WO2008068875A1 - Chemical adsorption solution - Google Patents

Chemical adsorption solution Download PDF

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Publication number
WO2008068875A1
WO2008068875A1 PCT/JP2006/324991 JP2006324991W WO2008068875A1 WO 2008068875 A1 WO2008068875 A1 WO 2008068875A1 JP 2006324991 W JP2006324991 W JP 2006324991W WO 2008068875 A1 WO2008068875 A1 WO 2008068875A1
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Prior art keywords
groups
compound
film
reactive functional
chemical adsorption
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PCT/JP2006/324991
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French (fr)
Inventor
Kazufumi Ogawa
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Kazufumi Ogawa
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Application filed by Kazufumi Ogawa filed Critical Kazufumi Ogawa
Priority to PCT/JP2006/324991 priority Critical patent/WO2008068875A1/en
Publication of WO2008068875A1 publication Critical patent/WO2008068875A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3405—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/42—Coatings comprising at least one inhomogeneous layer consisting of particles only

Definitions

  • the present invention generally relates to chemical adsorption solutions. More specifically, this invention relates to a chemical adsorption solution containing a substance at least comprising of reactive functional groups at one end of the molecules and alkoxysilyl groups at the other end, wherein the reactive functional groups and the alkoxysilyl groups are directly or indirectly connected with hydrocarbon groups, an organic solvent, and a silanol condensation catalyst.
  • the reactive functional groups include thermoreactive, photoreactive, radical reactive or ion reactive functional groups.
  • the Langmuir Blodgett (LB) is known in which amphiphilic organic molecules are arranged on water to accumulate monomolecular films on a surface of a substrate.
  • a chemical adsorption (CA) method is also known in which monomolecular films are accumulated in a solution of a surfactant using the chemical adsorption method.
  • a method of forming a layer of covalent reactive molecules (hereafter referred to as monolayer film) on a surface of an arbitrary substrate and a processing solution (hereafter referred to as chemical adsorption solution) excellent in reactivity to be used in the method are yet to be developed and provided.
  • a chemical adsorption solution to be used in a method of forming covalent reactive monomolecular films on a surface of an arbitrary substrate by mixing and dissolving a substance at least comprising reactive functional groups at one end of the molecules and alkoxysilyl groups at the other end, wherein the reactive functional groups and the alkoxysilyl groups are directly or indirectly connected with hydrocarbon groups, and a silanol condensation catalyst in an organic solvent.
  • the disclosed chemical adsorption solutions provide a particular effect capable of providing organic films such as monomolecular films, which are covalently bonded with a surface of a substrate and have various types of reactivity, at a low cost.
  • Fig. 1 is a schematic view of a reaction mechanism on a surface of a particulate enlarged to a molecular level in a first embodiment according to the invention
  • Fig.1A is a view of the particulate surface before a reaction
  • Fig.1B a view of the particulate surface after formation of a monomolecular film containing epoxy groups
  • Fig.1C a view of the particulate surface after the formation of a monomolecular film containing amino groups
  • Fig. 2 is a schematic view of a reaction mechanism on a surface of a glass substrate enlarged to a molecular level in a second embodiment according to the invention
  • Fig.2A is a view of the surface before a reaction
  • Fig.2B a view of the surface after formation of a monomolecular film containing epoxy groups
  • Fig.2C a view of the surface after formation of a monomolecular film containing amino groups
  • Fig. 3 is a schematic view of a reaction mechanism on a surface of a glass substrate enlarged to a molecular level in third and fourth embodiments according to the invention
  • Fig.3A is a view of the substrate surface after formation of a monolayer particulate film
  • Fig.3B a view of the substrate surface after formation of two layers of monolayer particulate film.
  • a chemical adsorption solution is disclosed that is capable of easily forming covalent reactive monomolecular films on a surface of an arbitrary substrate by mixing and dissolving a substance at least comprising reactive functional groups at one end of the molecules and alkoxysilyl groups at the other end, wherein the reactive functional groups and the alkoxysilyl groups are directly or indirectly connected with hydrocarbon groups, and a silanol condensation catalyst in an organic solvent.
  • thermoreactive, photoreactive, radical reactive or ion reactive functional groups can be used as reactive functional groups. If thermoreactive epoxy or imino groups, or photoreactive chalconyl groups are contained, reaction time of thermoreaction or photoreaction in the subsequent process can be effectively reduced. Additionally, if a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkyl alkoxysilane compound is used instead of a silanol condensation catalyst, film forming time can be effectively reduced.
  • silanol condensation catalyst mixed with at least one substance selected from a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkyl alkoxysilane compound as a co-catalyst is used, film forming time can be further reduced effectively.
  • a medicine containing reactive functional groups in functional locations as a chemical adsorbent for example, epoxy groups and imino groups at one end of the molecules, and alkoxysilyl groups at the other end, for example, a medicine shown by the formula (C1) or (C2) below was weighed so as to occupy 99 % by weight, and, for example, dibutyltin diacetylacetonate or acetic acid, one of organic acids, was weighed so as to occupy 1% by weight as a silanol condensation catalyst.
  • a silicone solvent for example, a solvent prepared by mixing hexamethyl disiloxane and dimethylformamide (50 to 50) to prepare a chemical adsorption solution so that the concentration is approximately 1% by weight (preferable concentration of the chemical adsorbent is approximately 0.5 to 3%).
  • This adsorption solution was added with the anhydrous silica particulates 1, agitated and subjected to a reaction in normal air (relative humidity 45%) for two hours. At this time, since a surface of the anhydrous silica particulate contains numerous hydroxyl groups 2 (Fig.
  • the -Si (OCH 3 ) groups of the chemical adsorbent and the hydroxyl groups were subjected to a dealcoholation reaction under existence of a silanol condensation catalyst or an acetic acid, one of the organic acids (in this case deCH 3 OH reaction) to form bonding as shown by the formula (C3) or (C4) below to form a chemically adsorbed monomolecular film 3, containing epoxy groups chemically bonded with a surface throughout the surface of the particulate or a chemically adsorbed film 4, containing amino groups with film thickness about 1 nm (Figs. 1B and 1C).
  • adsorbent comprising amino groups
  • an organic acid such as an acetic acid should be used because a tin-based catalyst causes sedimentation.
  • the amino groups contain imino groups.
  • substances containing imino groups in addition to amino groups are a pyrrole derivative, an imidazole derivative and so on.
  • a ketimine derivative was used, amino groups were easily introduced by hydrolysis after a film was formed.
  • a medicine containing reactive functional groups in functional locations as a chemical adsorbent for example, epoxy groups and imino groups at one end of the molecules and alkoxysilyl groups at the other end, for example, a medicine shown by the aforementioned formula (C1) or (C2) was weighed so as to occupy 99% by weight, and, for example, dibutyltin diacetylacetonate was weighed so as to occupy 1% by weight as a silanol condensation catalyst.
  • a silicone solvent for example, a solvent made of hexamethyl disiloxane to prepare a chemical adsorption solution so that the concentration is approximately 1% by weight (preferable concentration of the chemical adsorbent is approximately 0.5 to 3%).
  • the glass substrate 11 was immersed in this adsorption solution and subjected to a reaction in normal air (relative humidity 45%) for two hours. At this time, since a surface of the glass substrate 11 contains numerous hydroxyl groups 12 (Fig. 2A), the -Si (OCH 3 ) groups of the chemical adsorbent and the hydroxyl groups were subjected to a dealcoholation reaction under existence of a silanol condensation catalyst (in this case deCH3OH reaction) to form bonding as shown by the formula (C3) or (C4) to form a chemically adsorbed monomolecular film 13 (Fig. 2 B) containing epoxy groups chemically bonded with a surface throughout the surface of the glass substrate 11 , or a chemically adsorbed film 14 (Fig. 2C) containing amino groups with film thickness of around 1 nm.
  • a silanol condensation catalyst in this case deCH3OH reaction
  • a silica particulate 6 covered with a chemically adsorbed monomolecular film comprising amino groups and dispersed in alcohol was applied to the surface of glass substrate 15 covered with a chemically adsorbed monomolecular film comprising the epoxy groups (combination of the surface of a glass substrate covered with a chemically adsorbed monomolecular film comprising amino groups and the silica particulate covered with a chemically adsorbed monomolecular film comprising the epoxy groups is acceptable) and heated at around 100 0 C, the amino groups on the surface of a silica particulate in contact with the epoxy groups on the surface of the glass substrate were added in a reaction shown in the formula (C5) below, at which time the particulate and the glass substrate were bonded and solidified through two monomolecular films. At this time, it was evident that the uniformity of film thickness can be further improved by vaporizing alcohol in a condition of being exposed to ultrasonic wave. [C5]
  • a monolayer particulate film 17 with uniform thickness was formed in a condition that one layer of silica particulates covered with the chemically adsorbed monomolecular films comprising amino groups covalently bonded with the glass substrate surface 15 and a particle size level is arranged (Fig. 3A).
  • a silica particulate 5 covered with a chemically adsorbed monomolecular film comprising epoxy groups and dispersed in alcohol was applied to the surface of a glass substrate surface 15 on which a monolayer particulate film 17 with uniform thickness in a condition that only one layer of silica particulates covered with chemically adsorbed monomolecular films comprising covalent amino groups, is arranged and in a particle size level and heated at around 100 0 C, the epoxy groups on the silica particulate surface in contact with the amino groups on the glass substrate surface, on which a monolayer particulate film of silica particulates covered with the chemically adsorbed monomolecular films comprising amino groups are added into the reaction shown in the formula (C5), and the particulates covered with chemically adsorbed monomolecular films comprising amino groups, at which time the silica particulates covered with chemically adsorbed monomolecular films comprising epoxy groups are bonded
  • a monolayer particulate film 18 of a two-layer structure with uniform thickness was formed in a condition that only one layer of silica particulates of a second layer, covalently bonded with the glass substrate surface 15 and is arranged within a particle size level (Fig. 3B).
  • silica particulates covered with chemically adsorbed monomolecular films comprising amino groups and silica particulates covered with chemically adsorbed monomolecular films comprising epoxy groups were laminated alternately to accumulate and manufacture particulate films of multilayer structure.
  • the (CH 2 OCH) - group represents a functional group shown by the formula (C6) below
  • the (CH 2 CHOCH (CH 2 ) 2 ) CH - group represents a functional group shown by the formula (C7) below: [C ⁇ ]
  • (C 6 H 5 ) CO (CH) 2 (C 6 H 4 ) represents a chalconyl group.
  • metal carboxylate, carboxyl acid ester metallic salt, metal carboxylate polymer, metal carboxylate chelate, titanic acid ester, titanic acid ester chelate, etc. can be used as a silanol condensation catalyst.
  • an organochlorine-based solvent containing no water, hydrocarbon-based solvent, fluorocarbon-based solvent, silicone-based solvent, or mixtures of two or more of these can be used as a solvent for forming a film.
  • solvent with a boiling point of 50 to 250 0 C.
  • chlorosilane-based nonaqueous petroleum naphtha, solvent naphtha, petroleum ether, petrol benzin, isoparaffin, normal paraffin, decaline, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl silicone, alkyl degeneration silicone, polyether silicone, dimethyl formamide, etc. can be selected as an applicable solvent.
  • alcohol-based solvent such as methanol, ethanol, propanol, etc. or mixtures of them can be used.
  • fleon-based solvent manufactured by 3M Co.
  • afluid manufactured by Asahi Glass Co.
  • an organic chlorine-based solvent such as chloroform can be added.
  • processing speed can be increased several times (around 30 minutes as processing time) and film forming time can be reduced to a fraction of the original time.
  • reaction time can be reduced to around one hour while keeping the other results without change.
  • silanol catalyst was replaced with mixture of H3 manufactured by Japan Epoxy Resin Co., one of the ketimine compounds, and dibutyltin bisaetylacetonate, one of the silanol catalysts (mixing ratio at 1 :1), without changing other conditions, it was found that reaction time can be reduced to around 30 minutes while keeping the other results without change.
  • ketimine compounds for example, include: 2,5,8-triaza-1 , 8-nonadiene, 3,11-dimethyl-4, 7,10-triaza-3, 10-tridecadiene, 2,10-dimethyl-3, 6,9-triaza-2, 9-undecadiene, 2,4,12,14-tetramethyl-5, 8,11-triaza-4,
  • Applicable organic acids include: a formic acid, an acetic acid, a propionic acid, a lactic acid, a malonic acid, etc. without limited to these. They showed similar effects.
  • the chemical absorption solution according to this invention is applicable to any substrate and particulate only if the surface of the substrate or particulate contains active hydrogen such as hydrogen of a hydroxide group or hydrogen of an amino or imino group.
  • applicable substrates include unlimited types of materials such as metal, ceramics, glass, fiber, leather, fur, etc.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
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  • Organic Chemistry (AREA)
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Abstract

A chemical adsorption solution used in a method of forming a layer of covalent reactive molecules on a surface of an arbitrary substrate by mixing and dissolving (1) a substance at least comprising reactive functional groups at one end of the molecules and alkoxysilyl groups at the other end, wherein the reactive functional groups and the alkoxysilyl groups are directly or indirectly connected with hydrocarbon groups, and (2) a silanol condensation catalyst in an organic solvent, is manufactured and provided.

Description

DESCRIPTION
CHEMICALADSORPTION SOLUTION
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention generally relates to chemical adsorption solutions. More specifically, this invention relates to a chemical adsorption solution containing a substance at least comprising of reactive functional groups at one end of the molecules and alkoxysilyl groups at the other end, wherein the reactive functional groups and the alkoxysilyl groups are directly or indirectly connected with hydrocarbon groups, an organic solvent, and a silanol condensation catalyst.
In the invention, the reactive functional groups include thermoreactive, photoreactive, radical reactive or ion reactive functional groups. Description of Related Art
Conventionally, the Langmuir Blodgett (LB) is known in which amphiphilic organic molecules are arranged on water to accumulate monomolecular films on a surface of a substrate. A chemical adsorption (CA) method is also known in which monomolecular films are accumulated in a solution of a surfactant using the chemical adsorption method. However, a method of forming a layer of covalent reactive molecules (hereafter referred to as monolayer film) on a surface of an arbitrary substrate and a processing solution (hereafter referred to as chemical adsorption solution) excellent in reactivity to be used in the method are yet to be developed and provided.
SUMMARY OF THE INVENTION
In accordance with aspects of the invention a chemical adsorption solution to be used in a method of forming covalent reactive monomolecular films on a surface of an arbitrary substrate by mixing and dissolving a substance at least comprising reactive functional groups at one end of the molecules and alkoxysilyl groups at the other end, wherein the reactive functional groups and the alkoxysilyl groups are directly or indirectly connected with hydrocarbon groups, and a silanol condensation catalyst in an organic solvent. As described in further detail herein, the disclosed chemical adsorption solutions provide a particular effect capable of providing organic films such as monomolecular films, which are covalently bonded with a surface of a substrate and have various types of reactivity, at a low cost.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing aspects and many of the attendant advantages of this invention will become more readily appreciated as the same becomes better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein like reference numerals refer to like parts throughout the various views unless otherwise specified:
Fig. 1 , is a schematic view of a reaction mechanism on a surface of a particulate enlarged to a molecular level in a first embodiment according to the invention, while Fig.1A is a view of the particulate surface before a reaction, Fig.1B a view of the particulate surface after formation of a monomolecular film containing epoxy groups, and Fig.1C a view of the particulate surface after the formation of a monomolecular film containing amino groups;
Fig. 2 is a schematic view of a reaction mechanism on a surface of a glass substrate enlarged to a molecular level in a second embodiment according to the invention, while Fig.2A is a view of the surface before a reaction, Fig.2B a view of the surface after formation of a monomolecular film containing epoxy groups, and Fig.2C a view of the surface after formation of a monomolecular film containing amino groups; and
Fig. 3 is a schematic view of a reaction mechanism on a surface of a glass substrate enlarged to a molecular level in third and fourth embodiments according to the invention, while Fig.3A is a view of the substrate surface after formation of a monolayer particulate film, and Fig.3B a view of the substrate surface after formation of two layers of monolayer particulate film.
DETAILED DESCRIPTION
Embodiments of chemical adsorption solutions and method for manufacturing the same are described herein. In the following description, numerous specific details are set forth to provide a thorough understanding of embodiments of the invention. One skilled in the relevant art will recognize, however, that the invention can be practiced without one or more of the specific details, or with other methods, components, materials, etc. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of the invention.
According to aspects of the invention, a chemical adsorption solution is disclosed that is capable of easily forming covalent reactive monomolecular films on a surface of an arbitrary substrate by mixing and dissolving a substance at least comprising reactive functional groups at one end of the molecules and alkoxysilyl groups at the other end, wherein the reactive functional groups and the alkoxysilyl groups are directly or indirectly connected with hydrocarbon groups, and a silanol condensation catalyst in an organic solvent.
In accordance with various embodiments, thermoreactive, photoreactive, radical reactive or ion reactive functional groups can be used as reactive functional groups. If thermoreactive epoxy or imino groups, or photoreactive chalconyl groups are contained, reaction time of thermoreaction or photoreaction in the subsequent process can be effectively reduced. Additionally, if a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkyl alkoxysilane compound is used instead of a silanol condensation catalyst, film forming time can be effectively reduced. Moreover, if a silanol condensation catalyst mixed with at least one substance selected from a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkyl alkoxysilane compound as a co-catalyst is used, film forming time can be further reduced effectively.
Details of various embodiments of the invention are now described in further detail. It shall be noted that such details and embodiments are merely illustrative, and are not meant to be limiting.
First, a chemical adsorption solution using a substance containing epoxy or imino groups selected from solutions containing reactive functional groups such as thermoreactive, photoreactive, radical reactive or ion reactive functional groups is described. [Embodiment 1]
First, an anhydrous silica particulate 1, approximately 100 nm in size, was prepared and sufficiently dried. Then a medicine containing reactive functional groups in functional locations as a chemical adsorbent, for example, epoxy groups and imino groups at one end of the molecules, and alkoxysilyl groups at the other end, for example, a medicine shown by the formula (C1) or (C2) below was weighed so as to occupy 99 % by weight, and, for example, dibutyltin diacetylacetonate or acetic acid, one of organic acids, was weighed so as to occupy 1% by weight as a silanol condensation catalyst. These substances were dissolved in a silicone solvent, for example, a solvent prepared by mixing hexamethyl disiloxane and dimethylformamide (50 to 50) to prepare a chemical adsorption solution so that the concentration is approximately 1% by weight (preferable concentration of the chemical adsorbent is approximately 0.5 to 3%).
[C1]
Figure imgf000005_0001
[C2]
OCH3
H2N(CH2)SSi-OCH3 OCH3
This adsorption solution was added with the anhydrous silica particulates 1, agitated and subjected to a reaction in normal air (relative humidity 45%) for two hours. At this time, since a surface of the anhydrous silica particulate contains numerous hydroxyl groups 2 (Fig. 1A), the -Si (OCH3) groups of the chemical adsorbent and the hydroxyl groups were subjected to a dealcoholation reaction under existence of a silanol condensation catalyst or an acetic acid, one of the organic acids (in this case deCH3OH reaction) to form bonding as shown by the formula (C3) or (C4) below to form a chemically adsorbed monomolecular film 3, containing epoxy groups chemically bonded with a surface throughout the surface of the particulate or a chemically adsorbed film 4, containing amino groups with film thickness about 1 nm (Figs. 1B and 1C).
When using adsorbent comprising amino groups, it was found that an organic acid such as an acetic acid should be used because a tin-based catalyst causes sedimentation. The amino groups contain imino groups. On the other hand, substances containing imino groups in addition to amino groups are a pyrrole derivative, an imidazole derivative and so on. When a ketimine derivative was used, amino groups were easily introduced by hydrolysis after a film was formed. Then, the solution was added with chloroform, one of chlorine-based solvents, mixed and washed to enable preparation of a silica particulate 5 covered by a chemically adsorbed monomolecular film, comprising reactive functional groups, for example, epoxy groups on its surface or a silica particulate 6 covered by a chemically adsorbed monomolecular film, comprising amino groups. [C3]
O O—
CH2-CHCH2O(CH2J3Si -O-
O—
[C4]
O—
H2N(CH2J3Si - O — O—
Since this film is extremely thin at the nanometer level, a particle diameter was kept as it is without damage.
On the other hand, by taking out the film into air without washing, a solvent was vaporized and a chemical adsorbent left on the surface of the particle was reacted with moisture contained in the air to obtain a particulate on which surface a very thin polymer film made of the chemical adsorbent is formed, while reactivity was kept almost constant. This method has a wide applicable range, without regard to whether the particulate is an organic or inorganic substance because it utilizes a dealcoholation reaction. [Embodiment 2] First, a glass substrate 11 was prepared and sufficiently dried in the same way as Embodiment 1. Then a medicine containing reactive functional groups in functional locations as a chemical adsorbent, for example, epoxy groups and imino groups at one end of the molecules and alkoxysilyl groups at the other end, for example, a medicine shown by the aforementioned formula (C1) or (C2) was weighed so as to occupy 99% by weight, and, for example, dibutyltin diacetylacetonate was weighed so as to occupy 1% by weight as a silanol condensation catalyst. These substances were dissolved in a silicone solvent, for example, a solvent made of hexamethyl disiloxane to prepare a chemical adsorption solution so that the concentration is approximately 1% by weight (preferable concentration of the chemical adsorbent is approximately 0.5 to 3%).
The glass substrate 11 was immersed in this adsorption solution and subjected to a reaction in normal air (relative humidity 45%) for two hours. At this time, since a surface of the glass substrate 11 contains numerous hydroxyl groups 12 (Fig. 2A), the -Si (OCH3) groups of the chemical adsorbent and the hydroxyl groups were subjected to a dealcoholation reaction under existence of a silanol condensation catalyst (in this case deCH3OH reaction) to form bonding as shown by the formula (C3) or (C4) to form a chemically adsorbed monomolecular film 13 (Fig. 2 B) containing epoxy groups chemically bonded with a surface throughout the surface of the glass substrate 11 , or a chemically adsorbed film 14 (Fig. 2C) containing amino groups with film thickness of around 1 nm.
Then, the film was washed with chloroform, one of chlorine-based catalysts, to enable preparation of a glass substrate 15 covered by a chemically adsorbed monomolecular film comprising reactive functional groups, for example, epoxy groups on its surface or glass substrate 16 covered by a chemically adsorbed monomolecular film comprising amino groups. (Figs. 2B and 2C)
Since this film is extremely thin at the nanometer level, transparency of the glass substrate was kept as it is without damage. On the other hand, by taking out the substrate into the air without washing, the solvent was vaporized and chemical adsorbent left on the surface of the glass substrate was subjected to a reaction with moisture contained in the air to obtain a glass substrate on which surface a very thin polymer film made of the chemical adsorbent is formed, while reactivity was kept almost the same. [Embodiment 3]
A silica particulate 6 covered with a chemically adsorbed monomolecular film comprising amino groups and dispersed in alcohol was applied to the surface of glass substrate 15 covered with a chemically adsorbed monomolecular film comprising the epoxy groups (combination of the surface of a glass substrate covered with a chemically adsorbed monomolecular film comprising amino groups and the silica particulate covered with a chemically adsorbed monomolecular film comprising the epoxy groups is acceptable) and heated at around 1000C, the amino groups on the surface of a silica particulate in contact with the epoxy groups on the surface of the glass substrate were added in a reaction shown in the formula (C5) below, at which time the particulate and the glass substrate were bonded and solidified through two monomolecular films. At this time, it was evident that the uniformity of film thickness can be further improved by vaporizing alcohol in a condition of being exposed to ultrasonic wave. [C5]
O -(CH2)CH-CH2 + H2NCH2 —
► - (CH2)CHCH2 -NHCH2 -
OH
When the surface of the substrate was washed with alcohol to remove silica particulates covered with chemically adsorbed monomolecular films comprising left and unreacted amino groups, a monolayer particulate film 17 with uniform thickness was formed in a condition that one layer of silica particulates covered with the chemically adsorbed monomolecular films comprising amino groups covalently bonded with the glass substrate surface 15 and a particle size level is arranged (Fig. 3A).
On the other hand, when a film of silica particulates covered with the chemically adsorbed monomolecular film comprising epoxy groups is formed on the glass substrate surface, covered with the chemically adsorbed monomolecular film comprising amino groups, a monolayer particulate film with uniform thickness was formed in a condition that one layer of silica particulates, covered with the chemically adsorbed monomolecular film comprising epoxy groups, covalently bonded with the glass substrate surface and is arranged and in a particle size level.
Then, light transmittance of the glass substrate on which the monolayer particulate film of silica particulates formed was measured to find that the light transmittance is improved by around 2% in comparison with a glass substrate on which no monolayer particulate film of silica particulates was formed. Otherwise stated, this film has a function for preventing reflection.
In addition, no interference color was detected because the monolayer particulate film of silica particulates is around 100 nm in thickness, showing very high levels of uniformity. [Embodiment 4]
When greater thickness of a particulate film is desirable in addition to Embodiment 3, a silica particulate 5 covered with a chemically adsorbed monomolecular film comprising epoxy groups and dispersed in alcohol, was applied to the surface of a glass substrate surface 15 on which a monolayer particulate film 17 with uniform thickness in a condition that only one layer of silica particulates covered with chemically adsorbed monomolecular films comprising covalent amino groups, is arranged and in a particle size level and heated at around 1000C, the epoxy groups on the silica particulate surface in contact with the amino groups on the glass substrate surface, on which a monolayer particulate film of silica particulates covered with the chemically adsorbed monomolecular films comprising amino groups are added into the reaction shown in the formula (C5), and the particulates covered with chemically adsorbed monomolecular films comprising amino groups, at which time the silica particulates covered with chemically adsorbed monomolecular films comprising epoxy groups are bonded and solidified through two monomolecular films on the glass substrate surface. When the surface of the substrate was washed again with alcohol to remove silica particulates covered with chemically adsorbed monomolecular films comprising left and unreacted epoxy groups, a monolayer particulate film 18 of a two-layer structure with uniform thickness was formed in a condition that only one layer of silica particulates of a second layer, covalently bonded with the glass substrate surface 15 and is arranged within a particle size level (Fig. 3B).
Thus, in a similar way, silica particulates covered with chemically adsorbed monomolecular films comprising amino groups and silica particulates covered with chemically adsorbed monomolecular films comprising epoxy groups, were laminated alternately to accumulate and manufacture particulate films of multilayer structure.
In addition to the substance shown by formulas (C1) and (C2) used as a chemical adsorbent comprising reactive groups in the above Embodiments 1 and 2, it was discovered that the substances shown in (1) through (16) below can be also used. (1) (CH2OCH)CH2θ(CH2)7Si(OCH3)3 (2) (CH2OCH)CH2O(CH2)Ii Si(OCHs)3 (3) (CH2CHOCH(CH2)2)CH(CH2)2Si(OCH3)3
(4) (CH2CHOCH(CH2)2)CH(CH2)4Si(OCH3)3
(5) (CH2CHOCH(CH2)2)CH(CH2)6Si(OCH3)3 (6) (CH2OCH)CH2O(CH2)7Si(OC2H5)3
(7) (CH2OCH)CH2O(CH2)iiSi(OC2H5)3
(8) (CH2CHOCH(CH2)2)CH(CH2)2Si(OC2H5)3
(9) (CH2CHOCH(CH2)2)CH(CH2)4Si(OC2H5)3
(10) (CH2CHOCH(CH2)2)CH(CH2)6Si(OC2H5)3 (11) H2N(CH2)5Si(OCH3)3
(12) H2N(CH2)7Si(OCH3)3
(13) H2N(CH2)9Si(OCH3)3
(14) H2N(CH2)5Si(OC2H5)3
(15) H2N(CHz)7Si(OC2Hs)3 (16) H2N(CH2J9Si(OC2Hs)3
In these formulas, the (CH2OCH) - group represents a functional group shown by the formula (C6) below, and the (CH2CHOCH (CH2)2) CH - group represents a functional group shown by the formula (C7) below: [Cβ]
O CH2-CH-
[C7]
O — CH-CH2
\ / \
CH CH -
\ /
CH2 -CH2
It was found that the substances shown by (21) through (29) below can be used as substances comprising usable photoreactive functional groups. (21) CH ≡ C - C ≡ C (CH2)i5 Si (OCH3)3 (22) CH ≡ C - C ≡ C (CHa)2Si (CHs)2 (CH2)I5 Si (OCHa)3 (23) CH ≡ C - C ≡ C (CH2)2 Si (CH3)2 (CH2)9 Si (OCH3)3
(24) CH3 (CH2)3 C ≡ C - C ≡ C (CH2)i5 Si (OCH3)3
(25) CH3 (CH2)3 C ≡ C - C ≡ C (CH2)2 Si (CH3)2 (CHz)15 Si (OCH3)3
(26) CH3 (CHz)3 C ≡ C - C ≡ C (CH2)2 Si (CH3)2 (CH2)9 Si (OCH3)3
(27) (C6H5) (CH)2CO (C6H4) O (CH2)6OSi (OCH3)3 (28) (C6H5) (CH)2 CO (C6H4) O (CH2)8 OSi (OC2Hs)3
(29) (C6H5) CO (CH)2 (C6H4) O (CH2)6OSi (OCH3)3
In these formula, (C6H5) CO (CH)2 (C6H4) represents a chalconyl group.
In Embodiments 1 and 2, metal carboxylate, carboxyl acid ester metallic salt, metal carboxylate polymer, metal carboxylate chelate, titanic acid ester, titanic acid ester chelate, etc., can be used as a silanol condensation catalyst. More specifically, it was found that tinous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, tinous dioctate, lead naphthenate, cobalt naphthenate, iron 2-ethylhexanate, dioctyltin bisoctyl thioglycolic acid esterate, dioctyltin maleic acid esterate, dioctyltin maleinate polymer, dimethyltin mercaptopropionate polymer, dibutyltin bisacetylacetate, dioctyltin bisacetyllaurate, tetrabutyl titanate, tetranonyl titanate and bis (acetylacetonyl) dipropyl titanate can be used. It was found that an organochlorine-based solvent containing no water, hydrocarbon-based solvent, fluorocarbon-based solvent, silicone-based solvent, or mixtures of two or more of these can be used as a solvent for forming a film. When it is desirable to increase a particle concentration by vaporizing a solvent without washing, it is preferable to use solvent with a boiling point of 50 to 2500C. More specifically, chlorosilane-based nonaqueous petroleum naphtha, solvent naphtha, petroleum ether, petrol benzin, isoparaffin, normal paraffin, decaline, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl silicone, alkyl degeneration silicone, polyether silicone, dimethyl formamide, etc., can be selected as an applicable solvent. In addition to the above solvent, when it is desirable to form an organic film by using an alkoxysilane adsorbent and vaporizing a solvent, it was found that alcohol-based solvent such as methanol, ethanol, propanol, etc. or mixtures of them can be used.
Moreover, fleon-based solvent, fluorinate (manufactured by 3M Co.), afluid (manufactured by Asahi Glass Co.), etc. can be used as a fluorocarbon solvent. In addition to the case when one of these can be used independently, the combination of two or more of these can be used if they can be mixed well. Furthermore, an organic chlorine-based solvent such as chloroform can be added.
On the other hand, when a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkyl alkoxysilane compound is used instead of the above-mentioned silanol condensation catalyst, it was found that processing time can be reduced to a half to two thirds, even with the same concentration.
When a silanol condensation catalyst mixed with a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkyl alkoxysilane compound (mixing ratio at 1:9 to 9:1 is possible, but around 1 :1 is preferable) is used, processing speed can be increased several times (around 30 minutes as processing time) and film forming time can be reduced to a fraction of the original time.
For example, when dibutyltin oxide, one of the silanol catalysts, was replaced with H3 manufactured by Japan Epoxy Resin Co., one of the ketimine compounds without changing other conditions, it was found that reaction time can be reduced to around one hour while keeping the other results without change.
Further, when the silanol catalyst was replaced with mixture of H3 manufactured by Japan Epoxy Resin Co., one of the ketimine compounds, and dibutyltin bisaetylacetonate, one of the silanol catalysts (mixing ratio at 1 :1), without changing other conditions, it was found that reaction time can be reduced to around 30 minutes while keeping the other results without change.
Therefore, the above results clarified that a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, and an aminoalkyl alkoxysilane compound have higher activity than a silanol condensation catalyst.
Further, it was found that use of mixtures of one substance selected from a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, aminoalkyl alkoxysilane compound, and a silanol condensate catalyst further makes activity higher.
Here applicable ketimine compounds , for example, include: 2,5,8-triaza-1 , 8-nonadiene, 3,11-dimethyl-4, 7,10-triaza-3, 10-tridecadiene, 2,10-dimethyl-3, 6,9-triaza-2, 9-undecadiene, 2,4,12,14-tetramethyl-5, 8,11-triaza-4,
11-pentadecadiene, 2,4,15,17-tetramethyl-5, 8,11 ,14-tetraaza-4, 14-octadecadiene, 2,4,20,22-tetramethyl-5, 12,19-triaza-4, 19-trieicosadiene, etc. without limited to these.
Applicable organic acids , for example, include: a formic acid, an acetic acid, a propionic acid, a lactic acid, a malonic acid, etc. without limited to these. They showed similar effects.
Although a silica particulate and a glass substrate were taken as examples for explanation in the above Embodiments 1 through 4, the chemical absorption solution according to this invention is applicable to any substrate and particulate only if the surface of the substrate or particulate contains active hydrogen such as hydrogen of a hydroxide group or hydrogen of an amino or imino group.
More specifically, applicable substrates include unlimited types of materials such as metal, ceramics, glass, fiber, leather, fur, etc.

Claims

1. A chemical adsorption solution containing a substance at least comprising reactive functional groups at one end of the molecules and alkoxysilyl groups at another end, wherein said reactive functional groups and said alkoxysilyl groups are directly or indirectly connected with hydrocarbon groups, an organic solvent, and a silanol condensation catalyst.
2. A particulate according to Claim 1 , wherein reactive functional groups are thermoreactive, photoreactive, radical reactive or ion reactive groups.
3. A chemical adsorption solution according to Claims 1 and 2, wherein reactive functional groups are epoxy groups, imino groups, or chalconyl groups.
4. A chemical adsorption solution according to Claims 1 through 3, wherein a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, and an aminoalkyl alkoxysilane compound are used instead of a silanol condensation catalyst.
5. A chemical adsorption solution according to Claims 1 through 3, wherein a silanol condensation catalyst is used as a co-catalyst mixed with at least one substance selected from a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, and an aminoalkyl alkoxysilane compound.
PCT/JP2006/324991 2006-12-08 2006-12-08 Chemical adsorption solution WO2008068875A1 (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11274602A (en) * 1998-03-19 1999-10-08 Kawamura Inst Of Chem Res Optical semiconductor element

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11274602A (en) * 1998-03-19 1999-10-08 Kawamura Inst Of Chem Res Optical semiconductor element

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