JP2003321479A - Photodegradable silane coupling agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new photodegradable silane coupling agent comprising a silane compound having an amino group, etc., a new silane compound having the amino group, etc., a substrate treated with the new photodegradable silane coupling agent comprising the silane compound having the amino group, etc,. and a method for producing the substrate. <P>SOLUTION: The photodegradable silane coupling agent comprises the silane compound having the protected amino group, etc., with a photodegradable protective group, e.g. a silane compound represented by general formula [1] (X denotes an alkoxy group or a halogen atom; Y denotes the photodegradable protective group; R<SP>1</SP>s denote each an alkyl group; m denotes an integer of 0-3; and n denotes an integer), preferably general formula [2] (R<SP>2</SP>denotes a hydrogen atom or an alkyl group; and R<SP>3</SP>and R<SP>4</SP>denote each independently a hydrogen atom or an alkoxy group). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photodegradable silane coupling agent, and more particularly to a photodegradable silane coupling agent containing a silane compound having a functional group protected by a photodegradable protective group.

[0002]

2. Description of the Related Art For example, a silane compound having an amino group as a functional group is widely used as a compound for introducing an amino group onto the surface of an inorganic material such as silica gel or a silicon wafer. Utilizing the high reactivity of the introduced amino group, for example, a biological material such as DNA or protein is immobilized to form a composite material, and a biochemical phenomenon such as adsorption of cells using this is investigated, Applied research is being conducted as a new type of biosensor. Conventionally known amino group-containing silane compounds include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and N-β ( Aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-
[Bis (β-hydroxyethyl)]-aminopropyltriethoxysilane, (2-aminoethyl) aminopropyltrialkoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
3-Aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethylmethoxysilane, N- (2-aminoethyl) -3-aminopropyl Examples thereof include trimethoxysilane.

Further, as one of the methods for fixing a biological substance at a specific position on a substrate, there is, for example, one utilizing a photochemical reaction, and aminoethyl has been conventionally used as a silane compound having an amino group. Aminopropyltrimethoxysilane and the like are known. In the method of immobilizing a biological substance using these aminoethylaminopropyltrimethoxysilane and the like, it was necessary to react a molecule having a light-sensitive structure with a previously introduced amino group.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have succeeded in synthesizing a silane compound represented by the following general formula [20] in which a carboxy group is protected with o-nitrobenzyl ester. We succeeded in introducing a carboxy group to the surface of silica gel by light irradiation (Chem. Lett. 2000, 228-229), and also succeeded in introducing a carboxy group on a silicon wafer and its patterning.

[0005]

[Chemical 15]

By the way, the silane compound having an amino group is useful as described above, and a silane compound in which an amino group is protected by a protecting group instead of the carboxy group is desired.
For example, since the boiling point is high, it is difficult to isolate it by vacuum distillation like the silane compound represented by the above general formula [20], and it is also difficult to separate it by a silica gel column because the silyl group part reacts with silica gel. .

However, last year, it was reported that a certain silane compound containing a methoxysilyl group could be isolated by a silica gel column in which tetramethoxysilane was added as an elution solvent (Y. Barness, O. Gershevitz, M. .Serka
r, and C.N.Sukenik, Langmuir, 16, 247-251, 2000).
The present inventor has paid attention to the above report and thought that a novel silane compound can be synthesized by using a silica gel column in which tetramethoxysilane is added as an elution solvent. An object of the present invention is to provide a novel photodegradable silane coupling agent containing a silane compound having an amino group, a sulfo group, a thiol group or a phosphoric acid group, a novel photodegradable silane coupling agent having an amino group, a sulfo group, a thiol group or a phosphoric acid group. Another object of the present invention is to provide a substrate treated with a novel photodegradable silane coupling agent containing a novel silane compound, and a silane compound having an amino group, a sulfo group, a thiol group or a phosphoric acid group, and a method for producing the same.

[0008]

Means for Solving the Problems The present inventors have found that an amino group,
The effectiveness of silane compounds having a sulfo group, a thiol group or a phosphoric acid group, and the problems of conventional silane coupling agents (silane compounds) were thoroughly studied, and amino groups, sulfo groups, thiol groups or phosphoric acid groups were protected by protecting groups. As a result of trying the synthesis focusing on the usefulness of the silane compound in which the group is protected,
For example, an amino group protected with a photodegradable compound (for example, a 2-nitrobenzyl derivative) that has been difficult to synthesize by using a separation and purification method using silica gel column chromatography with tetramethoxysilane,
The silane compound having a sulfo group, a thiol group or a phosphoric acid group has been successfully synthesized, and the silane compound having an amino group, a sulfo group, a thiol group or a phosphoric acid group protected by such a photodegradable compound fixes a biological substance. It has been found that the silane coupling agent is useful as a silane coupling agent, etc., and the present invention has been completed.

That is, the present invention comprises a photodegradable silane coupling agent characterized by containing a silane compound in which an amino group, a sulfo group, a thiol group or a phosphoric acid group is protected by a photodegradable protective group. 1) or a silane compound is represented by the following general formula [1]

[0010]

[Chemical 16]

(In the general formula [1], X represents an alkoxy group or a halogen atom, Y represents a photodegradable protective group, and R ¹
Represents an alkyl group. m represents an integer of 1 to 3, and n represents an integer. ) Is a silane compound represented by the formula (1), the photodegradable silane coupling agent according to claim 1 (claim 2) and the silane compound represented by the general formula [1] are represented by the following general formula: [2]

[0012]

[Chemical 17]

(In the general formula [2], X represents an alkoxy group or a halogen atom, R ¹ represents an alkyl group, R ² represents a hydrogen atom or an alkyl group, and R ³ and R ⁴ are each independently. It represents a hydrogen atom or an alkoxy group, m represents an integer of 1 to 3, and n represents an integer.) The photodegradable silane coupling according to claim 2, which is a silane compound. The agent (claim 3) or the silane compound is represented by the following general formula [3]

[0014]

[Chemical 18]

(In the general formula [3], X represents an alkoxy group or a halogen atom, Y represents a photodegradable protecting group, and R ¹
Represents an alkyl group. m represents an integer of 1 to 3, and n represents an integer. ) The photodegradable silane coupling agent according to claim 1 (claim 4) or the silane compound represented by the general formula [3] is a silane compound represented by the following general formula: [4]

[0016]

[Chemical 19]

(In the general formula [4], X represents an alkoxy group or a halogen atom, R ¹ represents an alkyl group, R ² represents a hydrogen atom or an alkyl group, and R ³ and R ⁴ are each independently. Represents a hydrogen atom or an alkoxy group, m represents an integer of 1 to 3, and n represents an integer.) The photodegradable silane coupling according to claim 4, which is a silane compound. The agent (claim 5) or the silane compound is represented by the following general formula [5]

[0018]

[Chemical 20]

(In the general formula [5], X represents an alkoxy group or a halogen atom, Y represents a photodegradable protective group, and R ¹
Represents an alkyl group. m represents an integer of 1 to 3, and n represents an integer. ) Is a silane compound represented by the following general formula, wherein the photodegradable silane coupling agent according to claim 1 (claim 6) and the silane compound represented by the general formula [5] are [6]

[0020]

[Chemical 21]

(In the general formula [4], X represents an alkoxy group or a halogen atom, R ¹ represents an alkyl group, R ² represents a hydrogen atom or an alkyl group, and R ³ and R ⁴ are each independently. Represents a hydrogen atom or an alkoxy group, m represents an integer of 1 to 3, and n represents an integer.) The photodegradable silane coupling according to claim 6, which is a silane compound. Agent (Claim 7) or the photodegradable silane coupling agent according to any one of claims 1 to 7, wherein the silane compound in the silane coupling agent is coupled to the surface-modified coupling group. Material (Claim 8)
Regarding

Further, the present invention is characterized in that the silane compound in the silane coupling agent is coupled to a substrate with the photodegradable silane coupling agent according to any one of claims 1 to 7. A method for producing a coupling base material (claim 9) or a method for producing a surface-modified coupling base material according to claim 9, wherein the base material is a pretreated base material (claim). Item 10) or the photodegradable silane coupling agent according to any one of claims 1 to 7 is coated on a substrate, and the silane compound in the silane coupling agent is coupled to the substrate to form a surface-modified cup. A ring base material is prepared, and all or part of the surface of the surface-modified coupling base material is irradiated with light, and the photodegradable protective group in the light-irradiated portion is removed to leave an amino group, a sulfo group, a thiol group or phosphorus Expose the acid groups, Amino groups on the surface, a sulfo group, and the manufacturing method of the functional groups exposed coupling substrate, characterized in that to form a thiol group or a phosphate group (Claim 11),
The method for producing a functional group-exposed coupling base material according to claim 11, wherein the base material is a pre-treated base material, and the light is ultraviolet light. A method for producing a functional group-exposed coupling base material according to claim 11 or 12 (claim 13) or a photodegradable silane coupling agent according to any one of claims 1 to 7 as a base material. Coating, to prepare a surface-modified coupling substrate by coupling the silane compound in the silane coupling agent to the substrate, and irradiate all or part of the surface of the surface-modified coupling substrate with light, Amino group, sulfo group, thiol group or phosphoric acid group is exposed by leaving the photodegradable protective group in the light irradiation part, and the amino group, sulfo group, thiol group or phosphoric acid group formed on the substrate surface is chemically Chemistry characterized by modification 15. The method for producing a decorative coupling base material (claim 14), or the method for producing a chemically modified coupling base material according to claim 14, wherein the base material is a pre-treated base material ( (15) or the light is ultraviolet light, The method for producing the chemically modified coupling substrate according to (14) or (15) or the chemical modification is nucleic acid, sugar or protein. The method for producing a chemically modified coupling substrate according to any one of claims 14 to 16, which is performed using a biological substance such as (Claim 1).
Regarding 7).

Further, the present invention provides a silane compound (claim 18) characterized in that an amino group, a sulfo group, a thiol group or a phosphoric acid group is protected by a photodegradable protective group (claim 18) or the following general formula [1]: ]

[0024]

[Chemical formula 22]

(In the general formula [1], X represents an alkoxy group or a halogen atom, Y represents a photodegradable protective group, and R ¹
Represents an alkyl group. m represents an integer of 0 to 3, and n represents an integer. The silane compound according to claim 18 (claim 19) or the silane compound represented by the general formula [1] is represented by the following general formula [2].

[0026]

[Chemical formula 23]

(In the general formula [2], X represents an alkoxy group or a halogen atom, R ¹ represents an alkyl group, R ² represents a hydrogen atom or an alkyl group, and R ³ and R ⁴ are each independently. Represents a hydrogen atom or an alkoxy group, m represents an integer of 1 to 3, and n represents an integer.) The silane compound according to claim 19 (claim 20).
Or the following general formula [3]

[0028]

[Chemical formula 24]

(In the general formula [3], X represents an alkoxy group or a halogen atom, Y represents a photodegradable protective group, and R ¹
Represents an alkyl group. m represents an integer of 0 to 3, and n represents an integer. The silane compound according to claim 18 (claim 21) or the silane compound represented by the general formula [3] is represented by the following general formula [4]

[0030]

[Chemical 25]

(In the general formula [4], X represents an alkoxy group or a halogen atom, R ¹ represents an alkyl group, R ² represents a hydrogen atom or an alkyl group, and R ³ and R ⁴ are each independently. Represents a hydrogen atom or an alkoxy group, m represents an integer of 1 to 3, and n represents an integer.) The silane compound according to claim 21 (claim 22).
Or the following general formula [5]

[0032]

[Chemical formula 26]

(In the general formula [5], X represents an alkoxy group or a halogen atom, Y represents a photodegradable protective group, and R ¹
Represents an alkyl group. m represents an integer of 0 to 3, and n represents an integer. The silane compound according to claim 18 (claim 23) or the silane compound represented by the general formula [5] is represented by the following general formula [6]:

[0034]

[Chemical 27]

(In the general formula [6], X represents an alkoxy group or a halogen atom, R ¹ represents an alkyl group, R ² represents a hydrogen atom or an alkyl group, and R ³ and R ⁴ are each independently. Represents a hydrogen atom or an alkoxy group, m represents an integer of 1 to 3, and n represents an integer.) The silane compound according to claim 23 (claim 24).
Or in the general formulas [1] to [6], m is an integer of 1 to 3; the silane compound according to any one of claims 19 to 24 (claim 25); [7]

[0036]

[Chemical 28]

(In the general formula [7], Y represents a photodegradable protective group), and a photodegradable compound (claim 26), or a general formula [7]. Is a photodegradable compound represented by the following general formula [8]

[0038]

[Chemical 29]

(In the general formula [8], R ² represents a hydrogen atom or an alkyl group, and R ³ and R ⁴ each independently represent a hydrogen atom or an alkoxy group). A photodegradable compound according to claim 26 (claim 27) or the like.

[0040]

BEST MODE FOR CARRYING OUT THE INVENTION The photodegradable silane coupling agent of the present invention includes a photodegradable protective group, an amino group, a sulfo group, a thiol group or a phosphate group (hereinafter, these groups are collectively referred to as a functional group. Is not particularly limited as long as it contains a silane compound in which the silane compound is protected by the following general formula [1] to
[6] and general formula

The compounds represented by [9] to [11] are preferable.

[0041]

[Chemical 30]

In the general formula [1], X represents an alkoxy group or a halogen atom, and the alkoxy group represented by X has a carbon number of 1 although the carbon number is not particularly limited.
It is preferably an alkoxy group of 6 to 6, specifically, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, an s-butoxy group, a t-butoxy group, an n-pentyloxy group. , N-hexyloxy group and the like, and among them, a methoxy group and an ethoxy group are particularly preferable, and the halogen atom represented by X includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. Although it can be mentioned, X is preferably an alkoxy group rather than a halogen atom.

In the general formula [1], R ¹ represents an alkyl group. The alkyl group represented by R ¹ may be linear or branched, may have an unsaturated bond, and may be an alkoxy group such as a methoxy group or an ethoxy group, It may have a substituent such as an acyl group such as a formyl group and an acetyl group. The number of carbon atoms of the alkyl group is not particularly limited, but those having 1 to 6 carbon atoms are preferable, and specifically, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, s-butyl group,
alkyl groups such as t-butyl group, n-pentyl group, isopentyl group, neopentyl group and n-hexyl group, vinyl group, allyl group, 2-propenyl group, 2-butenyl group, 2
Specific examples thereof include an alkenyl group such as a -pentenyl group and a 2-heptynyl group, an alkynyl group such as a propargyl group, and among these, a methyl group is particularly preferable.

In the general formula [1], m represents an integer of 1 to 3 (when it is contained in the coupling agent), and the larger the number, the more preferable because it is easy to introduce the inorganic material or the like into the surface. Further, in the general formula [1], n represents an integer, and from the viewpoint of easy availability of starting materials, it is preferably an integer of 1 to 20, and more preferably an integer of 2 to 15.

In the general formula [1], Y represents a photodegradable protective group. The photodegradable protective group refers to any group that is released by irradiation with light, and includes, for example, a group having a 2-nitrobenzyl derivative skeleton, a dimethoxybenzoin group, a 2-nitropiperonyloxycarbonyl (NPOC) group, and a 2-nitro group. Veratryloxycarbonyl (NVOC) group, α-methyl-2-
Nitropiperonyloxycarbonyl (MeNPOC)
Group, α-methyl-2-nitroveratryloxycarbonyl (MeNVOC) group, 2,6-dinitrobenzyloxycarbonyl (DNBOC) group, α-methyl-2,6-
Dinitrobenzyloxycarbonyl (MeDNBOC)
Group, 1- (2-nitrophenyl) ethyloxycarbonyl (NPEOC) group, 1-methyl-1- (2-nitrophenyl) ethyloxycarbonyl (MeNPEOC)
Group, 9-anthracenylmethyloxycarbonyl (AN
MOC) group, 1-pyrenylmethyloxycarbonyl (P
YMOC) group, 3'-methoxybenzoinyloxycarbonyl (MBOC) group, 3 ', 5'-dimethoxybenzoyloxycarbonyl (DMBOC) group, 7-nitroindolinyloxycarbonyl (NIOC) group, 5,7-
Dinitroindolinyloxycarbonyl (DNIOC)
Group, 2-anthraquinonylmethyloxycarbonyl (A
QMOC) group, α, α-dimethyl-3,5-dimethoxybenzyloxycarbonyl group, 5-bromo-7-nitroindolinyloxycarbonyl (BNIOC) group, and the like. Groups having a 2-nitrobenzyl derivative backbone, as in the represented silane compounds, are particularly preferred.

[0046]

[Chemical 31]

Among the silane compounds represented by the above general formula [1], the silane compound represented by the above general formula [2] is preferable, and in the general formula [2], R ² is a hydrogen atom or an alkyl group. The alkyl group represented by R ² may be linear or branched, may have an unsaturated bond, and may be an alkoxy group such as a methoxy group or an ethoxy group. It may have a substituent such as a group and an acyl group such as a formyl group and an acetyl group. The number of carbon atoms of the alkyl group is not limited, but the number of carbon atoms is 1
To 6 are preferred, and specifically, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, s-
Alkyl groups such as butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, vinyl group, allyl group, 2-propenyl group, 2-butenyl group, 2-pentenyl group, Specific examples thereof include an alkenyl group such as a 2-heptynyl group and an alkynyl group such as a propargyl group, and among these, a methyl group is particularly preferable.

In the general formula [2], R ³ and R ⁴ each independently represent a hydrogen atom or an alkoxy group. That is, R
³ and R ⁴ may be the same substituent or different substituents, but are preferably the same group,
An alkoxy group is preferred because the protecting group can be removed with long-wavelength light when coupling is performed. The number of carbon atoms of the alkoxy group represented by R ³ and R ⁴ is not particularly limited, but the number of carbon atoms is 1
It is preferably an alkoxy group of 6 to 6, specifically, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, an s-butoxy group, a t-butoxy group, an n-pentyloxy group. , N-hexyloxy group and the like, and of these, a methoxy group and an ethoxy group are particularly preferable.

[0049]

[Chemical 32]

In the general formula [3], X represents an alkoxy group or a halogen atom, Y represents a photodegradable protective group, and R ¹ represents an alkyl group. m represents an integer of 1 to 3 (when contained in the coupling agent), and n represents an integer. Regarding X, Y and R ¹ in the general formula [3], the general formula [1]
Is the same as X, Y and R ¹ in. The m and n in the general formula [3] are the same as the m and n in the general formula [1].

[0051]

[Chemical 33]

Among the silane compounds represented by the above general formula [3], the silane compounds represented by the above general formula [4] are preferable, and in the general formula [4], R ² is a hydrogen atom or an alkyl group. R ³ and R ⁴ each independently represent a hydrogen atom or an alkoxy group. R in general formula [4]
² , R ³ and R ⁴ are R ² and R in the general formula [2].
^{The same as 3} and R ⁴ .

[0053]

[Chemical 34]

In the general formula [5], X represents an alkoxy group or a halogen atom, Y represents a photodegradable protective group, and R ¹ represents an alkyl group. m represents an integer of 1 to 3 (when contained in the coupling agent), and n represents an integer. Regarding X, Y and R ¹ in the general formula [5], the general formula [1]
Is the same as X, Y and R ¹ in. The m and n in the general formula [5] are the same as the m and n in the general formula [1].

[0055]

[Chemical 35]

Among the silane compounds represented by the above general formula [5], the silane compound represented by the above general formula [6] is preferable, and in the general formula [6], R ² is a hydrogen atom or an alkyl group. R ³ and R ⁴ each independently represent a hydrogen atom or an alkoxy group. R in general formula [6]
² , R ³ and R ⁴ are R ² and R in the general formula [2].
^{The same as 3} and R ⁴ .

[0057]

[Chemical 36]

General formula

In [9], X represents an alkoxy group or a halogen atom, Y represents a photodegradable protective group, and W represents Y.
Alternatively, it represents a hydrogen atom, and R ¹ represents an alkyl group. m is 1
Represents an integer of 3 (when contained in the coupling agent),
n represents an integer, and l represents 0 or 1. General formula

X in [9], Y, for R ¹ is the same formula in [1] X, Y, and R ^1. General formula

M in [9],
The same applies to n as m and n in the general formula [1].

[0059]

[Chemical 37]

The above general formula

Silane compound represented by [9]
Among the above, the formula [10] or the formula [11]
A silane compound represented by the formula [10]
And R in [11]²Represents a hydrogen atom or an alkyl group
And R³And R^FourAre each independently a hydrogen atom or an alcohol
Represents a xy group. R in the general formulas [10] and [11]
², R³, R^FourWith respect to R in the general formula [2]², R
³, R^FourIs the same as.

The silane compound of the present invention is not particularly limited as long as it is a silane compound in which an amino group, a sulfo group, a thiol group or a phosphoric acid group is protected by a photodegradable protective group, and the above-mentioned general formula is used. [1] to [6] and general formula

Silane compounds represented by [9] to [11] (including the case where m is 0) are preferable. In particular, general formula [2], general formula [4], general formula [6], general formula [10] and general formula [1]
1] is preferable, and among these, compounds in which m is an integer of 1 to 3 are preferable, and specifically, 1- (2-nitrophenyl) ethyl-N- (3- (triethoxysilyl). ) Propyl) carbamate (Specific Example 1), 1- (2-nitrophenyl) ethyl-N- (3-
(Trimethoxysilyl) propyl) carbamate (Specific Example 2), 1- (2-nitrophenyl) ethyl-N- (3
-(Methyldiethoxysilyl) propyl) carbamate (Specific Example 3), 1- (4,5-dimethoxy-2-nitrophenyl) ethyl-N- (3- (triethoxysilyl))
Propyl) carbamate (Specific Example 4), 1- (2-nitrophenyl) ethyl-N- (11-triethoxysilyl) propyl) carbamate (Specific Example 5), 2-nitrobenzyl-4- (trimethoxysilyl) butane Sulfonate (Specific Example 6), 2-nitrobenzyl-4- (triethoxysilyl) butane sulfonate (Specific Example 7), 2-
Examples thereof include nitrobenzyl-3- (trimethoxysilyl) propyl sulfide (Specific Example 8). The silane compound of the present invention can be used not only as a silane coupling agent but also as a binder by being mixed with a polymer compound, for example.

[0062]

[Chemical 38]

The silane coupling agent of the present invention has an organic functional group having an affinity and a reactivity with an organic polymer in one molecule as described above, and an affinity and a reactivity with an inorganic or metallic material. A silane compound having a hydrolyzable silyl group having ## STR3 ## can be mixed with a solvent to obtain an adhesion improver showing adequacy of adhesion improvement at the interface where the organic polymer and the inorganic or metal material are in contact. Examples of the solvent of the photodegradable silane coupling agent of the present invention include benzene, hexane, ethyl acetate, ethyl acetate, methanol, chloroform, dichloromethane, carbon tetrachloride, tetrahydrofuran and the like. Among them, benzene is preferable and dehydrated. It is particularly preferable to use one.

The photodegradable silane coupling agent of the present invention is one in which an amino group is protected by a photodegradable protective group and is easy to use. For example, an amino group protected by a photodegradable protective group is used as a group. It is formed on the surface of the material, the surface of the substrate is irradiated with ultraviolet rays, the protecting group is removed to expose the amino group, and DNA is
It becomes possible to manufacture a DNA chip to which a probe is bound.

In the production of the above-mentioned silane compound, a method of isolating with a silica gel column in which tetramethoxysilane is added as an elution solvent can be preferably exemplified.
As the elution solvent, hexane, ethyl acetate,
Methanol, chloroform, dichloromethane and the like can be used, and hexane and ethyl acetate are preferable.
These may be used alone or in combination of two or more. The amount of tetramethoxysilane added is preferably 0.1 to 3.0 vol%, more preferably 0.2 to 2.0 vol%, and 0.3 to the elution solvent. It is more preferable that the content is ˜1.5 vol%. By adding tetramethoxysilane in the above range, the silane compound can be efficiently separated.

An example of a method for chemically modifying a substrate made of an inorganic material such as silica gel, silicon wafer, glass or the like using the above photodegradable coupling agent will be described below with reference to the drawings. In addition to the inorganic material, the base material may be an organic material having a hydroxy group on the surface. Further, the shape of the substrate is not particularly limited,
It may be in a sheet shape, a honeycomb shape, a fiber shape, a bead shape, a foamed shape, or a combination thereof. FIG. 1 is an illustration of a chemical modification treatment process using the photodegradable coupling agent of the present invention, FIG. 2 is an illustration of pretreatment, and FIG.
FIG. 4 is an explanatory diagram of surface treatment, FIG. 4 is an explanatory diagram of protective group removal by light irradiation, and FIG. 5 is an explanatory diagram of chemical modification.
As shown in FIG. 1, in the treatment, the substrate is pretreated, if necessary, and then surface modification, light irradiation, and chemical modification are sequentially performed. Hereinafter, each step will be described.

As shown in FIG. 2, the pretreatment is performed by coating the surface of the substrate with an acidic solution. Examples of the acidic solution include sulfuric acid, hydrochloric acid, nitric acid, hydrogen peroxide, and the like. These may be used alone or in combination of two or more, but a combination of sulfuric acid and hydrogen peroxide is preferable, The combined use of sulfuric acid and hydrogen peroxide is particularly suitable for the pretreatment of silicon wafers. Also, as a means of coating,
There is no particular limitation as long as it can coat the surface of the base material, and examples thereof include coating, spraying and dipping. By this pretreatment, a hydrophilic group (silanol group) can be formed on the surface of the base material.

As shown in FIG. 3, the surface modification treatment is carried out by coating the substrate with the photodegradable silane coupling agent, coupling the silane compound in the silane coupling agent to the substrate, and using the silane compound. A surface-modified surface-modified coupling substrate is prepared. Examples of the coating means include coating, spraying and dipping as in the pretreatment. Of these, dipping is preferable, and not only room temperature treatment but also reflux treatment is preferably performed.

As shown in FIG. 4, in the light irradiation treatment, light is applied to all or part of the surface of the surface-modified coupling base material, and the photodegradable protective group in the light-irradiated portion is released to remove a functional group. A functional group-exposed coupling base material is prepared by exposing and forming a functional group on the surface of the base material. That is, by irradiating only a specific portion with light, a functional group can be formed only in that portion. The irradiation light is not particularly limited as long as it can remove the photodegradable protective group and expose the functional group,
Ultraviolet rays (1 to 400 nm) are preferable, and due to the optical resolution of the photodegradable protective group of the silane compound,
Light with a long wavelength (for example, 320 nm or more) can be used as appropriate.

As shown in FIG. 5, in the chemical modification treatment, the functional group-exposed coupling base material is coated with a solution containing an organic substance to be modified, and the functional group of the functional group-exposed coupling base material is reacted with the organic material. Then, a chemically modified coupling substrate is manufactured. The organic substance used for the chemical modification can be appropriately determined depending on the intended use of the product, and for example, a biological substance such as nucleic acid, sugar or protein can be used. The coating means is the same as in the case of surface modification.

The compound of the present invention in which an amino group is protected by a photodegradable protective group is not only useful as a modifier for a composite material, but also a self-assembled monolayer (Self assembled monolayer).
ER; SAM), mesoporous silica, microarrays, etc., can be widely used as a reagent for introducing a functional group into the surface, which has been difficult to introduce. Further, since it is possible to perform patterning for introducing a functional group by irradiation with light of 300 nm or more, it can be used as a new photoresist material and a basic technology of combinatorial chemistry. Further, it can be used as a chromatography carrier.

The photodecomposable compound represented by the general formula [7] of the present invention will be described. The photodecomposable compound represented by the general formula [7] can be used in the production of the silane compound represented by the general formula [1], and is very efficiently represented by the general formula [1]. The compound can be prepared.

[0073]

[Chemical Formula 39]

In the general formula [7], Y represents a photodegradable protective group. Y in the general formula [7] is Y in the general formula [1].
Is the same as. The photodegradable compound represented by the general formula [7] is preferably a photodegradable compound represented by the following general formula [8]. The photodecomposable compound represented by the general formula [8] can be used in the production of the silane compound represented by the general formula [2], and is a compound represented by the general formula [2] very efficiently. Can be manufactured.

[0075]

[Chemical 40]

In the general formula [8], R²Is a hydrogen atom or
Represents a kill group, R³, R^FourAre each independently a hydrogen atom or
Represents an alkoxy group. R in general formula [8]²,
R³, R ^FourIs R in the general formula [2]², R³, R^Foursame as
Is.

[0077]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
In the following examples, water refers to ion exchange distilled water.

[Example 1] <Synthesis of 1- (2-nitrophenyl) ethyl-N- (3- (triethoxysilyl) propyl) carbamate (Specific Example (1))> 1 in a 50 mL round-bottomed flask with nitrogen substitution. -(2-Nitrophenyl) ethanol 1.50 g
(8.97 mmol), N-N'-disuccinimidyl carbonate 2.31 g (9.02 mmol), triethylamine 2.02 mL (27.0 mmol) were added,
The mixture was stirred in 20 mL of DMF (N, N-dimethylformamide) at room temperature for 5 hours. After the reaction, DMF was distilled off to obtain 6.59 g of a crude product (black viscous body). This was subjected to column chromatography (hexane: ethyl acetate = 2: 1).
(V / v)) to obtain the desired product (1- (2
-Nitrophenyl) ethyl-N-hydroxysuccinimidyl carbonate) 2.00 g (6.49 mmol,
72.4%) was obtained.

[0079]

[Chemical 41]

1- (2-nitrophenyl) synthesized above
The identification results of ethyl-N-hydroxysuccinimidyl carbonate are shown below. ¹ H-NMR (400 MHz, CDCl ₃ / TMS) δ = 1.80 (d, J = 6.4 Hz, 3 H, methy)
l), 2.80 (s, 4H, methylene),
6.40 (q, J = 6.4Hz, 1H, method
e), 7.51 (m, 1H, aromatic), 7.
75 (m, 2H, aromatic), 8.03 (d,
J = 8.4 Hz, 1H, aromatic) IR (KBr) 1789 cm ^-1 (C = O) (ester), 1745c
m ^-1 (C = O) (succinyl), 1530 cm ^-1
and 1359 cm ^-1 (NO ₂ ) Rf: 0.18

Next, 1- (2-nitrophenyl) ethyl-synthesized above was placed in a 100 mL round-bottomed flask which had been purged with nitrogen.
N-hydroxysuccinimidyl carbonate 1.00
g (3.24 mmol), 3- (triethoxysilyl)
0.72 g (3.25 mmol) of propylamine was added, and the mixture was stirred in 50 mL of dry THF (tetrahydrofuran) at room temperature for 3 hours. After the reaction, the solvent was distilled off to obtain 2.30 g of a crude product. This was purified by column chromatography (hexane: ethyl acetate: tetramethoxysilane = 200: 100: 3 (v / v)) to obtain a yellow viscous product (1- (2-nitrophenyl) ethyl-N-).
(3- (triethoxysilyl) propyl) carbamate (Specific Example (1)) 1.19 g (2.87 mmol, 8)
8.6%) was obtained.

[0082]

[Chemical 42]

1- (2-nitrophenyl) synthesized above
Ethyl-N- (3- (triethoxysilyl) propyl)
The identification results of carbamate (specific example (1)) are shown below. ¹ H-NMR (400 MHz, CDCl ₃ / TMS) δ = 0.60 (t, J = 8.0 Hz, 2H, methy)
len), 1.22 (t, J = 6.8Hz, 9H, m
Ethyl), 1.61 (d, J = 6.4 Hz, 3H,
1.61 (m, 2H, methyl)
ne), 3.12 (m, 2H, methylene),
3.81 (q, J = 6.8Hz, 6H, methyl
ne), 5.04 (br, 1H, secondary
Amine), 6.23 (q, J = 6.8 Hz, 1H,
methine), 7.39 to 7.42 (m, 1H, a
romantic), 7.61 to 7.63 (m, 2H, a
romantic), 7.92 (d, J = 8.0 Hz, 1
H, aromatic) IR (Nacl) 3342 cm ^-1 (NH), 1718 cm ^-1 (C =
O), 1528 cm ^{-1 and} 1352 cm ^-1 (NO ₂ ) Rf: 0.56

[Example 2] <Synthesis of 1- (2-nitrophenyl) ethyl-N- (3- (trimethoxysilyl) propyl) carbamate (Specific Example (2))> A 100 mL round-bottomed flask containing nitrogen was replaced with the above. 1- (2-nitrophenyl) synthesized in Example 1
Ethyl-N-hydroxysuccinimidyl carbonate 1.00 g (3.24 mmol), 3- (trimethoxysilyl) propylamine 0.58 g (3.23 mmo)
1) was added, and the mixture was stirred in 50 mL of dry THF at room temperature for 3 hours. After the reaction, the solvent was distilled off to obtain 1.97 g of a crude yellow viscous product. This was purified by column chromatography (hexane: ethyl acetate: tetramethoxysilane = 200: 100: 3 (v / v)) to obtain a yellow viscous product (1- (2-nitrophenyl) ethyl-N-).
(3- (trimethoxysilyl) propyl) carbamate (Specific example (2)) 0.67 g (1.80 mmol, 5)
5.7%) was obtained.

[0085]

[Chemical 43]

1- (2-nitrophenyl) synthesized above
Ethyl-N- (3- (trimethoxysilyl) propyl)
The identification results of carbamate (Specific Example (2)) are shown below. ¹ H-NMR (400 MHz, CDCl ₃ / TMS) δ = 0.61 (t, J = 8.2 Hz, 2 H, methy)
len), 1.61 (d, J = 6.4 Hz, 3H, m
1.61 (m, 2H, methylen)
e), 3.12 (m, 2H, methylene),
3.56 (s, 9H, methyl), 4.95 (b
r, 1H, secondary amine), 6.2
3 (q, J = 6.4 Hz, 1H, methine),
7.40 (m, 1H, aromatic), 7.62
(M, 2H, aromatic), 7.93 (d, J =
8.4 Hz, 1H, aromatic) IR (Nacl) 3343 cm ^-1 (N-H), 1698 cm ^-1 (C =
O), 1525 cm ^{-1 and} 1352 cm ^-1 (NO ₂ ) Rf: 0.24

Example 3 <Synthesis of 1- (2-nitrophenyl) ethyl-N- (3- (dimethylethoxysilyl) propyl) carbamate (Specific Example (3))> A 100 mL round-bottomed flask containing nitrogen was replaced with the above. 2.03 g (6.59 mmol) of 1- (2-nitrophenyl) ethyl-N-hydroxysuccinimidyl carbonate synthesized in Example 1 was added, and dry was added.
It was dissolved in 50 mL of THF. 1.11 g (6.8 g of 3- (dimethylethoxysilyl) propylamine) was added to the solution.
8 mmol) was added, and the mixture was stirred under a nitrogen atmosphere at room temperature for 3 hours. After the reaction, when the product was confirmed by TLC (thin layer chromatography) (hexane: ethyl acetate = 2: 1), the raw materials still remained.
At reflux for 3 hours. After that, when checked again by TLC, the raw material remained, but the spot which seems to be the target was thick, so the reaction was stopped and the solvent was distilled off to give 3.49 g of a crude product (pale yellow viscous body). Got This was subjected to column chromatography (hexane: ethyl acetate: tetramethoxysilane = 200: 100: 1.5 (v /
v)) and the target product (1- (2-nitrophenyl) ethyl-N- (3- (dimethylethoxysilyl) propyl) carbamate (specific example (3)) 0.95 as a yellow viscous substance.
g (2.68 mmol, 40.7%) was obtained.

[0088]

[Chemical 44]

The identification results of the above-synthesized (1- (2-nitrophenyl) ethyl-N- (3- (dimethylethoxysilyl) propyl) carbamate (Specific Example (3)) are shown below: ¹ H-NMR ( 400 MHz, CDCl ₃ / TMS) δ = 0.10 (s, 6H, methyl), 0.55
(T, J = 8 Hz, 2H, methylene), 1.
19 (t, J = 7.2 Hz, 3H, methyl),
1.50 (m, 2H, methylene), 1.61
(D, J = 6.8 Hz, 3H, methyl), 3.1
2 (m, 2H, methylene), 3.65 (q,
J = 7.2 Hz, 2H, methylene), 4.9
8 (s, 1H, amine), 6.24 (q, J = 6.
4Hz, 1H, mean), 7.41 (m, 1)
H, aromatic), 7.61 (m, 2H, aro
matic), 7.92 (d, J = 8.4 Hz, 1H,
aromatic) IR (Nacl) 3332 cm ^-1 (N-H), 1722 cm ^-1 (C =
O), 1527cm ^{-1 and} 1351cm ^-1 (NO ₂ )

Example 4 <Synthesis of 1- (4,5-dimethoxy-2-nitrophenyl) ethyl-N- (3- (triethoxysilyl) propyl) carbamate (Specific Example (4))> Immerse in water bath 20
In a 0 mL eggplant flask, 50 mL of 61% HNO ₃ (670
mmol) and keep the temperature around 15 ° C,
3 ', 4'-dimethoxyacetophenone 5.00 g (2
(7.7 mmol) was added little by little, and the mixture was stirred in a water bath for 3 hours. The reaction solution was poured into 100 mL of ice water, and the resulting precipitate was filtered. The precipitate was washed with water and recrystallized from ethanol to give 1.15 g (5.11 mmol, 5.11 mmol, target product (4,5-dimethoxy-2-nitroacetophenone) of a yellow powder.
18.3%).

[0091]

[Chemical formula 45]

The identification results of the above-synthesized 4,5-dimethoxy-2-nitroacetophenone are shown below. ¹ H-NMR (400 MHz, CDCl ₃ / TMS) δ = 2.50 (s, 3H, methyl), 3.99
(S, 6H, methyl), 6.76 (s, 1H, a
romantic), 7.62 (s, 1H, aromat
ic) IR (KBr) 1701 cm ^-1 (C = O), 1516 cm ^{-1 and} 13
28 cm ^-1 (NO ₂ )

Next, 1.27 g (5.64 mmol) of the above-synthesized 4,5-dimethoxy-2-nitroacetophenone was put in a 300 mL eggplant flask placed in an ice bath,
It was dissolved in 200 mL of methanol. To this, sodium borohydride (tetrahydroborate sodium salt)
0.60 g (15.9 mmol) was added little by little, and the mixture was stirred as it was in the ice bath for 30 minutes. Then, the mixture was stirred at room temperature for 1 hour, the solvent was distilled off under reduced pressure, 200 mL of water was added, and the mixture was stirred for 30 minutes. This was extracted with chloroform (100 mL × 5), anhydrous magnesium sulfate was added to the chloroform layer, dried and filtered, and chloroform was distilled off to obtain 1.44 g of a crude product as a yellow powder. This was recrystallized from ethanol to give 0.91 g (4.01 mmo) of the target product (1- (4,5-dimethoxy-2-nitrophenyl) ethanol) as a yellow solid.
1, 71.1%) was obtained.

[0094]

[Chemical formula 46]

The above-synthesized 1- (4,5-dimethoxy-
The identification results of 2-nitrophenyl) ethanol are shown below. ¹ H-NMR (400 MHz, CDCl ₃ / TMS) δ = 1.56 (d, J = 6.0 Hz, 3 H, methy)
l), 2.26 (d, 1H, hydroxy), 3.9.
5 to 4.01 (s, 6H, methyl), 5.55
5.61 (m, 1H, methine), 7.31
(S, 1H, aromatic), 7.58 (s, 1
H, aromatic) IR (KBr) 3298 cm ^-1 (OH), 1522 cm ^{-1 and} 132
3 cm ^-1 (NO ₂ )

Next, 0.80 g (3.52 mmo) of 1- (4,5-dimethoxy-2-nitrophenyl) ethanol synthesized above was placed in a 100 mL round-bottomed flask which had been purged with nitrogen.
l), N, N'-disuccinimidyl carbonate 0.
90 g (3.51 mmol), dry DMF 50 mL
Then, 0.80 mL of triethylamine was added to the solution, and the mixture was stirred at room temperature for 5 hours under a nitrogen atmosphere. After the reaction, 50 mL of water and 16 mL of 2N hydrochloric acid were added, and the mixture was extracted with ethyl acetate (50 mL × 3). The ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution (150 mL × 1). Anhydrous magnesium sulfate was added to the ethyl acetate layer, dried, filtered and concentrated to give a yellow solid crude product.
38 g was obtained. This was recrystallized from ethanol to give 0.67 g (1.82 mmol, 51.51) of the target product (1- (4,5-dimethoxy-2-nitrophenyl) ethyl-N-hydroxysuccinimidyl carbonate) as a yellowish white solid. 7
%) Was obtained.

[0097]

[Chemical 47]

The above-synthesized 1- (4,5-dimethoxy-
The identification results of 2-nitrophenyl) ethyl-N-hydroxysuccinimidyl carbonate are shown below. ¹ H-NMR (400 MHz, CDCl ₃ / TMS) δ = 1.77 (d, J = 6.0 Hz, 3 H, methy)
l), 2.80 (s, 4H, methylene),
3.95 to 4.07 (s, 6H, methyl), 6.
51 (q, J = 6.2 Hz, 1H, methine),
7.08 (s, 1H, aromatic), 7.65
(S, 1H, aromatic) IR (KBr) 1783 cm ^-1 (C = O), 1752 cm ^-1 (C = O,
succinyl), 1524cm ^{-1 and} 1333c
m ^-1 (NO ₂ )

Next, 0.62 g (1.68 mmol) of 1- (4,5-dimethoxy-2-nitrophenyl) ethyl-N-hydroxysuccinimidyl carbonate synthesized above was placed in a 100 mL round-bottomed flask which had been purged with nitrogen. It was put and dissolved in 30 mL of dry THF. To this 3
-Aminopropyltriethoxysilane 0.48 g (2.
17 mmol) was added, and the mixture was stirred at room temperature for 3 hours under a nitrogen atmosphere. After the reaction, the solvent was distilled off to obtain 1.59 g of a crude product. This was subjected to column chromatography (hexane: ethyl acetate: tetramethoxysilane = 200: 10).
0: 1 (v / v)) to obtain a yellow viscous product (1-
(4,5-Dimethoxy-2-nitrophenyl) ethyl-
0.74 g (1.56 mmol, N- (3- (triethoxysilyl) propyl) carbamate (Specific Example (4))
92.9%).

[0100]

[Chemical 48]

The above-synthesized 1- (4,5-dimethoxy-
The identification results of 2-nitrophenyl) ethyl N- (3- (triethoxysilyl) propyl) carbamate (Specific Example (4)) are shown below. ¹ H-NMR (400 MHz, CDCl ₃ / TMS) δ = 0.61 (t, J = 8.0 Hz, 2H, methy)
len), 1.22 (t, J = 7.2 Hz, 9H, m
Ethyl), 1.58 to 1.60 (m, 3H, met
hyl), 1.58 to 1.60 (m, 2H, methy
len), 3.15 (m, 2H, methylen
e), 3.81 (q, 6H, J = 7.2 Hz, meth
ylen), 3.93 to 3.97 (s, 6H, met
hyl), 5.03 (br, 1H, amine), 6.
37 (q, J = 6.0 Hz, 1H, methine),
7.01 (s, 1H, aromatic), 7.58
(S, 1H, aromatic) IR (Nacl) 3392 cm ^-1 (N-H), 1717 cm ^-1 (C =
O), 1521 cm ^{-1 and} 1336 cm ^-1 (NO ₂ )

[Example 5] <Synthesis of 1- (2-nitrophenyl) ethyl-N-11- (triethoxysilyl) undecylcarbamate (Specific Example (5))> Potassium phthalimide 2. 07 g (11.2 mmol), dry
Add 100 mL of DMF and add 11-bromo-1 to the solution.
-Add 2.00 g (8.58 mmol) undecene,
Refluxed at 150 ° C. for 90 minutes. After the reaction, DMF was distilled off under reduced pressure, 30 mL of dichloromethane was added, and the mixture was stirred for 16 hours. The precipitated solid was filtered, anhydrous magnesium sulfate was added to the filtrate, dried and filtered. The filtrate was concentrated to obtain 2.56 g of a crude product as a yellowish white solid. Purification by column chromatography (hexane: ethyl acetate = 2: 1 (v / v)) gave a white solid of the desired product (N- (10-undecenyl)-).
1-phthalimide) 2.12 g (7.08 mmol, 8)
2.5%) was obtained.

[0103]

[Chemical 49]

N- (10-undecenyl) synthesized above
The identification results of -1-phthalimide are shown below. ¹ H-NMR (400 MHz, CDCl ₃ / TMS) δ = 7.84 (2H, m, aromatic), 7.7.
1 (2H, m, aromatic), 5.80 (1H,
m, methane), 4.96 (2H, m, meth)
ylen), 3.68 (2H, t, J = 7.6Hz,
2.02 (2H, q, J = 6.
8Hz, methylene), 1.67 (2H, m,
methylene), 1.27 to 1.33 (12H,
m, methylene) IR (KBr) 1696 cm ^-1 (C = O)

Next, in a 200 mL round-bottomed flask, 1.60 g (5.34 mmol) of N- (10-undecenyl) -1-phthalimide synthesized above, 743 μL (15.0 mmol) of hydrazine monohydrate, and 100 mL of ethanol were put, and Reflux at ~ 85 ° C for 2 hours. After the reaction, the solvent was distilled off, 200 mL of water and 16 mL of hydrochloric acid were added, and the mixture was extracted with chloroform (200 mL × 3). The organic layer was saturated aqueous sodium hydrogen carbonate solution (300 mL x 1)
It was washed with, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated to obtain 0.96 g of a crude product. This was subjected to column chromatography (methanol: chloroform = 2:
The target product (10-undecenyl-
1-amine) 0.45 g (2.66 mmol, 49.8)
%) Was obtained.

[0106]

[Chemical 50]

The identification results of the above-synthesized 10-undecenyl-1-amine are shown below. ¹ H-NMR (400 MHz, CDCl ₃ / TMS) δ = 5.76-5.86 (1 H, m, methin
e) 4.92 to 5.01 (2H, m, methyl)
ne), 2.67 (2H, t, J = 6.8Hz, met
Hylene), 2.04 (2H, q, J = 6.8H
z, methylene), 1.28 to 1.43 (14
H, m, methylene) IR (KBr) 3335 cm ^-1 (-NH ₂ ).

Next, 1- (2-nitrophenyl) ethyl-N-hydroxysuccinimidyl carbonate prepared in Example 1 was added to a 50 mL round-bottomed flask which had been purged with nitrogen.
82 g (2.66 mmol), 0.45 g (2.66 mmo) of the above-synthesized 10-undecenyl-1-amine.
l), 20 mL of dry THF was added, and under a nitrogen atmosphere,
Stir at room temperature for 3 hours. After the reaction, the solvent was distilled off under reduced pressure to obtain 1.60 g of a crude product. This was subjected to column chromatography (hexane: ethyl acetate = 2: 1 (v /
v)) and 0.95 g (2.62 mmol, 98.5%) of a yellow viscous product (1- (2-nitrophenyl) ethyl-N- (10-undecenyl) carbamate).
Obtained.

[0109]

[Chemical 51]

1- (2-nitrophenyl) synthesized above
The identification results of ethyl-N- (10-undecenyl) carbamate are shown below. ¹ H-NMR (400 MHz, CDCl ₃ / TMS) δ = 7.92 (1 H, d, J = 8.0 Hz, aroma)
tic), 7.60 to 7.63 (2H, m, aroma
tic), 7.38 to 7.42 (1H, m, methy
len), 6.23 (1H, q, J = 6.8Hz, m
ethine), 5.76 to 5.86 (1H, m, me
thin), 4.91 to 5.02 (2H, m, met
hylen), 4.71 (1H, br, amin
e), 3.07 to 3.16 (2H, m, methyl)
ne), 2.03 (2H, q, J = 6.6Hz, met
Hylene), 1.61 (3H, d, J = 6.8H
z, methyl), 1.26 to 1.45 (14H,
m, methylene) IR (NaCl) 3334 cm ^-1 (N-H), 1703 cm ^-1 (C =
O), 1526 and 1349 cm ^-1 (-NO ₂ ).

Next, 1- (2-nitrophenyl) ethyl-N synthesized above was placed in a 50 mL round-bottomed flask which had been purged with nitrogen.
-(10-Undecenyl) carbamate 0.95 g
(2.62 mmol), triethoxysilane 0.65 g
(3.96 mmol), hydrogen hexachloroplatinate hexahydrate (H ₂ PtCl ₆ · 6H)
₂ O) A very small amount was added, and the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then heated and stirred at 60 ° C. for 4 hours. After the reaction, excess triethoxysilane was distilled off under reduced pressure, and purified by column chromatography (hexane: ethyl acetate: tetramethoxysilane = 300: 100: 4 (v / v)) to obtain a yellow viscous product (1- ( 2-nitrophenyl) ethyl-
N-11- (triethoxysilyl) -undecylcarbamate (specific example (5))) 0.21 g (0.40 mmo)
1, 15.3%).

[0112]

[Chemical 52]

1- (2-nitrophenyl) synthesized above
The identification results of ethyl-N-11- (triethoxysilyl) undecylcarbamate (Specific Example (5)) are shown below. ¹ H-NMR (400 MHz, CDCl ₃ / TMS) δ = 7.92 (1 H, d, J = 8.0 Hz, aroma)
tic), 7.60 to 7.62 (2H, m, aroma)
tic), 7.38 to 7.43 (1H, m, aroma
tic), 6.23 (1H, q, J = 6.6Hz, me
thin), 4.71 (1H, br, amine),
3.82 (6H, q, J = 6.8Hz, methyl
ne), 3.07 to 3.16 (2H, m, methyl)
ene), 1.61 (3H, d, J = 6.4Hz, me
tyl), 1.24 to 1.45 (18H, m, met
hylen), 1.23 (9H, t, J = 7.2H
z, methylene), 0.63 (2H, t, J =
8.2 Hz, methylene) IR (NaCl) 3337 cm ^-1 (N-H), 1708 cm ^-1 (C =
O), 1528 and 1350 cm ^-1 (-NO ₂ ).

Example 6 <2-Nitrobenzyl-4- (trimethoxysilyl) butanesulfonate (Synthesis of Concrete Example (6)> 3 Ports 500 m
3.56 g of 4-bromo-1-butene in an L eggplant flask
(24.6 mmol), ethanol 250 mL, pure water 9
0 mL, a magnetic stir bar was placed. In the dropping funnel, 3.33 g (26.4 mmol) of sodium sulfite, 50 m of pure water
L was added. Heat and stir the eggplant flask in an oil bath,
The solution was added dropwise at 85 ° C. After dropping all the solutions, reflux was performed for 2 hours. The reaction solution was transferred to another 300 mL round-bottomed flask and concentrated by an evaporator. This was washed with 50 mL of ethanol, and the supernatant was filtered (5 times). After that, the filtrate is concentrated and dried to obtain a white powder of the desired product (3.27 g of sodium 3-butenesulfonate (22.2 mm).
ol, 78%).

[0115]

[Chemical 53]

The identification results of the above-synthesized sodium 3-butenesulfonate are shown below. ^{1 H-NMR (DSS / D} 2 O) 90MHz δ; 2.5 (m, 2H) = CH-CH 2 -CH 2 3.0 (m, 2H) -CH 2 -CH 2 -SO 2 - 5. _{2 (dd, 2H) CH 2} = CH- 5.9 (m, 1H) CH 2 = CH- IR (KBr) 1424 and 1190cm -1 (-S
(= O) ₂ −)

Next, 16.6 g (105 mmol) of sodium 3-butenesulfonate was placed in a 100 mL beaker and dissolved in 50 mL of pure water. A small amount of regenerated resin was put into this and melted. The column to be poured was kept in a state where the liquid surface was slightly above the uppermost resin, and was poured into the ion exchange resin together with the resin. Those remaining on the beaker were washed twice with pure water and poured into the column. Dropping was started at a rate of about 2 drops per second, and the outflow was stopped when the liquid surface was slightly above the uppermost resin. Next, pure water was continuously poured into the column to restart the outflow. The eluate until the effluent from the column became neutral was collected. The eluate was concentrated and dried to give 6.76 g (49.6 mmo) of brown liquid.
l) was obtained (ion exchange).

[0118]

[Chemical 54]

Next, to 2.77 g (20.3 mmol) of ion-exchanged 3-butenesulfonic acid, a CH ₂ Cl ₂ solution containing (2-nitrophenyl) diazomethane was added dropwise with stirring in an ice bath. did. After completion of dropping, the mixture was stirred overnight at room temperature. After the reaction solution was concentrated, it was roughly separated by a silica gel column (chloroform 100%), and a silica gel column (hexane: ethyl acetate = 10 :).
After separation and purification in 1) and vacuum drying, the desired product (2-nitrobenzyl-3-butene sulfonate) as a reddish brown viscous substance was obtained.
980 g (3.61 mmol, 17.8%) were obtained.

[0120]

[Chemical 55]

The identification results of the above-synthesized 2-nitrobenzyl-3-butenesulfonate are shown below. ¹ H-NMR (TMS / CDCl ₃ ) 400 MHz δ = 2.63-2.68 (m, 2H) = CH-CH ₂ -CH ₂ -SO ₂ 3.27-3.31 (m, 2H) = CH _{-CH 2 -CH 2 -SO 2 5.13-5.20 (} m, 2H) CH 2 = CH-CH 2 - 5.67 (S, 2H) S-O-CH 2 - 5.78-5. _{88 (m, 1H) CH 2} = CH-CH 2 - 7.6-7.8 (m, 3H) H-Ar 8.1-8.2 (m, 1H) H-Ar IR (NaCl): 1446and1167cm ^-1 (-S (= O) _2- ),
1528 and 1347 cm ^-1 (NO ₂ ) Rf value: 0.06

Next, in a 50 mL round-bottomed flask which had been purged with nitrogen, 2-nitrobenzyl-3-butenesulfonate (0.1%) was added.
652 g (2.40 mmol), trimethoxysilane _{0.352g (2.88mmol), H 2 PtCl} 6 · 6
A very small amount of H ₂ O was added. Under a nitrogen atmosphere, heat stirring (4
5 ° C) for 2 hours. A new product was confirmed by TLC. Subsequently, heating and stirring were carried out at the same temperature for 14 hours, but no change could be confirmed. It was purified by silica gel column chromatography (hexane: ethyl acetate: tetraethoxysilane = 300: 100: 6). The resulting crude product was vacuum dried on a water bath at 50 ° C. for 3 hours to remove tetraethoxysilane to obtain a colorless transparent viscous product (2-nitrobenzyl-4- (trimethoxysilyl) butanesulfonate (specific example (6))) 0.0
44 g (0.13 mmol, 6%) was obtained.

[0123]

[Chemical 56]

2-Nitrobenzyl-4-synthesized above
The identification results of (trimethoxysilyl) butanesulfonate (Specific Example (6)) are shown below. ¹ H-NMR (TMS / CDCl ₃ ) 400 MHz δ = 0.8 (m, 2 h) Si—CH ₂ —CH ₂ 1.6 (m, 2 h) CH ₂ —CH ₂ —CH ₂ —SO ₂ 1.9 _{(m, 2h) CH 2 -CH} 2 -CH 2 -SO 2 3.2 (m, 2h) CH 2 -CH 2 -SO 2 3.5-3.6 (m, 9h) (CH 3 O) 3 -Si 5.7 (s, 2h) S -O-CH 2 - 7.6-7.8 (m, 3h) H-Ar 8.2 (m, 1h) H-Ar Rf value: 0.13

Example 7 <Synthesis of 2-nitrobenzyl-4- (triethoxysilyl) butanesulfonate (Specific Example (7)> Synthesis was carried out in the same manner as in Example 6 on a 50 mL eggplant-shaped flask replaced with nitrogen. 2-nitrobenzyl-3-butene sulfonate 0.
755 g (2.78 mmol), triethoxysilane _{0.906g (3.34mmol), H 2 PtCl} 6 · 6
A very small amount of H ₂ O was added. Under a nitrogen atmosphere, heat and stir (5
5 ° C) for 1 hour. Here, it was confirmed that a new product was formed on TLC. Similarly, it was confirmed from TLC that the raw material remained, so 100 ° C after that.
The temperature was raised to 2 hours to complete the reaction. Silica gel column chromatography (hexane: ethyl acetate: tetraethoxysilane = 400: 100: 10 (v
/ V)), but could not be completely separated. The resulting crude product was vacuum dried at 60 ° C. for 2 hours to remove tetraethoxysilane. 0.13 g of the target product (2-nitrobenzyl-4- (triethoxysilyl) butanesulfonate (specific example (7))) as a colorless transparent viscous body.
(11%) was obtained.

[0126]

[Chemical 57]

2-Nitrobenzyl-4-synthesized above
The identification results of (triethoxysilyl) butanesulfonate (Specific Example (7)) are shown below. ^{1 H-NMR (TMS / CDCl} 3) 400MHz δ = 0.64-0.68 (m, 2H) Si-CH 2 -CH 2 1.21-1.26 (m, 9H) (CH 3 CH 2 O _{) 3 -Si 1.59-1.61 (m, 2H} ) CH 2 -CH 2 -CH 2 -SO 2 1.93-1.95 (m, 2H) CH 2 -CH 2 -CH 2 -SO 2 _{3.19-3.23 (m, 2H) CH 2} -CH 2 -SO 2 3.79-3.89 (m, 6H) (CH 3 CH 2 O) 3 -Si 5.65-5.66 ( m, 2H) S-O- CH 2 - 7.56-7.79 (m, 3H) H-Ar 8.17-8.19 (m, 1H) H-Ar

Example 8 <Synthesis of 2-nitrobenzyl-3- (trimethoxysilyl) propyl sulfide (Specific Example (8))> 100 mL
A stir bar was placed in a two-necked eggplant flask, and the atmosphere was sufficiently replaced with nitrogen. 0.07 g (3.00 mmol) of 60% NaH was added, the flask was placed in an ice bath, and 0.49 g of 3-mercaptropropyltrimethoxysilane (2.
50 mmol) was dissolved in 20 mL of dry-THF, and the solution was added dropwise over 20 minutes. Next, 0.54 g (2.50 mmol) of 2-nitrobenzyl bromide was dried.
-Dissolved in 10 mL of THF and added dropwise in 10 minutes. Then, the mixture was stirred overnight at room temperature under a nitrogen atmosphere. The reaction solution was concentrated, 30 mL of dichloromethane was added to the obtained crude product,
Stir for 30 minutes. The white solid that precipitated was removed by filtration, and the filtrate was concentrated to obtain a crude product. This was separated by column chromatography (hexane: ethyl acetate: tetramethoxysilane = 3: 1: 0.04 (v / v)).
Purified product (2-nitrobenzyl-3- (trimethoxysilyl) propyl sulfide (Specific Example (8)))
0.22 g (0.66 mmol, 26%) was obtained.

[0129]

[Chemical 58]

2-Nitrobenzyl-3-synthesized above
The identification results of (trimethoxysilyl) propyl sulfide (Specific Example (8)) are shown below. ¹ H-NMR (400 MHz, CDCl ₃ / TMS) δ = 0.71 (t, J = 8.0 Hz, 2H, methy)
len), 1.6 to 1.7 (m, 2H, methyl)
ene), 1.47 (t, 2H, J = 7.0 Hz, me
1.54 (s, 9H, methy)
l), 4.05 (s, 2H, benzyl), 7.37
~ 7.44 (m, 1H, aromatic), 7.46
~ 7.58 (m, 2H, aromatic), 7.95
(D, J = 8.0Hz, 1H, aromatic)

The above-synthesized compounds of the present invention represented by the general formula [1] (specific examples (1) to (4) and specific example (6))
Was used to chemically modify the surface of the silicon wafer. The evaluation in each treatment was performed by measuring the contact angle of the surface of the silicon wafer and investigating the hydrophilicity of the surface.
The contact angle was measured by the following method.

(Measurement of Contact Angle) As the water used for the measurement, ion exchange distilled water was used. The contact angle meter used was Kyowa Interface Science Co., Ltd. CA-DT • A type. The measurement was performed according to the “liquid proper measurement operation” described in the instruction manual for the contact angle meter manufactured by Kyowa Interface Science Co., Ltd. The measurement of 10 points was performed for one sample, the maximum value and the minimum value thereof were cut off, and the remaining average value was taken as the contact angle.

1. Pretreatment 14 mL of sulfuric acid and 6 mL of 30% hydrogen peroxide were placed in a 50 mL eggplant flask and shaken gently to prepare a mixed solution of sulfuric acid: 30% hydrogen peroxide = 7: 3 (v / v). 90 silicon to 2
Heated at 0 ° C. for 1 hour. Discard only the mixed solution, and add about 3 parts of water when the silicon wafer remains in the flask.
Put 0 mL, and put the silicon wafer and eggplant flask wall 3
The rinse solution was rinsed off. Then, about 50 mL of water was added and ultrasonic cleaning was performed for 5 minutes. The water was discarded, and the silicon wafers were taken one by one with the tweezers made of titanium, and the moisture on the surface of the silicon wafer was removed. As shown in FIG. 2, by this pretreatment, a hydrophilic silanol layer was formed on the surface of the silicon wafer. The contact angle of the silicon wafer surface at this time was 5 ° or less.

2. Surface Modification (Silane Compounds (Introduction of Specific Examples (1) to (4) and Specific Example (6))) Dry benzene (activated Molecular Sieves 3A in a 50 mL round-bottomed flask substituted with nitrogen).
20 mL of 1/8 (dehydrated with Wako Pure Chemical Industries 133-08645), silane compound (specific examples (1) to (4))
And concrete example (6)) add about 0.02g and shake lightly,
A dry benzene solution of 1.2 to 2.4 mM silane compound was prepared. Two pre-processed silicon wafers were put in together with the non-mirror-finished side, and allowed to stand at room temperature for a predetermined time. Discard only the dry benzene solution and add methanol to the flask where the silicon wafer remains in the flask for about 30 m.
L was put and the silicon wafer and the wall surface of the eggplant flask were rinsed three times. After discarding methanol and similarly rinsing with chloroform, about 50 mL of chloroform was added and ultrasonic cleaning was performed for 10 minutes. Then, add chloroform (2
(00-250 mL) and put a silicon wafer,
Ultrasonic cleaning was performed for 0 minutes. The silicon wafers were taken one by one with tweezers, the chloroform on the surface was blown off with a nitrogen stream and dried, and then the contact angle was measured. Further, instead of the room temperature treatment, the same operation as above was performed by a reflux treatment in a nitrogen atmosphere. Table 1 shows the contact angle measurement results of the specific examples (1) to (4) in the room temperature treatment, and Table 2 shows the contact angle measurement results of the reflux treatment. Further, FIG. 6 shows the measurement results of the contact angle by the room temperature treatment and the reflux treatment for the specific example (6).

[0135]

[Table 1]

[0136]

[Table 2]

From the results shown in Table 1 and FIG. 6, surface modification was performed with four silane compounds having a trialkoxysilyl group (specific example (1), specific example (2), specific example (4) and specific example (6)). The exposed wafers showed increased contact angles and increased hydrophobicity, revealing that these compounds settle at room temperature. Further, from the results of Table 2, it was revealed that the specific example (3), which was not fixed at room temperature, was also fixed by the reflux treatment.

3. Light irradiation (conversion into functional groups (amino group, sulfo group)) Water filter for removing photoheat, Pyrex (R) glass filter for blocking light of wavelength of 300 nm or less, and a silicon wafer for light irradiation are mounted. A sample stand was prepared. After that, the ultra-high pressure mercury lamp was started and warmed up for 1 hour until the amount of light became stable. While measuring the illuminance with an illuminometer, we searched for a position where the illuminance was the following conditions. Light irradiation is 1
I went one by one. Surface-modified silicon wafer (specific examples (1) to (3), which were subjected to a room temperature treatment for 7 hours and a reflux treatment for 7 hours,
Further, the specific example (6) which had been refluxed for 1 hour was fixed with ordinary stainless steel tweezers, and a quartz beaker was covered over the wafer so as to prevent dust and the like from adhering to the wafer and covered. After irradiating with light for a predetermined time, the surface of the wafer was rinsed with methanol for about 10 seconds and then with chloroform similarly. Then, ultrasonic cleaning was performed for 10 minutes in chloroform, the wafer was dried with a nitrogen stream, and then the contact angle was measured.

Light irradiation conditions Ultra-high pressure mercury lamp USH-500D (USHIO INC.
Ceremony company) Irradiance 330-390 nm 1 (according to UVD-365PD) 1
00-130mW / cm ² (Direct reading mode UVD-254P) 190-320
nm 50 mW / cm²

The same operation as described above was carried out for the case where the surface modification was carried out at room temperature for 1 hour using the specific example (1) and the surface modification was carried out for 1 hour at the room temperature using the specific example (4). , A copper sulfate aqueous filter that blocks light of 320 nm or less was used instead of the glass filter made of Pyrex (R) that blocks light of wavelength of 300 nm or less.

Surface treatment was performed for 7 hours at room temperature to 300n.
Specific example (1) after irradiation with light having a wavelength exceeding m
Table 3 shows the contact angle for (3). Table 4 shows contact angles of specific examples (1) to (3) after surface modification by refluxing for 7 hours and irradiation with light having a wavelength of more than 300 nm.
Shown in. FIG. 7 shows the contact angle for the specific example (6) after surface modification by reflux treatment for 1 hour and irradiation with light having a wavelength of more than 300 nm. 320 with copper sulfate filter
Table 5 shows the contact angles after irradiation with light having a wavelength of more than nm.

[0142]

[Table 3]

[0143]

[Table 4]

[0144]

[Table 5]

From the results shown in Table 3, for the wafers treated at room temperature using the specific examples (1) and (2), the contact angle was greatly reduced, and the carbamic acid 2-nitrobenzyl ester had amino groups on the surface thereof. It was shown to be converted to a group. Regarding the wafer processed at room temperature in the specific example (3),
As expected, no decrease in contact angle was observed and it was revealed that the specific example (3) was not introduced on the wafer surface. From the results in Table 4, it was found that the contact angles of all the wafers surface-modified in the specific examples (1) to (3) were greatly reduced, and the carbamic acid 2-nitrobenzyl ester was converted to an amino group on the surface. Was shown. From the results of FIG. 7, it was revealed that the contact angle of the wafer subjected to the reflux treatment using the specific example (6) was greatly reduced and the sulfo group was exposed on the surface of the wafer. From the results in Table 5, a specific example (4)
It can be seen that the surface-modified wafer can be photolyzed with long-wavelength light.

4. Chemical modification (reaction of amino group fixed on the surface) In order to confirm the introduced amino group, the sample after the light irradiation was treated so that a reaction peculiar to the amino group occurs, and the change of the contact angle was observed. Similarly, the same treatment was performed on the wafer after surface modification and before light irradiation. Specifically, 0.15 g (0.37 mmol) of heptafluoro-n-butyric anhydride, 20 mL of dichloromethane, and a very small amount of triethylamine were placed in a 50 mL round-bottomed flask that had been replaced with nitrogen.
Two light-irradiated silicon wafers were put therein and refluxed in a nitrogen atmosphere for 3 hours. Then, the reaction solution is discarded and the eggplant flask and the silicon wafer are washed with methanol (30
(mL × 3 times), and similarly washed with chloroform. The wafer was put into 200 to 250 mL of chloroform, and ultrasonic cleaning was performed twice. The wafer taken out was dried with a nitrogen stream and the contact angle was measured. Table 6 shows the contact angles after chemical modification.

[0147]

[Table 6]

From the results shown in Table 6, the contact angles of about 10 ° were obtained for the specific examples (1), the specific examples (2) and the specific examples (3) (reflux surface modification) which are considered to have introduced the amino group by irradiation with light. Was observed, and it became clear that the introduction of the amino group was certainly carried out.

On the other hand, in the specific example (6), the presence of the sulfo group was confirmed by performing a reversible chemical change peculiar to the sulfo group. FIG. 8 shows changes in the contact angle of the silicon wafer surface due to chemical changes. As shown in FIG. 8, the contact angle was changed in accordance with the chemical change, and the reversible chemical reaction peculiar to the sulfo group occurred, which revealed that the introduction of the sulfo group was reliably performed. . Further, patterning was performed on a silicon wafer using the specific example (6). The patterning mask and the image after patterning are shown in FIG. As shown in FIG. 9, an OHP film was formed using a character as a mask (right part of FIG. 9) and patterned by light irradiation. According to the photograph (left part of FIG. 9) taken in a state where water vapor adheres after patterning, although the image cannot be said to be clear in the drawing due to the water vapor adhering, patterning was clearly visible to the naked eye. The silane compound of the present invention can be applied to such patterning.

[0150]

According to the present invention, an amino group, a sulfo group,
Novel photodegradable silane coupling agent containing silane compound having thiol group or phosphoric acid group, novel silane compound having amino group, sulfo group, thiol group or phosphoric acid group, and amino group, sulfo group, thiol It is possible to provide a substrate treated with a novel photodegradable silane coupling agent containing a silane compound having a group or a phosphoric acid group, and a method for producing the same.

[Brief description of drawings]

FIG. 1 is an explanatory diagram of a chemical modification treatment process using the photodegradable coupling agent of the present invention.

FIG. 2 is an explanatory diagram of preprocessing.

FIG. 3 is an explanatory diagram of surface treatment.

FIG. 4 is an explanatory diagram of removal of a protective group by light irradiation.

FIG. 5 is an explanatory diagram of chemical modification.

FIG. 6 is a diagram showing changes in the contact angle on the surface of a silicon wafer during surface treatment with a silane coupling agent containing the silane compound of the present invention (Specific Example (6)).

FIG. 7 is a diagram showing changes in the contact angle on the surface of a silicon wafer treated by light irradiation of a silicon wafer treated with a silane coupling agent containing the silane compound of the present invention (Specific Example (6)).

FIG. 8 shows a change in contact angle of a silicon wafer surface with a chemical change of a silane compound having a sulfo group in a silicon wafer treated with a silane coupling agent containing the silane compound of the present invention (specific example (6)). FIG.

FIG. 9 is a diagram showing an image after patterning with a silane coupling agent containing the silane compound of the present invention (Specific Example (6)) and a mask used for patterning.

Claims (27)

[Claims] 1. A photodegradable silane coupling agent, comprising a silane compound in which an amino group, a sulfo group, a thiol group or a phosphoric acid group is protected by a photodegradable protective group. 2. The photodegradable silane coupling agent according to claim 1, wherein the silane compound is a silane compound represented by the following general formula [1]. [Chemical 1] (In the general formula [1], X represents an alkoxy group or a halogen atom, Y represents a photodegradable protective group, R ¹ represents an alkyl group, m represents an integer of 1 to 3, and n represents an integer. Represents.) 3. The photodegradable silane coupling agent according to claim 2, wherein the silane compound represented by the general formula [1] is a silane compound represented by the following general formula [2]. . [Chemical 2] (In the general formula [2], X represents an alkoxy group or a halogen atom, R ¹ represents an alkyl group, R ² represents a hydrogen atom or an alkyl group, and R ³ and R ⁴ are each independently a hydrogen atom or Represents an alkoxy group, m represents an integer of 1 to 3, and n
Represents an integer. ) 4. The photodegradable silane coupling agent according to claim 1, wherein the silane compound is a silane compound represented by the following general formula [3]. [Chemical 3] (In the general formula [3], X represents an alkoxy group or a halogen atom, Y represents a photodegradable protective group, R ¹ represents an alkyl group, m represents an integer of 1 to 3, and n represents an integer. Represents.) 5. The photodegradable silane coupling agent according to claim 4, wherein the silane compound represented by the general formula [3] is a silane compound represented by the following general formula [4]. . [Chemical 4] (In the general formula [4], X represents an alkoxy group or a halogen atom, R ¹ represents an alkyl group, R ² represents a hydrogen atom or an alkyl group, and R ³ and R ⁴ each independently represent a hydrogen atom or Represents an alkoxy group, m represents an integer of 1 to 3, and n
Represents an integer. ) 6. The photodegradable silane coupling agent according to claim 1, wherein the silane compound is a silane compound represented by the following general formula [5]. [Chemical 5] (In the general formula [5], X represents an alkoxy group or a halogen atom, Y represents a photodegradable protective group, R ¹ represents an alkyl group, m represents an integer of 1 to 3, and n represents an integer. Represents.) 7. The photodegradable silane coupling agent according to claim 6, wherein the silane compound represented by the general formula [5] is a silane compound represented by the following general formula [6]. . [Chemical 6] (In the general formula [4], X represents an alkoxy group or a halogen atom, R ¹ represents an alkyl group, R ² represents a hydrogen atom or an alkyl group, and R ³ and R ⁴ each independently represent a hydrogen atom or Represents an alkoxy group, m represents an integer of 1 to 3, and n
Represents an integer. ) 8. A surface-modified coupling base material, wherein the silane compound in the silane coupling agent is coupled with the photodegradable silane coupling agent according to any one of claims 1 to 7. 9. A surface-modified coupling group comprising the photodegradable silane coupling agent according to claim 1 for coupling a silane compound in the silane coupling agent to a substrate. Method of manufacturing wood. 10. The method for producing a surface-modified coupling base material according to claim 9, wherein the base material is a pre-treated base material. 11. A surface-modified cup by coating a substrate with the photodegradable silane coupling agent according to claim 1, and coupling the silane compound in the silane coupling agent to the substrate. A ring base material is prepared, and all or part of the surface of the surface-modified coupling base material is irradiated with light, and the photodegradable protective group in the light-irradiated portion is removed to leave an amino group, a sulfo group, a thiol group or phosphorus. A method for producing a functional group-exposed coupling substrate, which comprises exposing an acid group to form an amino group, a sulfo group, a thiol group or a phosphoric acid group on the surface of the substrate. 12. The method for producing a functional group-exposed coupling base material according to claim 11, wherein the base material is a pre-treated base material. 13. The method for producing a functional group-exposed coupling substrate according to claim 11, wherein the light is ultraviolet light. 14. A surface-modified cup by coating the substrate with the photodegradable silane coupling agent according to claim 1, and coupling the silane compound in the silane coupling agent to the substrate. A ring base material is prepared, and all or part of the surface of the surface-modified coupling base material is irradiated with light, and the photodegradable protective group in the light-irradiated portion is removed to leave an amino group, a sulfo group, a thiol group or phosphorus. A method for producing a chemically modified coupling base material, which comprises exposing an acid group and chemically modifying an amino group, a sulfo group, a thiol group or a phosphoric acid group formed on the surface of the base material. 15. The method for producing a chemically modified coupling base material according to claim 14, wherein the base material is a pre-treated base material. 16. The method for producing a chemically modified coupling substrate according to claim 14, wherein the light is ultraviolet light. 17. The chemical modification is carried out using a biological substance such as a nucleic acid, a sugar or a protein.
A method for producing the chemically modified coupling substrate according to any one of 4 to 16. 18. A silane compound, wherein an amino group, a sulfo group, a thiol group or a phosphoric acid group is protected by a photodegradable protective group. 19. The silane compound according to claim 18, which is represented by the following general formula [1]. [Chemical 7] (In the general formula [1], X represents an alkoxy group or a halogen atom, Y represents a photodegradable protective group, R ¹ represents an alkyl group, m represents an integer of 0 to 3, and n represents an integer. Represents.) 20. The silane compound according to claim 19, wherein the silane compound represented by the general formula [1] is represented by the following general formula [2]. [Chemical 8] (In the general formula [2], X represents an alkoxy group or a halogen atom, R ¹ represents an alkyl group, R ² represents a hydrogen atom or an alkyl group, and R ³ and R ⁴ are each independently a hydrogen atom or Represents an alkoxy group, m represents an integer of 1 to 3, and n
Represents an integer. ) 21. The silane compound according to claim 18, which is represented by the following general formula [3]. [Chemical 9] (In the general formula [3], X represents an alkoxy group or a halogen atom, Y represents a photodegradable protective group, R ¹ represents an alkyl group, m represents an integer of 0 to 3, and n represents an integer. Represents.) 22. The silane compound according to claim 21, wherein the silane compound represented by the general formula [3] is represented by the following general formula [4]. [Chemical 10] (In the general formula [4], X represents an alkoxy group or a halogen atom, R ¹ represents an alkyl group, R ² represents a hydrogen atom or an alkyl group, and R ³ and R ⁴ each independently represent a hydrogen atom or Represents an alkoxy group, m represents an integer of 1 to 3, and n
Represents an integer. ) 23. The silane compound according to claim 18, which is represented by the following general formula [5]. [Chemical 11] (In general formula [5], X represents an alkoxy group or a halogen atom, Y represents a photodegradable protective group, R ¹ represents an alkyl group, m represents an integer of 0 to 3, and n represents an integer. Represents.) 24. The silane compound according to claim 23, wherein the silane compound represented by the general formula [5] is represented by the following general formula [6]. [Chemical 12] (In the general formula [6], X represents an alkoxy group or a halogen atom, R ¹ represents an alkyl group, R ² represents a hydrogen atom or an alkyl group, and R ³ and R ⁴ each independently represent a hydrogen atom or Represents an alkoxy group, m represents an integer of 1 to 3, and n
Represents an integer. ) 25. In the general formulas [1] to [6], m is an integer of 1 to 3, wherein
The silane compound according to any one of 1. 26. A photodegradable compound represented by the following general formula [7]. [Chemical 13] (In the general formula [7], Y represents a photodegradable protective group.) 27. The photodegradable compound according to claim 26, wherein the photodegradable compound represented by the general formula [7] is represented by the following general formula [8]. [Chemical 14] (In the general formula [8], R ² represents a hydrogen atom or an alkyl group, and R ³ and R ⁴ each independently represent a hydrogen atom or an alkoxy group.)