JP7656895B2 - Composition, cured film, laminate, ship, underwater structure, medical device, and microchannel chip - Google Patents

Description

The present invention relates to a composition, a cured film, a laminate, a ship, an underwater structure, a medical device, and a microchannel chip.

Conventionally, coating materials for suppressing biofouling have been known. Patent Document 1 describes a biocompatible material that contains a graft polymer having graft chains composed of vinyl monomers and a surface occupancy rate (σ ^* ) defined by a specific calculation formula of 0.1 or more, and at least some of the graft polymer chains are crosslinked.

JP 2016-210956 A

The biocompatible material described in Patent Document 1 has excellent biofouling inhibition performance. However, the inventors have found that there is room for improvement in the long-term stability of the biocompatible material when exposed to saline.

Therefore, an object of the present invention is to provide a composition capable of forming a cured film that can maintain excellent biofouling inhibition performance for a long period of time even in a saline exposure environment.
Another object of the present invention is to provide a cured film, a laminate, a ship, an underwater structure, a medical device, and a microchannel chip.

As a result of extensive research into achieving the above object, the inventors have discovered that the above object can be achieved by the following configuration.

[1] A composition containing a first polymer compound having a repeating unit represented by formula 1 described later and a repeating unit represented by formula 2 described later, and a second polymer compound having a repeating unit represented by formula 3 described later.
[2] The composition according to [1], wherein the content of the repeating unit represented by the formula 2 relative to all repeating units of the first polymer compound is 10 mol % or less.
[3] The composition according to [1] or [2], wherein Z ¹ is a group represented by formula A described below.
[4] The composition according to any one of [1] to [3], wherein the hydrophilic group is a hydroxy group.
[5] The composition according to any one of [1] to [4], wherein the photoradical generating group is a group represented by the following formula g1:
[6] The composition according to any one of [1] to [5], wherein the photoradical generating group is a group represented by the following formula g2:
[7] A cured film obtained by curing the composition according to any one of [1] to [6].
[8] A laminate comprising a substrate and the cured film according to [7] formed on the substrate.
[9] A ship having the cured film according to [7].
[10] An underwater structure having the cured film according to [7].
[11] The underwater structure according to [10], which is a pollution-preventing membrane.
[12] A medical device having the cured film according to [7].
[13] The medical device according to [12], which is one selected from the group consisting of a cell culture vessel, a cell culture sheet, a cell capture filter, a vial, a plastic-coated vial, a syringe, a plastic-coated syringe, an ampoule, a plastic-coated ampoule, a cartridge, a bottle, a plastic-coated bottle, a pouch, a pump, a sprayer, a stopper, a plunger, a cap, a lid, a needle, a stent, a catheter, an implant, a contact lens, a microchannel chip, a drug delivery system material, an artificial blood vessel, an artificial organ, a hemodialysis membrane, a guard wire, a blood filter, a blood storage pack, an endoscope, a biochip, a glycosynthesis device, a molding auxiliary material, and a packaging material.
[14] A microchannel chip comprising a substrate and the cured film according to [7] disposed on the substrate.

The present invention provides a composition capable of forming a cured film that can maintain excellent biofouling inhibition performance for a long period of time even in a saline exposure environment. The present invention also provides a cured film, a laminate, a ship, an underwater structure, a medical device, and a microchannel chip.

1 is a schematic partial cross-sectional view of a ship according to an embodiment of the present invention. FIG. FIG. 2 is a schematic cross-sectional view of a selected substrate of a ship according to an embodiment of the present invention. 1 is a schematic diagram of an underwater structure according to an embodiment of the present invention. 1 is a perspective view of a medical device according to an embodiment of the present invention. 1 is a graph showing the average film thickness of the immersion experiment results (Examples 10 and 14). 1 is a graph showing the average film thickness of the immersion experiment results (Examples 9 and 13). 1 is a graph showing the average film thickness of the immersion experiment results (Examples 8 and 11). 1 is a graph showing the test results of biofouling inhibition performance in a saline exposure environment (immersion 0 days). 1 is a graph showing the test results of biofouling inhibition performance in a saline exposure environment (immersion for one month). 1 is a graph showing the test results of biofouling inhibition performance in a saline exposure environment (immersion for 2 months). 13 shows images of the results of an evaluation of biofouling inhibition performance in a saline exposure environment using Cyprus larvae. 1 is a graph showing the percentage of attached juvenile barnacles (per 100 seedings) in biofouling control performance under exposure to a saline environment. This is a captive-reared cypris larva. This is an image of the entire surface of the sample at the end of the test in Example 21. The black dots in the image are juvenile barnacles attached to the sample surface. 1 is an image of the entire surface of the sample at the end of the test in Example 22. 1 is an image of the entire sample at the end of the test in Example 23. This is an image of the entire sample at the end of the test in Example 24. 1 is an image of the entire sample at the end of the test in Example 25. 1 is an image of the entire sample at the end of the test in Example 26. 1 is an image of the entire sample surface at the end of the test in Example 27. 1 is an image of the entire sample surface at the end of the test in Example 28. 1 is a graph showing the number of cypris larvae attached to each sample. 1 is an NMR chart of polyHPA bottle brush (acrylamide type, Example 15) heat-treated in 1 M sodium hydroxide solution. 1 is an NMR chart of polyPEGMA bottle brush (methacrylate type, Example 29) heat-treated in 1 M sodium hydroxide solution. 1 is an NMR chart of PolyHPA bottle brush (acrylamide type, Example 15) heat-treated in 1 M hydrochloric acid. 1 is an NMR chart of PolyPEGMA bottle brush (methacrylate type, Example 29) heat-treated in 1 M hydrochloric acid. 1 is a GPC chart of polyHPA bottle brush (acrylamide type, Example 15) subjected to hydrolysis reaction in heavy water for 6 hours. 1 is a GPC chart of polyHPA bottle brush (acrylamide type, Example 15) subjected to a hydrolysis reaction in sodium hydroxide for 6 hours. 1 is a GPC chart of polyHPA bottle brush (acrylamide type, Example 15) subjected to a hydrolysis reaction in hydrochloric acid for 6 hours. 1 is a GPC chart of polyPEGMA bottle brush (methacrylate type, Example 29) subjected to a hydrolysis reaction in deuterium oxide for 6 hours. 1 is a GPC chart of polyPEGMA bottle brush (methacrylate type, Example 29) subjected to a hydrolysis reaction in sodium hydroxide for 6 hours. 1 is a GPC chart of polyPEGMA bottle brush (methacrylate type, Example 29) subjected to a hydrolysis reaction in hydrochloric acid for 6 hours. 1 is a photograph showing the state of a cured film formed on a silicon substrate using a binary copolymer (HPA/BPA=95/5) before and after cleaning. 1 is a photograph showing the state of a cured film formed on a silicon substrate using a terpolymer (HPA/BPA/DOPA=85/5/10) before and after cleaning. 1 is a photograph showing the appearance of a cured film formed on an aluminum substrate using a binary copolymer (HPA/BPA=95/5) after cleaning. 1 is a photograph showing the appearance of a cured film formed on an aluminum substrate using a terpolymer (HPA/BPA/DOPA=85/5/10) after cleaning. 1 is a photograph showing the appearance of a cured film formed on a silicon substrate using a binary copolymer (HPA/BPA=95/5) after ultrasonic cleaning. 1 is a photograph showing the appearance of a cured film formed on a silicon substrate using a terpolymer (HPA/BPA/DOPA=85/5/10) after ultrasonic cleaning. The number of L929 cells adhered onto the sample. Photograph of juvenile barnacles attached to the control at the end of the test (whole sample). 1 is a photograph (whole sample) of juvenile barnacles attached to a cured film of terpolymer (HPA/BPA/DOPA=85/5/10) at the end of the test. Photograph of juvenile barnacles attached to the cured HPA/BPA/DOPA-bottlebrush film at the end of the test (whole sample). This is a photograph of juvenile barnacles (whole sample) attached to a glass plate at the end of the test. This shows the number of cypris larvae attached to each sample 9 days after the attachment test.

The present invention will be described in detail below.
The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.
In this specification, a numerical range expressed using "to" means a range that includes the numerical values before and after "to" as the lower and upper limits.

In the description of groups (atomic groups) in this specification, the description without indicating whether substituted or unsubstituted includes both unsubstituted and substituted groups, as long as it does not impair the effects of the present invention. For example, "alkyl group" includes not only alkyl groups without a substituent (unsubstituted alkyl groups), but also alkyl groups with a substituent (substituted alkyl groups). This also applies to each compound.
In this specification, "(meth)acrylamide" refers to both or either of acrylamide and methacrylamide. Similarly, when written as "(meth)acryl", "(meth)acryloyl", or "(meth)acrylate", it refers to both or either of methacryl/acryl, methacryloyl/acryloyl, and methacrylate/acrylate, as described above.

[Composition]
A composition according to an embodiment of the present invention (hereinafter also referred to as "the composition") is a composition comprising a first polymer compound having a repeating unit represented by formula 1 described below and a repeating unit represented by formula 2 described below, and a second polymer compound having a repeating unit represented by formula 3 described below.
In the following description, the "repeating unit" will simply be referred to as "unit", the unit represented by formula 1 will be referred to as "unit 1", the unit represented by formula 2 will be referred to as "unit 2", the unit represented by formula 3 will be referred to as "unit 3", the first polymer compound will be referred to as "P1", and the second polymer compound will be referred to as "P2".

The mechanism by which the film obtained from the above composition can maintain excellent biofouling inhibition performance for a long period of time even in a saline exposure environment is not necessarily clear, but the inventors speculate as follows. Note that the following mechanism is merely speculation, and even if the problem of the present invention is solved by a mechanism other than the following mechanism, it is still within the scope of the present invention.

While the biocompatible material described in Patent Document 1 has excellent performance, its biofouling suppression performance may decrease over time when exposed to saline, and this tendency was more pronounced when it contained a polymer having a (meth)acrylate structure. As a result of intensive research, the inventors have found that one of the factors that causes the biofouling suppression performance to decrease over time is that the polymer is hydrolyzed and peels off and/or decomposes over time when exposed to saline.

Based on the above findings, the inventors searched for a large number of polymers that have excellent hydrolysis resistance in a saline exposure environment, and as a result, they tested polymers having a (meth)acrylamide structure, and completed the invention of a composition that can form a cured film that maintains excellent biofouling inhibition performance, as shown in the examples described below.
Each component contained in the composition will be described in detail below.

[P1]
The composition contains P1. The content of P1 in the composition is not particularly limited, but in order to obtain a composition having better effects of the present invention, it is generally preferable that the content of P1 is 0.1 to 99.9 mass% based on the total mass of the solid content of the composition.

The composition may contain one type of P1 alone or two or more types. When the composition contains two or more types of P1, the total content thereof is preferably within the above numerical range.
P1 has a unit 1 and a unit 2. Each unit contained in P1 will be described in detail below.

<Unit 1>
The content of unit 1 in P1 is not particularly limited, but in terms of obtaining a composition having better effects of the present invention, it is generally preferable that the content be 0.1 mol % to 99.9 mol % relative to all repeating units of P1 (hereinafter also referred to as "all units").
In particular, the content of unit 1 is preferably 90 mol % or more, and more preferably 95 mol % or more, of all units P1, in terms of obtaining a composition having more excellent effects of the present invention.
In addition, P1 may contain one type of unit 1 alone or two or more types. When P1 contains two or more types of unit 1, it is preferable that the total content is within the above numerical range.

Unit 1 is represented by the following formula 1.

In formula 1, R ¹ represents a hydrogen atom or an alkyl group, and Z ¹ represents a group having a hydrophilic group.
The alkyl group for ^R1 is not particularly limited, but is preferably an alkyl group having 1 to 10 carbon atoms.
The hydrophilic group of the group having a hydrophilic group of ^Z1 (hereinafter also referred to as "hydrophilic group-containing group") is not particularly limited, and examples thereof include groups having a hydroxy group, an amino group, a carboxy group, a sulfonic acid group, a phosphonic acid group, an alkoxy group, and a zwitterionic group, etc. The zwitterionic group is not particularly limited, and examples thereof include carboxybetaine, sulfobetaine, and phosphobetaine, etc.

The hydrophilic group-containing group is not particularly limited, but a group represented by the following formula A is preferred.

In the above formula, L ^A represents a single bond or a p+q+1 valent group, L ^B represents a single bond or a divalent group, Y represents a hydrophilic group (hydroxy group, amino group, carboxy group, sulfonic acid group, phosphonic acid group, alkoxy group, zwitterionic group, etc.), p represents an integer of 1 or more, R ⁶ represents a hydrogen atom, a halogen atom, or a monovalent organic group, q represents an integer of 0 or more, and * represents a bonding position. Also, when L ^A is a single bond or a divalent group, p is 1 and q is 0.
In formula A, a plurality of L ^B , R ⁶ and Y may be the same or different.

The divalent group for L ^A is not particularly limited, and examples thereof include -C(O)-, -C(O)O-, -OC(O)-, -O-, -S-, -NR2- (R2 represents a hydrogen atom or a monovalent organic group), an alkylene group (preferably having 1 to 10 carbon atoms), a cycloalkylene group (preferably having 3 to 10 carbon atoms), an alkenylene group (preferably having 2 to 10 carbon atoms), an arylene group, and combinations thereof.

The trivalent or higher valent group of L ^A is not particularly limited, but examples thereof include groups represented by the following formulae (3BRC) to (6BRC).

In formula 3BRC, _L3 represents a trivalent group. _T3 represents a single bond or a divalent group, and three _T3 may be the same or different.
_L3 includes a nitrogen atom, a trivalent hydrocarbon group (preferably having 1 to 10 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group), or a trivalent heterocyclic group (preferably a 5- to 7-membered heterocyclic group), and the hydrocarbon group may contain a heteroatom (for example, -O-). Specific examples of _L3 include a glycerin residue, a trimethylolpropane residue, a phloroglucinol residue, and a cyclohexanetriol residue.

In formula 4BRC, _L4 represents a tetravalent group. _T4 represents a single bond or a divalent group, and the four _T4s may be the same or different from each other.
Suitable forms of _L4 include a tetravalent hydrocarbon group (preferably having 1 to 10 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group) and a tetravalent heterocyclic group (preferably a 5- to 7-membered heterocyclic group), and the hydrocarbon group may contain a heteroatom (for example, -O-). Specific examples of _L4 include a pentaerythritol residue and a ditrimethylolpropane residue.

In formula 5BRC, _L5 represents a pentavalent group, _T5 represents a single bond or a divalent group, and the five _T5 may be the same or different from each other.
Suitable examples of _L5 include a pentavalent hydrocarbon group (preferably having 2 to 10 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group) or a pentavalent heterocyclic group (preferably a 5- to 7-membered heterocyclic group), and the hydrocarbon group may contain a heteroatom (for example, -O-). Specific examples of _L5 include an arabinitol residue, a phloroglucidol residue, and a cyclohexanepentanol residue.

In formula 6BRC, _L6 represents a hexavalent group, _T6 represents a single bond or a divalent group, and the six _T6 may be the same or different from each other.
Suitable examples of _L6 include a hexavalent hydrocarbon group (preferably having 2 to 10 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group) or a hexavalent heterocyclic group (preferably a 6- to 7-membered heterocyclic group), and the hydrocarbon group may contain a heteroatom (e.g., -O-). Specific examples of _L6 include a mannitol residue, a sorbitol residue, a dipentaerythritol residue, a hexahydroxybenzene residue, and a hexahydroxycyclohexane residue.

In formulae 3BRC to 6BRC, specific examples and preferred forms of the divalent groups represented by T ₃ to T ₆ may be the same as those of the divalent group of L ^A already explained.
When L ^{1 A} is a group with a valence of 7 or more, a group obtained by combining the groups represented by formulae 3BRC to 6BRC can be used.

In formula A, the divalent group of L ^B is not particularly limited, and examples thereof include the same groups as the divalent group of L ^A. In addition, the monovalent organic group of R ⁶ is not particularly limited, and examples thereof include monovalent hydrocarbon groups which may have a heteroatom, more specifically, linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms.

It is preferable that unit 1 is a unit based on a monomer represented by the following formula 1'.

In formula 1', ^R1 and ^Z1 have the same meanings as the respective symbols in formula 1, and the preferred embodiments are also the same.

In particular, from the viewpoint of obtaining a coating film having superior adhesion to metal substrates, silicon substrates, and the like, it is preferable that P1 contains two or more types of unit 1.
When P1 contains two or more types of unit 1, P1 preferably contains a unit represented by the following formula 1A (unit 1A) and a unit represented by the following formula 1B (unit 1B).

In formula 1A and formula 1B, L _C and L _D are linear or branched alkylene groups having 1 to 6 carbon atoms and may be the same or different from each other, r is an integer of 1 to 3, and R ¹ has the same meaning as R ¹ in formula 1, and the preferred embodiments are also the same.

When P1 contains unit 1B, the resulting cured film has excellent adhesion to metal substrates such as aluminum and titanium, and silicon substrates (hereinafter also referred to as "metal substrates, etc.").

The content of units 1A and units 1B in unit 1 (in other words, the composition of unit 1) is not particularly limited, but from the viewpoint of having better adhesion to metal substrates, etc., it is preferable that the mass ratio of the content of units 1B to the content of units 1A in P1 (1B/1A) is 0.01 to 0.4.

Unit 1 can be synthesized using monomers having a hydroxyl group-containing group such as N-(2-hydroxyethyl)acrylamide, N-(hydroxymethyl)acrylamide, and N-(2-hydroxypropyl)acrylamide; monomers having a carboxyl group-containing group such as 6-acrylamidohexanoic acid; monomers having a zwitterion-containing group such as 3-[(3-acryloylaminopropyl)dimethylammonio]propanoate; monomers having an alkoxyl group-containing group such as N-(butoxymethyl)acrylamide; monomers having an amino group-containing group such as N-[3-(dimethylamino)propyl]acrylamide and N-(3-dimethylaminopropyl)methacrylamide; monomers having a sulfonic acid group-containing group such as 2-acrylamido-2-methylpropanesulfonic acid; and the like.

The monomer for obtaining unit 1 can be easily synthesized by a known method, such as reacting a compound having an amino group and a hydroxyl group (e.g., dopamine) with (meth)acrylic acid chloride in the presence of a base catalyst to form an amide bond.

<Unit 2>
P1 has unit 2. Unit 2 has a photoradical generating group and generates radicals by irradiation with light, and therefore has a function as a photoradical initiator fixed in the molecule. Note that unit 2 means a repeating unit different from unit 1.
The content of unit 2 in P1 is not particularly limited, but is generally preferably 0.1 to 10 mol % based on the total units of P1, in order to obtain a composition having better effects of the present invention.
In addition, P1 may contain one type of unit 2 alone or two or more types. When P1 contains two or more types of unit 2, the total content thereof is preferably within the above numerical range.

Unit 2 is expressed by the following formula 2.

In formula 2, ^R2 represents a hydrogen atom or an alkyl group, and ^Z2 represents a photoradical generating group. The alkyl group of ^R2 is not particularly limited, but is preferably an alkyl group having 1 to 10 carbon atoms.

The photoradical generating group of ^Z2 means a group capable of generating radicals upon irradiation with light (ultraviolet rays, radiation, etc.). As the photoradical generating group, a group derived from a known photoradical generator can also be used.
Examples of the photoradical generating group include a group having a structure in which the α-position of a carbonyl is photocleaved, and a group having an oxime ester structure.
In addition, in terms of obtaining a composition having a more excellent effect of the present invention, the photoradical generating group is preferably a group represented by the following formula (g1).

In formula g1, R ⁷ represents an arylene group having 6 to 30 carbon atoms which may have a substituent, R ⁸ represents an aryl group having 6 to 30 carbon atoms which may have a substituent, and * represents a bonding position.
From the viewpoint of obtaining a composition having a more excellent effect of the present invention, R ⁷ is preferably a phenylene group, and R ⁸ is preferably a phenyl group. That is, the photoradical generating group is preferably a group represented by the following formula g2.

In formula g2, * indicates the bond position.

It is preferable that unit 2 is a unit based on a monomer represented by the following formula 2'.

In formula 2', ^R2 and ^Z2 have the same meanings as the respective symbols in formula 2, and the preferred embodiments are also the same.

The method for producing the above monomer is not particularly limited, but for example, it can be produced by reacting a photopolymerization initiator having an amino group with a (meth)acrylic acid halide. The above monomer is not particularly limited, but examples thereof include N-(4-benzoylphenyl)(meth)acrylamide.

<Production method of P1>
The method for producing P1 is not particularly limited, and for example, a composition containing each of the monomers represented by formula 1' and formula 2' may be prepared and copolymerized by a known method. Specifically, a polymerizable composition containing the monomers represented by the following formula, a radical polymerization initiator, and a solvent may be prepared, and the polymerized by applying energy (heating, light irradiation, etc.).

As the photopolymerization initiator, known compounds capable of generating active radicals upon irradiation with light can be used. Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., those having a triazine skeleton, those having an oxadiazole skeleton, and those having a trihalomethyl group, etc.); acylphosphine compounds such as acylphosphine oxides; hexaarylbiimidazoles and oxime compounds such as oxime derivatives; organic peroxides; sulfur-containing compounds; ketone compounds; aromatic onium salts; aminoacetophenone compounds; azo compounds; azide compounds; etc.

In addition to the above, the polymerizable composition may also contain a chain transfer agent and a polymerization inhibitor.

The molecular weight of P1 is not particularly limited, but the number average molecular weight (Mn) is typically preferably 10,000 to 1,000,000. The molecular weight distribution (particle dispersity index: PDI) is not particularly limited, but typically preferably 1.0 to 3.0. The number average molecular weight and molecular weight distribution refer to values measured using gel permeation chromatography under the conditions described below.

[P2]
The composition contains P2. The content of P2 in the composition is not particularly limited, but in order to obtain a composition having better effects of the present invention, it is generally preferably 0.1 to 99.9 mass% based on the total mass of the solid content of the composition.
The composition may contain one type of P2 alone or two or more types. When the composition contains two or more types of P2, it is preferable that the total content is within the above numerical range.
P2 has unit 3. Each unit contained in P2 will be described in detail below.

<Unit 3>
P2 has unit 3. The content of unit 3 in P2 is not particularly limited, but is generally preferably 50 to 100 mol % based on the total units of P2, in order to obtain a composition having better effects of the present invention.
In addition, P2 may contain one type of unit 3 alone or two or more types. When P2 contains two or more types of unit 3, it is preferable that the total content is within the above numerical range.
In addition, P2 may have a unit other than the unit 3.

Unit 3 is expressed by the following formula 3.

In formula 3, ^R3 and ^R4 each independently represent a hydrogen atom or an alkyl group and may be the same or different; ^Z3 represents a hydrophilic group-containing group; ^R5 represents a hydrogen atom, a halogen atom, or a monovalent substituent; ^L1 represents a group represented by formula 4a or formula 4b; ^L2 represents a single bond or a divalent group; and in formulas 4a and 4b, * represents a bonding position, and n represents an integer of 1 or greater.

The alkyl group for R ³ and R ⁴ is not particularly limited, but is preferably an alkyl group having 1 to 10 carbon atoms.
^Z3 is not particularly limited, but may be the same as ^Z1 in formula 1, and the preferred embodiments are also the same.
The monovalent substituent of ^R5 is not particularly limited, and examples thereof include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group. In one embodiment, ^R5 is preferably a halogen atom.
The divalent group for ^L2 is not particularly limited, but examples thereof include hydrocarbon groups having 1 to 10 carbon atoms which may have a heteroatom, and more specifically, alkylene groups having 1 to 10 carbon atoms.

(Structure of P2)
P2 has a unit 3, and the unit 3 is a unit having a polymer chain as a side group in a repeating unit. Since the unit 3 constitutes at least a part of the main chain of P2, the polymer chain is a side chain bonded to the main chain, and P2 is a graft polymer.
The three-dimensional structure of P2 is not particularly limited, but in terms of having better biofouling inhibition performance, it is preferable that the surface occupancy rate (σ ^* ) represented by the following formula be 0.1 or more, more preferably 0.2 or more, even more preferably 0.3 or more, particularly preferably 0.4 or more, and most preferably greater than 0.4.
In this specification, a graft chain possessed by a graft polymer having a surface occupancy (σ ^* ) of 0.1 or more is referred to as a "dense polymer brush."

Here, "polymer brush" refers to an assembly of polymer chains extending from the surface of the fiber in a direction approximately perpendicular to the long axis direction of the short fiber, and means multiple graft chains bonded to the main chain of the graft polymer.

The dense polymer brushes are described in detail in Reference 1 (Tsujii Y et al., "Structure and Properties of High-Density Polymer Brushes Prepared by Surface-Initiated Living Radical Polymerization.", Adv Polymer Sci., Vol. 197, pp. 1-45, 2006.).

FIG. 10 in Reference 1 shows the degree of extension of grafted chains versus graft density, indicating that the degree of extension of grafted chains in “concentrated polymer brushes” is greater than that in semi-dilute systems.
Generally, isolated polymer chains in a good solvent take a random coil shape due to the excluded volume effect, but it is known that they take a mushroom-like shape when one end is fixed to a solid. When the surface density of the grafted chains increases, the molecular chains overlap each other, increasing the density, so it is known that the mushroom-shaped molecular chains extend in the height direction to avoid this (scaling law).

However, in the high surface occupancy (high σ ^* ) region, the experimentally confirmed degree of elongation of the graft chains exceeds this theoretical prediction. In this specification, the term "concentrated polymer brush" refers to the region in which the degree of elongation of the graft chains exceeds the theoretical prediction, specifically, the polymer brush with a surface occupancy σ ^* of 0.1 or more, preferably 0.2 or ^more , more preferably 0.3 or more, even more preferably 0.4 or more, and particularly preferably more than 0.4.

The surface occupancy rate (dimensional graft density (σ ^* )) means a value obtained by normalizing the graft density with the cross-sectional area of the monomer, and its definition is in accordance with Reference 1.

In concentrated polymer brushes formed from such graft chains close to extended chains, the flexible polymer chains are in a state where they are highly oriented as if they were rigid molecules, and compared to semi-dilute systems, they are known to have unique properties such as (1) a large swollen film thickness (extended orientation) comparable to the extended chain length and high compression resistance, (2) a clear size exclusion effect (molecules larger than a certain size are not incorporated into the brush layer) both in the molten state and in the solvent due to the large osmotic pressure and highly extended molecular chain morphology, and (3) no interpenetration occurs even between homogeneous brushes, resulting in an extremely low coefficient of friction between swollen brushes.

Specifically, the surface occupancy (σ ^* ) is defined by the formula: surface occupancy (σ ^* ) = {volume per repeating unit of polymer chain portion ( ^nm3 /chain)/length of repeating unit of polymer chain portion (nm)} × σ (chain/ ^nm2 ).

In the above formula, σ is the effective graft density (chains/nm ² ).

The graft polymer P2 has a main chain and multiple polymer chains that extend radially from the main chain, forming a dense polymer brush. The surface occupancy is a parameter that can be described as the area of the polymer chains that occupies a cylindrical surface with the main chain of P2 as the central axis and the length of the polymer chain as the radius.

When the surface occupancy rate is high, it means that the proportion of the area of the imaginary cylindrical surface that is derived from the polymer chains is large. Therefore, it is presumed that the degree of freedom of the polymer chains is low, and it is easier for the polymer chains to maintain a state in which they are approximately perpendicular to the main chain of P2 and the cylindrical surface.

On the other hand, when the grafting efficiency is lower (described later) and when the polymer chain is longer (in other words, the degree of polymerization of the polymer chain portion is higher), the density of the polymer chains on the imaginary cylinder surface decreases. In such cases, the degree of freedom of the polymer chains becomes higher and the polymer chains can be folded freely.
Next, each term in the above formula for calculating the surface occupation ratio (σ ^* ) will be described in detail.

Effective graft density (σ _eff )
First, the effective graft density (σ _eff ) represents the number of graft chains per unit area of the imaginary cylindrical surface.

Formula: σ _eff (chain/nm ² )=1/{(2π×α×polymerization degree of grafted chain portion)×(α′/graft efficiency)}

In the above formula, α is the length (nm) of the repeating unit of the graft chain portion, and α' is the length (nm) of the repeating unit of the main chain. The method for calculating the length of the repeating unit of the polymer chain portion will be described later. The specific method for calculating σ _eff is as described in the Examples.

In addition, the degree of polymerization of the polymer chain portion of P2 can be determined by preparing a polymer (hereinafter also referred to as a "specific polymer") that would form a polymer chain if bound to P2 under the same conditions as when P2 is synthesized, and measuring the degree of polymerization.
More specifically, when synthesizing P2, a specific polymer is obtained using a compound (hereinafter also referred to as an "initiating point compound") that has one group (reactive group) capable of reacting with a monomer for forming a polymer chain and does not constitute (does not polymerize) the main chain of P2, and the degree of polymerization of the specific polymer is then measured.

The degree of polymerization of the specific polymer is considered to be equal to that of the polymer chain portion of P2 in terms of degree of polymerization, number average molecular weight, and molecular weight distribution. Therefore, the degree of polymerization of the specific polymer is taken to be the degree of polymerization of the polymer chain portion of P2.

At this time, the number average molecular weight (Mn) and molecular weight distribution (PDI) of the specific polymer are determined, whereby the number average molecular weight and molecular weight distribution of the polymer chain portion of P2 can also be determined.
Here, Mn and PDI are measured in terms of polystyrene using gel permeation chromatography (GPC) under the following conditions 1 or 2.

Condition 1 (DMF system)
Column: Shodex LF804 (300 x 80 mm; bead size = 6 μm)
Flow rate: 0.8ml/min (40°C)
Eluent: 10 mM lithium chloride in dimethylformamide (DMF)

Next, "grafting efficiency" is the molar ratio of units having polymer chains to the total units of P2. In other words, it is the number of polymer chains per repeat unit of P2.

All units of P2 are classified into units ^Pm1 having a polymer chain and units not having a polymer chain, and the units not having a polymer chain are classified into units ^Pm2 having a reactive group but not reacted and units ^Pm3 having no reactive group. In other words, P2 is expressed as follows using the above ^Pm1 , ^Pm2 , and ^Pm3 .

In the above formula, n1, n2, and n3 represent the molar ratio of each unit, n1 represents a number greater than 0, and n2 and n3 represent numbers of 0 or more.
Here, the grafting efficiency can be expressed as n1/(n1+n2+n3) using the above symbols.

The grafting efficiency can be calculated from the initiation efficiency (n1/( ⁿ¹ + ⁿ² )), which indicates the molar ratio of the content of units ( ^Pm1 ) that have reacted with the polymer chain to the content of units (Pm1 and Pm2) that have reactive groups in all units of P2, and the molar ratio ((n1+n2)/(n1+n2+n3)) of the content of units ( ^Pm1 , ^Pm2 ) that have (and had) reactive groups to all units of P2.

The molar ratio of units having reactive groups to the total units of P2 can be obtained by NMR (Nuclear Magnetic Resonance) measurement of the main chain before the polymer chain is bonded.

The initiation efficiency can be calculated based on the polymerization rate determined from the measurements of NMR and GPC.
The polymerization rate is determined as the ratio of the molar amount of the monomer bonded to the polymer chain to the molar amount of the monomer charged in the polymerization reaction by measuring the content of the unit having a polymer chain and the ratio of the solvent and the unreacted monomer using NMR. The polymerization rate can also be calculated from the peak area of GPC.

Specifically, the polymerization rate of a specific polymer is determined from the GPC peak area, and the polymerization rate assuming an initiation efficiency of 100% is calculated using GPC from the charge ratio of the main chain polymer and the initiation compound. Next, NMR is used to measure the content of units having a polymer chain in P2 and the ratio of the solvent to unreacted monomer, and the polymerization rate by NMR is determined as the ratio of the molar amount of monomer that contributed to the formation of the polymer chain to the molar amount of monomer used. The polymerization rate by NMR is compared with the approximate value of the polymerization rate by GPC to determine the initiation efficiency.

The degree of polymerization of the polymer chain portion can be calculated from the initiation efficiency of P2, the polymerization rate (polymerization rate measured by NMR), and the molecular weight of the monomer units that make up the graft chain.

The degree of polymerization of the polymer chain portion can also be determined by determining the absolute molecular weight of the bottle brush polymer using GPC equipped with a time-of-flight mass spectrometer (TOF-MASS) or a multi-angle light scattering (MALLS) and calculating the ratio to the monomer unit.

The grafting efficiency is not particularly limited, but is preferably 0.3 or more, and more preferably 0.4 or more, in that the surface occupancy rate is higher. There is no particular upper limit, but generally 1 or less is preferred.

Volume per repeat unit of the polymer chain portion ( ^nm3 /chain)
The volume per repeating unit of the polymer chain portion (v ₀ [nm ³ /chain]) is calculated by the following formula.

V ₀ = {molecular weight of monomer in polymer chain portion/Avogadro's constant}/(bulk density of monomer in polymer chain portion)

In the above formula, the bulk density of the monomer in the polymer chain portion means the bulk density at room temperature of the raw material (monomer) used to form the polymer chain.

Length of the repeating unit of the polymer chain (nm)
The length of the repeating unit in the polymer chain portion is determined by GPC (gel permeation chromatography, converted into standard polystyrene).
For example, the length of a unit based on a vinyl bond is 0.25 nm.

The surface occupancy is a parameter that reflects the degree of freedom of the polymer chain. It is considered that when the surface occupancy is higher, the structural freedom of the polymer chain is restricted, and the polymer chain is more likely to maintain a state in which it extends in a direction substantially perpendicular to the main chain. It is presumed that by the polymer chain extending in a direction substantially perpendicular to the main chain, the polymer chain is more likely to assume a structure in which it stands perpendicular to the main chain on the above-mentioned virtual cylindrical surface, and thus a more excellent effect of the present invention can be obtained.
More specifically, it is presumed that a surface with more densely packed polymer chains has less "room" for the attachment of proteins and other substances that are thought to cause biofouling, and as a result, biofouling is more suppressed.

<Other units>
P2 may have other units than unit 3. The other units are not particularly limited, and examples thereof include a unit having a polymerizable group, and a unit having a hydrophilic group or a hydrophobic group. When P2 has a polymerizable group, the adhesion to the substrate is further increased when the film is formed.

<Method of producing P2>
The method for producing P2 is not particularly limited, and known production methods can be applied. For example, a method of synthesizing a macromonomer having a predetermined polymer chain and a polymerizable group (e.g., an ethylenically unsaturated group) and then polymerizing the macromonomer to form a graft, and a "graft from" method described later can also be used.

As a method for producing P2, it is preferable to use a graft polymerization method using an atom transfer radical polymerization method (ATRP) in order to obtain a composition that has a more excellent effect of the present invention.

The ATRP method is a type of radical polymerization characterized by the fact that an active species having a growing radical (e.g., a functional group with a radicalized end) and a dormant species capped with a halogen atom (e.g., a functional group with a halogenated end) are in equilibrium, and the equilibrium is heavily biased toward the dormant species, suppressing the number of active species, promoting the growth reaction in which the active species react with monomers to grow larger, and suppressing the termination reaction.

In normal radical polymerization, in addition to the propagation reaction in which active radicals react with monomers, termination reactions such as recombination in which radicals bond with each other, disproportionation in which radicals form bonds within a molecule, and chain transfer in which radicals move to a solvent or the like can occur. One of the reasons for these termination reactions is thought to be an increase in the number of active species (radicals). Furthermore, under conditions in which termination reactions occur, it is difficult to control the molecular weight of the resulting polymer, and the molecular weight distribution tends to be broad. In addition, the terminal structure of the resulting polymer differs depending on the termination reaction, making it difficult to control.

In ATRP, the termination reaction is suppressed by the equilibrium with the active species that is heavily biased toward dormant species, so it is possible to obtain polymers with a narrow molecular weight distribution. In addition, since the ends of the polymers obtained by ATRP are dormant species, even if the growth reaction has once stopped, the growth reaction will proceed again if the reaction conditions are met again. This characteristic makes it easy to obtain polymers with the desired structure.

More specifically, as shown in the reaction scheme below, a polymer (b) (hereinafter also referred to as a "macroinitiator") is obtained based on a monomer having an ethylenically unsaturated group and a halogenated alkyl group (Scheme 1), and then a polymer chain is synthesized by a so-called "grafting from" process using the carbon radicals generated by eliminating halogen atoms as active sites (Scheme 2).

R ³ , L ¹ and L ² in Scheme 1 have the same meanings as the respective symbols in formula 3 already explained, and the preferred embodiments are also the same. X represents a halogen atom, and is preferably a chlorine atom or a bromine atom.
In Scheme 1, the method of polymerizing the monomer represented by (a) to obtain (b) is not particularly limited, and any known polymerization method can be applied. Among them, it is preferable to use the reversible addition-fragmentation chain transfer (RAFT) polymerization method, since it is possible to obtain a composition having the excellent effects of the present invention.

The RAFT method is a living radical polymerization method in which a compound capable of reversibly undergoing an addition-fragmentation-chain transfer reaction is used as a chain transfer agent (hereinafter referred to as a RAFT agent) to carry out polymerization. There are no particular limitations on the RAFT agent, but for example, various thiocarbonylthio compounds described in WO 98/01478, WO 99/31144, and WO 00/75207 can be used.

In Scheme 2, ^R3 , ^R4 , ^L1 , ^L2 , and ^Z3 have the same meanings as the symbols in Formula 3 already described, and the preferred forms are also the same. X represents a halogen atom, preferably a chlorine atom or a bromine atom. Mt represents a metal ion, and L represents a ligand.

The metal ions and ligands generate radicals by abstracting halogen atoms from the halogenated alkyl groups that are the reaction initiation points, and also form an equilibrium with the dormant species, suppressing the termination reaction of the radicals.

The metal ion is not particularly limited, but examples thereof include ions of copper, titanium, iron, cobalt, nickel, molybdenum, and ruthenium. Among these, copper ions are preferred from the viewpoint of reaction rate and the like. Metal ions are generally mixed in the form of metal salts when preparing the reaction solution. The metal salt is not particularly limited, but examples thereof include copper chloride (I), copper chloride (II), copper bromide (I), copper bromide (II), and copper iodide (I) when the metal ion is a copper ion.

The metal salt forms a metal complex in the presence of a specific ligand, and abstracts a halogen from an alkyl halide group to generate an initiating radical. The initiating radical and the propagating radical are in equilibrium with each other as active species and dormant species, and the termination reaction is greatly suppressed.
The ligand is not particularly limited, and may be appropriately selected depending on, for example, the type of metal ion used to form the complex.
When copper ions are used as metal ions, nitrogen-containing ligands are useful for complex formation. In addition, the binding constant with the metal ion varies depending on the structure of the ligand, so that the rate of generation of the initiation radical and the equilibrium constant between the dormant and active species change, and the ratio of the active species to the dormant species changes, which may result in a difference in the rate of graft polymerization.

Examples of the ligand include 2,2'-dipyridyl, 4,4'-dimethyl-2,2'-dipyridyl, 4,4'-ditertiarybutyl-2,2'-dipyridyl, 4,4'-dinonyl-2,2'-dipyridyl, N-butyl-2-pyridylmethanimine, N-octyl-2-pyridylmethanimine, N-dodecyl-N-(2-pyridylmethylene)amine, N-octadecyl-N-(2-pyridylmethylene)amine, N,N,N',N'',N''- Examples include pentamethyldiethylenetriamine, tris(2-pyridylmethyl)amine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, tris[2-(dimethylamino)ethyl]amine, 1,4,8,11-tetraazacyclotetradecane, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, and N,N,N',N'-tetrakis(2-pyridylmethyl)-ethylenediamine.

The method for preparing the reaction solution is not particularly limited, but examples include a method in which the raw materials are mixed in water and thoroughly mixed and stirred to dissolve each component to form an aqueous solution, and then unnecessary oxygen in the aqueous solution is removed by bubbling with an inert gas or degassing under reduced pressure.

[Other ingredients]
The composition may contain other components in addition to those described above within the scope of the effects of the present invention, such as copper pyrithione, zinc oxide, a rosin compound, a copper compound, a coloring pigment, an extender pigment, a pigment dispersant, a plasticizer, an anti-sagging agent, an anti-settling agent, a dehydrating agent, and a solvent.

When the present composition contains copper pyrithione, the content is not particularly limited, but is preferably 0.01 to 500 parts by mass when the total content of P1 and P2 in the composition is 100 parts by mass. A film obtained by using the present composition containing copper pyrithione has superior biofouling inhibition performance.

When the present composition contains zinc oxide, the content is not particularly limited, but is preferably 0.01 to 1000 parts by mass when the total content of P1 and P2 in the composition is 100 parts by mass. A film obtained by using the present composition containing zinc oxide has superior strength and superior biofouling inhibition performance.

When the present composition contains a rosin compound, the content is not particularly limited, but is preferably 0.1 to 70 parts by mass when the total content of P1 and P2 is 100 parts by mass. Examples of rosin compounds include rosins such as gum rosin, wood rosin, and tall oil rosin, hydrogenated rosin, and rosin derivatives such as disproportionated rosin. The present composition containing a rosin compound has superior biofouling inhibition performance.

When the composition contains a copper compound, the content is not particularly limited, but is preferably 0.01 to 2500 parts by mass when the total content of P1 and P2 in the composition is 100 parts by mass. Examples of copper compounds include cuprous oxide, copper thiocyanate, and cupronickel.
The films obtained using the present compositions containing copper compounds have better strength and better biofouling control performance.

When the composition contains a color pigment, the content is not particularly limited, but is preferably 0.01 to 100 parts by mass when the total content of P1 and P2 is 100 parts by mass. Examples of the color pigment include organic pigments and inorganic pigments, and specific examples thereof include carbon black, naphthol red, phthalocyanine blue, red iron oxide, baryte powder, titanium white, and yellow iron oxide.
Films obtained using the present compositions containing color pigments have better color tone.

When the present composition contains a body pigment, the content is not particularly limited, but is preferably 0.01 to 100 parts by mass when the total content of P1 and P2 is 100 parts by mass. Examples of the body pigment include talc, silica (diatomaceous earth, acid clay, etc.), mica, clay, potassium feldspar, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, and zinc sulfide.
Films obtained using the present compositions containing extender pigments have better mechanical properties.

When the composition contains a pigment dispersant, the content is not particularly limited, but is preferably 0.1 to 100 parts by mass when the total content of P1 and P2 is 100 parts by mass. Examples of the pigment dispersant include aliphatic amines or organic acids (e.g., "Duomin TDO" (manufactured by LION Co., Ltd.) and "Disperbyk101" (manufactured by BYK Co., Ltd.)).
When the present composition contains a pigment dispersant, it becomes easier to adjust the viscosity of the composition, resulting in improved handleability.

When the composition contains a plasticizer, the content is not particularly limited, but is preferably 0.1 to 300 parts by mass when the total content of P1 and P2 is 100 parts by mass. Examples of the plasticizer include chlorinated paraffin, petroleum resins, ketone resins, TCP (tricresyl phosphate), polyvinyl ethyl ether, and dialkyl phthalate.
The film obtained using the present composition containing a plasticizer has better crack resistance.

When the present composition contains an anti-sagging agent, the content is not particularly limited, but is preferably 0.1 to 100 parts by mass when the total content of P1 and P2 is 100 parts by mass. Examples of the anti-sagging agent include amide wax, hydrogenated castor oil wax, and synthetic fine silica (Aerosil (registered trademark), etc.).
The present composition containing an anti-sagging agent reduces the occurrence of "sagging" when applied to a substrate.

When the composition contains an anti-settling agent, the content is not particularly limited, but is preferably 0.1 to 100 parts by mass when the total content of P1 and P2 is 100 parts by mass. Examples of the anti-settling agent include stearates of Al, Ca, or Zn, polyethylene wax, and oxidized polyethylene wax.
The present compositions containing anti-settling agents exhibit less settling.

When the composition contains a dehydrating agent, the content is not particularly limited, but is preferably 0.1 to 50 parts by mass when the total content of P1 and P2 is 100 parts by mass. Examples of the dehydrating agent include inorganic dehydrating agents such as synthetic zeolite, anhydrous gypsum, and hemihydrate gypsum; and organic dehydrating agents such as alkoxysilane, polyalkoxysilanes, and alkyl orthoformate esters.
The present compositions containing a dehydrating agent have better storage stability.

When the composition contains a solvent, the content is not particularly limited. In one embodiment, the content of the solvent is preferably adjusted so that the solid content of the composition is 5 to 95 mass %. Examples of the solvent include water and organic solvents, and examples of the organic solvent include alcohol-based solvents such as methanol, ethanol, and isopropanol.

<Method of preparing the composition>
The method for preparing the composition is not particularly limited, and each component described above may be mixed. In this case, the order in which each component is mixed is not particularly limited, and the components may be mixed in any order. In addition, when the composition contains a sagging inhibitor, it is preferable to first mix the other components, homogenize them, and then add the sagging inhibitor.
The mixing method is not particularly limited, and a high-speed disperser, a sand grind mill, a basket mill, a ball mill, a three-roll mill, a Ross mixer, a planetary mixer, or the like can be used.

<Uses of the composition>
The cured film obtained by using the composition has excellent biofouling suppression performance. The composition can be used, for example, to form a cured film on a substrate to be prevented from biofouling, in other words, to manufacture a laminate having a substrate and a cured film formed on the substrate. In particular, it is preferable to use the composition to form a cured film on a substrate that is used in contact with salt water (seawater, body fluids of organisms, etc.).

Examples of the substrate include water supply and drainage outlets of power plants (thermal and nuclear), coastal roads, undersea tunnels, underwater structures such as sludge diffusion prevention membranes used in marine civil engineering works, ship shell panels (particularly the waterline to the bottom of a ship), and fishing materials (ropes, fishing gear such as fishing nets, buoys, etc.).
Examples of the substrate include cell culture vessels, cell culture sheets, cell capture filters, vials, plastic-coated vials, syringes, plastic-coated syringes, ampoules, plastic-coated ampoules, cartridges, bottles, plastic-coated bottles, pouches, pumps, sprayers, stoppers, plungers, caps, lids, needles, stents, catheters, implants, contact lenses, microchannel chips, drug delivery system materials, artificial blood vessels, artificial organs, hemodialysis membranes, guard wires, blood filters, blood storage packs, endoscopes, biochips, glycosynthesis equipment, molding auxiliary materials, and packaging materials.

[Cured film]
The cured film according to the embodiment of the present invention is a film obtained by curing the composition already described.
The method for producing the cured film is not particularly limited, but the film can be produced by forming a composition layer on a flat plate or a three-dimensional substrate having a curved surface using the composition, and drying the composition layer. From the viewpoint of achieving a better biofouling suppression performance, it is preferable to cure the composition layer by irradiating it with light. The wavelength of the light irradiation is not particularly limited, but it is preferable to irradiate ultraviolet light in the wavelength range of 300 to 400 nm, more preferably around 360 nm.

Since P1 has a photoradical generating group, when the composition layer is irradiated with light, an active radical is generated, P2 is fixed to P1, and a cured film is obtained. When the photoradical generating group is a group represented by formula g2 (benzophenone), an active radical is generated by irradiation with ultraviolet light having a wavelength of 250 to 365 nm, and this generates a covalent bond by abstracting hydrogen from a hydrocarbon (for example, a partial structure of P2).
Through the mechanism described above, P2 is fixed to P1, resulting in a cured film.

In addition, the adhesion between the substrate and the cured film is further improved by the reaction of the substituents (hydroxyl groups, carboxyl groups, etc.) on the surface of the substrate, which will be described later, with the above-mentioned active radicals.

The substrate is not particularly limited, but examples include metals such as steel and aluminum, wood, and resin.

The method of forming the composition layer is not particularly limited, and includes a method of coating the composition on a substrate. The coating method is not particularly limited, and a known method can be used. Examples of the coating method include spray coating and roller coating. In addition, a method of impregnating a substrate with the composition can also be used.
Alternatively, the composition layer may be formed in advance on a temporary substrate, and the composition layer formed on the temporary substrate may be attached to the substrate.

[Ships]
FIG. 1 is a schematic partial cross-sectional view of a ship according to an embodiment of the present invention, and FIG. 2 is a schematic cross-sectional view of a ship bottom base material.
In FIG. 1, the bottom shell plate of a ship 10 is a laminate having a metal substrate 11, a primer layer 12 disposed on the substrate 11, and a cured film 13 disposed on the primer layer.
Since the ship has the cured film on its outer plate, adhesion of aquatic organisms such as sea lettuce, barnacles, green laver, cerpula, oysters, and hairy bryozoans can be inhibited for a long period of time.

Although the above ship has a primer layer, the ship according to the embodiment of the present invention is not limited to the above and may not have a primer layer. In addition, another layer may be further provided between the substrate and the cured film.

[Underwater Structures]
3 is a schematic diagram of an underwater structure according to an embodiment of the present invention. The underwater structure 20 includes a float 21 disposed on the sea surface SL, a curtain 22 fixed to the float 21 and hanging down from the float 21 into the sea, a weight 23 fixed to the lower end of the curtain 22, an anchor rope 25 for connecting the float 21 to an anchor 24 disposed on the seabed OF, and a buoy 26 disposed on the sea surface SL and disposed midway on the anchor rope 25 to avoid contact between the curtain 22 and the anchor rope 25.

The underwater structure 20 is typically a pollution prevention membrane that is placed in the sea and is used to promote the sinking of pollution particles and suppress the diffusion of pollution.
Of these, the curtain 22 is a portion for preventing the diffusion of contamination, and is made of a polyester fiber woven fabric as a base material on which the cured film is disposed. Therefore, even if the curtain 22 is placed in water for a long period of time, adhesion of organisms to the curtain 22 is easily suppressed.

Furthermore, the float 21 and the buoy 26 are hollow members, and the above-mentioned hardened film is disposed on a resin substrate. Since the above-mentioned hardened film is disposed on the outside (sea) side of the float 21 and the buoy 26, biofouling is more easily suppressed even when the float 21 and the buoy 26 are placed in water for a long period of time.

In the underwater structure 20, the curtain, float, and buoy have a hardened film formed on their surface using the above composition, but the underwater structure according to the embodiment of the present invention is not limited to the above, and other parts may have the above hardened film.

The underwater structure 20 is a pollution prevention membrane, but the above is just one example of an underwater structure according to the present invention, and the underwater structure according to the embodiment of the present invention is not limited to the above and may be a water supply and drainage outlet of a power plant (thermal or nuclear), a coastal road, an undersea tunnel, and fishing equipment (ropes, fishing gear such as fishing nets, buoys, etc.), etc.

[Medical Devices]
4 is a perspective view of a medical device according to an embodiment of the present invention. The medical device 30 is a microchannel chip. The medical device 30 has a flat substrate 31 and a cured film 32 formed on the substrate 31.
A pattern of recesses 33 is formed on the surface of the cured film 32, and the cured film 32 is configured so that liquid can flow along the recesses.
The cured film 32 having a pattern of recesses 33 can be produced by pressing a mold having protrusions of a shape complementary to the pattern of the recesses 33 against a composition layer and curing the layer. In addition, since the composition can be crosslinked by irradiation with light, it can also be patterned using known photolithography techniques.

The material constituting the substrate 31 is not particularly limited, but examples include resin and glass. The thickness of the film is not particularly limited, but generally, a thickness of 100 nm to 10 mm is preferred.

In the above medical device, the recess 33 is formed on the hardened film 32, so that even when the solution to be tested is passed through the recess 33, biological substances are less likely to adhere to the recess 33, enabling more accurate measurements, etc.
The above is just one example of a medical device according to an embodiment of the present invention, and the medical device may be another article having the above-mentioned film.

Other articles may include, for example, cell culture vessels, cell culture sheets, cell capture filters, vials, plastic-coated vials, syringes, plastic-coated syringes, ampoules, plastic-coated ampoules, cartridges, bottles, plastic-coated bottles, pouches, pumps, sprayers, stoppers, plungers, caps, lids, needles, stents, catheters, implants, contact lenses, microchannel chips, drug delivery system materials, artificial blood vessels, artificial organs, hemodialysis membranes, guard wires, blood filters, blood storage packs, endoscopes, biochips, glycosynthesis equipment, molding aids, and packaging materials.

The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, processing contents, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.

Synthesis of PSTCl (macroinitiator)
4-(Chloromethyl)styrene (2.0 g, 13.1 mmol), 4-Cyano-4-(phenylcarbonothioylthio)pentanoic acid (10.1 mg, 2.6×10 ⁻² mmol), and AIBN (azobisisobutyronitrile, 2.6 mg, 10.5×10 ⁻³ mmol) were prepared under an argon atmosphere and stirred in an oil bath at 70° C. for 3 hours. After the reaction, the molecular weight and molecular weight distribution were determined by DMF-based GPC measurement. In terms of PST (polystyrene), Mn was 29600 and PDI (Poly Dispersity Index) was 1.2. PSTCl was purified by reprecipitation recovery using methanol, a poor solvent.

(P2 (bottle brush) synthesis 1)
N-(2- hydroxypropyl acrylate) (HPA) (0.4 g, 3.1 mmol), the macroinitiator (PSTC1) synthesized above (Mn=29600, 7.6 mg, 5.0× ⁻² mmol), free initiator (banzyl chloride) (1.56 mg, 1.24×10 ⁻² mmol), Tris[2-(dimethylamino)ethyl]amine (Me ₆ TREN) (28.5 mg, 1.24×10 ⁻¹ mmol), Cu(I)Cl (6 mg, 6.2×10 ⁻² A DMF/MeOH (0.95 g/0.40 g) mixture containing 10 mmol of 1,000 sucrose was prepared in a glove box and stirred in a 30° C. oil bath for 1.5 or 3 hours. After polymerization, the molecular weight and molecular weight distribution were determined by DMF-based GPC (PST conversion). The polymerization rate was determined by NMR. Table 1 shows the number average molecular weight and molecular weight dispersity of the obtained bottle brush.

In Table 1, "Free polymer" means a specific polymer, and "Bottle Brush" means a "bottle brush" polymer.
In Table 1, the initiation efficiency is approximately 100% based on the polymerization rate predicted from the free polymer area and the polymerization rate determined by NMR.

The graft density of the bottle brush of Example 1 was 0.28 chains/nm ² (0.24 in terms of surface occupancy), and the graft density of the bottle brush of Example 2 was 0.21 chains/nm ² (0.18 in terms of surface occupancy).

(Bottlebrush Synthesis 2)
HPA (2.0 g, 15.5 mmol), macroinitiator (PSTCl) (Mn=29600, 47 mg, 3.1×10 ⁻¹ mmol), Me ₆ TREN (14.27 mg, 6.2×10 ⁻¹ mmol), and Cu(I)Cl (31 mg, 3.1×10 ⁻¹ mmol) were added to DMF/MeOH (4.75 g/1.98 g) in a glove box and stirred in an oil bath at 30° C. for 3 hours. After polymerization, the molecular weight and molecular weight distribution were determined by DMF-based GPC (PST conversion). The bottle brush obtained was purified by reprecipitation recovery using acetone. Table 2 shows the number average molecular weight and molecular weight dispersity of the bottle brush obtained.

The graft density of the bottle brush of Example 3 was 0.13 chains/nm ² (0.11 in terms of surface occupancy), and the graft density of the bottle brush of Example 4 was 0.18 chains/nm ² (0.16 in terms of surface occupancy).
In addition, the "conversion" of Example 3 and Example 4 is 0.40 and 0.27, respectively, the degree of polymerization is 20 and 14, respectively, and σ _eff is 0.13 and 0.18, respectively.

Here, σ _eff represents the "effective graft density (the graft density on the outermost surface of the bottle brush)" and is defined by the following formula.

In the above formula, DP _n,graft represents the degree of polymerization, and ^a2 represents the monomer cross-sectional area, which is 0.86 ^nm2 in the case of HPA.

[Synthesis of P1]
The polymerization was carried out for 1.5 hours in an oil bath at 70°C in DMF under an argon atmosphere with a molar ratio of HPA/benzophenone acrylamide (BPA)/AIBN = (200-x)/x/0.2 (x is shown in Table 3). After the reaction, the molecular weight and molecular weight distribution were determined by DMF-based GPC measurement. The obtained polymer was purified by reprecipitation recovery using acetone. It was confirmed by ^1H NMR that the contents of HPA and BPA in the polymer chain were almost the same as the charging ratio. Table 3 shows the composition, abbreviation, number average molecular weight, and molecular weight dispersity of the polymerized polymers (Examples 5 to 7).

[Creation of cured film]
Ethanol solutions containing 3 mass% of P1 of Examples 5 to 7 and P2 (bottle brush) of Example 3 were prepared. Compositions were prepared using these and films were formed. Table 4 lists the contents of P1 and P2 in the compositions. For example, the composition of Example 8 means that the composition was prepared using P1 of Example 5 without using a bottle brush, i.e., an ethanol solution of P2 (i.e., simply using a 3 mass% ethanol solution of P1 of Example 5). The above is similar to Examples 9 and 10.

Example 11 means that a composition was prepared by mixing a 3 mass% solution of P1 from Example 5 with a 3 mass% solution of P2 (bottle brush) from Example 3 in a mass ratio of 1:1. The same applies to Examples 12 to 14.

These compositions were spin-coated onto a PET (polyethylene terephthalate) film (3000 rpm, 30 seconds). The spin-coated film was cured by irradiating it with ultraviolet light for 3 minutes. The cured film was immersed in ethanol and water and washed. It was confirmed that there was no change in the film thickness before and after washing. Table 4 shows the water contact angles of these cured films at 25°C.

[Immersion experiment in artificial seawater]
An immersion experiment was carried out using artificial seawater for breeding saltwater fish ("Instant Ocean", manufactured by Aquarium Systems Inc.).
The compositions of Examples 8 to 14 were spin-coated onto a PET film (diameter 2 cm ² ) and cured by UV irradiation. The films were then washed with ethanol and air-dried to obtain cured films. These were then placed in each well of a 24-well multi-well plate, and 1 ml of artificial seawater was added. The artificial seawater was replaced every 2 to 3 days.

(Film thickness measurement)
The thickness of the cured films was measured with an ellipsometer after immersion in seawater for 0 months (M0), 1 month (M1), 2 months (M2), and 3 months (M3). Five samples were prepared for each composition, and the film thickness was averaged. Figures 5 to 7 show the test results. No reduction in film thickness was observed for any of the cured films. Figures 5 to 7 show the change over time (horizontal axis, months) in film thickness (vertical axis, units of nm) of the cured films prepared using each composition.

[Biofouling prevention performance under salt water exposure environment (1)]
The biofouling inhibition performance was evaluated in a saline exposure environment using mouse fibroblast cells.
The PET film (2 cm ² ) laminated with the cured film was arranged on a Falcon (registered trademark) 24-well multiplate (1 well = ca 2 cm ² ) and sterilized with 70% ethanol aqueous solution. After sterilization, the sample was washed five times with PBS (Phosphate Buffered Saline). Then, mouse fibroblast cells (L929) were seeded at 50,000 cells/cm ² . After 24 hours, the sample was washed three times with PBS, and the adherent cells were fixed with 4% paraformaldehyde. The cell nuclei were fluorescently stained blue with DAPI (4',6-diamidino-2-phenylindole) and the cytoskeleton was fluorescently stained red with phalloidin, and observed under a fluorescent microscope. It was confirmed that the number of cells adhered to TCPS (tissue-culture-treated polystyrene) was almost equal to the number of cells seeded. Figures 8 to 10 show the test results. Figure 8 shows the number of adhered cells for each sample after 0 months of immersion, Figure 9 shows the number of adhered cells after 1 month of immersion, and Figure 10 shows the number of adhered cells after 2 months of immersion.

In the figure, the vertical axis "Adherent L929 cells/%" indicates the number of adherent cells as a percentage when the number of cells adhered to the PET film is taken as 100%.
8 to 10 show that the cured films of the compositions of the present invention, Examples 12 and 13, can maintain excellent biofouling inhibition performance for a long period of time even under exposure to saline water, compared with Examples 8 and 9. Note that "nd" indicates that no detection was detected.

[Biofouling prevention performance under salt water exposure environment (2)]
Cypris larvae were used to evaluate biofouling inhibition performance in a saline exposure environment. 100 cypris larvae were seeded on the PET film (4 x 4 ^cm2 ) coated with Examples 9 and 13, and the adhesion form and adhesion number were observed after 15 days. A glass plate was prepared as a reference sample. Figure 11 shows juvenile barnacles adhered to each surface. In Figure 11, barnacles were attached to the areas surrounded by white circles in the coatings of Examples 9 and 13. Note that many barnacles were attached to the glass substrate on the left of Figure 11. Barnacles were attached to the areas that look like white dots in the image. Note that white circles are not drawn on the glass substrate.

Figure 12 shows the percentage of attached juvenile barnacles (per 100 seeds). It was confirmed that attachment of juvenile barnacles was suppressed on the bottle brush-containing coating surface.

[Biofouling prevention performance in seawater exposure environment]
The biofouling control performance was evaluated in a seawater exposure environment using Cyprus larvae.

First, the bottle brush (P2) was prepared in the same manner as above. Table 5-1 shows the types of bottle brushes prepared. Of these, the bottle brush of Example 17 was used in the following experiments.

(Sample preparation)
An ethanol solution containing 3% by mass of each of P1 of Example 6 and P2 of Example 17 and a polyvinyl chloride (PVC) film (30×30×0.5 mm, transparent) were prepared.

Next, each sample was prepared as described in Table 5-2. First, for Examples 21 and 22, the above PVC film was used as is. For Examples 23 and 24, the P1 solution of Example 6 was used to spin coat (3000 rpm, 30 seconds) a PET (polyethylene terephthalate) film, and the film was then irradiated with ultraviolet light for 3 minutes to obtain a film. For Examples 25 and 26, a composition obtained by mixing the P1 solution of P6 and the P2 solution of Example 17 at a ratio of 1:1 (by volume) was used to spin coat (3000 rpm, 30 seconds) a PET (polyethylene terephthalate) film, and the film was then irradiated with ultraviolet light for 3 minutes to obtain a cured film. For Examples 27 and 28, a glass plate was used.

The cured film was then immersed in ethanol and water and washed. It was confirmed that there was no change in film thickness before and after washing. Table 5 summarizes the samples used.

(Preparation of test organisms)
We used the attachment stage larvae (cypris) of the Balanus fasciatus, which attach in large numbers to artificial structures in the inland bay area. Adult Balanus fasciatus (produced off the coast of Himeji) were maintained and raised by feeding them with Artemia in a circulating aquarium (water temperature 23±1°C). Nauplius larvae hatched from the adults were collected and transferred to a glass beaker filled with filtered seawater, and artificially obtained attachment stage larvae (cypris larvae) by feeding them with floating diatoms (Cheatoceros calcitrans) (Figure 13). The obtained cypris larvae were maintained by cold and dark treatment. These larvae were returned to room temperature before the test, and active swimming individuals were selected and used in the attachment test.

(Test Method)
The samples were placed on the bottom of a polypropylene container (111 x 81 x 46 mm), and seawater and attached larvae were added. Natural seawater collected from the coast of Himeji City was filtered through a mixed cellulose membrane with a pore size of 0.45 μm (Toyo Roshi Co., Ltd.) (salt concentration 2.86%, pH 8.06) for use. Approximately 100 larvae were placed in each test container and observed for 9 days at room temperature of around 25°C, under light (laboratory lighting) during the day and in the dark at night.

(result)
First, the results of Example 21 and the control of Example 22 (untreated vinyl chloride film) will be described.
In both Examples 21 and 22, the test larvae were actively swimming and engaged in exploratory behavior (one type of attachment behavior) toward the sample from the start of the test, but attachment to the sample was observed 7 days after the start of the test.
In Example 21, one juvenile barnacle was observed, and at the end of the test (nine days later), there were 18 juvenile barnacles and 10 metamorphosing barnacles, for a total of 28 barnacles (28.3%) attached.
In Example 22, after 7 days, 3 juvenile barnacles and 2 metamorphosing barnacles were found, and at the end of the test (after 9 days), there were 61 juvenile barnacles and 10 metamorphosing barnacles, totaling 71 (72.4%). The final attachment rate, calculated as the average of these, was 50.4%.
Figures 14 and 15 are images of the entire surface of the samples at the end of the tests in Examples 21 and 22. The black dots in the images are juvenile barnacles attached to the sample surface. The following table provides details of the results.

Next, the results of Examples 23 and 24 will be described.
In both Examples 23 and 24, the test larvae were actively swimming after the start of the test, but little exploration behavior toward the samples was observed until 7 days after the start of the test. Attachment was confirmed 9 days after the test ended. In Sample Example 23, there was one juvenile barnacle and two metamorphosing barnacles, and in Sample Example 24, there was one juvenile barnacle and one metamorphosing barnacle. The final attachment rate, calculated by averaging these, was 2.3%.
16 and 17 are images of the entire surface of the samples at the end of the test in Examples 23 and 24. The following table provides details of the results.

Next, the results of Examples 25 and 26 will be described.
In both Examples 25 and 26, the test larvae were actively swimming from the start of the test, but no exploration behavior or attachment to the sample was observed, and the final average attachment rate was 0%.
18 and 19 are images of the entire sample surface at the end of the test in Examples 25 and 26. The following table provides details of the results.

Next, the results of Examples 27 and 28 will be described.
This test area was established to confirm the morphology and behavior of the test larvae, as well as their attachment and metamorphosis processes. Attachment was observed five days after the start of the test, and gradually increased, with 106 and 102 juvenile barnacles observed at the end of the test. The final attachment rate, averaging these, was 97.2%. In the glass plate control area, no abnormalities were observed, particularly in the attachment, metamorphosis, or behavior of the cypris larvae, and the attachment rate was high at 97.2%, confirming that the cypris larvae were larvae with the ability to attach normally.
20 and 21 are images of the entire sample surface at the end of the test in Examples 27 and 28. The following table provides details of the results.

Figure 22 is a graph showing the number of cypris larvae attached to each sample. From the results in Figure 22, it was confirmed that the cured films of Examples 25 and 26 have excellent biofouling inhibition performance in a seawater environment.

[Long-term stability]
To predict the long-term stability of the cured film, we investigated the hydrolysis resistance of the polymer brush. In a saline exposure environment, the stability of the cured film may decrease due to the progress of hydrolysis of the polymer compound that constitutes the cured film. Here, for example, if the polymer brush has high hydrolysis resistance, it can be predicted that the cured film will have excellent long-term stability.

Synthesis of Methacrylate Macroinitiator (PBIME)
A methacrylate macroinitiator and a methacrylate bottle brush were synthesized according to the following scheme.

A toluene solution (50 mass%) containing BIEM (2-(2-bromoisobutyryloxy)ethyl methacrylate, 5.0 g, 17.9 mmol), cumyl dithiobenzoate (48.8 mg, 1.79×10 ⁻¹ mmol), and 2,2′-Azobis(isobutyronitrile) (AIBN) (5.88 mg, 3.58×10 ⁻² mmol) was prepared under an argon atmosphere and stirred in a 60° C. oil bath for 22 hours.
After the reaction, the molecular weight and molecular weight distribution were determined by DMF-based GPC measurement. The PMMA-equivalent Mn was 18,300 and PDI was 1.16. The polymerization rate was determined by NMR measurement and was 52% (polymerization degree 52). PBIEM was produced by reprecipitation recovery using methanol, a poor solvent (yield 2.61 g).

(Synthesis of methacrylate-based bottle brushes)
An anisole solution (31.58 g, 33 mass%) containing Poly(ethylene glycol) methyl ether methacrylate (PEGMA) (15.79 g, 31.6 mmol), macroinitiator (PBIEM) (Mn=18300, 0.2938 g, 1.05 mmol (bromine terminal)), dNbipy (4.4-dinonyl-2.2-dipyridyl, 0.8604 g, 2.1 mmol), Cu(I)Br (0.1611 g, 1.1 mmol), and Cu(II)Br ₂ (0.0502 g, 0.2246 mmol) was prepared in a glove box and stirred in a 65° oil bath for 40 minutes.

After polymerization, the molecular weight and molecular weight distribution were determined by DMF-based GPC (PMMA conversion). The conversion was determined by NMR. The results are shown in Table 10. The graft density was calculated to be 0.318 chains/ ^nm2 (surface occupancy rate: 0.92), which was confirmed to be in the density range of concentrated polymer brushes.
After polymerization, the bottle brush was purified by reprecipitation recovery with a hexane/diethyl ether = 70/30 mass/mass% solution. Table 10 shows the synthesis results. In Table 10, the polymerization degree was calculated from the conversion assuming the initiation efficiency to be 100%.

[Hydrolysis test]
The hydrolysis resistance of the bottle brush of Example 15 and the bottle brush of Example 29 was evaluated. First, 1M sodium hydroxide and 1M hydrochloric acid were prepared using heavy water for NMR. The bottle brush polymers of Example 15 and Example 29 represented by the following formula were dissolved (2.0 mass%) in each solution in Table 11. Then, NMR measurement was performed immediately (time 0 h), and the NMR tube was immersed in a water bath at 80 ° C., and after 3 hours (3 h) and 6 hours (6 h), the temperature was returned to room temperature, and NMR measurement was performed. In addition, the solution after 6 hours of heating was collected and GPC measurement was performed. The samples dissolved in 1M sodium hydroxide and 1M hydrochloric acid were neutralized before being used for GPC measurement.

(Confirmation of structural change by NMR measurement)
23 and 24 are NMR charts of polyHPA bottle brush (acrylamide type, Example 15) and polyPEGMA bottle brush (methacrylate type, Example 29) that were heat-treated in 1M sodium hydroxide solution. Almost no peak shift was observed in the polyHPA bottle brush (Example 15) (FIG. 23), but a peak shift was observed in the polyPEGMA bottle brush (Example 29) (FIG. 24, around 3.35 and 3.1 ppm).

Figures 25 and 26 are NMR charts of PolyHPA bottle brush (acrylamide type, Example 15) and PolyPEGMA bottle brush (methacrylate type, Example 29) that were heat-treated in 1M hydrochloric acid. A new peak appeared at about 3.7 ppm in the polyHPA bottle brush (Example 15), but otherwise almost no changes were observed (Figure 25). In contrast, a peak shift was observed in the polyPEGMA bottle brush (Example 29), similar to alkaline decomposition (Figure 26, around 3.1 ppm).

(Confirmation of molecular weight change by GPC measurement)
After heat treatment (hydrolysis reaction) in acid/alkali for 6 hours, GPC measurements were performed on the polyHPA bottle brush (acrylamide type, Example 15) and the polyPEGMA bottle brush (methacrylate type, Example 29). Figures 27 to 32 are GPC charts.

Figures 27 to 29 show the results for polyHPA bottle brush (Example 15). Figure 27 shows the result after 6 hours in heavy water (in the figure, "D2O" stands for heavy water), Figure 28 shows the result after 6 hours in 1M sodium hydroxide solution, and Figure 29 shows the result after 6 hours in 1M hydrochloric acid. From the above results, in either case of acid or alkali treatment, the peak (top) hardly shifted at all. This result was almost consistent with ^1H NMR.

Figures 30 to 32 show the results for polyPEGMA bottle brush (Example 29). Figure 30 shows the result after 6 hours in heavy water, Figure 31 shows the result after 6 hours in 1M sodium hydroxide solution, and Figure 32 shows the result after 6 hours in 1M hydrochloric acid. From the above results, it was found that the peak was significantly shifted to the lower molecular weight side in the case of alkali treatment. It is considered that the molecular weight was reduced because the carbonyl groups of the macroinitiator and the PEGMA monomer were hydrolyzed in the alkali treatment, and the graft polymer itself or the side chains (PEG) of the PEGMA were liberated.
From the above results, it was confirmed that the acrylamide-based polymers have superior hydrolysis resistance compared to the (methyl)acrylate-based polymers.

[Synthesis of DOPA Monomer]
Dopamine hydrochloride (8.0 g, 42.2 mmol) and triethylamine (4.3 g, 42.5 mmol) were dissolved in methanol and stirred in ice. To this solution, a tetrahydrofuran solution (4 ml) containing methacryloyl chloride (5.29 g, 50.8 mmol) and a methanol solution containing triethylamine were alternately dropped (adjusted so that the pH of the solution was 9.5 or higher). After reacting for 18 hours at room temperature, the solvent was removed by an evaporator. 300 ml of ethylacetate was added thereto, washed twice each with 1M HCl and saline, dehydrated with Na ₂ SO ₄ , and then ethylacetate was removed by an evaporator. The resulting impurities were purified by recrystallization to obtain the target compound, N-(3,4-dihydroxyphenethyl) methacrylamide (DOPA monomer) (yield: 3.4 g, 26%).

[Synthesis of poly(HPA-BPA-DOPA)]
The synthesized DOPA monomer was used to synthesize "poly(HPA-BPA-DOPA)".
HPA, BPA, and DOPA monomers were polymerized in an argon atmosphere in a DMF oil bath at 70°C for 3 hours in a molar ratio of HPA/BPA/DOPA = 85/5/10. After the reaction, the PMMA-equivalent molecular weight and molecular weight distribution were determined by DMF-based GPC measurement (Mn = 89,000, PDI = 2.2). The resulting polymer was purified by reprecipitation recovery using acetone. The structure of poly(HPA-BPA-DOPA) is as shown in the following formula, and the numbers to the right of each unit indicate the mol% of each unit.

[Evaluation of adhesion to silicon substrate]
An ethanol solution containing 3% by mass of a binary copolymer (HPA/BPA=95/5) (polymer of Example 6) or a ternary copolymer (HPA/BPA/DOPA=85/5/10) was spin-coated onto a silicon substrate and an aluminum plate (rotation speed: 3000 rpm, 30 seconds). Then, ultraviolet light was irradiated for 4 minutes to form a crosslinked film. Then, the film was immersed in ethanol for 1 hour and washed.

Figure 33 is a photograph showing the state of a cured film made using a binary copolymer (HPA/BPA = 95/5), and Figure 34 is a photograph showing the state of a cured film made using a ternary copolymer (HPA/BPA/DOPA = 85/5/10) before and after cleaning. There was no change in either cured film before and after cleaning. Therefore, it can be seen that the coating film made from the above copolymer has excellent adhesion to silicon substrates.

Figure 35 shows a binary copolymer (HPA/BPA = 95/5), and Figure 36 shows a ternary copolymer (HPA/BPA/DOPA = 85/5/10) used to form a film on an aluminum substrate, and then the hardened film was washed. In both cases, a hardened film with excellent surface quality was obtained.

Table 11 below shows the film thickness of the crosslinked film on the silicon substrate before and after cleaning, measured using an ellipsometer. As a result, there was almost no change in film thickness before and after cleaning for any of the copolymers.

In Table 11, the film thickness is in nm.

Next, the crosslinked film on the silicon substrate was immersed in ethanol and ultrasonically cleaned. It was confirmed that the crosslinked film of the binary copolymer (HPA/BPA = 95/5) began to peel off from the substrate one minute after ultrasonic cleaning (Figure 37). On the other hand, no peeling was observed for the ternary copolymer (HPA/BPA/DOPA = 85/5/10) (Figure 38). This confirmed that copolymers using DOPA are more stable when applied to the surface of substrates that do not contain hydrocarbons (such as metal substrates).

[Cell adhesion test]
An ethanol solution containing only the terpolymer or the terpolymer and 3% by weight of the bottle brush of Example 17 was spin-coated on an aluminum plate and a PET film (rotation speed: 3000 rpm, 30 seconds), followed by UV irradiation (4 minutes) to form a crosslinked film.

Each sample (1 x 1 ^cm2 ) was arranged on a "Falcon" 24-well multiplate (1 well = ca 2 ^cm2 ) and sterilized with 70% ethanol aqueous solution. Next, mouse fibroblasts (L929) were seeded on the samples at 50,000 cells/ ^cm2 . After 24 hours, the samples were washed three times with PBS (phosphate-buffered saline), and the adherent cells were fixed with 4% paraformaldehyde. The cell nuclei were fluorescently stained blue with DAPI (4',6-Diamidino-2-phenylindole), and the cytoskeleton was fluorescently stained red with phalloidin, and observed under a fluorescent microscope. It was confirmed that the number of cells adhered to TCPS (Tissue-culture-treated polystyrene) was almost the same as the number seeded. The results are shown in Figure 39.

In FIG. 39, "TCPS" indicates the number of cells adhered to a TCPS substrate. "PET" indicates the number of cells adhered to a polyethylene terephthalate (PET) substrate. "BB mix on PET" indicates the number of cells adhered to a cured film formed on a PET sheet using an ethanol solution containing 3% by mass of the terpolymer and the bottle brush of Example 17. "Al" indicates the number of cells adhered to an Al substrate. "Terpolymer" indicates the number of cells adhered to a terpolymer. "BB mix on Al Plate" indicates the number of cells adhered to a cured film formed on an Al substrate using an ethanol solution containing 3% by mass of the terpolymer and the bottle brush of Example 17. It was confirmed that the crosslinked film containing the bottle brush significantly suppressed cell adhesion compared to the sample not containing the bottle brush.

[Cypris larvae attachment test]
Various polymers were applied and fixed to a polyvinyl chloride (PVC) film (30 x 30 x 0.5 mm, transparent) using the same method as above (spin coating, UV irradiation). The crosslinked film was immersed in ethanol and water and washed. Next, the effect of each surface (Table 12) on inhibiting adhesion of cypris larvae was examined using the attachment stage larvae (cypris larvae) of the barnacle Balanus fasciatus. The bottle brush used in Example 17 was used. In addition, the test was performed with N=2 for each sample.

(Test organism (attached stage larvae of the striped barnacle))
We used the attachment stage larvae (cypris) of the Balanus fasciatus, which attach in large numbers to artificial structures in the inland bay area. Adult Balanus fasciatus (produced off the coast of Himeji) were maintained and raised by feeding them with Artemia in a circulating aquarium (water temperature 23±1°C). Nauplius larvae hatched from the adults were collected and transferred to a glass beaker filled with filtered seawater, and artificially obtained attachment stage larvae (cypris larvae) by feeding them with the floating diatom Cheatoceros calcitrans. The obtained cypris larvae were maintained by cold and dark treatment. These larvae were returned to room temperature before the test, and active swimming individuals were selected and used in the attachment test.

(Test method and test conditions)
The sample was placed on the bottom of a polypropylene container (111 x 81 x 46 mm), and seawater and the attached larvae were added. The seawater was natural seawater collected from the coast of Himeji City, filtered through a mixed cellulose membrane with a pore size of 0.45 μm (Toyo Roshi Co., Ltd.) (salt concentration 2.86%, pH 8.06). Approximately 100 larvae were placed in each test container, and observation and attachment tests were performed for 9 days at room temperature of around 25°C, under light (laboratory lighting) during the day and in the dark at night.

(Control (untreated polyvinyl chloride film))
In both Example 30 and Example 31, the test larvae were actively swimming and searching for the sample (one of the attachment behaviors) after the start of the test. Attachment to the sample was observed 3 or 7 days after the start of the test. In Example 30, 5 juvenile barnacles were confirmed after 7 days, and 13 juvenile barnacles (13.0%) were attached at the end of the test (9 days later). In Sample Example 31, 1 juvenile barnacle and 2 metamorphosing barnacles were confirmed after 3 days, and 17 juvenile barnacles and 1 metamorphosing barnacle were confirmed at the end of the test (9 days later), for a total of 18 barnacles (19.0%). The final attachment rate, averaging these, was 16.0%. In addition, 4 thoracic limbs protruded and no reaction were observed in Sample 1-1, and 13 in Sample 1-2. Attachment to the test container was confirmed at the end of the test (9 days later). Table 13 shows the results, and Figure 40 is a photograph (whole sample) of juvenile barnacles attached to the sample surface at the end of the test.

(HPA/BPA/DOPA=85/5/10)
In both Examples 32 and 33, the test larvae were actively swimming after the start of the test, but almost no exploration behavior was observed on the sample until 3 days after the start of the test. Attachment was confirmed after 5 days, and after 9 days for Examples 32 and 33. At the end of the test, Sample Example 32 had 21 juvenile barnacles and 2 individuals undergoing metamorphosis, while Sample Example 33 had 5 juvenile barnacles and 1 individual undergoing metamorphosis. The final attachment rate, averaging these, was 14.4%. In addition, 4 individuals had thoracic limb protrusion and no reaction in Sample 2-2, and 2 individuals in 2-2. Attachment to the test container was confirmed at the end of the test (after 9 days). Table 14 shows the results, and Figure 41 is a photograph of juvenile barnacles (whole sample) attached to the sample surface at the end of the test.

(HPA/BPA/DOPA-Bottle Brush)
In both Examples 34 and 35, the test larvae were actively swimming after the start of the test, but no exploration behavior or attachment to the samples was observed, and the final average attachment rate was 0%. Individuals with protruding thoracic limbs appeared after 5 days, and at the end of the test, there were 4 individuals in Sample 3-1 and 3 individuals in Sample 3-2. Attachment to the test container was confirmed after 7 days. Table 15 shows the results, and Figure 42 is a photograph of juvenile barnacles (whole sample) attached to the sample surface at the end of the test.

(Glass plate control)
This test area was established to confirm the morphology and behavior of the test larvae, as well as the attachment and metamorphosis process (Examples 36 and 37). Attachment was observed one day after the start of the test, and gradually increased, with 36 and 38 juvenile barnacles observed at the end of the test. The final attachment rate, averaging these, was 34.5%. Five and six juvenile barnacles showed protruding thoracic limbs and were unresponsive. Attachment to the test container was confirmed after 7 days. Table 16 shows the results, and Figure 43 is a photograph of juvenile barnacles (whole sample) attached to the sample surface at the end of the test.

Figure 44 shows the number of attached cypris larvae 9 days after the attachment test. It was found that the cured films of Examples 34 and 35 inhibited the attachment of cypris larvae. This confirmed that the bottle brush polymer was effective in preventing the attachment of cypris larvae even when a terpolymer containing DOPA was used.

10: Ship 11: Substrate 12: Primer layer 13: Cured film 20: Underwater structure 21: Float 22: Curtain 23: Weight 24: Anchor 25: Anchor rope 26: Buoy 40: Medical device 41: Substrate 42: Cured film 43: Recess

Claims (16)

a first polymer compound having only a repeating unit represented by the following formula 1 and a repeating unit represented by the following formula 2 as repeating units;
a second polymer compound having a repeating unit represented by the following formula 3, in which the molar ratio of the repeating unit represented by the formula 3 to all repeating units is 0.3 to 1.0 ;
A composition comprising :

(In formulas 1 to 3, R ¹ to R ⁴ each independently represent a hydrogen atom or an alkyl group, Z ¹ and Z ³ each independently represent a group having a hydrophilic group which may be the same or different, Z ² represents a photoradical generating group, L ¹ represents a group represented by formula 4a or formula 4b, L ² represents a single bond or a divalent group, R ⁵ represents a hydrogen atom, a halogen atom or a monovalent substituent, n represents an integer of 2 or more, and in formulas 4a and 4b, * represents a bonding position.) The composition according to claim 1, wherein the content of the repeating unit represented by formula 2 relative to the total repeating units of the first polymer compound is 10 mol % or less. The composition according to claim 1 or 2, wherein Z ¹ is a group represented by the following formula A:
(In formula A, L ^A represents a single bond or a p+q+1 valent group, L ^B represents a single bond or a divalent group, Y represents at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, a sulfonic acid group, a phosphonic acid group, an alkoxy group, and a zwitterionic group, p represents an integer of 1 or more, R ⁶ represents a hydrogen atom, a halogen atom, or a monovalent organic group, q represents an integer of 0 or more, * represents a bonding position, and when L ^A is a single bond or a divalent group, p is 1 and q is 0.) The composition according to any one of claims 1 to 3, wherein the hydrophilic group is a hydroxy group. The composition according to any one of claims 1 to 4, wherein the photoradical generating group is a group represented by the following formula g1:
(In formula g1, ^R7 represents an arylene group having 6 to 30 carbon atoms which may have a substituent, ^R8 represents an aryl group having 6 to 30 carbon atoms which may have a substituent, and * represents a bonding position.) The composition according to any one of claims 1 to 5, wherein the photoradical generating group is a group represented by the following formula g2:
(In formula g2, * represents a bonding position.)
The second polymer compound has, as a repeating unit,
or having only a repeating unit represented by the following formula 3:
The composition according to any one of claims 1 to 6, comprising only a repeating unit represented by the following formula 3 and a repeating unit represented by the following formula b-1:
(In Formula 3 and Formula b-1, R ³ ~R ⁴ each independently represents a hydrogen atom or an alkyl group; Z ³ represents a group having a hydrophilic group, L ¹ represents a group represented by formula 4a or 4b; L ² represents a single bond or a divalent group; R ⁵ represents a hydrogen atom, a halogen atom, or a monovalent substituent, X represents a halogen atom, n represents an integer of 2 or more, and in Formula 4a and Formula 4b, * represents a bonding position. The composition according to any one of claims 1 to 7, wherein the solvent is at least one selected from the group consisting of water, methanol, ethanol, and isopropanol. A cured film obtained by curing the composition according to any one of claims 1 to 8 . A laminate comprising a substrate and the cured film according to claim 9 formed on the substrate. A ship having the cured film according to claim 9 . An underwater structure having the cured film according to claim 9 . 13. The underwater structure according to claim 12 , which is a fouling prevention membrane. A medical device having the cured film of claim 9 . The medical device according to claim 14, which is one type selected from the group consisting of a cell culture vessel, a cell culture sheet, a cell capture filter, a vial, a plastic-coated vial, a syringe, a plastic-coated syringe, an ampoule, a plastic-coated ampoule, a cartridge, a bottle, a plastic-coated bottle, a pouch, a pump, a sprayer, a stopper, a plunger, a cap, a lid, a needle, a stent, a catheter, an implant, a contact lens, a microchannel chip, a drug delivery system material, an artificial blood vessel, an artificial organ, a hemodialysis membrane, a guard wire, a blood filter, a blood storage pack, an endoscope, a biochip , a glycosynthesis device, a molding auxiliary material, and a packaging material. A microchannel chip comprising: a substrate; and the cured film according to claim 9 disposed on the substrate.