JP4906305B2 - Photosensitive novel compound and organic thin film forming body - Google Patents

Description

  The present invention relates to a compound for forming an organic thin film capable of selectively converting surface physical properties by light irradiation in order to simplify a pattern formation manufacturing process and enhance reliability in an electronic product, and to change the corresponding physical properties. The present invention relates to a compound that can be used as a memory element, a method for producing the compound, and an organic thin film forming body in which an organic thin film containing the compound is formed on a substrate surface.

  In the manufacture of electronic products, the pattern formation process is generally complicated, but in order to simplify the process and increase the reliability, a thin film (self-organized) that can selectively convert surface properties by light irradiation. There is known a method for forming a fluorinated organic thin film.

As such a self-organized organic thin film, a thin film in which an arylsilane compound or an aralkylsilane compound is self-organized on a substrate is irradiated with a laser beam of 193 nm, and the irradiated portion is hydrophilic due to silicon-carbon bond cleavage. It is known that a surface is formed (Non-Patent Documents 1 and 2).
In addition, a film in which benzylphenyl sulfide is self-assembled is irradiated with light so that only organic molecules in a non-irradiated portion can be replaced, and surface physical properties at a desired location can be changed (Non-Patent Document 3), 4- Silicon-terminated benzylphenyl formed from benzyl-4- (2- (chlorodimethylsilyl) ethyl) phenylsulfone (Non-patent Document 4) synthesized by reacting benzylsulfonylstyrene and chlorodimethylsilane in the presence of a platinum catalyst It is also known that, in the self-assembled film of a sulfone compound, an absorber derived from a benzene ring on the surface is reduced and the contact angle of water is reduced by ultraviolet irradiation (Non-patent Document 5).

  On the other hand, in Patent Document 1, by selectively irradiating the hexamethyldisilazane film adsorbed on the resist surface with an electron beam, the corresponding part is removed, and then the oxygen plasma treatment is performed to remove the removed part. It is described that only the resist is etched. Patent Document 2 discloses a pattern forming body that utilizes the fact that the fluorine content is reduced by light irradiation to a composite layer containing a photocatalyst and fluorine. In Patent Document 3, a photodegradation active layer is placed between an uneven ground layer and a water-repellent monomolecular film, and the water-repellent layer is selectively removed by light irradiation to form a pattern of water-repellent portions and hydrophilic portions. A method is disclosed. Patent Document 4 discloses application to a resist or a memory element utilizing a monomolecular film of a porphyrin-copper complex using radiation including ultraviolet rays or partial change of molecular conformation due to heat. Has been. Patent Document 5 describes that the irradiated portion of the organic molecular film can be removed by irradiating the organic molecular film with ultraviolet rays of 200 nm or more and 380 nm or less. Further, Non-Patent Document 6 and Patent Document 6 disclose that a compound group consisting of 2-nitrobenzyl ester and ethers and a terminal silyl group is useful as a surface modifier capable of reducing the contact angle by ultraviolet irradiation. Has been.

  However, in the above prior art, although a self-assembled organic thin film or an organic molecular adsorption film is used for pattern formation, the molecular structure is limited, and it is necessary to use high-energy wavelength light, The molecular structure for controlling the film-forming property, which is important for obtaining the film, has not been sufficiently studied, and is not necessarily sufficient for realizing high reliability and photoresponsiveness. For example, the compound of Non-Patent Document 4 has a limited molecular structure due to its production method, and lacks diversity with respect to the partial structure necessary to obtain a good film as described in Non-Patent Document 7. There is a problem.

  In addition, the formula (1) in which a functional group capable of interacting with a linking group via an oxygen atom and a metal surface is introduced into the phenylsulfone compound by the present applicant.

It has been reported that the compound represented by the formula can be surface-converted with relatively low energy wavelength light and can form an organic thin film on a substrate with good reproducibility (Patent Document 7). However, Patent Document 7 does not specifically describe the compound according to the present invention.

Science, 1991, 252, 551-554. Langmuir, 1996, 12, pp. 1638-1650 Langmuir, 2000, 16, 9963-9967 Proceedings of the 79th Annual Meeting of the Chemical Society of Japan, 2001, 591 Proceedings of the 81st Annual Meeting of the Chemical Society of Japan, 2002, p.192 Chem. Lett. 2000, pp. 228-229 J. et al. Am. Chem. Soc. 1988, 110, 6136-6144. JP 7-297100 A JP 2001-109103 A JP 2001-129474 A JP 2001-215719 A JP 2002-23356 A Japanese Patent Laid-Open No. 2002-80481 WO2004 / 0675540

  The problem of the present invention is that it has excellent water repellency, can convert surface physical properties with light of relatively low energy, is excellent in the amount of change in the contact angle of water before and after light irradiation, and is immersed in a substrate. An object of the present invention is to provide a compound capable of forming a high-performance organic thin film even if it is short, and an organic thin film forming body having an organic thin film formed on a substrate surface from a composition containing the compound.

  The inventors of the present invention developed the structure of the compound represented by the formula (1) described in Patent Document 7, and in the compound, G1 represents a methylene group, n represents an integer of 6 or more, R Is a para-substitution, and the compound which represents a C3-C11 alkyl group or a C3-C11 alkoxy group is excellent in water repellency, and the change in the contact angle of water after light irradiation is excellent The present invention has been completed.

That is, the present invention
(1) Formula (I)

[Wherein, X represents a functional group containing a hetero atom, R ₁ represents an alkyl group having 3 to 11 carbon atoms which may have a substituent, and 3 carbon atoms which may have a substituent. Have an alkoxy group of -11, an alkylthio group having 3 to 11 carbon atoms which may have a substituent, an alkylcarbonyl group having 3 to 11 carbon atoms which may have a substituent, and a substituent. Represents an alkoxycarbonyl group having 3 to 11 carbon atoms, or an alkylamino group having 3 to 11 carbon atoms which may have a substituent, and R ₂ may have 1 substituent. An alkyl group having ˜4, an alkoxy group having 1 to 4 carbon atoms which may have a substituent, an alkylthio group having 1 to 4 carbon atoms which may have a substituent, and a substituent. C1-C4 alkylcarbonyl group, C1-C4 which may have a substituent An alkoxycarbonyl group, an optionally substituted alkylamino group having 1 to 4 carbon atoms, an optionally substituted dialkylamino group having 2 to 8 carbon atoms, and a substituent. Represents an aryl group or a halogen atom, and m represents an integer of 0 to 4. When m represents an integer of 2 or more, R ₂ may be the same or different. n represents an integer of 6 to 30. G ₁ represents a divalent saturated or unsaturated hydrocarbon group having 1 to 3 carbon atoms. Ar represents an aromatic group which may have a substituent. G ₂ represents a group represented by an oxygen atom, a sulfur atom, or Nr (r represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). ] Regarding the compound represented by

(2) The compound according to (1), wherein X is a silyl group having a chlorine atom or an alkoxy group having 1 to 4 carbon atoms as a substituent.

The present invention also provides:
(3) An organic thin film formed article having an organic thin film formed from a composition for forming an organic thin film containing a compound represented by formula (I) described in (1) or (2) on a substrate surface .

  The organic thin film obtained from the compound represented by the formula (I) of the present invention is excellent in water repellency, can convert surface properties with a relatively low energy wavelength light, and has a water contact angle before and after light irradiation. Excellent amount of change. For example, when irradiated with ultraviolet rays, only the irradiated part changes to a hydrophilic film, so that an organic thin film forming composition containing a compound represented by the formula (I) of the present invention is used on a substrate. After the thin film is formed, only a specific part can be converted into a hydrophilic thin film by irradiating ultraviolet rays through a mask having a predetermined pattern. Further, when an organic thin film is formed, a high performance organic thin film can be formed even if the immersion time of the substrate in the solution containing the compound represented by the formula (I) of the present invention is short. According to the present invention, a precise and fine functional thin film pattern can be easily formed on the surface of a substrate.

Hereinafter, the present invention will be described in detail.
The present invention is a compound represented by the formula (I).
In formula (I), X represents a functional group containing a hetero atom. In the present invention, the functional group means a group capable of interacting with a substrate surface, preferably a metal or metal oxide surface. Moreover, a hetero atom means atoms other than the carbon atom of Group 13-17 of a periodic table (long period type), for example, a boron atom, an aluminum atom, a silicon atom, a nitrogen atom, a phosphorus atom, an oxygen atom, A sulfur atom, a fluorine atom, a chlorine atom, etc. are mentioned. Examples of the functional group containing a hetero atom include a silyl group having a chlorine atom or an alkoxy group having 1 to 4 carbon atoms as a substituent, a mercapto group, an optionally substituted alkylthio group having 1 to 4 carbon atoms, carbon Examples thereof include an acylthio group having a number of 1 to 10, a disulfide group, an amino group, or a phosphono group which may have a substituent. Among these, a chlorine atom or an alkoxy group having 1 to 4 carbon atoms can be exemplified. A silyl group having a substituent is preferable, and a silyl group having an alkoxy group having 1 to 4 carbon atoms as a substituent is particularly preferable.

  Preferred examples of X include chlorodihydrosilyl group, chlorodimethylsilyl group, chlorodiethylsilyl group, chlorodiphenylsilyl group, chloromethylphenylsilyl group, dichlorohydrosilyl group, dichloromethylsilyl group, dichloroethylsilyl group, dichlorophenylsilyl. Group, silyl group having a chlorine atom as a substituent such as trichlorosilyl group; trimethoxysilyl group, dimethoxymethylsilyl group, dimethoxychlorosilyl group, dimethoxyethylsilyl group, dimethoxyphenylsilyl group, triethoxysilyl group, diethoxymethyl Silyl group, diethoxychlorosilyl group, diethoxyethylsilyl group, diethoxyphenylsilyl group, tripropoxysilyl group, dipropoxymethylsilyl group, dipropoxychlorosilyl group, dimethoxyethyl A silyl group having a C 1-4 alkoxy group such as a ryl group as a substituent; a mercapto group; a carbon optionally having a substituent such as a methylthio group, an ethylthio group, a methoxyethylthio group, or a carboxyethylthio group An alkylthio group having 1 to 4 carbon atoms; an acylthio group having 1 to 10 carbon atoms such as an acetylthio group, a propionylthio group, and a benzoylthio group; an alkyl disulfide group having 1 to 4 carbon atoms such as a methyl disulfide group;

[Wherein R ₁ , R ₂ , m, G ₁ , Ar, G ₂ , n represent the same meaning as described above. Disulfide group] such as; ;-P amino group which may have a substituent such as an alkyl group having 1 to 4 carbon atoms _{(= O) (OH) 2} , -P (= O) (OCH 3) 2 , -P (= O) (OC 2 H 5) 2, -P (= O) (OC 3 H 7) 2, -P (= O) (OC 4 H 9) 2, -P (= O) ( OPh) a phosphono group optionally having a substituent such as an alkyl group having 1 to 4 carbon atoms such as ₂ or an aryl group;

R ₁ may have a substituent (an alkyl group having 3 to 11 carbon atoms, an alkoxy group having 3 to 11 carbon atoms, an alkylthio group having 3 to 11 carbon atoms, or an alkylcarbonyl group having 3 to 11 carbon atoms). , An alkoxycarbonyl group having 3 to 11 carbon atoms, or an alkylamino group having 3 to 11 carbon atoms).

  Examples of the alkyl group having 3 to 11 carbon atoms include n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, and n-heptyl group. , N-octyl group, n-nonyl group, n-decyl group, n-undecyl group and the like. Among these, an alkyl group having 5 to 10 carbon atoms is preferable.

  Examples of the alkoxy group having 3 to 11 carbon atoms include n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, Examples include an n-octyloxy group, an n-nonyloxy group, an n-decyloxy group, and an n-undecyloxy group. Among these, a C5-C10 alkoxy group is preferable.

  Examples of the alkylthio group having 3 to 11 carbon atoms include n-propylthio group, isopropylthio group, n-butylthio group, t-butylthio group, n-pentylthio group, n-hexylthio group, n-heptylthio group, and n-octylthio group. Group, n-nonylthio group, n-decylthio group, n-undecylthio group and the like. Among these, a C5-C10 alkylthio group is preferable.

  Examples of the alkylcarbonyl group having 3 to 11 carbon atoms include n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, n-hexylcarbonyl group, n- Examples include heptylcarbonyl group, n-octylcarbonyl group, n-nonylcarbonyl group, n-decylcarbonyl group, n-undecylcarbonyl group and the like. Among these, an alkylcarbonyl group having 5 to 10 carbon atoms is preferable.

  Examples of the alkoxycarbonyl group having 3 to 11 carbon atoms include an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, a t-butoxycarbonyl group, an n-pentyloxycarbonyl group, and an n-hexyloxycarbonyl group. N-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group, n-undecyloxycarbonyl group and the like. Among these, a C5-C10 alkoxycarbonyl group is preferable.

  Examples of the alkylamino group having 3 to 11 carbon atoms include n-propylamino group, isopropylamino group, n-butylamino group, t-butylamino group, n-pentylamino group, n-hexylamino group, n- Examples include heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, n-undecylamino group and the like. Among these, an alkylamino group having 5 to 10 carbon atoms is preferable.

  The C3-C11 alkyl group, C3-C11 alkoxy group, C3-C11 alkylthio group, C3-C11 alkylcarbonyl group, C3-C11 alkoxycarbonyl group, and carbon The alkylamino group of formulas 3 to 11 may have a substituent at an arbitrary position, and may have a plurality of substituents which are the same or different.

  The C3-C11 alkyl group, C3-C11 alkoxy group, C3-C11 alkylthio group, C3-C11 alkylcarbonyl group, C3-C11 alkoxycarbonyl group, and carbon Although it does not restrict | limit especially as a substituent of the alkylamino group of 3-11, For example, C1-C4, such as halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; A methoxy group, an ethoxy group, etc. Alkoxy group; Cyano group; Nitro group; C1-C4 alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group; C1-C4 alkylthio group such as methylthio group and ethylthio group; Methylsulfonyl group and ethylsulfonyl group And the like, and the like.

Among these, R ₁ is preferably an alkyl group having 3 to 11 carbon atoms or an alkoxy group having 3 to 11 carbon atoms.

  m represents an integer of 0 to 4. Among these, m is preferably 0.

R ₂ may have a substituent (an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or an alkylcarbonyl group having 1 to 4 carbon atoms). Represents an alkoxycarbonyl group having 1 to 4 carbon atoms, an alkylamino group having 1 to 4 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms, or an aryl group), or a halogen atom.

  Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a t-butyl group.

  As a C1-C4 alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, an isopropoxy group, n-butoxy group, t-butoxy group etc. are mentioned, for example.

  Examples of the alkylthio group having 1 to 4 carbon atoms include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, and a t-butylthio group.

  Examples of the alkylcarbonyl group having 1 to 4 carbon atoms include acetyl group, ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, t-butylcarbonyl and the like.

  Examples of the alkoxycarbonyl group having 1 to 4 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, and a t-butoxycarbonyl group.

  Examples of the alkylamino group having 1 to 4 carbon atoms include a methylamino group, an ethylamino group, an n-propylamino group, an isopropylamino group, and an n-butylamino group.

  Examples of the dialkylamino group having 2 to 8 carbon atoms include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a methylethylamino group, and a methyl n-propylamino group.

  As an aryl group, a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group etc. are mentioned, for example.

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.

  The alkyl group having 1 to 4 carbon atoms, the alkoxy group having 1 to 4 carbon atoms, the alkylthio group having 1 to 4 carbon atoms, the alkylcarbonyl group having 1 to 4 carbon atoms, the alkoxycarbonyl group having 1 to 4 carbon atoms, the number of carbon atoms The alkylamino group having 1 to 4 carbon atoms, the dialkylamino group having 2 to 8 carbon atoms, and the aryl group may have a substituent at any position, and may have a plurality of the same or different substituents. It may be.

  The alkyl group having 1 to 4 carbon atoms, the alkoxy group having 1 to 4 carbon atoms, the alkylthio group having 1 to 4 carbon atoms, the alkylcarbonyl group having 1 to 4 carbon atoms, the alkoxycarbonyl group having 1 to 4 carbon atoms, the number of carbon atoms The substituent for the alkylamino group having 1 to 4 carbon atoms, the dialkylamino group having 2 to 8 carbon atoms, and the aryl group is not particularly limited, and examples thereof include halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom; C1-C4 alkoxy group such as ethoxy group; cyano group; nitro group; C1-C4 alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group; C1-C4 such as methylthio group and ethylthio group Alkylthio group; alkylsulfonyl group having 1 to 4 carbon atoms such as methylsulfonyl group and ethylsulfonyl group; phenyl group, 4-methylphenyl group, And the like; alkyl groups having 1 to 4 carbon atoms such as motor-fluorophenyl group, a phenyl group which may have a substituent such as a halogen atom.

Among these, R ₂ is preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. Moreover, when m represents an integer greater than or equal to ₂ , R <2> may be the same or different.

n represents an integer of 6 to 30. Further, n is preferably an integer of 6 to 12, and more preferably an integer of 8 to 10.
G ₁ represents a divalent saturated or unsaturated hydrocarbon group having 1 to 3 carbon atoms.
Specific examples of G ₁ include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, and a propylene group.

Ar represents an aromatic group which may have a substituent.
Examples of the aromatic group include a phenylene group, a biphenylene group, a triphenylene group, and a naphthylene group. Among these, a paraphenylene group, a parabiphenylene group, a paratriphenylene group, or a naphthylene group is preferable, and a paraphenylene group is particularly preferable.

G ₂ represents an oxygen atom, a sulfur atom, or a group represented by Nr. r represents a C 1-4 alkyl group such as a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or a t-butyl group.
Specific examples of G ₂ include an oxygen atom (—O—), a sulfur atom (—S—), —NH—, —N (CH ₃ ) —, —N (C ₂ H ₅ ) —, —N (n _{-C 3 H 7) -, -} N (i-C 3 H 7) - , and the like. Among these, an oxygen atom (—O—) is preferable.

(Production method)
The compound represented by the formula (I) can be produced, for example, as follows. A general production method is shown below.

In the formula, R ₁ , R ₂ , G ₁ , Ar, n, m and X represent the same meaning as described above. Hal represents a halogen atom such as a chlorine atom, a bromine atom or an iodine atom, G ′ represents an oxygen atom or Nr (where r represents the same meaning as described above), R ₃ represents a hydrogen atom; chlorine A halogen atom such as an atom; an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group; R ₄ is a hydrogen atom; an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group; a phenyl group optionally having a substituent such as a phenyl group; And the like.

(Production method 1) Production of compound (1-1) wherein X is a silyl group First, compound (3) is reacted with aromatic compound (2) in the presence of 1 to 2 equivalents of a base to obtain a sulfide compound. (4) is obtained. Next, the obtained sulfide compound (4) is oxidized with an appropriate oxidizing agent to obtain the corresponding sulfone compound (5). Next, the olefin body (6) is obtained by reacting the obtained sulfone body (5) with an alkyl halide or alcohol whose terminal is an olefin in the presence of a base or a condensing agent. Furthermore, the obtained olefin body (6) can be reacted with hydrosilane in the presence of an appropriate catalyst to obtain a compound (1-1) in which X is represented by a silyl group.

Examples of the base that can be used in the above reaction include tertiary amines such as triethylamine and tributylamine; metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide; alkali metal hydroxides such as sodium hydroxide And alkali metal carbonates such as potassium carbonate.
Examples of the oxidizing agent to be used include peroxides such as hydrogen peroxide, peracetic acid, and m-chloroperbenzoic acid.
Examples of the condensing agent to be used include a combination of azodicarboxylic acid esters such as azodicarboxylic acid diethyl ester and phosphines such as triphenylphosphine.
Moreover, as a catalyst used for reaction of hydrosilane, transition metals, such as platinum, palladium, nickel, ruthenium, rhodium, or its halide, and its organometallic complex are mentioned.

(Production method 2) Production of compound (1-2) wherein X is a phosphono group Compound (1-2) wherein X is a phosphono group is obtained by reacting compound (6) with phosphite diester in the presence of an appropriate catalyst. Followed by hydrolysis. Examples of the catalyst used for the reaction of phosphite diester include transition metals such as platinum, palladium, nickel, ruthenium and rhodium or halides thereof, and organometallic complexes thereof. Moreover, the compound whose X is a phosphono group can be manufactured also by the method of making the compound (7) mentioned later and phosphorous acid triester react and hydrolyzing.

(Manufacturing method 3) Manufacture of the compound (1-3) whose X is a mercapto group, a C1-C4 alkylthio group, or an amino group X is a mercapto group, a C1-C4 alkylthio group, or an amino group. A certain compound (1-3) is obtained by reacting the compound (5) with an α, ω-dihaloalkane to obtain a compound (7), and the terminal halogen of the obtained compound (7) is determined as a sulfur or nitrogen atom. It can be obtained by a nuclear substitution reaction.

(Production Method 4) Production of Compound (1-3) in which X is a Disulfide Group Compound (1-3) in which X is a disulfide group is obtained by oxidatively dimerizing a compound in which X is a mercapto group. be able to.

The compound in which G ₂ is S can be obtained by sulfurizing the compound (5) by a known method, and thereafter, in the same manner as in the production methods 1 to 4.

  In the above production methods 1 to 4, the solvent that can be used for the reaction is not particularly limited as long as it is an inert solvent for the reaction. For example, water; alcohols such as methanol and ethanol; nitriles such as acetonitrile; ethers such as diethyl ether, 1,2-dimethoxyethane and tetrahydrofuran (THF); aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated hydrocarbons such as dichloromethane and chloroform; and combinations of two or more thereof. A two-phase system of water-organic solvent can also be used. The reaction proceeds smoothly between −80 ° C. and + 200 ° C.

  In any reaction, after completion of the reaction, the desired product can be isolated by carrying out usual post-treatment operations, separation and purification in ordinary organic synthetic chemistry. The structure of the target product can be confirmed by performing NMR spectrum, mass spectrum, IR spectrum measurement, elemental analysis, and the like.

Representative examples of the compound represented by the formula (I) of the present invention obtained as described above are shown in Table 1, and ¹ H-NMR data are shown in Table 2.

(Organic thin film formation)
The organic thin film forming body of the present invention has an organic thin film formed from a composition for forming an organic thin film containing the compound represented by the formula (I) of the present invention.

  The substrate used in the present invention is not particularly limited as long as it can form an organic thin film using the composition for forming an organic thin film containing the compound represented by the formula (I). For example, a glass substrate such as a soda lime glass plate, a substrate with an electrode formed on the surface of ITO glass, a substrate with an insulating layer formed on the surface, a substrate with a conductive layer formed on the surface, silicon such as a silicon wafer substrate Examples include substrates and ceramic substrates. Further, the substrate is preferably used after being cleaned with ozone; ultrasonic; cleaning agent such as distilled water, ion exchange water, alcohol, etc. before forming the organic thin film.

The composition for forming an organic thin film can be prepared by dissolving the compound represented by the formula (I) in an appropriate solvent.
The solvent to be used is not particularly limited as long as it is inert to the compound represented by the formula (I) and dissolves the compound represented by the formula (I). For example, aromatic hydrocarbons such as benzene, toluene and xylene: aliphatic hydrocarbons such as pentane and hexane; halogenated carbonization such as benzotrifluoride, (nonafluorobutyl) ethyl ether, chloroform, dichloroethane and carbon tetrachloride Hydrogens; cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; esters such as methyl acetate and ethyl acetate; ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, THF, and 1,4-dioxane Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; These solvents can be used alone or in combination of two or more.

  It is preferable that water is present in the solution containing the compound represented by the formula (I) in that a dense organic thin film can be formed. Specifically, 50 ppm or more is preferable, and the range of the saturated water content from 50 ppm to the solvent to be used, more specifically, the range of 50 to 1000 ppm is preferable, and the range of 250 to 800 ppm is more preferable. If it is 50 ppm or more, an organic thin film can be formed rapidly, and if it is less than 1000 ppm, there is little problem that the compound represented by the formula (I) is deactivated.

Moreover, it is preferable to add a catalyst to the solution containing the compound represented by the formula (I) in order to promote the formation of the organic thin film.
Examples of the catalyst to be used include metals, metal oxides, metal salts, metal hydroxides, metal alkoxides, chelated or coordinated metal compounds, and hydrolysis products obtained by treating metal alkoxides with water; Acid; etc. are mentioned. These catalysts can be used alone or in combination of two or more.

The metal is not particularly limited, but a metal belonging to Group 10 of the periodic table is preferable, and palladium and platinum are particularly preferable.
Although it does not restrict | limit especially as a metal oxide, Palladium oxide (IV), platinum oxide (IV), etc. are mentioned.

  Although it does not restrict | limit especially as a metal salt, A chloride, nitrate, a sulfate, acetate, formate, an oxalate etc. are mentioned. More specifically, nickel (II) chloride, nickel (II) bromide, palladium (II) chloride, palladium (II) bromide, platinum (II) chloride, nickel (II) nitrate, palladium (II) nitrate, Examples thereof include nickel (II) sulfate, palladium (II) sulfate, platinum (II) bromide, nickel (II) acetate, palladium (II) acetate, platinum (II) acetate, and palladium (II) oxalate.

  As the metal hydroxide, any metal hydroxide may be used as long as it is a metal hydroxide. As a manufacturing method of a metal hydroxide, the method of hydrolyzing the metal alkoxide mentioned later, the method of making a metal salt react with a metal hydroxide, etc. are mentioned. Moreover, what is marketed as a metal hydroxide can also be refine | purified and used if desired.

  Although the kind of metal hydroxide is not particularly limited, a hydroxide of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten, or lead is preferable.

  Examples of the metal alkoxide used for the production of the metal hydroxide include the same ones that can be used for the production of the hydrolysis product of the metal alkoxides described later. Further, the metal salt used here is not particularly limited, and examples thereof include chloride, bromide, sulfate, nitrate, carbonate, bicarbonate, phosphate, acetate, formate, oxalate and the like. .

  The metal of the metal alkoxide is not particularly limited, but titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten, or the like because an organic thin film having excellent transparency can be obtained. Lead is preferred.

Specific examples of metal alkoxides include silicon alkoxides such as Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ -i) ₄ , and Si (OC ₄ H ₉ -t) _4. Titanium alkoxides such as Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₃ H ₇ -i) ₄ , Ti (OC ₄ H ₉ ) ₄ ; Ti [OSi (CH ₃ ) ₃ ] ₄ , Tetrakistrialkylsiloxytitanium such as Ti [OSi (C ₂ H ₅ ) ₃ ] ₄ ; Zr (OCH ₃ ) ₄ , Zr (OC ₂ H ₅ ) ₄ , Zr (OC ₃ H ₇ ) ₄ , Zr (OC ₄ H _{9) 4} such zirconium _{alkoxides; Al (OCH 3) 3,} Al (OC 2 H 5) 3, Al (OC 3 H 7 -i) 3, Al (OC 4 H 9) 3 and the like of aluminum alkoxide; Ge (OC ₂ H _{5) 4} and the like of germanium _{alkoxide; in (OCH 3) 3,} I _{(OC 2 H 5) 3,} In (OC 3 H 7 -i) 3, In (OC 4 H 9) indium alkoxides such as _{3; Sn (OCH 3) 4} , Sn (OC 2 H 5) 4, Sn ( OC ₃ H ₇ -i) ₄ , Sn (OC ₄ H ₉ ) _{4 and} other tin alkoxides; Ta (OCH ₃ ) ₅ , Ta (OC ₂ H ₅ ) ₅ , Ta (OC ₃ H ₇ -i) ₅ , Ta Tantalum alkoxides such as (OC ₄ H ₉ ) ₅ ; tungsten such as W (OCH ₃ ) ₆ , W (OC ₂ H ₅ ) ₆ , W (OC ₃ H ₇ -i) ₆ , W (OC ₄ H ₉ ) ₆ Alkoxides; zinc alkoxides such as Zn (OC ₂ H ₅ ) ₂ ; lead alkoxides such as Pb (OC ₄ H ₉ ) ₄ and Pb (OC ₃ H ₇ -i) ₂ ;

  Further, as a metal alkoxide, a composite alkoxide obtained by reaction of two or more metal alkoxides, a composite obtained by reaction of one or more metal alkoxides with one or more metal salts Alkoxides can also be used.

  The composite alkoxide obtained by the reaction of two or more kinds of metal alkoxides includes a complex alkoxide obtained by the reaction of an alkali metal or alkaline earth metal alkoxide and a transition metal alkoxide, or a complex salt by a combination of Group 3B elements. The compound alkoxide obtained by the form of this can be illustrated.

Specific _{examples, BaTi (OR) 6, SrTi} (OR) 6, BaZr (OR) 6, SrZr (OR) 6, LiNb (OR) 6, LiTa (OR) 6 , and, combinations thereof, LiVO ( OR) ₄ , MgAl ₂ (OR) ₈ , (RO) ₃ SiOAl (OR ′) ₂ , (RO) ₃ SiOTi (OR ′) ₃ , (RO) ₃ SiOZr (OR ′) ₃ , (RO) ₃ SiOB ( OR ′) ₂ , (RO) ₃ SiONb (OR ′) ₄ , (RO) ₃ SiOTa (OR ′) _{4 and the} like, and reaction products of the above metal alkoxides and polycondensates thereof. Here, R and R ′ represent an alkyl group.

  Examples of the composite alkoxide obtained by reaction of one or more metal alkoxides with one or more metal salts include compounds obtained by reaction of metal salts with metal alkoxides. . Examples of the metal salt used here include chlorides, nitrates, sulfates, acetates, formates, oxalates, and the like, and examples of the metal alkoxides include those similar to the metal alkoxides described above. .

  The chelated or coordinated metal compound can be prepared by adding a chelating agent or a coordination compound capable of forming a complex with the metal of the metal compound to a solution of the metal compound. When a chelated or coordinated metal compound is used, an organic thin film having desired physical properties can be formed with good reproducibility.

  As the metal compound, a metal, a metal oxide, a metal salt, a metal hydroxide, a metal alkoxide, and / or a hydrolysis product obtained by treating the metal alkoxide with water can be used. .

  The chelating agent or coordination compound is not particularly limited as long as it can chelate or coordinate to the metal of the metal compound to form a complex.

  Specific examples of chelating agents or coordination compounds include saturated aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, myristic acid, palmitic acid, stearic acid; oxalic acid, malonic acid, succinic acid Saturated aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, array acid, and maleic acid; benzoic acid, Aromatic carboxylic acids such as toluic acid and phthalic acid; Halogenocarboxylic acids such as chloroacetic acid and trifluoroacetic acid; β-diketones such as acetylacetone, benzoylacetone, and hexafluoroacetylacetone; β-diketones such as methyl acetoacetate and ethyl acetoacetate Ketoesters: tetrahydrofuran, furan, furancarbo And heterocyclic compounds such as acid, thiophene, thiophenecarboxylic acid, pyridine, nicotinic acid and isonicotinic acid; phosphine compounds such as triphenylphosphine and tributylphosphine; and the like.

The amount of chelating agent or coordination compound added is metal, metal oxide, metal salt, metal hydroxide,
0.1 to 10 times mol, preferably 0.3 to 2 times mol, more preferably 0.1 mol to 1 mol of metal of the metal alkoxide or the hydrolysis product obtained by treating metal alkoxide with water. 0.5 to 1.2 times mole.

  After adding the chelating agent or coordination compound, the solution of the metal complex can be obtained by thoroughly stirring the whole volume. The stirring temperature is usually in the temperature range from 0 ° C. to the boiling point of the solvent used. The stirring time is usually several minutes to several hours.

  As the chelated or coordinated metal compound, an isolated one can be used, or chelation or coordination obtained by adding a chelating agent or a coordination compound to the solution of the metal compound. It can also be used as a solution of the prepared metal compound.

  As a hydrolysis product obtained by treating a metal alkoxide with water, a product obtained by hydrolyzing the metal alkoxide with water can be used.

  Even if the hydrolysis product is obtained by hydrolyzing metal alkoxides with water at least twice as much as the metal alkoxides, the metal alkoxides are equivalent to twice the metal alkoxides. It may be obtained by partial hydrolysis with less water. In addition, after obtaining the partial hydrolysis product of the metal alkoxide, this partial hydrolysis product is further added to a predetermined amount of water (a total of 2 of the metal alkoxides with the amount of water used in the previous partial hydrolysis). It may be obtained by hydrolysis with an amount of water equivalent to a double equivalent or more.

  The reaction of metal alkoxides and water can be performed by mixing metal alkoxides and water in an organic solvent, or by directly mixing metal alkoxides and water without using an organic solvent. You can also.

  As a method of reacting metal alkoxides with water in an organic solvent, (i) a method of adding water or water diluted with an organic solvent to an organic solvent solution of metal alkoxides, (ii) water is suspended or Examples thereof include a method of adding a metal alkoxide or an organic solvent solution of a metal alkoxide to a dissolved organic solvent. The method (ii) is preferable when water is used in an amount twice or more equivalent to the metal alkoxide, and the method (i) is preferable when water is used less than twice the equivalent of the metal alkoxide. In this case, the concentration of the metal alkoxide in the organic solvent is not particularly limited as long as it has a fluidity capable of suppressing rapid heat generation and can be stirred, but a range of 5 to 30% by weight is preferable.

  As the organic solvent to be used, it is preferable that the hydrolysis product of the metal alkoxide is dispersed in the organic solvent, and the reaction of treating the metal surfactant with water is performed at a low temperature. Above, a solvent that has high water solubility and does not solidify at low temperatures is more preferred.

Specific examples of the organic solvent used include alcohol solvents such as methanol, ethanol and isopropanol; halogenated hydrocarbon solvents such as methylene chloride, chloroform and chlorobenzene; hydrocarbon solvents such as hexane, cyclohexane, benzene, toluene and xylene. Ether solvents such as tetrahydrofuran, diethyl ether and dioxane; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; amide solvents such as dimethylformamide and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; methyl polysiloxane , Silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentanesiloxane, and methylphenylpolysiloxane (JP-A-9-2084)
No. 38 publication etc.).

  These solvents can be used alone or in combination of two or more. When used as a mixed solvent, a combination of a hydrocarbon solvent such as toluene or xylene and a lower alcohol solvent system such as methanol, ethanol, isopropanol, or t-butanol is preferable. In this case, the lower alcohol solvent is more preferably a secondary or higher alcohol solvent such as isopropanol or t-butanol. The mixing ratio of the mixed solvent is not particularly limited, but it is preferable to use a hydrocarbon solvent and a lower alcohol solvent in a volume ratio of 99/1 to 50/50.

The water to be used is not particularly limited as long as it is neutral, but it is preferable to use pure water, distilled water or ion-exchanged water from the viewpoint of obtaining a dense organic thin film with few impurities.
The amount of water used is preferably 2.0 to 8 times equivalent and more preferably 3 to 5 times equivalent when used in an amount of 2 times equivalent or more relative to the metal alkoxide. When using less than 2 times equivalent with respect to the said metal alkoxide, 0.5-2.0 times equivalent is preferable.

Although the hydrolysis reaction temperature of metal alkoxides depends on the reactivity and stability of the metal alkoxide used, it is usually in the range of −100 ° C. to organic solvent reflux temperature.
In the case of reacting 0.5 to less than 1.0 equivalent of water with respect to the metal alkoxide, the reaction temperature is not particularly limited, and is usually −100 to + 100 ° C., preferably from −20 ° C., and the organic used. It is the range of the boiling point of the alcohol that is eliminated by the solvent or hydrolysis.

  When reacting 1.0 times equivalent or more of water to the metal alkoxide, the reaction temperature is usually −100 to −20 ° C., preferably −100 to −50 ° C. In this case, first, water less than 1.0 times equivalent may be reacted at an arbitrary temperature, and then water may be further added at a temperature of −20 ° C. or lower for reaction. Further, after adding water at a low temperature and aging for a certain period of time, the temperature of the reaction solution can be raised from room temperature to the reflux temperature of the solvent used for further reaction.

  In addition, in the hydrolysis reaction of metal alkoxides with water, an acid, a base, or a dispersion stabilizer may be added. Acids and bases were produced as a deflocculant for redispersing the precipitate formed by condensation, and as a catalyst for producing dispersoids such as colloidal particles by hydrolyzing and dehydrating metal alkoxides. There is no particular limitation as long as it functions as a dispersoid dispersant.

Examples of the acid used here include mineral acids such as hydrochloric acid, nitric acid, boric acid, and borohydrofluoric acid, and organic acids such as acetic acid, formic acid, oxalic acid, carbonic acid, trifluoroacetic acid, p-toluenesulfonic acid, and methanesulfonic acid. Examples include acids and the like; photoacid generators that generate an acid by light irradiation, such as diphenyliodonium hexafluorophosphate and triphenylphosphonium hexafluorophosphate.
Examples of the base include triethanolamine, triethylamine, 1,8-diazabicyclo [5.4.0] -7-undecene, ammonia, dimethylformamide, phosphine and the like.

The dispersion stabilizer refers to an agent such as a flocculating agent, a protective colloid, a coagulation inhibitor such as a surfactant and the like, which has the effect of stably dispersing the dispersoid in the dispersion medium. For example, polyhydric carboxylic acids such as glycolic acid, gluconic acid, lactic acid, tartaric acid, citric acid, malic acid, and succinic acid; hydroxycarboxylic acids; phosphoric acids such as pyrophosphoric acid and tripolyphosphoric acid; acetylacetone, methyl acetoacetate, ethyl acetoacetate, N-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, sec-butyl acetoacetate, t-butyl acetoacetate, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5- Dione, octane-2,4-dione, nonane-
Multidentate ligand compounds having strong chelating ability for metal atoms such as 2,4-dione and 5-methyl-hexane-2,4-dione; Sulperus 3000, 9000, 17000, 20000, 24000 ), Disperbyk-161, -162, -163, -164 (above, manufactured by BYK Chemie), etc., aliphatic amines, hydrostearic acid, polyesteramine; dimethylpolysiloxane and methyl (polysiloxyalkylene) siloxane Examples thereof include silicone compounds such as polymers, trimethylsiloxysilicic acid, carboxy-modified silicone oil, amine-modified silicone and the like (JP-A-9-208438, JP-A-2000-53421, etc.).

The hydrolysis product obtained as described above may be a metal hydroxide obtained by completely hydrolyzing a metal alkoxide in an organic solvent, or may exist in an oligomer state without being completely hydrolyzed. It may be a partially hydrolyzable product, or a mixture thereof.
Specifically, it is a dispersoid having a property of being stably dispersed without agglomeration in an organic solvent. In this case, the dispersoid refers to fine particles dispersed in the dispersion system, and specific examples include colloidal particles.

  Here, the state of being stably dispersed without agglomeration represents a state in which the dispersoid of the hydrolysis product is not condensed and not separated in an organic solvent, preferably transparent and homogeneous. Represents a state. Transparent means a state in which the transmittance in visible light is high. Specifically, the concentration of the dispersoid is 0.5% by weight in terms of oxide, the optical path length of the quartz cell is 1 cm, and the target sample is This is a state in which an organic solvent is used and the transmittance is preferably 80 to 100%, expressed by spectral transmittance measured under the condition that the wavelength of light is 550 nm.

  The particle size of the dispersoid of the hydrolysis product is not particularly limited, but is usually 1 to 300 nm, preferably 1 to 100 nm, more preferably 1 to 50 nm, and particularly preferably 1 in order to obtain a high transmittance in visible light. It is in the range of -10 nm.

  Although it does not restrict | limit especially as an acid used as a catalyst, It is preferable to use the organic acid or inorganic acid whose pKa value (logarithm value of the reciprocal number of an acid dissociation constant) is 1-6.

  Organic acids include saturated formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, hexanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, etc. Aliphatic monocarboxylic acids; saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid; unsaturated fats such as acrylic acid, propiolic acid, methacrylic acid, crotonic acid, isocrotonic acid, and oleic acid Monocarboxylic acids; unsaturated aliphatic dicarboxylic acids such as fumaric acid and maleic acid; aromatic carboxylic acids such as benzoic acid, 4-chlorobenzoic acid and naphthalenecarboxylic acid; substituted with halogen atoms such as monochloroacetic acid and trifluoroacetic acid Aliphatic carboxylic acids; hydroxycarboxylic acids such as glycolic acid, lactic acid, malic acid, citric acid; Acid, 3-phenylpropionic aliphatic carboxylic acid substituted with an aromatic group such as an acid; benzenesulfonic acid, p- toluenesulfonic acid, sulfonic acids such as methanesulfonic acid; and the like.

  Examples of the inorganic acid include hydrochloric acid, nitric acid, boric acid, borohydrofluoric acid, chloroplatinic acid and the like. Among these, an organic acid having a pKa value of 1 to 6 is more preferable, and an organic acid having a pKa value of 2 to 5 is particularly preferable because of its excellent ability to activate the functional group of the photosensitive compound and easy handling. preferable.

The acid dissociation constant Ka can be accurately measured by potentiometry using various electrodes such as a glass electrode, a metal electrode, a metal amalgam electrode, a redox electrode, and an ion selective electrode. In the present invention, the acid dissociation constant Ka can be determined by measuring the pH value in an aqueous solution (those that do not dissolve in water are a mixed solvent of water and a suitable organic solvent, or a suitable organic solvent). . The pKa value may differ by about ± 0.3 depending on the measurement conditions. The acid dissociation constants Ka or pKa values of various organic acids are as follows. E. Martell, R.A. M.M. Smith, Critical Stability Constants, Vol. 1, 2, 3, 5, Plenum Press (1974, 1975, 1977, 1982) and the like.

A silanol condensation catalyst or the like can be used in place of the acid.
Examples of the silanol condensation catalyst include carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters, and titanate ester chelates. Specific examples include stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, lead naphthenate, cobalt naphthenate , 2-ethylhexenoic acid iron, dioctyltin bisoctylthioglycolate ester salt, dioctyltin maleate ester salt, dibutyltin maleate polymer, dimethyltin mercaptopropionate polymer, dibutyltin bisacetylacetate, dioctyltin bisacetyllaurate , Titanium tetraethoxide, titanium tetrabutoxide, titanium tetraisopropoxide, titanium bis (acetylacetonyl) dipropoxide, and the like.

  The method for forming an organic thin film containing the compound represented by the formula (I) of the present invention on the substrate surface is not particularly limited. For example, the organic thin film forming composition is applied on a substrate by a known coating method, and the coating film is heated and dried. The coating method is not particularly limited, and a known method can be used. Specific examples include a dipping method, a spin coating method, a spray method, a roller coating method, a Meyer bar method, a screen printing method, a brush coating method, and the like. Among these, the dipping method is preferable.

  In addition, ultrasonic waves can be used to promote film formation. The step of applying to the substrate surface may be performed for a long time at a time, or a short time application may be performed in several steps.

  After applying the solution containing the compound represented by the formula (I) of the present invention to the surface of the substrate, a washing step may be provided in order to remove excess reagents, impurities and the like adhering to the film surface. By providing the cleaning step, the film thickness can be controlled more. The cleaning method is not particularly limited as long as it can remove surface deposits. Specifically, (a) a method of immersing the substrate in a solvent capable of dissolving the compound represented by the formula (I) used; (b) evaporation in a vacuum or under normal pressure in the atmosphere. (C) A method of blowing an inert gas such as dry nitrogen gas to blow it away. In the method (a), it is preferable to further perform ultrasonic treatment after the substrate is immersed in order to obtain a good organic thin film.

  After the solution containing the compound represented by formula (I) of the present invention is applied or washed on the substrate, the substrate is preferably heated in order to stabilize the film formed on the substrate surface. The heating temperature can be appropriately selected depending on the stability of the substrate and the formed organic thin film.

  When the solution containing the compound represented by the formula (I) of the present invention is applied on the substrate, the compound represented by the formula (I) in the solution is adsorbed on the substrate surface, and a thin film is formed. The details of the mechanism by which the compound represented by the formula (I) is adsorbed on the substrate surface are not clear, but in the case of a substrate having active hydrogen on the surface, it can be considered as follows. That is, in the solution, the functional group of the compound represented by formula (I) is hydrolyzed with water. Then, the compound represented by the formula (I) in this state reacts with active hydrogen on the surface of the substrate to form a thin film that forms a strong chemical bond with the substrate. This thin film is formed by reacting with the active hydrogen of the substrate and becomes a monomolecular film.

  The obtained organic thin film has a property that its physical properties change when irradiated with light. For example, when irradiated with ultraviolet rays, only the irradiated part changes to a hydrophilic thin film. This change can be confirmed, for example, by measuring a change in contact angle with water. Accordingly, after forming an organic thin film containing the compound represented by the formula (I) of the present invention on a substrate, only a specific part is made hydrophilic by irradiating with ultraviolet rays through a mask having a predetermined pattern. Can be converted into a thin film.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by the following Example.

Example 1
Synthesis of 4-hexylbenzyl 4- (10- (triethoxysilyl) decyloxy) phenyl sulfone (Compound No. 18) (1) Synthesis of 4-hexylbenzyl chloride In a 30 mL THF suspension of 1.0 g lithium aluminum hydride 4-hexylbenzoyl chloride was added dropwise under ice cooling. The mixture is heated under reflux for 1 hour, then hydrolyzed with ice water, 10% aqueous sodium hydroxide and water in order, ether is added, insoluble matter is filtered, and the filtrate is concentrated to obtain a crude product of benzyl alcohol. It was. This was dissolved in 30 mL of chloroform, and 1 drop of pyridine and 7 mL of thionyl chloride were added under ice cooling. The mixture was heated under reflux for 1 hour and concentrated. The residue was partitioned with hexane-sodium hydrogen carbonate aqueous solution, and the organic layer was dried over anhydrous sodium sulfate and concentrated to obtain the desired 4-hexylbenzyl chloride.

(2) Synthesis of 4-[(4-hexylphenyl) methanesulfonyl] phenol Into 20 mL of methanol in 1.2 g of potassium hydroxide, 10 mL of methanol in 2.5 g of 4-mercaptophenol was added dropwise under ice cooling. After stirring for 4 minutes, a solution of 4.3 g of 4-hexylbenzyl chloride in 10 mL of methanol was added under ice cooling. The mixture was stirred at room temperature for 18 hours, concentrated, ether and water were added, the organic layer was separated, dried over anhydrous magnesium sulfate and concentrated to obtain a crude product. This was dissolved in 50 mL of acetic acid, and 5 g of 30% aqueous hydrogen peroxide was added dropwise with heating to 80 ° C. The mixture was stirred at 90 ° C. for 3 hours and then poured into water. The precipitate was filtered, washed well with water, and then heat-dried under reduced pressure to obtain 4.30 g of the desired product.

(3) Synthesis of 4-hexylbenzyl 4- (9-decenyloxy) phenyl sulfone 4.3 g of 4-[(4-hexylphenyl) methanesulfonyl] phenol, 5.0 g of triphenylphosphine, 9-decethene-1-ol 6 g was dissolved in 50 mL of dichloromethane, and 7.1 g of 40% toluene solution of azodicarboxylic acid dimethyl ester was added dropwise thereto under ice cooling. After stirring at room temperature for 5 hours. After concentration, the residue was applied to a silica gel column (silica gel column; eluent = hexane-ethyl acetate, 4: 1) and purified to obtain 5.2 g of the desired product.

(4) Synthesis of 4-hexylbenzyl 4- (10- (triethoxysilyl) decyloxy) phenyl sulfone. Add 2.0 g of 4-hexylbenzyl 4- (9-decenyloxy) phenyl sulfone and 0.1 g of 10% platinum-activated carbon. The reaction vessel was purged with nitrogen, 5 mL of triethoxysilane was added, and the mixture was heated and stirred at 60 ° C. for 16 hours. After cooling to room temperature, the mixture was concentrated, 20 mL of toluene was added, the mixture was filtered through celite, and the filtrate was concentrated. 2.2 g of the target product of amorphous crystals was obtained.

(Example 2)
Synthesis of 4-hexylbenzyl 4- (10- (trimethoxysilyl) decyloxy) phenyl sulfone (Compound No. 17) 4-hexylbenzyl 4- (10- (triethoxysilyl) decyloxy) phenyl sulfone synthesized in Example 1 2.0 g was dissolved in 10 mL of methanol added with 1 drop of oxalic acid dichloride and 10 mL of toluene in advance, and the mixture was stirred at room temperature for 1 hour. The mixture was concentrated to obtain the desired methoxysilane compound.

Example 3
Synthesis of 4- (decyloxy) benzyl 4- (10- (trimethoxysilyl) decyloxy) phenyl sulfone (Compound No. 90) (1) Synthesis of 4-hydroxybenzyl 4- (9-decenyloxy) phenyl sulfone 4-Mercaptophenol 10.0 g of acetic acid 4-chloromethylphenyl ester was added to a slurry of 7.80 g and 5.45 g of potassium hydrogen carbonate in 50 mL of DMF. After stirring at room temperature for 5 hours, the mixture was separated with ether-water, and the organic layer was dried over anhydrous magnesium sulfate and concentrated to obtain 17.0 g of 4- (4-hydroxyphenylthiomethyl) phenylacetic acid. . This compound was added to a suspension of m-chlorobenzoic acid (26.6 g) in dichloromethane (100 mL) under ice-cooling, stirred at room temperature for 8 hours, the mixture was concentrated, and the residue was poured into an aqueous sodium hydrogen carbonate solution to precipitate. The crystals were filtered. The filtered crystals were recrystallized from ethyl acetate to obtain 14.5 g of 4-acetoxybenzyl 4-hydroxyphenyl sulfone.
2.92 g of this compound, 3.67 g of triphenylphosphine, and 2.06 g of 9-decethen-1-ol were dissolved in 50 mL of dichloromethane, and 5.11 g of a 40% toluene solution of azodicarboxylic acid dimethyl ester was added thereto under ice cooling. It was dripped. After stirring at room temperature for 5 hours. Concentrated. Methanol (30 mL) and 1N hydrochloric acid (10 mL) were added to the residue, and the mixture was heated under reflux for 4 hours. The mixture was concentrated and partitioned between ethyl acetate and water, and the organic layer was subjected to column chromatography (silica gel column; eluent = hexane-ethyl acetate, 7: 3). ) To obtain 3.00 g of the desired product.

(2) Synthesis of 4-decyloxybenzyl 4- (9-decenyloxy) phenyl sulfone 4-hydroxybenzyl 4- (9-decenyloxy) phenyl sulfone 2.0 g, 1-iododecane 1.87 g, potassium carbonate 1.38 g of acetonitrile 50 mL of the suspension was heated and stirred for 16 hours. The mixture was concentrated and partitioned with ethyl acetate-water, the organic layer was dried and concentrated, and the residue was washed with hexane to obtain 2.5 g of the desired product.

(3) Synthesis of 4- (decyloxy) benzyl 4- (10- (trimethoxysilyl) decyloxy) phenyl sulfone 2.5 g of 4-decyloxybenzyl 4- (9-decenyloxy) phenyl sulfone and 5% platinum-activated carbon The reaction vessel containing 3 g was purged with nitrogen, 5 mL of trimethoxysilane was added, and the mixture was heated and stirred at 60 ° C. for 72 hours. After cooling to room temperature, the mixture was concentrated, 20 mL of toluene was added, the mixture was filtered through celite, and the filtrate was concentrated. 2.6 g of the target product of amorphous crystals was obtained.

Example 4
4. Synthesis of 4- (hexyloxy) benzyl 4- (10- (trimethoxysilyl) decyloxy) phenyl sulfone (Compound No. 58) (1) Synthesis of 4- (4′-acetoxybenzylthio) phenol Potassium bicarbonate 5. In a suspension of 45 g of DMF 50 ml, 7.80 g of 4-mercaptophenol was added. Next, 10.1 g of 4-acetoxybenzyl chloride was added to this reaction solution under ice cooling, and the mixture was stirred at room temperature for 5 hours. The reaction solution was separated with water and diethyl ether, and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate and concentrated to obtain 14.7 g of the desired product.

(2) Synthesis of 4-[(4′-acetoxyphenyl) methanesulfonyl] phenol A solution of 14.7 g of 4- (4′-acetoxybenzylthio) phenol in 50 ml of dichloromethane was mixed with 26.6 g of m-chloroperbenzoic acid in dichloromethane. The mixture was added dropwise to 100 ml suspension under ice-cooling, and the mixture was stirred for 8 hours, then poured into an aqueous sodium bicarbonate solution, and the precipitate was collected by filtration. The filtered product was recrystallized from ethyl acetate to obtain 14.5 g of the desired product.

(3) Synthesis of 4- (acetoxy) benzyl-4- (9-decenyloxy) phenylsulfone 9.64 g of 4-[(4′-acetoxyphenyl) methanesulfonyl] phenol and 12.36 g of triphenylphosphine, 9-decene- 5.90 g of 1-ol was dissolved in 100 ml of dichloromethane, and 17.3 g of a 40% toluene solution of azodicarboxylic acid dimethyl ester was added dropwise thereto under ice cooling. After completion of the dropping, the reaction solution was returned to room temperature and stirred at room temperature for 16 hours. The reaction solution was concentrated, and the concentrate was recrystallized from methanol to obtain 7.62 g of the desired product.

(4) 4- (hexyloxy) benzyl 4- (10- (trimethoxysilyl) decyloxy) phenyl sulfone A 1 N aqueous NaOH solution was added to a methanol solution of 4- (acetoxy) benzyl-4- (9-decenyloxy) phenylsulfone. The mixture was further stirred at room temperature for 1 hour. The reaction mixture was poured into aqueous hydrochloric acid, and the precipitated crystals were filtered, washed well with water, and then dried to obtain a deacetylated compound. A suspension of 2.5 g of this deacetylated compound, 1.31 g of 1-bromohexane and 20 ml of acetonitrile of 1.19 g of potassium carbonate was heated to reflux for 3 hours, water was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated, and the residue was recrystallized from methanol to obtain 0.65 g of 4- (hexyloxy) benzyl 4- (decenyloxy) phenyl sulfone. This compound was reacted by the method described in Example 1 (4) and then in Example 2 to obtain 0.8 g of the desired compound.

(Example 5)
Synthesis of 4-isopropylbenzyl 4- (10- (trimethoxysilyl) decyloxy) phenylsulfone (Compound No. 106) In the method of Example 1 (2) to Example 2, instead of 4-hexylbenzyl chloride, 4 -The target compound (Compound No. 106) was synthesized by using isopropylbenzyl chloride. The amounts and yields used are as follows. Using 4.0 g of 4-isopropylbenzyl chloride, 4.65 g of a compound corresponding to Example 1 (2) was obtained, and then using the total amount, 3.38 g of a compound corresponding to Example 1 (3) was obtained. It was. In the subsequent methods of Example 1 (4) and Example 2, 1.05 g of the target compound (Compound No. 106) was obtained using 0.86 g of the olefin compound.

(Example 6) Formation of organic thin film 4-hexylbenzyl 4- (10- (trimethoxysilyl) decyloxy) phenyl sulfone synthesized in Example 2 was diluted with anhydrous toluene, and 5 mol% of the compound was used. Titanium tetraisopropoxide was added, and anhydrous toluene was added to prepare a solution having a solid concentration of 1.0% by weight. Furthermore, ion-exchanged water was added so that the concentration became 500 ppm or more, and the mixed solution was irradiated with ultrasonic waves to disperse water droplets, which was used as an immersion solution. After soaking the soda lime glass substrate in a dipping solution with ultrasonic cleaner, ion-exchanged water and ethanol in order, followed by drying at 60 ° C and washing in an ozone generator for 5 minutes and 60 minutes, the substrate is pulled out. Then, ultrasonic cleaning was performed in a solution of THF-water (4: 1), followed by drying at 60 ° C. for 10 minutes to form an organic thin film.

Example 7 Formation of Organic Thin Film In Example 6, instead of 4-hexylbenzyl 4- (10- (trimethoxysilyl) decyloxy) phenyl sulfone synthesized in Example 2, 4-synthesized in Example 3 An organic thin film was formed in the same manner as in Example 6 except that (decyloxy) benzyl 4- (10- (trimethoxysilyl) decyloxy) phenyl sulfone was used.

(Example 8) Formation of an organic thin film In Example 6, instead of 4-hexylbenzyl 4- (10- (trimethoxysilyl) decyloxy) phenyl sulfone synthesized in Example 2, 4-synthesized in Example 4 An organic thin film was formed in the same manner as in Example 6 except that (hexyloxy) benzyl 4- (10- (trimethoxysilyl) decyloxy) phenyl sulfone was used.

(Example 9) Formation of organic thin film In Example 6, instead of 4-hexylbenzyl 4- (10- (trimethoxysilyl) decyloxy) phenyl sulfone synthesized in Example 2, 4-synthesized in Example 5 An organic thin film was formed in the same manner as in Example 6 except that isopropylbenzyl 4- (10- (trimethoxysilyl) decyloxy) phenylsulfone was used.

(Comparative Example 1) Formation of Organic Thin Film In Example 4, instead of 4-hexylbenzyl 4- (10- (trimethoxysilyl) decyloxy) phenyl sulfone synthesized in Example 2, 4-methylbenzyl 4- (10 An organic thin film was formed in the same manner as in Example 4 except that-(trimethoxysilyl) decyloxy) phenyl sulfone (Compound No. 6 described in WO2004 / 0675540) was used.

(Comparative Example 2) Formation of Organic Thin Film In Example 4, instead of 4-hexylbenzyl 4- (10- (trimethoxysilyl) decyloxy) phenyl sulfone synthesized in Example 2, 4-dodecylbenzyl 4- (10 An organic thin film was formed in the same manner as in Example 4 except that-(trimethoxysilyl) decyloxy) phenyl sulfone (Compound No. 213 described in WO2004 / 0675540) was used.

(Comparative Example 3) Formation of Organic Thin Film In Example 4, instead of 4-hexylbenzyl 4- (10- (trimethoxysilyl) decyloxy) phenyl sulfone synthesized in Example 2, 4-decylbenzyl 4- (4 An organic thin film was formed in the same manner as in Example 4 except that-(trimethoxysilyl) butyloxy) phenyl sulfone (Compound No. 168 described in WO2004 / 0675540) was used.

Comparative Example 4 Formation of Organic Thin Film In Example 4, instead of 4-hexylbenzyl 4- (10- (trimethoxysilyl) decyloxy) phenyl sulfone synthesized in Example 2, 4-dodecylbenzyl 4- (5 An organic thin film was formed in the same manner as in Example 4 except that-(trimethoxysilyl) pentyloxy) phenyl sulfone (Compound No. 212 described in WO2004 / 0675540) was used.

(Test example) Contact angle change measurement by light irradiation of organic thin film A soda-lime glass substrate on which organic thin films obtained in Examples 6 to 9 and Comparative Examples 1 to 4 were formed was contact angle measuring device (Kyowa Interface Co., Ltd.). ), And a contact angle of water was measured by the θ / 2 method. The corresponding substrate was irradiated with a wavelength of 254 nm (sterilizing lamp, ² mW / cm ² ), and the contact angle after irradiation for 10 minutes was measured. Table 3 summarizes the contact angle and the amount of change in contact angle before and after light irradiation. Table 4 summarizes the comparison of performance depending on the immersion time of the substrate.

  As is clear from Tables 3 and 4, the organic thin films formed in Examples from the compounds represented by the formula (I) of the present invention are comparative examples from the compounds specifically described in WO2004 / 0675540. The initial contact angle, that is, the water repellency is superior to the organic thin film formed by (1), and the amount of change in the contact angle of water before and after light irradiation is excellent. Moreover, when forming an organic thin film, even if the immersion time of the base | substrate in the solution containing the compound represented by Formula (I) of this invention is short, it turns out that it is an organic thin film excellent in performance. .

Claims (3)

Formula (I)

[Wherein, X is a silyl group having a chlorine atom or an alkoxy group having 1 to 4 carbon atoms as a substituent, a mercapto group, an optionally substituted alkylthio group having 1 to 4 carbon atoms, or 1 carbon atom. 10 acylthio group, represents a disulfide group, an amino group, or may have a substituent group phosphono group, R ₁ represents an alkyl group having a carbon number of 5-7. m represents 0 . n represents any integer of 6 to 12 . G ₁ represents a divalent hydrocarbon group of saturated carbon number of 1-3. Ar represents a phenylene group. G ₂ is represents SansoHara child. ] The compound represented by this. The compound according to claim 1, wherein X is a silyl group having a chlorine atom or an alkoxy group having 1 to 4 carbon atoms as a substituent. An organic thin film forming body comprising an organic thin film formed from a composition for forming an organic thin film containing a compound represented by formula (I) according to claim 1 or 2 on the surface of a substrate.