Polymer composition for water- and oil-repellent agent, and water- and oil-repellent agent

Abstract

To provide a polymer composition for a water- and oil-repellent agent that enables the formation of a film having both water repellency and oil repellency, and a water- and oil-repellent agent.SOLUTION: A polymer composition for a water- and oil-repellent agent comprises a polymer and a solvent, where the polymer comprises (A) a constitutional unit derived from a reactive silicone represented by formula (1), (B) a constitutional unit derived from a (meth)acrylate having a cyclic structure, and (C) a constitutional unit derived from an alkyl (meth)acrylate having no cyclic structures, the content of the constitutional unit (A) is 1 mass% or more and less than 30 mass% relative to the total constitutional units, the alkyl moiety has 8 or more carbon atoms, and the content of (D) the constitutional unit derived from an alkyl (meth)acrylate having no cyclic structures is less than 50 mass% relative to the total constitutional units. [In the formula (1), R1: a hydrogen atom or a methyl group, R2-R6: a trialkyl siloxy group with a C1-5 alkyl group or a C1-3 alkyl group, m: 1-10, n: 0-200].SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a polymer composition for a water / oil repellent and the 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 have a lower impact on the environment and human body than the above-mentioned fluorine compounds having 8 or more carbon atoms in the alkyl portion, but may be subject to regulation in the future. In addition, the water repellency 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] The present disclosure has been made in consideration of the above-mentioned circumstances. An object of one embodiment of the present disclosure is to provide a polymer composition for a water / oil repellent 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 comprising the polymer composition for water / oil repellents. [Means for solving the problem]

[0006] Specific means for solving the problems include the following aspects. <1> A polymer composition for use in a water / oil repellent, comprising: a polymer which comprises a structural unit (A) derived from a reactive silicone represented by the following formula (1), a structural unit (B) derived from a (meth)acrylate having a cyclic structure, and a structural unit (C) derived from an alkyl (meth)acrylate not having a cyclic structure, the content of said structural unit (A) being in the range of 1 mass% or more and less than 30 mass% of all structural units, and the number of carbon atoms in the alkyl moiety being 8 or more and the content of structural units (C1) derived from an alkyl (meth)acrylate not having a cyclic structure being less than 50 mass% of all structural units, and a solvent.

[0007] [ka]

[0008] 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.

[0009] <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 polymer composition for use in a water / oil repellent according to claim 1. <3> The number average molecular weight of the reactive silicone represented by the formula (1) in the polymer is 8000 or more. <1> or <2> The polymer composition for use in a water / oil repellent according to claim 1. <4> the ratio of the content of the structural unit (B) to the content of the structural unit (A) in the polymer is in the range of 0.1 to 2.0 on a mass basis; <1> ~ <3> 2. The polymer composition for use in a water / oil repellent according to claim 1 . <5> the content of the structural unit (C2) derived from an alkyl (meth)acrylate having 1 to 4 carbon atoms in the alkyl moiety in the polymer is 40 mass% or more based on all structural units; <1> ~ <4> 2. The polymer composition for use in a water / oil repellent according to claim 1 . <6> <1> ~ <5> A water / oil repellent comprising the polymer composition for water / oil repellent according to any one of the above items. Effect of the Invention

[0010] According to one embodiment of the present disclosure, there is provided a polymer composition for a water / oil repellent capable of forming a film having both water and oil repellency. According to another embodiment of the present disclosure, there is provided a water / oil repellent comprising the above-mentioned polymer composition for water / oil repellent. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The polymer composition 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.

[0012] 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.

[0013] In the present disclosure, combinations of two or more preferred embodiments are more preferred embodiments.

[0014] In the present disclosure, when a polymer composition for water and oil repellents contains a plurality of substances corresponding to each component, the amount of each component in the polymer composition for water and oil repellents means the total amount of the plurality of substances present in the polymer composition for water and oil repellents, unless otherwise specified.

[0015] In the present disclosure, "(meth)acrylic monomer" means a monomer having a (meth)acryloyl group.

[0016] 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".

[0017] In this disclosure, "n-" means normal, "i-" means iso, "s-" means secondary, and "t-" means tertiary.

[0018] In the present disclosure, "mass %" and "weight %" are synonymous, and "parts by mass" and "parts by weight" are synonymous.

[0019] In the present disclosure, the terms "monomer" and "monomer component" are synonymous, and the terms "polymer" and "polymeric component" are synonymous.

[0020] 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.

[0021] [Polymer composition for water and oil repellent] The polymer composition for water / oil repellents of the present disclosure (hereinafter also simply referred to as the "polymer composition") comprises a polymer which contains a structural unit (A) derived from a reactive silicone represented by formula (1), a structural unit (B) derived from a (meth)acrylate having a cyclic structure, and a structural unit (C) derived from an alkyl (meth)acrylate not having a cyclic structure, the content of the structural unit (A) being 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 (C1) derived from an alkyl (meth)acrylate not having a cyclic structure is less than 50 mass% with respect to all structural units, and a solvent. The polymer composition of the present disclosure can form a film that is both water-repellent and oil-repellent. Although the reason why the polymer composition of the present disclosure can exhibit such an effect is unclear, the present inventors speculate as follows, however, the following speculation is not intended to limit the polymer composition of the present disclosure, but is merely an example.

[0022] 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 by incorporating a structural unit derived from a reactive silicone having a specific structure into a polymer 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, it is possible to develop oil repellency in addition to water repellency.

[0023] The polymer composition of the present disclosure may exhibit water repellency and oil repellency in the film formed by including the structural unit (A) derived from the reactive silicone represented by formula (1). It is believed that the surface energy of the film formed by including the structural unit (A) in the polymer 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 polymer composition of the present disclosure may exhibit oil repellency in the film formed by including the structural unit (B) derived from a (meth)acrylate having a cyclic structure. It is believed that the movement of the silicone chain is inhibited in the film formed by including the structural unit (B) in the polymer due to steric hindrance caused by the (meth)acrylate having a cyclic structure. It is presumed that the inhibition of this movement maintains a low state of surface energy, and therefore the film formed exhibits oil repellency. The polymer contained in the polymer composition of the present disclosure contains a structural unit (C) 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 (C1) 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 polymer composition of the present disclosure does not have too much structural unit (C1) in the polymer, and the lipophilicity of the film formed is not excessively high, so it is presumed that the oil repellency is not easily impaired. In addition, it is presumed that the polymer composition of the present disclosure does not have too much structural unit (A) in the polymer, and this is 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 polymer composition of the present disclosure can form a film that is both water-repellent and oil-repellent.

[0024] In the present disclosure, "a polymer which contains a structural unit (A) derived from a reactive silicone represented by formula (1), a structural unit (B) derived from a (meth)acrylate having a cyclic structure, and a structural unit (C) derived from an alkyl (meth)acrylate not having a cyclic structure, wherein the content of the structural unit (A) is 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 portion is 8 or more, and the content of the structural unit (C1) 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 a "specific polymer".

[0025] [Specific polymer] The polymer composition of the present disclosure includes a structural unit (A) derived from a reactive silicone represented by formula (1), a structural unit (B) derived from a (meth)acrylate having a cyclic structure, and a structural unit (C) derived from an alkyl (meth)acrylate not having a cyclic structure, wherein the content of the structural unit (A) 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 (C1) derived from an alkyl (meth)acrylate not having a cyclic structure is less than 50 mass% with respect to all structural units (i.e., a specific polymer). The polymer composition of the present disclosure may contain only one type of specific polymer, or may contain two or more types of specific polymers.

[0026] <Structural unit (A) derived from reactive silicone represented by formula (1)> The specific polymer contains a structural unit (A) derived from a reactive silicone represented by the following formula (1), and the content of the structural unit (A) is in the range of 1 mass % or more and less than 30 mass % with respect to all structural units of the specific polymer. The structural unit (A) derived from the reactive silicone represented by formula (1) can contribute to the development of water- and oil-repellency in the film that is formed.

[0027] 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).

[0028] [ka]

[0029] In formula (1), R 1 represents a hydrogen atom or a methyl group, and is preferably a methyl group.

[0030] 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 independently 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.

[0031] The number average molecular weight of the reactive silicone represented by formula (1) in the specific polymer is not particularly limited, but from the viewpoint of the oil repellency of the film formed, it is preferably 400 or more, more preferably 1000 or more, even more preferably 5000 or more, even more preferably 8000 or more, and particularly preferably 10000 or more. The number average molecular weight of the reactive silicone represented by formula (1) in the specific polymer is preferably less than 20,000, for example, from the viewpoint of easy availability of the reactive silicone represented by formula (1).

[0032] In the present 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 number average molecular weight is listed in the catalog of the commercially available product, the number average molecular weight listed in the catalog is used as the number average molecular weight. 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.

[0033] ~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: 100μL Flow rate: 0.8mL / min

[0034] In addition, when the specific polymer contains two or more reactive silicones represented by formula (1) with different number average molecular weights, "the number average molecular weight of the reactive silicone represented by formula (1) in the specific polymer" means 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 written as "reactive silicone". Number average molecular weight of reactive silicone in a specific polymer = [number average molecular weight of reactive silicone 1 x amount of reactive silicone 1 + number average molecular weight of reactive silicone 2 x amount of reactive silicone 2 + ··· + number average molecular weight of reactive silicone n x amount of reactive silicone n] / [amount of reactive silicone 1 + amount of reactive silicone 2 + ··· + amount of reactive silicone n]

[0035] 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): 10,000 (catalog value), manufactured by JNC Corporation], X-22-2404 [in formula (1), R 1 = methyl group, R 2 =R 3 =R6 = trimethylsiloxy group, m = 3, n = 0, number average molecular weight (Mn): 420 (catalog value), manufactured by Shin-Etsu Chemical Co., Ltd.

[0036] The specific polymer may contain only one type of structural unit (A), or may contain two or more types.

[0037] The content of the structural unit (A) in the specific polymer is in the range of 1 mass % or more and less than 30 mass % based on all structural units of the specific polymer. When the content of the structural unit (A) in the specific polymer is 1 mass % or more relative to all structural units of the specific polymer, this means that the polymer intentionally contains the structural unit (A). When the content of the structural unit (A) in the specific polymer is less than 30 mass % relative to all structural units of the specific polymer, the oil repellency of the film formed tends not to be impaired. The content of the structural unit (A) in the specific polymer 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 10 mass% or more and 20 mass% or less, based on all the structural units of the specific polymer.

[0038] <Structural Unit (B) Derived from a (Meth)acrylate Having a Cyclic Structure> The specific polymer contains a structural unit (B) derived from a (meth)acrylate having a cyclic structure. The structural unit (B) derived from a (meth)acrylate having a cyclic structure can contribute to the development of oil repellency in the film that is formed.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] The specific polymer may contain only one type of structural unit (B), or may contain two or more types.

[0043] The content of the structural unit (B) in the specific polymer is not particularly limited, but from the viewpoint of the oil repellency of the film to be formed, for example, it 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 specific polymer. The upper limit of the content of the structural unit (B) in the specific polymer 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, relative to all structural units of the specific polymer. In an embodiment, the content of the structural unit (B) in the specific polymer 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 specific polymer.

[0044] The ratio of the content of the structural unit (B) to the content of the structural unit (A) in the specific polymer [content of structural unit (B) / content of structural unit (A)] is, on a mass basis, preferably in the range of 0.1 or more and 2.0 or less, more preferably in the range of 0.15 or more and 2.0 or less, even more preferably in the range of 0.2 or more and 2.0 or less, and particularly preferably in the range of 0.25 or more and 2.0 or less. When the ratio of the content of the structural unit (B) to the content of the structural unit (A) in the specific polymer is within the above range on a mass basis, a film having a better balance of water repellency and oil repellency tends to be formed.

[0045] <Structural Unit (C) Derived from Alkyl (Meth)acrylate Not Having a Cyclic Structure> The specific polymer contains a structural unit (C) derived from an alkyl (meth)acrylate that does not have a cyclic structure. The structural unit (C) derived from an alkyl (meth)acrylate not having a cyclic structure can contribute to improving the flexibility and strength of the film that is formed.

[0046] 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 addition, the "alkyl(meth)acrylate having no cyclic structure" in the present disclosure does not include those corresponding to the monomer having a crosslinkable functional group described below. In other words, when a monomer having a crosslinkable functional group also corresponds to an alkyl(meth)acrylate having no cyclic structure, it is classified as a monomer having a crosslinkable functional group. As an example, 2-hydroxyethyl acrylate, which has a hydroxyl group as a crosslinkable 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 crosslinkable functional group.

[0047] 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, further preferably 1 to 8 carbon atoms, and particularly preferably 1 to 4 carbon atoms.

[0048] 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].

[0049] The specific polymer may contain only one type of structural unit (C), or may contain two or more types.

[0050] In the specific polymer, the content of the structural unit (C) is not particularly limited, but the content of the structural unit (C1) derived from an alkyl (meth)acrylate having 8 or more carbon atoms in the alkyl portion and not having a cyclic structure is less than 50 mass% of all the structural units of the specific polymer. When the content of the structural unit (C1) in the specific polymer is less than 50% by mass relative to the total structural units of the specific polymer, the oil repellency of the film formed tends not to be impaired. From this viewpoint, the content of the structural unit (C1) in the specific polymer is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, particularly preferably 10% by mass or less, and may be, for example, 0% by mass, relative to the total structural units of the specific polymer.

[0051] Furthermore, in the specific polymer, the content of the structural unit (C2) derived from an alkyl (meth)acrylate having 1 to 4 carbon atoms in the alkyl moiety is preferably 40 mass% or more, more preferably 50 mass% or more, even more preferably 60 mass% or more, and particularly preferably 70 mass% or more, based on all the structural units of the specific polymer. When the content of the structural unit (C2) in the specific polymer is 40 mass % or more relative to all structural units of the specific polymer, the flexibility and strength of the formed film tend to be better. The upper limit of the content of the structural unit (C2) in the specific polymer is not particularly limited, but for example, it is preferably 98 mass% or less, more preferably 95 mass% or less, and even more preferably 90 mass% or less, relative to all structural units of the specific polymer. In one embodiment, the content of the structural unit (C2) in the specific polymer may be 40% by mass to 95% by mass, 50% by mass to 90% by mass, 60% by mass to 90% by mass, or 70% by mass to 90% by mass, relative to all structural units of the specific polymer.

[0052] <Structural units derived from other monomers> The specific polymer 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 term "structural units derived from other monomers" refers to structural units formed by addition polymerization of other monomers.

[0053] Examples of the structural units derived from other monomers include monomers having a reactive functional group, such as acrylic acid and methacrylic acid. When the specific polymer contains a constituent unit derived from a monomer having a reactive functional group as a constituent unit derived from another monomer, the reactive group undergoes a crosslinking reaction with a crosslinking agent described below to form a crosslinked structure, which tends to enhance the oil resistance of the film formed. In the present disclosure, the term "reactive functional group" refers to a functional group that can react with a crosslinking agent described below to form a crosslinked structure. Examples of reactive functional groups 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.

[0054] In addition, examples of structural units derived from other monomers 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.

[0055] When the specific polymer contains a constituent unit derived from another monomer, it may contain only one type of constituent unit derived from another monomer, or may contain two or more types of constituent units derived from another monomer.

[0056] When the specific polymer contains constitutional units derived from other monomers, the content of the constitutional units derived from other monomers can be appropriately set within a range that does not impair the effects of the polymer composition of the present disclosure.

[0057] <<Weight average molecular weight of a specific polymer>> The weight average molecular weight (also referred to as "Mw") of the specific polymer is not particularly limited, but is, for example, 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 weight average molecular weight of the specific polymer is 10,000 or more, the coatability of the polymer composition tends to be superior. When the weight average molecular weight of the specific polymer is 1,000,000 or less, the viscosity of the polymer composition does not become too high, and the polymer composition tends to be easier to handle.

[0058] The weight average molecular weight of the specific polymer is a value measured by the following method, specifically, according to the following (1) to (3). (1) A solution of the specific polymer is applied to a release paper and dried at 100° C. for 1 minute to obtain a film of the specific polymer. (2) Using the film-like specific polymer 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 specific polymer to the sample solution. (3) The weight average molecular weight of a specific polymer is determined, in terms of standard polystyrene, by gel permeation chromatography (GPC) under the following conditions.

[0059] ~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: 100μL Flow rate: 0.8mL / min

[0060] The weight average molecular weight of the specific polymer 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, and the like when polymerizing the monomers.

[0061] <<Specific polymer content>> The content of the specific polymer in the polymer composition of the present disclosure is not particularly limited, but is, for example, preferably 10% by mass to 70% by mass, more preferably 15% by mass to 60% by mass, and even more preferably 20% by mass to 50% by mass, relative to the total mass of the polymer composition.

[0062] [Method for producing specific polymer] The method for producing the specific polymer is not particularly limited. The specific polymer 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 processing steps are relatively simple and can be carried out in a short time when preparing the polymer composition of the present disclosure after production.

[0063] 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 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.

[0064] Examples of the organic solvent used in the polymerization reaction include aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, alicyclic hydrocarbon compounds, ester compounds, ketone compounds, glycol ether compounds, and alcohol compounds. More specifically, examples of the organic solvent used in the polymerization reaction include aromatic hydrocarbon compounds such as benzene, toluene, ethylbenzene, n-propylbenzene, t-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, and aromatic naphtha; aliphatic or alicyclic hydrocarbon compounds such as n-hexane, n-heptane, n-octane, i-octane, n-decane, dipentene, petroleum spirit, petroleum naphtha, and turpentine oil; ethylene glycol compounds such as methyl acetate, ethyl acetate, n-butyl acetate, n-amyl acetate, n-butyl cellosolve acetate (so-called butyl cellosolve acetate), 2-hydroxyethyl acetate, 2-butoxyethyl acetate, 3-methoxybutyl acetate, and methyl benzoate; Examples of the alcohol compounds include ester compounds, ketone compounds represented by acetone, methyl ethyl ketone, methyl-i-butyl ketone, isophorone, cyclohexanone, and methylcyclohexanone, glycol ether compounds represented by ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether, and alcohol compounds represented by methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, s-butyl alcohol, and t-butyl alcohol.

[0065] In producing the specific polymer, it is preferable to use an organic solvent that is unlikely to cause chain transfer during the polymerization reaction, such as an aromatic hydrocarbon compound, an aliphatic hydrocarbon compound, an ester compound, or a ketone compound.

[0066] During the polymerization reaction, only one type of organic solvent may be used, or two or more types may be used.

[0067] 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)(tert-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.

[0068] In the polymerization reaction, only one type of polymerization initiator may be used, or two or more types may be used.

[0069] 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 target specific polymer.

[0070] In producing the specific polymer, 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.

[0071] When a chain transfer agent is used in producing the specific polymer, 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 specific polymer.

[0072] The polymerization temperature is not particularly limited and can be appropriately set depending on, for example, the molecular weight of the desired specific polymer.

[0073] 〔solvent〕 The polymer composition of the present disclosure includes a solvent. The solvent is preferably an organic solvent. As the organic solvent, for example, the same organic solvents as those used in the polymerization reaction of the specific polymer described above can be used. The organic solvent is preferably at least one selected from the group consisting of aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, ester compounds, and ketone compounds. Specific examples of the aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, ester compounds, and ketone compounds are as described above.

[0074] The polymer composition of the present disclosure may contain only one type of solvent, or may contain two or more types of solvent.

[0075] The content of the organic solvent in the polymer composition of the present disclosure is not particularly limited and can be appropriately set depending on the purpose. The content of the organic solvent in the polymer composition of the present disclosure is, for example, preferably 30% by mass to 90% by mass, more preferably 40% by mass to 85% by mass, and even more preferably 50% by mass to 80% by mass, relative to the total mass of the polymer composition.

[0076] [Crosslinking Agent] The polymeric compositions of the present disclosure may also 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.

[0077] 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.

[0078] 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.

[0079] As the polyisocyanate compound, an aromatic polyisocyanate compound is preferable, and a tolylene diisocyanate compound is more preferable. The "tolylene diisocyanate compound" includes, for example, TDI, a TDI polymer, an adduct of TDI and a polyol compound, and a biuret of TDI. As the tolylene diisocyanate compound, an adduct of TDI and TMP is preferred.

[0080] 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," 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.).

[0081] Examples of bifunctional or higher functional epoxy compounds 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, Examples of suitable glycidyl ethers include polyglycerol polyglycidyl 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).

[0082] As the epoxy 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).

[0083] 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.

[0084] 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.).

[0085] When the polymer composition 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.

[0086] When the polymer composition 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 polymer composition 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 of the specific polymer.

[0087] The crosslinking agent may be included as a component of the polymer composition of the present disclosure, but may not be included in the polymer composition of the present disclosure, but may be used in combination with the polymer composition of the present disclosure. When using a crosslinking agent, for example, the polymer composition of the present disclosure does not include a crosslinking agent as a component, and the polymer composition of the present disclosure and the crosslinking agent are mixed immediately before imparting water and oil repellency to the object, and then the polymer composition is applied to the object.

[0088] [Other ingredients] The polymer composition of the present disclosure may contain components other than the components described above (so-called other components) as necessary, as long as the effects of the polymer composition are not impaired. Examples of other components include various additives such as polymers other than the specific polymer, viscosity adjusters, thickeners, and pigments.

[0089] When the polymer composition 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 polymer composition of the present disclosure.

[0090] <<Applications of polymer compositions>> The polymer composition of the present disclosure is a polymer composition used in a water / oil repellent (i.e., a polymer composition for a water / oil repellent). The polymer composition of the present disclosure has both water repellency and oil repellency, and is therefore suitable for use in a water / oil repellent. Specific applications of the polymer composition of the present disclosure include, for example, water and oil repellents used in coating agents, paints, and the like, and raw materials for water and oil repellents.

[0091] [Water and oil repellent] The water / oil repellent of the present disclosure includes the polymer composition of the present disclosure described above. The water / oil repellent of the present disclosure may be composed of the polymer composition of the present disclosure, or may be composed of the polymer composition of the present disclosure containing various additives. Examples of various additives that may be contained in the water / oil repellent of the present disclosure include crosslinking agents and film-forming assistants. EXAMPLES

[0092] The polymer composition 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.

[0093] [Production of polymer composition] Example 1 Into a reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser, 2.6 parts by mass of ethyl acrylate (EA) [alkyl acrylate not having a cyclic structure, carbon number in the alkyl portion: 2], 5.2 parts by mass of methyl methacrylate (MMA) [alkyl methacrylate not having a cyclic structure, carbon number in the alkyl portion: 1], 5.2 parts by mass of i-butyl methacrylate (i-BMA) [alkyl methacrylate not having a cyclic structure, carbon number in the alkyl portion: 4], 1.5 parts by mass of Silaplane (registered trademark) FM-0711 [product name, reactive silicone represented by formula (1), manufactured by JNC Corporation], 0.37 parts by mass of benzyl methacrylate (BZMA) [methacrylate having a cyclic structure], 0.01 parts by mass of (2-ethylhexanoyl)(tert-butyl)peroxide [polymerization initiator], and 12.1 parts by mass of butyl cellosolve acetate [solvent] were placed, and the atmosphere in the reactor was replaced with nitrogen while stirring. Thereafter, the mixture in the reactor was heated to 90° C. while stirring. After the temperature in the reactor was kept at 90° C. for 30 minutes, a mixture of 2.1 parts by mass of ethyl acrylate (EA), 4.3 parts by mass of methyl methacrylate (MMA), 4.3 parts by mass of i-butyl methacrylate (i-BMA), 1.2 parts by mass of Silaplane (registered trademark) FM-0711, 0.31 parts by mass of benzyl methacrylate (BZMA), 15.1 parts by mass of butyl cellosolve acetate, and 0.01 parts by mass of (2-ethylhexanoyl) (tert-butyl) peroxide was successively added dropwise to the mixture in the reactor over 120 minutes. After the dropwise addition, the mixture was held for 60 minutes to allow polymerization, and then a mixture of 45.4 parts by mass of butyl cellosolve acetate and 0.08 parts by mass of (2-ethylhexanoyl) (tert-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 to a solid concentration of 27.0% by mass using butyl cellosolve acetate, and then cooled to obtain a polymer composition of Example 1 containing a polymer and a solvent.

[0094] The term "solid content" used herein means the mass ratio of the polymer in the polymer composition. The same applies to the polymer compositions of Examples 2 to 15 and Comparative Examples 1 to 5 produced below.

[0095] [Examples 2 to 15] In Examples 2 to 15, the same operation as in Example 1 was carried out except that the monomer composition of the polymer contained in the polymer composition was changed to the monomer composition shown in Table 1, thereby obtaining each of the polymer compositions of Examples 2 to 15 (solid concentration: 27.0% by mass).

[0096] [Comparative Examples 1 to 5] In Comparative Examples 1 to 5, the same operations as in Example 1 were carried out except that the monomer composition of the polymer contained in the polymer composition was changed to the monomer composition shown in Table 1, to obtain each of the polymer compositions of Comparative Examples 1 to 5 (solid concentration: 27.0% by mass).

[0097] The weight average molecular weight of the polymer contained in each of the polymer compositions of Examples 1 to 15 and Comparative Examples 1 to 5 was measured by the same method as the above-mentioned method for measuring the weight average molecular weight of the specific polymer, and was 280,000 in all cases.

[0098] [Table 1]

[0099] Details of each monomer listed in Table 1 are as follows. <Alkyl (meth)alkyl acrylate not having a cyclic structure> "EA": Ethyl acrylate (number of carbon atoms in the alkyl portion: 2) "MMA": Methyl methacrylate (number of carbon atoms in the alkyl portion: 1) "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) "2EHA": 2-ethylhexyl acrylate (number of carbon atoms in the alkyl portion: 8) "2HEMA": 2-ethylhexyl methacrylate (number of carbon atoms in the alkyl portion: 8) "LMA": Lauryl methacrylate (number of carbon atoms in the alkyl portion: 12) <Monomers having reactive functional groups> "AA": acrylic acid (reactive functional group: carboxy group) <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] <(Meth)acrylate Having a Cyclic Structure> "BZMA": Benzyl methacrylate "IBXA": Isobornyl acrylate "IBXMA": Isobornyl methacrylate

[0100] The monomer compositions of the polymer compositions of Examples 1 to 15 and Comparative Examples 1 to 5 are shown in Table 1. In Table 1, for the sake of convenience, the reactive silicone represented by formula (1) is represented as "a", and the (meth)acrylate having a cyclic structure is represented as "b". In Table 1, "b / a" means the ratio by mass of the content of the (meth)acrylate having a cyclic structure to the content of the reactive silicone represented by formula (1). In Table 1, "-" in the monomer composition column means that the monomer in that column was not used.

[0101] [evaluation] 1.Water repellency (1) Film formation (1-1) Polymer Compositions of Examples 1 to 14 and Comparative Examples 1 to 5 The polymer composition was applied onto a polyethylene terephthalate (PET) film using an 8 mil (≒ 203.2 μm) applicator to form a coating film, which 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 on the PET film.

[0102] (1-2) Polymer composition of Example 15 Takenate (registered trademark) D-101 (trade name, isocyanate-based crosslinking agent, manufactured by Mitsui Chemicals, Inc.) was added to the polymer composition in an amount of 5 parts by mass (solid content equivalent) per 100 parts by mass of the polymer contained in the polymer composition 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.

[0103] (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 Table 2. In the following evaluation criteria, "A" and "B" are practically acceptable levels, with "A" being the most preferable.

[0104] -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°.

[0105] 2.Oil repellency (1) Film formation A film was formed by the same procedure as in "(1) Film formation" in "1. Water repellency" above.

[0106] (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 contact angle of hexadecane was calculated using the 2θ method. Evaluation was performed according to the following evaluation criteria. The results are shown in Table 2. In the following evaluation criteria, "A" and "B" are practically acceptable levels, with "A" being the most preferable.

[0107] -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°.

[0108] [Table 2]

[0109] From the results shown in Table 2, it was confirmed that the films formed from the polymer compositions of Examples 1 to 15 had both water repellency and oil repellency. On the other hand, it was confirmed that the films formed from the polymer compositions of Comparative Examples 1 to 5 were inferior in at least one of water repellency and oil repellency to the films formed from the polymer compositions of the Examples.

Claims

1. The polymer composition for use in a water / oil repellent comprises: a polymer which comprises a structural unit (A) derived from a reactive silicone represented by the following formula (1), a structural unit (B) derived from a (meth)acrylate having a cyclic structure, and a structural unit (C) derived from an alkyl (meth)acrylate not having a cyclic structure, the content of said structural unit (A) being 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 structural unit (C1) derived from an alkyl (meth)acrylate not having a cyclic structure being less than 50 mass% with respect to all structural units, and a solvent. 【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 polymer composition 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. 2. The polymer composition for use in a water / oil repellent according to claim 1, wherein the number average molecular weight of the reactive silicone represented by formula (1) in the polymer is 8,000 or more.

4. 2. The polymer composition for water / oil repellents according to claim 1, wherein a ratio of a content of the structural unit (B) to a content of the structural unit (A) in the polymer is in a range of 0.1 or more and 2.0 or less on a mass basis.

5. 2. The polymer composition for water / oil repellents according to claim 1, wherein the content of the structural unit (C2) derived from an alkyl (meth)acrylate having 1 to 4 carbon atoms in the alkyl moiety in the polymer is 40 mass% or more based on all structural units.

6. A water / oil repellent comprising the polymer composition for water / oil repellents according to any one of claims 1 to 5.

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