JP2016222938A - Surface treatment agent for surface composed of inorganic material, apparatus coated with the surface treatment agent, method for producing the same, and new polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface treatment agent for a surface composed of an inorganic material, excellent in an effect of preventing nonspecific absorption, an apparatus coated with the surface treatment agent, a method for producing the same, and a new polymer.SOLUTION: Provided is a polymer having a hydrophilic repeating unit having a sulfinyl group at the side chain and a cationic repeating unit.SELECTED DRAWING: None

Description

  The present invention relates to a surface treatment agent for a surface composed of an inorganic material, a device coated with the surface treatment agent, a production method thereof, and a novel polymer.

A method of measuring a biological substance using various reagents using a glass cell as a reaction tube is widely used in the fields of clinical examinations, diagnostic agents and the like. There are two detection methods that use enzyme coloration, one that uses fluorescence and chemiluminescence, and one that uses turbidity using latex as an index. Proteins, lipids, nucleic acids, cells, etc. contained in molecules, secondary antibodies, luminescent substrates, etc. are adsorbed non-specifically to solid phases, containers, instruments, etc., resulting in noise and reducing sensitivity. ing.
Therefore, in general, measures such as treating the surface of solid phases, containers and instruments with biological materials such as albumin, casein, and gelatin for the purpose of preventing nonspecific adsorption of proteins, nucleic acids, cells, etc. Has been adopted.
However, such biological substances as described above are not sufficient in the effect of preventing non-specific adsorption on the surface composed of an inorganic material such as glass, and there is a concern of biological contamination represented by BSE.

  Therefore, the development of a surface treatment agent for a surface composed of an inorganic material by chemical synthesis is desired, and for example, one having poly (2-methacryloyloxyethyl phosphorylcholine) as an active ingredient has been reported (patent document) 1 and 2). This surface treatment agent is coated for the purpose of preventing non-specific adsorption of antibodies or the like to the glass microarray substrate.

JP 2006-84393 A International Publication No. 2010/032846

  Problems to be solved by the present invention include a surface treatment agent for a surface composed of an inorganic material excellent in the effect of preventing non-specific adsorption, a device coated with the surface treatment agent, a production method thereof, and a novel weight To provide coalescence.

  Therefore, the present inventor has found that the polymer having a hydrophilic repeating unit having a sulfinyl group in the side chain is excellent in the effect of preventing nonspecific adsorption to a surface composed of an inorganic material, and has completed the present invention. .

That is, the present invention provides a surface treatment agent for a surface made of an inorganic material (hereinafter also referred to as a surface treatment agent), which includes a polymer having a hydrophilic repeating unit having a sulfinyl group in the side chain. is there.
Moreover, this invention provides the instrument (henceforth an instrument) provided with the surface comprised with an inorganic material, and one part or all part of this surface is coated with the said surface treating agent.
Furthermore, the manufacturing method of an instrument including the process of making the said surface treating agent contact the part or all of the said surface of an instrument provided with the surface comprised with an inorganic material is provided.
Furthermore, this invention provides the polymer which has a hydrophilic repeating unit which has a sulfinyl group in a side chain, and a cationic repeating unit.

The surface treating agent of the present invention is excellent in the effect of preventing nonspecific adsorption to the surface composed of an inorganic material. Therefore, it is possible to provide an instrument in which non-specific adsorption is prevented by coating with such a surface treatment agent. Moreover, according to the production method of the present invention, a device in which non-specific adsorption is prevented can be produced simply and easily.
In addition, the novel polymer of the present invention is excellent in the effect of preventing nonspecific adsorption to the surface composed of an inorganic material, despite having a cationic repeating unit.

[Surface treatment agent]
The surface treating agent of the present invention contains a polymer having a hydrophilic repeating unit having a sulfinyl group in the side chain (hereinafter also referred to as repeating unit (A)).

<Repeating unit (A)>
The repeating unit (A) exhibits hydrophilicity. Here, in this specification, hydrophilic means that it has a property with strong affinity with water. Specifically, a homopolymer consisting of only one type of repeating unit (having a number average molecular weight of about 10,000 to 100,000 by the measurement method of the Examples) is 1 g or more per 100 g of pure water at room temperature (25 ° C.). When dissolved, the repeating unit is hydrophilic.
Moreover, as said repeating unit (A), Hydrophile-Lipophile Balance (HLB value) which shows the scale of hydrophilicity / hydrophobicity is preferably 10 or more, more preferably 15 or more, still more preferably 20 or more, 21 ~ 40 are more preferred, and 21-30 are particularly preferred.
Further, in this specification, the HLB value means a value calculated from the ratio of the organic value and the inorganic value of the compound (Oda equation), and “Formation Design with Organic Concept Diagram” [1998, NIHON]. EMULSION CO. , LTD]. For example, the HLB value of the hydrophilic repeating unit contained in the copolymer (O-1-1) described in Examples described later is ((60 × 1 + 140 × 1 + 100 × 3) / (20 × 10 + 40 × 1 + (− 10) × 3) × 10 = 23.8.

Moreover, as a repeating unit (A), a nonionic thing is preferable.
In addition to the sulfinyl group, the repeating unit (A) may have a hydrophilic group such as a hydroxy group, a carboxy group, an amino group, a sulfo group, a thiol group, a phosphoric acid group, or an aldehyde group. Further, the position and the number of such hydrophilic groups are arbitrary, but the position is preferably a side chain of the polymer. On the other hand, the number of hydrophilic groups other than the sulfinyl group is preferably 0 to 12 and preferably 0 to 10 in one repeating unit from the viewpoint of the effect of preventing nonspecific adsorption to the surface composed of an inorganic material. More preferably, 0 to 5 are more preferable, 0 to 3 are more preferable, 1 to 3 are further preferable, and 2 or 3 are particularly preferable. Among the hydrophilic groups, a hydroxy group is preferable from the viewpoint of non-specific adsorption preventing effect on the surface composed of an inorganic material. In addition, as long as the effect of this invention is not lost, some sulfinyl groups contained in a polymer may be sulfide groups or sulfonyl groups.

  Specific examples of the repeating unit (A) include a repeating unit containing at least one structure represented by the following formula (1) in the side chain. As the polymer species to be a repeating unit having the structure represented by the formula (1) in the side chain, known polymers can be used, among which (meth) acrylate polymer species and (meth) acrylamide polymer species Styrene-based polymer species are preferred. More specifically, a repeating unit represented by the following formula (2) is exemplified.

[In Formula (1), R < ³ > shows a direct bond or a C1-C24 bivalent organic group, and R < ⁴ > shows a C1-C10 organic group. ]

[In formula (2), R ¹ represents a hydrogen atom or a methyl group, R ² is a group -O-, a group * - (C = O) -O- , group * - (C = O) -NR ⁵ -, group * -NR ⁵ - (C = O) - (R ⁵ is a hydrogen atom or an organic group having 1 to 10 carbon atoms, and *, R ¹ in the formula (2) is attached R represents a position bonded to a carbon atom) or a phenylene group, and R ³ and R ⁴ are as defined above. ]
Here, each symbol in the formulas (1) and (2) will be described in detail.

R ¹ represents a hydrogen atom or a methyl group, preferably a methyl group.

R ² represents a group —O—, a group * — (C═O) —O—, a group * — (C═O) —NR ⁵ —, a group * —NR ⁵ — (C═O) — or phenylene. Indicates a group. Examples of such a phenylene group include a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group.

The number of carbon atoms of the organic group represented by the R ⁵ is preferably 1 to 10, more preferably from 2 to 8, more preferably from 2 to 6. Examples of the organic group include hydrocarbon groups. Such a hydrocarbon group is a concept including an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

The aliphatic hydrocarbon group in R ⁵ may be linear or branched, and specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group. Alkyl groups such as tert-butyl group, pentyl group, hexyl group, heptyl group and octyl group.
The alicyclic hydrocarbon group is roughly classified into a monocyclic alicyclic hydrocarbon group and a bridged ring hydrocarbon group. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopropyl group and a cyclohexyl group. Examples of the bridged ring hydrocarbon group include an isobornyl group.
Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group.

Among R ² as described above, from the viewpoint of the effect of preventing nonspecific adsorption to the surface composed of an inorganic material, a group * — (C═O) —O— or a phenylene group is preferable, and a group * — (C═O ) -O- is particularly preferred.

R ³ represents a direct bond or a divalent organic group having 1 to 24 carbon atoms. Such direct bonds include single bonds.

Among such R ^3, a divalent organic group having 1 to 24 carbon atoms is preferable. The carbon number of such a divalent organic group is preferably 2 to 18, more preferably 2 to 10, still more preferably 2 to 9, and particularly preferably 3 to 6.

  Examples of the divalent organic group include a divalent hydrocarbon group. The divalent hydrocarbon group is preferably a divalent aliphatic hydrocarbon group and may be linear or branched. Specifically, methane-1,1-diyl group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, Propane-1,3-diyl group, propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,4 -Diyl group, pentane-1,5-diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, etc. An alkanediyl group may be mentioned.

The divalent hydrocarbon group may have a substituent and may contain an ether bond between carbon-carbon bonds.
Examples of the substituent that the divalent hydrocarbon group may have include the hydrophilic group. The number of the substituents is preferably 1 to 5, more preferably 1 to 3, and further preferably 1 or 2.
Moreover, as the number of the ether bonds which the said bivalent hydrocarbon group may contain, 0-5 are preferable and 0-3 are more preferable.

  Specific examples of the divalent organic group include a linking group represented by the following formula (3) and an alkanediyl group having 1 to 24 carbon atoms, and more preferably represented by the formula (3). A linking group.

[In Formula (3), R ⁶ is a single bond, a group —R ⁸ —O— (R ⁸ represents an alkanediyl group having 1 to 4 carbon atoms) or a linking group represented by the following Formula (4). R ⁷ represents an alkanediyl group having 1 to 4 carbon atoms, n represents 1 or 2, and ** represents a position bonded to a sulfur atom in the formulas (1) and (2). ]

[In the formula (4), R ⁹ represents an alkanediyl group having 1 to 4 carbon atoms, R ¹⁰ represents an alkanediyl group having 2 or 3 carbon atoms, m ¹ represents 1 or 2, m ² Represents an integer of 1 to 3. ]

R ⁶ is preferably a single bond or a group —R ⁸ —O—, particularly preferably a single bond, from the viewpoint of the effect of preventing non-specific adsorption to a surface composed of an inorganic material.

The alkanediyl group represented by R ⁷ , R ⁸ and R ⁹ has 1 to 4 carbon atoms, but 1 or 2 is preferable.
The alkanediyl group may be linear or branched, and examples thereof include the same alkanediyl groups as described above.

The carbon number of the alkanediyl group represented by R ¹⁰ is preferably 2. Examples of the alkanediyl group include the same as those represented by R ⁷ . When m ² is 2 or 3, m ² R ¹⁰ may be the same or different.
Further, 1 is preferable as n and m ^1, 1 or 2 is preferable as m ^2.

R ⁴ represents an organic group having 1 to 10 carbon atoms. Examples of such an organic group include the same groups as those represented by R ⁵ . In addition, when R ⁴ is a hydrocarbon group, such a hydrocarbon group may have a substituent, and the substituent and the number thereof may be the divalent hydrocarbon group. The thing similar to a good thing is mentioned. From the viewpoint of hydrophilicity, R ⁴ preferably does not contain a ring structure such as a cycloalkyl group, an aryl group, or an aralkyl group.

Preferable specific examples of R ⁴ as described above include organic groups having 1 to 10 carbon atoms having the hydrophilic group, more preferably a monovalent group represented by the following formula (5), carbon. It is a C1-C10 alkyl group, More preferably, it is a monovalent group represented by Formula (5).

Wherein (5), k ¹ represents an integer of 1 to 4, k ² is an integer of 0 to 4, *** the formula (1), combined with the sulfur atom in (2) Indicates the position to perform. ]

In formula (5), k ¹ is preferably 1 or 2. As the k ^2, preferably an integer of 0 to 2, 0 or 1 are more preferable.

Further, the lower limit of the total content of the repeating unit (A) is preferably 5 mol% or more in all repeating units from the viewpoint of imparting water solubility and preventing nonspecific adsorption to the surface composed of inorganic materials. 10 mol% or more is more preferable and 15 mol% or more is still more preferable.
On the other hand, the upper limit is preferably 99 mol% or less, more preferably 95 mol% or less in all repeating units from the viewpoint of imparting water solubility and adsorption with the substrate.

Moreover, when the polymer used by this invention has the repeating unit (C) mentioned later, as total content of a repeating unit (A), 10-99 mol% is preferable, and 15-95 mol% is more preferable, 20-95 mol% is still more preferable.
The content of the repeating unit (A) can be measured by ¹³ C-NMR or the like.

  The polymer used in the present invention further includes a repeating unit selected from a hydrophobic repeating unit (hereinafter also referred to as a repeating unit (B)) and a cationic repeating unit (hereinafter also referred to as a repeating unit (C)). What has is preferable. These repeating units may be contained singly or in combination of two or more.

<Repeating unit (B)>
Here, “hydrophobic” means having a property of low affinity with water. Specifically, a homopolymer consisting of only one type of repeating unit (having a number average molecular weight of about 10,000 to 100,000 according to the measurement method in Examples) is dissolved in 100 g of pure water at room temperature (25 ° C.). If the amount is less than 1 g, the repeating unit is hydrophobic.
Moreover, as an HLB value of the said repeating unit (B), from a viewpoint of compatibility with the polarity of the surface comprised with an inorganic material, 20 or less are preferable, 1-17.5 are more preferable, 5-17.5 Is more preferable, and 6 to 17.5 is particularly preferable. A combination of HLB values of 10 or more and less than 10 may be used.

  Examples of the repeating unit (B) include known ones exhibiting hydrophobicity, and are not particularly limited. However, from the viewpoint of the effect of preventing nonspecific adsorption to the surface composed of an inorganic material, styrenes, (meth) acrylates, and Those derived from one or more monomers selected from (meth) acrylamides are preferred. The repeating unit (B) is preferably nonionic. Moreover, the thing without a hydrophilic group is preferable.

  As the repeating unit derived from the styrenes, a repeating unit represented by the following formula (6) is preferable.

[In Formula (6), R < ¹¹ > shows a hydrogen atom or a methyl group, R < ¹² > shows a C1-C10 organic group, and p shows the integer of 0-5. ]

In the formula (6), examples of the organic group represented by R ¹² include the same groups as those represented by R ⁵ , and the number of carbon atoms is from the viewpoint of imparting appropriate hydrophobicity to the copolymer. Preferably it is 1-6, More preferably, it is 1-3. Such an organic group may be substituted with an alkoxy group having 1 to 3 carbon atoms. Also, when p is integer of 2 to 5, p number of R ¹² may be the same or different.

  Moreover, although p shows the integer of 0-5, 0-3 are preferable and 0 is more preferable from a viewpoint which provides moderate hydrophobicity to a copolymer.

  Specific examples of the repeating unit derived from styrenes include styrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, 4-ethylstyrene, 4-isopropylstyrene, 4-tert- Examples thereof include repeating units derived from butylstyrene, α-methylstyrene and the like.

  Moreover, as a repeating unit derived from the said (meth) acrylates, the repeating unit represented by following formula (7) is preferable.

[In Formula (7), R < ¹³ > shows a hydrogen atom or a methyl group, R < ¹⁴ > shows a C1-C20 organic group. ]

In the formula (7), examples of the organic group represented by R ¹⁴ include the same groups as those represented by R ⁵ , and the number of carbon atoms is from the viewpoint of imparting appropriate hydrophobicity to the copolymer. Preferably it is 1-10, More preferably, it is 1-6, More preferably, it is 1-4, Most preferably, it is 1-3. Further, such an organic group may be substituted with an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 2 to 10 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, or the like. Such an alkoxy group preferably has 1 to 8, more preferably 1 to 4, still more preferably 1 to 3, particularly preferably 1 or 2, and the alkanoyl group preferably has 2 to 8 carbon atoms. More preferably, it is 2-4, More preferably, it is 2 or 3, The carbon number of the said aryloxy group becomes like this.

Specific examples of the repeating unit derived from the (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. (Meth) acrylic acid C _1-10 alkyl; (meth) acrylic acid C _6-10 cycloalkyl such as cyclohexyl (meth) acrylate; 1-methoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate (Meth) acrylic acid C _1-10 alkoxy C _1-10 alkyl; (meth) acrylic acid C _6-12 aryloxy C _1-10 alkyl; (meth) acrylic acid 1 -Adamantyl, 1-methyl (meth) acrylate- (1-adamantylethyl), tricyclo [5.2.1.0 ^2,6 ] decane (meth) acrylate Examples thereof include a repeating unit derived from a (meth) acrylic acid ester having a bridged ring hydrocarbon group having 8 to 16 carbon atoms such as -8-yl.

  Moreover, as a repeating unit derived from the said (meth) acrylamide, the repeating unit represented by following formula (8) is preferable.

Wherein (8), R ¹⁵ represents a hydrogen atom or a methyl group, R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or an organic group having 1 to 10 carbon atoms. ]

In the formula (8), examples of the organic group represented by R ¹⁶ and R ¹⁷ include the same organic groups as those represented by R ⁵ , but the carbon number imparts appropriate hydrophobicity to the copolymer. From a viewpoint, Preferably it is 1-6, More preferably, it is 1-4. Further, such an organic group may be substituted with an alkoxy group having 1 to 10 carbon atoms or an alkanoyl group having 2 to 10 carbon atoms. The preferable carbon number of such an alkoxy group or alkanoyl group is the same as that which may be substituted with the organic group represented by R ¹⁴ .

Specific examples of the repeating unit derived from the (meth) acrylamides include, for example, N-N such as N, N-diC _1-10 alkyl (meth) acrylamide; N-isopropyl (meth) acrylamide. C _1-10 alkyl (meth) acrylamide; N-C _2-10 alkanoyl C _1-10 alkyl such as N- (1,1-dimethyl-2-acetylethyl) (meth) acrylamide (also known as diacetone acrylamide) ( In addition to (meth) acrylamide, repeating units derived from (meth) acryloylpiperidine and the like can be mentioned.

  Moreover, when the polymer used by this invention has a repeating unit (B), as a minimum of the total content of a repeating unit (B), 1 mol% or more in all the repeating units from a viewpoint of adsorption | suction with a base material. Is preferably 10 mol% or more, more preferably 20 mol% or more, and particularly preferably 30 mol% or more. On the other hand, the upper limit is preferably 99 mol% or less, more preferably 90 mol% or less, and more preferably 85 mol% in all repeating units from the viewpoint of imparting water solubility and preventing nonspecific adsorption to the surface composed of inorganic materials. % Or less is more preferable.

Further, when the polymer used in the present invention has a repeating unit (B) having an HLB value of 10 or more, the total content thereof is 5 from the viewpoint of the effect of preventing nonspecific adsorption to the surface composed of an inorganic material. -60 mol% is preferable, 10-50 mol% is more preferable, and 20-40 mol% is still more preferable. On the other hand, when the polymer used in the present invention has a repeating unit (B) having an HLB value of less than 10, the total content is 20 from the viewpoint of the effect of preventing nonspecific adsorption to the surface composed of an inorganic material. -90 mol% is preferable, 40-80 mol% is more preferable, 60-70 mol% is still more preferable.
In addition, what is necessary is just to measure content of a repeating unit (B) similarly to content of a repeating unit (A).

  When the polymer used in the present invention has a repeating unit (B), the molar ratio [(A) :( B)] of the repeating unit (A) and the repeating unit (B) contained in the polymer is: From the viewpoint of the effect of preventing nonspecific adsorption to the surface composed of an inorganic material, 10: 1 to 10: 100 is preferable, 10: 1 to 10:75 is more preferable, and 10: 3 to 10:55 is still more preferable.

<Repeating unit (C)>
Further, examples of the repeating unit (C) include known ones exhibiting cationic properties, preferably repeating units having a cationic group. As the cationic group, a cationic organic group is preferable. In addition, even if the surface treatment agent for the surface composed of the inorganic material of the present invention has such a cationic repeating unit, it prevents non-specific adsorption to the surface composed of an excellent inorganic material. Show the effect of
Examples of the repeating unit (C) include styrenes having a cationic group, (meth) acrylates having a cationic group, (meth) acrylamides having a cationic group, propylene having a cationic group, and cationic groups. Examples thereof include a repeating unit derived from one or more monomers selected from 2-methylpropylene having a group. A counter ion may be bonded to the cationic group.
Moreover, as an HLB value of the said repeating unit (C), 20-80 are preferable from a viewpoint of compatibility with the polarity of the surface comprised with an inorganic material, and it was more suitable by the coating to the surface comprised with an inorganic material. From the viewpoint of making it, 30 to 70 are preferable, 30 to 60 are more preferable, and 40 to 55 are more preferable.

  Moreover, as said repeating unit (C), what has 1 or more types chosen from the group represented by following formula (9) and the group represented by following formula (10) in a side chain is preferable, Formula (9) It is more preferable to have a group represented by

[In Formula (9), R ^{18 to} R ²⁰ each independently represents a hydrogen atom or an organic group having 1 to 18 carbon atoms, and Z ⁻ represents a counter ion. ]

[In Formula (10), R ^{21 to} R ²⁴ each independently represents a hydrogen atom or an organic group having 1 to 18 carbon atoms, and Z ⁻ is as defined above. ]

Examples of the organic group represented by R ^{18 to} R ²⁰ in formula (9) and R ^{21 to} R ²⁴ in formula (10) include the same organic groups as those represented by R ⁵ , Preferably, it is 1-10, More preferably, it is 1-6, More preferably, it is 1-4, Especially preferably, it is 1-3. In addition, such an organic group may be substituted with an aryl group having 6 to 12 carbon atoms, preferably 6 carbon atoms. Such aryl groups include phenyl groups.
Z ⁻ is not particularly limited as long as it is negatively charged. For example, halogeno ions such as chlorine ion, bromine ion and iodine ion; hydrogen sulfate ion; alkyl sulfate ion such as methyl sulfate ion and ethyl sulfate ion Alkyl sulfonate ions; aryl sulfonate ions such as dodecylbenzene sulfonate ions and p-toluene sulfonate ions; alkenyl sulfonate ions such as sodium 2-methyl-2-propene-1-sulfonate; carboxylic acids such as acetate ions; And ions.

  Examples of the repeating unit derived from the styrenes having a cationic group include those in which a cationic group is introduced into the side chain of the repeating unit represented by the formula (6). ) Is preferred.

[In the formula (11), R ²⁵ represents a hydrogen atom or a methyl group, R ²⁶ represents a group represented by the formula (9) or (10), or a group represented by the formula (9) or (10). An organic group having 1 to 10 carbon atoms or an organic group having 1 to 10 carbon atoms having a group as a substituent, q represents an integer of 1 to 5, and at least one of q R ²⁶ is It is a C1-C10 organic group which has a group represented by Formula (9) or (10), or a group represented by Formula (9) or (10) as a substituent. ]

Examples of the organic group for R ²⁶ include the same organic groups as those described above for R ¹² . When q is an integer of 2 to 5, q R ^{26 s} may be the same or different.

  Moreover, although q shows the integer of 1-5, 1-3 are preferable and 1 is more preferable from a viewpoint which provides moderate hydrophobicity to a copolymer.

  Specific examples of the repeating unit derived from styrenes having a cationic group include repeating units derived from (4-vinylphenyl) trimethylaminium chloride, vinylbenzyltrimethylammonium chloride and the like.

  In addition, examples of the repeating unit derived from the (meth) acrylate having a cationic group include those in which a cationic group is introduced into the side chain of the repeating unit represented by the formula (7). What is represented by Formula (12) is preferable.

[In the formula (12), R ²⁷ represents a hydrogen atom or a methyl group, and R ²⁸ represents an organic group having 1 to 10 carbon atoms having a group represented by the formula (9) or (10) as a substituent. Indicates. ]

Examples of the organic group for R ²⁸ include the same organic groups as those for R ¹⁴ .

Specific examples of the repeating unit derived from (meth) acrylates having a cationic group include ((meth) acryloyloxy C _1-10 alkyl) tri C _1- such as ((meth) acryloyloxyethyl) trimethylammonium chloride. ₁₀ Repeating units derived from ((meth) acryloyloxy C _1-10 alkyl) di-C _1-10 alkyl C _6-12 aralkylammonium chloride such as ₁₀ alkylammonium chloride, ((meth) acryloyloxyethyl) dimethylbenzylammonium chloride Is mentioned.

  Examples of the repeating unit derived from the (meth) acrylamide having the cationic group include those in which a cationic group is introduced into the side chain of the repeating unit represented by the formula (8). What is represented by Formula (13) is preferable.

[In the formula (13), R ²⁹ represents a hydrogen atom or a methyl group, and R ³⁰ represents an organic group having 1 to 10 carbon atoms having a group represented by the formula (9) or (10) as a substituent. R ³¹ represents a hydrogen atom, an organic group having 1 to 10 carbon atoms, or an organic group having 1 to 10 carbon atoms having the group represented by the formula (9) or (10) as a substituent. ]

Examples of the organic group for R ³⁰ and R ³¹ include the same organic groups as those for R ¹⁶ .

Specific examples of the repeating unit derived from the (meth) acrylamide having a cationic group include (3- (meth) acrylamide C _1-10 alkyl such as (3- (meth) acrylamidepropyl) trimethylammonium chloride. ) Tri-C _1-10 alkyl ammonium chloride; (3- (meth) acrylamide C _1-10 alkyl) di-C _1-10 alkyl C _6-12 aralkyl ammonium such as (3- (meth) acrylamidopropyl) dimethylbenzylammonium chloride And repeating units derived from chloride and the like.

  The propylene having a cationic group and the 2-methylpropylene having a cationic group have a cationic group at the 3-position of propylene or 2-methylpropylene. As a repeating unit derived from these, what is represented by following formula (14) is preferable. Specific examples include repeating units derived from allylamine hydrochloride, 2-methyl-2-propenylamine hydrochloride and the like.

[In the formula (14), R ³¹ represents a hydrogen atom or a methyl group, and R ³² represents a group represented by the formula (9) or (10). ]

Moreover, when the polymer used by this invention has a repeating unit (C), as a minimum of the total content of a repeating unit (C), it is 1 mol% or more in all the repeating units from a viewpoint of adsorption | suction with a base material. Is preferable, 5 mol% or more is more preferable, and 8 mol% or more is still more preferable.
On the other hand, the upper limit is preferably 50 mol% or less, more preferably 40 mol% or less, and more preferably 30 mol% in all repeating units from the viewpoint of imparting water solubility and preventing nonspecific adsorption to the surface composed of inorganic materials. % Or less is more preferable, and 20 mol% or less is more preferable.
In addition, what is necessary is just to measure content of a repeating unit (C) similarly to content of a repeating unit (A).

  When the polymer used in the present invention has a repeating unit (C), the molar ratio of the repeating unit (A) and the repeating unit (C) contained in the polymer [(A) :( C)] From the viewpoint of the effect of preventing nonspecific adsorption to the surface composed of an inorganic material, 10: 0.5 to 10:50 is preferable, 10: 0.5 to 10:10 is more preferable, and 10: 0.5 to 10:10. 5 is more preferable, and 10: 0.5 to 10: 2.5 is particularly preferable.

  The polymer used in the present invention may have a hydrophilic repeating unit (D) in addition to the repeating units (A) to (C). Such hydrophilic repeating unit (D) is derived from an anionic monomer (anionic monomer), an amphoteric monomer (betaine monomer), or a nonionic monomer (nonionic monomer). The thing is mentioned, These may contain 1 type, or 2 or more types.

  Examples of the anionic monomer include unsaturated carboxylic acid monomers such as vinyl benzoic acid and (meth) acrylic acid; unsaturated sulfonic acid monomers such as styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and isoprene sulfonic acid. Can be mentioned.

  Moreover, as betaine monomers, (meth) acrylic acid carboxybetaine, carboxybetaine (meth) acrylamide, carboxybetaine type monomers such as carboxybetaine vinyl compounds; (meth) acrylic acid sulfobetaine, sulfobetaine (meth) acrylamide, sulfobetaine Examples include sulfobetaine monomers such as vinyl compounds; phosphorylbetaine monomers such as phosphorylbetaine (meth) acrylate, phosphorylbetaine (meth) acrylamide, and phosphorylbetaine vinyl compounds. As (meth) acrylic acid phosphoryl betaine, 2- (meth) acryloyloxyethyl-2 ′-(trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxypropyl-2 ′-(trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxyethoxyethyl-2 ′-(trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxydiethoxyethyl-2 ′-(trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxy And triethoxyethyl-2 ′-(trimethylammonio) ethyl phosphate.

  In addition, examples of nonionic monomers include unsaturated carboxylic acid ester monomers having a hydroxy group such as hydroxyethyl (meth) acrylate, glyceryl (meth) acrylate, and polyoxyethylene (meth) acrylate; N- (2-hydroxy And (meth) acrylamide monomers having a hydroxy group such as ethyl) (meth) acrylamide.

  The total content of the repeating unit (D) is preferably 0 to 49 mol%, more preferably 0 to 20 mol%, still more preferably 0 to 10 mol%, and more preferably 0 to 1 mol% in all repeating units. Particularly preferred.

In addition, when the polymer used in the present invention is a copolymer, the arrangement of the repeating units is not particularly limited, and the copolymer may be a block copolymer, a graft copolymer, a random copolymer, an alternating copolymer, or the like. Any of copolymers may be used.
Moreover, as a number average molecular weight ( _Mn ) of the polymer used by this invention, 5000-1 million are preferable, 7500-200000 are more preferable, 7500-150,000 are especially preferable. By setting the number average molecular weight to 5000 or more, the effect of preventing non-specific adsorption to the surface composed of an inorganic material is improved. On the other hand, by setting the number average molecular weight to 1 million or less, coating properties and handling properties are improved.
Moreover, as molecular weight distribution ( _Mw / _Mn ), 1-5 are preferable.
In addition, what is necessary is just to measure the said number average molecular weight and molecular weight distribution according to the method as described in the Example mentioned later.

  Moreover, as a polymer used by this invention, a water-soluble thing is preferable from a viewpoint of the nonspecific adsorption | suction prevention effect with respect to the surface comprised with an inorganic material. Here, in the present specification, water-soluble means that the polymer becomes transparent when added to and mixed with water (25 ° C.) so that the polymer solid content is 1% by mass.

  In addition, as the HLB value of the polymer used in the present invention, from the viewpoint of imparting water solubility, non-specific adsorption preventing effect on the surface composed of inorganic material, and compatibility with the polarity of the surface composed of inorganic material, The range of 1-40 is preferable, the range of 5-35 is more preferable, the range of 10-30 is still more preferable, and the range of 12.5-30 is especially preferable.

  Of the polymers used in the present invention, those having at least a hydrophilic repeating unit having a sulfinyl group in the side chain and a cationic repeating unit are novel compounds. Such a polymer is excellent in the effect of preventing non-specific adsorption to the surface composed of an inorganic material in spite of having a cationic repeating unit.

Next, the manufacturing method of the polymer used by this invention is demonstrated.
The polymer used in the present invention is (1) introducing a sulfide group into the side chain of a known polymer and converting the sulfide group to a sulfinyl group, and (2) forming a side chain when polymerized. A monomer having a sulfide group in a portion thereof is polymerized or copolymerized with another monomer, and the sulfide group of the obtained (co) polymer is converted into a sulfinyl group, (3) or when the side chain is polymerized A monomer having a sulfinyl group in the portion can be produced by polymerization or copolymerization with other monomers. Examples of the other monomer include those that induce the repeating units (B) to (D).
The said manufacturing method is concretely demonstrated for the example of the manufacturing method of the following copolymer (O-1-1).
That is, in step 1, a copolymer (M-1-1) is obtained, and a copolymer (O-1-1) is obtained through the copolymer (S-1-1) using this.

<Step 1>
Step 1 is a step of obtaining a copolymer (M-1-1) by polymerizing the compound (A-1) and the compound (B-1) in the presence of a polymerization initiator.
The amount of compound (B-1) to be used is generally about 0.01 to 2 molar equivalents relative to compound (A-1).

Examples of the polymerization initiator include 2,2′-azobis (isobutyronitrile), dimethyl 2,2′-azobis (2-methylpropionate), 2,2′-azobis (4-methoxy). Azo initiators such as -2,4-dimethylvaleronitryl; peroxides such as di (3,5,5-trimethylhexanoyl) peroxide, benzoyl peroxide, and the like. Can be used alone or in combination of two or more.
The total amount of the polymerization initiator used is usually about 0.0001 to 0.5 times by mass with respect to the compound (A-1).

In step 1, a solvent and a chain transfer agent may be used. Examples of the solvent include amide solvents such as dimethylformamide, dimethylacetamide, amphiphilic amides (Ecamide B-100, Ecamide M-100 (above, Idemitsu Kosan Co., Ltd.)); Sulfoxide solvents such as dimethyl sulfoxide; Ethyl acetate And ester solvents such as butyl acetate; and lactone solvents such as gamma butyrolactone and gamma valerolactone. These solvents can be used alone or in combination of two or more. The total amount of these solvents used is usually about 0.1 to 20 times the mass of the compound (A-1).
Examples of the chain transfer agent include mercaptoethanol, thioglycerol, tert-dodecyl mercaptan, and the like.

  The reaction time in Step 1 is not particularly limited, but is usually about 0.5 to 24 hours, and the reaction temperature may be appropriately selected below the boiling point of the solvent, but is usually about 0 to 120 ° C.

<Step 2>
Step 2 is a step of obtaining a copolymer (S-1-1) by ring-opening addition using thioglycerol to the glycidyl group of the copolymer (M-1-1) obtained in Step 1. is there.
The amount of thioglycerol to be used is generally 0.1 to 20 molar equivalents relative to the repeating unit derived from compound (B-1).

Step 2 is preferably performed in the presence of a catalyst. Examples of the catalyst include basic catalysts such as triethylamine and N, N-dimethyl-4-aminopyridine, and these catalysts can be used alone or in combination of two or more.
The total amount of the catalyst used is usually 0.01 to 32 molar equivalents with respect to the repeating unit derived from the compound (B-1).

  Step 2 is preferably performed in the presence of a solvent. As the solvent, in addition to the solvent that can be used in Step 1, an alcohol solvent such as ethanol and methanol, or a mixed solvent thereof can be mentioned, and the total amount used thereof is based on the copolymer (M-1-1). Usually, it is about 0.5-20 mass times.

The reaction time in step 2 is not particularly limited, but is usually about 1 to 8 hours, and the reaction temperature may be appropriately selected below the boiling point of the solvent, but is usually about 40 to 100 ° C.
Step 2 may be performed before step 1, and then polymerization in step 1 may be performed.

<Step 3>
Step 3 is a step of obtaining a copolymer (O-1-1) by converting the sulfide group of the copolymer (S-1-1) obtained in Step 2 into a sulfinyl group using an oxidizing agent. . In addition, as long as the effect of this invention is not lost, some sulfinyl groups contained in the copolymer may be sulfide groups or sulfonyl groups.

The oxidizing agent is roughly classified into an organic oxidizing agent and an inorganic oxidizing agent, and examples of the organic oxidizing agent include peracetic acid, perbenzoic acid, and metachloroperbenzoic acid. On the other hand, examples of the inorganic oxidizing agent include hydrogen peroxide, chromic acid, permanganate and the like. In addition, these oxidizing agents can be used individually by 1 type or in combination of 2 or more types.
Moreover, the usage-amount of an oxidizing agent is about 1.0-2.0 molar equivalent normally with respect to the repeating unit derived from a compound (B-1).

Step 3 is preferably performed in the presence of a solvent. Examples of such a solvent include water; amide solvents such as dimethylformamide and dimethylacetamide; alcohol solvents such as methanol and ethanol, and the like. These solvents can be used alone or in combination of two or more. Water and alcohol solvents are preferred.
The total amount of the solvent used is usually about 1 to 15 times by mass with respect to the copolymer (S-1-1).

  The reaction time in step 3 is not particularly limited, but is usually about 1 to 24 hours, and the reaction temperature may be appropriately selected below the boiling point of the solvent, but is usually about 25 to 70 ° C.

  In each step, isolation of each reaction product may be performed by filtration, washing, drying, recrystallization, reprecipitation, dialysis, centrifugation, extraction with various solvents, neutralization, chromatography, etc., if necessary. Ordinary means may be combined as appropriate.

The surface treatment agent of the present invention may contain a solvent, and examples of the solvent include water; alcohol solvents such as methanol, ethanol, isopropyl alcohol, and the like. These solvents may be used alone or in combination of two. A combination of the above may also be included. The content of such a solvent is preferably such that the polymer used in the present invention is 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, and 0.01 to 1% by mass. Is more preferred. Even at such a low concentration, the effect of preventing nonspecific adsorption to the surface composed of the inorganic material can be sufficiently obtained.
Moreover, the surface treatment agent for the surface comprised with the inorganic material of this invention may contain the disinfectant, antiseptic | preservative, etc. other than the said polymer and solvent.

And the surface treating agent for the surface comprised with the inorganic material of this invention is excellent in the nonspecific adsorption | suction prevention effect with respect to the surface comprised with an inorganic material, and has a protein activity maintenance effect. In particular, it is useful as a surface treatment agent for glass and a nonspecific adsorption inhibitor for glass.
Here, in this specification, prevention of non-specific adsorption refers to preventing non-specific adsorption of proteins, lipids, nucleic acids, cells, and the like to a surface composed of an inorganic material.
Therefore, the surface treatment agent of the present invention can be widely used in the field of clinical examinations / diagnostics and the like. For example, a glass solid phase such as glass beads, a clinical diagnosis apparatus, and a cell culture substrate made of glass. It can also be used as a coating agent for products made of glass (microarray substrate made of glass, etc.); a conditioning agent, a cleaning agent, a rinse solution, etc. for a measuring cell for a fully automatic analyzer used for diagnosis such as blood test.

[Equipment]
The instrument of the present invention has a surface composed of an inorganic material, and a part or all of the surface is coated with the surface treatment agent.
Examples of the inorganic material include oxide glass mainly composed of silicon dioxide, inorganic glass such as chalcogenide and halide, glass material such as metal alloy glass and quartz; gold, silver, copper, stainless steel, Ni—Ti alloy , Cu—Al—Mn alloy, tantalum, Co—Cr alloy, iridium, iridium oxide, niobium, silicon, aluminum, tantalum, titanium, iron, and other metal materials; silicon dioxide, aluminum oxide, titanium oxide, silver oxide, etc. Metal oxides; Metal nitrides such as silicon nitride and aluminum nitride; Ceramic materials such as oxide ceramics, nitride ceramics, carbide ceramics, silicide ceramics and boride ceramics; cement materials; Inorganic materials and the like as components are preferable. Different adsorption inhibitor is preferably used with respect to the light transmitting material since it can be coated without coloring the base material, the glass material is more preferable. Examples of the glass instrument having such a surface made of glass include glass beads, a glass microarray substrate, a glass microplate, and a glass cell.

  The said instrument can be manufactured by the method including the process of making the said surface treating agent contact the one part or all part of the said surface of an instrument provided with the surface comprised with an inorganic material. Since the surface treatment agent of the present invention is easily adsorbed and coated simply by contacting the surface composed of the inorganic material of the instrument, according to such a method, the instrument can be manufactured easily and easily.

  The contact time is usually 15 seconds to 48 hours, preferably 5 minutes to 24 hours. The contact temperature is usually 0 to 50 ° C., but may be room temperature (25 ° C.).

  Moreover, after making the surface treatment agent of this invention contact an instrument, you may remove or dry a solution as needed. The removal / drying means may be performed by appropriately combining treatments such as volatilization of the solvent by drying, tilting the instrument so that the solution flows out, lifting the instrument from the solution, blowing off the solution on the instrument, and pouring a large amount of the solvent. Good. Thereby, a dry film of the surface treatment agent of the present invention is formed on the surface of the instrument.

  In addition, the said instrument can be manufactured also by the method of coating the surface treatment agent of this invention on the inorganic material by the method similar to the said method (1), and shape | molding an instrument using such an inorganic material.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples. Examples 3, 4 and 5 are reference examples.

Each analysis condition in the examples is as follows.
<Molecular weight measurement>
Weight average molecular weight (Mw) and number average molecular weight (Mn) were measured using a TSKgel α-M column manufactured by Tosoh Corporation, flow rate: 0.5 ml / min, elution solvent: NMP solvent (H ₃ PO ₄ : 0.016M, LiBr: 0.030M), column temperature: 40 ° C., analysis by gel permeation chromatography (GPC) using polystyrene as a standard, flow rate: 0.5 ml / min, elution solvent: water (EtOH: It can be measured according to the polymer by gel permeation chromatography (GPC) using polyethylene glycol as a standard under analytical conditions of 20% (v / v), NaNO ₃ : 0.1 M), column temperature: 25 ° C. Measured using means.
<NMR spectrum>
^{The 13} C-NMR spectrum was measured by a model AVANCE 500 (500 MHz) manufactured by BRUKER using d6-DMSO as a solvent and an internal standard substance.

Example 1 Synthesis of Copolymer (O-1-1) A copolymer (O-1-1) was obtained according to the following synthesis route.

43.6 g of glycidyl methacrylate (GMA) and 8.48 g of (3-acrylamidopropyl) trimethylammonium chloride (APTAC) 75% aqueous solution, 0.500 g of 2,2′-azobis (isobutyronitrile) as a polymerization initiator, And 473 g of gamma butyrolactone were mixed and placed in a flask. Nitrogen was blown into this, it heated up to 75 degreeC, it was made to superpose | polymerize for 8 hours, and the copolymer (M-1-1) was obtained by cooling to room temperature after that.
In the obtained copolymer (M-1-1), the content of repeating units derived from glycidyl methacrylate is 91 mol%, and the content of repeating units derived from (3-acrylamidopropyl) trimethylammonium chloride. Was 9 mol%. These contents were calculated from the elemental composition obtained by ESCA after re-precipitation of the polymer solution after polymerization with hexane and drying under reduced pressure.

  Next, 300 g of the mixture containing the obtained copolymer (M-1-1), 16.3 g of thioglycerol, and 186 g of methanol were mixed and placed in a flask. The temperature was raised to 60 ° C. while blowing nitrogen into this, and 2.03 g of triethylamine was added as a catalyst, followed by reaction for 2 hours, and then cooled to room temperature to obtain a mixture containing the copolymer (S-1-1). It was.

Next, 504 g of a mixture containing the obtained copolymer (S-1-1) and 41.91 g of water were placed in a flask. To this, 34.20 g of a 30% aqueous hydrogen peroxide solution was added and reacted at 40 ° C. for 2 hours to obtain a copolymer (O-1-1). Moreover, the mixture after completion | finish of this reaction was dialyzed by substituting for water, and it was set as the aqueous solution containing a copolymer (O-1-1).
Moreover, the number average molecular weight (elution solvent: NMP) of the obtained copolymer (O-1-1) was 49700, and molecular weight distribution (elution solvent: NMP) was 1.98.
The structure of the copolymer (O-1-1) was confirmed by ¹³ C-NMR.

Example 2 Synthesis of Copolymer (O-1-2) A copolymer (O-1-2) was obtained according to the following synthesis route.

30.3 g of diacetone acrylamide (DAAM), 41.4 g of glycidyl methacrylate (GMA) and 17.1 g of (3-acrylamidopropyl) trimethylammonium chloride (APTAC) 75% aqueous solution, and 2,2′-azobis as a polymerization initiator (Isobutyronitrile) 0.845 g and gamma butyrolactone 358 g were mixed and placed in a flask. Nitrogen was blown into this, it heated up to 75 degreeC, it was made to superpose | polymerize for 8 hours, and the copolymer (M-1-2) was obtained by cooling to room temperature after that.
In the obtained copolymer (M-1-2), the content of repeating units derived from diacetone acrylamide is 32 mol%, and the content of repeating units derived from glycidyl methacrylate is 52 mol%. The content of repeating units derived from (3-acrylamidopropyl) trimethylammonium chloride was 16 mol%. These contents were calculated from the elemental composition obtained by ESCA after re-precipitation of the polymer solution after polymerization with hexane, followed by drying under reduced pressure.

  Next, 444 g of a mixture containing the obtained copolymer (M-1-2), 47.2 g of thioglycerol, and 247 g of methanol were mixed and placed in a flask. The temperature was raised to 60 ° C. while blowing nitrogen into this, and 5.89 g of triethylamine was added as a catalyst, followed by reaction for 2 hours, and then cooled to room temperature to obtain a mixture containing the copolymer (S-1-2). It was.

Next, 748 g of a mixture containing the obtained copolymer (S-1-2) and 10.7 g of water were placed in a flask. 98.9g of 30% hydrogen peroxide aqueous solution was added to this, and it was made to react at 40 degreeC for 2 hours, and the copolymer (O-1-2) was obtained. Moreover, the mixture after completion | finish of this reaction was dialyzed by substituting for water, and it was set as the aqueous solution containing a copolymer (O-1-2).
Moreover, the number average molecular weight (elution solvent: NMP) of the obtained copolymer (O-1-2) was 55100, and molecular weight distribution (elution solvent: NMP) was 2.93.
The structure of the copolymer (O-1-2) was confirmed by ¹³ C-NMR.

Example 3 Synthesis of Copolymer (O-1-3) A copolymer (O-1-3) was obtained according to the following synthesis route.

Diacetone acrylamide (DAAM) 7.84 g, 2-methoxyethyl acrylate (MEA) 15.7 g and glycidyl methacrylate (GMA) 4.49 g, 2,2′-azobis (isobutyronitrile) as a polymerization initiator 0.280 g and 66.0 g of gamma butyrolactone were mixed and placed in a flask. Nitrogen was blown into this, it heated up to 75 degreeC, it was made to superpose | polymerize for 8 hours, and the copolymer (M-1-3) was obtained by cooling to room temperature after that.
In the obtained copolymer (M-1-3), the content of the repeating unit derived from diacetone acrylamide was 23 mol%, and the content of the repeating unit derived from 2-methoxyethyl acrylate was 61 mol. %, And the content of repeating units derived from glycidyl methacrylate was 16 mol%. These contents were calculated from the elemental composition obtained by ESCA after re-precipitation of the polymer solution after polymerization with hexane, followed by drying under reduced pressure.

  Subsequently, 10.0 g of the mixture containing the obtained copolymer (M-1-3), 8.48 g of thioglycerol, and 4.83 g of methanol were mixed and placed in a flask. The temperature was raised to 60 ° C. while blowing nitrogen into this, and 0.068 g of triethylamine was added as a catalyst, followed by reaction for 2 hours, and then cooled to room temperature to obtain a mixture containing the copolymer (S-1-3). It was.

Next, 15.4 g of a mixture containing the obtained copolymer (S-1-3), 2.33 g of methanol, and 4.62 g of water were placed in a flask. To this, 1.14 g of 30% aqueous hydrogen peroxide solution was added and reacted at 40 ° C. for 2 hours to obtain a copolymer (O-1-3). Moreover, the mixture after completion | finish of this reaction was dialyzed by substituting for water, and it was set as the aqueous solution containing a copolymer (O-1-3).
Moreover, the number average molecular weight (elution solvent: NMP) of the obtained copolymer (O-1-3) was 38700, and molecular weight distribution (elution solvent: NMP) was 3.50.
The structure of the copolymer (O-1-3) was confirmed by ¹³ C-NMR.

Example 4 Synthesis of Copolymer (O-1-4) A copolymer (O-1-4) was obtained according to the following synthesis route.

14.7 g of diacetone acrylamide (DAAM) and 25.3 g of glycidyl methacrylate (GMA), 0.400 g of 2,2′-azobis (isobutyronitrile) as a polymerization initiator, and 49.4 g of gamma butyrolactone are mixed. And placed in a flask. Nitrogen was blown into this, it heated up to 75 degreeC, it was made to superpose | polymerize for 8 hours, and the copolymer (M-1-4) was obtained by cooling to room temperature after that.
In the obtained copolymer (M-1-4), the content of repeating units derived from diacetone acrylamide was 33 mol%, and the content of repeating units derived from glycidyl methacrylate was 67 mol%. It was. These contents were calculated from the elemental composition by ESCA after drying the polymer solution after polymerization under reduced pressure and reprecipitating with hexane.

  Subsequently, 89.8 g of the mixture containing the obtained copolymer (M-1-4), 28.85 g of thioglycerol, and 34.1 g of methanol were mixed and placed in a flask. The temperature was raised to 60 ° C. while blowing nitrogen into this, and 3.60 g of triethylamine was added as a catalyst, followed by reaction for 2 hours, and then cooled to room temperature to obtain a mixture containing the copolymer (S-1-4). It was.

Next, 156 g of a mixture containing the obtained copolymer (S-1-4), 93.0 g of methanol, and 83.3 g of water were placed in a flask. To this, 18.1 g of 30% aqueous hydrogen peroxide solution was added and reacted at 40 ° C. for 2 hours to obtain a copolymer (O-1-4). Moreover, the mixture after completion | finish of this reaction was dialyzed by substituting for water, and it was set as the aqueous solution containing a copolymer (O-1-4).
Moreover, the number average molecular weight (elution solvent: NMP) of the obtained copolymer (O-1-4) was 27800, and molecular weight distribution (elution solvent: NMP) was 2.99.
The structure of the copolymer (O-1-4) was confirmed by ¹³ C-NMR.

Example 5 Synthesis of Copolymer (O-1-5) A copolymer (O-1-5) was obtained according to the following synthesis route.

19.1 g of 2-methoxyethyl acrylate (MEA) and 10.9 g of glycidyl methacrylate (GMA), 0.300 g of 2,2′-azobis (isobutyronitrile) as a polymerization initiator, and 1-methyl-2 -70.7 g of pyrrolidone (NMP) was mixed and placed in a flask. Nitrogen was blown into this, the temperature was raised to 70 ° C., polymerized for 8 hours, and then cooled to room temperature to obtain a copolymer (M-1-5).
In the obtained copolymer (M-1-5), the content of repeating units derived from 2-methoxyethyl acrylate is 66 mol%, and the content of repeating units derived from glycidyl methacrylate is 34 mol. %Met. These contents were calculated from the elemental composition obtained by ESCA after re-precipitation of the polymer solution after polymerization with hexane, followed by drying under reduced pressure.

  Next, 16.0 g of a mixture containing the obtained copolymer (M-1-5), 1.98 g of thioglycerol, and 7.72 g of methanol were mixed and placed in a flask. The temperature was raised to 60 ° C. while blowing nitrogen, and 0.246 g of triethylamine was added as a catalyst, followed by reaction for 2 hours. Then, it cooled to room temperature and obtained the mixture containing a copolymer (S-1-5).

Next, 25.9 g of a mixture containing the obtained copolymer (S-1-5), 5.30 g of methanol, and 6.95 g of water were placed in a flask. To this, 4.14 g of 30% aqueous hydrogen peroxide solution was added and reacted at 40 ° C. for 2 hours to obtain a copolymer (O-1-5). Moreover, the mixture after completion | finish of this reaction was dialyzed by substituting for water, and it was set as the aqueous solution containing a copolymer (O-1-5).
Moreover, the number average molecular weight (elution solvent: NMP) of the obtained copolymer (O-1-5) was 41100, and molecular weight distribution (elution solvent: NMP) was 2.42.
The structure of the copolymer (O-1-5) was confirmed by ¹³ C-NMR.

Example 6 Synthesis of Copolymer (O-1-6) A copolymer (O-1-6) was obtained according to the following synthesis route.

2-methoxyethyl acrylate (MEA) 52.48 g, glycidyl methacrylate (GMA) 21.1 g and (3-acrylamidopropyl) trimethylammonium chloride (APTAC) 75% aqueous solution 15.9 g, and 2,2 as a polymerization initiator 0.855 g of '-azobis (isobutyronitrile) and 361 g of gamma butyrolactone were mixed and placed in a flask. Nitrogen was blown into this, the temperature was raised to 75 ° C., the mixture was polymerized for 8 hours, and then cooled to room temperature to obtain a copolymer (M-1-6).
In the obtained copolymer (M-1-6), the content of repeating units derived from 2-methoxyethyl acrylate is 67 mol%, and the content of repeating units derived from glycidyl methacrylate is 24 mol. %, And the content of repeating units derived from (3-acrylamidopropyl) trimethylammonium chloride was 9 mol%. These contents were calculated from the elemental composition obtained by ESCA after re-precipitation of the polymer solution after polymerization with hexane, followed by drying under reduced pressure.

  Next, 200 g of a mixture containing the obtained copolymer (M-1-6), 6.10 g of thioglycerol, and 110 g of methanol were mixed and placed in a flask. The temperature was raised to 60 ° C. while nitrogen was blown into this, 0.76 g of triethylamine was added as a catalyst, the reaction was performed for 2 hours, and then cooled to room temperature to obtain a mixture containing the copolymer (S-1-6). It was.

Next, 317 g of a mixture containing the obtained copolymer (S-1-6) and 62.0 g of water were placed in a flask. To this, 12.8 g of 30% aqueous hydrogen peroxide solution was added and reacted at 40 ° C. for 2 hours to obtain a copolymer (O-1-6). Moreover, the mixture after completion | finish of this reaction was dialyzed by substituting for water, and it was set as the aqueous solution containing a copolymer (O-1-6).
Moreover, the number average molecular weight (elution solvent: water) of the obtained copolymer (O-1-6) was 8830, and molecular weight distribution (elution solvent: water) was 4.72.
The structure of the copolymer (O-1-6) was confirmed by ¹³ C-NMR.

  Table 1 below shows the HLB values (Oda formula) of the copolymers (O-1-1) to (O-1-6) obtained in Examples 1 to 6. In addition, when the homopolymer which consists of a repeating unit derived from the said glycidyl methacrylate was synthesize | combined and 1 g was added to 100 g of pure water, it melt | dissolved at normal temperature (25 degreeC). Further, when a homopolymer composed of repeating units derived from 2-methoxyethyl acrylate and a homopolymer composed of repeating units derived from diacetone acrylamide were synthesized and 1 g was added to 100 g of pure water, room temperature (25 ° C.) It did not completely dissolve.

Test Example 1 Antibody Adsorption Amount Measurement A 0.1-mass% aqueous solution of the copolymer obtained in Examples 1 to 6 is filled in a 96-well glass microplate (FUJI-96 manufactured by Nippon Sheet Glass Co., Ltd.) and incubated at room temperature for 5 minutes. Then, it was washed 4 times with ultrapure water. Next, an aqueous solution of horseradish peroxidase-labeled mouse IgG antibody (AP124P: manufactured by Millipore) was filled in the glass microplate, incubated at room temperature for 1 hour, washed 4 times with PBS buffer, and TMB (3, 3 ', 5 , 5′-tetramethylbenzidine) / hydrogen peroxide solution / sulfuric acid, and the absorbance at 450 nm was measured using a microplate reader (Model 680, manufactured by Nippon Bio-Rad Laboratories). From this absorbance, a calibration curve method was used. The amount of antibody adsorption was calculated.
Further, as Comparative Example 1, the test was performed in the same procedure as above except that the 0.1% by mass aqueous solution of the copolymer obtained in Examples 1 to 6 was changed to ultrapure water, and the antibody adsorption amount was calculated. did.
The results of Test Example 1 are shown in Table 2.

  As shown in Table 2, the copolymers (O-1-1) to (O-1-6) have an excellent non-specific adsorption preventing effect on glass.

Claims (7)

  A polymer having a hydrophilic repeating unit having a sulfinyl group in the side chain and a cationic repeating unit.   The polymer according to claim 1, wherein the hydrophilic repeating unit further has a hydroxy group in its side chain.   The polymer according to claim 2, wherein the number of the hydroxy groups is 1 to 12 in one hydrophilic repeating unit. The polymer according to claim 1, wherein the hydrophilic repeating unit is a hydrophilic repeating unit having a structure represented by the following formula (1) in a side chain.

[In Formula (1), R < ³ > shows a direct bond or a C1-C24 bivalent organic group, and R < ⁴ > shows a C1-C10 organic group. ]   The polymer according to claim 4, wherein the hydrophilic repeating unit is selected from a (meth) acrylate-based hydrophilic repeating unit, a (meth) acrylamide-based hydrophilic repeating unit, and a styrene-based hydrophilic repeating unit. The polymer according to claim 1, wherein the hydrophilic repeating unit is represented by the following formula (2).

[In formula (2), R ¹ represents a hydrogen atom or a methyl group, R ² is a group -O-, a group * - (C = O) -O- , group * - (C = O) -NR ⁵ -, group * -NR ⁵ - (C = O) - (R ⁵ is a hydrogen atom or an organic group having 1 to 10 carbon atoms, and *, R ¹ in the formula (2) is attached Or a phenylene group, R ³ represents a direct bond or a divalent organic group having 1 to 24 carbon atoms, and R ⁴ represents an organic group having 1 to 10 carbon atoms. . ]   The polymer according to any one of claims 1 to 6, wherein the hydrophilic repeating unit is nonionic.