Composition containing polyoxyalkylene (POLY)glycerin-based alkoxysilane

Abstract

The purpose of the present invention is to provide a composition that makes it possible to obtain a cured coating film or a cured film which is resistant to water stains and oil stains while having flexibility when, for example, used for coating a substrate such as a film or produced as a film.　The problem has been solved by a composition containing: [A] a polyoxyalkylene (poly)glycerin-based alkoxysilane that has a skeleton in which polyoxyalkylene is condensed with (poly)glycerin having an average degree of polymerization of 1-100 and that has a plurality of alkoxysilyl groups at the terminals; [B] a silicate oligomer; and [C] a silicone-based leveling agent.

Description

Composition containing polyoxyalkylene (poly)glycerol-based alkoxysilane

[0001] The present invention relates to a composition containing polyoxyalkylene (poly)glycerin-based alkoxysilanes, etc., used for coating a substrate or producing a film.

[0002] Flexible coatings are a technology with promising future growth potential, particularly for applications in foldable displays such as those found in foldable smartphones. Flexible coatings utilize organic crosslinked polymers, inorganic crosslinked polymers, and organic-inorganic hybrid materials. Organic crosslinked polymers offer a high degree of freedom in molecular design and are advantageous for imparting functionality, but they are less rigid than inorganic crosslinked polymers, posing a challenge in terms of durability. On the other hand, inorganic crosslinked polymers are suitable for durability, but it is difficult to impart functions related to softness, such as flexibility. Therefore, to achieve more advanced flexible coatings, there is great expectation for organic-inorganic hybrid materials that combine the properties of both organic and inorganic polymers.

[0003] For example, Patent Documents 1 and 2 disclose polyglycerin-based alkoxysilanes having a polyglycerin skeleton with alkoxysilyl groups at the terminals, obtained by reacting 3-isocyanatetopropyltriethoxysilane with an ethylene oxide adduct of polyglycerin. It is disclosed that the cured coating films produced from these compounds have sufficient flexibility despite containing inorganic components derived from alkoxysilyl groups.

[0004] Japanese Patent Publication No. 2022-178714, International Publication No. 2022 / 244859

[0005] However, the cured coating films produced from polyglycerin-based alkoxysilanes disclosed in Patent Documents 1 and 2 do not have sufficient water repellency, and their oil repellency and water-slip properties have not been investigated. Therefore, when applied to foldable displays, including foldable smartphones, there is a problem in that they do not have sufficient resistance to water and oil stains, i.e., they do not have sufficient stain resistance.

[0006] Therefore, the present invention aims to provide a composition that, when used for coating a substrate such as a film or for manufacturing a film, provides a cured coating or film that is flexible yet resistant to water and oil stains.

[0007] [1] That is, the composition disclosed in this application is characterized by containing [A] a polyoxyalkylene (poly)glycerol-based alkoxysilane having a backbone in which polyoxyalkylene is condensed on (poly)glycerol having an average degree of polymerization of 1 to 100 and having a plurality of alkoxysilyl groups at its terminals, [B] a silicate oligomer, and [C] a silicone-based leveling agent.

[0008] [2] The composition according to [1], wherein the [A] polyoxyalkylene (poly)glycerin-based alkoxysilane is a reaction product obtained by reacting a polyoxyalkylene (poly)glyceryl ether derivative obtained by condensing a polyoxyalkylene (poly)glyceryl ether having a hydroxyl group at one end or a compound having a first reactive functional group at one end with an alkoxysilane having a second reactive functional group at one end, characterized in that the product is obtained by the reaction of the hydroxyl group or the first reactive functional group with the second reactive functional group.

[0009] [3] The composition according to [2] is characterized in that the polyoxyalkylene (poly)glyceryl ether or polyoxyalkylene (poly)glyceryl ether derivative described in [2] is represented by the structure of the following formula (1). (n, p, q, and r each represent the number of repeating units, where n is an integer from 1 to 100, and the sum of p, q, and r is an integer from 2 to 300. AO indicates an alkylene oxide with 1 to 4 carbon atoms. X 1 , X 2 and X 3 Each substituent independently contains at its terminal side either hydrogen or a reactive functional group selected from the group consisting of a thiol group, (meth)acryloyl group, epoxy group, glycidyl group, or allyl group.

[0010] [4] The composition according to [2] or [3] above, wherein the alkoxysilane having a second reactive functional group at its terminal end is characterized in that the second reactive functional group is one selected from the group consisting of a vinyl group, an isocyanate group, a thiol group, a (meth)acryloyl group, an epoxy group, a glycidyl group, a hydroxyl group, an amino group, and hydrogen.

[0011] [5] The composition according to [1] or [2], characterized in that the [B] silicate oligomer is at least one selected from a linear silicate oligomer, a branched silicate oligomer, or a cyclic silicate oligomer represented by the structure of formula (2) below. (R 1 and R 2 Each of these is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and m is an integer from 1 to 100. 1 and Y 2 Each of these is independently either hydrogen or an alkoxysilyl group having 1 to 3 carbon atoms.

[0012] [6] The composition according to [1] or [2] above, wherein the [C] silicone leveling agent is a polysiloxane having a reactive functional group selected from hydrogen, a hydroxyl group, an alkoxysilyl group, an amino group, a (meth)acryloyl group, an allyl group, an epoxy group, a carboxyl group, or a mercapto group at one end, both ends, or side chain, or a polysiloxane that does not have the reactive functional group but has at least an alkyl group, a phenyl group, or hydrogen at one side chain.

[0013] [7] The composition according to [1] or [2], characterized in that the blending ratio of [A] polyoxyalkylene (poly)glycerol-based alkoxysilane and [B] silicate oligomer is [A] polyoxyalkylene (poly)glycerol-based alkoxysilane : [B] silicate oligomer = 20:80 to 70:30.

[0014] According to the composition of the present invention, when used for coating a substrate or producing a film, etc., it is possible to provide a cured coating film or a cured film that has flexibility and is difficult to be soiled by water stains or oil stains, that is, has excellent antifouling properties.

[0015] Hereinafter, the composition of the present invention will be described in detail. The embodiments described below are preferred specific examples for implementing the present invention, and thus various technical limitations are imposed. However, the present invention is not limited to this embodiment unless it is specifically stated in the following description that the invention is limited. And when a range is represented using the symbol "~" in the description, it includes the upper and lower limits of the range.

[0016] The composition of the present invention is a composition containing [A] a polyoxyalkylene (poly) glycerin-based alkoxysilane having a skeleton in which polyoxyalkylene is condensed with (poly) glycerin having an average degree of polymerization of 1 to 100 and having a plurality of alkoxysilyl groups at the terminals, [B] a silicate oligomer, and [C] a silicone-based leveling agent.

[0017] [[A] Polyoxyalkylene (poly) glycerin-based alkoxysilane] The polyoxyalkylene (poly) glycerin-based alkoxysilane of the present invention is a compound having a skeleton in which polyoxyalkylene is condensed with (poly) glycerin having an average degree of polymerization of 1 to 100 and having a plurality of alkoxysilyl groups at the terminals. By using such a compound, sufficient flexibility and water repellency are imparted to the produced cured coating film or cured film. Note that (poly) glycerin represents at least one of glycerin or polyglycerin.

[0018] In the polyoxyalkylene (poly) glycerin-based alkoxysilane of the present invention, the average degree of polymerization n of (poly) glycerin is preferably 1 to 100, more preferably 2 to 20, and most preferably 2 to 15. Here, the average degree of polymerization n can be calculated from the hydroxyl value by the terminal analysis method using the following formula (α) and the following formula (β). The hydroxyl value in formula (β) is a numerical value that serves as an index of the number of hydroxyl groups contained in (poly) glycerin, and refers to the number of milligrams of potassium hydroxide required to neutralize acetic acid necessary for acetylating the free hydroxyl groups contained in 1 g of (poly) glycerin. The number of milligrams of potassium hydroxide is calculated according to "Standard Oil Analysis Test Methods Established by the Japan Oil Chemists' Society, 2013 Edition" edited by the Japan Oil Chemists' Society. Molecular weight = 74n + 18... (α) Hydroxyl value = 56110(n + 2) / Molecular weight... (β)

[0019] The polyoxyalkylene (poly) glycerin-based alkoxysilane of the present invention according to the present invention is preferably a reaction product obtained by reacting a polyoxyalkylene (poly) glyceryl ether having a hydroxyl group at the terminal or a polyoxyalkylene (poly) glyceryl ether derivative in which a compound having a first reactive functional group at the terminal is condensed with an alkoxysilane having a second reactive functional group at the terminal.

[0020] The polyoxyalkylene (poly) glyceryl ether or polyoxyalkylene (poly) glyceryl ether derivative is preferably a compound represented by the structure of the following formula (1). (n, p, q, r each represent the number of repeating units, n is an integer of 1 to 100, and the sum of p, q and r is an integer of 2 to 300. AO represents an alkylene oxide having 1 to 4 carbon atoms. X 1 , X 2 and X 3 are each independently a substituent containing, at the terminal, any reactive functional group selected from the group consisting of hydrogen, a thiol group, a (meth) acryloyl group, an epoxy group, a glycidyl group, and an allyl group.)

[0021] Examples of AO include ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO), with ethylene oxide (EO) and propylene oxide (PO) being preferred. In formula (1), p, q, and r all represent the number of alkylene oxides added to one hydroxyl group of polyglycerin (rational numbers), and the sum of p, q, and r is an integer between 2 and 300, more preferably an integer between 9 and 240, and even more preferably an integer between 12 and 180. Furthermore, p, q, and r are each preferably rational numbers between 1 and 30, and more preferably rational numbers between 3 and 20.

[0022] Preferably, the polyoxyalkylene (poly)glyceryl ethers having hydroxyl groups at their terminals include polyoxyethylene (poly)glyceryl ether, polyoxypropylene (poly)glyceryl ether, and polyoxybutylene (poly)glyceryl ether. Furthermore, preferred polyoxyalkylene (poly)glyceryl ether derivatives obtained by condensing a compound having a first reactive functional group at its terminal are compounds obtained by reacting the aforementioned polyoxyalkylene (poly)glyceryl ether with a compound selected from vinyl chloride, vinyl bromide, vinyl iodide, 3-hydroxypropionic acid, glycolic acid, lactic acid, 3-mercaptopropionic acid, thioglycolic acid, thiolactic acid, acrylic acid, methacrylic acid, and the like.

[0023] The second reactive functional group is not particularly limited, but preferred examples include vinyl groups, isocyanate groups, thiol groups, (meth)acryloyl groups, epoxy groups, glycidyl groups, hydroxyl groups, amino groups, and hydrogen. Preferred alkoxysilanes having a second reactive functional group at the terminal include vinyltrimethoxysilane, vinyltriethoxysilane, 3-isocyanatetopropyltriethoxysilane, 3-isocyanatetopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-aminopropyltriethoxysilane, and triethoxysilane.

[0024] The polyoxyalkylene (poly)glycerin-based alkoxysilane of the present invention is preferably formed by the reaction of a first reactive functional group located at the terminal of a polyoxyalkylene (poly)glyceryl ether or a polyoxyalkylene (poly)glyceryl ether derivative with a second reactive functional group located at the terminal of the alkoxysilane. Specifically, preferred reaction products include those of polyoxyalkylene (poly)glyceryl ether or a polyoxyalkylene (poly)glyceryl ether derivative with a thiol group introduced at the terminal, and an alkoxysilane containing any of a vinyl group, isocyanate group, epoxy group, glycidyl group, amino group, or hydrogen at the terminal; those of polyoxyalkylene (poly)glyceryl ether derivative with a (meth)acryloyl group introduced at the terminal, and an alkoxysilane having a vinyl group, thiol group, or (meth)acryloyl group at the terminal; and those of polyoxyalkylene (poly)glyceryl ether derivative with an epoxy group or glycidyl group introduced at the terminal, and an alkoxysilane containing a thiol group, hydroxyl group, amino group, or hydrogen at the terminal. In the reaction products obtained, it is preferable that 20 to 100% of the hydroxyl groups of the polyoxyalkylene (poly)glyceryl ether or the first reactive functional groups of the polyoxyalkylene (poly)glyceryl ether derivative are reacted and bonded, and it is even more preferable that 50 to 100% are reacted and bonded.

[0025] [B] Silicate Oligomer The silicate oligomer of the present invention is an oligomer obtained by hydrolysis and dehydration condensation of a predetermined alkoxysilane. By using such a compound, sufficient oil repellency is imparted to the cured coating or cured film produced.

[0026] The silicate oligomer of the present invention is preferably at least one selected from, for example, a linear silicate oligomer, a branched silicate oligomer, or a cyclic silicate oligomer, represented by the structure of formula (2) below. (R 1 and R 2 Each of these is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and m is an integer from 1 to 100.1 and Y 2 Each of these is independently hydrogen or an alkoxysilyl group having 1 to 3 carbon atoms. Specifically, the silicate oligomer of the present invention is preferably a compound having an average degree of polymerization m of 1 to 100 obtained by hydrolysis and dehydration condensation, or by hydrolysis alone, of an alkoxysilane such as tetraethoxysilane or tetramethoxysilane. More specifically, the silicate oligomer is ethyl silicate 40 (an oligomer using tetraethoxysilane, with an average degree of polymerization m: 5), ethyl silicate 48 (an oligomer using tetraethoxysilane, with an average degree of polymerization m: 10), methyl silicate 51 (an oligomer using tetramethoxysilane, with an average degree of polymerization m: 4), methyl silicate 53 (an average degree of polymerization m: 7), and MS51 (an oligomer using tetramethoxysilane) manufactured by Mitsubishi Chemical Corporation. It is preferable to use oligomers using tetramethoxysilane, MS56, MS57, MS56S, or ProtectorS-6140 and ProtectorHB-7000 from Okuno Pharmaceutical Co., Ltd., or Honey Chemical Co., Ltd.'s Honey Chemical Co., Ltd.'s Honey Chemical Co., Ltd.'s Honey Chemical Co., Ltd.'s Honey Chemical Co., Ltd.'s Honey Chemical Co., Ltd.'s Honey Chemical Co., Ltd.'s Honey Chemical Co., Ltd.'s Honey Chemical Co., Ltd.'s Honey Chemical Co., Ltd.'s Honey Chemical Co., Ltd.'s Honey Chemical Co., Ltd.'s

[0027] The blending ratio of [A] polyoxyalkylene (poly)glycerin-based alkoxysilane and [B] silicate oligomer is preferably [A] polyoxyalkylene (poly)glycerin-based alkoxysilane : [B] silicate oligomer = 20:80 to 70:30, and more preferably 30:70 to 50:50. When these blending ratios are within this range, a cured coating or film with excellent stain resistance while maintaining flexibility can be produced.

[0028] [C] Silicone-based leveling agent The silicone-based leveling agent of the present invention is a compound having a polysiloxane skeleton that reduces the surface tension of the coating film surface. Specifically, the silicone-based leveling agent is a polysiloxane having a third reactive functional group selected from a hydroxyl group, alkoxysilyl group, amino group, (meth)acryloyl group, allyl group, epoxy group, carboxyl group, or mercapto group at one end, both ends, or side chain, or a polysiloxane that does not have the third reactive functional group but has at least one alkyl group, phenyl group, or hydrogen in its side chain. The former is also called reactive silicone, and the latter is also called straight silicone. Among the polysiloxanes having the former reactive functional group, polysiloxanes having a hydroxyl group or an alkoxysilyl group are particularly preferred compounds because they react with [A] polyoxyalkylene (poly)glycerin-based alkoxysilane or [B] silicate oligomer and are fixed in the cured product. Furthermore, among the polysiloxanes having the former type of reactive functional group, those having a reactive functional group other than a hydroxyl group or an alkoxysilyl group, or the latter type of polysiloxane, do not necessarily react with [A] polyoxyalkylene (poly)glycerol-based alkoxysilane or [B] silicate oligomer to be immobilized in the cured product, but they are compatible and dispersed in the cured product, making them preferred compounds. Of these polysiloxanes, it is preferable to use a polysiloxane having a third reactive functional group at one end. The use of such compounds imparts oil repellency to the cured coating or film and makes it easier for water droplets or oil droplets adhering to the cured coating or film to slide off.

[0029] The [C] silicone-based leveling agent of the present invention is preferably a compound represented by the structure of the following formula (3). (R 3 and R 4 Each of these substituents independently contains a reactive functional group at its terminal end, selected from hydrogen, a C1-C6 alkyl group, a phenyl group, or a hydroxyl group, an alkoxysilyl group, an amino group, a (meth)acryloyl group, an allyl group, an epoxy group, a carboxyl group, or a mercapto group, and k is an integer from 1 to 250.1 and Z 2 At least one of them is a reactive functional group selected from the group consisting of a hydroxyl group, an alkoxysilyl group, an amino group, a (meth)acryloyl group, an allyl group, an epoxy group, a carboxyl group, or a substituent containing hydrogen at its terminus. Specifically, the compound having a reactive functional group among the [C] silicone leveling agents of the present invention is Z from Cylaprene <registered trademark> manufactured by JNC Corporation. 2 FM-0411P, FM-0421, FM-0425, Z have one hydroxyl group at the end. 2 FM-DA11, FM-DA21, FM-DA26, Z have two hydroxyl groups at their terminal ends. 2 FM-0815J, Z, which have an alkoxysilyl group at the terminal end. 2 It is preferable to use FM-0711, FM-0721, FM-0725, etc., which have a methacryloyl group at the terminal end. Also, Z, also manufactured by JNC Corporation. 1 and Z 2 FM-3311, FM-3321, FM-3325, Z each have an amino group at their respective termini. 1 and Z 2 FM-4411, FM-9915, FM-4421, FM-4425, Z each have a hydroxyl group at their respective ends. 1 and Z 2 It is preferable to use FM-7711, FM-7721, etc., which have methacryloyl groups at each of their ends. And Z manufactured by Shin-Etsu Chemical Co., Ltd. 2 X-22-170BX, X-22-170DX, X-22-176DX, X-22-176F, X-22-176GX-A, Z, which have one or two hydroxyl groups at their terminals. 2 X-22-174ASX, X-22-174BX, KF-2012, X-22-2426, X-22-2404, Z, which have a methacrylic group at their terminus. 2 X-22-173BX, X-22-173DX, Z have epoxy groups at their ends. 2 It is preferable to use X-22-3710, which has a carboxyl group at its terminus. Also, Z, also manufactured by Shin-Etsu Chemical Co., Ltd. 1 and Z 2KF-6000, KF-6001, KF-6002, KF-6003, X-21-5841, KF-9701, Z, each having a hydroxyl group at its terminal end. 1 and Z 2 PAM-E, KF-8010, X-22-161A, X-22-161B, Z, each having an amino group at its terminal end. 1 and Z 2 X-22-2445, Z, each having an acryloyl group at its terminal end. 1 and Z 2 X-22-164, X-22-164AS, X-22-164A, X-22-164B, X-22-164C, X-22-164E, Z, each having a methacryloyl group at its terminal 1 and Z 2 X-22-163, KF-105, X-22-163A, X-22-163B, X-22-163C, X-22-169AS, X-22-169B, Z, each having an epoxy group at its terminal end. 1 and Z 2 X-22-162C, Z, each having a carboxyl group at its terminal end. 1 and Z 2 It is preferable to use X-22-167B, X-22-167C, etc., which have epoxy groups at each end. Also, R, manufactured by Shin-Etsu Chemical Co., Ltd. 4 X-22-4039, X-22-4015, R, which have one hydroxyl group at their terminal end. 4 KF-877, X-22-3939A, R, which have an amino group at their terminus. 4 X-22-343, KF-101, KF-102, R, which have epoxy groups at their terminals 4 X-22-3701E, R, which have a carboxyl group at the terminal end. 4 It is preferable to use KF-2001, KF-2004, etc., which have a mercapto group at the terminal. Furthermore, among the [C] silicone leveling agents of the present invention, compounds that do not have reactive functional groups are KF-96L, KF-96, KF-96H, and some R dimethyl silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. 3 and R 4KF-50, KF-54, KF-56, and some R are methylphenyl silicone oils with phenyl groups. 3 It is preferable to use hydrogen methylhydrogen silicone oils such as KF-99 and KF-9901. For example, the above Z 2 FM-0815J, which has an alkoxysilyl group at its terminus, is a compound represented by the structure of formula (4) below, Z 2 Since this corresponds to a substituent that is a (2-trimethoxysilylethyl)dimethylsilyl group having an alkoxysilyl group at its terminus, it is a compound included in formula (3) above.

[0030] [C] The blending ratio of the silicone-based leveling agent is preferably 0.01 to 1% by weight, and more preferably 0.05 to 0.5% by weight, based on 100 parts by weight of [A] polyoxyalkylene (poly)glycerin-based alkoxysilane and [B] silicate oligomer. When the blending ratio of [C] silicone-based leveling agent is within this range, the resulting cured coating or film is given oil-repellent properties, and water droplets or oil droplets adhering to the resulting cured coating or film are made to slide off more easily.

[0031] The composition of the present invention is used in the form of a film produced by coating and curing it on various substrates such as polyethylene terephthalate, polycarbonate, acrylic and other plastics, glass, metal, and rock. The curing method of the coating film is not particularly limited, but curing by a sol-gel reaction is preferred, for example. When the composition of the present invention is cured by a sol-gel reaction, water necessary for the hydrolysis of the metal alkoxide is added. Furthermore, it is preferable to use a catalyst to promote the hydrolysis and polycondensation reaction of the metal alkoxide, and as such catalysts, acid catalysts and alkali catalysts used in conventional sol-gel methods are preferred. As acid catalysts, hydrochloric acid, nitric acid, sulfuric acid, formic acid, organic acids, and photoacid generators are preferred. As alkali catalysts, inorganic base compounds such as metal hydroxides and ammonia, organic base compounds such as amines and phosphines, and photoacid generators are preferred.

[0032] The composition of the present invention may further contain water, an alcohol having 1 to 4 carbon atoms, or the like, in order to produce a film-like substance.

[0033] When producing a film-like material using the composition of the present invention, the coating method is not particularly limited, and preferred methods include cast coating, spin coating, blade coating, dip coating, roll coating, bar coating, die coating, etc.

[0034] The film thickness of the film-like material can be appropriately changed from 0.1 to 100 μm depending on the application. Generally, it is considered difficult to form sol-gel films with a high proportion of inorganic components into thick films of 1 μm or more because they are prone to cracking. However, since the composition of the present invention contains [A] polyoxyalkylene (poly)glycerol-based alkoxysilane, it is possible to form thick films of 30 μm or more.

[0035] The film-like material produced by the composition of the present invention can be used, for example, as a coating for automobile windshields, lamp covers, camera lenses, goggles, and the like. Furthermore, because the film-like material has flexibility, it can also be used in touch panel displays, electronic paper, organic EL lighting, substrate glass for solar cells, and components for flexible devices.

[0036] The present invention will be described below with reference to examples, but the present invention is not limited in any way by these examples.

[0037] [Synthesis Example 1] In a reaction vessel equipped with a thermometer and a stirrer, 10.0 g of a 60-mol adduct of tetraglycerin (polyglycerin with an average degree of polymerization of 4) with propylene oxide (PO), 4.1 g of 3-isocyanatetopropyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.002 g of dibutyltin dilaurate were charged and stirred at 60°C for 18 hours to obtain 14 g of polyglycerin polyoxyalkylene-based alkoxysilane. Note that 100% of the hydroxyl groups at the ends of the above polyoxypropylene polyglyceryl ether were reacted.

[0038] [Synthesis Example 2] In a reaction vessel equipped with a thermometer and a stirrer, 37 g of a 12-mol adduct of tetraglycerin (polyglycerin with an average degree of polymerization of 4) with ethylene oxide (EO), 63 g of 3-isocyanatetopropyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.01 g of dibutyltin dilaurate were charged and stirred at 60°C for 5 hours to obtain 100 g of polyglycerin polyoxyalkylene-based alkoxysilane. Note that 100% of the hydroxyl groups at the ends of the polyoxyethylene polyglyceryl ether were reacted.

[0039] [Example 1] The following were uniformly mixed by stirring in the amounts and proportions shown in parts by weight in Table 1: [A] polyglycerin polyoxyalkylene alkoxysilane obtained in Synthesis Example 1, [B] methyl silicate as a silicate oligomer (manufactured by Colcoat Co., Ltd., Methyl Silicate 51 (average degree of polymerization = 4)), and [C] polysiloxane modified to have a reactive functional group at one end (manufactured by JNC Corporation, FM-0815J), 1-methoxy-2-propanol, water, and nitric acid, respectively, to obtain a liquid composition. This composition was then applied to a PET film with a thickness of 100 μm (manufactured by Toyobo Co., Ltd., Cosmoshine A4310) using an applicator (manufactured by Coating Tester Industry Co., Ltd., 250 μm applicator). Subsequently, the PET film coated with the composition was air-dried at room temperature for more than one hour, and then further dried for 30 minutes in a dryer (SPHH-101, manufactured by ESPEC Corporation) set to 80°C. As a result, a cured coating film with a thickness of 10 μm was formed on the PET film.

[0040] [Examples 2-14] Except that the compounds and proportions of [A] polyglycerin polyoxyalkylene alkoxysilane, [B] silicate oligomer, and [C] silicone leveling agent used in Example 1 were blended in the same manner as in Example 1, as shown in Table 1, a composition was obtained. A cured coating film with a thickness of 10 μm was then formed on a PET film. In Example 8, ethyl silicate (manufactured by Colcoat Co., Ltd., Ethyl Silicate 40 (average degree of polymerization = 5)) was used as the [B] silicate oligomer. In Examples 9 and 10, a mixed solution of methyl silicate and a mixed aqueous alcohol solution of methanol, ethanol, isopropyl alcohol, isobutanol, and water (manufactured by Honey Chemical Co., Ltd., Honeyselan PI-200) was used as the [B] silicate oligomer. In Example 14, polysiloxane modified to have reactive functional groups at both ends (manufactured by JNC Corporation, FM-9915) was used as the [C] silicone leveling agent.

[0041] [Comparative Examples 1-3] The compositions were prepared in the same manner as in Example 1, except that the compounds and proportions of [A] polyglycerin polyoxyalkylene alkoxysilane, [B] silicate oligomer, and [C] silicone leveling agent used in Synthesis Example 1 were blended as shown in Table 1. In Comparative Example 1, a sufficient cured coating film was not formed for the tests described later, but in Comparative Examples 2 and 3, a cured coating film with a thickness of 10 μm was formed on the PET film.

[0042] The following tests were performed on the PET films on which the cured coatings of each example and comparative example were formed, and the performance of the cured coatings was evaluated.

[0043] [Mandrel Test] The mandrel test is one method for confirming the flexibility of a coating film. In the present invention, the mandrel test was performed to confirm cracking and peeling of the cured coating film from the PET film in each example and comparative example. The test apparatus used for the mandrel test has a hinge-like shape that allows two plate members to be bent via a cylindrical member called a mandrel, which has a diameter of 2 mm. The PET film on which the above-mentioned cured coating film is formed is inserted between the two plate members and the mandrel so that the coating film faces the two plate members. Then, one of the plate members is rotated 180° around the mandrel over a period of 1 to 2 seconds. As a result, it is visually confirmed whether the cured coating film formed on the PET film has cracked or peeled off from the PET film. Specifically, this test was performed in accordance with JIS K5600-5-1. In this test, the cured coating formed on the PET film was evaluated as ○ if it did not crack or peel off the PET film, and as × if it cracked or peeled off at least once. Examples of ○ were judged as good, and examples of × were judged as poor.

[0044] [Pencil Hardness Test] The pencil hardness test is one method for confirming the hardness of a coating film. In this invention, the pencil hardness test was used to confirm whether the cured coating films of each example and comparative example corresponded to a hardness scale ranging from a soft 6B pencil to a hard 6H pencil. Specifically, the test was conducted in accordance with JIS K5600-5-4, using a pencil hardness tester (manufactured by Allgood Co., Ltd.), with a load of 750g applied. As a result, the hardest pencil on the hardness scale that did not produce any damage (plastic deformation or cohesive failure) in the cured coating films was recorded as the "pencil hardness".

[0045] [Water and Oil Repellency Test] The water and oil repellency test is one method to confirm the static repulsion of water and oil to a coating film, and serves as an indicator of water and oil staining of the coating film. Specifically, this test was conducted using a fully automatic contact angle meter (Kyowa Interface Science Co., Ltd., DMo-702), and the contact angles of water and oil (oleic acid) to the coating film of each example and comparative example were measured. In all measurements, 1.0 μL of water or oleic acid was dropped onto the coating film using a 22G stainless steel needle, and the contact angle after 1 second from application was determined by the θ / 2 method. Each of the three coating films was measured five times, and the arithmetic mean of these contact angles was taken as the measured value. This test was conducted in an environment of 23°C and 50% RH. The results of the test showed that for each cured coating formed on the PET film, a water contact angle of 90° or higher was judged to be the best, repelling water better; an angle between 80° and 90° was judged to be good, repelling water well; and an angle below 80° was judged to be poor, repelling water poorly. Similarly, for oil contact angles, an angle of 30° or higher was judged to be good, repelling oil well; and an angle below 30° was judged to be poor, repelling oil poorly.

[0046] [Water and Oil Repelling Test] The water and oil repelling test is one method to confirm the dynamic repulsion of water and oil to a coating film and serves as an indicator of water and oil staining of the coating film. In this test, a fully automatic contact angle meter (Kyowa Interface Science Co., Ltd., DMo-702) was used, and the inclination angle of the coating film at which water begins to slide downwards and the inclination angle from the horizontal at which oleic acid begins to slide downwards were measured for each example and comparative example coating film. Specifically, the sliding angle of water was measured by dropping 20 μL of water onto an 18G stainless steel needle, and the sliding angle of oleic acid was measured by dropping 10 μL of oleic acid onto an 18G stainless steel needle. In each case, the coating film was tilted at a speed of 2° / s from the point of application, and the angle at which each droplet slid was measured. Each of the three coating films was measured five times, and the arithmetic mean of the contact angles was taken as the measured value. The test was conducted under conditions of 23°C and 50% RH. The results showed that for each cured coating formed on the PET film, a water sliding angle of 30° or less was judged as the best for most effective water sliding, an angle greater than 30° but 35° or less was judged as good for good water sliding, and an angle greater than 35° was judged as poor for poor water sliding. Similarly, for oil sliding angles, an angle of 20° or less was judged as good for good oil sliding, and an angle greater than 20° was judged as poor for poor oil sliding.

[0047] The formulations and evaluation results for each example and comparative example are shown in Tables 1 to 3.

[0048]

[0049]

[0050]

[0051] As shown in each example, the cured coating obtained from the composition of the present invention containing [A] polyoxyalkylene (poly)glycerin-based alkoxysilane, [B] silicate oligomer, and [C] silicone-based leveling agent has significantly better flexibility compared to each comparative example, and while possessing a predetermined hardness, it repels and easily slides off water and oil, thus exhibiting the effect of being resistant to water and oil stains.

Claims

1. A composition characterized by containing: [A] a polyoxyalkylene (poly)glycerol-based alkoxysilane having a backbone in which polyoxyalkylene is condensed onto (poly)glycerol with an average degree of polymerization of 1 to 100, and having a plurality of alkoxysilyl groups at its terminals; [B] a silicate oligomer; and [C] a silicone-based leveling agent.

2. The composition according to claim 1, wherein the [A] polyoxyalkylene (poly)glycerol-based alkoxysilane is a reaction product obtained by reacting a polyoxyalkylene (poly)glyceryl ether derivative obtained by condensing a polyoxyalkylene (poly)glyceryl ether having a hydroxyl group at one end or a compound having a first reactive functional group at one end with an alkoxysilane having a second reactive functional group at one end, characterized in that the product is obtained by the reaction of the hydroxyl group or the first reactive functional group with the second reactive functional group.

3. The composition according to claim 2, characterized in that the polyoxyalkylene (poly)glyceryl ether or polyoxyalkylene (poly)glyceryl ether derivative described in claim 2 is represented by the structure of the following formula (1). (n, p, q, and r each represent the number of repeating units, where n is an integer from 1 to 100, and the sum of p, q, and r is an integer from 2 to 300. AO indicates an alkylene oxide with 1 to 4 carbon atoms. X 1 , X 2 and X 3 Each substituent independently contains at its terminal side either hydrogen or a reactive functional group selected from the group consisting of a thiol group, (meth)acryloyl group, epoxy group, glycidyl group, or allyl group.

4. The composition according to claim 2 or 3, characterized in that an alkoxysilane having a second reactive functional group at its terminal end is one selected from the group consisting of a vinyl group, an isocyanate group, a thiol group, a (meth)acryloyl group, an epoxy group, a glycidyl group, a hydroxyl group, an amino group, and hydrogen.

5. The composition according to claim 1 or 2, characterized in that the [B] silicate oligomer is at least one selected from a linear silicate oligomer, a branched silicate oligomer, or a cyclic silicate oligomer represented by the structure of formula (2) below. (R 1 and R 2 Each of these is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and m is an integer from 1 to 100. 1 and Y 2 Each of these is independently either hydrogen or an alkoxysilyl group having 1 to 3 carbon atoms.

6. The composition according to claim 1 or 2, characterized in that the [C] silicone leveling agent is a polysiloxane having a third reactive functional group selected from hydrogen, a hydroxyl group, an alkoxysilyl group, an amino group, a (meth)acryloyl group, an allyl group, an epoxy group, a carboxyl group, or a mercapto group at one end, both ends, or side chain, or a polysiloxane that does not have the third reactive functional group but has at least an alkyl group, a phenyl group, or hydrogen at one side chain.

7. The composition according to claim 1 or 2, characterized in that the blending ratio of [A] polyoxyalkylene (poly)glycerol-based alkoxysilane and [B] silicate oligomer is [A] polyoxyalkylene (poly)glycerol-based alkoxysilane : [B] silicate oligomer = 20:80 to 70:30.

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