JP5013575B2 - Material surface treatment method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for readily introducing a phosphorylcholine group in very good efficiency to an arbitrary material, the surface treatment of which by using a conventional silane coupler has been difficult, by reacting the surface with a specific phosphorylcholine group-containing silane coupler. <P>SOLUTION: The method for treating the surface of the material comprises subjecting the surface of the material to vapor deposition of a metal oxide or silica, and treating the deposited surface with a phosphorylcholine-containing compound represented by formula (1) (wherein, m is 2-6; n is 1-4; X<SP>1</SP>, X<SP>2</SP>and X<SP>3</SP>are each independently a methoxy group, an ethoxy group or a halogen, with the proviso that up to two of the X<SP>1</SP>, X<SP>2</SP>and X<SP>3</SP>can be any of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group). <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a surface treatment method using a surface modifier containing a phosphorylcholine group, and a resin, a modified powder, a metal, a ceramic, and a fiber modified by the surface treatment method.

  The surface treatment method of the present invention imparts biomaterials, moisture retention, and other various useful functions to any material.

  Polymers having phosphorylcholine groups have been studied as biocompatible polymers, and biocompatible materials in which this polymer is coated on various bases have been developed.

  For example, Patent Document 1 discloses a cosmetic material in which a powder coated with a homopolymer and a copolymer of 2-methacryloyloxyethyl phosphorylcholine is used as a cosmetic powder to improve moisture retention and skin adhesion. Has been.

  Patent Documents 2 and 3 disclose medical materials and separating agents coated with a polymer having a phosphorylcholine group.

  The above materials have a phosphorylcholine structure by reacting mainly an acrylic monomer having a hydroxyl group with 2-chloro-1,3,2-dioxaphosphorane-2-oxide and further converting to quaternary ammonium with trimethylamine. The surface is coated with a polymer obtained by synthesizing and polymerizing the monomer (see Patent Documents 4 and 5 for the method for producing the polymer).

  In Patent Document 4, a copolymer of 2-methacryloyloxyethyl phosphorylcholine and methacrylic acid ester is produced. In Patent Document 5, a homopolymer of 2-methacryloyloxyethyl phosphorylcholine is produced.

  Non-Patent Document 1 describes that the adsorption of proteins is reduced by a phosphorylcholine group chemically grafted on a carrier.

  However, in the method of coating and modifying the surface of an object with a polymer having a phosphorylcholine group, the coated polymer is peeled off from the object, which may cause a problem in durability. In particular, when a hydrophilic surface is coated with a polymer using phosphorylcholine, the polymer easily drops off with water or the like. In addition, when coating a hydrophobic surface, a phosphorylcholine polymer having a hydrophobic group is synthesized, and the durability is exhibited by using hydrophobic interaction. However, conditions such as an organic solvent can cancel the hydrophobic interaction. Underneath, there is still a problem that the polymer falls off easily.

  In order to solve the above problems, the inventors of the present application developed a silane coupler having a phosphorylcholine group, and by introducing the phosphorylcholine group into the material by a strong covalent bond, the durability of the phosphorylcholine group introduced on the material surface is improved. It has been confirmed that it is greatly improved and the expected functions are fully exhibited (Patent Document 6).

JP 7-118123 A JP 2000-279512 A JP 2002-98676 A JP-A-9-3132 JP-A-10-298240 JP 2005-187456 A Jian R. Lu et al., Langmuir 2001, 17, 3382-3389.

  However, materials that are effective for surface treatment with a silane coupler are limited to metal oxides and some metals, and among them, it has been found that the reaction efficiency varies depending on the metal species. That is, the silane coupler is not necessarily an effective means for a material that does not necessarily have a scaffold for reacting with the silane coupler, such as a resin.

  The present invention provides a silane coupler on the surface of a material by vapor deposition of a metal oxide or silica, or treatment with an alkoxysilane compound or polysilazane treatment on any material that has been difficult to surface-treat using a conventional silane coupler. By introducing a group that reacts with silica (silanol vapor deposition, alkoxysilane compound treatment, or silanol group when polysilazane treatment is performed) and reacting with a specific phosphorylcholine group-containing silane coupler, the phosphorylcholine has excellent durability. The present invention provides a method for introducing a group extremely efficiently and simply.

（１）
式中、ｍは２〜６、ｎは１〜４である。
Ｘ₁、Ｘ₂、Ｘ₃は、それぞれ単独に、メトキシ基、エトキシ基またはハロゲンである。ただし、Ｘ₁、Ｘ₂、Ｘ₃のうち、２つまではメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基のいずれでも良い。
Ｒは下記式（２）〜（４）中の構造のいずれかである（ただし、下記式（２）〜（４）構造において、式（１）の化合物をＡ−Ｒ−Ｂで表す）。

（２）

（３）

（４）
That is, the present invention provides a material surface treatment in which the surface of a material is treated with trialkoxymonoalkylsilane or dialkoxydialkylsilane to introduce a silanol group, and then treated with a phosphorylcholine group-containing compound represented by the following formula (1). A method is provided.

(1)
In the formula, m is 2 to 6, and n is 1 to 4.
X ₁ , X ₂ and X ₃ are each independently a methoxy group, an ethoxy group or a halogen. However, up to _{two of} X ₁ , X ₂ , and X ₃ may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, and isobutyl group.
R is any of the structures in the following formulas (2) to (4) (however, in the structures of the following formulas (2) to (4), the compound of the formula (1) is represented by A—R—B).

(2)

(3)

(4)

  Furthermore, this invention provides the resin raw material (synthetic resin or natural resin) processed by the said surface treatment method.

  Moreover, this invention provides the modified powder processed by the said surface treatment method.

  Furthermore, this invention provides the metal raw material processed by the said surface treatment method.

  Moreover, this invention provides the ceramic raw material processed by the said surface treatment method.

  Furthermore, this invention provides the fiber raw material processed by the said surface treatment method.

  According to the surface treatment method of the present invention, it is possible to introduce any desired amount of phosphorylcholine groups to the surface of a material by a very simple reaction on the surface of various objects that are usually difficult to treat with a silane coupler. It is. That is, surface modification is possible regardless of the material and shape of the material. As a result, resins, modified powders, metals, ceramics and fibers having various desired functions such as protein adsorption suppression can be easily produced by phosphorylcholine groups.

  More specifically, phosphorylcholine groups with very little protein or polypeptide adsorption can be introduced into various materials simply and quantitatively with high durability. Further, since an unreacted functional group other than the phosphorylcholine group is not introduced, it is possible to provide a material with extremely high biocompatibility.

  Synthetic and natural resins, modified powders, metals, ceramics, and fibers having phosphorylcholine groups introduced on the surface by the method of the present invention are extremely excellent in biocompatibility. Moreover, since there is little protein adsorption to the surface, it can be applied to medical materials, analyzers, diagnostic / analytical particles, cosmetics and the like.

（１）
式中、ｍは２〜６、ｎは１〜４である。
Ｘ₁、Ｘ₂、Ｘ₃は、それぞれ単独に、メトキシ基、エトキシ基またはハロゲンである。ただし、Ｘ₁、Ｘ₂、Ｘ₃のうち、２つまではメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基のいずれでも良い。
Ｒは下記式（２）〜（４）中の構造のいずれかである（ただし、下記式（２）〜（４）構造において、式（１）の化合物をＡ−Ｒ−Ｂで表す）。

（２）

（３）

（４）
式（２）〜（４）中、Ｌは１〜６、Ｐは０〜３を表す。

（５）

（６）
式中、ｍは２〜６、ｎは１〜４である。Ｘ₁、Ｘ₂、Ｘ₃は、それぞれ単独に、メトキシ基、エトキシ基またはハロゲンである。ただし、Ｘ₁、Ｘ₂、Ｘ₃のうち、２つまではメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基のいずれでも良い。 "Surface treatment agent (surface modifier)"
The surface treating agent (surface modifier) used in the present invention is a phosphorylcholine group-containing compound represented by the following formula (1), (5) or (6). Japanese Patent Laid-Open No. 2005-187456 describes the manufacturing method in detail.

(1)
In the formula, m is 2 to 6, and n is 1 to 4.
X ₁ , X ₂ and X ₃ are each independently a methoxy group, an ethoxy group or a halogen. However, up to _{two of} X ₁ , X ₂ , and X ₃ may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, and isobutyl group.
R is any of the structures in the following formulas (2) to (4) (however, in the structures of the following formulas (2) to (4), the compound of the formula (1) is represented by A—R—B).

(2)

(3)

(4)
In formulas (2) to (4), L represents 1 to 6, and P represents 0 to 3.

(5)

(6)
In the formula, m is 2 to 6, and n is 1 to 4. X ₁ , X ₂ and X ₃ are each independently a methoxy group, an ethoxy group or a halogen. However, up to _{two of} X ₁ , X ₂ , and X ₃ may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, and isobutyl group.

（７） “Method for Producing Phosphorylcholine Group-Containing Compound of Formula (1), (5) or (6)”
A phosphorylcholine derivative represented by the following formula (7) is dissolved in distilled water. The phosphorylcholine derivative of the following formula (7) is a known compound and is commercially available.

(7)

（８） An aqueous solution of the compound of formula (7) was cooled in an ice-water bath, sodium periodate was added, and the mixture was stirred for 5 hours. The reaction solution is concentrated under reduced pressure and dried under reduced pressure, and a phosphorylcholine derivative having an aldehyde group represented by the following formula (8) is extracted with methanol.

(8)

  Next, 0.5 equivalent of 3-aminopropyltrimethoxysilane is added to the methanol solution of the formula (8). The mixed solution is stirred at room temperature for a predetermined time, and then ice-cooled, an appropriate amount of sodium cyanohydroborate is added, and the mixture is returned to room temperature and stirred for 16 hours. During this time, dry nitrogen is continuously supplied to the reaction vessel. After filtering the precipitate, a methanol solution of formula (5) is obtained.

（Ａ） An aqueous solution of the compound of formula (7) is cooled in an ice-water bath, sodium periodate and a catalytic amount of ruthenium trichloride are added and stirred for 3 hours. The reaction solution is concentrated under reduced pressure and dried under reduced pressure, and the phosphorylcholine derivative (A) having a carboxyl group represented by the following formula is extracted with methanol.

(A)

（Ｂ） Next, 1.2 equivalent of thionyl chloride is added to the acetonitrile or N, N-dimethylformamide dispersion of formula (A), and 0.9 equivalent of 3-aminopropyltrimethoxysilane is added to the stirred solution for 30 minutes. The mixed solution is stirred at room temperature for 4 hours. In this method, the compound of the following formula (B) is obtained as the compound of the formula (6). By a similar method, the compound of the general formula (1) or the formula (6) is obtained using another silane compound instead of 3-aminopropyltrimethoxysilane.

(B)

  In addition to thionyl chloride, the reagent used for the above condensation reaction can be used as long as it generally produces a carboxylic acid halide, such as phosphorus pentachloride, phosphorus oxychloride, phosphorus tribromide, oxalyl chloride. Can be used. Purification can be performed in the same manner as the compound of the above formula (5).

The above procedure can be carried out in the same manner even if m and n in the compound represented by formula (5) or (6) are changed. The procedure shown here is for m = 3 and n = 2. Furthermore, by using 3- (2-aminoethylaminopropyl) trimethoxysilane or the like as the silane compound having an amino group, it is possible to insert a secondary amine between the silane moiety and the phosphorylcholine group. The same procedure can be used. The reaction solvent is not particularly limited, and water, alcohols such as ethanol, propanol and butanol, and aprotic solvents such as N, N-dimethylformamide and dimethyl sulfoxide can be used in addition to the above-described methanol. However, a dehydrated solvent is preferred in order to prevent polymerization of the organosilane compound during the reaction.
Further, when the methoxy group (OCH ₃ ) in the formula (5) or (6) is an ethoxy group (OC ₂ H ₅ ), the reaction is carried out by changing methanol to ethanol, and in the case of Cl, dimethylformamide or dimethyl Change to sulfoxide.
Further, when two or one of methoxy group, ethoxy group or Cl bonded to Si is substituted with any of methyl group, ethyl group, propyl group, isopropyl group, butyl group and isobutyl group, It can be manufactured in exactly the same way.

Next, the purification method of the said compound is demonstrated. The method for purifying the compound of the present invention is not limited to the following.
The obtained methanol solution of the above compound is concentrated under reduced pressure, and the residue is dissolved in distilled water. This aqueous solution is used as a sample. Capsule pack SCX UG80 S-5 (size: 4.6 mm.d. × 250 mm) (Shiseido Co., Ltd.), which is a column for high performance liquid chromatography having hydrophobic interaction and cation exchange ability, was connected to an HPLC apparatus. After equilibration by flowing 0.2 mmol / L phosphate buffer (pH 3.5) at a flow rate of 1 mL / min, 10 μL of sample is injected. By using a differential refractometer as a detector, a chromatogram can be obtained and the target compound can be isolated.

The compounds of the above formulas (5) and (6) are useful as surface modifiers for various substances. That is, a desired amount of phosphorylcholine group is easily introduced into the surface of the substance for modification. Specifically, in the case of a substance having a hydroxyl group on its surface, a chemical bond is formed by a dehydration reaction from the hydroxyl group on the substance surface and Si—OCH ₃ of the compounds of formulas (5) and (6). This chemical reaction proceeds very easily and quantitatively in most organic solvents or water in the temperature range of 10 ° C to 250 ° C. By this reaction, surface modification with a chemically and physically extremely stable phosphorylcholine group can be performed.

"Metal oxide or silica deposition method"
A general method can be used as a method for depositing the metal oxide or silica on the surface of the material. Vacuum vapor deposition, sputtering, thermal CVD, photo CVD, plasma CVD, reactive vapor deposition and the like can be suitably used.
As the metal oxide, silicon oxide, titanium oxide, zinc oxide, aluminum oxide, or the like can be used. These may be used alone or in combination of two or more. The thickness of the vapor deposition is not particularly limited as long as the surface is uniformly coated.

"Treatment with alkoxysilane compounds"
As the alkoxysilane compound for treating the surface of the material, tetraalkoxysilane, trialkoxymonoalkylsilane, and dialkoxydialkylsilane are preferable, but are not limited thereto. The treatment method is not particularly limited, but as a general method, the material is immersed in a solution containing an alkoxysilane compound, or the solution is applied to the surface of the material and dried to form a film. You may add water or an alkali to a solution as needed. Moreover, you may heat when making it dry. Further, after drying, water treatment may be performed in order to hydrolyze the remaining alkoxy groups into hydroxyl groups.
In the present invention, a material surface having a relatively high polarity to a medium polarity is preferably treated with an alkoxysilane compound. For example, PMMA, polyamide, nylon and the like are preferably treated with an alkoxysilane compound.

"Processing with polysilazane"
The treatment method with polysilazane involves immersing the material in a polysilazane solution or applying the solution to the surface of the material and drying it, and heating or water treatment may be performed as necessary.
In the present invention, a material having a medium to relatively low polarity on the material surface is preferably treated with polysilazane. For example, alkyl silicone, Teflon (registered trademark) and the like are preferably treated with polysilazane.

“Treatment with phosphorylcholine group-containing compounds”
The treatment method according to the above formula (1) {(5), (6)} is not particularly limited with respect to a material subjected to metal oxide or silica vapor deposition, or an alkoxysilane compound or polysilazane treatment. As a general method, it can be achieved by applying the solution (5) or (6) to the material, or immersing the material in the solution and drying it. If necessary, water, acid or alkali can be added to the solution, the treatment time can be extended, or the solution can be heated. Further, the solvent can be appropriately selected according to the durability of the material to the organic solvent. The processing method is described in detail in Japanese Patent Application Laid-Open No. 2005-187456.

  The various materials modified by the surface treatment method of the present invention are materials and molded articles excellent in biocompatibility and hydrophilicity. As a material having a phosphorylcholine group directly and strongly covalently bonded to the material surface, protein adsorption is possible in the fields of cosmetics, medical materials (artificial organs, surgical instruments, etc.), chromatographic fillers, paints, etc. The present invention can be applied to a wide range of uses that require problems and biocompatibility.

Next, the present invention will be described in more detail based on examples. The present invention is not limited to these examples.

“Synthesis Example 1: Production of Compound of Formula (A) (Production of Amine-Type Silane Coupler Containing Phosphorylcholine Group)”
L-α-glycerophosphorylcholine (450 mg) was dissolved in 15 ml of distilled water and cooled in an ice-water bath. Sodium periodate (750 mg) was added and stirred for 5 hours. The reaction solution was concentrated under reduced pressure and dried under reduced pressure, and the target product represented by chemical formula (5) was extracted with methanol. Subsequently, 3-aminopropyltrimethoxysilane (300 mg) was added to the above methanol solution, and the mixture was stirred at room temperature for 5 hours, then cooled with ice, sodium cyanohydroborate (100 mg) was added, and the temperature was returned to room temperature. Stir for hours. During this time, dry nitrogen is continuously supplied to the reaction vessel. After filtering the precipitate, a methanol solution of formula (A) is obtained.
FIG. 1 shows ¹ H-NMR data of the compound of the formula (A).

“Synthesis Example 2: Production of Compound of Formula (B) (Production of Amide Type Silane Coupler Having Phosphorylcholine Group)”
5 g of 1-α-glycerophosphorylcholine was dissolved in 70 ml of water-30 ml of acetonitrile. Under ice cooling, 17 g of sodium periodate and 80 mg of ruthenium trichloride were added and stirred overnight. The precipitate was filtered, concentrated under reduced pressure, and extracted with methanol to obtain the desired carboxymethyl phosphorylcholine represented by chemical formula (6). Subsequently, the compound of formula (6) and 3 g of thionyl chloride were added to acetonitrile under ice-cooling, stirred for 30 minutes, 3.8 g of 3-aminopropyltrimethoxysilane was added, and dry nitrogen was continuously passed through the reaction vessel. Stir for an hour at room temperature to obtain the desired compound of formula (B).
FIG. 2 shows ¹ H-NMR data of the compound of the formula (B).

"Example 1: Treatment of PET film with compound of formula (A)"
Silicon oxide was deposited on the surface of a 1 cm × 1 cm PET film by vacuum deposition. Subsequently, it was immersed in 5 ml of a methanol solution containing the compound of Synthesis Example 1 at a concentration of 1 mmol, heated at 60 ° C. for 1 hour, and washed with water to obtain a treated PET film.

"Example 2: Treatment of PET film with compound of formula (B)"
Silicon oxide was deposited on the surface of a 1 cm × 1 cm PET film by vacuum deposition. Subsequently, it was immersed in 5 ml of an acetonitrile solution containing the compound of Synthesis Example 2 at a concentration of 1 mmol, heated at 60 ° C. for 1 hour, and washed with water to obtain a treated PET film.

"Example 3: Treatment of polycarbonate film with compound of formula (A)"
Silicon oxide was deposited on the surface of a 1 cm × 1 cm polycarbonate film by a vacuum deposition method. Subsequently, it was immersed in 5 ml of a methanol solution containing the compound of Synthesis Example 1 at a concentration of 1 mmol, heated at 60 ° C. for 1 hour, and washed with water to obtain a treated polycarbonate film.

"Example 4: Treatment of polycarbonate film with compound of formula (B)"
Silicon oxide was deposited on the surface of a 1 cm × 1 cm polycarbonate film by a vacuum deposition method. Subsequently, it was immersed in 5 ml of an acetonitrile solution containing the compound of Synthesis Example 2 at a concentration of 1 mmol, heated at 60 ° C. for 1 hour, and washed with water to obtain a treated polycarbonate film.

"Example 5: Treatment of PMMA film with compound of formula (A)"
Silicon oxide was deposited on the surface of 1 cm × 1 cm PMMA film by vacuum deposition. Subsequently, it was immersed in 5 ml of a methanol solution containing the compound of Synthesis Example 1 at a concentration of 1 mmol, heated at 60 ° C. for 1 hour, and washed with water to obtain a treated PMMA film.

"Example 6: Treatment of PMMA film with compound of formula (B)"
Silicon oxide was deposited on the surface of 1 cm × 1 cm PMMA film by vacuum deposition. Subsequently, it was immersed in 5 ml of an acetonitrile solution containing the compound of Synthesis Example 2 at a concentration of 1 mmol, heated at 60 ° C. for 1 hour, and washed with water to obtain a treated PMMA film.

"Example 7: Treatment of PMMA film with compound of formula (A)"
Titanium oxide was deposited on the surface of 1 cm × 1 cm PMMA film by plasma PVD deposition. Subsequently, it was immersed in 5 ml of a methanol solution containing the compound of Synthesis Example 1 at a concentration of 1 mmol, heated at 60 ° C. for 1 hour, and washed with water to obtain a treated PMMA film.

"Example 8: Treatment of PMMA film with compound of formula (B)"
Zinc oxide was deposited on the surface of 1 cm × 1 cm PMMA film by plasma PVD deposition. Subsequently, it was immersed in 5 ml of an acetonitrile solution containing the compound of Synthesis Example 2 at a concentration of 1 mmol, heated at 60 ° C. for 1 hour, and washed with water to obtain a treated PMMA film.

"Example 9: Treatment of nylon particles with compound of formula (A)"
Silicon oxide was deposited on 10 g of nylon particles having an average particle diameter of 100 μm by a vacuum deposition method. Subsequently, 20 ml of a methanol solution containing the compound of Synthesis Example 1 at a concentration of 1 mmol was added, heated at 60 ° C. for 1 hour, and washed with water to obtain treated nylon particles.

"Example 10: Treatment of stainless steel with compound of formula (B)"
Silicon oxide was deposited on the surface of a 1 cm × 1 cm stainless steel plate by a vacuum deposition method. Subsequently, it was immersed in 5 ml of an acetonitrile solution containing the compound of Synthesis Example 2 at a concentration of 1 mmol, heated at 60 ° C. for 1 hour, and washed with water to obtain a treated stainless steel plate.

"Example 11: Treatment of PMMA film with tetrabutoxysilane"
On a 1 cm × 1 cm PMMA film, a mixture of 0.1 ml of tetrabutoxysilane, 0.01 ml of water and 0.01 ml of ethanol was applied and heated at 60 ° C. for 3 hours. The film was immersed in a water-ethanol mixed solution for 1 hour, further immersed in water for 1 hour, immersed in 5 ml of an acetonitrile solution containing the compound of Synthesis Example 2 at a concentration of 1 mmol, heated at 60 ° C. for 1 hour, Washed with water to obtain a treated PMMA film.

"Results of introduction of phosphorylcholine group by quantitative phosphorus analysis"
The phosphorylcholine group introduced by the surface treatment method of the present invention performed as described above was quantified by a quantitative analysis of phosphorus by the molybdenum blue method after pretreatment with perchloric acid (Reference: Experimental Chemistry Course ( 14) Fourth edition analysis, 3.8.2 Rin Maruzen). The results are shown in “Table 1”. In any of the examples, it was confirmed that phosphorischoline groups were efficiently introduced on the surfaces of various materials.

"Non-specific protein adsorption test results"
The non-specific adsorption amount of bovine serum albumin and egg yolk lysozyme was quantified by micro BCA method. Untreated PET was evaluated as Comparative Example 1, untreated polycarbonate as Comparative Example 2, untreated PMMA as Comparative Example 3, and untreated stainless steel as Comparative Example 4. The results are shown in “Table 2”. In any of the examples, the adsorption of the protein to the surface of the material into which the phosphorylcholine group was introduced was greatly suppressed.

  Materials that are effective for surface treatment with a silane coupler are limited to metal oxides and some metals. And reaction efficiency changes with metal seed | species. There are also materials that do not necessarily have a scaffold that reacts with the silane coupler, such as a resin. The present invention introduces the phosphorylcholine group very efficiently and easily by reacting with a specific phosphorylcholine group-containing silane coupler on any material that has been difficult to surface-treat using a conventional silane coupler. A method is provided.

According to the surface treatment method of the present invention, it is possible to introduce any desired amount of phosphorylcholine groups to the surface of a material by a very simple reaction on the surface of various objects that are usually difficult to treat with a silane coupler. It is. That is, surface modification is possible regardless of the material and shape of the material. As a result, resins, modified powders, metals, ceramics and fibers having various desired functions such as protein adsorption suppression can be easily produced by phosphorylcholine groups.
That is, a phosphorylcholine group with very little protein or polypeptide adsorption can be introduced into various materials simply and quantitatively with high durability. Further, since an unreacted functional group other than the phosphorylcholine group is not introduced, it is possible to provide a material with extremely high biocompatibility. Moreover, since there is little protein adsorption to the surface, it can be applied to medical materials, analyzers, diagnostic / analytical particles, cosmetics and the like.

¹ is a ¹ H-NMR spectrum of a compound of formula (A). ¹ is a ¹ H-NMR spectrum of a compound of formula (B).

Claims (6)

A surface treatment method for a material, wherein the surface of the material is treated with trialkoxymonoalkylsilane or dialkoxydialkylsilane to introduce a silanol group, and then treated with a phosphorylcholine group-containing compound represented by the following formula (1).

(1)
In the formula, m is 2 to 6, and n is 1 to 4.
X ₁ , X ₂ and X ₃ are each independently a methoxy group, an ethoxy group or a halogen. However, up to _{two of} X ₁ , X ₂ , and X ₃ may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, and isobutyl group.
R is any of the structures in the following formulas (2) to (4) (however, in the structures of the following formulas (2) to (4), the compound of the formula (1) is represented by A—R—B).

(2)

(3)

(4)
In formulas (2) to (4), L represents 1 to 6, and P represents 0 to 3.   A resin material treated by the surface treatment method according to claim 1.   A modified powder treated by the surface treatment method according to claim 1.   A metal material treated by the surface treatment method according to claim 1.   A ceramic material treated by the surface treatment method according to claim 1.   A fiber material treated by the surface treatment method according to claim 1.

Images