JP2002356519A - Phosphorylcholine analog containing polymer and application - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copolymer composed of a novel phosphorylcholine analog, glycerol ester and hydrophobic groups which is excellent in biocompatibility. SOLUTION: The phosphorylcholine analog containing polymer having a weight average molecular weight of 5,000-2,000,000 comprises a monomer containing a phosphorylcholine analog (M<1> ), a glycerol mono(meth)acrylate (M<2> ) and on a hydrophobic monomer (M<3> ).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymer containing a phosphorylcholine-like group, a coating film, a film and a hydrogel comprising the polymer.

[0002]

2. Description of the Related Art Conventionally, a polymer containing a phosphorylcholine-like group has a structure similar to a phospholipid derived from a biological membrane.
It is known to have excellent biocompatibility such as blood compatibility, deactivation of complement, and non-adsorption of biological substances, very high hydrophilicity, and excellent properties such as high moisture retention. Research and development on the synthesis of polymers for the purpose of developing bio-related materials utilizing their functions and their uses have been actively conducted.

For example, JP-A-9-3132 and JP-A-3-39309 disclose a copolymer of a hydrophobic alkyl methacrylate and a phosphorylcholine-like group-containing monomer and a medical device using the copolymer. Techniques for coating are disclosed. However, since a copolymer of a hydrophobic alkyl methacrylate and a phosphorylcholine-like group-containing monomer forms a coating film by the cohesive force of the hydrophobic functional groups of the alkyl methacrylate, it is necessary to improve the water resistance of the film. It is necessary to increase the content of the hydrophobic alkyl methacrylate, but in that case, there is a problem that the hydrophilicity of the coating film is reduced and the performance related to the hydrophilicity such as the water content and the water absorption rate is reduced. .

[0004] For example, Japanese Patent Publication No. 7-502053 discloses a technique relating to a copolymer of a phosphorylcholine-like group-containing monomer and a monomer having a reactive functional group, and coating with the copolymer. It has been disclosed. However, coating using chemical bonding by reactive functional groups requires complicated operations such as control of reaction conditions and removal of residues, which makes quality control difficult and reduces the efficiency of coating operations. There is a point.

[0005]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a constitutional unit based on a novel phosphorylcholine-like group-containing monomer, a constitutional unit based on glycerol mono (meth) acrylate, and a hydrophobic group-containing monomer. To provide a copolymer having a structural unit based on the above. Also,
A second object of the present invention is to provide a coating film using the phosphorylcholine group-containing polymer.
A third object of the present invention is to provide an article having a coating film formed by treating the phosphorylcholine group-containing polymer. A fourth object of the present invention is to provide a film using the phosphorylcholine group-containing polymer. A fifth object of the present invention is to provide a hydrogel using the phosphorylcholine group-containing polymer.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above problems, and as a result, have found that a specific phosphorylcholine analog-containing monomer, a glycerin ester group-containing monomer, and a hydrophobic group When polymerized with the containing monomer, a novel copolymer is obtained, and the above-mentioned polymer is particularly excellent in biocompatibility, with the knowledge that it becomes a material having high hydrophilicity,
The present invention has been completed. That is, the present invention includes the following [1] to [10].

[1] Based on a structural unit based on a phosphorylcholine analog-containing monomer (M ¹ ), a structural unit based on glycerol mono (meth) acrylate (M ² ), and a hydrophobic monomer (M ³ ) A phosphorylcholine-like group-containing polymer having a weight average molecular weight of 5,000 to 2,000,000 and a structural unit. [2] The phosphorylcholine analog-containing polymer of the above-mentioned [1], represented by the following formula (1) and having a weight average molecular weight of 5,000 to 2,000,000.

[0008]

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In the formula, Q ¹ , Q ² , and Q ³ represent a hydrogen atom or a methyl group, and n ¹ , n ² , and n ³ represent M ¹ ,
The number of moles of the structural unit based on M ² and M ³ , n ¹ is 1 to 3,
000, n ² is 3~10,000, n ³ is 3～10,00
Indicates the number of ^{0, n 1: n 2:} n 3 = (5~80) :( 10
-80): shows a molar ratio in the range of (10-80). Z is a hydrogen atom or R ⁵ —O— (C ＝ O) — (where R ⁵ is an alkyl group having 1 to 10 carbon atoms or 1 to ⁵ carbon atoms)
Represents 10 hydroxyalkyl groups. ). X ¹ is the following formula (2)

[0010]

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[0011] {In the formula, X represents a divalent organic residue, Y represents an alkyleneoxy group having 1 to 6 carbon atoms, also, R ¹
Represents a hydrogen atom or a methyl group; R ² , R ³ and R
⁴ is the same or different and represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group. m ¹ represents an integer of 0 to 20. m ² represents an integer of 1 to 4. Shows a phosphorylcholine analogous group represented by 示 す.
X ² is the following formula (3)

[0012]

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A glycerin ester group represented by
X ³ is the following formula (4)

[0014]

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(Wherein L ¹ is —C ₆ H ₄ —, —C ₆ H
₁₀ -,-(C = O) O-, -O-,-(C = O) NH
—, —O— (C ＝ O) —, —O— (C ＝ O) —O—, and L ² represents a hydrogen atom or — (CH ₂ )
p ¹ -L ^3, - shows a ^{_{((CH 2) p 2 -O}} ) hydrophobic functional group selected from the p1-L ^3. p ¹ is 1 to 24, p ² is 3-5
L ³ represents a hydrogen atom or a methyl group, -C ₆
H _5, illustrates a functional group selected from -O-C ₆ H _5. ) Represents a hydrophobic group. In addition, the inside may be in a block shape or a random shape. V ¹ and V ² each represent a group derived from a radical polymerization initiation or termination reaction such as an initiator, a chain transfer agent, a solvent, and a monomer during polymerization. ]

[3] The phosphorylcholine-like group-containing polymer according to the above [1], obtained by radical polymerization of a monomer composition containing the following monomers M ¹ , M ² and M ^3. . Monomer M ¹ ; the following formula (5)

[0017]

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In the formula, X represents a divalent organic residue, Y represents an alkyleneoxy group having 1 to 6 carbon atoms, and Z represents a hydrogen atom or R ⁵ —O— (C ＝ O) — (provided that R ⁵ has 1 carbon atom
Represents an alkyl group having 10 to 10 or a hydroxyalkyl group having 1 to 10 carbon atoms. ). R ¹ represents a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴ are the same or different groups and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group. m ¹ represents an integer of 0 to 20. m ² represents an integer of 1 to 4. ｝
A monomer containing a phosphorylcholine-like group represented by the following formula: monomer M ² ; glycerol mono (meth) acrylate; monomer M ³ ;

[0019]

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In the formula, R ⁶ represents a hydrogen atom or a methyl group, and L ¹ represents —C ₆ H ₄ —, —C ₆ H ₁₀ —, — (C ＝ O)
O-, -O-,-(C = O) NH-, -O- (C = O)
-, -O- (C = O) -O-, a group selected from
² is a hydrogen atom or ^{_{- (CH 2) p 1 -L}} 3, - ((CH
₂₎ shows the hydrophobic functional group selected from ^{p 2 -O) p 1 -L 3} . p ¹ is 1 to 24, p ² represents an integer of 3 to 5, L
³ is a hydrogen atom or a methyl group, —C ₆ H ₅ , —O—C ₆ H
₅ represents a functional group selected from A hydrophobic monomer represented by｝.

[4] The above-mentioned [2], wherein the phosphorylcholine-like group-containing monomer of the monomer M ² is 2-((meth) acryloyloxy) ethyl-2 ′-(trimethylammonio) ethyl phosphate. A polymer containing a phosphorylcholine-like group. [5] The hydrophobic monomer of the monomer M ³ is C1-18
The polymer having a phosphorylcholine-like group according to the above [2] or [3], which is a (meth) acrylate of an alkyl group of the above. [6] phosphorylcholine-like group-containing polymer, a phosphorylcholine-like group-containing monomer of the monomer M ¹ 5 to 80 mol%, 10 to 80 mol% of glycerol mono (meth) acrylate monomer M ² and made by polymerizing a monomer composition containing a hydrophobic monomer of the monomer M ³ 10 to 80 mol%, weight average molecular weight, 5,000～2,000,00
The phosphorylcholine analog-containing polymer according to any one of the above [2] to [4], which is in the range of 0. [7] A coating film using the phosphorylcholine analog-containing polymer according to any one of [1] to [5]. [8] An article obtained by forming a coating film using the phosphorylcholine analog-containing polymer according to any one of [1] to [5].

[9] A film using the phosphorylcholine analog-containing polymer according to any one of [1] to [5].

[10] A hydrogel comprising the phosphorylcholine-like group-containing polymer according to any one of [1] to [5].

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The phosphorylcholine-like group-containing polymer of the present invention (hereinafter abbreviated as PC polymer) comprises a structural unit based on a specific phosphorylcholine-like group-containing monomer (M ¹ ) and glycerol mono ( (Meth) acrylate (M ² )
Weight average molecular weight containing a structural unit based on styrene and a structural unit based on a hydrophobic group-containing monomer (M ³ )
It is a polymer of 2,000,000. Specifically, it is a polymer represented by the following formula (1).

[0024]

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Here, in the formula, Q ¹ , Q ² and Q ³ represent a hydrogen atom or a methyl group, and n ¹ , n ² and n ³ represent
In molarity of the constituent units derived from the respective monomers of the, n ¹ is 1
~3,000, n ² is 3~10,000, n ³ is 3 to 1
It is a number of 0000. n ¹ : n ² : n ³ is (5 to 8)
0): (10-80): shows a molar ratio in the range of (10-80). Z is a hydrogen atom or R ⁵ —O— (C =
O) - (where R ⁵ is shown) a hydroxyalkyl group having 1 to 10 carbon alkyl group or a C 1 to 10 carbon atoms..

X ¹ is the following formula (2)

[0027]

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[0028] {In the formula, X represents a divalent organic residue, Y represents an alkyleneoxy group having 1 to 6 carbon atoms, also, R ¹
Represents a hydrogen atom or a methyl group; R ² , R ³ and R
⁴ is the same or different and represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group. m ¹ represents an integer of 0 to 20. m ² represents an integer of 1 to 4. Shows a phosphorylcholine analogous group represented by 示 す.
X ² is given by the following equation (3).

[0029]

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An ester group based on glycerol mono (meth) acrylate represented by X ³ is the following formula (4)

[0031]

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(Where L¹Is -C₆H_Four-, -C₆H
_Ten-,-(C = O) O-, -O-,-(C = O) NH
-, -O- (C = O)-, -O- (C = O) -O-
Represents a selected group;^TwoIs a hydrogen atom or-(CH_Two)
p¹-L^Three,-((CH_Two) P^Two-O) p ¹-L^ThreeChosen from
A hydrophobic functional group. p¹Is 1 to 24, p^TwoIs 3-5
Indicates an integer and L^ThreeIs a hydrogen atom or a methyl group, -C₆H
_Five, -OC₆H_FiveRepresents a functional group selected from )
Represents a hydrophobic group.

Assuming that the number of moles of the structural unit based on the components of the monomers M ¹ , M ² and M ³ is n ¹ , n ² and n ³ , n ¹ is 1
~3,000, n ² is 3~10,000, n ³ is 3 to 1
Indicates a number of 0000. The ratio of the phosphorylcholine analogous group, the glycerin ester group and the hydrophobic group is n ¹ :
It corresponds to the ratio of n ² : n ³ , and n ¹ : n ² : n ³ = (5-8
0) :( 10-80) :( 10-80) is desirable, and more preferably, n ¹ : n ² : n ³ = (10
To 50): (30 to 70): (20 to 50). If the phosphorylcholine-like group is less than 5 mol%, the biocompatibility is not sufficient, and if the glycerin ester group is less than 10 mol%, the self-crosslinking property due to hydrogen bond of the glycerin ester group is not sufficient. When the hydrophobic group is less than 10 mol%, the adhesion to the substrate due to the hydrophobic interaction is not sufficient, so that the water resistance cannot be sufficiently exhibited.

The PC polymer of the present invention comprises a specific monomer M ¹
Of a phosphorylcholine analog-containing monomer (hereinafter abbreviated as PC monomer) and glycerol mono (meth) of monomer M ²
A monomer composition comprising a hydrophobic group-containing monomer of acrylate and monomer M ³ can be easily obtained by radical polymerization. The monomer composition may contain other polymerizable monomers other than the PC monomer, glycerol mono (meth) acrylate, and the hydrophobic monomer. Further, the monomer composition for the PC polymer,
5-80 mol% of PC monomer of the monomer M ^1, 10 to 80 mol% of glycerol mono (meth) acrylate monomer M ² and a hydrophobic monomer of the monomer M ³ 10 Preferred is a monomer composition comprising 80 mol%. More preferably, a phosphorylcholine-like group-containing monomer of the monomer M ¹ 10 to 50 mol%, a glycerol mono (meth) acrylate monomer M ² 30 to 70 mol%
And, a hydrophobic monomer of the monomer M ³ 20 to 50 mol%
It is a monomer composition containing. A is a biocompatible insufficient PC monomer of the monomer M ¹ is less than 5 mole%, glycerol mono (meth glycerol mono (meth) acrylate monomer M ² is less than 10 mol% ) The water resistance of the coating film cannot be sufficiently exhibited because the self-crosslinking property due to the hydrogen bond of the acrylate is not sufficient. Monomer M ³
If the hydrophobic monomer is less than 10 mol%, the water resistance cannot be sufficiently exhibited because the adhesion to the base material due to the hydrophobic interaction is insufficient. In addition, in the above description, it may be either a block shape or a random shape. In the formula, V ¹ , V
² is not particularly limited, and represents a group derived from a radical polymerization initiation reaction or termination reaction of an initiator, a chain transfer agent, a solvent and a monomer during polymerization. Here, the PC monomer is represented by the following formula (5)

[0035]

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In the formula, X represents a divalent organic residue, Y represents an alkyleneoxy group having 1 to 6 carbon atoms, and Z represents a hydrogen atom or R ⁵ —O— (C ＝ O) — (provided that R ⁵ has 1 carbon atom
Represents an alkyl group having 10 to 10 or a hydroxyalkyl group having 1 to 10 carbon atoms. ). R ¹ represents a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴ are the same or different groups and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group. m ¹ represents an integer of 0 to 20. m ² represents an integer of 1 to 4. ｝
It is represented by

[0037] The divalent organic residue X in the formula (5), for _{example, -C 6 H 4 -, -} C 6 H 10 -, - (C = O)
O -, - O -, - CH 2 -O -, - (C = O) NH-,
-O- (C = O) -, - O- (C = O) -O -, - C 6
H ₄ —O—, —C ₆ H ₄ —CH ₂ —O—, —C ₆ H ₄ — (C =
O) -O- and the like. Y in the formula (5) is an alkyleneoxy group having 1 to 6 carbon atoms, and examples thereof include a methyloxy group, an ethyloxy group, a propyloxy group, a butyloxy group, a pentyloxy group, and a hexyloxy group.

Z in the formula (1) is a hydrogen atom or R ^5-
O- (C = O) - is an organic residue represented by, R ⁵ is
It is an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group,
Examples include an octyl group, a nonyl group, and a decyl group. Examples of the hydroxyalkyl group having 1 to 10 carbon atoms include a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, a 2-hydroxybutyl group, and a 5-hydroxy Pentyl group, 2-hydroxypentyl group, 6-hydroxyhexyl group, 2-hydroxyhexyl group, 7-
Hydroxyheptyl group, 2-hydroxyheptyl group, 8
-Hydroxyoctyl group, 2-hydroxyoctyl group,
9-hydroxynonyl group, 2-hydroxynonyl group, 1
Examples thereof include a 0-hydroxydecyl group and a 2-hydroxydecyl group.

As the PC monomer, specifically, for example,
2-{(meth) acryloyloxy} ethyl-2 '-(trimethylammonio) ethyl phosphate, 3-{(meth) acryloyloxy} propyl-2'-(trimethylammonio) ethyl phosphate, 4-{( (Meth) acryloyloxy {butyl-2 ′-(trimethylammonio) ethyl phosphate, 5-{(meth) acryloyloxy} pentyl-2 ′-(trimethylammonio) ethylphosphate, 6-{(meth) acryloyl Oxy {hexyl-2 ′-(trimethylammonio) ethyl phosphate, 2-{(meth) acryloyloxy} ethyl-
2 ′-(triethylammonio) ethyl phosphate,
2-{(meth) acryloyloxy} ethyl-2 ′-(tripropylammonio) ethyl phosphate, 2-
{(Meth) acryloyloxy} ethyl-2 '-(tributylammonio) ethyl phosphate, 2-{(meth)
Chryloyloxy {ethyl-2 ′-(tricyclohexylammonio) ethyl phosphate, 2-{(meth) acryloyloxy} ethyl-2 ′-(triphenylammonio) ethyl phosphate, 2-{(meth) acryloyl Oxydiethyl-2 '-(trimethanol ammonium)
Ethyl phosphate, 2-{(meth) acryloyloxy} propyl-2 ′-(trimethylammonio) ethyl phosphate, 2-{(meth) acryloyloxy} butyl-2 ′-(trimethylammonio) ethylphosphate, 2 -{(Meth) acryloyloxy} pentyl-2 '
-(Trimethylammonio) ethyl phosphate, 2-
{(Meth) acryloyloxy} hexyl-2 ′-(trimethylammonio) ethyl phosphate,

2- (vinyloxy) ethyl-2 '-(trimethylammonio) ethylphosphate, 2- (allyloxy) ethyl-2'-(trimethylammonio) ethylphosphate, 2- (p-vinylbenzyloxy)
Ethyl-2 ′-(trimethylammonio) ethyl phosphate, 2- (p-vinylbenzoyloxy) ethyl-
2 ′-(trimethylammonio) ethyl phosphate,
2- (styryloxy) ethyl-2 '-(trimethylammonio) ethyl phosphate, 2- (p-vinylbenzyl) ethyl-2'-(trimethylammonio) ethyl phosphate, 2- (vinyloxycarbonyl) ethyl-2 '-(Trimethylammonio) ethyl phosphate, 2- (allyloxycarbonyl) ethyl-2'-
(Trimethylammonio) ethyl phosphate, 2-
(Acryloylamino) ethyl-2 '-(trimethylammonio) ethylphosphate, 2- (vinylcarbonylamino) ethyl-2'-(trimethylammonio) ethylphosphate, ethyl- (2'-trimethylammonioethylphosphorylethyl) Fumarate, butyl-
(2′-trimethylammonioethyl phosphorylethyl) fumarate, hydroxyethyl- (2′-trimethylammonioethyl phosphorylethyl) fumarate, ethyl- (2′-trimethylammonioethyl phosphorylethyl) malate, butyl- (2′-) Trimethylammonioethyl phosphorylethyl) malate, hydroxyethyl- (2'-trimethylammonioethyl phosphorylethyl) malate and the like can be mentioned. Here, (meth) acryloyl means acryloyl and / or methacryloyl.

Of these, 2-((meth) acryloyloxy) ethyl-2 '-(trimethylammonio) ethyl phosphate is preferred, and 2- (methacryloyloxy) ethyl-2'-(trimethylammonio) ethyl phosphate (abbreviation) MPC) is more preferred from the viewpoint of availability and the like.

When polymerizing the PC monomer, the above-mentioned PC
One monomer may be used alone, or two or more monomers may be used as a mixture. The PC monomer can be produced by a known method. For example, a method of reacting a compound obtained by reacting a hydroxyl group-containing polymerizable monomer with 2-bromoethyl phosphoryl dichloride in the presence of a tertiary base and a tertiary amine disclosed in JP-A-54-63025. , JP 58
It can be produced by, for example, a method of reacting a hydroxyl group-containing polymerizable monomer with a tubular phosphorus compound to obtain a cyclic compound and then performing a ring-opening reaction with a tertiary amine as described in JP-A-154591.

The glycerol mono (meth) acrylate of the monomer M ² is glycerin monoacrylate or monomethacrylate. Hydrophobic monomers of the monomer M ³ are, the formula (6)

[0044]

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In the formula, R ⁶ represents a hydrogen atom or a methyl group, and L ¹ represents —C ₆ H ₄ —, —C ₆ H ₁₀ —, — (C ＝ O)
O-, -O-,-(C = O) NH-, -O- (C = O)
-, -O- (C = O) -O-, a group selected from
² is a hydrogen atom or ^{_{- (CH 2) p 1 -L}} 3, - ((CH
₂₎ shows the hydrophobic functional group selected from ^{p 2 -O) p 1 -L 3} . p ¹ is 1 to 24, p ² represents an integer of 3 to 5, L
³ is a hydrogen atom or a methyl group, —C ₆ H ₅ , —O—C ₆ H
₅ represents a functional group selected from It is represented by｝.

[0046] As the hydrophobic monomer of the monomer M ^3, specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-
Linear or branched alkyl (meth) acrylates such as ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate; cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate; benzyl (meth) acrylate; Aromatic group-containing (meth) acrylates such as phenoxyethyl (meth) acrylate; hydroxyl-containing (meth) acrylates such as polypropylene glycol (meth) acrylate; styrene-based monomers such as styrene, methylstyrene, and chloromethylstyrene; methyl vinyl ether And vinyl ether monomers such as butyl vinyl ether; and vinyl ester monomers such as vinyl acetate and vinyl propionate.

Among the hydrophobic monomers of the monomer M ³ ,
(Meth) acrylic acid esters of alkyl groups having 1 to 18 carbon atoms are more preferable, and specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth)
Examples include acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate.

The monomer composition constituting the PC polymer includes:
Other than the monomers M ¹ , M ² and M ³ , other polymerizable monomers may be mixed and used as long as the effects of the present invention are not impaired. Specific examples of other polymerizable monomers include, for example, polyethylene glycol (meth) acrylate, 2-vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl ( Hydrophilic hydroxyl group-containing (meth) acrylates such as (meth) acrylates; acid group-containing monomers such as (meth) acrylic acid, styrene sulfonic acid and (meth) acryloyloxyphosphonic acid; (meth)
Nitrogen-containing monomers such as acrylamide, aminoethyl methacrylate, and dimethylaminoethyl (meth) acrylate; and cationic group-containing monomers such as 2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride.

[0049] Single PC polymer containing a hydrophobic monomer glycerol (meth) acrylate and monomer M ³ of the PC monomers of the monomer M ¹ as the monomer M ² Can be obtained by radical polymerization of the monomer composition,
Since the adhesion to the substrate differs depending on the type of the other polymerizable monomer, it is desirable to select another polymerizable monomer in consideration of the properties of the substrate to be coated. Among other monomers, hydroxyalkyl groups such as 2-hydroxyethyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate are preferred from the viewpoints of biocompatibility of the PC polymer and adhesion to the substrate. Monomer and (meth) acryloyloxyethyltrimethylammonium chloride, 2-
Cationic group-containing monomers such as hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride are preferred.

The weight average molecular weight of the PC polymer is 5,000
The range is from 0 to 2,000,000. More preferably, it is in the range of 50,000 to 500,000. When the weight average molecular weight is less than 5,000, the water resistance is inferior due to insufficient adhesion of the polymer to the substrate,
If it exceeds 2,000,000, the viscosity of the working fluid becomes too high, making it difficult to coat the substrate uniformly and making it difficult to sufficiently exhibit biocompatibility, which is not preferable.

The copolymer of the present invention can be easily produced by mixing the above-mentioned monomers and by a usual method. For example, the polymer comprises a 2- (meth) acryloyloxyethyl phosphorylcholine monomer of monomer M ¹ and a monomer M ¹
And ² of glycerol (meth) acrylate monomer, and further blending a hydrophobic group-containing monomer of the monomer M ^3, blended with other monomers if necessary, the presence of a polymerization initiator, nitrogen It can be prepared by a known method such as radical polymerization, for example, bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization in an atmosphere replaced with an inert gas such as carbon dioxide, helium or the like. Solution polymerization is preferred from the viewpoint of purification and the like. The polymer can be purified by a general purification method such as a reprecipitation method, a dialysis method, and an ultrafiltration method.

In the polymerization, the terminal structures V ¹ and V
² is a group generated by initiation reaction or termination reaction at the time of radical polymerization, specifically, for example, when using an initiator of azobisbutyronitrile, ethanol solvent,
Examples include a terminal group derived from a polymerization initiator represented by the following formula (7) and a terminal group derived from a solvent or a monomer represented by the formulas (8) to (10).

[0053]

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[0054]

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[0055]

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[0056]

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Further, a polymerization terminal derived from a chain transfer agent or a solvent may be used. Examples of the radical polymerization initiator include 2,2-azobis (2-amidinopropyl) dihydrochloride and 2,2-azobis (2- (5-methyl-
2-imidazolin-2-yl) propane) dihydrochloride,
4,4-azobis (4-cyanovaleric acid), 2,2-azobisisobutylamide dihydrate, 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobisisobutyro Nitrile (AIBN), dimethyl-2,
2'-azobisisobutyrate, 1-((1-cyano-
1-methylethyl) azo) formamide, 2,2'-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis (2-
Methyl-N- (2-hydroxyethyl) -propionamide), 2,2'-azobis (2-methylpropionamide) dihydrate, 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis And azo radical polymerization initiators such as (2- (hydroxymethyl) propionitrile). Benzoyl peroxide,
Diisopropyl peroxy dicarbonate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy pivalate, t-butyl peroxy diisobutyrate, lauroyl peroxide, t-butyl peroxy neodecanoate, succinic peroxide (= Succinyl peroxide), glutar peroxide, succinyl peroxyglutarate, t-butyl peroxymalate,
t-butyl peroxypivalate, di-2-ethoxyethyl peroxycarbonate, 3-hydroxy-1,1
-Organic peroxides such as dimethylbutyl peroxypivalate. Still further, there may be mentioned persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate. These radical polymerization initiators may be used alone or in a mixture. The amount of the polymerization initiator to be used is generally 0.001 to 10 parts by weight, preferably 0.01 to 5.0 parts by weight, based on 100 parts by weight of the monomer composition.

As a solvent for producing the copolymer, any solvent can be used as long as it does not dissolve the monomer which is a constituent unit of the copolymer and does not react. As the solvent,
For example, alcohol solvents such as water, methanol, ethanol, and isopropanol; ketone solvents such as acetone, methyl ethyl ketone and diethyl ketone; ester solvents such as ethyl acetate; and linear solvents such as ethyl cellosolve, tetrahydrofuran, and N-methylpyrrolidone; Cyclic ether solvents; and nitrogen-containing solvents such as acetonitrile and nitromethane. Preferably, the solvent is water,
Alternatively, a water-alcohol-based mixed solvent may be used.

[0059] The coating film of the present invention comprises the above-mentioned PC
It suffices if a film can be formed using a polymer,
A film can be obtained by any of the existing coating methods. It can be obtained mainly by a method in which a solution of a PC polymer is applied to a substrate and dried, a method in which the substrate is immersed in a solution of the PC polymer and dried. Further, the hydrogel of the present invention only needs to be able to form a hydrogel using the above-mentioned PC polymer, and can be obtained by any existing method. A method of absorbing water after drying a solution of mainly a PC polymer on a substrate or in a container, PC
The polymer solution can be obtained by, for example, a method of drying other than necessary water on a substrate or in a container.

The film of the present invention can be formed by any of the existing methods as long as the film can be formed using the above-mentioned PC polymer.
The polymer solution can be obtained by a method of drying the solution on a substrate or in a container.

The most preferable solvent for the PC polymer used in producing the coating film, the hydrogel and the film is water, but it is also possible to use an organic solvent such as an alcohol solvent, a ketone solvent and an ester solvent. It is possible, or a mixture of two or more such as a mixture of water and alcohol may be used as a solvent. In producing a coating film, a hydrogel, and a film, a coating film, a hydrogel, and a film having higher water resistance can be obtained by mixing a binder component with a PC polymer.

The binder component includes a compound having a component having a strong hydrophobic cohesive force such as an alkyl group and a phenyl group, an ionic bond such as an amino group, a carboxyl group, a hydroxy group, an epoxy group and an isocyanate group, and a hydrogen bond. A compound having chemical reactivity can be preferably used, and among the compounds, an acrylic resin, a polyester resin, a glyoxal resin, an epoxy resin, a urethane resin,
It is desirable to use polymers such as melamine resins, vinyl acetate resins, polyether resins, and cellulose resins.

As the polymer suitable for the binder component, specifically, for example, polydimethylaminoethyl methacrylate, acrylic acid-alkyl methacrylate copolymer,
2-hydroxyethyl methacrylate-methacrylic acid copolymer, poly 2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride,
Polyethylene glycol-terephthalic acid polycondensate, polyethylene glycol terminal carboxylate, partially saponified polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose, poly 4-aminostyrene, polyethylene imine, styrene-maleic acid copolymer, maleic acid-methyl vinyl ether copolymer Preferred examples thereof include polymers, chitosan, pullulan, casein, xanthan gum, collagen, hyaluronic acid, gelatin, alginic acid, and dextran.

As a binder component, a monomer having any one of an alkyl group, a phenyl group, an amino group, a carboxyl group, a hydroxy group, and an epoxy group, and a PC
Copolymers with monomers can also be used. Specifically, for example, MPC-lauryl methacrylate copolymer,
MPC-methacrylic acid copolymer, MPC-2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride copolymer, MPC-2-hydroxyethyl methacrylate copolymer and the like are preferably exemplified.

The coating film of the present invention, an article formed with the coating film, a hydrogel, and a film are:
It can be used in various fields such as medical tools, cosmetics, and biochemical analysis. In particular, it is suitable for a medical device particularly requiring biocompatibility. The coating film, hydrogel, and film of the present invention can be used for any medical device. Specifically, for example, an artificial blood vessel, a catheter, a dialyzer, a contact lens, a blood filter,
It can be used as a drug delivery carrier, a wound dressing and the like.

[0066]

The polymer containing a phosphorylcholine-like group according to the present invention is a novel polymer having excellent biocompatibility based on a PC polymer and is industrially useful. In addition, it is a highly water-resistant material having hydrophilicity based on glycerol mono (meth) acrylate but based on a hydrophobic group-containing monomer. Furthermore, the coating film, film, and hydrogel using the phosphorylcholine-like group-containing polymer of the present invention have excellent biocompatibility based on PC polymer, have hydrophilicity based on glycerol mono (meth) acrylate, and have hydrophobicity. It has water resistance based on a functional group-containing monomer and can be used in various fields such as medical devices, cosmetics, and biochemical analysis. In particular, it is suitable for a medical device particularly requiring biocompatibility.

[0067]

The present invention will be described below in more detail with reference to examples. 1. <Method of analyzing molecular weight of polymer><Measurement of number average molecular weight of copolymer> The number average molecular weight of the copolymer is a value of the number average molecular weight measured by gel permeation chromatography (GPC) using polyethylene glycol as a standard sample. is there. That is, the obtained aqueous copolymer solution was diluted with distilled water to a concentration of 0.5% by weight, and the solution was filtered through a 0.45 μm membrane filter to obtain a test solution. The measurement conditions of the GPC analysis are as follows. <Measurement conditions for GPC analysis> Column: G3000PW _xl x
2 (Tosoh), elution solvent; 20 mM phosphate buffer, standard substance: polyethylene glycol (manufactured by Polymer Laboratory), detection; parallax refractometer, weight average molecular weight (Mw), number average molecular weight measurement (Mn) , Molecular weight distribution (M
w / Mn); molecular weight calculation program with built-in integrator manufactured by Tosoh Corporation (GPC program for SC-8020), flow rate: 0.5 mL / min, amount of sample solution used: 10 μm
L, column temperature; 2. Organic element analysis: Elemental analysis is performed using a polymer sample using a model Perkin Elmer 2400II-CHNS / i analyzer. 3. Component quantification method of MPC; Cosmetic raw material standard General test method The nitrogen content is measured according to the nitrogen determination method (Kjeldahl method). 4. Calculation of composition ratio in polymer; Phosphorylcholine group is determined from N value of analytical value in polymer from raw material used, molecular weight, organic element analysis, nitrogen content, and then to other monomers from GPC molecular weight. Calculate the ratio of constituent units based on this.

Example 1 (Polymer 1; MPC0.4-B
MA0.2-GLM0.4, weight average molecular weight 341,0
00) MPC; 11.2 g, butyl methacrylate (BM
A); 2.7 g, glycerol monomethacrylate (G
LM); 6.1 g dissolved in ethanol; 180 g, placed in a four-necked flask, blown with nitrogen for 30 minutes, and then heated to 50 ° C.
Add azobisisobutyronitrile; 0.85 g and add 8
The polymerization reaction was carried out for an hour. The polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 16.1 g of powder.
I got The molecular weight evaluated by GPC was 341,000 weight average molecular weight. This is designated as polymer 1. The data of IR, NMR and elemental analysis are shown below. IR data: 3413 cm ^-1 (-OH), 2954 cm
^-1 (-CH), 1732 cm ^-1 (C = O), 1489c
m ^-1 (-CH), 1246 cm ^-1 (P = O), 1161
^{cm -1 (C-O-C} ), 1088cm -1 (P-O-
C). NMR Data: 0.8-1.2ppm (CH ₃ -C
_{-), 1.4ppm (-CH 2 CH} 2 -), 3.3ppm
_{(-N (CH 3) 3)} , 3.5-4.4ppm (-CH 2
_{CH 2 O -, - CH 2} CH (OH) CH 2 OH). Elemental analysis data: Found: C; 50.19%, H: 7.79%, N;
66%, theoretical: C; 50.02%, H; 7.92%, N;
61%. Kjeldahl nitrogen content 2.58% (theoretical value 2.66%) The chemical structure of polymer 1 obtained from the above results has the following random structure.

[0069]

Embedded image

Example 2 (Polymer 2; MPC0.4-B
MA0.4-GLM0.2, weight average molecular weight 294,0
00) MPC; 11.4 g, BMA; 5.5 g, GLM;
1 g was dissolved in 180 g of ethanol, placed in a four-necked flask, and blown with nitrogen for 30 minutes. Then, at 50 ° C., 0.85 g of azobisisobutyronitrile was added, and a polymerization reaction was performed for 8 hours. The polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 17.3 g of a powder. GP
The molecular weight evaluated by C was 294,00 weight average molecular weight.
It was 0. This is designated as polymer 2. Below, IR,
The data of NMR and elemental analysis are shown. IR data: 3408 cm ^-1 (-OH), 2952 cm
^-1 (-CH), 1729 cm ^-1 (C = O), 1491c
m ^-1 (-CH), 1249 cm ^-1 (P = O), 1163
^{cm -1 (C-O-C} ), 1087cm -1 (P-O-
C). NMR Data: 0.8-1.2ppm (CH ₃ -C
_{-), 1.4ppm (-CH 2 CH} 2 -), 3.3ppm
_{(-N (CH 3) 3)} , 3.5-4.4ppm (-CH 2
_{CH 2 O -, - CH 2} CH (OH) CH 2 OH). Elemental analysis data: Found: C; 52.22%, H: 8.12%, N;
71%, theory: C; 51.98%, H; 8.26%, N;
68%. Kjeldahl nitrogen content 2.63% (theoretical value 2.71%) The chemical structure of polymer 2 obtained from the above results has the following random structure.

[0071]

Embedded image

Example 3 (Polymer 3; MPC0.5-L)
MA0.2-GLM0.3, weight average molecular weight 293,0
00) MPC; 12.0 g, lauryl methacrylate (LM
A); 4.1 g, GLM; 3.9 g ethanol; 18
0 g, put in a four-necked flask, and blown with nitrogen for 30 minutes, then azobisisobutyronitrile at 50 ° C .;
85 g was added and a polymerization reaction was carried out for 8 hours. The polymerization solution was added dropwise while stirring into 3 liters of diethyl ether, and the deposited precipitate was filtered and vacuum-dried at room temperature for 48 hours to obtain 16.3 g of powder. The molecular weight evaluated by GPC was 293,000. This is designated as polymer 3. The data of IR, NMR and elemental analysis are shown below. IR data: 3413 cm ^-1 (-OH), 2927 cm
^-1 (-CH), 1727 cm ^-1 (C = O), 1488c
m ^-1 (-CH), 1239 cm ^-1 (P = O), 1165
^{cm -1 (C-O-C} ), 1088cm -1 (P-O-
C). NMR Data: 0.8-1.2ppm (CH ₃ -C
_{-), 1.4ppm (-CH 2 CH} 2 -), 3.3ppm
_{(-N (CH 3) 3)} , 3.5-4.4ppm (-CH 2
_{CH 2 O -, - CH 2} CH (OH) CH 2 OH). Elemental analysis data: Found: C; 52.62%, H: 8.36%, N;
84%, theoretical: C; 52.78%, H: 8.33%, N;
77%. Kjeldahl nitrogen content 2.82% (theoretical value 2.84%) The chemical structure of polymer 3 obtained from the above results has the following random structure.

[0073]

Embedded image

Example 4 (Polymer 4; MPC0.4-B
ZMA0.3-GLM0.3, weight average molecular weight 358,
000) MPC; 10.8 g, benzyl methacrylate (BZM
A); 4.8 g, GLM; 4.4 g ethanol;
0 g, put in a four-necked flask, and blown with nitrogen for 30 minutes, then azobisisobutyronitrile at 50 ° C .;
85 g was added and a polymerization reaction was carried out for 8 hours. The polymerization solution was added dropwise to 3 liters of diethyl ether while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 17.3 g of a powder. The molecular weight evaluated by GPC was 358,000 weight average molecular weight. This is designated as polymer 4. The data of IR, NMR and elemental analysis are shown below. IR data: 3421 cm ^-1 (-OH), 2954 cm
^-1 (-CH), 1728 cm ^-1 (C = O), 1489c
m ^-1 (-CH), 1243 cm ^-1 (P = O), 1160
^{cm -1 (C-O-C} ), 1087cm -1 (P-O-
C). NMR Data: 0.7-1.2ppm (CH ₃ -C
-), 3.3ppm (-N (CH 3) 3), 3.5-4.
_{4ppm (-CH 2 CH 2 O -} , - CH 2 CH (OH) C
_{H 2 OH), 7.4ppm (-C} 6 H 6). Elemental analysis data: Found: C; 53.75%, H: 7.31%, N;
56%, Theory: C; 53.48%, H; 7.19%, N;
48%. Kjeldahl nitrogen content 2.61% (theoretical 2.56%) The chemical structure of polymer 4 obtained from the above results has the following random structure.

[0075]

Embedded image

Comparative Reference Example 1 (Polymer 5; MPC0.4
-BMA 0.6, weight average molecular weight 225,000) MPC; 11.6 g, BMA; 8.4 g ethanol;
Dissolve in 180 g, put into a four-necked flask, blow nitrogen for 30 minutes, then azobisisobutyronitrile at 50 ° C;
0.85 g was added and a polymerization reaction was carried out for 8 hours. Polymerization solution 3
The mixture was added dropwise to a liter of diethyl ether with stirring, and the deposited precipitate was filtered and vacuum-dried at room temperature for 48 hours to obtain 15.8 g of a powder. The molecular weight evaluated by GPC was 225,000 weight average molecular weight. This is designated as Polymer 5.

Comparative Reference Example 2 (Polymer 6; MPC 0.4
-GLM 0.6, weight average molecular weight 214,000) MPC; 11.0 g, GLM; 9.0 g of ethanol;
Dissolve in 180 g, put into a four-necked flask, blow nitrogen for 30 minutes, then azobisisobutyronitrile at 50 ° C;
0.85 g was added and a polymerization reaction was carried out for 8 hours. Polymerization solution 3
The mixture was added dropwise to a liter of diethyl ether with stirring, and the deposited precipitate was filtered and vacuum-dried at room temperature for 48 hours to obtain 15.1 g of a powder. The molecular weight evaluated by GPC was 214,000 as the weight average molecular weight. This is designated as polymer 6. Table 1 shows the results.

[0078]

[Table 1]

Examples 5 to 8 and Comparative Examples 1 to 3 (1) Test for Inhibiting Protein Adsorption on Coating Film 0.5 g of Polymer 1 was dissolved in 49.5 g of ethanol to prepare a coating solution. Polystyrene test tube (10
mmφ × 75 mm) and left for 10 minutes, after which the coating solution was discarded and dried at 50 ° C. for 2 hours. To confirm the water resistance, a part of the coated test tube was immersed in running water, taken out 24 hours later, and used as a sample. Test tubes prepared as above with 4.0 mL of a phosphate buffer (hereinafter abbreviated as PBS) containing 0.6% by weight of bovine serum albumin (test tubes for drying only after coating and test tubes for confirming water resistance) ) And incubated at 4 ° C. overnight, followed by washing three times with 4.0 mL of PBS. Then, PBS containing sodium dodecyl sulfate was added.
The protein adsorbed on the inner wall of the test tube was eluted by adding 4.0 mL, and the concentration of the protein in the PBS was measured using a “micro BCA protein assay kit” (PIERCE).
Was used for the measurement. Table 2 shows the results. Further, the test tube coated with the polymers 2 to 6 and the test tube not coated (Comparative Example 3) were also subjected to the protein adsorption suppression test by the same method as described above.
Table 2 shows the results.

(2) Water Absorption Test of Film 2.0 g of Polymer 1 was dissolved in 18.0 g of a mixed solution of pure water / ethanol (weight ratio: 6/4) to prepare a coating solution. 5.0 g of this solution was taken in a polytetrafluoroethylene petri dish (50 mmφ), and after evaporating water slowly at 70 ° C., dried at 105 ° C. for 2 hours. 0.5 g). The film was peeled off from the petri dish, immersed in pure water for 3 seconds, immediately removing excess water, and the amount of water absorption was measured from the change in weight before and after that. The initial water absorption at the time of short-time water contact is used as an index of hydrophilicity,
It is shown in Table 2. In addition, a water absorption test was performed on polymers 2 to 6 in the same manner as described above, and the results are shown in Table 2.

(3) Moisture content and water resistance of hydrogel (dissolution test) 2.0 g of polymer 1 was dissolved in 18.0 g of a mixed solution of pure water / ethanol (weight ratio: 6/4) to obtain a stock solution of hydrogel. And A sample bottle (inner diameter 38 mmφ, capacity 1
10 mL), slowly evaporate water at 70 ° C., and dry at 105 ° C. for 2 hours to form a dry gel (polymer weight; about 0.2 g) at the bottom of the sample bottle.
The total weight [3B] at this time was measured and subtracted from the weight of the sample bottle, and the weight of the dried gel [3C] (= [3B])
-[3A]) was calculated. Thereafter, 100 g of pure water was put into the sample bottle, and water was absorbed at 70 ° C. for 48 hours while stirring slowly. After evaluating the weight [3E] (= [3D]-[3A]) of the hydrogel remaining in the sample bottle from the total weight [3D] after removing the pure water from the supernatant, the water was removed again by drying. , Then the total weight [3
F] was measured and the remaining dry gel weight [3G] (= [3
F]-[3A]). The ratio of the residual dry gel weight to the initial dry gel weight was determined as the gel residual ratio [3
H] = ([3G] / [3C]) × 100, which is shown in Table 3 as an index of water resistance of the hydrogel. The ratio of the water content [3I] (= [3E]-[3G]) to the weight of the hydrogel, which was obtained by subtracting the weight of the remaining dry gel from the weight of the hydrogel, was calculated as the water content [3J] (= [3I ]
/ [3E]) and is shown in Table 2. In addition, polymers 2 to 6
Was also tested in the same manner as described above, and the results are shown in Table 2.

[0082]

[Table 2]

As compared with Comparative Examples 1 to 3, according to Examples 5 to 6 using the PC polymer of the present invention, a coating film having a small amount of protein adsorption and a high water resistance, and a film having a high initial water absorption amount It can be seen that a hydrogel having a high water content and a high water resistance was obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 216/14 C08F 230/02 220/12 C08J 5/18 CEY 230/02 C08L 43:02 C08J 5/18 CEY A61L 33/00 C // C08L 43:02 15/01 (72) Inventor Hirofumi Irie 2-14-23 Kamikashida, Ushiku City, Ibaraki Prefecture (72) Inventor Ken Suzuki 1-4-3 Azuma, Tsukuba City, Ibaraki Prefecture F-term (reference) 4C076 EE10 EE12 FF35 4C081 AA03 AA12 AB13 AB23 AC08 BA02 CA082 DA02 DA12 DC03 4F071 AA03X AA33X AA81 AF52 AH19 BA02 BB02 BC01 BC02 4J100 AL03R AL08P AL08Q AL41P BA03Q BA63P BA65BA

Claims (10)

[Claims] 1. A structural unit based on a phosphorylcholine analog-containing monomer (M ¹ ), a structural unit based on glycerol mono (meth) acrylate (M ² ), and a structural unit based on a hydrophobic monomer (M ³ ) And a phosphorylcholine-like group-containing polymer having a weight average molecular weight of 5,000 to 2,000,000. 2. A polymer containing a phosphorylcholine-like group,
Weight average molecular weight of 5,000 to
2. The phosphorylco according to claim 1, which is 2,000,000.
Phosphorus-like group-containing polymer. Embedded image[Where Q¹, Q^Two, Q^ThreeRepresents a hydrogen atom or a methyl group
And n¹, N^Two, N^ThreeIs the monomer M¹, M^Two, M^Three
The number of moles of the structural unit based on¹Is 1-3000
0, n^TwoIs 3 to 10,000, n^ThreeIs between 3 and 10,000
Indicates a number, n¹: N^Two: N^Three= (5-80): (10-8
0): shows a molar ratio in the range of (10 to 80). Also, Z
Is a hydrogen atom or R^Five-O- (C = O)-(where R^FiveIs
An alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms
Shows a droxyalkyl group. ). X¹Is the following formula
(2)Ｘ In the formula, X represents a divalent organic residue, and Y has 1 to 6 carbon atoms.
And an alkyleneoxy group of¹Is also a hydrogen atom
Or a methyl group;^Two, R^ThreeAnd R^FourAre the same if
Or different groups, each having a hydrogen atom or a group having 1 to 6 carbon atoms.
It represents an alkyl group or a hydroxyalkyl group. m¹Is
Shows an integer of 0 to 20. m^TwoRepresents an integer of 1 to 4. ｝
And a phosphorylcholine analogous group represented by X^TwoIs below
Formula (3) ofA glycerin ester group represented by X^ThreeIs
Formula (4) of(Where L¹Is -C₆H_Four-, -C₆H_Ten-,-(C =
O) O-, -O-,-(C = O) NH-, -O- (C =
O)-and -O- (C = O) -O-
Then L^TwoIs a hydrogen atom or-(CH_Two) P¹-L^Three, −
((CH_Two) P^Two-O) p ¹-L^ThreeHydrophobic function selected from
Represents a group. p¹Is 1 to 24, p^TwoRepresents an integer of 3 to 5,
L^ThreeIs a hydrogen atom or a methyl group, -C₆H_Five, -OC₆
H_FiveRepresents a functional group selected from ) Hydrophobic group
Is shown. Also, in the middle of で も で も で も で も で も
Good. V¹, V^TwoIs the initiator, chain transfer agent,
Reaction or termination of radical polymerization reaction of chemicals and monomers
It shows the group derived from the reaction. ] 3. The following monomer M ¹ , monomer M ² , monomer M ³
The phosphorylcholine-like group-containing polymer according to claim 1, obtained by radical polymerization of a monomer composition containing: Monomer M ¹ ; the following formula (5): [Wherein, X represents a divalent organic residue, and Y represents 1-6 carbon atoms.
Wherein Z is a hydrogen atom or R
⁵ -O- (C = O) - indicating (but R ⁵ represents an alkyl or hydroxyalkyl group having 1 to 10 carbon atoms having 1 to 10 carbon atoms.). R ¹ represents a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴ are the same or different groups and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group. m ¹ represents an integer of 0 to 20. m ² represents an integer of 1 to 4. A monomer containing a phosphorylcholine analogous group represented by the following formula: monomer M ² ; glycerol mono (meth) acrylate, monomer M ³ ; In the formula, R ⁶ represents a hydrogen atom or a methyl group, and L ¹ represents
_{-C 6 H 4 -, - C} 6 H 10 -, - (C = O) O -, - O
-,-(C = O) NH-, -O- (C = O)-, -O-
(C = O) represents a group selected from -O-, L ² is a hydrogen atom or ^{_{- (CH 2) p 1 -L}} 3, - ((CH 2) p 2 -
O) represents a hydrophobic functional group selected from p ¹ -L ³ . p ¹ is 1 to 24, p ² represents an integer of 3 to 5, L ³ represents a hydrogen atom or a methyl group, -C ₆ H _5, a functional group selected from -O-C ₆ H _5. A hydrophobic monomer represented by｝. 4. A phosphorylcholine-like group-containing monomer comprising 2
3. The phosphorylcholine-like group-containing polymer according to claim 2, which is-((meth) acryloyloxy) ethyl-2 '-(trimethylammonio) ethyl phosphate. 5. The hydrophobic monomer of the monomer M ³ is from 1 to carbon atoms
The phosphorylcholine-like group-containing polymer according to any one of claims 1 to 3, which is a (meth) acrylate ester of an alkyl group of 18. 6. phosphorylcholine-like group-containing polymer, a phosphorylcholine-like group-containing monomer of the monomer M ¹ 5 to 8
0 mol%, 10 to 80 mol% of glycerol mono (meth) acrylate monomer M ² and, polymerizing a monomer composition comprising 10 to 80 mol% of a hydrophobic monomer of the monomer M ³ And a weight average molecular weight of 5,000 to 2,000
The phosphorylcholine analog-containing polymer according to any one of claims 2 to 4, which is a polymer in the range of 000. 7. A coating film using the phosphorylcholine-like group-containing polymer according to any one of claims 1 to 5. 8. An article formed by forming a coating film using the phosphorylcholine-like group-containing polymer according to any one of claims 1 to 5. 9. A film comprising the phosphorylcholine-like group-containing polymer according to any one of claims 1 to 5. 10. A hydrogel comprising the phosphorylcholine analog-containing polymer according to any one of claims 1 to 5.