containing short-chain perfluoroalkyl groups. For this reason, water- and oil-repellent compositions that do not contain fluorine compounds have been proposed.

[0007] For example, Patent Document 3 describes an oil-repellent composition comprising an aqueous emulsion in which a copolymer (A) containing constituent units based on ethylenically unsaturated carboxylic acid monomers is dispersed in an aqueous medium (B), and a polyether-modified polydimethylsiloxane (C).

[0008] Patent Document 4 describes a fiber treatment oil repellent containing a silicone-acrylic copolymer obtained by polymerizing a monomer having a quaternary ammonium group (meth)acrylate, a (meth)acrylic modified silicone oil at both ends, and a nonionic hydrophobic ethylenically unsaturated monomer. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] Japanese Patent Publication No. 2012-031285 [Patent Document 2] International Publication No. 2012 / 020806 [Patent Document 3] International Publication No. 2018 / 163911 [Patent Document 4] Japanese Patent Publication No. 2016-102272 [Overview of the Initiative] [Problems that the invention aims to solve]

[0010] However, conventional water- and oil-repellent compositions that do not contain fluorine compounds sometimes failed to impart sufficient oil and water repellency to the substrate. This invention has been made in view of the above circumstances, and aims to provide a water- and oil-repellent composition that can impart high oil-repellency and water-repellency to a substrate. Another object of the present invention is to provide a fiber treating agent, a paper treating agent, and a coating agent that can impart high oil repellency and water repellency to a substrate.

Means for Solving the Problems

[0011] The present inventors have intensively studied to solve the above problems. As a result, it has been found that a water and oil repellent composition containing a copolymer having a structural unit derived from a compound having an ethylenically unsaturated bond and an amide bond, and a copolymer having a structural unit derived from a compound having an ethylenically unsaturated bond and an amide bond and a structural unit derived from a polydimethylsiloxane having an ethylenically unsaturated bond can be used, and the present invention has been conceived. That is, the present invention relates to the following matters.

[0012] The first aspect of the present invention provides the following water and oil repellent composition. [1] 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) A structural unit (a1) derived from a compound having an ethylenically unsaturated bond and an ester bond and not having an amide bond, A structural unit (a2) derived from a compound having an ethylenically unsaturated bond and an amide bond Consisting of only , The copolymer (B) A structural unit (b1) derived from a compound having an ethylenically unsaturated bond and an ester bond and not having an amide bond, A structural unit (b2) derived from a compound having an ethylenically unsaturated bond and an amide bond, and a structural unit (b3) derived from a polydimethylsiloxane having an ethylenically unsaturated bond.

[0013] The water and oil repellent composition of the first aspect of the present invention preferably has the characteristics described in the following [2] to

[12] . It is also preferable to arbitrarily combine two or more of the characteristics described in the following [2] to

[12] . [2] The structural unit (a1) and the structural unit (b1) are structural units derived from either or both of a hydrocarbon having an ethylenic unsaturated bond or an alkyl (meth)acrylate, the water and oil repellent composition described in [1]. [3] The structural unit (a2) and the structural unit (b2) are structural units derived from (meth)acrylamide, the water and oil repellent composition described in [1] or [2].

[0014] [4] The structural unit (b3) is a structural unit derived from a compound represented by the following formula (1), the water and oil repellent composition described in any one of [1] to [3].

[0015] [Chemical formula] (In formula (1), R 1 represents a hydrogen atom or a methyl group; R [[ID=T19]] 2 represents a divalent aliphatic group having 1 to 6 carbon atoms which may 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, 2. j represents an integer of 0 to 500.)

[0016] [5] The mass ratio of the copolymer (A) to the copolymer (B) (A / B) is 10 / 90 or more and 90 / 10 or less, the water and oil repellent composition described in any one of [1] to [4]. [6] The water-repellent and oil-repellent composition according to [5], wherein the mass ratio (A / B) of copolymer (A) to copolymer (B) is 10 / 90 or more and 80 / 20 or less. 7 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 described in any one of [1] to 6 8 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 described in [1] to​​7 A water-repellent and oil-repellent composition as described in any of the following. [ 9 The copolymer (B) contains 3.0% by mass or more and 50% by mass or less of the structural unit (b3) [1]~[ 8 A water-repellent and oil-repellent composition as described in any of the following.

[0017] [ 10 The polyether-modified polydimethylsiloxane (C) has hydroxyl groups at the end of the polyether chain [1]~[ 9 A water-repellent and oil-repellent composition as described in any of the following. [ 11 ] 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 per 100 parts by mass of the copolymer (A) and the copolymer (B) in total [1]~[ 10 A water-repellent and oil-repellent composition as described in any of the following.

[0018] [ 12 Furthermore, it contains surfactants (E) [1]~[ 11 A water-repellent and oil-repellent composition as described in any of the following. [ 13 The surfactant (E) is a cationic surfactant. 12 A water-repellent and oil-repellent composition as described in [ ].

[0019] A second aspect of the present invention provides the following fiber treatment agent. [ 14 ] [1]~[ 13 A textile treatment agent comprising a water-repellent and oil-repellent composition as described in any of the following. A third aspect of the present invention provides a method for processing the following fibers. [ 15 ] [ 14 A method for treating fibers using the fiber treatment agent described in [ ]. A fourth aspect of the present invention provides the following coating agent. [ 16 ] [1]~[ 13 A coating agent comprising a water-repellent and oil-repellent composition as described in any of the following. A fifth aspect of the present invention provides the following textile processed product. [ 17 ] [ 14 A textile product in which solid components contained in the textile treatment agent have adhered to the fibers. [Effects of the Invention]

[0020] The water- and oil-repellent composition of the present invention can impart high oil-repellency and water-repellency to a substrate. Furthermore, since the fiber treatment agent, paper treatment agent, and coating agent of the present invention contain the water-repellent and oil-repellent composition of the present invention, they can impart high oil-repellency and water-repellency to the substrate. [Modes for carrying out the invention]

[0021] The water-repellent and oil-repellent compositions, fiber treatment agents, paper treatment agents, and coating agents of the present invention will be described in detail below. However, the present invention is not limited to the embodiments shown below. The configurations described below can be modified as appropriate without departing from the scope of the present invention. For example, the present invention is not limited to the following examples, and additions, omissions, substitutions, or changes can be made to the number, quantity, ratio, composition, type, position, material, configuration, etc., without departing from the spirit of the present invention.

[0022] In the following explanation, "monomer" refers to a compound having a radically polymerizable ethylene unsaturated bond. "Ethylene unsaturated bond" refers to a double bond between carbon atoms, excluding the carbon atoms that form the aromatic ring. "(Meth)acrylic" means "acrylic" or "methacrylic." "(Meth)acrylate" means "acrylate" or "methacrylate."

[0023] "Non-volatile content" refers to components in a composition, etc., whose boiling point at 1 atmosphere (1013 hPa) is 130°C or higher. The term "active ingredient" refers to the components within a mixture, such as a solution, that belong to a particular category of components. For example, in a propylene glycol 1-monomethyl ether solution of polyether-modified polydimethylsiloxane, the active ingredient refers to all compounds in that solution that are polyether-modified polydimethylsiloxane.

[0024] The number-average molecular weight and weight-average molecular weight are polystyrene-converted values ​​measured using gel permeation chromatography (GPC).

[0025] Unless otherwise specified, "ethylenically unsaturated bond" refers to an ethylenically unsaturated bond that exhibits radical polymerization properties. In polymers of compounds having ethylenically unsaturated bonds, a structural unit derived from a compound having an ethylenically unsaturated bond is defined as having the same chemical structure in the polymer as the chemical structure in the portion of that compound other than the ethylenically unsaturated bond. For example, a structural unit derived from acrylic acid has a structure represented as -CH2CH(COOH)- in the polymer.

[0026] In the following explanation, the compounds from which the structural units of a polymer originate refer to compounds that have a corresponding relationship with those structural units, and do not necessarily have to match the monomers used in the actual polymer manufacturing process. Unless otherwise specified, if a polymer has structural units derived from a compound that has an ionic functional group such as a carboxyl group and an ethylenically unsaturated bond, then even if some of those functional groups are ion-exchanged or not, they shall be considered structural units derived from the same compound. For example, in a polymer, not only the structure represented by -CH2-C(CH3)(COOH)- but also the structural unit represented by -CH2-C(CH3)(COONa)- shall be considered structural units derived from methacrylic acid.

[0027] If, after polymerization, the chemical structure of the monomer used does not match the chemical structure of the portion of the polymer other than the chain portion corresponding to the ethylenically unsaturated bond, due to chemical reactions of the portion other than the chain portion corresponding to the ethylenically unsaturated bond, the structural units of the polymer shall be based on the chemical structure after the aforementioned chemical reactions have been carried out. For example, if vinyl acetate is polymerized and then the resulting polymer is saponified, the chemical structure of the polymer obtained by saponification shall be used as the basis. Therefore, the saponified structural units shall be structural units derived from vinyl alcohol, not structural units derived from vinyl acetate.

[0028] <1. Water-repellent and oil-repellent composition> The water- and oil-repellent composition of this embodiment comprises a copolymer (A) that does not contain structural units having siloxane bonds (-Si-O-Si-), a copolymer (B) that contains structural units having siloxane bonds, a polyether-modified polydimethylsiloxane (C), and an aqueous medium (D). The water- and oil-repellent composition of this embodiment may optionally further contain other components such as a surfactant (E). The water- and oil-repellent composition of this embodiment does not have to contain compounds having perfluoroalkyl groups with 8 or more carbon atoms. The water- and oil-repellent composition of this embodiment does not have to contain fluorine-containing compounds.

[0029] In the water-repellent and oil-repellent composition of this embodiment, copolymer (A) and copolymer (B) preferably form an emulsion in the aqueous medium (D). Here, even if copolymer (A) and copolymer (B) are solids, they are considered to form an emulsion if dispersed in the aqueous medium (D). That is, copolymer (A) and copolymer (B) may form liquid particles or solid particles.

[0030] [1-1. Copolymer (A)] Copolymer (A) does not contain structural units having siloxane bonds. Copolymer (A) has structural units (a1) (hereinafter sometimes abbreviated as "structural unit (a1)") derived from a compound having ethylenically unsaturated bonds and ester bonds but no amide bonds, and structural units (a2) (hereinafter sometimes abbreviated as "structural unit (a2)") derived from a compound having ethylenically unsaturated bonds and amide bonds. Preferably, copolymer (A) consists only of structural units (a1) and structural units (a2) except for the terminal structures. Copolymer (A) imparts good oil repellency to a substrate to which the water-repellent and oil-repellent composition of this embodiment is attached.

[0031] [1-1-1. Structural Unit (a1)] The copolymer (A), having a structural unit (a1), can impart high oil repellency to the substrate and provide a highly stable water- and oil-repellent composition. The structural unit (a1) may consist of one type of structure or may contain two or more types of structures. The type and content of the compounds from which structural units (a1) originate may be determined as appropriate, for example, to adjust the glass transition temperature (Tg) of copolymer (A). Specifically, to lower the glass transition temperature of copolymer (A), a large amount of compounds whose homopolymer has a low glass transition temperature should be included as the compounds from which structural units (a1) originate. To raise the glass transition temperature of copolymer (A), a large amount of compounds whose homopolymer has a high glass transition temperature should be included as the compounds from which structural units (a1) originate.

[0032] The structural unit (a1) is preferably derived from either or both a hydrocarbon having an ethylenically unsaturated bond or an alkyl (meth)acrylate, and more preferably from an alkyl (meth)acrylate. When the compound from which structural unit (a1) is derived is an alkyl (meth)acrylate, it is even more preferable that the alkyl (meth)acrylate has 1 to 8 carbon atoms in the hydrocarbon structure of the part other than the (meth)acryloyloxy group. The number of carbon atoms is preferably 2 to 7, more preferably 3 to 6, and even more preferably 4 to 5. This is because it facilitates the adjustment of the texture of the substrate treated with the water-repellent and oil-repellent composition according to this embodiment.

[0033] Examples of alkyl (meth)acrylates in which the hydrocarbon structure of the part other than the (meth)acryloyloxy group has 1 to 8 carbon atoms 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.

[0034] When the water- and oil-repellent composition of this embodiment is included in a paper treatment agent used for processing paper or a fiber treatment agent used for processing fibers, it is particularly preferable that the compound from which the structural unit (a1) originates is one or more types selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0035] The compound from which structural unit (a1) is derived may include an alkyl (meth)acrylate having a chain-like hydrocarbon structure with 9 or more carbon atoms as the hydrocarbon structure of the part other than the (meth)acryloyloxy group. In this case, a water- and oil-repellent composition is obtained that provides better water repellency to the substrate while maintaining oil repellency.

[0036] When the structural unit (a1) is 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, and p-methylstyrene.

[0037] [1-1-2. Structural Units (a2)] The copolymer (A) having structural units (a2) results in a water- and oil-repellent composition that can impart high oil repellency to a substrate. The structural units (a2) may consist of one type of structure or may contain two or more types of structures. The compound from which structural unit (a2) is derived is a compound having an ethylenically unsaturated bond and an amide bond. Examples of compounds from which structural unit (a2) is derived include acrylamide, methacrylamide, N-vinylacetamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-methyl-N-ethyl(meth)acrylamide, and N,N-diethyl(meth)acrylamide. The compound from which structural unit (a2) is derived preferably contains either acrylamide or methacrylamide, or both, and more preferably either acrylamide or methacrylamide, or both. Structural unit (a2) may or may not contain an ester bond.

[0038] [1-1-3. Content of each structural unit in copolymer (A)] The content of structural unit (a1) in copolymer (A) is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, and particularly preferably 85% by mass or more. This is because it results in a water-repellent and oil-repellent composition with good stability. The content of structural unit (a1) in copolymer (A) is preferably 99% by mass or less, more preferably 98% by mass or less, even more preferably 97% by mass or less, and particularly preferably 96% by mass or less, as this makes it easier to ensure the content of structural unit (a2). The content of structural unit (a1) in copolymer (A) may be, as needed, for example, 30% to 99% by mass, 40% to 60% by mass, 60% to 70% by mass, 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.

[0039] When the compound from which structural unit (a1) is derived is an alkyl (meth)acrylate having 1 to 8 carbon atoms in the hydrocarbon structure of the part other than the (meth)acryloyloxy group, the content of structural unit (a1) in copolymer (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 it makes it easier to adjust the texture of the substrate treated with the water-repellent and oil-repellent composition according to this embodiment. When the compound from which structural unit (a1) is derived is an alkyl (meth)acrylate having 1 to 8 carbon atoms in the hydrocarbon structure of the part other than the (meth)acryloyloxy group, the content of structural unit (a1) in copolymer (A) is preferably 99% by mass or less, and more preferably 98% by mass or less, in order to ensure the content of structural unit (a2).

[0040] The content of structural unit (a2) in copolymer (A) is preferably 0.10% by mass or more, more preferably 0.50% by mass or more, even more preferably 1.0% by mass or more, and particularly preferably 1.8% by mass or more. This is because it results in a water- and oil-repellent composition that can impart better oil repellency to the substrate. The content of structural unit (a2) in copolymer (A) is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5.0% by mass or less, and particularly preferably 3.0% by mass or less. This is because it results in a low-cost water-repellent and oil-repellent composition. Furthermore, it becomes easier to ensure the content of structural unit (a1), which makes it easier to ensure good water repellency in the substrate treated with the water-repellent and oil-repellent composition. The content of structural unit (a2) in copolymer (A) may be, as needed, for example, 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.

[0041] Copolymer (A) may contain polymerization initiators used during polymerization to produce copolymer (A). Polymerization initiators can be arbitrarily selected and include, for example, hydrogen peroxide, azo compounds, organic peroxides, etc. The polymerization initiator may also be included as a redox initiator in combination with a reducing agent. Only one type of polymerization initiator may be included, or two or more types may be included. Copolymer (A) may contain a chain transfer agent used during polymerization to produce copolymer (A). The chain transfer agent adjusts the molecular weight of copolymer (A) produced by polymerization. Examples of chain transfer agents include mercaptans, thioglycolic acid and its esters, β-mercaptopropionic acid and its esters, etc. Only one type of chain transfer agent may be included, or two or more types may be included. The amounts of polymerization initiators and chain transfer agents can be arbitrarily selected. For example, the content of these compounds per 100 parts by mass of the total monomers may be 0.1 to 10.0% by mass, 0.5 to 5.0% by mass, or 1.0 to 3.0% by mass, but is not limited to these examples.

[0042] [1-2. Copolymer (B)] Copolymer (B) has structural units (b1) derived from a compound having ethylenically unsaturated bonds and ester bonds but no amide bonds (hereinafter sometimes abbreviated as "structural unit (b1)"), structural units (b2) derived from a compound having ethylenically unsaturated bonds and amide bonds (hereinafter sometimes abbreviated as "structural unit (b2)"), and structural units (b3) derived from polydimethylsiloxane having ethylenically unsaturated bonds (hereinafter sometimes abbreviated as "structural unit (b3)"). In this embodiment, structural units (b1) and (b2) do not include structural units having siloxane bonds. The copolymer (B) preferably consists of structural units (b1), (b2), and (b3) other than the terminal structures. Copolymer (B) imparts oil repellency and good water repellency to a substrate to which the water-repellent and oil-repellent composition of this embodiment is attached.

[0043] [1-2-1. Structural Unit (b1) and Structural Unit (b2)] The required structure, preferred structure, and specific examples of structural unit (b1) are the same as those for structural unit (a1). In the water-repellent and oil-repellent composition of this embodiment, the structural unit (a1) of copolymer (A) and the structural unit (b1) of copolymer (B) may be the same or different. The required structure, preferred structure, and specific examples of structural unit (b2) are the same as those for structural unit (a2). In the water-repellent and oil-repellent composition of this embodiment, the structural unit (a2) of copolymer (A) and the structural unit (b2) of copolymer (B) may be the same or different.

[0044] [1-2-2. Structural Units (b3)] The structural unit (b3) is a structural unit derived from a polydimethylsiloxane having an ethylenically unsaturated bond, and is a part that forms a polysiloxane side chain in the copolymer (B). By the copolymer (B) having the structural unit (b3), it becomes a water- and oil-repellent agent composition that can impart high water repellency to the substrate. The structural unit (b3) may consist of one type of structure, or may contain two or more types of structures. The structural unit (b3) is preferably a structural unit derived from the compound represented by the following formula (1).

[0045]

Chemical formula

[0046] R in formula (1) 1 represents a hydrogen atom or a methyl group. R in formula (1) 2 is a divalent aliphatic group having 1 to 6 carbon atoms which may contain an ether bond. The number of carbon atoms of R 2 is preferably 1 to 4, and may be 1 to 4 or 2 to 3 if necessary. This is because it becomes a water- and oil-repellent agent composition that can impart high oil repellency to the substrate. R 2 is more preferably a hydrocarbon chain, and more preferably a linear hydrocarbon chain. This is because it becomes a water- and oil-repellent agent composition that can impart high water repellency to the substrate.

[0047] R in formula (1) 3 is an aliphatic group, an aromatic group, or a hydroxyl group having 1 to 30 carbon atoms. R 3It is preferably an aliphatic group having 1 to 30 carbon atoms, more preferably an aliphatic group having 2 to 18 carbon atoms, even more 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 number of carbon atoms may be 3 to 5 or 2 to 4. 3 It is more preferable that the hydrocarbon chain is a hydrocarbon chain, and even more preferable that it is a linear hydrocarbon chain. This is because it results in a water- and oil-repellent composition that can impart high water repellency to the substrate.

[0048] In formula (1), j is an integer between 0 and 500, and is preferably an integer between 1 and 400, and more preferably an integer between 10 and 300, as it represents the number-average molecular weight of the compound represented by formula (1). For example, j may 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 from which structural unit (b3) originates may be one of the compounds represented by formula (1), or it may contain two or more.

[0049] The number-average molecular weight of the compound represented by formula (1) is preferably 300 or more, more preferably 1,000 or more, even more preferably 3,000 or more, and particularly preferably 7,000 or more. This is because better water repellency can be obtained in a substrate treated with the water-repellent 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 formula (1) during polymerization to produce copolymer (B) is improved.

[0050] [1-2-3. Content of each structural unit in copolymer (B)] The content of structural unit (b1) in copolymer (B) is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 70% by mass or more. This is because it results in a water-repellent and oil-repellent composition with good stability. The content of structural unit (b1) in copolymer (B) is preferably 96% by mass or less, more preferably 93% by mass or less, and even more preferably 90% by mass or less, in order to facilitate the content of structural unit (b2) and structural unit (b3). The content of structural unit (b1) in copolymer (B) may 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.

[0051] When the compound from which structural unit (b1) is derived is an alkyl (meth)acrylate having 1 to 8 carbon atoms in the hydrocarbon structure of the part other than the (meth)acryloyloxy group, the content of structural unit (b1) in copolymer (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 it makes it easier to adjust the texture of the substrate treated with the water-repellent and oil-repellent composition according to this embodiment. When the compound from which structural unit (b1) is derived is an alkyl (meth)acrylate having 1 to 8 carbon atoms in the hydrocarbon structure of the part other than the (meth)acryloyloxy group, the content of structural unit (b1) in copolymer (B) is preferably 96% by mass or less, and more preferably 93% by mass or less, in order to ensure the content of structural units (b2) and (b3).

[0052] The content of structural unit (b2) in copolymer (B) is preferably 0.10% by mass or more, more preferably 0.50% by mass or more, even more preferably 0.85% by mass or more, and particularly preferably 1.8% by mass or more. This is because it results in a water- and oil-repellent composition that can impart better oil repellency to the substrate. The content of structural unit (b2) in copolymer (B) is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5.0% by mass or less, and particularly preferably 3.0% by mass or less. This is because it results in a low-cost water-repellent and oil-repellent composition. Furthermore, it becomes easier to ensure the content of structural unit (b1) and structural unit (b3), making it easier to ensure good water repellency in the substrate treated with the water-repellent and oil-repellent composition. The content of structural unit (b2) in 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, or 1.5% by mass to 3.0% by mass.

[0053] The content of structural unit (b3) in copolymer (B) is preferably 3.0% by mass or more, more preferably 5.0% by mass or more, and even more preferably 7.0% by mass or more. This is because it results in a water-repellent and oil-repellent composition that can impart better water repellency to the substrate. The content of structural unit (b3) in 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 it is easier to ensure the content of structural unit (b1) and structural unit (b2), and the texture of the substrate treated with the water-repellent and oil-repellent composition can be well maintained. The content of structural unit (b3) in 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, or 15.0% by mass to 20.0% by mass.

[0054] In this embodiment, the content of structural unit (b3) in the total amount of copolymer (A) and copolymer (B) is preferably 1.5% by mass or more, more preferably 2.5% by mass or more, and even more preferably 3.5% by mass or more. This is because it results in a water-repellent and oil-repellent composition that can impart better water repellency to the substrate. The content of structural unit (b3) in the total amount of copolymer (A) and copolymer (B) is preferably 30% by mass or less, more preferably 15% by mass or less, and even more preferably 7.5% by mass or less. This is because it is easier to ensure the content of structural units (a1), (a2), (b1), and (b2), resulting in a water-repellent and oil-repellent composition that can impart better water-repellency and oil-repellency to the substrate. For example, the content of structural unit (b3) in the total amount may be 1.5% by mass or more and 30% by mass or less, 2.0% by mass or more and 25% by mass or less, 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.

[0055] Copolymer (B) may contain a polymerization initiator used during polymerization to produce copolymer (B). Examples of polymerization initiators include the same ones that may be contained in copolymer (A). In the water-repellent and oil-repellent composition of this embodiment, if copolymer (A) and copolymer (B) contain polymerization initiators, the polymerization initiator contained in copolymer (A) and the polymerization initiator contained in copolymer (B) may be the same or different. Copolymer (B) may contain a chain transfer agent used during polymerization to produce copolymer (B). Examples of chain transfer agents include those that may be contained in copolymer (A). In the water-repellent and oil-repellent composition of this embodiment, if copolymer (A) and copolymer (B) contain a chain transfer agent, the chain transfer agent contained in copolymer (A) and the chain transfer agent contained in copolymer (B) may be the same or different.

[0056] [1-3. Mixing ratio of copolymer (A) and copolymer (B)] In the water-repellent and oil-repellent composition according to this embodiment, the blending ratio value based on the 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. This is because it results in a water-repellent and oil-repellent composition that can impart better oil repellency to the substrate. In the water-repellent and oil-repellent composition according to this embodiment, the blending ratio value based on the mass of copolymer (A) and copolymer (B) may be 30 / 70 or more, or 40 / 60 or more. In the water-repellent and oil-repellent composition according to this embodiment, the mass-based blending ratio of copolymer (A) to copolymer (B) is preferably 90 / 10 or less, more preferably 80 / 20 or less, even more preferably 70 / 30 or less, and particularly preferably 60 / 40 or less. This is because it results in a water-repellent and oil-repellent composition that can impart better water repellency to the substrate.

[0057] [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. In other words, polyether-modified polydimethylsiloxane is a graft copolymer in which the main chain is polysiloxane and the side chains are polyether. Polyether-modified polydimethylsiloxane (C) imparts good water and oil repellency to a substrate to which the water and oil repellent composition of this embodiment is attached.

[0058] 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. When the polyether-modified polydimethylsiloxane (C) has a hydroxyl group at the end of the polyether chain, it results in a water- and oil-repellent composition that can impart better oil repellency to the substrate. For example, the type and number of polyether chains can be arbitrarily selected. For example, the position and number of polyether chains bonded to the Si of the polydimethylsiloxane can be arbitrarily selected. An example of a polyether chain is -(CH2O) x (C2H4O) y (C3H6O) z Examples include R, but the system is not limited to these examples. x, y, and z are each 0 or an integer of 1 or more, and they cannot all be 0 at the same time. R is preferably either an alkyl group having 1 to 10 carbon atoms or hydrogen. x, y, and z may each 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 consecutive, alternating, or randomly arranged. Examples of commercially available compositions containing polyether-modified polydimethylsiloxane (C) having hydroxyl groups at the ends of the polyether chains include BYK SILCLEAN 3720 from BYK, TEGO® Protect 5100N from Evonik, and KP-109 from Shin-Etsu Silicone Co., Ltd.

[0059] The weight-average molecular weight of the polyether-modified polydimethylsiloxane (C) is preferably 1,000 or more, more preferably 5,000 or more, and even more preferably 7,000 or more. This is because it results in a water- and oil-repellent composition that 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, and even more preferably 14,000 or less. This is because it results in a water-repellent and oil-repellent composition that can impart better water repellency to the substrate.

[0060] The content of polyether-modified polydimethylsiloxane (C) is preferably 0.10 parts by mass or more, more preferably 0.20 parts by mass or more, even more preferably 0.50 parts by mass or more, and particularly preferably 0.90 parts by mass or more, based on 100 parts by mass of the total of copolymer (A) and copolymer (B). This is because it results in a water- and oil-repellent composition that can impart better oil repellency to the substrate. The content of polyether-modified polydimethylsiloxane (C) is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, even 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, based on 100 parts by mass of the total of copolymer (A) and copolymer (B). This is to improve the texture of the fibers or paper treated with the water-repellent and oil-repellent composition. The content of polyether-modified polydimethylsiloxane (C) may be, for example, 0.10 parts by mass or more and 5.0 parts by mass or less, 0.20 parts by mass or more and 3.0 parts by mass or less, 0.30 parts by mass or more and 2.0 parts by mass or less, or 0.40 parts by mass or more and 1.0 part by mass or less.

[0061] [1-5. Aqueous medium (D)] The aqueous medium (D) has water as an essential component. The aqueous medium (D) may also contain a hydrophilic solvent in addition to water. The water content in the aqueous medium (D) can be arbitrarily selected, but is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 98% by mass or more, and 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. The aqueous medium (D) may contain only one type of hydrophilic solvent, or two or more types. The hydrophilic solvent content in the aqueous medium (D) is preferably 10% by mass or less, and more preferably 5.0% by mass or less. A hydrophilic solvent content of 10% by mass or less helps to suppress the cost increase associated with using a hydrophilic solvent.

[0062] The content of the aqueous medium (D) contained in the water-repellent and oil-repellent composition is preferably determined so that the non-volatile content of the water-repellent and oil-repellent composition reaches a desired value. The non-volatile content concentration 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 it results in a water- and oil-repellent composition that can efficiently impart a water- and oil-repellent effect to the substrate with a small amount of use. The non-volatile content concentration 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 it results in a water- and oil-repellent composition that has good storage stability and can be easily applied uniformly to the substrate. The content of the aqueous medium (D) contained in the water-repellent and oil-repellent composition can be arbitrarily selected, for example, 2% to 95% by mass, 5% to 90% by mass, 10% to 80% by mass, 30% to 70% by mass, 40% to 60% by mass, etc., but is not limited to these examples.

[0063] [1-6. Other ingredients] The water-repellent and oil-repellent composition of this embodiment may contain, as necessary, other components in addition to copolymer (A), copolymer (B), polyether-modified polydimethylsiloxane (C), and aqueous medium (D). Other components that may be included in the water-repellent and oil-repellent composition of this embodiment include resins, crosslinking agents, thickeners, pH adjusters, film-forming aids, plasticizers, preservatives, defoaming agents, and surfactants (E). Depending on the specifications of the water-repellent and oil-repellent composition, one or more of these other components may be included, to the extent that the objectives of the present invention can be achieved.

[0064] [1-6-1. Surfactants (E)] As surfactant (E), anionic surfactants, nonionic surfactants, and cationic surfactants can be used, and commercially available products may also be used. Surfactant (E) does not have an ethylenically unsaturated bond. In this embodiment, surfactants having copolymerizability such as an ethylenically unsaturated bond are included in the compound from which structural unit (a1) is derived.

[0065] Examples of anionic surfactants include alkylbenzene sulfonates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, and fatty acid salts. Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polycyclic phenyl ethers, polyoxyalkylene alkyl ethers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters.

[0066] Examples of cationic surfactants include alkyltrimethylammonium chloride, ceciltrimethylammonium bromide, and laurylpyridinium chloride. It is preferable that the surfactant (E) includes a cationic surfactant. This is because it results in a water- and oil-repellent composition with high adhesion to the substrate, and also increases the variety of additives that can be selected, such as antibacterial agents. As the cationic surfactant, it is preferable to use the hydrochloride salt of a compound having an ammonium group, and more preferably to use a quaternary ammonium chloride.

[0067] When the water-repellent and oil-repellent composition of this embodiment contains a surfactant (E), the amount of surfactant (E) per 100 parts by mass of copolymer (A) and copolymer (B) 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 copolymer (A) and copolymer (B) can be stably dispersed in the water-repellent and oil-repellent composition. In the water-repellent and oil-repellent composition of this embodiment, the amount of surfactant (E) per 100 parts by mass of copolymer (A) and copolymer (B) is preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, and even more preferably 1.5 parts by mass or less. This is because the adhesion of the coating layer obtained by the water-repellent and oil-repellent composition to the substrate can be maintained without impairing water resistance.

[0068] The surfactant (E) contained in the water-repellent and oil-repellent composition of this embodiment may be part or all of the surfactant used during polymerization to produce copolymer (A) and / or the surfactant used during polymerization to produce copolymer (B). The surfactant used during polymerization to produce copolymer (A) and the surfactant used during polymerization to produce copolymer (B) may be different or the same. Furthermore, the surfactant (E) contained in the water-repellent and oil-repellent composition of this embodiment may be partially or entirely added after the copolymer (A) and copolymer (B) have been manufactured.

[0069] <2. Method for producing a water-repellent and oil-repellent composition> The water- and oil-repellent composition of this embodiment can be manufactured, for example, by the method shown below. The method for manufacturing the water- and oil-repellent composition of 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 copolymer (A) is dispersed in an aqueous medium (D). Then, a second polymerization step is performed to produce an aqueous emulsion (β) in which copolymer (B) is dispersed in an aqueous medium (D). Subsequently, a mixing step is performed in which aqueous emulsion (α), aqueous emulsion (β), and polyether-modified polydimethylsiloxane (C) are mixed. Through these steps, the water-repellent and oil-repellent composition of this embodiment is obtained.

[0070] [2-1-1. First polymerization step] In the first polymerization step, it is preferable to perform emulsion polymerization by mixing monomers containing the compound from which structural unit (a1) and the compound from which structural unit (a2) is derived, a surfactant (E), an aqueous medium (D), a polymerization initiator used as needed, and a chain transfer agent. This generates a copolymer (A) formed by copolymerization of monomers containing the compound from which structural unit (a1) and the compound from which structural unit (a2) is derived, and an aqueous emulsion (α) containing the surfactant (E) and in which copolymer (A) is dispersed in the aqueous medium (D). In the first polymerization step, emulsion polymerization can be carried out at a temperature of, for example, 30 to 85°C.

[0071] As illustrated in the example described here, if the chemical structure of the copolymer (A) obtained by polymerization is not altered (however, ion exchange may be performed), each monomer used as a material for the aqueous emulsion (α) maintains its structure other than the ethylenically unsaturated bond even after polymerization (excluding ion exchange).

[0072] The amount of aqueous medium (D) used as a material for the aqueous emulsion (α) 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, per 100 parts by mass of the total of the compounds from which structural units (a1) and structural units (a2) are derived (total monomers). This is because the compounds from which structural units (a1) and structural units (a2) are derived can be emulsified in the aqueous medium (D) for efficient emulsion polymerization, and the copolymer (A) produced by emulsion polymerization can be stably dispersed in the aqueous medium (D).

[0073] The amount of aqueous medium (D) used as a material for the aqueous emulsion (α) is 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, based on 100 parts by mass of the total of the compound from which structural unit (a1) and the compound from which structural unit (a2) originates. This is because reducing the amount of excess aqueous medium (D) makes it possible to improve productivity, suppress increases in manufacturing and handling costs by miniaturizing manufacturing and storage equipment, and further reduce transportation costs.

[0074] In this embodiment, the amount of surfactant (E) used relative to the total mass of monomers used as materials for the aqueous emulsion (α) is the same as the amount of surfactant (E) per 100 parts by mass of copolymer (A) in the aqueous emulsion (α).

[0075] In the first polymerization step, it is preferable to use the polymerization initiator described above. The amount of polymerization initiator used is preferably 0.01 to 1.0 parts by mass, more preferably 0.05 to 0.80 parts by mass, and even more preferably 0.1 to 0.5 parts by mass, per 100 parts by mass of the total of the compounds from which structural unit (a1) and structural unit (a2) originates (total monomers), in order to achieve an appropriate polymerization rate.

[0076] In the first polymerization step, each component to be used as material for the aqueous emulsion (α) may be charged together and emulsion polymerization may be carried out, or each component may be supplied continuously while emulsion polymerization is carried out. When emulsion polymerization is carried out while supplying each component continuously, for example, the method shown below can be used. First, a portion of the aqueous medium (D) and a portion of the surfactant (E) are mixed to form a mixture. A portion of the polymerization initiator is then added to the resulting mixture to form a polymerization initiator solution. On the other hand, a mixed emulsion is obtained by mixing and emulsifying the compound from which structural unit (a1) is derived, the compound from which structural unit (a2) is derived, the remainder of the aqueous medium (D), and the remainder of the surfactant (E). Alternatively, a method of emulsion polymerization can be used in which the mixed emulsion and the remainder of the polymerization initiator are simultaneously and continuously supplied to the polymerization initiator solution while stirring.

[0077] [2-1-2. Second polymerization step] In the second polymerization step, it is preferable to perform emulsion polymerization by mixing a monomer containing the compound from which structural unit (b1), the compound from which structural unit (b2), and the compound from which structural unit (b3) originates with a surfactant (E), an aqueous medium (D), a polymerization initiator used as needed, and a chain transfer agent. This generates a copolymer (B) formed by copolymerization of the compound from which structural unit (b1), the compound from which structural unit (b2), and the compound from which structural unit (b3) originates, and obtains an aqueous emulsion (β) containing the surfactant (E) and in which copolymer (B) is dispersed in the aqueous medium (D).

[0078] In the second polymerization step, emulsion polymerization can be carried out at a temperature of, for example, 30 to 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.

[0079] As illustrated in the example described here, if the chemical structure of the copolymer (B) obtained by polymerization is not altered (however, ion exchange may be performed), each monomer used as a material for the aqueous emulsion (β) maintains its structure other than the ethylenically unsaturated bond even after polymerization (excluding ion exchange).

[0080] The preferred amount of aqueous medium (D) used as a material for aqueous emulsion (β) (preferred amount relative to the total amount of monomers) is the same as the preferred amount of aqueous medium (D) used as a material for aqueous emulsion (α).

[0081] In this embodiment, the amount of surfactant (E) used relative to the total mass of monomers used as materials for the aqueous emulsion (β) is the same as the amount of surfactant (E) per 100 parts by mass of copolymer (B) in the aqueous emulsion (β). The preferred amount of surfactant (E) used as a material for aqueous emulsion (β) (preferred amount relative to the total amount of monomers) is the same as the preferred amount of surfactant (E) used as a material for aqueous emulsion (α).

[0082] In the second polymerization step, it is preferable to use the polymerization initiator described above, similar to the first polymerization step. The amount of polymerization initiator used (preferred amount relative to the total amount of monomers) is the same as when the polymerization initiator is used in the first polymerization step.

[0083] In the second polymerization step, each component used as material for the aqueous emulsion (β) may be charged together and emulsion polymerization may be carried out, or each component may be supplied continuously while emulsion polymerization is carried out. When emulsion polymerization is carried out while supplying each component continuously, for example, a method similar to the one used in the first polymerization step can be used.

[0084] [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. A known mixing method can be used. For example, one mixing method involves using a Homodisper 2.5 type (manufactured by PRIMIX) and stirring for 5 minutes at a temperature of 23°C and a rotation speed of 500 rpm.

[0085] In the method for producing the water-repellent and oil-repellent composition of this embodiment, the example described was one in which a water-based emulsion (α) is produced using a surfactant (E) in the first polymerization step and a water-based emulsion (β) is produced using a surfactant (E) in the second polymerization step. However, the timing of adding the surfactant (E) can be appropriately adjusted depending on the purpose for which the surfactant (E) is used.

[0086] Specifically, surfactant (E) may be used not only in the first and second polymerization steps, but may also be added to aqueous emulsion (α) and / or aqueous emulsion (β) as needed after the first and second polymerization steps and before the mixing step. In this case, copolymer (A) can be dispersed more stably in aqueous emulsion (α), and / or copolymer (B) can be dispersed more stably in aqueous emulsion (β). Furthermore, the surfactant (E) may be added together with the aqueous emulsion (α) and aqueous emulsion (β) during the mixing process as needed, or it may be added to the water-repellent and oil-repellent composition obtained after the mixing process. In this case, copolymers (A) and (B) can be stably dispersed in the water-repellent and oil-repellent composition.

[0087] In the method for producing the water-repellent and oil-repellent composition of this embodiment, the case in which an aqueous medium (D) is used as the material for the aqueous emulsion (α) and aqueous emulsion (β) has been described as an example. However, the aqueous medium (D) may be added to the aqueous emulsion (α) and / or aqueous emulsion (β) after the first polymerization step and the second polymerization step, and before the mixing step, as needed. Furthermore, the aqueous medium (D) may be added together with the aqueous emulsion (α) and aqueous emulsion (β) in the mixing step as needed, or it may be further added to the water-repellent and oil-repellent composition obtained after the mixing step. Also, after the mixing step, a portion of the aqueous medium (D) may be removed by concentrating the water-repellent and oil-repellent composition using a known method as needed.

[0088] The water-repellent and oil-repellent composition of this embodiment contains copolymer (A) and copolymer (B), and can therefore impart high water-repellency and oil-repellency to the substrate. In contrast, for example, in a water- and oil-repellent composition containing only copolymer (B) and not copolymer (A), if the content of structural unit (b3) is the same as in the water- and oil-repellent composition of this embodiment, the oil repellency that can be imparted to the substrate will be inferior. This is presumed to be because, in a water- and oil-repellent composition containing only copolymer (B), the structural unit (b3) in copolymer (B) attracts oil, thereby reducing the oil repellency that can be imparted to the substrate.

[0089] <3. Applications of water-repellent and oil-repellent compositions> The water- and oil-repellent composition of this embodiment can impart high oil- and water-repellent properties to a substrate, and also exhibits good adsorption to the substrate. The water- and oil-repellent composition of this embodiment can impart high oil- and water-repellent properties to substrates such as fibers, paper, and glass. Therefore, suitable applications of the water- and oil-repellent composition of this embodiment include materials for fiber treatment agents, paper treatment agents, and coating agents.

[0090] [3-1. Fiber treatment agents] The fiber treatment agent of this embodiment includes the water-repellent and oil-repellent agent composition of this embodiment, or it may consist solely of the water-repellent and oil-repellent agent composition of this embodiment, or it may contain, in addition to the water-repellent and oil-repellent agent composition, known and conventional additives such as defoaming agents, preservatives, pH adjusters, surfactants, crosslinking agents, antistatic agents, wetting agents, thickeners, and pigments, selected as appropriate to the extent that the objectives of the present invention can be achieved.

[0091] The fiber treatment agent of this embodiment can impart high oil and water repellency to fibers. In this specification, "fiber" means fibers and articles made from fibers. The fibers treated with the fiber treatment agent may be in any form, such as short fibers, linters, rovings, slivers, yarns, woven fabrics, knitted fabrics, nonwoven fabrics, and paper. In this specification, fibers also include paper. Examples of materials for the fibers to be treated include cotton, flax, jute, hemp, ramie, regenerated cellulose fibers, cellulose fibers such as rayon, polyvinyl alcohol-based synthetic fibers, and pulp. It is preferable that the fibers treated with the fiber treatment agent contain 30% by mass or more of the above materials. The fiber treatment agent of this embodiment can impart high oil and water repellency to paper. The paper treated with the fiber treatment agent is not particularly limited, but examples include general-purpose paper using pulp cellulose.

[0092] In the water- and oil-repellent fibers treated with the fiber treatment agent of this embodiment, the fiber treatment agent, which includes the water- and oil-repellent composition of this embodiment, is attached to the base fiber. The total amount of the water- and oil-repellent composition attached per 100 parts by mass of the base fiber is preferably 1.0 part by mass or more, and more preferably 2.0 parts by mass or more. This is because the water- and oil-repellent properties of the water- and oil-repellent fibers are improved. The amount of the water- and oil-repellent composition attached per 100 parts by mass of the base fiber is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less. This is because the attachment of the fiber treatment agent to the fiber can suppress damage to the texture and suppress an increase in mass.

[0093] A method for treating fibers as a base material using the fiber treatment agent of this embodiment, that is, a method for manufacturing a fiber processed product using the fiber treatment agent, is as follows: First, the fibers, which serve as the base material, are impregnated or coated with a fiber treatment agent. Methods for impregnation or coating include, for example, dipping, spray coating, and roll coating. After impregnating or coating the fibers with the fiber treatment agent, the amount of the agent adhering to the fibers is adjusted. Methods for adjusting the amount of adhering agent include, but are not limited to, squeezing using a mangle roll. After impregnating or coating the fibers with the fiber treatment agent, it is preferable to dry the fibers. The drying temperature of the fibers is preferably 80°C to 170°C, and more preferably 90°C to 150°C. A textile processed product is obtained by impregnating or coating fibers with the textile treatment agent of this embodiment and then drying them. In other words, a textile processed product refers to an article in which the solid components (non-volatile components) contained in the textile treatment agent adhere to the fibers.

[0094] [3-3. Coating Agents] The coating agent of this embodiment includes the water-repellent and oil-repellent composition of this embodiment, or it may consist solely of the water-repellent and oil-repellent composition of this embodiment, or, in addition to the water-repellent and oil-repellent composition, it may optionally contain known and conventional additives such as defoamers, preservatives, pH adjusters, surfactants, crosslinking agents, antistatic agents, wetting agents, thickeners, and pigments, selected at the discretion of the present invention without impairing its purpose.

[0095] Examples of substrates to be coated with the coating agent of this embodiment include, but are not limited to, glass, polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile butadiene styrene copolymers (ABS resins), polystyrene resins, etc., or molded products thereof (films, sheets, cups, etc.), metals, etc.

[0096] Examples of methods for treating the above-mentioned substrate using the coating agent of this embodiment include the methods shown below. First, the coating agent is applied to the substrate. Methods for applying the coating agent to the substrate include, for example, spraying, brushing, roller application, trowel application, dipping, air knife application, flow coating, bar coating, roll coating, gravure coating, and the use of an applicator.

[0097] It is preferable to dry the substrate after applying the coating agent to it. The drying temperature when drying the substrate coated with the coating agent is preferably 80°C or higher, and more preferably 100°C or higher. This is because the drying time can be shortened and high productivity can be obtained. The drying temperature when drying the substrate coated with the coating agent is preferably 170°C or lower, and more preferably 150°C or higher. If the drying temperature is 170°C or lower, deterioration of the water-repellent and oil-repellent agent composition contained in the coating agent can be suppressed. The drying time can be determined according to the amount of coating agent applied to the substrate, etc., and is not particularly limited. [Examples]

[0098] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to the following examples. <1. Manufacturing of aqueous emulsion (α-1)> A five-necked separable flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, reflux condenser, and dropping funnel was filled with 120 g of deionized water as the aqueous medium (D) and 1 g of Catiogen® TML as the surfactant (E), and heated to 80°C to prepare a mixture. The resulting mixture was kept at 80°C, and 10 g of a 3% by mass aqueous solution of AAPH (2,2'-azobis(2-methylpropionamidine) dihydrochloride) was added to the mixture as a polymerization initiator to prepare a polymerization initiator solution.

[0099] On the other hand, monomers (a1) and (a2) shown in Table 1 were placed in a 1-liter beaker in the proportions shown in Table 1, 420 g of deionized water as the aqueous medium (D) and 15 g of Catiogen® TML as the surfactant (E) were added, and the mixture was emulsified using a homomixer to obtain a mixed emulsion.

[0100] Then, while maintaining the temperature of the five-necked flask containing the polymerization initiator solution at 80°C, the mixed emulsion and 44g of AAPH 3% by mass aqueous solution (as a polymerization initiator) were simultaneously and continuously added dropwise from a funnel over a period of 3 hours while stirring to carry out emulsion polymerization. After the dropwise addition was complete, the temperature inside the five-necked flask was maintained at 80°C for one hour while stirring. Then, the cooling of the five-necked flask was started, and the temperature inside the flask was cooled to 30°C. Through these steps, an aqueous emulsion (α-1) containing copolymer (A) was obtained.

[0101] <2. Manufacturing of aqueous emulsions (α-2)(β-1)~(β-6)> An aqueous emulsion (α-2) containing copolymer (A) was obtained in the same manner as the production of aqueous emulsion (α-1), except that monomers (a1) and monomer (a2) shown in Table 1 were used in the proportions shown in Table 1. Aqueous emulsions (β-1) to (β-6) containing copolymer (B) were obtained in the same manner as the production of aqueous emulsion (α-1), except that monomers (b1), (b2), and (b3) shown in Table 1 were used in the proportions shown in Table 1 instead of monomers (a1) and monomer (a2) shown in Table 1.

[0102] [Table 1]

[0103] In Table 1, monomer (a1) or (b1) is the compound from which structural unit (a1) or (b1) is derived. Monomer (a2) or (b2) is the compound from which structural unit (a2) or (b2) is derived. Monomer (b3) is the compound from which structural unit (b3) is derived.

[0104] The materials used in Table 1 are as follows: Monomer (b3); polydimethylsiloxane having an ethylenically unsaturated bond (manufactured by JNC Corporation, Cyraplane® FM-0725 (a compound represented by formula (1), where R in formula (1) is 1 R indicates a methyl group. 2 This indicates -CH2CH2CH2-. 3 The symbol indicates an n-butyl group. h is 2. j is 125. The number-average molecular weight (Mn) is 10,000. Surfactant (E); Catiogen™ (registered trademark) (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.: alkyltrimethylammonium chloride (containing lauryltrimethylammonium chloride) (cationic surfactant), 30% by mass aqueous solution) Polymerization initiator; 3% by mass aqueous solution of AAPH (3% by mass aqueous solution of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (AAPH))

[0105] The values ​​shown in the columns for aqueous medium (D), surfactant (E), and polymerization initiator in Table 1 represent the total mass (sum of monomers) used as materials for aqueous emulsions (α-1), (α-2), and aqueous emulsions (β-1) to (β-6). Therefore, the values ​​for aqueous medium (D) shown in Table 1 do not include the water contained in surfactant (E) and polymerization initiator.

[0106] <3. Preparation of water-repellent and oil-repellent composition> The aqueous emulsion (α-1) or (α-2) shown in Table 1, the aqueous emulsions (β-1) to (β-6) shown in Table 1, and polyether-modified polydimethylsiloxane (C) were mixed in the proportions shown in Table 2 or Table 3 to obtain water- and oil-repellent compositions of Examples 1 to 12 and Comparative Examples 1 to 8, each containing copolymer (A), copolymer (B), and polyether-modified polydimethylsiloxane (C) in the proportions shown in Table 2 or Table 3.

[0107] The values ​​shown in the Copolymer (A) column in Tables 2 and 3 represent the masses of the aqueous emulsions (α-1) and (α-2) used in the water-repellent and oil-repellent compositions of Examples 1 to 12 and Comparative Examples 1 to 8, with the values ​​in parentheses representing the mass of copolymer (A) contained in the aqueous emulsions (α-1) and (α-2). The content of copolymer (A) in aqueous emulsions (α-1) and (α-2) is the proportion of the monomer to the total amount of monomer, surfactant, polymerization initiator, and aqueous medium in Table 1.

[0108] The values ​​shown in the Copolymer (B) column in Tables 2 and 3 represent the masses of the aqueous emulsions (β-1) to (β-6) used in the water-repellent and oil-repellent compositions of Examples 1 to 12 and Comparative Examples 1 to 8. The values ​​in parentheses represent the mass of copolymer (B) contained in each of the aqueous emulsions (β-1) to (β-6). The mass of copolymer (B) in aqueous emulsions (β-1) to (β-6) represents the proportion of the monomer to the total amount of monomer, surfactant, polymerization initiator, and aqueous medium in Table 1.

[0109] [Table 2] [Table 3]

[0110] The polyether-modified polydimethylsiloxane (C) used in Tables 2 and 3 is as follows: BYK SILCLEAN 3720; a polyether-modified polydimethylsiloxane with hydroxyl groups at the ends of its polyether chains, weight-average molecular weight (Mw) 10,000, and a solvent (methoxypropanol) other than the active ingredient. (Manufactured by BYK) TEGO® Protect 5100N; a polyether-modified polydimethylsiloxane with hydroxyl groups at the ends of its polyether chains, weight-average molecular weight (Mw) 10,000, and the solvent (water) is used in addition to the active ingredient. (Manufactured by Evonik) KP-109; Polyether-modified polydimethylsiloxane, weight-average molecular weight (Mw) 10,000. The solvent (propylene glycol monomethyl ether) is used in addition to the active ingredient. (Manufactured by Shin-Etsu Silicone Co., Ltd.)

[0111] <4. Oil repellency evaluation> The water-repellent and oil-repellent compositions of Examples 1 to 12 and Comparative Examples 1 to 8 obtained in this manner were used to evaluate their oil repellency in the first and second tests described below. The results are shown in Tables 2 and 3.

[0112] [4-1. First Examination] The water-repellent and oil-repellent composition was diluted to twice its mass with deionized water. A square piece of cotton cloth (cotton cloth no. 3) measuring 200 mm in length and 200 mm in width was immersed in the diluted water-repellent and oil-repellent composition. The cotton cloth was then dried in an oven at 130°C for 5 minutes to prepare the test cloth. The test cloth was prepared so that the amount of water-repellent and oil-repellent composition components attached after drying was 20 parts by mass per 100 parts by mass of cotton cloth.

[0113] 0.03 ml of the test solution was dropped onto one side of the obtained test cloth and left to stand. After 1 minute, the state of the test solution was visually observed and evaluated according to the following criteria. The first test was conducted using two test solutions: one using a Grade 1 oil-repellent test solution (Nujol) as specified in the AATCC118 oil-repellent test method, and the other using a Grade 2 oil-repellent test solution (Nujol / n-hexadecane = 65 / 35). Both the test cloth and test solution were kept at 23°C. The standing and visual observation of the test solution on the test cloth were performed in a constant temperature room at 23°C.

[0114] "Evaluation Criteria" Excellent: The test solution maintains its droplet form. Good: The spherical droplets of the test solution break down, wetting and spreading the test solution onto the test cloth, but without soaking into the cloth. Fairly good: The test solution soaks into the test cloth within 30 seconds to 1 minute after the test solution has been allowed to stand. Poor: The test solution soaks into the test cloth within 30 seconds of being allowed to stand.

[0115] [4-2. Second Examination] A water-repellent and oil-repellent composition was applied to a glass plate, which served as a substrate, using an applicator to a thickness of 150 μm (in a non-dry state). The sample was then heat-treated in an oven at 130°C for 5 minutes to dry, and a test specimen (coating material) was obtained. On the surface of the obtained test specimen coated with the water- and oil-repellent composition, 2 μl of oil-repellent test solution (Nujol), which is classified as Grade 1 oil-repellent according to the AATCC118 method of oil repellency testing, was gently placed, and the contact angle of the test solution after 10 seconds was measured using the θ / 2 method with an automatic contact angle meter CA-VP type (manufactured by Kyowa Interface Science Co., Ltd.). A larger contact angle indicates superior oil repellency.

[0116] <5. Water repellency evaluation> The water-repellent and oil-repellent compositions of Examples 1-12 and Comparative Examples 1-8 were used in accordance with the water repellency test (spray test) described in JIS L 1092 (2009), Section 7.2. The evaluation criteria are as follows: A higher grade number indicates better water repellency. The test results are shown in Tables 2 and 3.

[0117] "Evaluation Criteria" Grade 1: The entire surface shows signs of wetting. Grade 2: Shows moisture over more than half of the surface area, with small, individual wet spots penetrating the fabric. Grade 3: The wetted area is less than half of the surface, and the surface shows small, individual water droplets of wetting. Grade 4: The surface does not show wetting, but there are small water droplets attached. Grade 5: No moisture or water droplets on the surface.

[0118] <6. Evaluation Results> [6-1. Oil repellency] As shown in Table 2, the substrates treated with the water- and oil-repellent compositions of Examples 1 to 12 were resistant to penetration by both Nujol and the Nujol / n-hexadecane = 65 / 35 test solution (Test 1), and the contact angle value of the test solution (Nujol) with respect to the droplets was also large (Test 2). From this, it was found that the water- and oil-repellent compositions of Examples 1 to 12 can impart high oil repellency to the substrates. In contrast, as shown in Table 3, the substrates treated with the water- and oil-repellent compositions of Comparative Examples 2 to 8, which did not contain the aqueous emulsion (α-1) or (α-2) (polymer (A)), were easily penetrated by Nujol / n-hexadecane = 65 / 35, and were not able to impart sufficient oil repellency to the substrates.

[0119] [6-2. Water repellency] As shown in Table 2, the substrates treated with the water- and oil-repellent compositions of Examples 1 to 12 did not show widespread wetting in the water-repellency test. This indicates that the water- and oil-repellent compositions of Examples 1 to 12 can impart high water repellency to substrates. In contrast, as shown in Table 3, the substrates treated with the water-repellent and oil-repellent compositions of Comparative Example 1, which did not contain the aqueous emulsion (β-1) to (β-6) (polymer (B)), and Comparative Examples 3, 4, and 8, which did not contain the aqueous emulsion (α-1) or (α-2) (polymer (A)), showed wetting over more than half of the surface area in the water repellency test. Therefore, the water-repellent and oil-repellent compositions of Comparative Examples 1, 3, 4, and 8 were not able to impart sufficient water repellency to the substrates. From the above, it has been found that the water- and oil-repellent composition according to the present invention can impart high oil-repellency and water-repellency to the substrate. [Industrial applicability]

[0120] The present invention provides a water- and oil-repellent composition that can impart high oil-repellency and water-repellency to a substrate.

Claims

1. A copolymer (A) that does not contain structural units having siloxane bonds, A copolymer (B) containing structural units having siloxane bonds, Polyether-modified polydimethylsiloxane (C) and Aqueous medium (D) is included, The copolymer (A) is A structural unit (a1) derived from a compound having ethylenically unsaturated bonds and ester bonds, and lacking amide bonds, It consists only of structural units (a2) derived from compounds having ethylenically unsaturated bonds and amide bonds, The copolymer (B) is A structural unit (b1) derived from a compound having ethylenically unsaturated bonds and ester bonds, and lacking amide bonds, A structural unit (b2) derived from a compound having an ethylenically unsaturated bond and an amide bond, A water-repellent and oil-repellent composition having a structural unit (b3) derived from polydimethylsiloxane having an ethylenically unsaturated bond.

2. The water-repellent and oil-repellent composition according to claim 1, wherein the structural unit (a1) and the structural unit (b1) are structural units derived from either or both of a hydrocarbon having an ethylenically unsaturated bond or an alkyl (meth)acrylate.

3. The water-repellent 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)acrylamide.

4. The water-repellent and oil-repellent composition according to any one of claims 1 to 3, wherein the structural unit (b3) is a structural unit derived from a compound represented by the following formula (1). 【Chemistry 1】 (In equation (1), R １ R represents a hydrogen atom or a methyl group; ２ R represents a divalent aliphatic group having 1 to 6 carbon atoms, which may contain an ether bond; ３ (where 'h' represents an aliphatic group, aromatic group, or hydroxyl group with 1 to 30 carbon atoms; 'h' is 0, 1, or 2; 'j' is an integer from 0 to 500.)

5. The water-repellent and oil-repellent composition according to any one of claims 1 to 4, wherein the mass ratio (A / B) of copolymer (A) to copolymer (B) is 10 / 90 or more and 90 / 10 or less.

6. The water-repellent and oil-repellent composition according to claim 5, wherein the mass ratio (A / B) of copolymer (A) to copolymer (B) is 10 / 90 or more and 80 / 20 or less.

7. The water-repellent and oil-repellent composition according to any one of claims 1 to 6, wherein the copolymer (A) contains 0.10% by mass or more and 20% by mass or less of the structural unit (a2).

8. The water-repellent and oil-repellent composition according to any one of claims 1 to 7, wherein the copolymer (B) contains 0.10% by mass or more and 20% by mass or less of the structural unit (b2).

9. The water-repellent and oil-repellent composition according to any one of claims 1 to 8, wherein the copolymer (B) contains 3.0% by mass or more and 50% by mass or less of the structural unit (b3).

10. The water-repellent and oil-repellent composition according to any one of claims 1 to 9, wherein the polyether-modified polydimethylsiloxane (C) has a hydroxyl group at the end of the polyether chain.

11. The water-repellent and oil-repellent composition according to any one of claims 1 to 10, wherein 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).

12. Furthermore, the water-repellent and oil-repellent composition according to any one of claims 1 to 11, further comprising a surfactant (E).

13. The water-repellent and oil-repellent composition according to claim 12, wherein the surfactant (E) is a cationic surfactant.

14. A textile treatment agent comprising the water-repellent and oil-repellent composition according to any one of claims 1 to 13.

15. A method for treating fibers using the fiber treatment agent described in claim 14.

16. A coating agent comprising the water-repellent and oil-repellent composition according to any one of claims 1 to 13.

17. A textile product in which the solid components contained in the textile treatment agent of claim 14 are attached to the fibers.

18. 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. The structural unit (a2) and the structural unit (b2) are at least one selected from the group consisting of acrylamide and methacrylamide. The aforementioned structural unit (b3) is a structural unit derived from a compound represented by the following formula (1), 【Chemistry 2】 (In equation (1), R １ R represents a hydrogen atom or a methyl group; ２ R3 represents a divalent aliphatic group having 1 to 6 carbon atoms, which may contain an ether bond; R3 represents an aliphatic group, aromatic group, or hydroxyl group having 1 to 30 carbon atoms; h is 0, 1, or 2; j is an integer from 0 to 500. 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 copolymer (A) and copolymer (B) is 1.5% by mass or more and 30% by mass or less. The ratio of the mass of copolymer (A) to the mass of copolymer (B) is 10 / 90 to 90 / 10. The water-repellent and oil-repellent composition according to claim 1, wherein the weight-average molecular weight of the polyether-modified polydimethylsiloxane (C) is 7,000 or more and 14,000 or less.

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