WO2008044521A1 - Composition polymère comprenant un produit de condensation d'un alcoxyde métallique, un composé organosilane et un composé du bore - Google Patents
Composition polymère comprenant un produit de condensation d'un alcoxyde métallique, un composé organosilane et un composé du bore Download PDFInfo
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- WO2008044521A1 WO2008044521A1 PCT/JP2007/069179 JP2007069179W WO2008044521A1 WO 2008044521 A1 WO2008044521 A1 WO 2008044521A1 JP 2007069179 W JP2007069179 W JP 2007069179W WO 2008044521 A1 WO2008044521 A1 WO 2008044521A1
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/56—Boron-containing linkages
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/58—Metal-containing linkages
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
- C08L85/04—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing boron
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D185/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers
- C09D185/04—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers containing boron
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
- C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/14—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J185/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Adhesives based on derivatives of such polymers
- C09J185/04—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Adhesives based on derivatives of such polymers containing boron
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Definitions
- the present invention relates to a reaction product obtained by reacting an organosilane compound and a boron compound.
- the present invention relates to a polymer composition containing a metal alkoxide condensate, and a coating agent, an adhesive, a glass substrate and a functional material using the same.
- a coating agent containing a metal alkoxide such as tetraethoxysilane (TEOS) and an aminosilane compound has been known for a long time.
- TEOS tetraethoxysilane
- an aminosilane compound has been known for a long time.
- a coating agent is inferior in film property and difficult to form into a film.
- the coating strength was insufficient.
- Patent Document 1 describes a coating resin composition comprising a metal alkoxide such as tetraethoxysilane (TEOS) or its condensate and an aminosilane compound.
- TEOS tetraethoxysilane
- an aminosilane compound such as tetraethoxysilane (TEOS)
- Patent Document 1 JP-A-8-295826
- the present inventor has found that the coating properties are improved by further adding boric acid to a coating agent containing a metal alkoxide and an aminosilane compound. Furthermore, in the case of a metal alkoxide monomer, if the amount added is too large, the film property will be reduced.
- the present invention relates to a polymer composition that is a raw material for a coating agent that is excellent in film formability (film formability) and has sufficient hardness (film strength), a coating agent and an adhesive containing the same as a main component, And the base material, glass base material, and functional material using them are provided.
- R represents an amino group-containing organic group
- R ′ represents a methyl group, an ethyl group or a propyl group
- n represents an integer selected from;! To 3
- R 1 represents an alkyl group, part of which may be hydrogen; R 1 may be independently the same or different; m is selected from 2 to 20; M represents at least one metal selected from the group consisting of Si, Ti and Zr.
- the present invention also relates to a polymer composition comprising the polymer composition and a synthetic resin.
- the present invention also relates to the polymer composition, which is in a fibrous form or a particulate form.
- the present invention also relates to a coating agent or an adhesive containing the polymer composition as a main component.
- the present invention also provides the above polymer composition, coating agent or contact.
- the present invention relates to a functional material obtained by applying an adhesive to an inorganic substrate or an organic substrate.
- the present invention also relates to a glass substrate obtained from the polymer composition or the functional material.
- the present invention relates to a base material or glass group obtained by firing the polymer composition in the form of fibers or particles or the functional material at a temperature of 1000 ° C or lower. Regarding materials.
- the obtained polymer substance and polymer substance composition can be applied to ceramics or glass as a coating agent or adhesive having excellent film properties and sufficient hardness.
- a synthetic resin when added, it can be used as a resin hard coat agent.
- component (organosilane compound) and (b) component (boron compound) reacts to become a transparent and viscous liquid in several minutes to several tens of minutes and solidifies. This is presumably because the boron compound acts as a crosslinking agent via the amino group in component (a), polymerizes these components, resulting in a viscous liquid and solidifies. .
- the component (a) is a liquid. In the present invention, water is not used in the reaction between the component (a) and the component (b).
- Component (a) is a silane compound containing an amino group represented by the following formula.
- R represents an amino group-containing organic group
- R ′ represents a methyl group, an ethyl group or a propyl group
- n represents an integer selected from;! To 3).
- R represents an amino group-containing organic group, for example, monoaminomethyl, diaminomethinole, ⁇ minominochinole, monominoyuchinole, diminochinole, ⁇ minominotinole, tetraaminoethyl, monoaminopropyl, diaminopropyl, Triaminopropyl, tetraaminopropylene, monoaminobutyl, diaminobutyl, triaminobutynole, tetraaminobutyl, and organic groups having more carbon atoms than these, alkyl groups or aryl groups.
- the powers you can list are not limited to them.
- ⁇ -Aminopropyl and aminoethylenoaminopropyl 7-aminopropyl is particularly preferred.
- R 'in component (a) represents a methyl group, an ethyl group or a propyl group. Of these, methyl and ethyl groups are preferred!
- n represents an integer selected from 1 to 3. Among them, n is preferably 2 to 3, and n is particularly preferably 3.
- ⁇ -aminopropyltriethoxysilane and ⁇ - / 3- (aminoethyl) - ⁇ -aminopropyltrimethoxysilane are particularly preferable.
- the component (b) is at least one boronated selected from the group consisting of H BO and B O forces.
- the component (b) is preferably HBO.
- the amount of both components used in the reaction between the component (a) and the component (b) is an arbitrary force.
- the ratio of the component (b) is 0 ⁇ 02 mol or more with respect to 1 mol of the component (a). More preferably, the ratio is 0.02 to 8 moles, still more preferably 0.02 to 5 moles, and still more preferably 0.2 to 5 moles.
- component (b) If the amount of component (b) is less than 0.02 moles per mole of component (a), the time required for solidification may become long, or sufficient solidification may occur. In addition, when component (b) exceeds 8 moles, component (b) may remain undissolved in component (a).
- the mixing conditions (temperature, mixing time, mixing method, etc.) of the polymer substance (a) and component (b) of the present invention can be appropriately selected. Under normal room temperature conditions, it becomes a transparent and viscous liquid in several minutes to several tens of minutes, and then solidifies. The time for solidification and the viscosity and rigidity of the reaction product (c) obtained also differ depending on the proportion of the boron compound.
- the boron compound (b) is preferably a boron compound alcohol solution dissolved in an alcohol having 1 to 7 carbon atoms.
- the alcohol having 1 to 7 carbon atoms include methyl alcohol, ethyl alcohol, various propyl alcohols, various butyl alcohols, and glycerin, and methyl alcohol, ethyl alcohol, and isopropyl alcohol are preferable.
- the concentration of the boron compound in the alcohol is preferably high.
- the reaction product is not subjected to hydrolysis by adding water.
- This is a reaction product obtained by reacting the component and the component (b).
- the polymer composition of the present invention has the following formulas (dl) and ( and a condensate (d) of a metal alkoxide represented by at least one formula selected from the group consisting of d2).
- R 1 represents an alkyl group, part of which may be hydrogen; R 1 may be independently the same or different; m is selected from 2 to 20; M represents at least one metal selected from the group consisting of Si, Ti and Zr.
- the component (d) is added during or after the reaction between the component (a) and the component (b).
- component (d) By adding component (d), the hardness can be increased, the electrical and chemical properties can be further improved, and since it becomes a viscous liquid state, it is processed into a fiber or film form. Can do.
- the addition amount of the condensate of the metal alkoxide as component (d) is preferably 2 to 50 mol in terms of the weight of metal alkoxide monomer with respect to 1 mol of component (a).
- the above is more preferable. That is, when the amount of component (d) added is too large, the hardness tends to decrease. On the other hand, when the amount is too small, the Si content decreases, so that the hardness may decrease depending on the application. Durability issues may occur.
- R 1 in component represents an alkyl group
- Yogu R 1 be a part thereof hydrogen may be different even with the same each independently
- R 1 Is a methyl group, an ethyl group, a propyl group, a butyl group, or an alkyl group having a carbon number higher than that. Is preferably an ethyl group.
- m is a force representing an integer selected from 2 to 20, 3 to 10 and preferably 5 is most preferable.
- M in the component (d) represents at least one metal selected from the group consisting of Si, Ti and Zr, and S and Ti are preferred, and Si is most preferred.
- the metal alkoxide monomer unit constituting the component (d) includes tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methinoretrimethoxylane, tetramethoxytitanium, tetraethoxytitanium, tetrapropoxy.
- the component (d) is represented by the above formula (dl), it is preferably a tetraethoxysilane condensate (pentamer) or a tetramethoxysilane condensate (pentamer).
- it is preferable that it is a condensate (pentamer) of ethyltriethoxysilane or a condensate (pentamer) of methyltrimethoxysilane! /.
- the polymer composition of the present invention can further include a metal alkoxide monomer in addition to the component (d). Since the viscosity of the metal alkoxide monomer is lower than that of the condensate as component (d), the adhesion of the resulting polymer composition to the substrate may be improved by further containing the metal alkoxide monomer. If the content of the metal alkoxide monomer is increased to the same amount or more as the component (d), the lifetime of the coating when the coating is thickened may be reduced.
- the amount of the metal alkoxide monomer used is preferably a ratio of 10 mol or less per 1 mol of component (a). More preferably, the ratio is 0.1 mol to 5 mol. (A) If the amount used is less than 0.1 mol per 1 mol of the component, the effect of addition may not be obtained, and if the amount used exceeds 5 mol, it may become cloudy.
- the metal of the metal alkoxide monomer include Si, Ta, Nb, Ti, Zr, Al, Ge, B, Na, Ga, Ce, V, Ta, P, and Sb. It is not limited to. Si, Ti, and Zr are preferable, and since liquid is preferable, Si and Ti are particularly preferable.
- alkoxide (alkoxy group) of the metal alkoxide monomer examples include methoxy, ethoxy, propoxy, butoxy, and alkoxy groups having more carbon atoms. Methoxy and ethoxy are more preferred, with methoxy, ethoxy, propoxy and butoxy being preferred. More preferable metal alkoxide monomers are the same as the monomer unit of the component (d), and tetraethoxysilane, tetramethoxysilane, ethyltriethoxysilane, and methyltrimethoxysilane are more preferable.
- the polymer composition of the present invention can further include a synthetic resin and / or a diol compound (component (e)). That is, during the reaction between the ⁇ component and the component (b) or after the reaction, the component (e) can be added in addition to the component (d). By adding the component (e), cracking resistance can be imparted to the resulting reaction product, and the polymer composition containing the component (e) can be used as a resin hard coat agent.
- component (e) a synthetic resin and / or a diol compound
- the synthetic resin of component (e) is not particularly limited, and examples thereof include thermosetting resins, thermoplastic resins, and ultraviolet curable resins. Specific examples include acrylic resins and epoxy resins. Examples thereof include resins, polyester resins, amino resins, urethane resins, furan resins, silicone resins, and modified products of these resins, and synthetic resins having various degrees of polymerization (molecular weight) can be used. Of these, epoxy resin, dipentaerythritol hexaacrylate, epoxy acrylate, silicone resin, bull ester resin, polybutyral, polybulu alcohol, etc. are preferred.
- the diol compound of component (e) is not particularly limited, but it has the ability to list polycabutlactone diol monole, 1,6 hexane dinore, polycarbonate dinore, polyesteroresin dire. . Among them, polyester diol is particularly preferable.
- the amount of the component (e) used is preferably a ratio of 50% by weight or less based on the entire composition. More preferably, the ratio is 1 to 40% by weight. If the component (e) is less than 1% by weight, the effect of adding the component (e) as described above may not be obtained, and if the component ( e ) exceeds 40% by weight, the resin curing agent It may be necessary to add high hardness It may not be possible.
- the addition amount of the component (d) is preferably 2 to 20 mol in terms of the weight of the metal alkoxide monomer with respect to 1 mol of the component (a)! /.
- a nonwoven fabric having excellent heat resistance and chemical resistance can be obtained.
- the fiberizing method include a melt spinning method, a centrifugal method, and an electrospinning method.
- the polymer composition of the present invention By making the polymer composition of the present invention into a particulate form, it can be used as an inorganic filler.
- the granulation method include a method of solidifying a sphere by spraying, a method of forming a thin film by spin coating, and a method of pulverizing.
- the substrate obtained by firing the polymer composition in the fibrous form or the particulate form of the present invention at a temperature of 1000 ° C or lower can increase the density by firing. It can be used as an inorganic filler. In particular, a particulate polymer composition can be increased in Si content by firing.
- the polymer composition of the present invention may have a coloring agent, an antifungal agent, a photocatalytic material, an antifungal agent, an anticorrosive, an algaeproofing agent, an anti-repellent agent, depending on its use.
- a coloring agent an antifungal agent, a photocatalytic material, an antifungal agent, an anticorrosive, an algaeproofing agent, an anti-repellent agent, depending on its use.
- Liquid agents, conductive materials, heat ray absorbers, heat ray reflectors, and the like can be included.
- a coating agent or an adhesive By containing the polymer composition of the present invention as a main component, a coating agent or an adhesive can be obtained.
- a functional material can be obtained by applying the polymer composition, coating agent, or adhesive of the present invention to an inorganic substrate or an organic substrate.
- inorganic or organic substrates include wood, stone, plastic, and textile products.
- the polymer composition of the present invention can be applied to a liquid or a liquid. If applied to a cloth such as glass cloth in the candy state, Loss or heat-resistant cloth can be obtained.
- the polymer composition of the present invention can be applied even with a viscosity of 1 boise or less, so that the base material is impregnated to improve the material of the base material while energizing it. Is also possible.
- inorganic powders such as alumina, silica, glass, etc.
- metal powder or metal ions it can be used as a conductive paint or conductive adhesive.
- metal ions, organic colorants and organic fluorescent agents can be added, and the discoloration of organic fluorescent agents can be greatly reduced.
- an inorganic or organic antibacterial or antifungal agent can be added for use as a sanitary material.
- a functional material obtained by applying the polymer composition, coating agent, or adhesive of the present invention to a substrate such as glass fiber cloth or glass cloth is heated at a temperature of iooo ° C or lower. By baking, a glass substrate having an inorganic film can be obtained.
- the application as the coating agent of the present invention is useful for hard coating of optical display materials and devices.
- liquid crystal specifically, AG.AR film, TAC film, polarizing film, separate film, transparent electrode, color filter, alignment film, retardation film, prism sheet, diffuser plate, light guide plate, reflector plate, etc.
- hard coats of PC and PP and PC coats are useful for hard coats of PC and PP and PC coats.
- the polymer composition of the present invention has an inorganic substance (Si) as a skeleton, it is decomposed and deteriorated even when used as an adhesive for a photocatalyst, compared to an organic (carbon skeleton) adhesive. It tends to be difficult to do.
- the polymer composition of the present invention may further contain a near-infrared shielding material (component (cl)).
- component (cl) component examples include conductive metal oxides and / or near infrared absorbing dyes. By adding the component (cl), near infrared rays can be blocked.
- the conductive metal oxide of the component (cl) is not particularly limited, but for example, Au, Ag, It is at least one oxide selected from the group consisting of at least one metal oxide selected from Ni, Cu, In, Sn, and Sb forces.
- the transparency of the film obtained from the coating composition is a force determined by the haze value (the ratio of the scattered light component to the total transmitted light). Therefore, the haze value is preferably 2% or less.
- the haze value is preferably 2% or less.
- particles having a refractive index of about 2 such as ultrafine particles of 2% or less oxide
- the average particle size is too small, the transparency increases, but the near-infrared shielding property may decrease. Therefore, in order to obtain a certain level of near-infrared shielding property, It is not preferable that the ultrafine particles are dispersed too much to make the dispersed particle size too small to be l Onm or less. Therefore, in consideration of the balance between transparency and near-infrared shielding property, it is preferable to use an average particle size adjusted to an appropriate range.
- the amount of the conductive metal oxide used as the component (cl) is not particularly limited, but is 100 parts by weight of a polymer substance containing a reaction product obtained by reacting the component (a) and the component (b). On the other hand, it is preferably 0.5 to 50 parts by weight, more preferably 1 to 20 parts by weight, still more preferably 2 to 10 parts by weight.
- the near-infrared-absorbing dye of component (cl) is not particularly limited as long as it has a near-infrared-absorbing ability. Mention may be made of at least one near-infrared absorbing dye selected from metal complex-based, nosquarium-based and phthalocyanine-based near infrared absorbing dyes. Of these, dimonium-based and phthalocyanine-based near-infrared absorbing dyes are preferable.
- Such near-infrared absorbing dyes include [bis (4-tert-butyl-1,2,2-dithiophenolate) Copper-tetra-n-butylammonium] (BBT manufactured by Sumitomo Seika Co., Ltd.), 1, 1, 5, 5-tetrakis
- the coating composition of the present invention is in the form of a solution dissolved in such a solvent.
- a pigment that does not dissolve in such a solvent it may be contained in the coating composition of the present invention as it is in the form of particles or the like.
- the near-infrared absorbing pigment of the (cl) component is contained in the form of such particles, it is preferable to use those having an average particle size similar to that of the conductive metal oxide of the (cl) component. .
- the amount of the near-infrared absorbing dye used as the component (cl) is not particularly limited, but when used in the form of a solution dissolved in the solvent as described above, the components (a) and (b) Preferably, it is at least 0.01 parts by weight, more preferably from 0.;! To 50 parts by weight, and even more preferably 0.2 parts per 100 parts by weight of the polymer substance containing the reaction product obtained by reacting the components. ⁇ 25 parts by weight, particularly preferably 0.5 ⁇ ; 15 parts by weight.
- the amount used when the near-infrared absorbing pigment of component (cl) is used in the form of solids such as particles includes reaction products obtained by reacting component (a) with component (b). The amount is preferably 0.5 to 50 parts by weight, more preferably 0.5 to 25 parts by weight, and still more preferably 15 parts by weight with respect to 100 parts by weight of the polymer substance.
- the conductive metal oxide of component (cl) and the near-infrared absorbing dye can be used in combination.
- the polymer composition of the present invention further containing a component (cl) can be produced without requiring a complicated process such as hydrolysis required in a sol-gel method and without requiring a long time,
- a near-infrared ray shielding coating composition having excellent optical properties (transparency, etc.) with high weather resistance and hard coat properties.
- the resulting coating composition can be applied to glass, ceramics and transparent plastics.
- the polymer composition of the present invention comprises an antifungal function-imparting agent (antifungal agent) ((c2) component and / or (c3) instead of (cl) component or in addition to (cl) component).
- antifungal agent an antifungal function-imparting agent
- an antifungal function is imparted to the polymer composition of the present invention.
- Component (c2) is selected from the group consisting of imidazole nitrogen heterocycles, triazole nitrogen heterocycles, tetrazole nitrogen heterocycles, pyrazole nitrogen heterocycles, and salts of these compounds. It can further comprise at least one selected compound.
- Preferred examples of the component (c2) include 3 amino-1, 2, 4 triazole and 2 phenyl 4- (4-methylphenylmethyl) imidazole.
- the component (c2) is preferably added to the polymer composition of the present invention in an amount of 1 to 50% by weight, more preferably 5 to 30% by weight.
- the fender resistance depends on the concentration of the fungicide, but if the amount of the (c2) component is less than 1% by weight, it may be difficult to show the fouling effect. Is not preferable in terms of economy.
- an imidazolesilane compound can be contained.
- Examples of the component (c3) include an imidazole silane compound represented by the following formula (1) and an acid salt derivative thereof, and a mixture of two or more of these compounds. .
- R 2 and R 3 are each independently hydrogen, Bulle group, the carbon number;! Alkyl group of 1-2 0, a benzyl group, a phenyl group, a and a group derived therefrom, with R 2 and R 3 R 4 and R 5 , which may form an aromatic ring, each independently represents an alkyl group having 1 to 20 carbon atoms, the bond between N—Si represents an organic group, and n is Represents 0-3.
- imidazole silane compound represented by the above formula (1) examples include, for example, the imidazole silane compound represented by the following formula (2), (3), (4), (5) or (6). That's the power S.
- R 2 and R 3 each independently represent hydrogen, a bur group, an alkyl group having 1 to 20 carbon atoms, a benzyl group, a phenyl group, a group derived therefrom, or the like, and R 2 and R 3 are aromatic.
- R 1 may represent a ring, for example, hydrogen, an alkyl group having 1 to 20 carbon atoms, a benzyl group, a phenyl group, or a group derived therefrom.
- R 2 is hydrogen.
- a bur group an alkyl group having 1 to 5 carbon atoms, a benzyl group, a phenyl group, or a group derived therefrom, wherein R 4 and R 5 are each independently a carbon number:! To 5, preferably Represents an alkyl group having 1 to 3 carbon atoms, m represents;! To 10, preferably m represents, for example, 3; in formula (2), n represents 0 to 3 and formula (3 ), N represents;!-3. )
- R 1 represents hydrogen or an alkyl group having 1 to 20 carbon atoms
- R 2 represents hydrogen, a bur group or an alkyl group having 1 to 5 carbon atoms
- R 3 represents hydrogen, a vinyl group, an alkyl group having 1 to 20 carbon atoms, preferably hydrogen or the like, and may form an aromatic ring with R 2 R 4 , R 5 , R 6 and R 7 are each independently an alkyl group having carbon numbers of !! to 3
- h is an integer of 1 to 3
- 1 and k are each independently an integer of! To 5
- n represents 0 to 3
- n represents;! To 3.
- R is hydrogen or an alkyl group having 1 to 20 carbon atoms
- R is hydrogen, a bur group or an alkyl group having 1 to 5 carbon atoms
- R 5 has a carbon number;! To 5 And preferably represents 1 to 3 alkyl groups.
- Examples of the component (c3) include imidazole silane compounds represented by the following formula (7) and acid salt derivatives thereof, and further include mixtures of two or more of these compounds. Can do.
- R ⁇ R 2 and R 3 are each independently hydrogen, a bur group, an alkyl group having 1 to 20 carbon atoms, a benzyl group, a phenyl group, or a group derived therefrom)
- R 1 and R 2 may form an aromatic ring.
- R 1 is, for example, hydrogen, an alkyl group having 1 to 20 carbon atoms, a benzyl group, a phenyl group, or a derivative thereof.
- R 2 preferably represents hydrogen, a bur group, an alkyl group having 1 to 5 carbon atoms, a benzyl group, a phenyl group, or a group derived therefrom, preferably R 3 represents hydrogen.
- R 4 and R 5 each independently represents a carbon number;! To 5, preferably an alkyl group having 1 to 3 carbon atoms, m represents 1 to 10 and preferably represents m. Represents, for example, 3 and n represents;! To 3)
- the imidazole silane compound of the component (c3) represented by the above formulas (2) to (3) and (6) to (7) can be obtained by, for example, reacting a specific imidazole compound with a specific glycidoxy silane compound. Can also be prepared.
- specific imidazole compounds include, but are not limited to, imidazole, 2-substituted imidazole, 4-substituted imidazole, 5-substituted imidazo'monore, 2,4 di-substituted imidazo'monore, 4,5-disubstituted imidazo.
- Is for example, imidazole; as 2-alkylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-butylimidazole, 2-undecylimidazole, 2heptadecylimidazole; , 4 Dialkyl imidazoles include 2,4 dimethylimidazole, 2 methyl-4-ethyl imidazole, 2 methyl-4-propylimidazole, 2 methyl-4-butylimidazole, 2 ethinole 4-methinoreidamidole, 2, 4 Getinoreidamidole, 2 ethinolere 4 pro pinoleidae zonole, 2 ethyl 4 butylimidazole, 2 propyl 1-4 methylimidazole, 2 propyl 4 -ethylimidazole, 2, 4 dipropylimidazole, 2 propyl 1-4
- More preferred examples include imidazole, 2-methyl Examples include imidazole, 2-ethyl imidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-ethyl 4-methylimidazole, and 4-butyrimidazole.
- 2,4 di-substituted imidazole 2,4,5 tri-substituted imidazole, for example, 2 methylolene 4,5 dibenzenore imidazole, 2 methyl-4 1 (4 monocyclic methinore) imidazole
- 2 Examples include 4-methyl 4-methyl imidazole.
- the specific glycidoxysilane compound that can be reacted with the specific imidazole compound in order to prepare the imidazolesilane compound as the component (c3) is not particularly limited.
- Examples of the specific glycidoxysilane compound include 3-glycidoxyanolyltrialkoxysilane, 3-glycidoxyalkyldialkoxyalkylsilane, and 3-alkylsilane. Among these, 3-glycidoxysilane compound is preferable.
- 3-glycidoxy 3-glycidoxypropyl dialkoxyalkylsilanes such as cidoxypropyl trimethoxysilane and 3-glycidoxypropyl triethoxysilane; 3-glycidoxypropyl et Cite silane, etc.
- the imidazole silane compound of the component (c3) represented by the above formulas (4) and (5) can be obtained by, for example, reacting a specific imidazole compound, a specific glycidoxy silane compound, and a specific isocyanate silane compound. It can also be prepared. Examples of such specific imidazole compounds and specific glycidoxy silane compounds include those listed above. Such specific isocyanate silane compounds include, for example, isocyanate alkyl dialkoxyalkyl silanes, isocyanate alkylalkoxydialkyl silanes, isocyanate alkyltrialkoxysilanes, or isocyanate alkyls. A trialkylsilane etc. can be mentioned.
- isocyanatopropyl propyldialkoxyalkylsilanes such as 3-isocyanatepropyltriethoxysilane; isocyanatopropylalkoxydialkylsilanes; isocyanatopropyltrialkoxysilanes; Examples thereof include cyanate propyl trialkyl silane.
- Examples of the component (c3) include N- ⁇ 3- (triethoxysilyl) propyl ⁇ 4,5-dihydroimidazole.
- the acid salt derivative of the imidazole silane compound represented by the above formula (1) or the above formula (7) of the component (c3) there is an organic acid derivative! / ⁇ indicates an inorganic acid derivative.
- the organic acid include carboxylic acid.
- the component (c3) is preferably added to the polymer composition of the present invention in an amount of 3 wt% to 50 wt%, more preferably 5 to 20 wt%.
- Antifungal power depends on the concentration of the antifungal agent, but if the amount of the (c3) component is less than 1% by weight, it may be difficult to show the antifungal effect. Since the force is saturated, it is not preferable in terms of economy.
- the present invention is a method in which a metal surface is washed with an acidic aqueous solution containing an amminesulfone-based water-soluble polymer, and then contains a component (c2) and / or a component (c3).
- a force S is also provided to provide a method of treating a metal surface, including applying a molecular composition to the cleaned metal surface.
- the method for treating a metal surface is an antifungal treatment, and the metal surface is treated with an aminsulfone-based water. It includes an anti-fouling pretreatment step of washing with an acidic aqueous solution containing a soluble polymer, and then an anti-fouling post-treatment step of applying the polymer composition to the washed metal surface.
- Examples of the metal used in the metal surface treatment method include iron and iron alloys such as iron, pig iron, carbon steel, and stainless steel, copper and copper alloys such as copper, brass, and white copper, Mention may be made of metals such as lead and zinc alloys, aluminum and aluminum alloys, magnesium and magnesium alloys, nickel and nickel alloys, chromium and chromium alloys, and metal products using these metals.
- iron and iron alloys such as iron, pig iron, carbon steel, and stainless steel
- copper and copper alloys such as copper, brass, and white copper
- metals such as lead and zinc alloys, aluminum and aluminum alloys, magnesium and magnesium alloys, nickel and nickel alloys, chromium and chromium alloys, and metal products using these metals.
- Examples of the amine water-soluble water-soluble polymer used in the method for treating a metal surface include polyamine sulfone, diallylamine carbonate 'sulfur dioxide copolymer, diallylamine acetate' sulfur dioxide copolymer, List at least one compound selected from diallyldimethylammonium chloride ', maleic acid, sulfur dioxide terpolymers, etc.
- Physical properties and chemical properties such as molecular weight and monomer composition of these ammine sulfone-based water-soluble polymers are not particularly limited.
- the weight average molecular weight may be 20000 to 00000. .
- the means for preparing the acidic aqueous solution containing the amine water-soluble polymer used in the above is not particularly limited.
- the amine water-soluble polymer is dissolved in water, hydrochloric acid, sulfuric acid, mixed acid or other acid.
- an acidic aqueous solution can be prepared.
- the concentration of the amine sulfone water-soluble polymer in the acidic aqueous solution when dissolved is not particularly limited! / Is, for example, preferred;! To 50% by weight;! To 10% by weight is more preferred.
- the concentration of the amine amine water-soluble polymer in the acidic aqueous solution is less than 1% by weight, it may be difficult to exert the effect of preventing the corrosion of the metal surface, and if it exceeds 50% by weight, it is economical. This is not preferable.
- Means for cleaning the metal surface with an acidic aqueous solution are not particularly limited in the above-described treatment method.
- a target metal foil, plate, product part, or the like is immersed in an acidic aqueous solution. Or spraying an acidic aqueous solution on the metal surface.
- This metal surface cleaning process removes the scale of the metal surface and removes the oxide film to activate the surface, but at the same time, the amine poles on the micropolarized metal surface
- the water-soluble polymer amino groups and sulfur dioxide adhere to each other, forming a corrosion-preventing film on the metal surface and acting to suppress acid corrosion.
- the step of applying the polymer composition of the present invention to the metal surface that has been cleaned in the above-described treatment method in the metal surface cleaning step is an antifungal treatment step.
- the method is not particularly limited.
- the polymer composition is sprayed or brushed on the metal surface, or the metal is immersed in the polymer composition solution or the solution thereof. Can be done.
- the coating temperature is not particularly limited, but for example, room temperature to;
- the drying temperature that can be dried after coating is not particularly limited, and examples include room temperature to 200 ° C. Drying time is not particularly limited.
- drying may be completed in a few minutes to several tens of minutes in the drying until the anti-fouling film becomes tack-free.
- the thickness of the coating is not particularly limited, but, for example, by changing the concentration of the polymer composition, the coating can be formed with a thickness ranging from several meters to several tens of inches. In particular, the function and performance can be exhibited remarkably.
- the above-described polymer composition further containing the component (c2) and / or the component (c3) is washed with an acidic aqueous solution containing the above-described amminesulfone-based water-soluble polymer (that is, before the antifouling).
- an acidic aqueous solution containing the above-described amminesulfone-based water-soluble polymer that is, before the antifouling.
- the component (c2) and / or the component (c3) By further containing the component (c2) and / or the component (c3), a complicated process such as hydrolysis required in a sol-gel method or the like is not required, and the strength and weather resistance are reduced. A high molecular composition having excellent optical properties (for example, transparency) and hard coating properties, and antifungal properties can be obtained.
- the polymer composition or anti-fouling coating composition further containing the component (c2) and / or the component (c3) can be applied to glass, ceramics, metals, plastics and the like.
- the metal surface treatment method described above provides surface activation and anti-corrosion measures in the pre-fouling pretreatment process by washing the metal surface with an acidic aqueous solution containing an ammine sulfone water-soluble polymer as an acid corrosion inhibitor.
- the heat resistance and oxidation resistance of the polymer composition in the polymer composition is improved, the pencil hardness of the film surface is improved, (c2) the nitrogen heterocyclic compound and / or (c3) )
- Component imidazole silane compound and modification Improved corrosion resistance due to integrated anti-corrosive force, improved anti-corrosion skin by amino group and sulfur dioxide group, improved adhesion between film and metal, functional group of anti-corrosion film and paint Demonstrates the effect of improving adhesion.
- the polymer composition of the present invention comprises a conductive property-imparting agent (conductive material) (in addition to the components (cl) to (c3) or in addition to the components (cl) to (c3) ( (c4) Component S) can be further included.
- a conductive property-imparting agent conductive material
- Component S can be further included.
- the polymer composition of the present invention is imparted with conductivity.
- the component ( C4 ) can be at least one component selected from the group consisting of carbon nanotubes and polymer organic semiconductors.
- the carbon nanotube of component (c4) is expected as a new material having strength, electrical conductivity, thermal conductivity and high slidability, and is extremely important for the present invention.
- the carbon nanotube (c4) component (hereinafter referred to as “CNT”! /, U) is a generic name for substances in which a six-membered ring network (graph ensheet) made of carbon is a single-layer or multilayer coaxial tube. is there.
- Single-walled nanotubes are called single-walled nanotubes (SWNT), and multi-walled ones are called mono-reticular nanotubes (MWNT).
- SWNT single-walled nanotubes
- MWNT mono-reticular nanotubes
- the two-layer type is also called double wall nanotube (DWNT)!
- CNTs can be dispersed in alcohol at the molecular level.
- Cushioned wall nanotubes are the most preferred to maintain conductivity and transparency, especially when dispersed materials are preferred.
- the arrangement of the six-membered ring of CNT, the abundance ratio of five-membered or seven-membered ring, diameter, length, and molecular weight are not particularly limited. For example, diameter 0.4 to 10 nm, length 10 nm ⁇ ;! OOOnm power S is preferred.
- the blending amount of these various types of CNTs is not limited, but it is sufficient to blend the polymer composition with an amount capable of imparting conductivity (antistatic performance).
- an amount capable of imparting conductivity antistatic performance.
- the polymer composition solid component
- the polymer organic semiconductor of component (c4) is also referred to as a conductive polymer.
- a conductive polymer Conventionally, general polymer materials have the property of not conducting electricity, but recently, various polymer organic semiconductors have been developed from the study of the physical properties of polyacetylene, and their application! / ! /, Has come to be considered. In general, many organic polymer semiconductors are insoluble in solvents, but recently several types of organic polymer semiconductors that are soluble in various solvents are being developed. In addition, the conductive performance of polymer organic semiconductors has been significantly improved, and the field of use is expanding, centering on electronic components.
- the polymer organic semiconductor of component (c4) is not particularly limited, but is preferably polyaniline, polyparaphenylene, polyparaphenylene vinylene, polyimidazole, polybase.
- a conductive polymer is not particularly limited, but is preferably polyaniline, polyparaphenylene, polyparaphenylene vinylene, polyimidazole, polybase.
- the conjugated double bond may be susceptible to air oxidation and may be unstable, which is particularly preferred in the present invention. Not a thing!
- Examples of the more preferable polymer organic semiconductor as the component (c4) include polythiophene, polyaniline, polypyrrole, derivatives thereof, and those into which a dopant is introduced. These may be used alone.
- As the polymer organic semiconductor of component (c4) it is particularly preferable that a dopant is introduced into polyaniline and / or its conductor.
- the dopant is not particularly limited, but is preferably an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, chloric acid; benzenesulfonic acid, P-toluenesulfonic acid, m-nitrobenzoic acid.
- Protonic acid dopants such as acids, organic acids such as trichlorodiacetic acid; polymer acids such as polystyrene sulfonic acid and polyvinyl sulfuric acid; These may be used alone or in combination of two or more.
- the doping amount of these dopants is not particularly limited, but for example;
- the amount of the polymer organic semiconductor (ie, the conductive polymer) as the component (c4) is not particularly limited, but it is transparent and has a hard coat property in the present invention, and the conductivity of the antistatic region.
- the polymer organic semiconductor (ie, the conductive polymer) as the component (c4) is not particularly limited, but it is transparent and has a hard coat property in the present invention, and the conductivity of the antistatic region.
- the component (c4) By further containing the component (c4), a complicated process such as hydrolysis required in the sol-gel method is not required, and the strength, transparency, and heat resistance are excellent.
- a polymer composition having optical properties, hard coat properties and conductive properties can be obtained.
- the polymer composition further containing the component ( c4) is capable of imparting high functionality to a resin product by being applied as a coating agent to at least one surface of a resin film, a sheet and a resin molded product. S can. It can also be used for anti-corrosion coatings.
- the polymer composition of the present invention comprises a photocatalyst function-imparting agent (photocatalyst material) ((in addition to the components (cl) to (c4) or in addition to the components (cl) to (c4)) (( c5) Including component) With force S.
- a photocatalyst function-imparting agent photocatalyst material
- an oxide semiconductor having photocatalytic activity can be given.
- titanium dioxide anatase
- high photocatalytic activity was confirmed particularly in the ultraviolet region.
- Titanium dioxide is a typical oxide semiconductor. It becomes a high energy state, emits electrons on the surface exposed to light, and exerts a photocatalytic function.
- oxide semiconductors and nitride semiconductors that exhibit high photocatalytic activity under visible light have been developed, and the range of use of photocatalysts has been expanded.
- the type of the oxide semiconductor having photocatalytic activity as component (c5) is not particularly limited, but is preferably an oxide semiconductor that exhibits a photocatalytic function with visible light having a wavelength of 380 nm or more ( Photocatalyst). That is, the photocatalytic oxide semiconductor that is component (c5) is preferably a visible light responsive photocatalyst! /.
- a part of the surface of the oxide semiconductor fine particles is coated with a protective substance that is inactive with respect to the photocatalytic function, or a part of the oxide semiconductor. It may be substituted with a nitrogen atom and / or a sulfur atom.
- the oxide semiconductor particles that exhibit the photocatalytic function that appears in visible light with a wavelength of 380 nm or more include Fe O, CuO, In O, WO, Fe TiO, PbO, V O, FeTiO, and Bi O.
- oxide semiconductor is preferably a fine particle.
- oxides such as titanium oxide, tin oxide, zinc oxide, strontium titanate, tungsten oxide, zirconium oxide, niobium oxide, iron oxide, copper oxide, iron titanate, nickel oxide, and bismuth oxide
- semiconductors that have been modified so that the photocatalyst is expressed by visible light can be mentioned.
- the form of the oxide semiconductor that is the component (c5) is not particularly limited! /, But may include, for example, the form of organic solvent sol or colloid dispersed in a polar solvent such as powder or alcohol. it can.
- the oxide semiconductor of component (c5) is sol! /, Is in the form of a colloid, the solid content concentration is preferably 40% by weight or less.
- the primary particle size of the oxide semiconductor is preferably 200 nm or less, particularly preferably 1 OO nm or less! /. When the primary particle diameter exceeds 200 nm, the transparency is inferior and ⁇ may exceed a force 3 ⁇ 4.
- the oxide semiconductor as component (c5) is preferably used in the polymer composition with respect to the nonvolatile component of the composition (a component that does not volatilize by heating at 105 ° C for 30 minutes). It is preferable to add 1 to 90% by weight, more preferably 3 to 50% by weight, and still more preferably 5 to 30% by weight.
- the amount of the oxide semiconductor (c5) component is less than 1% by weight, visible light photocatalytic action may not be exhibited. If it exceeds 90% by weight, whitening phenomenon (choking) occurs when forming a coating film. May occur and the film-forming property may be inferior.
- the component (c5) By further containing the component (c5), a complicated process such as hydrolysis required in the sol-gel method is not required, and it has excellent weatherability (for example, transparency). And a polymer composition having photocatalytic properties and excellent hard coat properties.
- the polymer composition (photocatalyst coating composition) further containing the component (c5) can be applied to glass, ceramics, metals and plastics.
- the polymer composition of the present invention can be spheroidized by spraying at a high drying rate.
- the polymer composition of the present invention can include the uses listed below in addition to the above-described methods of use.
- Anti-foaming agent and anti-fingerprinting agent by adding 2 ( ⁇ 111 or less filler such as acrylic or silica
- TEOS monomer was added as component (d) as a pentamer of ethyl silicate 40 (manufactured by Colcoat Co.) (ie, pentamer of tetraethoxysilane (TEOS)). (5.5 mol in terms of weight) was also added, and the mixture was further stirred for 5 minutes and allowed to stand to prepare a sample.
- the molecular weight of TEOS is 208, and the average molecular weight of component (d) used (TEOS pentamer) is 745.
- a sample was prepared in the same manner as in Example 1 except that 11 mol of component (d) was used in terms of TEOS monomer weight.
- Example 4 A sample was prepared in the same manner as in Example 1 except that component (d) was used in an amount of 16.7 mol in terms of TEOS monomer weight. [0114]
- Example 4 A sample was prepared in the same manner as in Example 1 except that component (d) was used in an amount of 16.7 mol in terms of TEOS monomer weight.
- Example 2 A sample was prepared in the same manner as in Example 1 except that component (d) was used in an amount of 22 mol in terms of TEOS monomer weight.
- Example 2 A sample was prepared in the same manner as in Example 1 except that 33.2 mol of component (d) was used in terms of TEOS monomer weight. From this result, it was found that the effect of the present invention was sufficiently obtained even when component (d) was used in an amount of 30 mol or more in terms of monomer weight.
- Example 2 A sample was prepared in the same manner as in Example 1 except that the component (d) was not used and 2500 g (12 mol) of TEOS monomer was used. The color of the obtained cured product was white, lacked transparency, and could not obtain a film having a dense hardness in a phase-separated state.
- Example 2 A sample was prepared in the same manner as in Example 1 except that the component (d) was not used and 3333 g (16 mol) of TEOS monomer was used. The color of the obtained cured product was white and lacked transparency.
- Example 2 A sample was prepared in the same manner as in Example 1 except that the component (d) was not used and 5000 g (24 mol) of TEOS monomer was used. The color of the obtained cured product was white and lacked transparency.
- the hardness of the film when applied to a mild steel plate and heated at 120 ° C for 1 hour is indicated by pencil hardness (based on JIS K54 00 8.4, 2).
- the color of the obtained cured product was visually determined.
- Comparative Example 4 100 parts by weight of epoxy resin (trade name “DENATITE CY—23 2” manufactured by Nagase Chemtech Co., Ltd.) and 30 parts by weight of curing agent (trade name “HY956” manufactured by Nagase Chemtech Co., Ltd.) Kneaded and cured at 110 ° C for 1 hour.
- epoxy resin trade name “DENATITE CY—23 2” manufactured by Nagase Chemtech Co., Ltd.
- curing agent trade name “HY956” manufactured by Nagase Chemtech Co., Ltd.
- Comparative Example 5 100 parts by weight of dipentaerythritol hexatatalylate was kneaded with 3 parts by weight of an ultraviolet curing agent (Irgacure 184 (manufactured by Chinoku Specialty Chemicals Co., Ltd.)) and cured with ultraviolet rays. Pencil hardness was measured.
- an ultraviolet curing agent Irgacure 184 (manufactured by Chinoku Specialty Chemicals Co., Ltd.)
- the polymer composition of the present invention is more rigid than the resin (Comparative Examples 4 and 5) in which only the curing agent is used in each resin (component (e)). An improvement in (pencil hardness) was confirmed.
- the polymer composition of the present invention can be used as a coating agent or an adhesive.
- a functional material can be obtained by applying to an inorganic substrate or an organic substrate, and a glass substrate can be obtained by applying to a glass cloth.
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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AT07828919T ATE536392T1 (de) | 2006-10-13 | 2007-10-01 | Polymerzusammensetzung mit metallalkoxidkondensationsprodukt, organischer silanverbindung und borverbindung |
JP2008538654A JP5594558B2 (ja) | 2006-10-13 | 2007-10-01 | 金属アルコキシド縮合物と、有機シラン化合物と、ホウ素化合物を含む高分子組成物 |
US12/440,669 US9029449B2 (en) | 2006-10-13 | 2007-10-01 | Polymeric composition comprising metal alkoxide condensation product, organic silane compound and boron compound |
EP07828919A EP2072582B1 (en) | 2006-10-13 | 2007-10-01 | Polymeric composition comprising metal alkoxide condensation product, organic silane compound and boron compound |
KR1020097007467A KR101399260B1 (ko) | 2006-10-13 | 2007-10-01 | 금속 알콕시드 축합 생성물, 유기 실란 화합물 및 붕소 화합물을 포함하는 중합체 조성물 |
CN2007800381660A CN101522809B (zh) | 2006-10-13 | 2007-10-01 | 含金属醇盐缩合产物、有机硅烷化合物和硼化合物的聚合物组合物 |
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PCT/JP2007/069179 WO2008044521A1 (fr) | 2006-10-13 | 2007-10-01 | Composition polymère comprenant un produit de condensation d'un alcoxyde métallique, un composé organosilane et un composé du bore |
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US (1) | US9029449B2 (ja) |
EP (1) | EP2072582B1 (ja) |
JP (1) | JP5594558B2 (ja) |
KR (1) | KR101399260B1 (ja) |
CN (1) | CN101522809B (ja) |
AT (1) | ATE536392T1 (ja) |
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JP2010006997A (ja) * | 2008-06-28 | 2010-01-14 | Matsumoto Fine Chemical Co Ltd | 無機粒子バインダー組成物 |
JP2010016455A (ja) * | 2008-07-01 | 2010-01-21 | Foster Electric Co Ltd | 電気音響変換器用振動系部品の製造方法およびこの方法で製造した電気音響変換器用振動系部品 |
JP2011026473A (ja) * | 2009-07-27 | 2011-02-10 | Nitto Boseki Co Ltd | 表面保護剤 |
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CN102037088B (zh) * | 2008-04-14 | 2014-08-06 | 陶氏康宁公司 | 胀流性有机基聚硅氧烷的乳液 |
JP2010006997A (ja) * | 2008-06-28 | 2010-01-14 | Matsumoto Fine Chemical Co Ltd | 無機粒子バインダー組成物 |
JP2010016455A (ja) * | 2008-07-01 | 2010-01-21 | Foster Electric Co Ltd | 電気音響変換器用振動系部品の製造方法およびこの方法で製造した電気音響変換器用振動系部品 |
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JP2011026473A (ja) * | 2009-07-27 | 2011-02-10 | Nitto Boseki Co Ltd | 表面保護剤 |
JP2011111558A (ja) * | 2009-11-27 | 2011-06-09 | Asahi Kasei E-Materials Corp | コーティング組成物及びエネルギー変換用部材 |
JP2011208085A (ja) * | 2010-03-30 | 2011-10-20 | Asahi Kasei E-Materials Corp | 塗膜、その製造方法、並びに積層体及び保護部材 |
JP2012092277A (ja) * | 2010-10-29 | 2012-05-17 | Nitto Boseki Co Ltd | 表面保護剤 |
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JP2015034281A (ja) * | 2013-07-11 | 2015-02-19 | セントラル硝子株式会社 | 紫外線遮蔽被膜付き板ガラスとその製造方法、及び紫外線遮蔽被膜付き板ガラスの被膜形成用塗布液 |
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Also Published As
Publication number | Publication date |
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CN101522809A (zh) | 2009-09-02 |
KR20090074761A (ko) | 2009-07-07 |
EP2072582B1 (en) | 2011-12-07 |
EP2072582A4 (en) | 2010-06-16 |
US9029449B2 (en) | 2015-05-12 |
CN101522809B (zh) | 2011-10-26 |
US20090252970A1 (en) | 2009-10-08 |
JP5594558B2 (ja) | 2014-09-24 |
EP2072582A1 (en) | 2009-06-24 |
JPWO2008044521A1 (ja) | 2010-02-12 |
KR101399260B1 (ko) | 2014-05-27 |
ATE536392T1 (de) | 2011-12-15 |
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