WO2008136128A1 - Particulate film and manufacturing method thereof - Google Patents

Particulate film and manufacturing method thereof Download PDF

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Publication number
WO2008136128A1
WO2008136128A1 PCT/JP2007/059278 JP2007059278W WO2008136128A1 WO 2008136128 A1 WO2008136128 A1 WO 2008136128A1 JP 2007059278 W JP2007059278 W JP 2007059278W WO 2008136128 A1 WO2008136128 A1 WO 2008136128A1
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Prior art keywords
particulate
reactive
particulates
film
organic
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PCT/JP2007/059278
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French (fr)
Inventor
Kazufumi Ogawa
Original Assignee
Kazufumi Ogawa
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Publication date
Application filed by Kazufumi Ogawa filed Critical Kazufumi Ogawa
Priority to PCT/JP2007/059278 priority Critical patent/WO2008136128A1/en
Publication of WO2008136128A1 publication Critical patent/WO2008136128A1/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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/34—Applying different liquids or other fluent materials simultaneously
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
    • 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
    • B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
    • B05D2401/30—Form of the coating product, e.g. solution, water dispersion, powders or the like the coating being applied in other forms than involving eliminable solvent, diluent or dispersant
    • B05D2401/32—Form of the coating product, e.g. solution, water dispersion, powders or the like the coating being applied in other forms than involving eliminable solvent, diluent or dispersant applied as powders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy

Definitions

  • the present invention relates to a film formed using particulates and a manufacturing method thereof. More specifically, the invention relates to a film with high anti-peeling strength formed using particulates of which surfaces are stabilized, or are provided with a thermo reactive, photo reactive, radical reactive or ion reactive property, and a manufacturing method thereof.
  • an "inorganic particulate” includes a conductor particulate, a semiconductor particulate, an insulator particulate, a magnetic particulate, a fluorescent particulate, a light absorption particulate, a light transmission particulate and a pigment particulate.
  • An “organic particulate” includes an organic fluorescent particulate, an organic light absorption particulate, an organic light transmission particulate, an organic pigment particulate and an organic chemical agent particulate.
  • An "organic/inorganic hybrid particulate” includes a chemical agent particulate for
  • DDS drug delivery system
  • a particulate for cosmetics and an organic/inorganic hybrid pigment particulate.
  • the purpose of the invention is to provide a particulate film not containing a binder resin at all and having high anti-peeling strength, and a manufacturing method thereof considering the aforementioned problems.
  • the first invention made as a means for solving the aforementioned problems provides a particulate film, wherein a mixture of particulates of which surfaces are covered with first reactive organic films and particulates of which surfaces are covered with second reactive organic films is hardened and coated on a substrate surface.
  • the second invention provides a particulate film according to the first invention, wherein a third reactive organic film that reacts with particulates covered with particulates first reactive organic films in advance or particulates covered with second reactive organic films in advance is formed on a substrate surface and the organic film is hardened and coated by bonding at least the first reactive organic films or the second reactive organic films and the third reactive organic film on the substrate surface.
  • This method can conveniently improve an anti-peeling strength.
  • the third invention provides a particulate film according to the second invention, wherein a first reactive organic film is identical to a third reactive organic film or a second reactive organic film is identical to a third reactive organic film. This method can conveniently improve process efficiency.
  • the fourth invention provides a particulate film according to the first through third inventions, wherein a reactive organic film is thermo reactive, photo reactive, radical reactive or ion reactive. This method can conveniently improve an anti-peeling strength.
  • the fifth invention provides a particulate film according to the second and third inventions, wherein an organic film having epoxy groups or imino groups as reactive functional groups is used. This method can conveniently improve an anti-peeling strength.
  • the sixth invention provides a manufacturing method of a particulate film comprising a process for mixing first reactive particulates and second reactive particulates in an organic solvent to make a paste, a process for applying to a substrate surface and a process for hardening and coating.
  • the seventh invention provides a manufacturing method of a particulate film according to the sixth invention, wherein an organic film having functional groups that react with first reactive particulates or second reactive particulates is formed in advance on a substrate surface before application. This method can conveniently improve an anti-peeling strength.
  • the invention has an excellent effect that enables to provide a particulate film not containing a binder resin at all and having high anti-peeling strength, and a manufacturing method thereof.
  • Fig. 1 is a schematic sectional view showing a reaction mechanism of a particulate enlarged to a molecular level in the first embodiment according to the invention, while (a) is a view of the particulate surface before reaction, (b) a view of the particulate surface after formation of a monomolecular film having epoxy groups, and (c) a view of the particulate surface after formation of a monomolecular film having amino groups.
  • Fig. 2 is a schematic sectional view showing a reaction mechanism of a particulate film enlarged to a molecular level in the second embodiment according to the invention, while (a) is a view of the particulate film before treatment of a substrate surface, and (b) a view of the particulate film after formation of a monomolecular film having epoxy groups on the substrate surface.
  • the invention provides a particulate film, wherein a mixture of particulates of which surfaces are covered with first reactive organic films and particulates of which surfaces are covered with second reactive organic films is hardened and coated on a substrate surface using a process for mixing first reactive particulates and second reactive particulates in an organic solvent to make a paste, a process for applying to a substrate surface and a process for hardening and coating.
  • the invention has an effect that enables to provide a particulate film not containing a binder resin at all and having high anti-peeling strength.
  • Particulates relating to the invention are mainly "inorganic particulates” including a conductor particulate, a semiconductor particulate, an insulator particulate, a magnetic particulate, a fluorescent particulate, a light absorption particulate, a light transmission particulate and a pigment particulate. They are also “organic particulates” including an organic fluorescent particulate, an organic light absorption particulate, an organic light transmission particulate, an organic pigment particulate and an organic chemical agent particulate. Further they are “organic/inorganic hybrid particulates” including a chemical agent particulate for DDS (drug delivery system), a particulate for cosmetics and an organic/inorganic hybrid pigment particulate. Now a silica particulate is taken as a typical one for description.
  • silica particulates 1 were prepared and sufficiently dried. Then a chemical agent having reactive functional groups, for example epoxy groups and imino groups, in functional locations, and alkoxysilyl groups, for example groups shown by the formula (C1 ) or (C2) below at the other end was weighed as a chemical adsorbent so as to occupy 99 % by weight, and a silanol condensation catalyst, for example dibutyltin diacetylacetonate or acetic acid, one of organic acids, was weighed so as to occupy 1 % by weight.
  • a chemical agent having reactive functional groups for example epoxy groups and imino groups, in functional locations, and alkoxysilyl groups, for example groups shown by the formula (C1 ) or (C2) below at the other end was weighed as a chemical adsorbent so as to occupy 99 % by weight
  • a silanol condensation catalyst for example dibutyltin diacetylacetonate or acetic acid, one of organic acids
  • This adsorption solution was added with silica particulates, agitated and subjected to a reaction in normal air (relative humidity 45%) for about two hours. At this time, since a dangling bond on a surface of the silica particulate is bonded with numerous hydroxyl groups 2 (Fig.
  • amino groups contain imino groups.
  • substances having imino groups in addition to amino groups are a pyrrole derivative, an imidazole derivative and so on.
  • Equal amounts of silica particulates 11 and 12 covered with a chemically adsorbed monomolecular film having epoxy groups or amino groups were sufficiently mixed in isopropyl alcohol to make paste.
  • the paste was applied to the surface of the substrate 13 and heated at a temperature approximately between 50 0 C and
  • Embodiment 2 In embodiment 1 , formation of an organic film having reactive functional groups, for example a chemically adsorbed monomolecular film 15 having epoxy groups on the surface of the substrate 13 in a similar method in advance allowed amino groups on the surface of the silica particulate 12 covered with a chemically adsorbed monomolecular film having amino groups to react with epoxy groups on the surface of the silica particulate 11 covered with a chemically adsorbed monomolecular film having epoxy groups and simultaneously react with epoxy groups of the monomolecular film 15 having epoxy groups present on the substrate surface to be covalently bonded on the substrate surface, thus enabling to manufacture a film 16 containing particulates with high anti-peeling strength.
  • Fig. 2 a chemically adsorbed monomolecular film 15 having epoxy groups
  • particulates of lead oxide or the like to a surface of a zinc-coated steel plate or the like through the monomolecular film in a similar method enabled to realize coating with extremely high anti-peeling strength and excellent durability because of binder resin free composition and covalent bonding with the substrate surface.
  • (26) below can be also used as a chemical adsorbent having reactive functional groups that cause radical reaction with energy beam such as light and electron beam.
  • energy beam such as light and electron beam.
  • hardening is performed by radiating energy beam such as light and electron beam needless to say.
  • 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 alcoxysilane-based solvent, a chlorosilane-based solvent, an organochlorine-based solvent, hydrocarbon-based solvent, fluorocarbon-based solvent, silicone-based solvent, or mixtures of two or more of these solvents, each of which contains no water, can be used as a chemical adsorbent.
  • a solvent with a boiling point of 50 to 25O 0 C it is preferable to use a solvent with a boiling point of 50 to 25O 0 C.
  • an organochlorine-based solvent 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 thereof can be 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.
  • 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 ketimine compounds, and dibutyltin bisaetylacetonate, one of 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 include, for example, 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, for example, a formic acid, an acetic acid, a propionic acid, a butyric acid, a malonic acid, etc. without limited to these. They showed similar effects. Although a silica particulate was described as an example in the above two
  • inorganic particulates include a conductor particulate, a semiconductor particulate, an insulator particulate, a magnetic particulate, a fluorescent particulate, a light absorption particulate, a light transmission particulate and a pigment particulate.
  • Organic particulates include an organic fluorescent particulate, an organic light absorption particulate, an organic light transmission particulate, an organic pigment particulate and an organic chemical agent particulate.
  • Further organic/inorganic hybrid particulates include a chemical agent particulate for DDS (drug delivery system), a particulate for cosmetics and an organic/inorganic hybrid pigment particulate.

Abstract

A particulate film is provided, wherein a mixture of particulates of which surfaces are covered with first reactive organic films and particulates of which surfaces are covered with second reactive organic films is hardened and coated on a substrate surface using a process for mixing first reactive particulates and second reactive particulates in an organic solvent to make a paste, a process for applying to a substrate surface and a process for hardening and coating; and which solves a big problem that a binder resin used in a conventional film containing particulates causes significant loss of properties and functions inherent to the particulates and that the formed film not bonded with a substrate at all has only low anti-peeling strength.

Description

DESCRIPTION
PARTICULATE FILM AND MANUFACTURING METHOD THEREOF
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a film formed using particulates and a manufacturing method thereof. More specifically, the invention relates to a film with high anti-peeling strength formed using particulates of which surfaces are stabilized, or are provided with a thermo reactive, photo reactive, radical reactive or ion reactive property, and a manufacturing method thereof.
In the invention, an "inorganic particulate" includes a conductor particulate, a semiconductor particulate, an insulator particulate, a magnetic particulate, a fluorescent particulate, a light absorption particulate, a light transmission particulate and a pigment particulate. An "organic particulate" includes an organic fluorescent particulate, an organic light absorption particulate, an organic light transmission particulate, an organic pigment particulate and an organic chemical agent particulate.
An "organic/inorganic hybrid particulate" includes a chemical agent particulate for
DDS (drug delivery system), a particulate for cosmetics and an organic/inorganic hybrid pigment particulate.
Description of Related Art
Conventionally, various methods of forming a film using particulates are known. In all of these methods, a film containing particulates was formed by applying and hardening particulates dispersed in a binder resin.
SUMMARY OF THE INVENTION
There was a big problem that containing of a binder resin results in significant loss of properties and functions inherent to the particulates. There also was a problem that the formed film not bonded with a substrate has only low anti-peeling strength.
The purpose of the invention is to provide a particulate film not containing a binder resin at all and having high anti-peeling strength, and a manufacturing method thereof considering the aforementioned problems.
The first invention made as a means for solving the aforementioned problems provides a particulate film, wherein a mixture of particulates of which surfaces are covered with first reactive organic films and particulates of which surfaces are covered with second reactive organic films is hardened and coated on a substrate surface.
The second invention provides a particulate film according to the first invention, wherein a third reactive organic film that reacts with particulates covered with particulates first reactive organic films in advance or particulates covered with second reactive organic films in advance is formed on a substrate surface and the organic film is hardened and coated by bonding at least the first reactive organic films or the second reactive organic films and the third reactive organic film on the substrate surface. This method can conveniently improve an anti-peeling strength.
The third invention provides a particulate film according to the second invention, wherein a first reactive organic film is identical to a third reactive organic film or a second reactive organic film is identical to a third reactive organic film. This method can conveniently improve process efficiency.
The fourth invention provides a particulate film according to the first through third inventions, wherein a reactive organic film is thermo reactive, photo reactive, radical reactive or ion reactive. This method can conveniently improve an anti-peeling strength.
The fifth invention provides a particulate film according to the second and third inventions, wherein an organic film having epoxy groups or imino groups as reactive functional groups is used. This method can conveniently improve an anti-peeling strength.
The sixth invention provides a manufacturing method of a particulate film comprising a process for mixing first reactive particulates and second reactive particulates in an organic solvent to make a paste, a process for applying to a substrate surface and a process for hardening and coating. The seventh invention provides a manufacturing method of a particulate film according to the sixth invention, wherein an organic film having functional groups that react with first reactive particulates or second reactive particulates is formed in advance on a substrate surface before application. This method can conveniently improve an anti-peeling strength.
As mentioned above, the invention has an excellent effect that enables to provide a particulate film not containing a binder resin at all and having high anti-peeling strength, and a manufacturing method thereof.
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 sectional view showing a reaction mechanism of a particulate enlarged to a molecular level in the first embodiment according to the invention, while (a) is a view of the particulate surface before reaction, (b) a view of the particulate surface after formation of a monomolecular film having epoxy groups, and (c) a view of the particulate surface after formation of a monomolecular film having amino groups.
Fig. 2 is a schematic sectional view showing a reaction mechanism of a particulate film enlarged to a molecular level in the second embodiment according to the invention, while (a) is a view of the particulate film before treatment of a substrate surface, and (b) a view of the particulate film after formation of a monomolecular film having epoxy groups on the substrate surface.
DETAILED DESCRIPTION
The invention provides a particulate film, wherein a mixture of particulates of which surfaces are covered with first reactive organic films and particulates of which surfaces are covered with second reactive organic films is hardened and coated on a substrate surface using a process for mixing first reactive particulates and second reactive particulates in an organic solvent to make a paste, a process for applying to a substrate surface and a process for hardening and coating.
Therefore the invention has an effect that enables to provide a particulate film not containing a binder resin at all and having high anti-peeling strength.
Details of the invention are hereafter described using embodiments, although the invention is not limited by these embodiments.
Particulates relating to the invention are mainly "inorganic particulates" including a conductor particulate, a semiconductor particulate, an insulator particulate, a magnetic particulate, a fluorescent particulate, a light absorption particulate, a light transmission particulate and a pigment particulate. They are also "organic particulates" including an organic fluorescent particulate, an organic light absorption particulate, an organic light transmission particulate, an organic pigment particulate and an organic chemical agent particulate. Further they are "organic/inorganic hybrid particulates" including a chemical agent particulate for DDS (drug delivery system), a particulate for cosmetics and an organic/inorganic hybrid pigment particulate. Now a silica particulate is taken as a typical one for description.
Embodiment 1
Firstly silica particulates 1 were prepared and sufficiently dried. Then a chemical agent having reactive functional groups, for example epoxy groups and imino groups, in functional locations, and alkoxysilyl groups, for example groups shown by the formula (C1 ) or (C2) below at the other end was weighed as a chemical adsorbent so as to occupy 99 % by weight, and a silanol condensation catalyst, for example dibutyltin diacetylacetonate or acetic acid, one of organic acids, was weighed so as to occupy 1 % by weight. These substances were dissolved in a solvent prepared by mixing the same amounts of silicone and dimethylformamide, for example, a solvent prepared by mixing 50% of hexamethyl disiloxane and 50% of dimethylformamide 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]
O OCH3
CH2-CHCH2O(CH2)SSi -OCH3
OCH3 [C2]
OCH3
H2N(CH2)SSi -OCH3 OCH3
This adsorption solution was added with silica particulates, agitated and subjected to a reaction in normal air (relative humidity 45%) for about two hours. At this time, since a dangling bond on a surface of the silica particulate is bonded with numerous hydroxyl groups 2 (Fig. 1 (a)), the -Si (OCH3) groups of the chemical adsorbent and the hydroxyl groups were subjected to a dealcoholation reaction (in this case deChbOH reaction) under existence of a silanol condensation catalyst and an organic acid to form a bond as shown by the formula (C3) or (C4) below to form a chemically adsorbed monomolecular film 3 having epoxy groups chemically bonded with a surface all over the surface of the particulate or a chemically adsorbed film 4 having amino groups with film thickness about 1 nm (Figs. 1 (b) and 1 (c)).
It was found that, when using adsorbent having amino groups, an organic acid such as an acetic acid should be used instead of a tin-based catalyst because the tin-based catalyst causes sedimentation. The amino groups contain imino groups. On the other hand, substances having 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 catalysts, agitated and washed to enable preparation of a silica particulate covered with a chemically adsorbed monomolecular film having reactive functional groups, for example, epoxy groups or amino groups on a surface thereof. [C3]
O O—
CH2—CHCH2O(CH2)3Si — O —
O—
[C4] o—
H2N(CH2J3Si-O- O—
Since this film is extremely thin, namely in a nanometer level, a particle diameter was kept as it is without damaged.
On the other hand, by taking out the film into the air without washing, a solvent was vaporized and a chemical adsorbent left on the surface of the particle was reacted with moisture contained in 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.
Equal amounts of silica particulates 11 and 12 covered with a chemically adsorbed monomolecular film having epoxy groups or amino groups were sufficiently mixed in isopropyl alcohol to make paste. When the paste was applied to the surface of the substrate 13 and heated at a temperature approximately between 500C and
1000C, the particulate is added with the epoxy groups and amino groups in a reaction shown in the formula (C5) below, thus enabling to form a coating film 14 containing particulates even without containing a binder. (Fig. 2 (a))
[C5]
O
/ \ -(CH2)CH -CH2 + H2NCH2 -
► - (CH2)CHCH2 -NHCH2 -
OH
Embodiment 2 In embodiment 1 , formation of an organic film having reactive functional groups, for example a chemically adsorbed monomolecular film 15 having epoxy groups on the surface of the substrate 13 in a similar method in advance allowed amino groups on the surface of the silica particulate 12 covered with a chemically adsorbed monomolecular film having amino groups to react with epoxy groups on the surface of the silica particulate 11 covered with a chemically adsorbed monomolecular film having epoxy groups and simultaneously react with epoxy groups of the monomolecular film 15 having epoxy groups present on the substrate surface to be covalently bonded on the substrate surface, thus enabling to manufacture a film 16 containing particulates with high anti-peeling strength. (Fig. 2
(b))
Application of particulates of lead oxide or the like to a surface of a zinc-coated steel plate or the like through the monomolecular film in a similar method enabled to realize coating with extremely high anti-peeling strength and excellent durability because of binder resin free composition and covalent bonding with the substrate surface.
By the way, in addition to the substance shown by formulae (C1 ) and (C2) used as a chemical adsorbent having thermoreactive or ion reactive groups in the above Embodiment 1, it was found that the substances shown in the formulae (1) through (16) below can be also used.
(1) (CH2OCH) CH2O (CH2)7 Si (OCH3)3
(2) (CH2OCH) CH2O (CH2)I1 Si (OCH3)3
(3) (CH2CHOCH (CH2J2) CH (CH2)2 Si (OCH3)3
(4) (CH2CHOCH (CH2)2) CH (CH2)4 Si (OCH3)3 (5) (CH2CHOCH (CH2)2) CH (CH2)6 Si (OCH3)3
(6) (CH2OCH) CH2O (CH2)7 Si (OC2Hs)3
(7) (CH2OCH) CH2O (CH2)ii Si (OC2Hs)3
(8) (CH2CHOCH (CHz)2) CH (CH2)2 Si (OC2Hs)3
(9) (CH2CHOCH (CH2J2) CH (CH2)4 Si (OC2Hs)3 (10) (CH2CHOCH (CH2)2) CH (CH2)6 Si (OC2Hs)3
(11 ) H2N (CH2)S Si (OCHs)3
(12) H2N (CH2)T Si (OCH3)3
(13) H2N (CH2)9 Si (OCHs)3
(14) H2N (CH2)s Si (OC2Hs)3 (15) H2N (CH2)7 Si (OC2Hs)3
(16) H2N (CH2J9 Si (OC2Hs)3 where the (CH2OCH) - group represents a functional group shown by the formula (C7) below, and the (CH2CHOCH (CH2)2) CH - group represents a functional group shown by the formula (C8) below:
[C6]
O CH2-CH -
[C7]
O CH-CH2
\ / \
CH CH
\ /
CH2 -CH2
Further it was found that the substances shown in the formulae (21) through
(26) below can be also used as a chemical adsorbent having reactive functional groups that cause radical reaction with energy beam such as light and electron beam. In this case hardening is performed by radiating energy beam such as light and electron beam needless to say.
(21) CH = C - C 5= C - (CH2)I5SiCI3
(22) CH s C - C ≡ C - (CH2)2 Si(CHs)2 (CH2)is SiCI3
(23) CH = C - C ≡ C - (CH2)2 Si (CH3)2 (CH2)9 SiCI3 (24) (C6H5) (CH)2 CO (C6H4) O (CH2)6 OSi (OCH3)3
(25) (C6H5) (CH)2CO (C6H4) O (CH2)6 OSi (OC2Hs)3
(26) (C6H5) CO (CH)2(C6H4) O (CH2)6 OSi (OCH3)3 where (C6H5) CO (CH)2 (C6H4) represents a chalconyl group.
In Embodiment 1 , 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 tin acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, tin dioctate, lead naphthenate, cobalt naphthenate, iron 2-ethylhexanate, dioctyltin bisoctyl thioglycolic acid ester salt, dioctyltin maleic acid ester salt, 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 alcoxysilane-based solvent, a chlorosilane-based solvent, an organochlorine-based solvent, hydrocarbon-based solvent, fluorocarbon-based solvent, silicone-based solvent, or mixtures of two or more of these solvents, each of which contains no water, can be used as a chemical adsorbent. When it is desirable to increase a particle concentration by vaporizing a solvent without washing, it is preferable to use a solvent with a boiling point of 50 to 25O0C.
More specifically, an organochlorine-based solvent, 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 thereof can be used. Moreover, fleon-based solvent, fluorinate (manufactured by 3M Co.), Aflude
(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, combination of two or more of these can be used if they can be mixed well. Further, it is possible to add an organochlorine-based solvent such as chloroform. On the other hand, when a ketimine compound, an organic acid, an aldimine compound, an enamine compound, an 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 in the same concentration. When a silanol condensation catalyst mixed with a ketimine compound, an organic acid, an aldimine compound, an enamine compound, an 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 silanol catalysts, was replaced with H3 manufactured by Japan Epoxy Resin Co., one of 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 ketimine compounds, and dibutyltin bisaetylacetonate, one of 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, an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound and an aminoalkyl alkoxysilane compound have higher activity than a silanol condensation catalyst.
Further it was found that use of mixture of one substance selected from a ketimine compound, an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound and an aminoalkyl alkoxysilane compound and a silanol condensate catalyst further makes activity higher.
Here applicable ketimine compounds include, for example, 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 include, for example, a formic acid, an acetic acid, a propionic acid, a butyric acid, a malonic acid, etc. without limited to these. They showed similar effects. Although a silica particulate was described as an example in the above two
Embodiments, this invention is applicable to any particulate only if the surface of the particulate contains active hydrogen such as hydrogen of a hydroxide group. More specifically, inorganic particulates include a conductor particulate, a semiconductor particulate, an insulator particulate, a magnetic particulate, a fluorescent particulate, a light absorption particulate, a light transmission particulate and a pigment particulate. Organic particulates include an organic fluorescent particulate, an organic light absorption particulate, an organic light transmission particulate, an organic pigment particulate and an organic chemical agent particulate. Further organic/inorganic hybrid particulates include a chemical agent particulate for DDS (drug delivery system), a particulate for cosmetics and an organic/inorganic hybrid pigment particulate.

Claims

1. A particulate film, wherein a mixture of particulates of which surfaces are covered with first reactive organic films and particulates of which surfaces are covered with second reactive organic films is hardened and coated on a substrate surface.
2. A particulate film according to Claim 1 , wherein a third reactive organic film that reacts with particulates covered with first reactive organic films in advance or particulates covered with second reactive organic films in advance is formed on a substrate surface and said organic film is hardened and coated by bonding between at least said first reactive organic films or said second reactive organic films and said third reactive organic film on said substrate surface.
3. A particulate film according to Claim 2, wherein the first reactive organic film is identical to a third reactive organic film or the second reactive organic film is identical to the third reactive organic film.
4. A particulate film according to any one of Claims 1 through 3, wherein the reactive organic film is thermoreactive, photoreactive, radical reactive or ion reactive.
5. A particulate film according to Claims 2 and 3, wherein an organic film having epoxy groups or imino groups as reactive functional groups is used.
6. A manufacturing method of a particulate film comprising a process for mixing first reactive particulates and second reactive particulates in an organic solvent to make a paste, a process for applying to a substrate surface and a process for hardening and coating.
7. A manufacturing method of a particulate film according to Claim 6, wherein an organic film having functional groups that react with the first reactive particulates or the second reactive particulates is formed in advance on the substrate surface before application.
PCT/JP2007/059278 2007-04-23 2007-04-23 Particulate film and manufacturing method thereof WO2008136128A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01309902A (en) * 1988-06-07 1989-12-14 Matsushita Electric Ind Co Ltd Metal fine particle aggregate and manufacture thereof and magnetic recording medium using metal fine particle aggregate and manufacture thereof
JP2002341161A (en) * 2001-05-21 2002-11-27 Kunihito Kawamoto Photonic crystal and method for producing the same
JP2003168606A (en) * 2001-01-24 2003-06-13 Matsushita Electric Ind Co Ltd Fine particle array, its manufacturing method and device using the method
JP2005264347A (en) * 2004-03-16 2005-09-29 Nbc Inc Method for producing fine particle-fixed material
JP2006068964A (en) * 2004-08-31 2006-03-16 Nbc Inc Member for cutting off near infrared rays
WO2006054709A1 (en) * 2004-11-19 2006-05-26 Matsushita Electric Industrial Co., Ltd. Field-effect transistor, process for producing the same and electronic appliance utilizing the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01309902A (en) * 1988-06-07 1989-12-14 Matsushita Electric Ind Co Ltd Metal fine particle aggregate and manufacture thereof and magnetic recording medium using metal fine particle aggregate and manufacture thereof
JP2003168606A (en) * 2001-01-24 2003-06-13 Matsushita Electric Ind Co Ltd Fine particle array, its manufacturing method and device using the method
JP2002341161A (en) * 2001-05-21 2002-11-27 Kunihito Kawamoto Photonic crystal and method for producing the same
JP2005264347A (en) * 2004-03-16 2005-09-29 Nbc Inc Method for producing fine particle-fixed material
JP2006068964A (en) * 2004-08-31 2006-03-16 Nbc Inc Member for cutting off near infrared rays
WO2006054709A1 (en) * 2004-11-19 2006-05-26 Matsushita Electric Industrial Co., Ltd. Field-effect transistor, process for producing the same and electronic appliance utilizing the same

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