Resin dispersion for water- and oil-repellent agent and water- and oil-repellent agent

Abstract

To provide a resin dispersion for a water- and oil-repellent agent and a water- and oil-repellent agent which are capable of forming a coating film having both water repellency and oil repellency.SOLUTION: A resin dispersion for a water- and oil-repellent agent comprises: a dispersant (A) which is a (meth)acrylic copolymer comprising a reactive silicone unit (a1) represented by formula (1), a (meth)acrylate unit (a2) having a cyclic structure, and an alkyl (meth)acrylate unit (a3) having no cyclic structure, wherein the content of the reactive silicone unit (a1) is 1 mass% or more and less than 30 mass% relative to the total structural units, the alkyl moiety has 8 or more carbon atoms, and the content of the alkyl (meth)acrylate unit (a3-1) having no cyclic structure is less than 50 mass% relative to the total structural units; dispersed particles (B) which are polymers different from the (meth)acrylic copolymer; and a non-aqueous solvent (C). (In formula (1), R1 is a methyl group or the like; R2 to R6 are alkyl groups having 1 to 5 carbon atoms or the like; m is 1 to 10; and n is 0 to 200).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a resin dispersion for a water / oil repellent and a water / oil repellent. [Background technology]

[0002] Conventionally, many antifouling coating agents using water- and oil-repellent technology that use fluorine compounds have been on the market. Fluorine compounds are compounds that can be expected to have both water- and oil-repellent effects, and so there have been reports on water- and oil-repellent agents that use fluorine compounds (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2015-67679 A Summary of the Invention [Problem to be solved by the invention]

[0004] Incidentally, fluorine compounds having a perfluoroalkyl group with 8 or more carbon atoms in the alkyl portion are known to have high performance in both water repellency and oil repellency, and have been widely used as raw materials for water and oil repellents, surface treatment agents, etc. However, the above-mentioned fluorine compounds having 8 or more carbon atoms in the alkyl portion are difficult to decompose, and there are concerns about their long-term impact on the environment and human body, so there is a growing movement to regulate their use. On the other hand, the above-mentioned fluorine compounds having 6 or less carbon atoms in the alkyl portion used in the water and oil repellent agent described in Patent Document 1 have a lower impact on the environment and human body compared to the above-mentioned fluorine compounds having 8 or more carbon atoms in the alkyl portion, but there is a possibility that they will be subject to regulation in the future. In addition, the water and / or oil repellency tends to be significantly inferior. For this reason, research on water and oil repellents using alternative compounds to fluorine compounds having perfluoroalkyl groups has been conducted in recent years.

[0005] In addition, since the water / oil repellent described in Patent Document 1 is a so-called resin solution in which a fluorine-containing polymer is dissolved in an organic solvent, it is difficult to increase the solid content concentration or impart thixotropy while suppressing the liquid viscosity. For this reason, in recent years, attention has been focused on non-aqueous dispersion (NAD) type water / oil repellents, which are resin dispersions obtained by dispersing resin particles in a non-aqueous solvent, as water / oil repellents that are relatively easy to impart high solid content and thixotropy to.

[0006] The present disclosure has been made in consideration of the above-mentioned circumstances. An object of the present invention is to provide a resin dispersion for a water / oil repellent agent that can form a film having both water and oil repellency. Another problem to be solved by another embodiment of the present disclosure is to provide a water / oil repellent containing the above-mentioned resin dispersion for water / oil repellent. [Means for solving the problem]

[0007] Specific means for solving the problems include the following aspects. <1> a dispersing agent (A) which is a (meth)acrylic copolymer comprising a structural unit (a1) derived from a reactive silicone represented by the following formula (1), a structural unit (a2) derived from a (meth)acrylate having a cyclic structure, and a structural unit (a3) ​​derived from an alkyl (meth)acrylate not having a cyclic structure, the content of the structural unit (a1) being in the range of 1 mass % or more and less than 30 mass % with respect to all structural units, the number of carbon atoms in the alkyl moiety being 8 or more, and the content of the structural unit (a3-1) derived from an alkyl (meth)acrylate not having a cyclic structure being less than 50 mass % with respect to all structural units; Dispersed particles (B) which are polymers different from the (meth)acrylic copolymer; A non-aqueous solvent (C); A resin dispersion for a water / oil repellent comprising:

[0008] [ka]

[0009] In formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 , R 3 , R 4 , R 5 and R 6 each independently represents an alkyl group having 1 to 5 carbon atoms or a trialkylsiloxy group having an alkyl group having 1 to 3 carbon atoms, m represents an integer of 1 to 10, and n represents an integer of 0 to 200.

[0010] <2> The (meth)acrylate having a cyclic structure is at least one selected from the group consisting of benzyl (meth)acrylate and isobornyl (meth)acrylate. <1> The resin dispersion for a water / oil repellent according to claim 1. <3> The polymer contains a structural unit (b2) derived from a polyfunctional monomer. <1> or <2> The resin dispersion for a water / oil repellent according to claim 1. <4> The polyfunctional monomer is a silicone compound having (meth)acryloyl groups at both ends. <3> The resin dispersion for a water / oil repellent according to claim 1.

[0011] <5> the number average molecular weight of the reactive silicone represented by the formula (1) in the (meth)acrylic copolymer is 8000 or more, and the number average molecular weight of the reactive silicone represented by the formula (2) in the polymer is in the range of 4000 or more and less than 10000; <4> The resin dispersion for a water / oil repellent according to claim 1. <6> The resin dispersion for the water / oil repellent agent contains a crosslinking agent, and the (meth)acrylic copolymer contains a structural unit derived from a monomer having a reactive functional group. <1> ~ <5> 10. The resin dispersion for a water / oil repellent according to claim 9, <7> <1> ~ <6> 13. A water / oil repellent comprising the resin dispersion for water / oil repellent according to any one of claims 1 to 12. Effect of the Invention

[0012] According to one embodiment of the present disclosure, there is provided a resin dispersion for a water / oil repellent agent capable of forming a film having both water repellency and oil repellency. According to another embodiment of the present disclosure, there is provided a water / oil repellent comprising the above-mentioned resin dispersion for water / oil repellent. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The resin dispersion for water / oil repellent and the water / oil repellent of the present disclosure will be described in detail below. The following description of the requirements may be based on a representative embodiment of the present disclosure, but the present disclosure is not limited to such an embodiment, and can be modified as appropriate within the scope of the purpose of the present disclosure.

[0014] In the present disclosure, a numerical range indicated using "to" means a range that includes the numerical values ​​before and after "to" as the lower limit and upper limit, respectively. In the numerical ranges described in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in the present disclosure. In addition, in the numerical ranges described in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.

[0015] In the present disclosure, combinations of two or more preferred embodiments are more preferred embodiments.

[0016] In the present disclosure, when a plurality of substances corresponding to each component are present in the resin dispersion for the water / oil repellent agent, the amount of each component in the resin dispersion for the water / oil repellent agent means the total amount of the plurality of substances present in the resin dispersion for the water / oil repellent agent, unless otherwise specified.

[0017] In the present disclosure, "(meth)acrylic monomer" means a monomer having a (meth)acryloyl group. In the present disclosure, the term "(meth)acrylic polymer" refers to a polymer that contains structural units derived from (meth)acrylic monomers and in which the proportion of the structural units derived from (meth)acrylic monomers is 50 mass % or more. The same applies to the term "(meth)acrylic copolymer."

[0018] In this disclosure, "(meth)acrylic" is a term that encompasses both "acrylic" and "methacrylic", "(meth)acrylate" is a term that encompasses both "acrylate" and "methacrylate", and "(meth)acryloyl" is a term that encompasses both "acryloyl" and "methacryloyl".

[0019] In this disclosure, "n-" means normal, "i-" means iso, "s-" means secondary, and "t-" means tertiary.

[0020] In the present disclosure, "mass %" and "weight %" are synonymous, and "parts by mass" and "parts by weight" are synonymous.

[0021] In the present disclosure, the terms "monomer" and "monomer" are synonymous, and the terms "polymer" and "polymeric material" and "copolymer" are synonymous.

[0022] In the present disclosure, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

[0023] [Resin dispersion for water and oil repellents] The resin dispersion for water / oil repellents of the present disclosure (hereinafter also simply referred to as "resin dispersion") comprises a dispersant (A) which is a (meth)acrylic copolymer comprising a structural unit (a1) derived from a reactive silicone represented by formula (1), a structural unit (a2) derived from a (meth)acrylate having a cyclic structure, and a structural unit (a3) ​​derived from an alkyl (meth)acrylate not having a cyclic structure, the content of the structural unit (a1) being in the range of 1 mass% or more and less than 30 mass% with respect to all structural units, the number of carbon atoms in the alkyl moiety being 8 or more, and the content of the structural unit (a3-1) derived from an alkyl (meth)acrylate not having a cyclic structure being less than 50 mass% with respect to all structural units, dispersed particles (B) which are polymers different from the (meth)acrylic copolymer, and a non-aqueous solvent (C). According to the resin dispersion of the present disclosure, a film having both water repellency and oil repellency can be formed. The reason why the resin dispersion of the present disclosure can exhibit such an effect is unclear, but the present inventors speculate as follows: However, the following speculation is not intended to limit the interpretation of the resin dispersion of the present disclosure, but is merely an example.

[0024] The present inventor has focused on silicone compounds as an alternative compound to fluorine compounds having perfluoroalkyl groups. Generally, silicone compounds can be used to form a film with water repellency, but it is difficult to make the film have oil repellency, which repels oil that has a lower surface tension than water. In the course of research into water and oil repellents using silicone compounds, the present inventor has found that the (meth)acrylic copolymer obtained by incorporating a structural unit derived from a reactive silicone having a specific structure together with a structural unit derived from a (meth)acrylate having a cyclic structure and a structural unit derived from an alkyl (meth)acrylate having no cyclic structure can be used to form a film with both water repellency and oil repellency.

[0025] The resin dispersion of the present disclosure is a so-called NAD type resin dispersion containing a dispersant (A), dispersed particles (B), and a non-aqueous solvent (C), and the dispersed particles (B) are dispersed in the non-aqueous solvent (C) by the dispersant (A). In the resin dispersion of the present disclosure, the (meth)acrylic copolymer as the dispersant (A) contains a structural unit (a1) derived from a reactive silicone represented by formula (1), so that the film formed can exhibit water repellency and oil repellency. It is considered that the surface energy of the film formed by the (meth)acrylic copolymer as the dispersant (A) containing the structural unit (a1) is reduced due to the structure of the reactive silicone represented by formula (1). It is presumed that the film formed by reducing the surface energy exhibits water repellency and oil repellency. In addition, the resin dispersion of the present disclosure is a dispersant (A) containing a structural unit (a2) derived from a (meth)acrylate having a cyclic structure, so that the film formed can exhibit oil repellency. It is believed that the (meth)acrylic copolymer, which is the dispersant (A), contains the structural unit (a2), and in the film formed, the movement of the silicone chain is inhibited due to steric hindrance caused by the (meth)acrylate having a cyclic structure. It is presumed that the inhibition of this movement keeps the surface energy low, and therefore the film formed exhibits oil repellency. The (meth)acrylic copolymer, which is the dispersant (A) contained in the resin dispersion of the present disclosure, contains a structural unit (a3) ​​derived from an alkyl (meth)acrylate having no cyclic structure, the number of carbon atoms in the alkyl portion is 8 or more, and the content of the structural unit (a3-1) derived from an alkyl (meth)acrylate having no cyclic structure is less than 50 mass% with respect to the total structural units. Since the alkyl (meth)acrylate having no cyclic structure contains a hydrophobic alkyl group, it has low affinity for water (so-called hydrophilicity) and high affinity for oil (so-called lipophilicity). The lipophilicity of the alkyl (meth)acrylate having no cyclic structure tends to increase as the number of carbon atoms in the alkyl group increases, but the resin dispersion of the present disclosure is presumed to be less likely to impair oil repellency because the proportion of the structural unit (a3-1) in the (meth)acrylic copolymer, which is the dispersant (A), is not too high, and the lipophilicity of the film formed is not excessively high. In addition, in the resin dispersion of the present disclosure, the proportion of the structural unit (a1) in the (meth)acrylic copolymer, which is the dispersant (A), is not too high, which is presumably one of the reasons why the lipophilicity of the film formed is not excessively high and the oil repellency is not easily impaired. From the above, it is presumed that the resin dispersion of the present disclosure can form a film that is both water-repellent and oil-repellent.

[0026] Furthermore, the resin dispersion of the present disclosure can have the effect of forming a film that is oil-resistant in addition to water- and oil-repellent.

[0027] [Dispersant (A)] The resin dispersion of the present disclosure comprises a dispersing agent (A) which is a (meth)acrylic copolymer comprising a structural unit (a1) derived from a reactive silicone represented by formula (1), a structural unit (a2) derived from a (meth)acrylate having a cyclic structure, and a structural unit (a3) ​​derived from an alkyl (meth)acrylate not having a cyclic structure, wherein the content of the structural unit (a1) is in the range of 1 mass% or more and less than 30 mass% with respect to all structural units, and the number of carbon atoms in the alkyl moiety is 8 or more and the content of the structural unit (a3-1) derived from an alkyl (meth)acrylate not having a cyclic structure is less than 50 mass% with respect to all structural units. In the resin dispersion of the present disclosure, the dispersant (A) functions as a dispersant that disperses the dispersed particles (B) in the non-aqueous solvent (C). The resin dispersion of the present disclosure may contain only one type of dispersant (A), or may contain two or more types.

[0028] The dispersant (A) is a dispersant that is soluble in the non-aqueous solvent (C) described below. "The dispersant (A) is soluble in the non-aqueous solvent (C)" means that the solubility of the dispersant (A) in the non-aqueous solvent (C) at a liquid temperature of 25° C. is 90% by mass or more. The solubility of the dispersant (A) in the non-aqueous solvent (C) at a liquid temperature of 25° C. is preferably 99% by mass or more, and may be, for example, 100% by mass.

[0029] Hereinafter, the dispersant (A) "a (meth)acrylic copolymer which contains a structural unit (a1) derived from a reactive silicone represented by formula (1), a structural unit (a2) derived from a (meth)acrylate having a cyclic structure, and a structural unit (a3) ​​derived from an alkyl (meth)acrylate not having a cyclic structure, in which the content of the structural unit (a1) is in the range of 1 mass% or more and less than 30 mass% with respect to all structural units, the alkyl moiety has 8 or more carbon atoms, and the content of the structural unit (a3-1) derived from an alkyl (meth)acrylate not having a cyclic structure is less than 50 mass% with respect to all structural units" is also referred to as "(meth)acrylic copolymer (a)".

[0030] <Structural unit (a1) derived from reactive silicone represented by formula (1)> The (meth)acrylic copolymer (a) contains a structural unit (a1) derived from a reactive silicone represented by the following formula (1), and the content of the structural unit (a1) is in the range of 1 mass % or more and less than 30 mass % based on all structural units of the (meth)acrylic copolymer (a). The structural unit (a1) derived from the reactive silicone represented by formula (1) can contribute to the development of oil repellency in the film that is formed. Furthermore, the structural unit (a1) derived from the reactive silicone represented by formula (1) can contribute to improving the oil resistance of the film that is formed.

[0031] In the present disclosure, the term "structural unit derived from the reactive silicone represented by formula (1)" refers to a structural unit formed by addition polymerization of the reactive silicone represented by formula (1).

[0032] [ka]

[0033] In formula (1), R 1 represents a hydrogen atom or a methyl group, and is preferably a methyl group.

[0034] In formula (1), R 2 , R 3 , R 4 , R 5 and R 6 each independently represents an alkyl group having 1 to 5 carbon atoms or a trialkylsiloxy group having an alkyl group having 1 to 3 carbon atoms. In formula (1), R 2 , R 3 , R 4 , R 5 or R 6 The alkyl group represented by the formula (I) may be either linear or branched. In formula (1), R 2 , R 3 , R 4 , R 5 and R 6 are each preferably an alkyl group having 1 to 5 carbon atoms, and more preferably, R 2 , R 3 , R 4 and R 5 is an alkyl group having one carbon atom (i.e., a methyl group), and R 6 is an alkyl group having 4 carbon atoms. In formula (1), m represents an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 3. In formula (1), n ​​represents an integer of 0 to 200, and is preferably an integer of 5 to 150.

[0035] The number average molecular weight of the reactive silicone represented by formula (1) in the (meth)acrylic copolymer (a) is not particularly limited, but from the viewpoint of the oil repellency of the film to be formed, it is preferably 400 or more, more preferably 1000 or more, even more preferably 5000 or more, particularly preferably 8000 or more, and most preferably 10000 or more. The number average molecular weight of the reactive silicone represented by formula (1) in the (meth)acrylic copolymer (a) is preferably less than 20,000, for example, from the viewpoint of easy availability of the reactive silicone represented by formula (1).

[0036] In this disclosure, the number average molecular weight of the reactive silicone represented by formula (1) is measured by the following method. However, when a commercially available product is used as the reactive silicone represented by formula (1), and the catalog of the commercially available product contains the number average molecular weight, the number average molecular weight described in the catalog is used as a priority. In addition, when a commercially available product is used as the reactive silicone represented by formula (1), even if the catalog of the commercially available product does not contain the number average molecular weight, if the catalog contains the functional group equivalent and the number average molecular weight can be calculated, the calculated number average molecular weight is used as a priority.

[0037] <<Method for measuring the number average molecular weight of reactive silicone represented by formula (1)>> Using the reactive silicone represented by formula (1) and tetrahydrofuran, a sample solution with a solid content concentration of 0.2% by mass is obtained. The "solid content concentration" here means the mass ratio of the reactive silicone represented by formula (1) in the sample solution. Next, the number average molecular weight of the reactive silicone represented by formula (1) is measured in terms of standard polystyrene using gel permeation chromatography (GPC) under the following conditions.

[0038] ~Conditions~ Measurement equipment: High-speed GPC [Model: HLC-8420 GPC, manufactured by Tosoh Corporation] Detector: Differential refractometer (RI) [installed in HLC-8420, manufactured by Tosoh Corporation] Column: TSKgel GMH XL Two Tosoh products are used. Column temperature: 40℃ Eluent: Tetrahydrofuran Sample solution injection volume: 100 μL Flow rate: 0.8mL / min

[0039] When the (meth)acrylic copolymer (a) contains structural units (a1) derived from reactive silicones represented by two or more types of formula (1) with different number average molecular weights, the "number average molecular weight of the reactive silicone represented by formula (1) in the (meth)acrylic copolymer (a)" refers to an arithmetic average value, specifically, a value calculated by the following formula: In the following formula, the "reactive silicone represented by formula (1)" is simply referred to as "reactive silicone". Number average molecular weight of reactive silicone in (meth)acrylic copolymer (a) = [number average molecular weight of reactive silicone 1 × amount of reactive silicone 1 + number average molecular weight of reactive silicone 2 × amount of reactive silicone 2 + ··· + number average molecular weight of reactive silicone n × amount of reactive silicone n] / [amount of reactive silicone 1 + amount of reactive silicone 2 + ··· + amount of reactive silicone n]

[0040] A specific example of the compound represented by formula (1) is Silaplane (registered trademark) FM-0711 [in formula (1), R 1 =R 2 =R 3 =R 4 =R 5 = methyl group, R 6 = n-butyl group, m = 3, number average molecular weight (Mn): 1000 (catalog value), manufactured by JNC Corporation], Silaplane (registered trademark) FM-0721 [in formula (1), R 1 =R 2 =R 3 =R 4 =R 5 = methyl group, R 6= n-butyl group, m = 3, number average molecular weight (Mn): 5000 (catalog value), manufactured by JNC Corporation], Silaplane (registered trademark) FM-0725 [in formula (1), R 1 =R 2 =R 3 =R 4 =R 5 = methyl group, R 6 = n-butyl group, m = 3, number average molecular weight (Mn): 10000 (catalog value), manufactured by JNC Corporation], and X-22-2404 [in formula (1), R 1 = methyl group, R 2 =R 3 =R 6 = trimethylsiloxy group, m = 3, n = 0, number average molecular weight (Mn): 420 (catalog value), manufactured by Shin-Etsu Chemical Co., Ltd.

[0041] The (meth)acrylic copolymer (a) may contain only one type of structural unit (a1), or may contain two or more types.

[0042] The content of the structural unit (a1) in the (meth)acrylic copolymer (a) is in the range of 1% by mass or more and less than 30% by mass based on all structural units of the (meth)acrylic copolymer (a). The content of the structural unit (a1) in the (meth)acrylic copolymer (a) being 1 mass% or more relative to all structural units of the (meth)acrylic copolymer (a) means that the (meth)acrylic copolymer (a) actively contains the structural unit (a1). When the content of the structural unit (a1) in the (meth)acrylic copolymer (a) is less than 30 mass% based on all structural units of the (meth)acrylic copolymer (a), the oil repellency of the formed film tends not to be impaired. The content of the structural unit (a1) in the (meth)acrylic copolymer (a) is preferably in the range of 1 mass % or more and 25 mass % or less, more preferably in the range of 5 mass % or more and 20 mass % or less, and even more preferably in the range of 8 mass % or more and 15 mass % or less, based on all structural units of the (meth)acrylic copolymer (a).

[0043] <Structural Unit (a2) Derived from a (Meth)acrylate Having a Cyclic Structure> The (meth)acrylic copolymer (a) contains a structural unit (a2) derived from a (meth)acrylate having a cyclic structure. The structural unit (a2) derived from a (meth)acrylate having a cyclic structure can contribute to the development of water repellency and oil repellency in the film that is formed. Furthermore, the structural unit (a2) derived from a (meth)acrylate having a cyclic structure can contribute to improving the oil resistance of the film that is formed.

[0044] In the present disclosure, the term "structural unit derived from a (meth)acrylate having a cyclic structure" refers to a structural unit formed by addition polymerization of a (meth)acrylate having a cyclic structure.

[0045] The type of (meth)acrylate having a cyclic structure is not particularly limited. The (meth)acrylate having a cyclic structure may be a methacrylate or an acrylate. Examples of the cyclic structure include an aromatic ring and an aliphatic ring. Examples of the aromatic ring include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and an anthracene ring; and aromatic heterocycles such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, and a pyridine ring. Examples of the aliphatic ring include aliphatic hydrocarbon rings represented by a cyclohexane ring, a cyclopentane ring, a pinane ring, a norpinane ring, a norbornane ring, an isobornane ring, a bicyclooctane ring, a bicyclononane ring, a homobredane ring, an adamantane ring, a tetrahydrodicyclopentadiene ring, a 5,6-dihydrodicyclopentadiene ring, a tricycloundecane ring, and a tetracyclododecane ring; and aliphatic heterocycles represented by an oxolane ring, an oxane ring, a piperidine ring, and a piperazine ring.

[0046] Specific examples of the (meth)acrylate having a cyclic structure include benzyl (meth)acrylate, isobornyl (meth)acrylate, and phenoxyethyl (meth)acrylate. The (meth)acrylate having a cyclic structure is preferably at least one selected from the group consisting of benzyl (meth)acrylate and isobornyl (meth)acrylate, and more preferably at least one selected from benzyl methacrylate and isobornyl methacrylate.

[0047] The (meth)acrylic copolymer (a) may contain only one type of structural unit (a2), or may contain two or more types.

[0048] The content of the structural unit (a2) in the (meth)acrylic copolymer (a) is not particularly limited, but from the viewpoint of the water repellency, oil repellency, and oil resistance of the film to be formed, the content is preferably 1 mass% or more, more preferably 1.5 mass% or more, even more preferably 2 mass% or more, and particularly preferably 2.5 mass% or more, based on the total structural units of the (meth)acrylic copolymer (a), although not particularly limited thereto. The upper limit of the content of the structural unit (a2) in the (meth)acrylic copolymer (a) is, for example, from the viewpoint of the strength of the film to be formed, preferably 40 mass % or less, more preferably 30 mass % or less, even more preferably 25 mass % or less, and particularly preferably 20 mass % or less, based on all structural units of the (meth)acrylic copolymer (a). In one embodiment, the content of the structural unit (a2) in the (meth)acrylic copolymer (a) may be 1 mass % to 40 mass %, 1.5 mass % to 30 mass %, 2 mass % to 25 mass %, or 2.5 mass % to 20 mass %, relative to all structural units of the (meth)acrylic copolymer (a).

[0049] <Structural Unit (a3) ​​Derived from Alkyl (Meth)acrylate Not Having a Cyclic Structure> The (meth)acrylic copolymer (a) contains a structural unit (a3) ​​derived from an alkyl (meth)acrylate that does not have a cyclic structure. The structural unit (a3) ​​derived from an alkyl (meth)acrylate that does not have a cyclic structure can contribute to improving the flexibility and strength of the film that is formed.

[0050] In the present disclosure, a "structural unit derived from an alkyl(meth)acrylate not having a cyclic structure" refers to a structural unit formed by addition polymerization of an alkyl(meth)acrylate not having a cyclic structure. In the present disclosure, the term "alkyl(meth)acrylate having no cyclic structure" does not include monomers having a reactive functional group, which will be described later. In other words, when a monomer having a reactive functional group also falls under the category of an alkyl(meth)acrylate having no cyclic structure, it is classified as a monomer having a reactive functional group. For example, 2-hydroxyethyl acrylate, which has a hydroxyl group as a reactive functional group, also falls under the category of alkyl (meth)acrylates that do not have a cyclic structure, but in the present disclosure, it is classified as a monomer having a reactive functional group.

[0051] The type of alkyl(meth)acrylate not having a cyclic structure is not particularly limited. The alkyl (meth)acrylate having no cyclic structure may be either an alkyl methacrylate or an alkyl acrylate. The alkyl group in the alkyl (meth)acrylate having no cyclic structure may be unsubstituted or may have a substituent, but is preferably unsubstituted. The alkyl group in the alkyl (meth)acrylate having no cyclic structure may be linear or branched. The alkyl moiety of the alkyl (meth)acrylate not having a cyclic structure preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 1 to 8 carbon atoms.

[0052] Specific examples of alkyl (meth)acrylates not having a cyclic structure include methyl (meth)acrylate (number of carbon atoms in the alkyl portion: 1), ethyl (meth)acrylate (number of carbon atoms in the alkyl portion: 2), n-butyl (meth)acrylate (number of carbon atoms in the alkyl portion: 4), i-butyl (meth)acrylate (number of carbon atoms in the alkyl portion: 4), s-butyl (meth)acrylate (number of carbon atoms in the alkyl portion: 4), t-butyl (meth)acrylate (number of carbon atoms in the alkyl portion: 4), n-octyl (meth)acrylate (number of carbon atoms in the alkyl portion: [number of carbon atoms in the alkyl portion: 8], i-octyl (meth)acrylate [number of carbon atoms in the alkyl portion: 8], 2-ethylhexyl (meth)acrylate [number of carbon atoms in the alkyl portion: 8], n-nonyl (meth)acrylate [number of carbon atoms in the alkyl portion: 9], i-nonyl (meth)acrylate [number of carbon atoms in the alkyl portion: 9], n-decyl (meth)acrylate [number of carbon atoms in the alkyl portion: 10], lauryl (meth)acrylate [number of carbon atoms in the alkyl portion: 12], and stearyl (meth)acrylate [number of carbon atoms in the alkyl portion: 18]. The alkyl (meth)acrylate not having a cyclic structure preferably includes at least one selected from the group consisting of i-butyl methacrylate, t-butyl methacrylate, and 2-ethylhexyl methacrylate, and more preferably includes at least one selected from the group consisting of i-butyl methacrylate, t-butyl methacrylate, and 2-ethylhexyl methacrylate.

[0053] The (meth)acrylic copolymer (a) may contain only one type of structural unit (a3), or may contain two or more types.

[0054] The content of the structural unit (a3) ​​in the (meth)acrylic copolymer (a) is not particularly limited, but for example, it is preferably 50% by mass or more, more preferably in the range of 50% by mass or more and 98% by mass or less, even more preferably in the range of 60% by mass or more and 95% by mass or less, and particularly preferably in the range of 70% by mass or more and 90% by mass or less, based on all structural units of the (meth)acrylic copolymer (a). When the content of the structural unit (a3) ​​in the (meth)acrylic copolymer (a) is 50 mass% or more based on all structural units of the (meth)acrylic copolymer (a), the flexibility and strength of the film formed tends to be further improved.

[0055] In the (meth)acrylic copolymer (a), the content of structural units (a3-1) derived from an alkyl (meth)acrylate having an alkyl moiety with 8 or more carbon atoms and not having a cyclic structure is less than 50 mass% of all structural units of the (meth)acrylic copolymer (a). If the content of the structural unit (a3-1) in the (meth)acrylic copolymer (a) is less than 50% by mass relative to the total structural units of the (meth)acrylic copolymer (a), the oil repellency of the film formed tends not to be impaired. From this viewpoint, the content of the structural unit (a3-1) in the (meth)acrylic copolymer (a) is preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less relative to the total structural units of the (meth)acrylic copolymer (a). The lower limit of the content of the structural unit (a3-1) in the (meth)acrylic copolymer (a) is not particularly limited and may be, for example, 0 mass %. However, from the viewpoint of the strength of the formed film, it is preferably 20 mass % or more based on the total structural units of the (meth)acrylic copolymer (a).

[0056] <Structural Unit (a4) Derived from Other Monomers> The (meth)acrylic copolymer (a) may contain a structural unit derived from a monomer (so-called other monomer) that does not fall into any of the reactive silicone represented by formula (1), the (meth)acrylate having a cyclic structure, and the alkyl (meth)acrylate not having a cyclic structure. In the present disclosure, the "structural unit derived from other monomer" contained in the (meth)acrylic copolymer (a) is also referred to as the "structural unit (a4)". In the present disclosure, the term "structural units derived from other monomers" refers to structural units formed by addition polymerization of other monomers.

[0057] Examples of the structural unit (a4) include structural units derived from monomers having a reactive functional group. In the present disclosure, the term "reactive functional group" refers to a functional group that can form a crosslinked structure by reacting with a crosslinking agent described below, and examples of the reactive functional group include a carboxy group, a hydroxyl group, and an amino group. In the present disclosure, the term "amino group" includes a primary amino group, a secondary amino group, and a tertiary amino group.

[0058] When the resin dispersion of the present disclosure contains a crosslinking agent and the (meth)acrylic copolymer (a) which is the dispersing agent (A) contains a structural unit derived from a monomer having a reactive functional group, the reactive group in the (meth)acrylic copolymer (a) reacts with the crosslinking agent to form a crosslinked structure, which tends to improve the oil resistance of the film formed. Also, the strength of the film formed tends to increase.

[0059] Further examples of the structural unit (a4) include structural units derived from vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; structural units derived from vinyl ester compounds such as vinyl formate, vinyl acetate, vinyl propionate, and vinyl versatate; and the like.

[0060] When the (meth)acrylic copolymer (a) contains the structural unit (a4), it may contain only one type of structural unit (a4), or may contain two or more types of structural unit (a4).

[0061] When the (meth)acrylic copolymer (a) contains the structural unit (a4), the content of the structural unit (a4) can be set appropriately as long as the effects of the resin dispersion of the present disclosure are not impaired.

[0062] <<Weight average molecular weight of (meth)acrylic copolymer (a)>> The weight average molecular weight (also referred to as "Mw") of the (meth)acrylic copolymer (a) is not particularly limited, but is preferably from 10,000 to 1,000,000, more preferably from 15,000 to 800,000, and even more preferably from 20,000 to 600,000. When the (meth)acrylic copolymer (a) has a weight average molecular weight of 10,000 or more, the coatability of the resin dispersion tends to be superior. When the weight average molecular weight of the (meth)acrylic copolymer (a) is 1,000,000 or less, the viscosity of the resin dispersion does not become too high, and the handleability of the resin dispersion tends to be improved.

[0063] The weight average molecular weight of the (meth)acrylic copolymer (a) is a value measured by the following method, specifically, according to the following (1) to (3). (1) A solution of the (meth)acrylic copolymer (a) is applied to a release paper and dried at 100° C. for 1 minute to obtain a film of the (meth)acrylic copolymer (a). (2) Using the film-like (meth)acrylic copolymer (a) obtained in (1) above and tetrahydrofuran, a sample solution having a solid content concentration of 0.2% by mass is obtained. Note that the "solid content concentration" here means the mass ratio of the (meth)acrylic copolymer (a) in the sample solution. (3) The weight average molecular weight of the (meth)acrylic copolymer (a) is determined, in terms of standard polystyrene, by gel permeation chromatography (GPC) under the following conditions:

[0064] ~Conditions~ Measurement equipment: High-speed GPC [Model: HLC-8420 GPC, manufactured by Tosoh Corporation] Detector: Differential refractometer (RI) [installed in HLC-8420, manufactured by Tosoh Corporation] Column: TSKgel GMH XL Two Tosoh products are used. Column temperature: 40℃ Eluent: Tetrahydrofuran Sample solution injection volume: 100 μL Flow rate: 0.8mL / min

[0065] The weight average molecular weight of the (meth)acrylic copolymer (a) can be adjusted to a desired value by adjusting the polymerization temperature, polymerization time, amount of organic solvent used, type of polymerization initiator, amount of polymerization initiator used, etc. when polymerizing the monomer.

[0066] <<Dispersant (A) content>> The content of the dispersant (A) [i.e., the (meth)acrylic copolymer (a)] in the resin dispersion of the present disclosure is not particularly limited, but is, for example, preferably 1 mass % to 30 mass %, more preferably 2 mass % to 25 mass %, and even more preferably 4 mass % to 20 mass %, relative to the total mass of the resin dispersion.

[0067] In the resin dispersion of the present disclosure, the ratio of the mass content of the dispersant (A) to the mass content of the dispersed particles (B) [mass content of the dispersant (A) / mass content of the dispersed particles (B)] is not particularly limited, but from the viewpoint of the oil repellency of the formed film, for example, it is preferably 10 / 90 to 50 / 50, more preferably 20 / 80 to 40 / 60, and even more preferably 25 / 75 to 35 / 65.

[0068] [Method for producing dispersant (A)] The method for producing the dispersant (A) [that is, the (meth)acrylic copolymer (a)] is not particularly limited. The (meth)acrylic copolymer (a) can be produced by polymerizing the above-mentioned monomers by a known polymerization method typified by, for example, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, or a bulk polymerization method. As a polymerization method, a solution polymerization method is preferred in that the treatment steps for preparing the resin dispersion of the present disclosure after production are relatively simple and can be carried out in a short time.

[0069] In the solution polymerization method, a predetermined organic solvent, a monomer, a polymerization initiator, and a chain transfer agent used as required are generally charged into a polymerization tank, and the mixture is heated and reacted for several hours with stirring, for example, at the reflux temperature of the organic solvent. In this case, at least a part of the organic solvent, the monomer, the polymerization initiator, and the chain transfer agent used as required may be added successively. The reaction may also be carried out in a nitrogen gas flow.

[0070] The organic solvent used in the polymerization reaction is preferably the non-aqueous solvent (C) described below, and an organic solvent other than the non-aqueous solvent (C) may be used in combination. Examples of organic solvents other than the nonaqueous solvent (C) used in the polymerization reaction include alcohol solvents (methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, s-butyl alcohol, t-butyl alcohol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), and ester solvents (ethyl acetate, butyl acetate, etc.).

[0071] During the polymerization reaction, only one type of organic solvent may be used, or two or more types may be used.

[0072] Examples of the polymerization initiator include organic peroxides and azo compounds that are used in ordinary solution polymerization methods. Specific examples of organic peroxides include t-butyl peroxy-2-ethylhexanoate [so-called (2-ethylhexanoyl)(t-butyl) peroxide], t-butyl hydroperoxide, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, di-i-propyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-butyl peroxypivalate, 2,2-bis(4, 4-di-t-butylperoxycyclohexyl)propane, 2,2-bis(4,4-di-t-amylperoxycyclohexyl)propane, 2,2-bis(4,4-di-t-octylperoxycyclohexyl)propane, 2,2-bis(4,4-di-α-cumylperoxycyclohexyl)propane, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)butane, and 2,2-bis(4,4-di-t-octylperoxycyclohexyl)butane. Specific examples of azo compounds include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile) (ABVN), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), and 2,2'-azobis(isobutyrate) dimethyl.

[0073] In the polymerization reaction, only one type of polymerization initiator may be used, or two or more types may be used.

[0074] The amount of the polymerization initiator used is not particularly limited, and can be appropriately set depending on, for example, the molecular weight of the desired (meth)acrylic copolymer (a).

[0075] In producing the (meth)acrylic copolymer (a), a chain transfer agent may be used, if necessary. Examples of the chain transfer agent include cyanoacetic acid, alkyl ester compounds of cyanoacetic acid having 1 to 8 carbon atoms, bromoacetic acid, alkyl ester compounds of bromoacetic acid having 1 to 8 carbon atoms, aromatic compounds such as α-methylstyrene, anthracene, phenanthrene, fluorene, and 9-phenylfluorene, aromatic nitro compounds such as p-nitroaniline, nitrobenzene, dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol, and p-nitrotoluene, benzoquinone derivatives such as benzoquinone and 2,3,5,6-tetramethyl-p-benzoquinone, borane derivatives such as tributylborane, carbon tetrabromide, ... Examples of the halogenated hydrocarbon compounds include carbon chloride, 1,1,2,2-tetrabromoethane, tribromoethylene, trichloroethylene, bromotrichloromethane, tribromomethane, and 3-chloro-1-propene, aldehyde compounds such as chloral and furaldehyde, alkyl mercaptan compounds having 1 to 18 carbon atoms, aromatic mercaptan compounds such as thiophenol and toluene mercaptan, mercaptoacetic acid, alkyl ester compounds of mercaptoacetic acid having 1 to 10 carbon atoms, hydroxyalkyl mercaptan compounds having 1 to 12 carbon atoms, and terpene compounds such as pinene and terpinolene.

[0076] When a chain transfer agent is used in producing the (meth)acrylic copolymer (a), the amount of the chain transfer agent used is not particularly limited and can be appropriately set depending on, for example, the molecular weight of the target (meth)acrylic copolymer (a).

[0077] The polymerization temperature is not particularly limited and can be appropriately set depending on, for example, the molecular weight of the desired (meth)acrylic copolymer (a).

[0078] [Dispersed particles (B)] The resin dispersion of the present disclosure contains dispersed particles (B) which are a polymer different from the above-mentioned (meth)acrylic copolymer (a). The resin dispersion of the present disclosure may contain only one type of dispersed particles (B), or may contain two or more types.

[0079] In the resin dispersion of the present disclosure, the dispersed particles (B) are in the form of dispersed particles and are substantially insoluble in the non-aqueous solvent (C). Here, "substantially insoluble in the non-aqueous solvent (C)" means that the dispersed particles (B) have a clear particle shape even when swollen by the non-aqueous solvent (C), and the interface between the dispersed particles (B) and the non-aqueous solvent (C) can be confirmed. Such a state can be confirmed by observation with an optical microscope or by observation using a light scattering method.

[0080] Hereinafter, the "polymer different from the (meth)acrylic copolymer (a)" which is the dispersed particle (B) will also be referred to as "polymer (b)".

[0081] The polymer (b) is a polymer different from the (meth)acrylic copolymer (a) and is not particularly limited in type as long as it is a polymer that takes the form of particles dispersed in the resin dispersion of the present disclosure. The polymer (b) may be a homopolymer or a copolymer. The polymer (b) is, for example, preferably a (meth)acrylic polymer, more preferably a (meth)acrylic copolymer. The structural units that the polymer (b) may contain will be described below.

[0082] <Structural unit (b1) derived from alkyl (meth)acrylate> The polymer (b) preferably contains a structural unit derived from an alkyl (meth)acrylate. In the present disclosure, the "structural unit derived from alkyl (meth)acrylate" contained in polymer (b) is also referred to as "structural unit (b1)". When the polymer (b) contains the structural unit (b1), the dispersion stability of the dispersed particles (B) which are the polymer (b) tends to be improved.

[0083] In the present disclosure, a "structural unit derived from an alkyl (meth)acrylate" refers to a structural unit formed by addition polymerization of an alkyl (meth)acrylate. In addition, the "alkyl (meth)acrylate" in the present disclosure does not include those that fall under the category of monomers having a reactive functional group described below. In other words, when a monomer having a reactive functional group also falls under the category of alkyl (meth)acrylate, it is classified as a monomer having a reactive functional group. For example, 2-hydroxyethyl acrylate, which has a hydroxyl group as a reactive functional group, also falls under the category of alkyl (meth)acrylate, but in the present disclosure, it is classified as a monomer having a reactive functional group.

[0084] The type of alkyl (meth)acrylate is not particularly limited. The alkyl (meth)acrylate may be either an alkyl methacrylate or an alkyl acrylate. The alkyl group of the alkyl (meth)acrylate may be unsubstituted or may have a substituent, but is preferably unsubstituted. The alkyl group in the alkyl (meth)acrylate may be linear, branched, or cyclic. The alkyl moiety of the alkyl (meth)acrylate preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 1 to 8 carbon atoms.

[0085] Specific examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, n-octyl (meth)acrylate, i-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, i-nonyl (meth)acrylate, n-decyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate. The alkyl (meth)acrylate preferably includes at least one selected from the group consisting of methyl methacrylate, ethyl acrylate, n-butyl methacrylate, and 2-ethylhexyl acrylate, and more preferably includes at least one selected from the group consisting of methyl methacrylate, ethyl acrylate, n-butyl methacrylate, and 2-ethylhexyl acrylate.

[0086] When the polymer (b) contains the structural unit (b1), it may contain only one type of the structural unit (b1), or may contain two or more types of the structural unit (b1).

[0087] When the polymer (b) contains the structural unit (b1), the content of the structural unit (b1) is not particularly limited, but for example, relative to all structural units of the polymer (b), it is preferably 50% by mass or more, more preferably in the range of 50% by mass or more and 99.8% by mass or less, even more preferably in the range of 60% by mass or more and 99.8% by mass or less, and particularly preferably in the range of 70% by mass or more and 99.8% by mass or less. When the content of the structural unit (b1) in the polymer (b) is 50 mass % or more based on all structural units of the polymer (b), the dispersed particles (B) which are the polymer (b) tend to be more stably dispersed.

[0088] <Structural unit (b2) derived from polyfunctional monomer> The polymer (b) preferably contains a structural unit derived from a polyfunctional monomer. In the present disclosure, the "structural unit derived from a polyfunctional monomer" contained in the polymer (b) is also referred to as the "structural unit (b2)". When the polymer (b) contains the structural unit (b2), the oil resistance of the film that is formed tends to be improved.

[0089] In the present disclosure, a "structural unit derived from a polyfunctional monomer" refers to a structural unit formed by addition polymerization of a polyfunctional monomer.

[0090] The polyfunctional monomer is not particularly limited as long as it is a monomer having two or more polymerizable groups. Examples of polyfunctional monomers include polyfunctional allyl ether compounds and polyfunctional allyl ester compounds having two or more allyloxy groups, and polyfunctional (meth)acrylic acid ester compounds having two or more (meth)acryloyl groups (so-called polyfunctional (meth)acrylates).

[0091] Specific examples of polyfunctional allyl ether compounds include triallyl cyanurate (TAC), 1,3-diallyloxy-2-propanol, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, and pentaerythritol tetraallyl ether.

[0092] Specific examples of polyfunctional allyl ester compounds include diallyl fumarate, diallyl adipate, triallyl citrate, and diallyl hexahydrophthalate.

[0093] Specific examples of polyfunctional (meth)acrylic acid ester compounds include 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol diacrylate, neopentyl glycol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylethylpropanediol (meth)acrylate, 3-methyl-1,5 pentanediol diacrylate, dimethylol-tricyclodecane diacrylate, EO adduct diacrylate of bisphenol A, PO adduct diacrylate of bisphenol A, neopentyl glycol / hydroxypivalic acid ester diacrylate, and silicone compounds having (meth)acryloyl groups at both ends. trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, and glycerin propoxy triacrylate; tetrafunctional (meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, sorbitol tetra(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate; pentafunctional (meth)acrylate compounds such as sorbitol penta(meth)acrylate and dipentaerythritol penta(meth)acrylate; and hexafunctional (meth)acrylate compounds such as dipentaerythritol hexa(meth)acrylate and sorbitol hexa(meth)acrylate.

[0094] The polyfunctional monomer is preferably a polyfunctional (meth)acrylic acid ester compound, more preferably a bifunctional (meth)acrylate compound, further preferably a silicone compound having (meth)acryloyl groups at both ends, and particularly preferably a reactive silicone represented by the following formula (2).

[0095] [ka]

[0096] In formula (2), R 11 and R 18 each independently represents a hydrogen atom or a methyl group, and is preferably a methyl group.

[0097] In formula (2), R 12 , R 13 , R 14 , R 15 , R 16 and R 17 each independently represents an alkyl group having 1 to 5 carbon atoms or a trialkylsiloxy group having an alkyl group having 1 to 3 carbon atoms. In formula (2), R 12 , R 13 , R 14 , R 15 , R 16 or R 17 The alkyl group represented by the formula (I) may be either linear or branched. In formula (2), R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are each preferably an alkyl group having 1 to 5 carbon atoms, and more preferably, R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are all alkyl groups having one carbon atom (i.e., methyl groups). In formula (2), l represents an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 3. In formula (2), m represents an integer of 0 to 200, and is preferably an integer of 5 to 150. In formula (2), n represents an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 3.

[0098] When the polymer (b) contains a structural unit derived from the reactive silicone represented by formula (2) as the structural unit (b2), the number average molecular weight of the reactive silicone represented by formula (2) in the polymer (b) is not particularly limited, but from the viewpoint of the oil repellency of the film to be formed, it is preferably in the range of 1,000 or more and 15,000 or less, more preferably in the range of 1,000 or more and less than 10,000, even more preferably in the range of 4,000 or more and less than 10,000, and particularly preferably in the range of 4,000 or more and 8,000 or less.

[0099] When the polymer (b) contains a structural unit derived from the reactive silicone represented by formula (2) as the structural unit (b2), the number average molecular weight of the reactive silicone represented by formula (1) in the (meth)acrylic copolymer (a) and the number average molecular weight of the reactive silicone represented by formula (2) in the polymer (b) are preferably such that the number average molecular weight of the reactive silicone represented by formula (1) in the (meth)acrylic copolymer (a) is 8000 or more and the number average molecular weight of the reactive silicone represented by formula (2) in the polymer (b) is 4000 or more and less than 10000, from the viewpoint of the water repellency, oil repellency, and oil resistance of the formed film, and more preferably the number average molecular weight of the reactive silicone represented by formula (1) in the (meth)acrylic copolymer (a) is 10000 or more and the number average molecular weight of the reactive silicone represented by formula (2) in the polymer (b) is 4000 or more and less than 10000.

[0100] In the present disclosure, the number average molecular weight of the reactive silicone represented by formula (2) is measured by the same method as the method for measuring the number average molecular weight of the reactive silicone represented by formula (1) described above. However, when a commercially available product is used as the reactive silicone represented by formula (2), and the catalog of the commercially available product contains the number average molecular weight, the number average molecular weight described in the catalog is used as a priority. In addition, when a commercially available product is used as the reactive silicone represented by formula (2), even if the catalog of the commercially available product does not contain the number average molecular weight, if the catalog contains the functional group equivalent and the number average molecular weight can be calculated, the calculated number average molecular weight is used as a priority.

[0101] When the polymer (b) contains structural units (b2) derived from two or more reactive silicones represented by formula (2) having different number average molecular weights, the "number average molecular weight of the reactive silicone represented by formula (2) in the polymer (b)" means an arithmetic average value, and is calculated in the same manner as the above-mentioned method for calculating the number average molecular weight of the reactive silicone represented by formula (1) in the (meth)acrylic copolymer (a).

[0102] A specific example of the compound represented by formula (2) is Silaplane (registered trademark) FM-7711 [in formula (2), R 11 =R 12 =R 13 =R 14 =R 15 =R 16 =R 17 =R 18 = methyl group, l = 3, n = 3, number average molecular weight (Mn): 1000 (catalog value), manufactured by JNC Corporation], Silaplane (registered trademark) FM-7725 [in formula (2), R 11 =R 12 =R 13 =R 14 =R 15 =R 16 =R 17 =R 18 = methyl group, l = 3, n = 3, number average molecular weight (Mn): 10000 (catalog value), manufactured by JNC Corporation], X-22-164A [in formula (2), R 11 =R12 =R 13 =R 14 =R 15 =R 16 =R 17 =R 18 = methyl group, functional group equivalent: 860 g / mol (catalog value), number average molecular weight: 1720 (calculated value based on functional group equivalent), manufactured by Shin-Etsu Chemical Co., Ltd.], X-22-164C [in formula (2), R 11 =R 12 =R 13 =R 14 =R 15 =R 16 =R 17 =R 18 = methyl group, functional group equivalent: 2400 g / mol (catalog value), number average molecular weight: 4800 (calculated value based on functional group equivalent), manufactured by Shin-Etsu Chemical Co., Ltd.], and X-22-164E [in formula (2), R 11 =R 12 =R 13 =R 14 =R 15 =R 16 =R 17 =R 18 = methyl group, functional group equivalent: 3900 g / mol (catalog value), number average molecular weight: 7800 (calculated value based on functional group equivalent), manufactured by Shin-Etsu Chemical Co., Ltd.

[0103] When the polymer (b) contains the structural unit (b2), it may contain only one type of the structural unit (b2), or may contain two or more types of the structural unit (b2).

[0104] When the polymer (b) contains the structural unit (b2), the content of the structural unit (b2) is not particularly limited, but is, for example, preferably from 0.1% by mass to 20% by mass, more preferably from 0.5% by mass to 15% by mass, and even more preferably from 1% by mass to 10% by mass, relative to all structural units of the polymer (b). When the content of the structural unit (b2) in the polymer (b) is at least 0.1 mass % based on all structural units of the polymer (b), the oil resistance of the film formed tends to be further improved. When the content of the structural unit (b2) in the polymer (b) is 20 mass % or less based on all structural units of the polymer (b), the oil repellency of the formed film tends not to be impaired.

[0105] <Structural units derived from other monomers (b3)> The polymer (b) may contain a structural unit derived from a monomer (so-called other monomer) other than the alkyl (meth)acrylate and the polyfunctional monomer. In the present disclosure, the "structural unit derived from other monomer" contained in the polymer (b) is also referred to as the "structural unit (b3)".

[0106] An example of the structural unit (b3) is a structural unit derived from a monomer having a reactive functional group. When the resin dispersion of the present disclosure contains a crosslinking agent and the polymer (b) which is the dispersed particle (B) contains a structural unit derived from a monomer having a reactive functional group, the reactive group in the polymer (b) reacts with the crosslinking agent, causing interparticle crosslinking of the dispersed particle (B), and the strength of the formed film tends to be increased. Furthermore, when the resin dispersion of the present disclosure contains a crosslinking agent, the (meth)acrylic copolymer (a) which is the dispersant (A) contains a constituent unit derived from a monomer having a reactive functional group, and the polymer (b) which is the dispersed particle (B) contains a constituent unit derived from a monomer having a reactive functional group, in addition to the crosslinking reaction between the reactive group in the polymer (b) and the crosslinking agent, a crosslinking reaction also occurs between the reactive group in the (meth)acrylic copolymer (a) and the reactive group in the polymer (b), and the oil resistance of the formed film tends to be further improved.

[0107] Examples of the structural unit (b3) include structural units derived from (meth)acrylates having an aromatic ring, such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate; structural units derived from alkoxyalkyl (meth)acrylates, such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; structural units derived from vinyl cyanide, such as acrylonitrile and methacrylonitrile; structural units derived from aromatic monovinyls, such as styrene, α-methylstyrene, t-butylstyrene, p-chlorostyrene, chloromethylstyrene, and vinyl toluene; and structural units derived from vinyl esters, such as vinyl formate, vinyl acetate, vinyl propionate, and vinyl versatate.

[0108] When the polymer (b) contains the structural unit (b3), it may contain only one type of the structural unit (b3), or it may contain two or more types of the structural unit (b3).

[0109] When the polymer (b) contains the structural unit (b3), the content of the structural unit (b3) can be set appropriately as long as the effects of the resin dispersion of the present disclosure are not impaired.

[0110] <<Weight average molecular weight of polymer (b)>> The weight average molecular weight (Mw) of the polymer (b) is not particularly limited, but is preferably, for example, 10,000 or more, and more preferably 15,000 or more. When the weight average molecular weight of the polymer (b) is 10,000 or more, the polymer (b) tends to easily maintain the shape of dispersed particles. The upper limit of the weight average molecular weight of the polymer (b) may be, for example, 3,000,000 or less.

[0111] The weight average molecular weight (Mw) of the polymer (b) is measured by the same method as that for the (meth)acrylic copolymer (a) described above.

[0112] The weight average molecular weight of the polymer (b) can be adjusted to a desired value by adjusting the polymerization temperature, polymerization time, amount of organic solvent used, type of polymerization initiator, amount of polymerization initiator used, etc. when polymerizing the monomers.

[0113] <<Average particle size of dispersed particles (B)>> The average particle size of the dispersed particles (B) is not particularly limited, but from the viewpoint of the dispersion stability of the dispersed particles (B), it is preferably 0.1 μm to 5 μm, more preferably 0.2 μm to 3 μm, and even more preferably 0.5 μm to 2 μm.

[0114] In the present disclosure, the "average particle size of dispersed particles (B)" is a value measured by a laser diffraction method, and the particle size distribution of dispersed particles (B) is measured using a laser diffraction type particle size distribution measuring device, and the median size (d50) calculated from the obtained particle size distribution is defined as the average particle size (unit: μm) of dispersed particles (B). The specific measurement method is as follows. The resin dispersion is collected in a 10 mm x 75 mm x 85 mm glass cell using a Pasteur pipette, and this is set in a laser diffraction particle size distribution measurement device. The concentration of the diluted solution of the dispersed particles (B) is adjusted so that the laser light transmittance is 85%, and then the particle size distribution is measured at a measurement temperature of 25°C. The measurement results are processed by computer to determine the median diameter of the dispersed particles (B). Specifically, the particle diameter at an integrated value of 50% (d50) in the obtained particle size distribution is taken as the median diameter. As the laser diffraction type particle size distribution measuring device, for example, "Laser Scattering Particle Size Distribution Analyzer LA-960" manufactured by Horiba, Ltd. can be suitably used. However, the laser diffraction type particle size distribution measuring device is not limited to this.

[0115] The refractive index of the resin dispersion sample is measured according to the A method of JIS K 7142:2014. An Abbe refractometer is used as the measuring device. The refractive index of the dispersion medium is the refractive index of the non-aqueous solvent, and in the case of mineral turpentine, 1.48 is used.

[0116] [Method for producing dispersed particles (B)] The method for producing the dispersed particles (B) [that is, the polymer (b)] is not particularly limited. The polymer (b) can be produced by the same method as the above-mentioned production method for the (meth)acrylic copolymer (a). When the "Method for Producing Resin Dispersion" described later (3) is adopted, the organic solvent used in the polymerization reaction is a non-aqueous solvent (C) containing the (meth)acrylic copolymer (a).

[0117] [Non-aqueous solvent (C)] The resin dispersion of the present disclosure includes a non-aqueous solvent (C). In the resin dispersion of the present disclosure, the non-aqueous solvent (C) functions as a dispersion medium. The non-aqueous solvent (C) is preferably a solvent having low solubility in water, and more preferably a solvent having a solubility in water at 25° C. of 0.05 mass % or less.

[0118] The non-aqueous solvent (C) is not particularly limited as long as it is a good solvent for the (meth)acrylic copolymer (a) which is the dispersant (A) and a poor solvent for the polymer (b) which is the dispersed particles (B).

[0119] It is preferable that the absolute value of the difference between the solubility parameter (also referred to as the "SP value") of the (meth)acrylic copolymer (a) which is the dispersant (A) and the solubility parameter of the non-aqueous solvent (C) is smaller than the absolute value of the difference between the solubility parameter of the polymer (b) which is the dispersed particle (B) and the solubility parameter of the non-aqueous solvent (C). When the non-aqueous solvent (C) is a mixture of two or more kinds, the solubility parameter of the non-aqueous solvent (C) is a weighted average value. The same applies to the solubility parameters of the (meth)acrylic copolymer (a) and the polymer (b). In the present disclosure, the solubility parameter used is the Fedors solubility parameter.

[0120] It is particularly preferable that the non-aqueous solvent (C) is a solvent that can completely dissolve the (meth)acrylic copolymer (a) that is the dispersant (A) and does not dissolve the polymer (b) that is the dispersed particles (B) at all.

[0121] Examples of the non-aqueous solvent (C) include aliphatic hydrocarbon solvents, petroleum-based hydrocarbon solvents, aromatic hydrocarbon solvents, polyol-based solvents, and carbitol-based solvents.

[0122] An example of the aliphatic hydrocarbon solvent is isoparaffin. As the isoparaffin, commercially available products can be used. Examples of commercially available isoparaffins include "IP Solvent 1016," "IP Solvent 1620," "IP Solvent 2028," and "IP Solvent 2835" (all manufactured by Idemitsu Kosan Co., Ltd.), as well as "Isopar C," "Isopar E," "Isopar G," "Isopar H," and "Isopar L" (all manufactured by Exxon Mobil Corporation).

[0123] An example of the petroleum-based hydrocarbon solvent is mineral turpentine. As the mineral turpentine, commercially available products can be used. Examples of commercially available mineral turpentine products include "IPZOL TP" (manufactured by Idemitsu Kosan Co., Ltd.), as well as "Vegasol AN45" and "Vegasol 3040" (all manufactured by Exxon Mobil Corporation).

[0124] Examples of aromatic hydrocarbon solvents include benzene, toluene, ethylbenzene, propylbenzene, t-butylbenzene, o-xylene, m-xylene, and p-xylene. As the aromatic hydrocarbon solvent, commercially available products can be used. Commercially available examples of aromatic hydrocarbon solvents include "Solvesso 100" and "Solvesso 150" (both manufactured by ExxonMobil Corporation). The aromatic hydrocarbon solvent is preferably used in combination with other non-aqueous solvents, for example, for the purpose of increasing the solubility of the (meth)acrylic copolymer (a) which is the dispersant (A) or adjusting the viscosity of the final resin dispersion. When the non-aqueous solvent (C) contains an aromatic hydrocarbon solvent, the proportion of the aromatic hydrocarbon solvent in the non-aqueous solvent (C) is preferably 50 mass% or less, more preferably 40 mass% or less, and even more preferably 30 mass% or less, relative to the total mass of the non-aqueous solvent (C).

[0125] Examples of polyol-based solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether acetate, and propylene glycol monomethyl ether acetate, as well as derivatives thereof.

[0126] Examples of carbitol-based solvents include methyl carbitol, ethyl carbitol, n-propyl carbitol, i-propyl carbitol, n-butyl carbitol, i-butyl carbitol, i-amyl carbitol, phenyl carbitol, benzyl carbitol, diethyl carbitol, butyl carbitol acetate (BCA), and carbitol acetate esters.

[0127] NAD-type resin dispersions are generally used for coating applications. From this viewpoint, mineral turpentine is preferred as the non-aqueous solvent (C).

[0128] The resin dispersion of the present disclosure may contain only one type of non-aqueous solvent (C), or may contain two or more types.

[0129] The content of the nonaqueous solvent (C) in the resin dispersion of the present disclosure is not particularly limited, but for example, it is preferably 35 mass% to 90 mass%, more preferably 40 mass% to 80 mass%, and even more preferably 50 mass% to 70 mass%, relative to the total mass of the resin dispersion. When the content of the nonaqueous solvent (C) in the resin dispersion of the present disclosure is within the above range relative to the total mass of the resin dispersion, the handleability of the resin dispersion when forming a film tends to be better.

[0130] [Crosslinking Agent] The resin dispersion of the present disclosure may include a crosslinking agent. The type of crosslinking agent is not particularly limited. Examples of the crosslinking agent include an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, and a metal chelate-based crosslinking agent. In this disclosure, the term "isocyanate-based crosslinking agent" refers to a compound having two or more isocyanate groups in one molecule (so-called polyisocyanate-based compound). The term "epoxy-based crosslinking agent" refers to a compound having two or more epoxy groups in one molecule (so-called bifunctional or higher epoxy-based compound). The term "metal chelate-based crosslinking agent" refers to a metal chelate-based compound that functions as a crosslinking agent.

[0131] The crosslinking agent is preferably at least one selected from the group consisting of an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, and a metal chelate-based crosslinking agent, and more preferably an isocyanate-based crosslinking agent.

[0132] Examples of the polyisocyanate compound include an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, and an aromatic polyisocyanate compound. The "aliphatic polyisocyanate compound" includes, for example, an aliphatic polyisocyanate compound, a polymer of an aliphatic polyisocyanate compound, an adduct of an aliphatic polyisocyanate compound and a polyol compound (e.g., trimethylolpropane (TMP); the same applies below), and a biuret of an aliphatic polyisocyanate compound. Specific examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate (PDI), tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate. The "alicyclic polyisocyanate compound" includes, for example, an alicyclic polyisocyanate compound, a polymer of an alicyclic polyisocyanate compound, an adduct of an alicyclic polyisocyanate compound and a polyol compound, and a biuret of an alicyclic polyisocyanate compound. Specific examples of the alicyclic polyisocyanate compound include isophorone diisocyanate (IPDI), hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate. The "aromatic polyisocyanate compound" includes, for example, an aromatic polyisocyanate compound, a polymer of an aromatic polyisocyanate compound, an adduct of an aromatic polyisocyanate compound and a polyol compound, and a biuret of an aromatic polyisocyanate compound. Specific examples of the aromatic polyisocyanate compound include tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), and 4,4'-diphenylmethane diisocyanate.

[0133] As the polyisocyanate compound, an aliphatic polyisocyanate compound is preferable, and a hexamethylene diisocyanate compound is more preferable. The "hexamethylene diisocyanate-based compound" includes, for example, HMDI, a polymer of HMDI, an adduct of HMDI and a polyol-based compound, and a biuret of HMDI. As the hexamethylene diisocyanate-based compound, a polymer of HMDI is preferable.

[0134] As the isocyanate-based crosslinking agent, a commercially available product can be used. Examples of commercially available isocyanate crosslinking agents include "Coronate (registered trademark) HX", "Coronate (registered trademark) HL-S", "Coronate (registered trademark) L", "Coronate (registered trademark) L-45E", "Coronate (registered trademark) 2031", "Coronate (registered trademark) 2037", "Coronate (registered trademark) 2234", "Coronate (registered trademark) 2785", "Aquanate (registered trademark) 200", and "Aquanate (registered trademark) 210" (all manufactured by Tosoh Corporation), "Sumidur (registered trademark) N3300", "Desmodur (registered trademark) N3400", and "Sumidur (registered trademark) N75" (all manufactured by Sumika Covestro Urethane Co., Ltd.), "Duranate (registered trademark) D201", "Duranate (registered trademark) E405-70B", "Duranate (registered trademark) E405-80T", "Duranate (registered trademark) AE700-100, "Duranate (registered trademark) 24A-100, "Duranate (registered trademark) TSA-100, and "Duranate (registered trademark) TSE-100" (all manufactured by Asahi Kasei Corporation), as well as "Takenate (registered trademark) D-110N", "Takenate (registered trademark) D-101", "Takenate (registered trademark) D-120N", "Takenate (registered trademark) D-140N", "Takenate (registered trademark) M-631N", "MT-Olestar (registered trademark) NP1200", and "STABIO (registered trademark) XD-340N" (all manufactured by Mitsui Chemicals, Inc.).

[0135] Examples of epoxy compounds having two or more functionalities include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, diglycerol polyglycidyl ether, poly triglycidyl ether, resorcinol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, tris(glycidyl)isocyanurate, tris(glycidoxyethyl)isocyanurate, 1,3-bis(N,N-glycidylaminomethyl)cyclohexane, and N,N,N',N'-tetraglycidyl-1,3-benzenedi(methanamine).

[0136] As the epoxy-based crosslinking agent, a commercially available product can be used. Examples of commercially available epoxy crosslinking agents include "TETRAD (registered trademark)-X" and "TETRAD (registered trademark)-C" (both manufactured by Mitsubishi Gas Chemical Company, Inc.), as well as "Denacol (registered trademark) EX-201" and "Denacol (registered trademark) EX-931" (both manufactured by Nagase ChemteX Corporation).

[0137] Examples of metal chelate compounds include aluminum chelate compounds such as aluminum monoacetylacetonate bis(ethylacetoacetate), aluminum tris(ethylacetoacetate), and aluminum tris(acetylacetonate), titanium chelate compounds, zirconium chelate compounds, and cobalt chelate compounds.

[0138] As the metal chelate crosslinking agent, commercially available products can be used. Examples of commercially available metal chelate crosslinking agents include "Aluminum Chelate A," "Aluminum Chelate D," and "ALCH-TR" (all manufactured by Kawaken Fine Chemicals Co., Ltd.).

[0139] When the resin dispersion of the present disclosure contains a crosslinking agent, it may contain only one type of crosslinking agent, or may contain two or more types of crosslinking agents.

[0140] When the resin dispersion of the present disclosure contains a crosslinking agent, the content of the crosslinking agent is not particularly limited. The content of the crosslinking agent in the resin dispersion of the present disclosure may be, for example, 0.1 parts by mass to 10.0 parts by mass, 0.5 parts by mass to 8.0 parts by mass, or 1.0 parts by mass to 5.0 parts by mass, relative to 100 parts by mass in total of the (meth)acrylic copolymer (a) and the polymer (b).

[0141] The crosslinking agent may be included as a component of the resin dispersion of the present disclosure, but may not be a component included in the resin dispersion of the present disclosure, but may be a component used in combination with the resin dispersion of the present disclosure. When using a crosslinking agent, for example, the resin dispersion of the present disclosure does not include a crosslinking agent as a component, and the resin dispersion of the present disclosure and the crosslinking agent are mixed immediately before imparting water and oil repellency to the object, and the resulting mixed liquid is applied to the object.

[0142] [Other ingredients] The resin dispersion of the present disclosure may contain components other than the components already described (so-called other components) as necessary. Examples of other components include various additives such as ultraviolet absorbers, fillers, viscosity adjusters, thickeners, and pigments.

[0143] When the resin dispersion of the present disclosure contains other components, the content of the other components can be appropriately set within a range that does not impair the effects of the resin dispersion of the present disclosure.

[0144] <<Applications of resin dispersion>> The resin dispersion of the present disclosure is a resin dispersion used for water and oil repellents (i.e., a resin dispersion for water and oil repellents). The resin dispersion of the present disclosure is suitable for use in water and oil repellents because it has both water repellency and oil repellency. The resin dispersion of the present disclosure also has oil resistance, and preferred applications include, for example, water and oil repellents used in coating agents, paints, etc., or raw materials for water and oil repellents.

[0145] [Water and oil repellent] The water / oil repellent of the present disclosure contains the resin dispersion of the present disclosure described above. The water / oil repellent of the present disclosure may be composed of the resin dispersion of the present disclosure, or may be composed of the resin dispersion of the present disclosure containing various additives. Additives that may be contained in the water / oil repellent of the present disclosure include crosslinking agents, film-forming assistants, and the like.

[0146] [Method of manufacturing resin dispersion] The method for producing the resin dispersion of the present disclosure is not particularly limited. Examples of methods for producing the resin dispersion of the present disclosure include the methods described in [1], [2], and [3] below. [1] A method for obtaining a resin dispersion by dispersing dispersed particles (B) which are a polymer (b) in a non-aqueous solvent (C) in which a dispersant (A) which is a (meth)acrylic copolymer (a) is dissolved. [2] A method in which dispersed particles (B), which are a polymer (b), are dispersed in a non-aqueous solvent (C), and then a dispersant (A), which is a (meth)acrylic copolymer (a), is added and dissolved to obtain a resin dispersion. [3] A method of producing a dispersant (A) which is a (meth)acrylic copolymer (a) by polymerizing at least a reactive silicone represented by formula (1), a (meth)acrylate having a cyclic structure, and an alkyl (meth)acrylate not having a cyclic structure in a non-aqueous solvent (C), and then producing dispersed particles (B) by polymerizing a monomer for forming a polymer (b) in the non-aqueous solvent (C) containing the dispersant (A) to obtain a resin dispersion. Among these, the above method [3] is preferred as the method for producing the resin dispersion of the present disclosure from the viewpoint of industrial productivity. EXAMPLES

[0147] The resin dispersion of the present disclosure will be described in more detail below with reference to examples. The present disclosure is not limited to the following examples as long as it does not deviate from the gist of the disclosure.

[0148] [Production of resin dispersion] Example 1 1. Preparation of dispersant solution Into a reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser, 4.1 parts by mass of 2-ethylhexyl methacrylate (2EHMA) [alkyl methacrylate having no cyclic structure, number of carbons in the alkyl moiety: 8], 6.3 parts by mass of i-butyl methacrylate (i-BMA) [alkyl methacrylate having no cyclic structure, number of carbons in the alkyl moiety: 4], 1.4 parts by mass of t-butyl methacrylate (t-BMA) [alkyl methacrylate having no cyclic structure, number of carbons in the alkyl moiety: 4], 0.27 parts by mass of ARONIX (registered trademark) M-5300 [product name, components: ω-carboxy-polycaprolactone (n≒2) monoacrylate, monomer having a reactive functional group, reactive functional group: carboxy group, manufactured by Toagosei Co., Ltd.], 0.34 parts by mass of benzyl methacrylate (BZMA) [methacrylate having a cyclic structure], and Silaplane (registered trademark) were added. 1.4 parts by mass of FM-0725 (product name, reactive silicone represented by formula (1), manufactured by JNC Corporation), 11.1 parts by mass of mineral turpentine (non-aqueous solvent), and 0.01 parts by mass of (2-ethylhexanoyl)(t-butyl)peroxide (polymerization initiator) were added, and the atmosphere in the reactor was replaced with nitrogen while stirring. Then, the mixture in the reactor was heated to 90°C while stirring. After maintaining the temperature in the reactor for 30 minutes, a mixture of 3.4 parts by mass of 2-ethylhexyl methacrylate (2EHMA), 5.1 parts by mass of i-butyl methacrylate (i-BMA), 1.1 parts by mass of t-butyl methacrylate (t-BMA), 0.22 parts by mass of Aronix (registered trademark) M-5300, 0.28 parts by mass of benzyl methacrylate (BZMA), 1.1 parts by mass of Silaplane (registered trademark) FM-0725, 13.9 parts by mass of mineral turpentine, and 0.01 parts by mass of (2-ethylhexanoyl)(t-butyl)peroxide was successively added dropwise to the mixture in the reactor over a period of 120 minutes. After the dropwise addition, the mixture was held for 60 minutes to allow polymerization, and then a mixture of 41.6 parts by mass of mineral turpentine and 0.07 parts by mass of (2-ethylhexanoyl)(t-butyl)peroxide was successively dropped over 60 minutes. After the dropwise addition, the mixture was held for another 90 minutes to allow polymerization, and a polymerization reaction product was obtained. The obtained polymerization reaction product was diluted with mineral turpentine to adjust the solid content concentration to 25.0% by mass.In this manner, a dispersant solution containing a (meth)acrylic copolymer as a dispersant was obtained.

[0149] 2. Manufacturing of resin dispersion In a reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser, 12.0 parts by mass of the dispersant solution obtained above was placed, and then the inside of the reactor was replaced with nitrogen. Then, the dispersant solution A-1 in the reactor was heated to 90°C while stirring. Next, a mixture of 16.0 parts by mass of ethyl acrylate (EA) [alkyl acrylate], 5.4 parts by mass of methyl methacrylate (MMA) [alkyl methacrylate], 5.6 parts by mass of n-butyl methacrylate (nBMA) [alkyl methacrylate], 24.9 parts by mass of mineral turpentine, and 0.11 parts by mass of (2-ethylhexanoyl) (t-butyl) peroxide [polymerization initiator] was successively dropped over 180 minutes into the dispersant solution A-1 in the reactor whose liquid temperature was kept at 90°C. After the dropwise addition, the mixture was held for 60 minutes to allow polymerization, and then a mixture of 8.2 parts by mass of mineral turpentine and 0.03 parts by mass of (2-ethylhexanoyl)(t-butyl)peroxide was successively dropped over 60 minutes. After the dropwise addition, the mixture was held for another 120 minutes to allow polymerization, and a polymerization reaction product was obtained. The obtained polymerization reaction product was diluted with mineral turpentine to adjust the solid content concentration to 30.0% by mass. In this manner, the resin dispersion of Example 1 was obtained.

[0150] Example 2 1. Preparation of dispersant solution The same operation as in Example 1 was carried out to obtain a dispersant solution (solid content concentration: 25.0% by mass) containing a (meth)acrylic copolymer as a dispersant.

[0151] 2. Manufacturing of resin dispersion The same operation as in Example 1 was carried out except that the amount of the dispersant solution put into the reactor was changed from "12.0 parts by mass" to "26.9 parts by mass" in Example 1, thereby obtaining a resin dispersion of Example 2 (solid content concentration: 30.0% by mass).

[0152] Example 3 1. Preparation of dispersant solution The same operation as in Example 1 was carried out to obtain a dispersant solution (solid content concentration: 25.0% by mass) containing a (meth)acrylic copolymer as a dispersant.

[0153] 2. Manufacturing of resin dispersion The same operation as in Example 1 was carried out except that the amount of the dispersant solution put into the reactor was changed from "12.0 parts by mass" to "46.1 parts by mass" in Example 1, thereby obtaining a resin dispersion of Example 3 (solid content concentration: 30.0% by mass).

[0154] Example 4 1. Preparation of dispersant solution The same operation as in Example 1 was carried out to obtain a dispersant solution (solid content concentration: 25.0% by mass) containing a (meth)acrylic copolymer as a dispersant.

[0155] 2. Manufacturing of resin dispersion The same operation as in Example 1 was carried out except that the amount of the dispersant solution put into the reactor was changed from "12.0 parts by mass" to "71.7 parts by mass" in Example 1, thereby obtaining a resin dispersion of Example 4 (solid content concentration: 30.0% by mass).

[0156] Example 5 1. Preparation of dispersant solution The same operation as in Example 1 was carried out to obtain a dispersant solution (solid content concentration: 25.0% by mass) containing a (meth)acrylic copolymer as a dispersant.

[0157] 2. Manufacturing of resin dispersion The same procedure as in Example 3 was carried out except that the monomer composition of the polymer, which is the dispersed particles, was changed to the monomer composition shown in Table 1, thereby obtaining a resin dispersion liquid of Example 5 (solid content concentration: 30.0% by mass).

[0158] Example 6 1. Preparation of dispersant solution The same operation as in Example 1 was carried out to obtain a dispersant solution (solid content concentration: 25.0% by mass) containing a (meth)acrylic copolymer as a dispersant.

[0159] 2. Manufacturing of resin dispersion The same procedure as in Example 3 was carried out except that the monomer composition of the polymer, which is the dispersed particles, was changed to the monomer composition shown in Table 1, thereby obtaining a resin dispersion liquid of Example 6 (solid content concentration: 30.0% by mass).

[0160] Example 7 1. Preparation of dispersant solution The same operation as in Example 1 was carried out to obtain a dispersant solution (solid content concentration: 25.0% by mass) containing a (meth)acrylic copolymer as a dispersant.

[0161] 2. Manufacturing of resin dispersion The same procedure as in Example 3 was carried out except that the monomer composition of the polymer, which is the dispersed particles, was changed to the monomer composition shown in Table 1, thereby obtaining a resin dispersion liquid of Example 7 (solid content concentration: 30.0% by mass).

[0162] Example 8 1. Preparation of dispersant solution The same operation as in Example 1 was carried out to obtain a dispersant solution (solid content concentration: 25.0% by mass) containing a (meth)acrylic copolymer as a dispersant.

[0163] 2. Manufacturing of resin dispersion The same procedure as in Example 3 was carried out except that the monomer composition of the polymer, which is the dispersed particles, was changed to the monomer composition shown in Table 1, thereby obtaining a resin dispersion liquid of Example 8 (solid content concentration: 30.0% by mass).

[0164] Example 9 1. Preparation of dispersant solution The same operation as in Example 1 was carried out to obtain a dispersant solution (solid content concentration: 25.0% by mass) containing a (meth)acrylic copolymer as a dispersant.

[0165] 2. Manufacturing of resin dispersion The same procedure as in Example 3 was carried out except that the monomer composition of the polymer, which is the dispersed particles, was changed to the monomer composition shown in Table 1, thereby obtaining a resin dispersion liquid of Example 9 (solid content concentration: 30.0% by mass).

[0166] Example 10 1. Preparation of dispersant solution The same operation as in Example 1 was carried out to obtain a dispersant solution (solid content concentration: 25.0% by mass) containing a (meth)acrylic copolymer as a dispersant.

[0167] 2. Manufacturing of resin dispersion The same procedure as in Example 3 was carried out except that the monomer composition of the polymer, which is the dispersed particles, was changed to the monomer composition shown in Table 1, thereby obtaining a resin dispersion liquid of Example 10 (solid content concentration: 30.0% by mass).

[0168] Example 11 1. Preparation of dispersant solution The same operation as in Example 1 was carried out to obtain a dispersant solution (solid content concentration: 25.0% by mass) containing a (meth)acrylic copolymer as a dispersant.

[0169] 2. Manufacturing of resin dispersion The same procedure as in Example 3 was carried out except that the monomer composition of the polymer, which is the dispersed particles, was changed to the monomer composition shown in Table 1, thereby obtaining a resin dispersion liquid of Example 11 (solid content concentration: 30.0% by mass).

[0170] Example 12 1. Preparation of dispersant solution The same operation as in Example 1 was carried out to obtain a dispersant solution (solid content concentration: 25.0% by mass) containing a (meth)acrylic copolymer as a dispersant.

[0171] 2. Manufacturing of resin dispersion The same procedure as in Example 3 was carried out except that the monomer composition of the polymer, which is the dispersed particles, was changed to the monomer composition shown in Table 1, thereby obtaining a resin dispersion of Example 12 (solid concentration: 30.0% by mass).

[0172] Example 13 1. Preparation of dispersant solution In Example 1, except that the monomer composition of the (meth)acrylic copolymer as the dispersant was changed to the monomer composition shown in Table 1, the same operation as in Example 1 was performed to obtain a dispersant solution (solid content concentration: 25.0 mass%) containing the (meth)acrylic copolymer as a dispersant.

[0173] 2. Manufacturing of resin dispersion The same operation as in Example 10 was carried out except for using the dispersant solution obtained above, to obtain a resin dispersion of Example 13 (solid content concentration: 30.0% by mass).

[0174] Example 14 1. Preparation of dispersant solution In Example 1, except that the monomer composition of the (meth)acrylic copolymer as the dispersant was changed to the monomer composition shown in Table 1, the same operation as in Example 1 was performed to obtain a dispersant solution (solid content concentration: 25.0 mass%) containing the (meth)acrylic copolymer as a dispersant.

[0175] 2. Manufacturing of resin dispersion The same operation as in Example 10 was carried out except for using the dispersant solution obtained above, to obtain a resin dispersion of Example 14 (solid content concentration: 30.0% by mass).

[0176] Example 15 1. Preparation of dispersant solution In Example 1, except that the monomer composition of the (meth)acrylic copolymer as the dispersant was changed to the monomer composition shown in Table 1, the same operation as in Example 1 was performed to obtain a dispersant solution (solid content concentration: 25.0 mass%) containing the (meth)acrylic copolymer as a dispersant.

[0177] 2. Manufacturing of resin dispersion The same operation as in Example 10 was carried out except for using the dispersant solution obtained above, to obtain a resin dispersion of Example 15 (solid content concentration: 30.0% by mass).

[0178] Example 16 1. Preparation of dispersant solution In Example 1, except that the monomer composition of the (meth)acrylic copolymer as the dispersant was changed to the monomer composition shown in Table 1, the same operation as in Example 1 was performed to obtain a dispersant solution (solid content concentration: 25.0 mass%) containing the (meth)acrylic copolymer as a dispersant.

[0179] 2. Manufacturing of resin dispersion The same operation as in Example 10 was carried out except for using the dispersant solution obtained above, to obtain a resin dispersion of Example 16 (solid content concentration: 30.0% by mass).

[0180] Example 17 1. Preparation of dispersant solution In Example 1, except that the monomer composition of the (meth)acrylic copolymer as the dispersant was changed to the monomer composition shown in Table 1, the same operation as in Example 1 was performed to obtain a dispersant solution (solid content concentration: 25.0 mass%) containing the (meth)acrylic copolymer as a dispersant.

[0181] 2. Manufacturing of resin dispersion The same operation as in Example 10 was carried out except for using the dispersant solution obtained above, to obtain a resin dispersion of Example 17 (solid content concentration: 30.0% by mass).

[0182] Example 18 1. Preparation of dispersant solution The same operation as in Example 15 was carried out to obtain a dispersant solution (solid content concentration: 25.0% by mass) containing a (meth)acrylic copolymer as a dispersant.

[0183] 2. Manufacturing of resin dispersion The same procedure as in Example 3 was carried out except that the monomer composition of the polymer, which is the dispersed particles, was changed to the monomer composition shown in Table 1, thereby obtaining a resin dispersion of Example 18 (solid content concentration: 30.0% by mass).

[0184] Example 19 1. Preparation of dispersant solution The same operation as in Example 15 was carried out to obtain a dispersant solution (solid content concentration: 25.0% by mass) containing a (meth)acrylic copolymer as a dispersant.

[0185] 2. Manufacturing of resin dispersion The same procedure as in Example 3 was carried out except that the monomer composition of the polymer, which is the dispersed particles, was changed to the monomer composition shown in Table 1, thereby obtaining a resin dispersion liquid of Example 19 (solid content concentration: 30.0% by mass).

[0186] Example 20 1. Preparation of dispersant solution The same operation as in Example 1 was carried out to obtain a dispersant solution (solid content concentration: 25.0% by mass) containing a (meth)acrylic copolymer as a dispersant.

[0187] 2. Manufacturing of resin dispersion The same procedure as in Example 3 was carried out except that the monomer composition of the polymer, which is the dispersed particles, was changed to the monomer composition shown in Table 1, thereby obtaining a resin dispersion of Example 20 (solid content concentration: 30.0% by mass).

[0188] Example 21 1. Preparation of dispersant solution In Example 1, except that the monomer composition of the (meth)acrylic copolymer as the dispersant was changed to the monomer composition shown in Table 1, the same operation as in Example 1 was performed to obtain a dispersant solution (solid content concentration: 25.0 mass%) containing the (meth)acrylic copolymer as a dispersant.

[0189] 2. Manufacturing of resin dispersion The same operation as in Example 10 was carried out except for using the dispersant solution obtained above, to obtain a resin dispersion of Example 21 (solid content concentration: 30.0% by mass).

[0190] Example 22 1. Preparation of dispersant solution In Example 1, except that the monomer composition of the (meth)acrylic copolymer as the dispersant was changed to the monomer composition shown in Table 1, the same operation as in Example 1 was performed to obtain a dispersant solution (solid content concentration: 25.0 mass%) containing the (meth)acrylic copolymer as a dispersant.

[0191] 2. Manufacturing of resin dispersion The same operation as in Example 10 was carried out except for using the dispersant solution obtained above, to obtain a resin dispersion of Example 22 (solid content concentration: 30.0% by mass).

[0192] Example 23 1. Preparation of dispersant solution In Example 1, except that the monomer composition of the (meth)acrylic copolymer as the dispersant was changed to the monomer composition shown in Table 1, the same operation as in Example 1 was performed to obtain a dispersant solution (solid content concentration: 25.0 mass%) containing the (meth)acrylic copolymer as a dispersant.

[0193] 2. Manufacturing of resin dispersion The same operation as in Example 10 was carried out except for using the dispersant solution obtained above, to obtain a resin dispersion of Example 23 (solid content concentration: 30.0% by mass).

[0194] Example 24 1. Preparation of dispersant solution In Example 1, except that the monomer composition of the (meth)acrylic copolymer as the dispersant was changed to the monomer composition shown in Table 1, the same operation as in Example 1 was performed to obtain a dispersant solution (solid content concentration: 25.0 mass%) containing the (meth)acrylic copolymer as a dispersant.

[0195] 2. Manufacturing of resin dispersion The same operation as in Example 10 was carried out except for using the dispersant solution obtained above, to obtain a resin dispersion of Example 24 (solid content concentration: 30.0% by mass).

[0196] The weight average molecular weight of the (meth)acrylic copolymer, which is the dispersant contained in each of the resin dispersions of Examples 1 to 24, was measured by a method similar to the method for measuring the weight average molecular weight of the specific (meth)acrylic copolymer described above, and all were within the range of 100,000 to 300,000. Furthermore, the average particle diameters of the dispersed particles were measured by the same method as the above-mentioned method for measuring the average particle diameter of the dispersed particles, and all were within the range of 0.5 μm to 1.5 μm.

[0197] Comparative Example 1 1. Preparation of dispersant solution In Example 1, the same operation as in Example 1 was performed except that the monomer composition of the (meth)acrylic copolymer as the dispersant was changed to the monomer composition shown in Table 2, thereby obtaining a dispersant solution (solid content concentration: 25.0 mass%) containing the (meth)acrylic copolymer as a dispersant.

[0198] 2. Manufacturing of resin dispersion The same operation as in Example 3 was carried out except for using the dispersant solution obtained above, to obtain a resin dispersion of Comparative Example 1 (solid content concentration: 30.0% by mass).

[0199] Comparative Example 2 1. Preparation of dispersant solution In Example 1, the same operation as in Example 1 was performed except that the monomer composition of the (meth)acrylic copolymer as the dispersant was changed to the monomer composition shown in Table 2, thereby obtaining a dispersant solution (solid content concentration: 25.0 mass%) containing the (meth)acrylic copolymer as a dispersant.

[0200] 2. Manufacturing of resin dispersion The same operation as in Example 3 was carried out except for using the dispersant solution obtained above, to obtain a resin dispersion of Comparative Example 2 (solid content concentration: 30.0% by mass).

[0201] Comparative Example 3 1. Preparation of dispersant solution In Example 1, the same operation as in Example 1 was performed except that the monomer composition of the (meth)acrylic copolymer as the dispersant was changed to the monomer composition shown in Table 2, thereby obtaining a dispersant solution (solid content concentration: 25.0 mass%) containing the (meth)acrylic copolymer as a dispersant.

[0202] 2. Manufacturing of resin dispersion The same operation as in Example 3 was carried out except for using the dispersant solution obtained above, to obtain a resin dispersion of Comparative Example 3 (solid content concentration: 30.0% by mass).

[0203] Comparative Example 4 1. Preparation of dispersant solution In Example 1, the same operation as in Example 1 was performed except that the monomer composition of the (meth)acrylic copolymer as the dispersant was changed to the monomer composition shown in Table 2, thereby obtaining a dispersant solution (solid content concentration: 25.0 mass%) containing the (meth)acrylic copolymer as a dispersant.

[0204] 2. Manufacturing of resin dispersion The same operation as in Example 10 was carried out except for using the dispersant solution obtained above, to obtain a resin dispersion of Comparative Example 4 (solid content concentration: 30.0% by mass).

[0205] Comparative Example 5 1. Preparation of dispersant solution In Example 1, the same operation as in Example 1 was performed except that the monomer composition of the (meth)acrylic copolymer as the dispersant was changed to the monomer composition shown in Table 2, thereby obtaining a dispersant solution (solid content concentration: 25.0 mass%) containing the (meth)acrylic copolymer as a dispersant.

[0206] 2. Manufacturing of resin dispersion The same operation as in Example 10 was carried out except for using the dispersant solution obtained above, to obtain a resin dispersion of Comparative Example 5 (solid content concentration: 30.0% by mass).

[0207] The resin dispersions of Examples 1 to 24 and Comparative Examples 1 to 5 all contain a (meth)acrylic copolymer as a dispersant, a polymer as dispersed particles, and mineral turpentine as a non-aqueous solvent, with the polymer as dispersed particles being dispersed in a mineral turpentine solution of the (meth)acrylic copolymer as a dispersant.

[0208] The monomer composition (unit: mass%) of the (meth)acrylic copolymer serving as the dispersant, the monomer composition (unit: mass%) of the polymer serving as the dispersed particles, and the mass ratio of the dispersant to the dispersed particles (dispersant / dispersed particles) contained in each of the resin dispersions of Examples 1 to 24 and Comparative Examples 1 to 5 are shown in Tables 1 and 2. In Tables 1 and 2, "-" in the columns for the monomer composition of the (meth)acrylic copolymer serving as the dispersant and the monomer composition of the polymer serving as the dispersed particles means that the monomer in that column was not used.

[0209] [Table 1]

[0210] [Table 2]

[0211] Details of each monomer listed in the column of the monomer composition of the (meth)acrylic copolymer in Tables 1 and 2 are as follows. <Alkyl (meth)alkyl acrylate not having a cyclic structure> "2EHMA": 2-ethylhexyl methacrylate (number of carbon atoms in the alkyl portion: 8) "i-BMA": i-butyl methacrylate (number of carbon atoms in the alkyl portion: 4) "t-BMA": t-butyl methacrylate (number of carbon atoms in the alkyl portion: 4) <Monomers having reactive functional groups> "M-5300": Aronix (registered trademark) M-5300 [Component: ω-carboxy-polycaprolactone (n≒2) monoacrylate, reactive functional group: carboxy group, manufactured by Toagosei Co., Ltd.] <(Meth)acrylate Having a Cyclic Structure> "BZMA": Benzyl methacrylate "IBXMA": Isobornyl methacrylate <Reactive silicone represented by formula (1)> "FM-0711": Silaplane (registered trademark) FM-0711 [number average molecular weight: 1000 (catalog value), manufactured by JNC Corporation] "FM-0721": Silaplane (registered trademark) FM-0721 [number average molecular weight: 5000 (catalog value), manufactured by JNC Corporation] "FM-0725": Silaplane (registered trademark) FM-0725 [number average molecular weight: 10,000 (catalog value), manufactured by JNC Corporation]

[0212] Details of each monomer listed in the column of the monomer composition of the polymer in Table 1 are as follows. <Alkyl (meth)alkyl acrylate> "EA": Ethyl acrylate "MMA": Methyl methacrylate "n-BMA": n-butyl methacrylate "2EHA": 2-Ethylhexyl acrylate <Monomers having reactive functional groups> "MAA": methacrylic acid (reactive functional group: carboxy group) <Polyfunctional Monomer> "FM-7711": Silaplane (registered trademark) FM-7711 [number average molecular weight: 1000 (catalog value), reactive silicone represented by formula (2), manufactured by JNC Corporation] "FM-7725": Silaplane (registered trademark) FM-7725 [number average molecular weight: 10,000 (catalog value), reactive silicone represented by formula (2), manufactured by JNC Corporation] "X-22-164A": X-22-164A (model number) [functional group equivalent: 860 g / mol (catalog value), number average molecular weight: 1720 (calculated value based on functional group equivalent), reactive silicone represented by formula (2), manufactured by Shin-Etsu Chemical Co., Ltd.] "X-22-164C": X-22-164C (model number) [functional group equivalent: 2400 g / mol (catalog value), number average molecular weight: 4800 (calculated value based on functional group equivalent), reactive silicone represented by formula (2), manufactured by Shin-Etsu Chemical Co., Ltd.] "X-22-164E": X-22-164E (model number) [functional group equivalent: 3900 g / mol (catalog value), number average molecular weight: 7800 (calculated value based on functional group equivalent), reactive silicone represented by formula (2), manufactured by Shin-Etsu Chemical Co., Ltd.] "EGDM": Ethylene glycol dimethacrylate [molecular weight: 198.22, manufactured by Mitsubishi Chemical Corporation]

[0213] [evaluation] 1.Water repellency (1) Film formation (1-1) Resin dispersions of Examples 1 to 9, 11 to 19, 21 to 24, and Comparative Examples 1 to 5 The resin dispersion was applied onto a polyethylene terephthalate (PET) film using an 8 mil (≒ 203.2 μm) applicator to form a coating film. The coating film was then dried using a hot air circulation dryer at a heating temperature of 100°C for a heating time of 5 minutes to form a coating film on the PET film.

[0214] (1-2) Resin dispersion of Example 10 The resin dispersion was applied onto a polyethylene terephthalate (PET) film using an 8 mil (≒ 203.2 μm) applicator to form a coating film. The coating film was then dried using a hot air circulation dryer at a heating temperature of 100°C for a heating time of 5 minutes to form a coating film on the PET film.

[0215] In addition, a film was formed using a crosslinking agent. Duranate (registered trademark) TSA-100 (trade name, isocyanate-based crosslinking agent, hexamethylene diisocyanate (HMDI), manufactured by Mitsui Chemicals, Inc.) was added to the resin dispersion in an amount of 4 parts by mass (solid content equivalent) per 100 parts by mass of the resin content (i.e., the total of (meth)acrylic copolymer and polymer) contained in the resin dispersion and mixed. The resulting mixture was applied to a polyethylene terephthalate (PET) film using an 8 mil (≒ 203.2 μm) applicator to form a coating film. The formed coating film was then dried using a hot air circulation dryer under conditions of a heating temperature of 100°C and a heating time of 5 minutes. The dried coating film was then aged for 3 days in an environment with an atmospheric temperature of 40°C to form a coating film on the PET film.

[0216] (1-3) Resin dispersion of Example 20 "Duranate (registered trademark) TSA-100" [product name, isocyanate-based crosslinking agent, hexamethylene diisocyanate (HMDI), manufactured by Mitsui Chemicals, Inc.] was added to the resin dispersion in an amount of 4 parts by mass (solid content equivalent) per 100 parts by mass of the resin content [i.e., the total of (meth)acrylic copolymer and polymer] contained in the resin dispersion and mixed. The resulting mixture was applied to a polyethylene terephthalate (PET) film using an 8 mil (≒ 203.2 μm) applicator to form a coating film. The formed coating film was then dried using a hot air circulation dryer under conditions of a heating temperature of 100°C and a heating time of 5 minutes. The dried coating film was then aged for 3 days in an environment with an atmospheric temperature of 40°C to form a film on the PET film.

[0217] (2) Measurement of water contact angle Deionized water was dropped onto the surface of the coating formed above, and the contact angle of water was measured using a contact angle measuring device (device name: fully automatic contact angle meter DM-701, manufactured by Kyowa Interface Science Co., Ltd.). The 2θ method was used to calculate the contact angle of water. Evaluation was performed according to the following evaluation criteria. The results are shown in Tables 3 and 4. In the following evaluation criteria, "A" and "B" are practically acceptable levels, with "A" being the most preferable.

[0218] -Evaluation criteria- A: The contact angle of water is 110° or more. B: The contact angle of water is 100° or more and less than 110°. C: The contact angle of water is less than 100°.

[0219] 2.Oil repellency (1) Film formation A film was formed on a PET film by the same procedure as in "(1) Formation of film" in "1. Water repellency" above.

[0220] (2) Measurement of the contact angle of hexadecane Hexadecane was dropped onto the surface of the coating formed above, and the contact angle of hexadecane was measured using a contact angle measuring device (device name: fully automatic contact angle meter DM-701, manufactured by Kyowa Interface Science Co., Ltd.). The 2θ method was used to calculate the contact angle of hexadecane. Evaluation was performed according to the following evaluation criteria. The results are shown in Tables 3 and 4. In the following evaluation criteria, "A" and "B" are practically acceptable levels, with "A" being the most preferable.

[0221] -Evaluation criteria- A: The contact angle of hexadecane is 40° or more. B: The contact angle of hexadecane is 30° or more and less than 40°. C: The contact angle of hexadecane is less than 30°.

[0222] 3.Oil resistance (1) Film formation A film was formed on a PET film by the same procedure as in "(1) Formation of film" in "1. Water repellency" above.

[0223] (2) Evaluation test After dropping hexadecane onto the surface of the coating film formed above, it was left as it is for 5 minutes. After leaving it, the dropped hexadecane was lightly wiped off, and the state of the coating film was visually confirmed. Then, it was evaluated according to the following evaluation criteria. The results are shown in Tables 3 and 4. In the following evaluation criteria, "AA" is the most preferable.

[0224] -Evaluation criteria- AA: The film remains completely after the hexadecane is wiped off. A: The film is seen to dissolve, but most of the film remains after the hexadecane is wiped off. B: The film is seen to dissolve, but some of the film remains after the hexadecane is wiped off. C: The film was dissolved, and no film remained after wiping off the hexadecane.

[0225] [Table 3]

[0226] [Table 4]

[0227] The results shown in Table 3 reveal that the films formed from the resin dispersions of Examples 1 to 24 have both water repellency and oil repellency. On the other hand, as shown in Table 4, it was confirmed that the films formed using the resin dispersions of Comparative Examples 1 to 5 were inferior in at least one of water repellency and oil repellency to the films formed using the resin dispersions of the Examples.

[0228] The results shown in Table 3 also reveal that the films formed from the resin dispersions of Examples 1 to 24 have oil resistance. It was confirmed that a film formed from a resin dispersion containing a polymer having structural units derived from a polyfunctional monomer as resin particles has superior oil resistance compared to a film formed from a resin dispersion containing a polymer not having structural units derived from a polyfunctional monomer as resin particles. In addition, it was confirmed that a resin dispersion containing a (meth)acrylic copolymer containing structural units derived from a monomer having a reactive functional group as a dispersant, when used in combination with a crosslinking agent, further improves the oil resistance of the film formed.

Claims

1. a dispersing agent (A) which is a (meth)acrylic copolymer comprising a structural unit (a1) derived from a reactive silicone represented by the following formula (1), a structural unit (a2) derived from a (meth)acrylate having a cyclic structure, and a structural unit (a3) ​​derived from an alkyl (meth)acrylate not having a cyclic structure, the content of said structural unit (a1) being in the range of 1 mass % or more and less than 30 mass % with respect to all structural units, the number of carbon atoms in the alkyl moiety being 8 or more, and the content of structural units (a3-1) derived from an alkyl (meth)acrylate not having a cyclic structure being less than 50 mass % with respect to all structural units; Dispersed particles (B) which are polymers different from the (meth)acrylic copolymer; A non-aqueous solvent (C); A resin dispersion for a water / oil repellent comprising: 【Chemistry 1】 In formula (1), R １ represents a hydrogen atom or a methyl group, R ２ , R ３ , R ４ , R ５ and R ６ each independently represents an alkyl group having 1 to 5 carbon atoms or a trialkylsiloxy group having an alkyl group having 1 to 3 carbon atoms, m represents an integer of 1 to 10, and n represents an integer of 0 to 200.

2. 2. The resin dispersion for a water / oil repellent according to claim 1, wherein the (meth)acrylate having a cyclic structure is at least one selected from the group consisting of benzyl (meth)acrylate and isobornyl (meth)acrylate.

3. The resin dispersion for a water / oil repellent according to claim 1 , wherein the polymer contains a structural unit (b2) derived from a polyfunctional monomer.

4. The resin dispersion for a water / oil repellent according to claim 3 , wherein the polyfunctional monomer is a silicone compound having (meth)acryloyl groups at both ends.

5. 5. The resin dispersion for a water / oil repellent according to claim 4, wherein the number average molecular weight of the reactive silicone represented by formula (1) in the (meth)acrylic copolymer is 8,000 or more, and the number average molecular weight of the reactive silicone represented by formula (2) in the polymer is in the range of 4,000 or more and less than 10,000.

6. 2. The resin dispersion for a water / oil repellent according to claim 1, wherein the resin dispersion for a water / oil repellent contains a crosslinking agent, and the (meth)acrylic copolymer contains a structural unit derived from a monomer having a reactive functional group.

7. A water / oil repellent comprising the resin dispersion for water / oil repellents according to any one of claims 1 to 6.

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