DE112018002879T5 - METHOD FOR FORMING A POLYMER BRUSH LAYER - Google Patents

Abstract

The present invention provides a method of forming a polymer brush layer on a surface of a substrate, the method comprising the steps of: forming a layer on the substrate, the layer comprising a solution or dispersion of a monomer mixed or dispersed in a non-volatile solvent is, is formed; and polymerizing the monomer contained in the solution or the dispersion in the non-volatile solvent to form a polymer brush layer having a thickness of 20 µm or less on at least a part of the surface of the substrate.

Description

TECHNICAL AREA

The present invention relates to a method of forming a polymer brush layer by which a polymer brush layer having a low dynamic friction coefficient can be successfully formed.

STATE OF THE ART

It is well known that sliding surfaces with a polymer brush layer have a low coefficient of friction. For example, Patent Document 1 discloses a sliding structure that includes a block with a polymer brush coating on a DLC-Si coating and a ring with a similar polymer brush coating.

In Patent Document 2, a detailed study of a sliding mechanism between polymer brush layers is performed using an atomic force microscope, and the technique disclosed therein enables micrometer sliding between such polymer brush layers that an atomic force microscope can measure.

RELATED DOCUMENTS OF THE PRIOR ART

Patent Document

• Patent document 1: JP-A 2012-56165
• Patent document 2: JP-A 2006-316169

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

Unfortunately, the techniques of the patent documents 1 and 2 due to the limited materials that can be used as substrates on which polymer brush layers are to be formed and the considerably high installation costs, this is not practical. Another problem with these techniques is the difficulty in forming a polymer brush layer with an area large enough for practical use as a sliding mechanism.

In response to the above-mentioned problems, it is an object of the present invention to provide a polymer brush layer forming method by which a polymer brush layer having a low dynamic friction coefficient can be successfully formed.

MEANS TO SOLVE THE PROBLEMS

As a result of intensive studies to achieve the above object, the inventors of the present invention have found that a polymer brush layer having a low dynamic coefficient of friction can be successfully formed by a solution or dispersion of a monomer mixed or dispersed in a non-volatile solvent is used, and the monomer contained in the solution or the dispersion is polymerized in the non-volatile solvent on a substrate. This finding has led to the completion of the present invention.

• Bilden einer Schicht auf dem Substrat, wobei die Schicht aus einer Lösung oder Dispersion eines Monomers, das in einem nichtflüchtigen Lösungsmittel gemischt oder dispergiert ist, gebildet wird;
• und Polymerisieren des in der Lösung oder der Dispersion enthaltenen Monomers in dem nichtflüchtigen Lösungsmittel, um eine Polymerbürstenschicht mit einer Dicke von 20 µm oder weniger auf mindestens einem Teil der Oberfläche des Substrats zu bilden.

In particular, the first aspect of the present invention provides a method of forming a polymer brush layer on a surface of a substrate, the method comprising the following steps:

• Forming a layer on the substrate, the layer being formed from a solution or dispersion of a monomer mixed or dispersed in a non-volatile solvent;
• and polymerizing the monomer contained in the solution or the dispersion in the non-volatile solvent to form a polymer brush layer having a thickness of 20 µm or less on at least a part of the surface of the substrate.

• Ermöglichen, dass eine Lösung oder Dispersion eines Monomers, das in einem nichtflüchtigen Lösungsmittel gemischt oder dispergiert ist, in den kontinuierlichen porösen Körper oder den röhrenförmigen Körper eindringt; und
• Polymerisieren des Monomers, das in der Lösung oder Dispersion enthalten ist, in dem nichtflüchtigen Lösungsmittel, um eine Polymerbürstenschicht auf mindestens einem Teil der Innenflächen der Poren des kontinuierlichen porösen Körpers zu bilden, oder um eine Polymerbürstenschicht auf mindestens einem Teil der Innenfläche des röhrenförmigen Körpers zu bilden.

The second aspect of the present invention provides a method of forming a polymer brush layer on the inner surfaces of pores of a continuous porous body or a method of forming a polymer brush layer on the inner surface of a tubular body, the methods comprising the steps of:

• Allowing a solution or dispersion of a monomer mixed or dispersed in a non-volatile solvent to enter the continuous porous body or the tubular body; and
• Polymerizing the monomer contained in the solution or dispersion in the non-volatile solvent to form a polymer brush layer on at least a portion of the inner surfaces of the pores of the continuous porous body or a polymer brush layer on at least a portion of the inner surface of the tubular body form.

EFFECTS OF THE INVENTION

The first aspect of the present invention can provide a polymer brush layer forming method by which a polymer brush layer having a low dynamic coefficient of friction can be successfully formed.

According to the second aspect of the present invention, a polymer brush layer having a low dynamic friction coefficient can be successfully formed inside a continuous porous body or a tubular body, and as a result, a desired function can be given to the inside of the continuous porous body or the inside of the tubular body ,

list of figures

• 1 12 is a schematic view illustrating a polymer brush layer formed by a method according to the first embodiment of the present invention.
• 2 12 is a schematic view illustrating a polymer brush layer formed by a method according to the second embodiment of the present invention.

DESCRIPTION OF EMBODIMENTS

<First embodiment>

The following description describes the first embodiment with reference to these figures.

1 12 is a schematic view illustrating a polymer brush layer formed by a method according to the first embodiment of the present invention. In 1 is a polymer brush layer 20 according to the first embodiment of the present invention on a substrate 10 educated.

The substrate 10 is not particularly limited. Iron or iron alloy substrates such as cast iron substrates, steel substrates, stainless steel substrates and the like, non-iron or non-iron alloy substrates such as aluminum substrates, copper substrates and the like, and non-metal substrates such as silicon wafer substrates, glass substrates, quartz substrates and the like can be used. Other preferred examples include cleavable minerals such as mica flakes and the like, flat substrates comprising a thin polymer coating with a reactive substituent group (e.g. hydroxyl group) on the surface, and the like.

The polymer brush layer 20 is formed by the formation method according to the first embodiment, and is specifically composed of a plurality of polymer graft chains that are covalent on the substrate 10 immobilized and swollen with a liquid substance, as in 1 shown, formed.

• Bilden einer Schicht auf dem Substrat 10, wobei die Schicht aus einer Lösung oder Dispersion eines Monomers, das in einem nichtflüchtigen Lösungsmittel gemischt oder dispergiert ist, gebildet wird; und
• Polymerisieren des in der Lösung oder der Dispersion enthaltenen Monomers in dem nichtflüchtigen Lösungsmittel auf dem Substrat 10, um die Polymerbürstenschicht 20 mit einer Dicke von 20 um oder weniger auf mindestens einem Teil der Oberfläche des Substrats 10 zu bilden.

The method of forming a polymer brush layer according to the first embodiment is a method of forming the polymer brush layer 20 on the surface 10 , as in 1 and includes the following steps:

• Form a layer on the substrate 10 the layer being formed from a solution or dispersion of a monomer mixed or dispersed in a non-volatile solvent; and
• Polymerizing the monomer contained in the solution or the dispersion in the non-volatile solvent on the substrate 10 to the polymer brush layer 20 with a thickness of 20 µm or less on at least a part of the surface of the substrate 10 to build.

In the first embodiment, the polymer brush layer 20 to form the monomer to form the polymer graft chains that make up the polymer brush layer 20 constitute, polymerized in the non-volatile solvent, while the monomer is mixed or dispersed in the non-volatile solvent. This allows the monomer to polymerize more stably, resulting in longer polymer brush lengths of the polymer graft chains (in other words, a higher absolute average molecular weight of the polymer graft chains) in the polymer brush layer 20 leads. Due to the longer polymer brush lengths of the polymer graft chains, the polymer brush layer has 20 , which consists of the polymer graft chains, has a low dynamic coefficient of friction. Especially when the polymer brush layer 20 When a sliding surface is used, the longer polymer brush lengths of the polymer graft chains provide a higher buffering effect on a sliding counterpart, which leads to low friction properties and high friction resistance. This effect is particularly advantageous if the sliding counterpart has a low surface smoothness.

According to the first embodiment, since the monomer is polymerized in the non-volatile solvent, the thickness of the resulting polymer brush layer can be 20 by adjusting the content of the monomer contained in the solution or the dispersion before the polymerization, the thickness of the layer of the solvent or the dispersion which is on the substrate 10 is formed before the polymerization, and the polymerization conditions are controlled. In particular, the thin polymer brush layer 20 be successfully formed by adjusting these factors. In particular, the polymer brush layer 20 as thin as 20 µm or less, preferably 15 µm or less, more preferably 10 µm or less, more preferably 1 µm or less. The lower limit thereof is typically 10 nm or more.

When the monomer is polymerized in a volatile solvent instead of the non-volatile solvent, a solution is prepared by dissolving the monomer in the volatile solvent, and a large amount of the solution must be used so that the polymerization reaction can continue while the substrate 10 is immersed in the solution. In such a process, it is difficult to control the polymerization reaction, resulting in difficulty in precisely controlling the thickness of the resulting polymer brush layer 20 leads. In addition, in the case of polymerization of the monomer in the volatile solvent, a convection flow may arise during the polymerization reaction because the polymerization is carried out in a large amount of the solution. Accordingly, when polymer graft chains with long polymer brush lengths (high molecular weight) are formed, the polymer graft chains formed can have a wide polymer brush length distribution (wide molecular weight distribution). Therefore the desired friction properties could not be achieved.

In contrast, the formation method according to the first embodiment can effectively solve the above problems, and therefore enables formation of polymer graft chains with a high molecular weight and a narrow molecular weight distribution. Since the polymer graft chains can be formed with a high molecular weight and a narrow molecular weight distribution, the resulting polymer brush layer has 20 a further reduced dynamic coefficient of friction during sliding. In particular, the narrow molecular weight distribution of the polymer graft chains shows that the polymer graft chains have essentially the same polymer brush length. This feature is more effective in reducing the dynamic coefficient of friction. The other problem of polymerizing the monomer in the volatile solvent is that the thickness of the resulting polymer brush layer 20 is difficult to control because the polymerization should be carried out in a large amount of solution, and therefore the thin polymer brush layer 20 cannot be successfully formed. The formation method according to the first embodiment can adequately solve this problem and successfully enables the thin polymer brush layer to be formed precisely 20 with a thickness of 20 µm or less.

With a view to further reducing the dynamic coefficient of friction during sliding, the number average molecular weight (Mn) of the polymer graft chains comprising the polymer brush layer is 20 constitute, preferably 500 to 10,000,000, more preferably 200,000 to 10,000,000. With a view to further reducing the dynamic coefficient of friction during sliding, this is weight average molecular weight (Mw) of the polymer graft chains forming the polymer brush layer 20 constitute, preferably 500 to 10,000,000, more preferably 200,000 to 10,000,000. With a view to further reducing the dynamic coefficient of friction during sliding, there is also the molecular weight distribution (Mw / Mn) of the polymer graft chains that make up the polymer brush layer 20 , preferably close to 1, desirably 1.5 or less, more preferably 1.3 or less, more preferably 1.2 or less, particularly preferably 1.01 to 1.15.

The number average molecular weight (Mn), the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of the polymer graft chains comprising the polymer brush layer 20 can be determined, for example, by a method that includes: cutting out some polymer graft chains from the substrate 10 by hydrofluoric acid treatment; Measuring the cut polymer graft chains by gel permeation chromatography; and calculating the number average molecular weight (Mn), the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) using a polyethylene oxide calibration curve. Another method can be used in which, assuming that the molecular weight of the free polymers produced during the polymerization is the same molecular weight as the molecular weight of those in the substrate 10 introduced polymer graft chains, the free polymers are measured by gel permeation chromatography, and the number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) thereof are calculated using a polyethylene oxide calibration curve, and without further calculation as those of the polymer graft chains can be considered.

The area coverage relative to the area of the surface of the substrate 10 (the occupancy in the cross-sectional area of the polymer) or, in other words, the graft density of the polymer graft chains is preferably 10% or more, more preferably 15% or more, even more preferably 20% or more. The graft density can be determined from the absolute value of the weight average molecular weight (Mw) of the graft chains, the amount of the grafted polymer and the surface of the substrate 10 be calculated. The surface coverage in the polymer brush layer 20 can be calculated by determining the cross-sectional area from the length of the repeating units of the polymer in the fully stretched state and the bulk density of the polymer and multiplying the cross-sectional area by the graft density. The area coverage gives the percentage of grafting points (first monomers) that make up the surface of the substrate 10 on (the chains cannot be grafted beyond the maximum fill density of 100%).

The monomer used to form the polymer graft chains that make up the polymer brush layer 20 are not particularly limited. Preferably at least one monomer with an ionic dissociable group (in particular a monomer with an ionic dissociable group and a reactive double bond group) is used, since such a monomer affects the coefficient of friction of the surface of the polymer brush layer 20 can further reduce, and is less volatile, and therefore can prevent compositional variations during the formation of the polymer brush layer, thereby ensuring that the resulting polymer brush layer 20 has a desired composition. As a result of using the monomer having an ionic dissociable group, the polymer graft chains generated by the polymerization have the ionic dissociable group. In addition to the monomer having an ionic dissociable group, a monomer copolymerizable with the previous monomer can be used as the monomer to form the polymer graft chains. The monomer having an ionic dissociable group is not particularly limited. Examples thereof include compounds represented by the following general formula (1) and the like.

[In the general formula (1), m represents an integer from 1 to 10, n represents an integer from 1 to 5, R ^{1 represents} a hydrogen atom or a C ₁ to C ₃ alkyl group, and R ² represents R ³ and R ^{4 represent} a C ₁ to C ₅ alkyl group. R ² , R ³ and R ⁴ may contain one or more heteroatoms selected from an oxygen atom, a sulfur atom and a fluorine atom, and two or more of R ² , R ³ and R ⁴ can be linked to form a ring structure. Y represents a monovalent anion.]

The monovalent anion Y in the general formula (1) is not particularly limited, and any of the following anions can be used: BF ₄ ^- , PF ₆ ^- , AsF ₆ ^- , SbF ₆ ^- , AlCl ₄ ^- , NbF ₆ ^- , HSO ₄ ^- , ClO ₄ ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , CF ₃ CO ₂ ^- , (CF ₃ SO ₂ ) ₂ N ^- , Cl ^- , Br ^- , I ^- and the like. Regarding the degree of dissociation in a liquid substance caused by swelling of the graft polymer with the liquid substance, safety, mobility and the like are BF ₄ ^- , PF ₆ ^- , (CF ₃ SO ₂ ) ₂ N ^- , CF ₃ SO ₃ ^- and CF ₃ CO ₂ ^- particularly suitable.

Among the compounds represented by the general formula (1), the compounds represented by the general formulas (2) to (9) are particularly suitably used for a greater effect in reducing the coefficient of friction of the sliding surface , Each of these compounds can be used individually or in combination.

[In the general formulas (2) to (9) are m, R ¹ , R ² and Y the same as those defined in the general formula (1).]

The non-volatile solvent can be any solvent with a vapor pressure at 25 ° C of less than 10 Pa. Solvents with a vapor pressure at 25 ° C. of less than 1 Pa are preferred. An ionic liquid is preferred in view of the excellent non-volatility and high ability to dissolve various monomers.

In the first embodiment, it is particularly preferred that the monomer having an ionic dissociable group as the monomer for forming the polymer brush layer 20 is used and the ionic liquid is used as the non-volatile solvent (namely, the combination of the monomer with an ionic dissociable group and the ionic liquid is particularly advantageous). The use of the ionic liquid in the polymerization system can relatively increase the viscosity of the solution at an initial stage of the polymerization. This can lead to difficulties in forming the desired polymer graft chains. However, due to their high compatibility, the combination of the monomer with an ionic dissociable group and the ionic liquid enables the polymerization reaction of the monomer with an ionic dissociable group to proceed successfully. Accordingly, the desired polymer graft chains can be formed relatively easily. As a result, the polymer brush layer having a low dynamic friction coefficient can be suitably formed with high productivity.

In the first embodiment, the monomer is polymerized to form the polymer graft chains in the non-volatile solvent while the monomer is mixed or dispersed in the non-volatile solvent. The non-volatile solvent used in the polymerization is preferably left without being removed. In this case, in the polymer brush layer ultimately obtained 20 the polymer graft chains are swollen with the non-volatile solvent used in the polymerization. In particular, in such a process, by selecting a non-volatile solvent that is very compatible with the monomer to form the polymer graft chains and the polymerized polymer graft chains, the amount of the non-volatile solvent to be used can be reduced to the amount required to form the polymer brush layer 20 is required. As a result, the solvent removal step can be omitted, thereby improving productivity. From this point of view, when the monomer having an ionic dissociable group is used as the monomer for forming the polymer graft chains, the ionic liquid is preferably used as the non-volatile solvent in consideration of mutual compatibility.

For example, the ionic liquid is preferably an ionic liquid represented by the general formula (10) below and has a melting point of 50 ° C or less, preferably 25 ° C or less.

[In the general formula (10), R ³ to R ⁶ , which may be the same or different, represent a C ₁ to Cs alkyl group or an alkoxyalkyl group represented by R'-O- (CH ₂ ) _n - (wherein R 'represents a methyl group or an ethyl group and n is an integer from 1 to 4), and any two of R ³ , R ⁹ , R ⁵ and R ^{6 may form} a ring, provided that at least one of R ³ to R ^{6 is} the alkoxyalkyl group. X is a nitrogen atom or a phosphorus atom and Y is a monovalent anion.]

Examples of the C ₁ to Cs alkyl group include a methyl group, an ethyl group, a propyl group, a 2-propyl group, a butyl group, a pentyl group and the like. Examples of the alkoxyalkyl group represented by R'-O- (CH ₂ ) _n - include a methoxymethyl or ethoxymethyl group, a methoxyethyl or ethoxyethyl group, a methoxypropyl or ethoxypropyl group, a methoxybutyl or ethoxybutyl group and the like.

Examples of compounds in which two of R ³ , R ⁴ , R ⁵ and R ^{6 form} a ring include quaternary ammonium salts with an aziridine ring, an azetidine ring, a pyrrolidine ring, a piperidine ring or the like (where X is a nitrogen atom); and quaternary phosphonium salts with a pentamethylene phosphine (phosphorinane) or the like (where X is a phosphorus atom).

Quaternary ammonium salts which have a methoxyethyl group as at least one substituent are particularly suitable, where R 'is a methyl group and n is 2.

Quaternary ammonium salts represented by the general formula (11) and having a methyl group, two ethyl groups and an alkoxyethyl group are also suitably used.

[In the general formula (11), R 'represents a methyl group or an ethyl group, X is a nitrogen atom or a phosphorus atom, and Y represents a monovalent anion. Me represents a methyl group and Et represents an ethyl group.]

The monovalent anion Y in general formulas (10) and (11) is not particularly limited, and any of the following anions can be used: BF ₄ ^- , PF ₆ ^- , AsF ₆ ^- , SbF ₆ ^- , AlCl ₄ ^- , NbF ₆ ^- , HSO ₄ ^- , ClO ₄ ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , CF ₃ CO ₂ ^- , (CF ₃ SO ₂ ) ₂ N ^- , Cl ^- , Br ^- , I ^- and the like. BF ₄ ^- , PF ₆ ^- , (CF ₃ SO ₂ ) ₂ N ^- , CF ₃ SO ₃ ^- and CF ₃ CO ₂ ^{- are} particularly suitable with regard to the degree of dissociation in a non-aqueous organic solvent, the safety, mobility and the like ,

Specific examples of quaternary ammonium salts and quaternary phosphonium salts which are preferably used among the quaternary salts represented by the general formulas (10) and (11) include the compounds shown below ( 12 ) to (20) (where Me represents a methyl group and Et represents an ethyl group). In particular, the quaternary ammonium salts of formulas (12) and (17) are more preferably used to obtain an energy storage device with excellent properties at low temperatures and the like. In particular, the quaternary ammonium salt of the formula (17) is preferred because it has a low viscosity and can therefore further reduce the dynamic coefficient of friction during sliding.

Ionic liquids other than the compounds represented by the general formula (10) can be used. Examples of such ionic liquids include ionic liquids containing an imidazolium ion represented by the general formula (21), ionic liquids containing other aromatic cations represented by the formulas (22) to (27), and the same. Examples of counter anions for the ionic liquids containing an imidazolium ion and for the ionic liquids containing other aromatic cations include the same monovalent anions as those of the compounds represented by the general formulas (10) and (11).

[In the general formula (21), R ^{7 represents} a C ₁ -C ₄ alkyl group or a hydrogen atom, and is preferably a methyl group having a carbon atom. R ⁸ represents an alkyl group with C ₁₀ or less (which may contain an ether bond) and is preferably, for example, an ethyl group. R ⁹ , R ¹⁰ and R ¹¹ independently represent a C ₁ -C ₂₀ alkyl group which may have an oxygen atom. R ⁹ , R ¹⁰ and R ¹¹ may be a hydrogen atom.]

In the first embodiment, any method can be used to coat the solution or dispersion of the monomer mixed or dispersed in the non-volatile solvent on the substrate 10 to build. Examples include a method of applying the solution or dispersion to the substrate 10 by a doctor blade process or a spin coating process (spin coating process); a method of dropping the solution or dispersion onto the substrate 10 ; a method of immersing the substrate 10 in the solution or dispersion of the monomer that is mixed or dispersed in the non-volatile solvent; and the same.

Any method can be used to remove the monomer contained in the solution or dispersion in the non-volatile solvent on the substrate 10 to polymerize. Examples include a method of surface initiated living radical polymerization and the like.

The method of surface initiated living radical polymerization is a technique in which polymerization initiation groups are formed in the surface of the substrate before the formation of the layer of solution or dispersion of the monomer mixed or dispersed in the non-volatile solvent 10 are introduced, and then polymer graft chains are formed by living radical polymerization from the polymerization initiation groups as initiation points. For example, the in JP-A 2009-59659 and JP-A 2010 - 218984 disclosed methods and the like can be used.

Any method can be used to add the polymerization initiation groups to the surface of the substrate prior to polymerization by the method of surface-initiated, living radical polymerization 10 bring. Examples include a method that involves dissolving or dispersing a polymerization initiator in a solvent to prepare a polymerization initiator solution, and immersing the substrate 10 into the prepared polymerization initiator solution, and the like.

The polymerization initiator is not particularly limited, but is preferably a compound having a group capable of being attached to the substrate 10 bind, and a radical formation group. For example, the in JP-A 2010-218984 disclosed polymerization initiators, in particular TEMPO-based, ATRP-based, RAFT-based and RTCP-based polymerization initiators can be used. Among these, the TEMPO-based, RAFT-based and RTCP-based polymerization initiators are more preferred. Among the TEMPO-based polymerization initiators, DEPN-based polymerization initiators are particularly preferred. Examples of the group that is able to attach to the substrate 10 to bind include -SiCl ₃ , -Si (CH ₃ ) Cl ₂ , -Si (CH ₃ ) ₂ Cl, -Si (OR) ₃ (where R is methyl, ethyl, propyl or butyl) and the like.

When the polymerization is carried out by the method of surface-initiated living radical polymerization, the polymerization initiator described above is used and on the surface 10 immobilized to the polymerization initiation groups in the surface of the substrate 10 bring. Then the layer of the solution or dispersion of the monomer mixed or dispersed in the non-volatile solvent on the substrate 10 , which has the polymerization initiation groups incorporated therein, and is heated in a non-oxidizing gas atmosphere or exposed to ultraviolet, electron beam or γ radiation to allow the polymerization of the monomer in the non-volatile solvent to continue, thereby causing the polymer graft chains to open the surface of the substrate 10 be formed. Consequently, the polymer brush layer can 20 consisting of the polymer graft chains swollen with the non-volatile solvent used in the polymerization on the surface of the substrate 10 be formed. The polymerization reaction can be carried out under a pressure condition (under a pressure condition of 50 to 500 MPa) to further increase the molecular weight (in other words, the polymer brush lengths) of the polymer graft chains.

The thickness of the polymer brush layer formed in the first embodiment 20 is typically 20 µm or less, preferably 5 µm or less, more preferably 1 µm or less. The lower limit thereof is typically 10 nm or more.

The solution of the monomer mixed or dispersed in the non-volatile solvent for the polymerization may contain other components necessary for the polymerization reaction, such as any kind of radical initiator and the like.

The polymer brush layer formed by the formation method according to the first embodiment 20 has a low dynamic coefficient of friction and can therefore be suitably used, for example, as a sliding element or as a sliding structure, the polymer brush layer serving as a sliding surface.

<Second embodiment>

The second embodiment of the present invention will now be described.

2 FIG. 11 is a schematic view illustrating a polymer brush layer formed by the method according to the second embodiment of the present invention. In 2 is a polymer brush layer 20a according to the second embodiment of the present invention in the space between a substrate 10a and a second substrate 10b educated.

The first substrate 10a and the second substrate 10b are not particularly limited and may be the same substrates as that of the first embodiment.

The polymer brush layer 20a is a layer formed by the formation method according to the second embodiment, and is made of multiple polymer graft chains that are covalent on the first substrate 10a are immobilized and swollen with a liquid substance, formed like the polymer brush layer 20 according to the first embodiment.

The polymer brush layer forming method according to the second embodiment is a method of forming the polymer brush layer 20a in the narrow space that extends over a distance d of 500 µm or less between the first substrate 10a and the second substrate 10b extends as in 2 shown. According to the second embodiment, the polymer brush layer can 20a with a low dynamic coefficient of friction in such a narrow space.

• Ermöglichen, dass eine Lösung oder Dispersion eines Monomers, das in einem nichtflüchtigen Lösungsmittel gemischt oder dispergiert ist, in den engen Raum eindringt, der sich über einen Abstand d von 500 µm oder weniger zwischen dem ersten Substrat 10a und dem zweiten Substrat 10b erstreckt; und
• Polymerisieren des Monomers, das in der eingedrungenen Lösung oder Dispersion enthalten ist, in dem nichtflüchtigen Lösungsmittel, um die Polymerbürstenschicht 20a auf mindestens einem Teil der Oberflächen des ersten Substrats 10a und des zweiten Substrats 10b, die den Raum definieren, zu bilden.

In particular, the method for forming a polymer brush layer according to the second embodiment comprises the following steps:

• Allow a solution or dispersion of a monomer mixed or dispersed in a non-volatile solvent to enter the narrow space that is a distance d of 500 µm or less between the first substrate 10a and the second substrate 10b extends; and
• Polymerizing the monomer contained in the penetrated solution or dispersion in the non-volatile solvent around the polymer brush layer 20a on at least part of the surfaces of the first substrate 10a and the second substrate 10b that define the space to form.

According to the method of forming a polymer brush according to the second embodiment, the polymer brush layer can 20a with a low dynamic coefficient of friction can be successfully formed even if the distance d of the minute space between the first substrate 10a and the second substrate 10b preferably 500 µm or less, more preferably 100 µm or less.

In the second embodiment, the polymer brush layer 20a to form allows the solution or dispersion in which the monomer to form the polymer graft chains that the polymer brush layer 20a make up in the non-volatile solvent mixed or dispersed in the space between the first substrate 10a and the second substrate 10b penetrates, and then the monomer is polymerized to form the polymer graft chains in the non-volatile solvent in the room. Accordingly, the polymer brush layer 20a be successfully formed even in such a tiny space.

In particular, according to the second embodiment, the solution or dispersion of the monomer mixed or dispersed in the nonvolatile solvent is allowed to enter such a narrow space, and the monomer is polymerized in the narrow space. As an advantage of the narrow reaction space, the generation of convection currents during the polymerization reaction can be largely suppressed, thereby effectively preventing an increase in the width of the distribution of the resulting polymer brush lengths (an increase in the width of the molecular weight distribution). As a result, the polymer graft chains with a high molecular weight and a narrow molecular weight distribution can be formed. Since the polymer graft chains can be formed with a high molecular weight and a narrow molecular weight distribution, the resulting polymer brush layer has 20a a further reduced dynamic coefficient of friction during sliding. In particular, the narrow molecular weight distribution of the polymer graft chains shows that the polymer graft chains have essentially the same polymer brush length. This feature is more effective in reducing the dynamic coefficient of friction.

With a view to further reducing the dynamic coefficient of friction during sliding, the number average molecular weight (Mn) of the polymer graft chains comprising the polymer brush layer is 20a constitute, preferably 500 to 10,000,000, more preferably 200,000 to 10,000,000. With a view to further reducing the dynamic coefficient of friction during sliding, the weight average molecular weight (Mw) of the polymer graft chains comprising the polymer brush layer 20 constitute, preferably 500 to 10,000,000, more preferably 200,000 to 10,000,000. With a view to further reducing the dynamic coefficient of friction during sliding, the molecular weight distribution (Mw / Mn) of the polymer graft chains that make up the polymer brush layer 20a make up, preferably close to 1, desirably 1.5 or less, more preferably 1.3 or less, more preferably 1.2 or less, particularly preferably 1.01 to 1.15. The thickness of the polymer brush layer 20a is not particularly limited, but preferably corresponds to the distance d between the first substrate 10a and the second substrate 10b or, in other words, is preferably substantially equal to the distance d, preferably 500 µm or less, more preferably 100 µm or less.

In the second embodiment, the monomer used to form the polymer graft chains in the non-volatile solvent in the space between the first substrate 10a and the second substrate 10b polymerizes while the monomer is mixed or dispersed in the non-volatile solvent. In the case where the non-volatile solvent used in the polymerization is left without being removed, the polymer brush layer finally obtained can 20a have the polymer graft chains swollen with the non-volatile solvent used in the polymerization.

In particular, according to the second embodiment, since the monomer is polymerized in the non-volatile solvent, in the process of forming the polymer brush layer 20a in the narrow space between the first substrate 10a and the second substrate 10b only that to form the polymer brush layer 20a required amount for the penetration of the solution or the dispersion used before the polymerization. In addition, the polymer brush layer formed reflects 20a the amount of solvent or dispersion that has penetrated prior to polymerization (in other words, the polymer brush layer 20a is formed at a position corresponding to the place where the solution or the dispersion has penetrated before the polymerization, and has an area corresponding to that where the solution or the dispersion has penetrated before the polymerization). Thus, the polymer brush layer 20a be successfully formed in such a confined space.

According to the second embodiment, it is in the formation of the polymer brush layer 20a in that through the first substrate 10a and the second substrate 10b formed narrow space is not necessary to use the following procedure, where once the first substrate 10a and the second substrate 10b facing each other, disassembled, a polymer brush layer is formed on the surface of each substrate, and then the first substrate 10a and the second substrate 10b after the formation of the polymer brush layer, be arranged so that they face each other; this can significantly improve productivity. If the first substrate 10a and the second substrate 10b be arranged so that they face each other after polymer brush layers are separated on the surface of the first substrate 10a and the surface of the second substrate 10b The polymer brush layers formed do not always match the size of the space between the first substrate 10a and the second substrate 10b match (for example, the polymer brush layers for the space between the first substrate 10a and the second substrate 10b too thick or too thin). Unfortunately, this can lead to insufficient sliding properties. Although the polymer brush layer is formed in the space defined by the two surfaces of the first substrate 10a and the second substrate 10b is formed, for example in the 2 aspect, such a problem is more clearly visible in the case where the polymer brush layer is more clearly visible in a space with a curved surface, a space formed by a scraped surface, or a space with a more complex shape.

In contrast, the second embodiment can effectively solve such a problem.

The monomer used to form the polymer graft chains that make up the polymer brush layer 20a is not particularly limited, and the same monomers as those described in the first embodiment can be used. At least one monomer with an ionic dissociable group (in particular a monomer with an ionic dissociable group and a reactive double bond group) is preferably used. In addition to the monomer having an ionic dissociable group, a monomer copolymerizable with the previous monomer can be used. As the monomer having an ionic dissociable group, those described in the first embodiment can be used. In particular, the monomer with an ionic dissociable group shows an excellent ability to enter a narrow space. From this point of view, the monomer having an ionically dissociable group is preferably used.

The non-volatile solvent is not particularly limited, and the same solvents as those described in the first embodiment above can be used. Ionic liquids are preferred in terms of excellent non-volatility, high ability to dissolve various monomers, and high ability to enter a narrow space. The same ionic liquids as those described above in the first embodiment can be used.

In particular, in the second embodiment, it is particularly preferred that the monomer having an ionic dissociable group as the monomer for forming the polymer brush layer 20a is used, and the ionic liquid is used as the non-volatile solvent (namely, the combination of the monomer with an ionic dissociable group and the ionic liquid is particularly advantageous). The use of the ionic liquid in the polymerization system can relatively increase the viscosity of the solution at an initial stage of the polymerization. This can lead to difficulties in forming the desired polymer graft chains. However, due to their high compatibility and the polymerization environment in the narrow space, the combination of the monomer with an ionic dissociable group and the ionic liquid enables the polymerization reaction of the monomer with an ionic dissociable group to proceed successfully. Accordingly, the desired polymer graft chains can be formed relatively easily. As a result, the polymer brush layer having a low dynamic friction coefficient can be suitably formed with high productivity.

In the second embodiment, any method can be used to allow the solution or dispersion in which the monomer to form the polymer graft chains to form the polymer brush layer 20a make up in the non-volatile solvent mixed or dispersed in the space between the first substrate 10a and the second substrate 10b penetrates. Examples include a method of spotting the solution or the dispersion near an opening of the space to allow the solution or the dispersion to enter therein by capillary action, and the like.

In the second embodiment, the monomer contained in the solution or dispersion which has entered such a space can be in the non-volatile solvent by any method be polymerized. Examples of this include the surface-initiated living radical polymerization method and the like described above in the first embodiment.

In particular, in the second embodiment, polymerization initiation groups are formed before the solution or dispersion of the monomer mixed or dispersed in the nonvolatile solvent penetrates into the surfaces of the first substrate 10a and the second substrate 10b inserted, and then the polymer graft chains, which are covalent on the surface of the first substrate 10a are immobilized, and the polymer graft chains, which are covalent on the surface of the second substrate 10b are immobilized, formed by living radical polymerization from the polymerization initiation groups as initiation points.

Any method can be used to get the polymerization initiation groups into the surface of the first substrate 10a and the surface of the second substrate 10b in the process of polymerization by the process of surface-initiated living radical polymerization. Examples of this include a method of dissolving or dispersing a polymerization initiator in a solvent to prepare a polymerization initiator solution, allowing the manufactured polymerization initiator solution to enter the space between the first substrate 10a and the second substrate 10b penetrates, and includes removal of the solvent and the like.

The polymerization initiator is not particularly limited, and for example, the same polymerization initiators as those described in the first embodiment can be used.

When the polymerization is carried out by the method of surface-initiated living radical polymerization, the polymerization initiator described above is used to break the polymerization initiation groups into the surfaces of the first substrate 10a and the second substrate 10b bring. Then the solution or dispersion of the monomer mixed or dispersed in the non-volatile solvent in the space between the first substrate 10a and the second substrate 10b and is heated in a non-oxidizing gas atmosphere or exposed to ultraviolet, electron beam or γ radiation to allow the polymerization of the monomer in the non-volatile solvent to continue, thereby placing multiple polymer graft chains on each of the surfaces of the first substrate 10a and the second substrate 10b be formed. Thus, the polymer brush layer 20a composed of the plurality of polymer graft chains swollen with the non-volatile solvent used in the polymerization in the minute space between the first substrate 10a and the second substrate 10b be formed.

In the polymer brush layer formed as described above 20a they stand on the first substrate 10a covalently immobilized several polymer graft chains and those on the second substrate 10b opposite covalently immobilized multiple polymer graft chains while the multiple polymer graft chains are swollen with the non-volatile solvent. Thus, according to the second embodiment, the polymer brush layer 20a with a low dynamic coefficient of friction can be successfully formed in the tiny space.

The solution of the monomer mixed or dispersed in the non-volatile solvent used in the polymerization may contain other components necessary for the polymerization reaction, such as any kind of radical initiator and the like.

In the aspect of the second embodiment described above as an example, multiple polymer graft chains are on each of the surfaces of the first substrate 10a and the second substrate 10b educated. In another aspect, multiple polymer graft chains can only be on one of the surfaces of the first substrate 10a and the second substrate 10b be formed.

The polymer brush layer formed according to the formation method according to the second embodiment has a low dynamic coefficient of friction, and therefore can be suitably used, for example, as a sliding member or as a sliding structure acting as a sliding mechanism by the first substrate 10a and the second substrate 10b using the polymer brush layer 20a be slid as a sliding surface relative to each other.

<Other Embodiments>

Although in the aspect of the second embodiment described above as an example, the polymer brush layer 20a in the space between the first substrate 10a and the second substrate 10b is formed, the method for forming a polymer brush layer according to the present invention is not limited to this aspect and can be used for various types of rooms.

In the aspect of the second embodiment described above as an example, the polymer brush layer 20a formed in the space between the two surfaces of the first substrate 10a and the second substrate 10b is formed as in 2 shown. According to the second embodiment described above, the polymer brush layer can 20a with a low dynamic coefficient of friction not only suitably in a space formed by flat surfaces, but also, for example, in a space with a curved surface, a space formed by a scraped surface, or a space with a more complex one Form are formed.

• Ermöglichen, dass eine Lösung oder Dispersion eines Monomers, das in einem nichtflüchtigen Lösungsmittel gemischt oder dispergiert ist, in den kontinuierlichen porösen Körper eindringt; und
• Polymerisieren des Monomers, das in der Lösung oder der Dispersion enthalten ist, in dem nichtflüchtigen Lösungsmittel, um eine Polymerbürstenschicht auf mindestens einem Teil der Innenflächen der Poren des kontinuierlichen porösen Körpers zu bilden.

The present invention can also provide a method of forming a polymer brush layer on the inner surfaces of pores of a continuous porous body, the method comprising the steps of:

• Allowing a solution or dispersion of a monomer mixed or dispersed in a non-volatile solvent to enter the continuous porous body; and
• Polymerizing the monomer contained in the solution or the dispersion in the non-volatile solvent to form a polymer brush layer on at least a part of the inner surfaces of the pores of the continuous porous body.

The continuous porous body is not particularly limited. Examples thereof include porous bodies with a continuous three-dimensional, mesh-like framework and cavities or, in other words, those with a monolith structure and the like. According to the method of the present invention, the polymer brush layer can be formed on the inner surfaces of the pores of such a continuous porous body, thereby making it possible to adjust the inner pore size of the pores of the continuous porous body (the pore size can be adjusted by adjusting the thickness of the polymer brush layer to be formed become). By forming the polymer brush layer on the inner surfaces of the pores of the continuous porous body, various functions can be given to the inner surfaces of the pores. In particular, by introducing a functional group corresponding to a desired function into the monomer for forming the polymer brush layer, the desired function can be given to the inner surfaces of the pores, thereby enabling the continuous porous body to be used for a wide range of applications.

• Ermöglichen, dass eine Lösung oder Dispersion eines Monomers, das in einem nichtflüchtigen Lösungsmittel gemischt oder dispergiert ist, in den röhrenförmigen Körper eindringt; und
• Polymerisieren des Monomers, das in der Lösung oder der Dispersion enthalten ist, in dem nichtflüchtigen Lösungsmittel, um eine Polymerbürstenschicht auf mindestens einem Teil der Innenfläche des röhrenförmigen Körpers zu bilden.

In addition, the present invention can provide a method of forming a polymer brush layer on the inner surface of a tubular body, the method comprising the steps of:

• Allowing a solution or dispersion of a monomer mixed or dispersed in a non-volatile solvent to enter the tubular body; and
• Polymerizing the monomer contained in the solution or dispersion in the non-volatile solvent to form a polymer brush layer on at least a portion of the inner surface of the tubular body.

The tubular body is not particularly limited. Examples include capillary tubes, microflow channels, and the like. According to the method according to the present invention, the polymer brush layer can be formed on the inner surface of such a tubular body to give various functions to the inner surface of the tubular body. In particular, by introducing a functional group corresponding to a desired function into the monomer for forming the polymer brush layer, the desired function of the inner surface of the tubular body can be imparted, thereby enabling the tubular body to be used for a wide range of applications.

Both the method of forming a polymer brush layer on the inner surfaces of pores of a continuous porous body and the method of forming a polymer brush layer on the inner surface of a tubular body can use the same materials and factors as those of the first Embodiment and the second embodiment can be used without restriction (for example, the same monomer and non-volatile solvent as those described above can be used, and the polymerization method and the polymerization condition can be the same as those in these embodiments).

EXAMPLES

The following description illustrates the present invention in more detail by way of examples. These examples should not be construed as limiting the present invention.

<Example 1>

An amount of 0.4 g of 3 - ((3- (triethoxysilyl) propyl) thio) propyl-2-bromo-2-methylpropanoate (BPTPE) as the polymerization initiator and 20 ml of ethanol were mixed, and 20 ml of ethanol containing 1.8 g containing ammonium hydroxide was added to the resulting solution to prepare a solution containing immobilization initiator. A silicon substrate was immersed in the prepared solution containing immobilization initiator for 18 hours to prepare the silicon substrate having surface-mounted polymerization initiation groups.

Separately from the above, 16 g of N, N-diethyl-N- (2-methacryloylethyl) -N-methylammonium bis (trifluoromethylsulfonyl) imide (DEMM-TFSI) as a monomer having an ionic dissociable group (ionic liquid monomer), 0.013 g of ethyl 2-bromo-2-methylpropionate ( EBIB ) as a radical initiator, 0.033 g of 2,2-dipyridyl as a ligand and 0.132 g of CuCl and 0.0448 g of CuCl ₂ as copper catalysts in 3.95 g of N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethylsulfonyl) imide (DEME-TFSI) dissolved as a non-volatile solvent (ionic liquid) to produce a monomer solution.

The resulting monomer solution was applied to the surface of the silicon substrate prepared above having the polymerization initiation groups introduced therein, and then the substrate 32 Heated to 70 ° C in an argon atmosphere in an incubator for hours to allow atom transfer radical polymerization (ATRP) to continue, thereby forming polymer graft chains on the surface of the silicon substrate. Thus, a polymer brush layer with a thickness of 0.5 µm (a polymer brush layer made of poly (DEMM-TFSI) swollen with DEME-TFSI) was formed. The number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of free polymers produced simultaneously in the synthesis system in this process were measured to determine that Mn = 6.68 x 10 ⁵ , Mw = 7.93 x 10 ⁵ and Mw / Mn = 1.18. Based on this, it can be assumed that the polymer graft chains introduced into the surface of the silicon substrate have a similar number-average molecular weight and a similar molecular weight distribution.

The number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) of the free polymers were determined by gel permeation chromatography (GPC). In the measurement, "Shodex GPC-101" (available from SHOWA DENKO KK) (with two columns ("Shodex OHpak SB-806M HQ" available from SHOWA DENKO KK) connected in series) was used as the measuring device, and a 1: 1 ( Volume ratio) Mixture of 0.2 M sodium nitrate in water and 0.5 M acetic acid in acetonitrile was used as the eluent. The measurement was carried out at 40 ° C and the flow rate was controlled at 1.0 ml / min. Based on the measurement results, the number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) of the free polymers were determined using a polyethylene oxide calibration curve obtained using Shodex 480II.

• - Messgerät: Oberflächeneigenschaftsmessgerät „TRIBOGEAR, TYP 38“ (erhältlich bei Shinto Scientific Co., Ltd.)
• - Belastung: 500 g (Oberflächendruck: 301 MPa)
• - Bewegungsgeschwindigkeit: 600 mm/min (10 mm/sec)
• - Testtemperatur: 24,0°C
• - Testfeuchtigkeit: 25%.

The silicon substrate prepared above with the polymer brush layer formed thereon was slid while a silica ball with a thin silica film (a silica ball made by bonding a 3 µm thick silica thin film to an untreated surface of the silica ball with an adhesive) was subjected to a load shown below the surface with the polymer brush layer formed thereon was pressed. The dynamic coefficient of friction was determined from the frictional force recorded by a load cell. The measurement conditions were as shown below. From the results, it was found that the dynamic friction coefficient of the present example is reduced to 0.004.

• - Measuring device: surface property measuring device "TRIBOGEAR, TYPE 38" (available from Shinto Scientific Co., Ltd.)
• - load: 500 g (surface pressure: 301 MPa)
• - Movement speed: 600 mm / min (10 mm / sec)
• - Test temperature: 24.0 ° C
• - Test moisture: 25%.

<Example 2>

Two sliding glasses were prepared and a 0.1 mm thick silicone rubber spacer was inserted between the two sliding glasses to form a narrow space. Then, a solution containing an immobilization initiator was prepared in the same manner as in Example 1, and the two sliding glasses with the narrow space maintained therebetween were immersed in the prepared solution containing an immobilization initiator for 18 hours in the same manner as in Example 1 contains, immersed to introduce polymerization initiation groups into the surfaces of the two sliding glasses.

A monomer solution was prepared in the same manner as in Example 1. The monomer solution prepared was dropped near an opening of the space between the two sliding glasses with the polymerization initiation groups inserted therein, causing the monomer solution to enter the space by capillary action. Then the two sliding glasses 32 Heated to 70 ° C in an argon atmosphere in an incubator for hours to allow the atom transfer radical polymerization ( ATRP ) is continued, whereby polymer graft chains were formed on the surfaces of the two sliding glasses. Thus, a polymer brush layer (a polymer brush layer made of poly (DEMM-TFSI) swollen with DEME-TFSI) was formed in the narrow space between the two sliding glasses.

The number average molecular weight (Mn), the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of the polymer brush layer (Poly (DEMM-TFSI)) obtained above were measured in the same manner as in Example 1 and were found to be are substantially the same as that of Example 1. The dynamic coefficient of friction of the polymer brush layer obtained above was measured and found to be reduced to a similar level to that of Example 1.

<Example 3>

A solution containing an immobilization initiator was prepared in the same manner as in Example 1, and a silica monolith (fine pore size: about 2 µm) as a porous substrate was immersed in the prepared solution containing an immobilization initiator to introduce polymerization initiation groups into the inner surfaces of the pores of the silica monolith.

Then a monomer solution was prepared in the same manner as in Example 1. The silica monolith prepared above with the polymer initiation groups incorporated therein was immersed in the monomer solution and pulled out of the monomer solution. This allowed the monomer solution to penetrate into the fine pores of the monolith. The monolith was then heated to 70 ° C in an argon atmosphere in an incubator for 32 hours to allow atom transfer radical polymerization (ATRP) to continue, thereby forming polymer graft chains on the inner surfaces of the fine pores in the silica monolith. Thus, a polymer brush layer (a polymer brush layer made of poly (DEMM-TFSI) swollen with DEME-TFSI) was formed within the fine pores in the monolith.

The number average molecular weight (Mn), the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of the polymer brush layer (Poly (DEMM-TFSI)) obtained above were measured in the same manner as in Example 1 and were found to be are substantially the same as that of Example 1. The dynamic coefficient of friction of the polymer brush layer obtained above was measured and found to be reduced to a similar level to that of Example 1.

<Example 4>

A monomer solution was prepared in the same manner as in Example 1. The monomer solution prepared was applied to the surface of a silicon substrate having polymerization initiation groups introduced therein and prepared in the same manner as in Example 1, and the substrate was sealed inside a Teflon container (registered trademark) in an argon atmosphere. The container was heated in a medium pressure polymerization tank at 100 MPa for 5 hours at 70 ° C (polymerization condition at medium pressure) to allow atom transfer radical polymerization (ATRP) to continue, thereby forming polymer graft chains on the surface of the silicon substrate. Thus, a 0.2 µm thick polymer brush layer (a polymer brush layer made of poly (DEMM-TFSI) swollen with DEME-TFSI) (the thickness was estimated based on the molecular weight) was formed on the surface of the silicon substrate. The number average molecular weight (Mn), the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of free polymers produced simultaneously in the synthesis system in this process were measured. The following results were obtained for the polymerization condition at medium pressure: degree of polymerization = 2215, Mn = 3.01 × 10 ⁵ , Mw = 3.88 × 10 ⁵ and Mw / Mn = 1.29. When using an ambient pressure incubator under the same conditions, the following results were obtained: degree of polymerization = 805, Mn = 9, 65 × 10 ⁵ , Mw = 1.12 × 10 ⁵ and Mw / Mn = 1.16. In comparison to the condition at ambient pressure, the use of polymerization at medium pressure achieved a degree of polymerization which was about 2.8 times higher.

The dynamic coefficient of friction of the polymer brush layer (Poly (DEMM-TFSI)) obtained above was measured and found to be reduced to a level similar to that of Example 1.

QUOTES INCLUDE IN THE DESCRIPTION

This list of documents listed by the applicant has been generated automatically and is only included for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

• JP 2012056165 A [0003]
• JP 2006316169 A [0003]
• JP 2009059659 A [0044]
• JP 2010 A [0044]
• JP 218984 [0044]
• JP 2010218984 A [0046]

Claims (9)

A method of forming a polymer brush layer on a surface of a substrate, the method comprising the steps of: Forming a layer on the substrate, the layer being formed from a solution or dispersion of a monomer mixed or dispersed in a non-volatile solvent; and Polymerizing the monomer contained in the solution or the dispersion in the non-volatile solvent to form a polymer brush layer having a thickness of 20 µm or less on at least a part of the surface of the substrate. A method of forming a polymer brush layer, the method comprising the steps of: Allow a solution or dispersion of a monomer mixed or dispersed in a non-volatile solvent to enter a space that is between a first substrate and a second substrate that are opposite to each other and spaced apart by a distance of 500 µm or less , is formed; and Polymerizing the monomer contained in the permeated solution or dispersion in the non-volatile solvent to form a polymer brush layer on at least a portion of a surface of at least one of the first substrate and the second substrate defining the space. A method for forming a polymer brush layer on inner surfaces of pores of a continuous porous body or for forming a polymer brush layer on an inner surface of a tubular body, the method comprising the following steps: Allowing a solution or dispersion of a monomer mixed or dispersed in a non-volatile solvent to enter the continuous porous body or the tubular body; and Polymerizing the monomer contained in the solution or dispersion in the non-volatile solvent to form a polymer brush layer on at least a portion of the inner surfaces of the pores of the continuous porous body or a polymer brush layer on at least a portion of the inner surface of the tubular body form. A method of forming a polymer brush layer according to one of the Claims 1 to 3 wherein the non-volatile solvent has a vapor pressure of less than 10 Pa at a temperature of 25 ° C or lower. A method of forming a polymer brush layer according to one of the Claims 1 to 4 , the non-volatile solvent being an ionic liquid. A method of forming a polymer brush layer according to one of the Claims 1 to 5 wherein the monomer is polymerized by a method of surface initiated living radical polymerization on the surface of the substrate. A method of forming a polymer brush layer according to Claim 6 , wherein a compound having a group capable of binding to the surface of the substrate is selected from the group consisting of -SiCl ₃ , -Si (CH ₃ ) Cl ₂ , -Si (CH ₃ ) ₂ Cl and -Si (OR) ₃ (wherein R is methyl, ethyl, propyl or butyl), and a radical generation group is used as a polymerization initiator. A method of forming a polymer brush layer according to Claim 6 or 7 , wherein the polymerization is carried out by the process of surface-initiated, living radical polymerization under a pressure condition of 50 to 500 MPa. A method of forming a polymer brush layer according to one of the Claims 1 to 8th wherein at least one compound having an ionic dissociable group is used as the monomer.

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