Polymer-coated glass base material

Abstract

The present invention provides a polymer-coated glass base material on which the adsorption of normal cells such as blood cells is prevented and onto which a specific type of cells such as cancer cells, stem cells, and T cells can be selectively adsorbed. The present invention pertains to a polymer-coated glass base material in which one or more polymer layers are formed on the surface of a glass base material, wherein the glass is a soda lime glass having a contact angle of an air bubble in water of 100 degrees to 120 degrees inclusive, and the surface of an outermost layer among the polymer layers has an elastic modulus of 1.20 MPa or less in water or in an aqueous solution.

Description

Polymer-coated glass substrate

[0001] The present invention relates to polymer-coated glass substrates.

[0002] A technology has been proposed to coat the surface of a substrate with a special polymer in order to create devices that can adsorb specific cells in blood and body fluids (blood cells, cancer cells present in blood and body fluids, stem cells, T cells, etc.).

[0003] However, there is a concern that specific cells such as cancer cells, stem cells, and T cells may be adsorbed onto the surface of the substrate at the same time as blood cells are adsorbed. Therefore, there is a need for a polymer-coated substrate that can more selectively adsorb specific cells such as cancer cells, stem cells, and T cells while suppressing the adsorption of normal cells such as blood cells.

[0004] The present invention aims to solve the above-mentioned problems and to provide a polymer-coated glass substrate that can suppress the adsorption of normal cells such as blood cells and selectively adsorb specific cells such as cancer cells, stem cells, and T cells.

[0005] The present invention relates to a polymer-coated glass substrate having one or more polymer layers formed on the surface of a glass substrate, wherein the glass is soda-lime glass having a contact angle of air bubbles in water of 100 degrees or more and 120 degrees or less, and the surface of the outermost layer of the polymer layer has an elastic modulus of 1.20 MPa or less in water or an aqueous solution.

[0006] According to the present invention, there is provided a polymer-coated glass substrate having one or more polymer layers formed on the surface of a glass substrate, wherein the glass is soda-lime glass having a contact angle of air bubbles in water of 100° to 120°, and the surface of the outermost layer of the polymer layer has an elastic modulus of 1.20 MPa or less in water or an aqueous solution, thereby making it possible to suppress the adsorption of normal cells such as blood cells and to selectively adsorb specific cells such as cancer cells, stem cells, and T cells. Therefore, the polymer-coated glass substrate is expected to have improved adsorption performance for specific cells such as cancer cells, stem cells, and T cells.

[0007] The polymer-coated glass substrate is a polymer-coated glass substrate having one or more polymer layers formed on the surface of a glass substrate, the glass being soda-lime glass having a contact angle of air bubbles in water of 100 degrees or more and 120 degrees or less, and the surface of the outermost layer of the polymer layer having an elastic modulus of 1.20 MPa or less in water or an aqueous solution.

[0008] Tumor cells (e.g., cancer cells) that appear in bodily fluids, such as circulating tumor cells in the blood (several to several hundred cells per mL of blood), are very rare. Therefore, it is considered important to adsorb as many tumor cells present in the collected bodily fluid as possible for testing. The polymer-coated glass substrate uses soda-lime glass, which has a water-borne contact angle of 100° to 120°, as the glass substrate to be coated with the polymer, and the outermost layer of the polymer layer formed on the substrate surface has a surface elastic modulus of 1.20 MPa or less in water or aqueous solution. Compared to normal cells such as blood cells, specific cells such as cancer cells are generally known to be soft. This is related to the fact that, when specific cells such as cancer cells metastasize, they significantly deform their shape and move through gaps. For this reason, normal cells such as blood cells, which are resistant to deformation and are hard, are less likely to be adsorbed by polymer substrates with soft surfaces. On the other hand, specific cells such as cancer cells that have acquired deformability are easily adsorbed even by polymer substrates with soft surfaces. Furthermore, if the surface elastic modulus is too low, adsorption ability is reduced. That is, there is an optimum value for the surface elastic modulus. The polymer-coated glass substrate, in particular, uses soda-lime glass, which has a contact angle of air bubbles in water of 100° to 120°, and forms one or more polymer layers on the outermost surface of the substrate, the surface elastic modulus of which in water or an aqueous solution is 1.20 MPa or less. This significantly suppresses the adsorption of normal cells such as blood cells while selectively adsorbing specific cells such as cancer cells, stem cells, and T cells. Furthermore, measuring the number of tumor cells adsorbed to the polymer layer of the polymer-coated glass substrate can determine the number of tumor cells in body fluids, which can be expected to confirm the effectiveness of cancer treatment. Furthermore, culturing the adsorbed tumor cells and confirming the efficacy of anticancer drugs, etc., outside the body before administering them can confirm the efficacy of the anticancer drugs, etc., and is also useful for selecting anticancer drugs, etc. Furthermore, genetic analysis of the adsorbed tumor cells can be useful for selecting anticancer drugs, etc. Furthermore, genetic analysis can be performed on adsorbed or cultured tumor cells to examine the mutation and expression states of the tumor cells, which can be used to select anticancer drugs, etc., and to help elucidate the mechanisms of cancer.

[0009] The glass constituting the glass substrate is soda lime glass. The soda lime glass has a surface of -N(R １ ) ２ and / or -N(R ２ ) ３ ＋ (R １ and R ２ are the same or different and are substituted or unsubstituted hydrocarbon groups which may contain a hydrogen atom or a heteroatom. In this case, the effect of suppressing adsorption of normal cells such as blood cells and selectively adsorbing specific cells such as cancer cells, stem cells, and T cells tends to be effectively exerted.

[0010] "-N(R １ ) ２ and / or -N(R ２ ) ３ ＋ With respect to "a group represented by -N(R １ ) ２ R in the group represented by １ , -N(R ２ ) ３ ＋ R in the group represented by ２ are the same or different and each is (1) a hydrogen atom or (2) a substituted or unsubstituted hydrocarbon group which may contain a heteroatom.

[0011] R １ ~R ２ The substituted or unsubstituted hydrocarbon group, which may contain a heteroatom, may be any of linear, branched, or cyclic groups. The heteroatom is not particularly limited, and examples thereof include oxygen, nitrogen, etc. The substituent is not particularly limited, and examples thereof include known groups such as a hydroxyl group and a halogen group (-Cl, -Br, etc.). The group may have one or more of these heteroatoms and substituents.

[0012] The substituted or unsubstituted hydrocarbon group which may contain a heteroatom preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 8 carbon atoms.

[0013] The substituted or unsubstituted hydrocarbon group which may contain a heteroatom includes a monovalent hydrocarbon group and a divalent hydrocarbon group.

[0014] Examples of the substituted or unsubstituted monovalent hydrocarbon group which may contain a heteroatom include a substituted or unsubstituted linear alkyl group, branched alkyl group, cyclic alkyl group, cyclic ether group, aryl group, aralkyl group, and alkoxy group which may contain a heteroatom.

[0015] Examples of substituted or unsubstituted linear alkyl groups and branched alkyl groups which may contain heteroatoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, and groups containing these heteroatoms. Examples of substituted or unsubstituted cyclic alkyl groups which may contain heteroatoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, 1-ethylcyclopentyl, 1-ethylcyclohexyl, and groups containing these heteroatoms. Examples of substituted or unsubstituted cyclic ether groups which may contain heteroatoms include oxirane groups, oxetane groups, oxolane groups, oxane groups, oxepane groups, oxocane groups, oxonane groups, oxecane groups, oxete groups, oxole groups, dioxolane groups, dioxane groups, dioxepane groups, dioxecane groups, etc., and groups containing these heteroatoms. Examples of substituted or unsubstituted aryl groups which may contain heteroatoms include phenyl groups, tolyl groups, xylyl groups, biphenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, and groups containing these heteroatoms. Examples of substituted or unsubstituted aralkyl groups which may contain heteroatoms include benzyl groups, phenethyl groups, and groups containing these heteroatoms. Examples of the substituted or unsubstituted alkoxy group which may contain a hetero atom include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a t-butoxy group, an n-pentyloxy group, an n-hexyloxy group, and groups containing these hetero atoms.

[0016] Examples of the substituted or unsubstituted divalent hydrocarbon group which may contain a heteroatom include a substituted or unsubstituted alkylene group, alkenylene group, cycloalkylene group, cycloalkylalkylene group, arylene group, aralkylene group, and oxyalkylene group which may contain a heteroatom.

[0017] Specific examples of substituted or unsubstituted alkylene groups which may contain heteroatoms include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octylene, nonylene, decylene, 1,2-propylene, and groups containing these heteroatoms. Specific examples of substituted or unsubstituted alkenylene groups which may contain heteroatoms include vinylene, 1-propenylene, 2-propenylene, and groups containing these heteroatoms. Specific examples of substituted or unsubstituted cycloalkylene groups which may contain heteroatoms include cyclohexylene and groups containing this heteroatom. Specific examples of substituted or unsubstituted cycloalkylalkylene groups which may contain heteroatoms include cyclohexylmethylene and groups containing this heteroatom. Specific examples of substituted or unsubstituted arylene groups which may contain heteroatoms include phenylene, tolylene, xylylene, and groups containing these heteroatoms. Examples of substituted or unsubstituted aralkylene groups which may contain a heteroatom include a benzylidene group and groups containing this heteroatom, etc. Examples of substituted or unsubstituted oxyalkylene groups which may contain a heteroatom include an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxytetramethylene group, and groups containing these heteroatoms, etc.

[0018] "-N(R １ ) ２ and / or -N(R ２ ) ３ ＋ The surface of the soda-lime glass substrate having a group represented by -N(R １ ) ２ and / or -N(R ２ ) ３ ＋ The compound can be prepared by using any method capable of introducing a group represented by the formula: １ ) ２ and / or -N(R ２ ) ３ ＋ Treatment of the substrate surface with a silane coupling agent having a group represented by the formula: NH ３Treatment of the substrate surface with gas (NH ３ Among these, the treatment with a silane coupling agent is preferred.

[0019] -N(R) that can be used for silane coupling agent treatment １ ) ２ and / or -N(R ２ ) ３ ＋ The silane coupling agent having a group represented by the formula (I) is not particularly limited, and examples thereof include —N(R １ ) ２ and / or -N(R ２ ) ３ ＋ and a group represented by —Si(R ３ ) ３ and a compound (R １ and R ２ are the same or different and each represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group which may contain a heteroatom. ３ are the same or different and are substituted or unsubstituted hydrocarbon groups which may contain heteroatoms.

[0020] "-Si(R ３ ) ３ R in "a group represented by ３ are the same or different and are substituted or unsubstituted hydrocarbon groups which may contain a heteroatom. Examples of the substituted or unsubstituted hydrocarbon groups which may contain a heteroatom include the above-mentioned R １ and R ２ Examples of the substituted or unsubstituted monovalent hydrocarbon groups which may contain heteroatoms include the same groups as those of the substituted or unsubstituted monovalent hydrocarbon groups which may contain heteroatoms. Among these, linear alkyl groups, branched alkyl groups, cyclic alkyl groups, and alkoxy groups are preferred. Specific examples of the linear alkyl groups, branched alkyl groups, cyclic alkyl groups, and alkoxy groups include the above-mentioned R １ and R ２ and R ３ Preferably, at least one of these is an alkoxy group, more preferably two, and even more preferably three.

[0021] -N(R１ ) ２ and / or -N(R ２ ) ３ ＋ and a group represented by —Si(R ３ ) ３ As the compound having a group represented by the following formula (A-1) or (A-2), for example, compounds represented by the following formula (A-1) or (A-2) can be suitably used.

[0022] (In the formula, R １１ ~R １２ are the same or different and are hydrogen atoms or substituted or unsubstituted monovalent hydrocarbon groups which may contain heteroatoms. １６ ~R １８ are the same or different and are substituted or unsubstituted monovalent hydrocarbon groups which may contain heteroatoms. １９ is a substituted or unsubstituted divalent hydrocarbon group which may contain a heteroatom.

[0023] (In the formula, R １１ ~R １３ are the same or different and are hydrogen atoms or substituted or unsubstituted monovalent hydrocarbon groups which may contain heteroatoms. １６ ~R １８ are the same or different and are substituted or unsubstituted monovalent hydrocarbon groups which may contain heteroatoms. １９ is a substituted or unsubstituted divalent hydrocarbon group which may contain a heteroatom; and X is a halogen.

[0024] R in formulas (A-1) and (A-2) １１ , R １２ , R １３ Examples of the "substituted or unsubstituted monovalent hydrocarbon group which may contain a heteroatom" include the above-mentioned R １ ~R ２ Examples include the same groups as the substituted or unsubstituted monovalent hydrocarbon groups which may contain a hetero atom as shown in R １１ , R １２ , R １３ is preferably a hydrogen atom, a linear alkyl group or a branched alkyl group which may contain a heteroatom, and is preferably a hydrogen atom, a linear alkyl group, a branched alkyl group, -C ｐ H２ｐ -O-C ｑ H ２ｑ＋１ (p and q are integers) are more preferred.

[0025] R in formulas (A-1) and (A-2) １６ , R １７ , R １８ Examples of the "substituted or unsubstituted monovalent hydrocarbon group which may contain a heteroatom" include the above-mentioned R １ ~R ２ Examples include the same groups as the substituted or unsubstituted monovalent hydrocarbon groups which may contain a hetero atom as shown in R １６ , R １７ , R １８ is preferably a substituted or unsubstituted alkoxy group which may contain a hetero atom, more preferably an alkoxy group, and further preferably a methoxy group or an ethoxy group.

[0026] R in formulas (A-1) and (A-2) １９ Examples of the "substituted or unsubstituted divalent hydrocarbon group which may contain a heteroatom" include the above-mentioned R １ ~R ２ Examples of the substituted or unsubstituted divalent hydrocarbon group which may contain a hetero atom include the same groups as those of the above-mentioned R １ In addition to the specific examples of the substituted or unsubstituted divalent hydrocarbon group which may contain a hetero atom, —CO—N(R １１１ )-(R １１２ )-- (R １１１ represents a hydrogen atom or an alkyl group. １１２ Ha-C ｐ H ２ｐ - (p is an integer of 1 to 8). １９ is a substituted or unsubstituted alkylene group which may contain a heteroatom, —CO—N(R １１１ )-(R １１２ )- is preferred, and a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a —CO—N(R １１１ )-(R １１２ )- is more preferred.

[0027] Examples of the halogen represented by X in formula (A-2) include chlorine (chlorine ion) and bromine (bromine ion).

[0028] -NR １ ２ and / or -NR １ ３ ＋ and a group represented by —Si(R ２ ) ３ As the compound having a group represented by the following formula (A-3), a compound represented by the following formula (A-3) can also be suitably used.

[0029] (In the formula, R ２１ ~R ２３ are the same or different and are hydrogen atoms or substituted or unsubstituted monovalent hydrocarbon groups which may contain heteroatoms. ２４ ~R ２６ are the same or different and are substituted or unsubstituted monovalent hydrocarbon groups which may contain heteroatoms. ２７ ~R ３０ represents a substituted or unsubstituted divalent hydrocarbon group which may contain a heteroatom; X represents a halogen; and n represents the number of repetitions.

[0030] R in formula (A-3) ２１ , R ２２ , R ２３ Examples of the "substituted or unsubstituted monovalent hydrocarbon group which may contain a heteroatom" include the above-mentioned R １ ~R ２ Examples include the same groups as the substituted or unsubstituted monovalent hydrocarbon groups which may contain a hetero atom as shown in R ２１ , R ２２ , R ２３ is preferably a hydrogen atom, a linear alkyl group or a branched alkyl group which may contain a hetero atom, and more preferably a hydrogen atom.

[0031] R in formula (A-3) ２４ , R ２５ , R ２６ Examples of the "substituted or unsubstituted monovalent hydrocarbon group which may contain a heteroatom" include the above-mentioned R １ ~R ２Examples include the same groups as the substituted or unsubstituted monovalent hydrocarbon groups which may contain a hetero atom as shown in R ２４ , R ２５ , R ２６ is preferably a substituted or unsubstituted alkoxy group which may contain a hetero atom, more preferably an alkoxy group, and further preferably a methoxy group or an ethoxy group.

[0032] R in formula (A-3) ２７ , R ２８ , R ２９ , R ３０ Examples of the "substituted or unsubstituted divalent hydrocarbon group which may contain a heteroatom" include the above-mentioned R １ ~R ２ Examples include the same groups as the substituted or unsubstituted divalent hydrocarbon groups which may contain a hetero atom as shown in R ２７ , R ２８ , R ２９ , R ３０ is preferably a substituted or unsubstituted alkylene group which may contain a hetero atom, and more preferably a methylene group, an ethylene group, a trimethylene group or a tetramethylene group.

[0033] Examples of the halogen represented by X in formula (A-3) include chlorine (chlorine ion) and bromine (bromine ion).

[0034] The degree of polymerization of the structural unit represented by formula (A-3) is not particularly limited, and may be appropriately selected taking into consideration the processability (coatability) of the compound, adhesion to the hydrophilic polymer layer, and the like.

[0035] The number average molecular weight (Mn) of the compound (polymer) represented by the above formula (A-3) is preferably 500 to 6,000, more preferably 1,000 to 4,000, and even more preferably 1,000 to 3,000.

[0036] -N(R １ ) ２Specific examples of the silane coupling agent having a group represented by the formula (I) include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriisopropoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropylmethyldiethoxysilane, 3-(2-aminoethyl)aminopropyltriisopropoxysilane, 3-(2-(2-aminoethyl)aminopropyltriisopropoxysilane, amino group-containing silane coupling agents such as (aminoethyl)aminoethyl)aminopropyltrimethoxysilane, 3-(6-aminohexyl)aminopropyltrimethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltrimethoxysilane, N-vinylbenzyl-3-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, and (2-aminoethyl)aminomethyltrimethoxysilane;3-Ureidopropyltrimethoxysilane (1-[3-(trimethoxysilyl)propyl]urea), 3-Ureidopropyltriethoxysilane, 3-Ureidopropyltriisopropoxysilane, 3-Ureidopropylmethyldimethoxysilane, 3-Ureidopropylmethyldiethoxysilane, Ureidomethyltrimethoxysilane, Ureidomethyltriethoxysilane, Ureidomethyltriisopropoxysilane, Ureidomethylmethyldimethoxysilane, Ureidomethylmethyldiethoxysilane, 3-[(2-Ureidoethyl)amino]propyltrimethoxysilane, 1,3-Bis[3-(trimethoxysilyl)propyl]urea , silane coupling agents having a urea group such as 1,3-bis[3-(triethoxysilyl)propyl]urea, 1-[3-(triethoxysilyl)propyl]-3-phenylurea, 1,3-bis[3-(tripropylsilyl)propyl]urea, 1-[3-(triethoxysilyl)propyl]-3,3-dioctylurea, 1-[3-(triethoxysilyl)propyl]-3,3-dihexadecylurea, 1-[3-(triethoxysilyl)propyl]-3-propylurea, 3-(3-dodecylureido)propyltriethoxysilane, and N-(1-phenylethyl)-N'-[3-(triethoxysilyl)propyl]urea; and the like.

[0037] -N(R １ ) ３ ＋Specific examples of the silane coupling agent having a group represented by the formula (I) include N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride (N-TRIMETHOXYSILYLPROPYL-N,N,N-TRI-METHYLAMMONIUM CHLORIDE), N-trimethoxysilylpropyl-N,N,N-tri-n-butylammonium chloride (N-TRIMETHOXYSILYLPROPYL-N,N,N-TRI-n-BUTYLAMMONIUM CHLORIDE), octadecyldimethyl(3-trimethoxysilyl-propyl)ammonium chloride (OCTADECYLDIMETHYL(3-TRIMETHOXYSILYL-PROPYL)AMMONIUM CHLORIDE), N-(trimethoxysilylethyl)benzyl-N,N,N-trimethylammonium chloride (N-(TRIMETHOXYSILYLETHYL)BENZYL-N,N,N-TRIMETHYLAMMONIUM CHLORID), N,N-didecyl-N-methyl-N-(3-trimethoxysilyl-propyl)ammonium chloride (N,N-DIDECYL-N-METHYL-N-(3-TRIMETHOXYSILYL-PROPYL)AMMONIUM CHLORIDE), Bis(methoxyethyl)-3-trimethoxysilylpropylammonium chloride (BIS(METHOXYETHYL)-3-TRIMETHOXYSILYLPROPYLAMMONIUM CHLORIDE), trimethoxysilylpropyl-modified (polyethyleneimine) (TRIMETHOXYSILYLPROPYL MODIFIED (POLYETHYLENIMINE)), dimethoxymethylsilylpropyl-modified (polyethyleneimine) (DIMETHOXYMETHYLSILYLPROPYL MODIFIED (POLYETHYLENIMINE)).

[0038] Among these, 3-aminopropyltriethoxysilane, bis(methoxyethyl)-3-trimethoxysilylpropylammonium chloride (BIS(METHOXYETHYL)-3-TRIMETHOXYSILYLPROPYLAMMONIUM CHLORIDE), trimethoxysilylpropyl-modified (polyethyleneimine) (TRIMETHOXYSILYLPROPYL MODIFIED(POLYETHYLENIMINE)), and N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride (N-TRIMETHOXYSILYLPROPYL-N,N,N-TRI-METHYLAMMONIUM CHLORIDE) are preferred. １ ) ２ and / or -N(R １ ) ３ ＋ -N(R １ ) ２ and / or -N(R １ ) ３ ＋ The silane coupling agents having a group represented by the formula (I) may be used alone or in combination of two or more.

[0039] Silane coupling agent treatment (-N(R １ ) ２ and / or -N(R １ ) ３ ＋ The method for treating the substrate surface with a silane coupling agent having a group represented by is not particularly limited, and any method that can coat (treat) the substrate surface with a silane coupling agent can be used. Specifically, a substrate whose surface is coated (treated) with a silane coupling agent can be produced by known techniques such as coating (applying), spraying (spraying), or immersing a silane coupling agent solution or dispersion prepared by dissolving or dispersing the silane coupling agent in various solvents onto the substrate surface. Known methods can be used for the coating method, spraying method, and immersion method.

[0040] The solvent is not particularly limited as long as it can dissolve and disperse the silane coupling agent, and may be appropriately selected depending on the silane coupling agent used. Examples of the solvent include water, organic solvents, and mixed solvents thereof. Examples of the organic solvent include alcohols such as methanol, ethanol, n-propanol, i-propanol, and methoxypropanol; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran, acetonitrile, ethyl acetate, and toluene.

[0041] The concentration of the silane coupling agent solution or dispersion may be appropriately set depending on the type of silane coupling agent, the type of solvent, the treatment method (coating method, spraying method, immersion method), and the like.

[0042] The treatment conditions such as the treatment temperature and treatment time of the silane coupling agent treatment may be appropriately set according to the type of silane coupling agent, solvent, treatment method, etc., but it is preferable to treat (maintain) the silane coupling agent solution / dispersion on the substrate surface (coating, spraying, immersion, etc.) under conditions of humidity of 50% or more. This tends to strengthen the chemical bond between the substrate surface and the silane coupling agent. The humidity is more preferably 60% or more, and even more preferably 80% or more. The upper limit is not particularly limited, but for example, it is preferably 100% or less.

[0043] When treating (holding) under conditions of humidity of 50% or higher, the treatment time and treatment temperature may be appropriately set from the viewpoint of strengthening the chemical bond between the substrate surface and the silane coupling agent, economic viewpoints, etc. For example, the treatment time (holding time) is preferably 1 to 60 hours, more preferably 1 to 20 hours. The treatment temperature (holding temperature) is preferably 20 to 65°C, more preferably 25 to 50°C.

[0044] As the substrate whose surface is coated (treated) with a silane coupling agent, in addition to those prepared by the above-mentioned method, commercially available products can be used. Examples of commercially available products treated with a silane coupling agent that can be used include MAS-coated slide glass, MAS-GP type-coated slide glass, Frontier-coated slide glass, and APS-coated slide glass (manufactured by Matsunami Glass Industry Co., Ltd.).

[0045] -N(R １ ) ２ and / or -N(R ２ ) ３ ＋ From the viewpoint of adhesion of the polymer layer to the substrate surface, at least a part (part or all) of the substrate surface having a group represented by the formula (I) preferably has a water contact angle of 50 to 120 degrees, more preferably 70 to 100 degrees.

[0046] The soda-lime glass has a contact angle of air bubbles in water of 100 degrees or more and 120 degrees or less. The soda-lime glass having a contact angle of air bubbles in water of 100 degrees or more and 120 degrees or less can be appropriately selected from commercially available products.

[0047] The contact angle of air bubbles in water of the soda-lime glass is more preferably 103 degrees or more, and more preferably 117 degrees or less. In this specification, the "contact angle of air bubbles in water" refers to the value obtained by attaching air bubbles (air) to the surface of a substrate in water and measuring the contact angle between the air bubbles and the surface of the substrate. Measurement can be performed under the following conditions: water temperature is room temperature (20°C) and the amount of air bubbles is 2 μL.

[0048] The thickness of the glass substrate made of soda-lime glass is not particularly limited, but the average thickness is preferably 100 μm or more and 5000 μm or less, and more preferably 500 μm or more and 3000 μm or less. The average thickness is determined by measuring the thickness at any 10 points using a micrometer and averaging the measured values.

[0049] The polymer-coated glass substrate has one or more polymer layers formed on the surface of the glass substrate. The polymer layer may be formed of one layer or two or more layers. In particular, the surface of the soda-lime glass substrate is -N(R １ ) ２ and / or -N(R ２ ) ３ ＋ (R １ and R ２and are the same or different and each represent a hydrogen atom, or a substituted or unsubstituted hydrocarbon group which may contain a hetero atom. In the case of a polymer having a group represented by the following formula (I), it is desirable that two or more polymer layers are formed.

[0050] As the polymer constituting the one or more polymer layers, known polymers can be appropriately used. Examples of the polymer include a homopolymer of one type of monomer and a copolymer of two or more types of monomers. For example, a polymer having hydrophilic properties (hydrophilic polymer) can be suitably used as the polymer. The polymers can be used alone or in combination of two or more types.

[0051] The polymer can be produced by a known method, for example, by polymerizing a solution of the monomers constituting the polymer by a known method. The solvent for the monomer solution is not particularly limited, and the solvents described below can be used. Among them, toluene and methanol are preferred.

[0052] In order to obtain a more effective polymer-coated glass substrate, it is desirable that the outermost surface layer (the polymer layer formed on the outermost side (surface side)) of the one or more polymer layers is formed from a hydrophilic polymer.

[0053] Examples of the hydrophilic polymer include homopolymers and copolymers of one or more hydrophilic monomers, copolymers of one or more hydrophilic monomers with one or more other monomers, etc. These may be used alone or in combination of two or more.

[0054] The hydrophilic monomer is not particularly limited, and various monomers having a hydrophilic group can be used, for example. Examples of the hydrophilic group include known hydrophilic groups such as an amide group, a sulfate group, a sulfonic acid group, a carboxylic acid group, a hydroxyl group, an amino group, and an oxyethylene group.

[0055] Specific examples of the hydrophilic monomer include (meth)acrylic acid, (meth)acrylic acid esters (alkoxyalkyl (meth)acrylates such as methoxyethyl (meth)acrylate, hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, etc.), (meth)acrylamide, and (meth)acrylamide derivatives having a cyclic group ((meth)acryloylmorpholine, etc.). Of these, (meth)acrylic acid, (meth)acrylic acid esters, and alkoxyalkyl (meth)acrylates are preferred, alkoxyalkyl (meth)acrylates are more preferred, and 2-methoxyethyl acrylate is particularly preferred. These may be used alone or in combination of two or more.

[0056] The other monomers may be appropriately selected within a range that does not inhibit the effects of the hydrophilic polymer. Specific examples of the other monomers include aromatic monomers such as styrene, vinyl acetate, and N-isopropylacrylamide, which can impart temperature responsiveness. These may be used alone or in combination of two or more.

[0057] Specific examples of the above-mentioned homopolymers and copolymers include homopolymers composed of one hydrophilic monomer such as polyacrylic acid, polyacrylic acid esters, polymethacrylic acid, polymethacrylic acid esters, polyacryloylmorpholine, polymethacryloylmorpholine, polyacrylamide, polymethacrylamide, polyalkoxyalkyl acrylates, and polyalkoxyalkyl methacrylates; copolymers composed of two or more of the above-mentioned hydrophilic monomers; copolymers composed of one or more of the above-mentioned hydrophilic monomers and one or more of the above-mentioned other monomers; etc. The above-mentioned hydrophilic polymers may be used alone or in combination of two or more.

[0058] Among these, the hydrophilic polymer is preferably a polymer represented by the following formula (I): These may be used alone or in combination of two or more kinds. (In the formula, R ５１ is a hydrogen atom or a methyl group, R ５２ represents an alkyl group, p is 1 to 8, m is 1 to 5, and n is the number of repetitions.

[0059] As the polymer represented by the formula (I), for example, a polymer represented by the following formula (I-1) can be suitably used. These may be used alone or in combination of two or more kinds. (In the formula, R ５１ is a hydrogen atom or a methyl group, R ５２ represents an alkyl group, m is 1 to 5, and n is the number of repetitions.

[0060] R ５２ The number of carbon atoms in the alkyl group of R is preferably 1 to 10, and more preferably 1 to 5. ５２ is particularly preferably a methyl group or an ethyl group. p is preferably 1 to 5, more preferably 1 to 3. m is preferably 1 to 3. n (the number of repeating units) is preferably 15 to 1,500, more preferably 40 to 1,200.

[0061] As the hydrophilic polymer, a copolymer of a compound represented by the following formula (II) and other monomers can also be suitably used. These may be used alone or in combination of two or more kinds.

[0062] (In the formula, R ５１ , R ５２ , p, m are the same as above.)

[0063] As the compound represented by formula (II), for example, a compound represented by formula (II-1) below can be suitably used. These may be used alone or in combination of two or more kinds. (In the formula, R ５１ , R ５２ , m is the same as above.)

[0064] Among the above-mentioned hydrophilic polymers, the hydrophilic polymer represented by the above formula (I) is preferred, and the hydrophilic polymer represented by the above formula (I-1) is particularly preferred, from the viewpoint of obtaining better effects.

[0065] From the viewpoint of obtaining a better effect, the number average molecular weight (Mn) of the polymer constituting the outermost layer of the one or more polymer layers is preferably 8,000 to 150,000, more preferably 10,000 to 60,000, and even more preferably 10,000 to 39,000. When the polymer is a hydrophilic polymer, it is desirable that the number average molecular weight (Mn) is similar.

[0066] In this specification, the number average molecular weight (Mn) and weight average molecular weight (Mw) can be determined in terms of standard polystyrene based on measured values ​​obtained by gel permeation chromatography (GPC) (GPC-8000 series manufactured by Tosoh Corporation, detector: differential refractometer, column: TSKGEL SUPERMULTIPORE HZ-M manufactured by Tosoh Corporation).

[0067] The total thickness of the one or more polymer layers (total thickness of one or more polymer layers) is preferably 10 to 4000 nm, more preferably 30 to 2000 nm, and even more preferably 50 to 500 nm. By adjusting the thickness within the above range, good low adsorption to proteins and cells and selective adsorption to cancer cells can be expected. Furthermore, even when the outermost layer is a hydrophilic polymer layer (a layer formed from a hydrophilic polymer), it is desirable for the total thickness (total film thickness) to be similar. In this specification, the total thickness of the polymer layer can be measured using a transmission electron microscope (TEM).

[0068] At least a part (part or all) of the surface of the polymer layer (the surface of the outermost layer of one or more polymer layers in the polymer-coated glass substrate) preferably has a water contact angle of 65° or less, more preferably 60° or less, and even more preferably 55° or less. The water contact angle is preferably 25° or more, and more preferably 35° or more.

[0069] The polymer-coated glass substrate may also be one in which a polymer layer (hereinafter also referred to as a "blend polymer layer") made of a blend of polymers with different molecular weights is formed on the surface of the soda-lime glass substrate. The hydrophilic polymers with different molecular weights may be one containing two polymers of the same polymer but with different molecular weights (e.g., a blend of polymers containing poly-2-methoxyethyl acrylate having a number-average molecular weight of 16,000 and poly-2-methoxyethyl acrylate having a number-average molecular weight of 80,000), or one containing different polymers (polymers with different structures) with different molecular weights (e.g., a blend of polymers containing poly-2-methoxyethyl acrylate having a number-average molecular weight of 16,000 and polyacryloylmorpholine having a number-average molecular weight of 80,000). In particular, the blend polymer layer is preferably one formed of polymers of the same polymer but with different molecular weights.

[0070] The polymers constituting the blend polymer layer preferably include polymers represented by formula (I) having different molecular weights. Here, the polymers represented by formula (I) having different molecular weights may include two or more polymers having the same structural unit but different molecular weights (for example, a polymer including poly-2-methoxyethyl acrylate having a number-average molecular weight of 16,000 and poly-2-methoxyethyl acrylate having a number-average molecular weight of 80,000), or may include two or more polymers having different structural units but different molecular weights (for example, a polymer including poly-2-methoxyethyl acrylate having a number-average molecular weight of 16,000 and poly-2-ethoxyethyl methacrylate having a number-average molecular weight of 80,000). The polymer represented by formula (I) may be of one type or two or more types.

[0071] The molecular weight of the polymers having different molecular weights is not particularly limited, and examples thereof include number average molecular weight (Mn), weight average molecular weight (Mw), etc. In particular, a blend of polymers having different Mn can be preferably used.

[0072] When a blend of polymers with different Mn is used, it is preferable that the blend contains polymers with a difference in Mn of 30,000 or more, and more preferable that the blend contains hydrophilic polymers with a difference in Mn of 50,000 or more.

[0073] The blend of polymers of different molecular weights desirably contains a low-molecular-weight polymer having a number-average molecular weight (Mn) of 5,000 or more and 25,000 or less. The Mn of the low-molecular-weight polymer is preferably 10,000 or more, more preferably 14,000 or more, and preferably 23,000 or less. The blend of polymers of different molecular weights desirably contains a high-molecular-weight polymer having a number-average molecular weight (Mn) of 35,000 or more and 200,000 or less. The Mn of the high-molecular-weight polymer is preferably 40,000 or more, more preferably 50,000 or more, and preferably 150,000 or less, more preferably 130,000 or less.

[0074] The polymer layer can be produced by known methods such as (1) injecting a polymer solution or dispersion, prepared by dissolving or dispersing a polymer in various solvents, onto the surface of a glass substrate (e.g., into recesses in the substrate), holding the polymer for a predetermined period of time, and drying, or (2) applying (spraying) the polymer solution or dispersion onto the surface of the glass substrate and drying as needed. By adding other components to the polymer-coated glass substrate as needed, a device capable of adsorbing, culturing, testing, etc., specific cells can be produced.

[0075] Conventionally known materials and methods can be used for the solvent, injection method, coating (spraying) method, etc. The holding and drying times of (1) and (2) may be set appropriately depending on the size of the substrate, the type of liquid to be introduced, etc. The holding time is preferably 10 seconds to 10 hours, more preferably 1 minute to 5 hours, and even more preferably 5 minutes to 2 hours. Drying is preferably carried out at room temperature (about 23°C) to 80°C, more preferably room temperature to 60°C. Drying may also be carried out under reduced pressure. Furthermore, after a certain period of holding, excess polymer solution / dispersion may be appropriately discharged and dried.

[0076] The solvent is not particularly limited as long as it can dissolve the polymer, and may be appropriately selected depending on the polymer to be used. Examples of the solvent include water, organic solvents, and mixed solvents thereof. Examples of the organic solvent include alcohols such as methanol, ethanol, n-propanol, i-propanol, and methoxypropanol; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran, acetonitrile, ethyl acetate, and toluene.

[0077] The concentration of the polymer solution or dispersion is not particularly limited and may be appropriately selected in consideration of injectability, coatability, sprayability, productivity, etc., but the concentration of the polymer in the polymer solution or dispersion (100% by mass) is preferably 0.1 to 10.0% by mass, more preferably 0.2 to 5.0% by mass.

[0078] The polymer-coated glass substrate has an elastic modulus of 1.20 MPa or less in water or an aqueous solution at the surface of the outermost layer of one or more polymer layers formed on the surface of the glass substrate. From the viewpoint of suppressing the adsorption of normal cells such as blood cells and selectively adsorbing specific cells such as cancer cells, the elastic modulus is preferably 1.00 MPa or less, more preferably 0.85 MPa or less, and even more preferably 0.75 MPa or less. The lower limit is preferably 0.02 MPa or more, more preferably 0.04 MPa or more, even more preferably 0.45 MPa or more, and particularly preferably 0.50 MPa or more.

[0079] The elastic modulus of the surface of the outermost layer in water or an aqueous solution can be adjusted by changing the molecular weight of the polymer forming the outermost layer or the film thickness. Specifically, the elastic modulus tends to increase as the molecular weight of the polymer increases, and the elastic modulus tends to decrease as the film thickness of the polymer layer increases. The elastic modulus of the surface of the outermost layer in water or an aqueous solution can also be adjusted by previously subjecting the glass substrate to a surface treatment such as a primer treatment or a silane coupling agent treatment.

[0080] In this specification, unless otherwise specified, the elastic modulus of the surface of the outermost layer in water or an aqueous solution means the elastic modulus in water or an aqueous solution measured using an atomic force microscope (AFM).

[0081] An atomic force microscope (AFM) is a type of scanning probe microscope that detects the force acting between atoms in a sample and a probe. The probe is attached to the tip of a cantilever (cantilever spring). The force (deflection) acting on the cantilever is measured while changing the distance between the sample and the probe, and a curve (force curve) plotting the relationship between the two is obtained. By analyzing this force curve, the elastic modulus (hardness) of the sample surface can be determined, and the elastic modulus can be measured at the nanometer level. The method of determining the elastic modulus of a sample surface by force curve measurement is known to those skilled in the art, and the elastic modulus can be determined using such a known method.

[0082] One method for calculating the elastic modulus from a force curve is to fit the force curve using the Johnson-Kendall-Roberts (JKR) theory, where the force F applied to the cantilever and the sample deformation δ are expressed by the following equations (1) and (2), where w is the adhesion energy. In the formula, a represents the radius of the contact line between the probe and the sample, R represents the radius of curvature of the probe tip, and K represents the elastic modulus.

[0083] The elastic modulus can be determined by fitting the F-δ curve obtained by force curve measurement with the formulas (1) and (2).

[0084] Here, the elastic modulus of the surface of the outermost layer in water or an aqueous solution specifically refers to a measured value measured by the following method. The measured value of the surface of the outermost layer in water or an aqueous solution can be measured by AFM after dripping water or an aqueous solution onto the surface of the outermost layer of a sample so that a droplet (a convex meniscus) is formed. As the aqueous solution, for example, phosphate buffered saline (PBS) can be suitably used.

[0085] The elastic modulus of the sample (surface of the outermost layer) can be determined, for example, by scanning within a predetermined range on the surface of the outermost layer of the sample to obtain force curves at multiple points within the predetermined range, determining the elastic modulus from each force curve, and calculating the average value.

[0086] The polymer-coated glass substrate prepared by the above-mentioned method has one or more polymer layers formed on the surface of a glass substrate made of soda-lime glass having a contact angle of air bubbles in water of 100° to 120°, and the outermost layer of the polymer layers has a surface elastic modulus of 1.20 MPa or less in water or an aqueous solution, making the surface soft. Therefore, the polymer-coated glass substrate has low adsorption of normal cells such as blood cells, but high adsorption of specific cells such as cancer cells, stem cells, and T cells, and is therefore excellent in selective adsorption of specific cells.

[0087] The present invention will be specifically described below based on examples, but the present invention is not limited to these examples.

[0088] Example 1 (Preparation of Polymer) 2-Methoxyethyl acrylate (2.5 wt % toluene) was thermally polymerized using a 12.5 mg / ml toluene solution of AIBN (azobisisobutyronitrile) at 60° C. for 7 hours to prepare poly(2-methoxyethyl acrylate) (PMEA).

[0089] A 0.25 wt % solution of PMEA in methanol (80 μL) was poured into a two-chamber chamber slide (Matsunami Glass Industry Co., Ltd., uncoated soda-lime glass, average thickness 1300 μm, contact angle of air bubbles in water 109.9°), and then immediately vacuum-dried (coated) in an oven at 50°C for 20 minutes to prepare a polymer-coated glass substrate.

[0090] Example 2 (Preparation of Polymer) 2-Methoxyethyl acrylate (2.5 wt % toluene) was thermally polymerized using a 12.5 mg / ml toluene solution of AIBN (azobisisobutyronitrile) at 60° C. for 7 hours to prepare poly(2-methoxyethyl acrylate) (PMEA).

[0091] A 145 μL solution of 0.155 wt % PMEA in methanol was poured into a two-chamber chamber slide (Matsunami Glass Industry Co., Ltd., uncoated soda-lime glass, average thickness 1300 μm, contact angle of air bubbles in water 109.9°), and then immediately dried in an oven at 60°C for 15 minutes under normal pressure (coating) to prepare a polymer-coated glass substrate.

[0092] Example 3 (Preparation of Polymer) 2-Methoxyethyl acrylate (2.5 wt % toluene) was thermally polymerized using a 12.5 mg / ml toluene solution of AIBN (azobisisobutyronitrile) at 60° C. for 7 hours to prepare poly(2-methoxyethyl acrylate) (PMEA).

[0093] A 90 μL solution of 0.50 wt % PMEA in methanol was poured into a two-chamber chamber slide (Matsunami Glass Industry Co., Ltd., uncoated soda-lime glass, average thickness 1300 μm, contact angle of air bubbles in water 109.9°), and then immediately dried in a 50°C oven for 20 minutes (coating) to prepare a polymer-coated glass substrate.

[0094] Comparative Example 1 (Preparation of Polymer) 2-Methoxyethyl acrylate (5.0 wt % methanol) was thermally polymerized using a 12.5 mg / ml methanol solution of AIBN (azobisisobutyronitrile) at 60° C. for 7 hours to prepare poly(2-methoxyethyl acrylate) (PMEA).

[0095] A 145 μL solution of 0.155 wt % PMEA in methanol was poured into a two-chamber chamber slide (Matsunami Glass Industry Co., Ltd., uncoated soda-lime glass, average thickness 1300 μm, contact angle of air bubbles in water 109.9°), and then immediately vacuum-dried (coated) in an oven at 50°C for 20 minutes to prepare a polymer-coated glass substrate.

[0096] Example 4 (Preparation of Polymer 1) 2-Methoxyethyl acrylate (50 wt % methanol) was thermally polymerized using a 1.25 mg / ml AIBN (azobisisobutyronitrile) methanol solution at 60°C for 7 hours to prepare poly-2-methoxyethyl acrylate (PMEA) (Mn 80,000). (Preparation of Polymer 2) 2-Methoxyethyl acrylate (25 wt % toluene) was thermally polymerized using a 1.25 mg / ml AIBN (azobisisobutyronitrile) toluene solution at 60°C for 7 hours to prepare poly-2-methoxyethyl acrylate (PMEA) (Mn 16,000).

[0097] Into one well of a slide chamber (2-well type) (non-coated, manufactured by Matsunami Glass Industry Co., Ltd., bottom: soda-lime glass, contact angle of air bubbles in water: 109.9°, average thickness: 1.35 μm), 80 μl of a 0.0375% methanol solution of PMEA (Mn 80,000) prepared in the preparation of polymer 1 above was injected. The substrate was then immediately vacuum-dried in an oven at 40°C for 5 minutes. After cooling to room temperature, 90 μl of a 0.16% methanol solution of PMEA (Mn 16,000) prepared in the preparation of polymer 2 above was injected onto the PMEA coating layer. The substrate was then immediately vacuum-dried in an oven at 40°C for 5 minutes to prepare a polymer-coated glass substrate.

[0098] Example 5 Into one well of a slide chamber (two-well type) (non-coated, manufactured by Matsunami Glass Industry Co., Ltd.; bottom: soda-lime glass; contact angle of air bubbles in water: 109.9°; average thickness: 1.35 μm), 80 μl of a 0.0375% methanol solution of PMEA (Mn 80,000) prepared in the preparation of polymer 1 above was injected. The resultant was then immediately vacuum-dried in an oven at 40° C. for 5 minutes. After cooling to room temperature, 90 μl of a 0.19% methanol solution of PMEA (Mn 16,000) prepared in the preparation of polymer 2 above was injected onto the PMEA coating layer. The resultant was then immediately vacuum-dried in an oven at 40° C. for 5 minutes to prepare a polymer-coated glass substrate.

[0099] Example 6 Into one well of a slide chamber (two-well type) (non-coated, manufactured by Matsunami Glass Industry Co., Ltd.; bottom: soda-lime glass; contact angle of air bubbles in water: 109.9°; average thickness: 1.35 μm), 80 μl of a 0.0375% methanol solution of PMEA (Mn 80,000) prepared in the preparation of polymer 1 above was injected. The resultant was then immediately vacuum-dried in an oven at 40° C. for 5 minutes. After cooling to room temperature, 90 μl of a 0.23% methanol solution of PMEA (Mn 16,000) prepared in the preparation of polymer 2 above was injected onto the PMEA coating layer. The resultant was then immediately vacuum-dried in an oven at 40° C. for 5 minutes to prepare a polymer-coated glass substrate.

[0100] Example 7: NH ３ ＋Into one well of a slide chamber (2-well type) (MAS-coated type manufactured by Matsunami Glass Industry Co., Ltd., bottom: soda-lime glass, contact angle of air bubbles in water: 109.9°, average thickness: 1.35 μm) into which groups had been introduced, 80 μl of a 0.0375% methanol solution of PMEA (Mn 80,000) prepared in the preparation of polymer 1 above was injected. The substrate was then immediately vacuum-dried in an oven at 40°C for 5 minutes. After cooling to room temperature, 90 μl of a 0.19% methanol solution of PMEA (Mn 16,000) prepared in the preparation of polymer 2 above was injected onto the PMEA coating layer. The substrate was then immediately vacuum-dried in an oven at 40°C for 5 minutes to prepare a polymer-coated glass substrate.

[0101] Example 8: NH ３ ＋ Into one well of a slide chamber (2-well type) (MAS-coated type manufactured by Matsunami Glass Industry Co., Ltd., bottom: soda-lime glass, contact angle of air bubbles in water: 109.9°, average thickness: 1.35 μm) into which groups had been introduced, 80 μl of a 0.0750% methanol solution of PMEA (Mn 80,000) prepared in the preparation of polymer 1 above was injected. The substrate was then immediately vacuum-dried in an oven at 40°C for 5 minutes. After cooling to room temperature, 90 μl of a 0.19% methanol solution of PMEA (Mn 16,000) prepared in the preparation of polymer 2 above was injected onto the PMEA coating layer. The substrate was then immediately vacuum-dried in an oven at 40°C for 5 minutes to prepare a polymer-coated glass substrate.

[0102] Example 9: 640 μL of a 0.0375 wt % methanol solution of PMEA (Mn 80,000) prepared in the preparation of Polymer 1 (methanol solution heated to 40°C) and 720 μL of a 0.19 wt % methanol solution of PMEA (Mn 16,000) prepared in the preparation of Polymer 2 (methanol solution heated to 40°C) were mixed, and 85 μL of this solution was injected into one well of a slide chamber (2-well type) (non-coated, manufactured by Matsunami Glass Industry Co., Ltd., bottom: soda-lime glass, contact angle of air bubbles in water: 109.9°, average thickness: 1.35 mm) (methanol solution heated to 40°C). The mixture was then immediately vacuum-dried in a 40°C oven for 5 minutes. After cooling to room temperature, 85 μL of the mixed solution was injected onto the PMEA coating layer. The mixture was then immediately vacuum-dried in a 50°C oven for 20 minutes to prepare a polymer-coated glass substrate.

[0103] For the polymer-coated glass substrates prepared in the above Examples and Comparative Examples, the thickness of the polymer layer and the elastic modulus in PBS (phosphate buffer solution) were measured by AFM using the following methods. The results are shown in Table 1.

[0104] [Thickness of Polymer Layer] The thickness (film thickness) of the polymer layer formed on the polymer-coated glass substrate was measured by TEM under the condition of an accelerating voltage of 200 kV (JEM-2800, manufactured by JEOL).

[0105] [Elastic modulus measurement in PBS (phosphate buffer aqueous solution) by AFM] Phosphate buffered saline was dropped onto the surface of the polymer layer of a polymer-coated glass substrate to form a droplet (convex meniscus), and the elastic modulus was measured using the following method with the following device (AFM). The obtained elastic modulus is the elastic modulus measured in water or aqueous solution. When measuring the elastic modulus, the elastic modulus was determined by analysis based on the JKR contact theory from the obtained force curve. <Method for measuring elastic modulus> Device (AFM): Jupiter XR manufactured by Oxford Instruments Measurement mode: AFM force curve mapping Cantilever: Material: Si, tip curvature radius R = 150 nm, spring constant 0.67 N / m Measurement range: 20 μm × 20 μm scan, elastic modulus calculated using the JKR two-point method Scan speed: 1 Hz Measurement atmosphere: in PBS Measurement temperature: 23°C

[0106]

[0107]

[0108] Comparative Example 1 has an elastic modulus of 2 MPa or more, which is thought to result in reduced adsorptive properties for specific cells such as cancer cells, and high adsorptive properties for leukocytes.

[0109] In contrast, Example 3 has an elastic modulus of 1.20 MPa or less, and is thought to have improved adsorption of specific cells such as cancer cells compared to Comparative Example 1. It is also thought that the adsorption of leukocytes is lower than Comparative Example 1. Example 1 has an elastic modulus of around 0.057 MPa, and is thought to have improved adsorption of specific cells such as cancer cells compared to Example 3, which has an elastic modulus of less than 0.04 MPa. It is also thought that the adsorption of leukocytes is lower than Example 3.

[0110] In Example 2, the elastic modulus is around 0.07 MPa, and therefore it is thought that the adsorptivity of specific cells such as cancer cells is improved compared to Example 1. It is also thought that the adsorptivity of leukocytes is lower than that of Example 1.

[0111] In Examples 4 to 6, two polymer layers with different molecular weights were formed on the surface of uncoated soda lime glass. ３ ＋In Examples 7 and 8, in which two polymer layers with different molecular weights were formed on the surface of soda-lime glass into which groups had been introduced, and in Example 9, in which two polymer layers made of blend polymers with different molecular weights were formed on the surface of uncoated soda-lime glass, the low elastic modulus is also believed to improve the adsorptivity of specific cells such as cancer cells. It is also believed that the adsorptivity of leukocytes is reduced.

[0112] The present invention (1) is a polymer-coated glass substrate having one or more polymer layers formed on the surface of a glass substrate, wherein the glass is soda-lime glass having a contact angle of air bubbles in water of 100 degrees or more and 120 degrees or less, and the surface of the outermost layer of the polymer layer has an elastic modulus of 1.20 MPa or less in water or an aqueous solution.

[0113] The present invention (2) is the polymer-coated glass substrate according to the present invention (1), wherein the elastic modulus is 0.85 MPa or less.

[0114] The present invention (3) is the polymer-coated glass substrate according to the present invention (1), wherein the elastic modulus is 0.75 MPa or less.

[0115] The present invention (4) is the polymer-coated glass substrate according to the present invention (1), wherein the elastic modulus is 0.04 MPa or more.

[0116] The present invention (5) is a polymer-coated glass substrate in any combination with any of the present inventions (1) to (4), in which the outermost surface layer is formed from a polymer represented by the following formula (I): (In the formula, R ５１ is a hydrogen atom or a methyl group, R ５２ represents an alkyl group, p is 1 to 8, m is 1 to 5, and n is the number of repetitions.

[0117] The present invention (6) is a polymer-coated glass substrate in any combination with any of the present inventions (1) to (4), wherein the outermost surface layer is formed from a polymer represented by the following formula (I-1): (In the formula, R ５１ is a hydrogen atom or a methyl group, R ５２ represents an alkyl group, m is 1 to 5, and n is the number of repetitions.

[0118] The present invention (7) is a polymer-coated glass substrate in any combination with any of the present inventions (1) to (4), wherein the outermost layer is formed from a copolymer of a compound represented by the following formula (II) and another monomer: (In the formula, R ５１ is a hydrogen atom or a methyl group, R ５２ represents an alkyl group, p represents 1 to 8, and m represents 1 to 5.

[0119] The present invention (8) is a polymer-coated glass substrate in any combination with any of the present inventions (1) to (4), wherein the outermost layer is formed from a copolymer of a compound represented by the following formula (II-1) and another monomer: (In the formula, R ５１ is a hydrogen atom or a methyl group, R ５２ represents an alkyl group; and m represents 1 to 5.

[0120] The present invention (9) is a polymer-coated glass substrate in any combination with any of the present inventions (5) to (8), wherein the outermost surface layer is formed from the polymer having a number-average molecular weight of 10,000 to 60,000.

[0121] The present invention (10) is a polymer-coated glass substrate in any combination with any of the present inventions (1) to (9), wherein the total thickness of the polymer layer is 10 to 4,000 nm.

[0122] The present invention (11) is a polymer-coated glass substrate in any combination with any of the present inventions (1) to (10), wherein the elastic modulus is a value measured using an atomic force microscope.

[0123] The present invention (12) is a glass substrate having two or more polymer layers, and a surface of the glass substrate having -N(R １ ) ２ and / or -N(R ２ ) ３ ＋ (R １ and R ２ are the same or different and each is a hydrogen atom or a substituted or unsubstituted hydrocarbon group which may contain a heteroatom.)

[0124] The present invention (13) is a polymer-coated glass substrate in any combination with any of the present inventions (1) to (12), in which the outermost surface layer is formed from a blend of hydrophilic polymers having different molecular weights.

Claims

1. A polymer-coated glass substrate having one or more polymer layers formed on the surface of a glass substrate, wherein the glass is soda-lime glass having a contact angle of air bubbles in water of 100 degrees or more and 120 degrees or less, and the surface of the outermost layer of the polymer layer has an elastic modulus of 1.20 MPa or less in water or an aqueous solution.

2. The polymer-coated glass substrate according to claim 1, wherein the elastic modulus is 0.85 MPa or less.

3. The polymer-coated glass substrate according to claim 1, wherein the elastic modulus is 0.75 MPa or less.

4. The polymer-coated glass substrate according to claim 1, wherein the elastic modulus is 0.04 MPa or more.

5. The polymer-coated glass substrate according to any one of claims 1 to 4, wherein the outermost surface layer is formed of a polymer represented by the following formula (I). (In the formula, R ５１ represents a hydrogen atom or a methyl group, and R ５２ represents an alkyl group. p represents an integer of 1 to 8, m represents an integer of 1 to 5, and n represents the number of repetitions.) 6. The polymer-coated glass substrate according to any one of claims 1 to 4, wherein the outermost surface layer is formed of a polymer represented by the following formula (I-1). (In the formula, R ５１ represents a hydrogen atom or a methyl group, and R ５２ represents an alkyl group. m represents an integer of 1 to 5, and n represents the number of repetitions.) 7. The polymer-coated glass substrate according to any one of claims 1 to 4, wherein the outermost layer is formed of a copolymer of a compound represented by the following formula (II) and another monomer. (In the formula, R ５１ represents a hydrogen atom or a methyl group, and R ５２ represents an alkyl group. p represents 1 to 8, and m represents 1 to 5.) 8. The polymer-coated glass substrate according to any one of claims 1 to 4, wherein the outermost surface layer is formed of a copolymer of a compound represented by the following formula (II-1) and another monomer. (In the formula, R ５１ represents a hydrogen atom or a methyl group, and R ５２ represents an alkyl group. m represents 1 to 5.) 9. The polymer-coated glass substrate according to any one of claims 5 to 8, wherein the outermost layer is formed of the polymer having a number average molecular weight of 10,000 to 60,000.

10. The polymer-coated glass substrate according to any one of claims 1 to 9, wherein the total thickness of the polymer layer is 10 to 4000 nm.

11. The polymer-coated glass substrate according to any one of claims 1 to 10, wherein the elastic modulus is a value measured using an atomic force microscope.

12. The above two or more polymer layers are formed, and the surface of the glass substrate has -N(R １ ), ２ and / or -N(R ２ ), ３ ＋ (R １ and R ２ are each independently a hydrogen atom or a substituted or unsubstituted hydrocarbon group which may contain a hetero atom.) The polymer-coated glass substrate according to any one of claims 1 to 11 having a group represented by 13. The polymer-coated glass substrate according to any one of claims 1 to 12, wherein the outermost layer is formed of a blend of hydrophilic polymers having different molecular weights.

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