JP2006326915A - Composite material and sink - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite material constituted so that the design properties of its base material are kept even in a case that an external force is applied. <P>SOLUTION: The composite material has the ductile base material and the coating part provided on the ductile base material. The coating part comprises silica or at least one kind of a compound selected from the group of compounds represented by an average compositional formula, R<SB>p</SB>SiO<SB>(4-p)/2</SB>, (wherein R is at least one kind of a group selected from the group consisting of an organic group, halogen and a nitrogen-containing group and p is a number satisfying 0<p<4), has an average density of 1.9 g/cm<SP>3</SP>or above and is almost transparent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a composite material that maintains the design of a substrate even when an external force is applied.

  In general, ductile substrates are used as various industrial products because they have excellent processability. For example, metals such as stainless steel and aluminum are typical examples of ductile materials, and are used in cooking utensils, kitchen sinks, and the like. However, the ductile base material has a problem that the surface hardness is low due to its characteristics, and the design is impaired due to the occurrence of scratches when an external force is applied.

In order to solve such problems, a stainless steel sink (for example, refer to Patent Document 1) in which a metal oxide film is formed to improve the antifouling property, and a glaze prevention layer in which a glaze layer is formed on the stainless steel surface are conventionally used. Disclosed are dirty products (see, for example, Patent Document 2), stainless steel plates for sinks (see, for example, Patent Document 3) in which unevenness is provided on the stainless steel surface to improve the scratch resistance and stain resistance. Yes.
JP-A-2004-76071 JP 2001-152367 A JP 2004-137796

  However, in the stainless steel sink in which the metal oxide film described in Patent Document 1 is formed, the surface hardness has been improved to some extent, but it is easily scratched by contact with, for example, a ceramic made of fired metal oxide. Generated and scratch resistance was not sufficient.

  Moreover, in the antifouling product in which the glaze layer described in Patent Document 2 is formed, since the glaze layer is formed by firing, it is necessary to fire at a temperature of 800 ° C. or higher. Since there is a problem that it is oxidized and discolored to impair the appearance, it is necessary to form a colored and opaque glaze layer, and there is a problem that the texture of the base material is inevitably lost.

  In the stainless steel plate described in Patent Document 3, the original texture of the sink has been lost.

  The present invention has been made to solve the above-described problems, and provides a composite material in which the design properties of a substrate are maintained even when an external force is applied.

In order to solve the above-described problems, the present invention has a ductile base material and a coating portion provided on the ductile base material, and the coating portion is silica or an average composition formula R _p SiO _{(4-p). / 2} (wherein R is at least one selected from the group of organic groups, halogens and nitrogen-containing groups, and p is a number satisfying 0 <p <4). The composite material is characterized by having an average density of 1.9 g / cm ³ or more and substantially transparent.

  In a preferred embodiment of the present invention, the covering portion is formed by converting a polysilazane-containing liquid applied to a ductile substrate into silica.

  In the preferable aspect of this invention, the said coating | coated part is formed by heating the polysilazane containing liquid apply | coated to the ductile base material in the temperature range of 450 degrees C or less with the base material.

  In a preferred aspect of the present invention, the covering portion does not include a grain boundary.

  In a preferred embodiment of the present invention, the polysilazane-containing liquid contains a catalyst.

  A sink provided with the composite material of the present invention on at least a part on the use surface side maintains the design of the substrate when an external force such as sliding wear due to contact with tableware or the like is applied.

According to the present invention, the ductility substrate, and a covering portion provided on a ductile base material, the coating unit is silica or average composition formula _{R p SiO (4-p)} / 2 ( _wherein, , R is at least one selected from the group consisting of an organic group, a halogen, and a nitrogen-containing group, and p is at least one selected from the group of 0 <p <4), and the average density is 1 It is possible to provide a composite material in which the design property of the base material is maintained even when an external force is applied, which is 0.9 g / cm ³ or more and substantially transparent.

Hereinafter, the composite material, the sink, and the method for producing the composite material of the present invention will be specifically described.
Maintaining designability in the present invention means that the gloss, texture, and color tone of the substrate are maintained.

  In the present invention, even when an external force is applied, maintaining the design property of the base material means, for example, an action of suppressing a decrease in design property due to the occurrence of scratches due to contact with a solid material, and more specifically For example, in the case of a sink, it means an action that suppresses the occurrence of scratches due to sliding of tableware or the like and the deterioration of the design.

  In the present invention, the ductile base material means a base material having a property that the substance is stretched without breaking beyond the limit of elasticity, and particularly a metal material such as stainless steel and aluminum as a material having high ductility. Is mentioned.

In the present invention, silica or an average composition formula R _p SiO _{(4-p) / 2} (wherein R is at least one selected from the group consisting of an organic group, a halogen, and a nitrogen-containing group, and p is 0 <p < And at least one selected from the group of (a number satisfying 4) is to build a siloxane network on a ductile substrate.

In the present invention, the average density is an average value of the density of a part of the covering portion.
When the average density of the covering portion is 1.9 g / cm ³ or more, it is easy to obtain an effect of maintaining the design property of the base material when an external force is applied, and when it is 2.15 g / cm ³ or more, the design property is more enhanced. This is desirable because it is easy to maintain.

In the present invention, the term “substantially transparent” means transparency that does not impair the texture of the base material, and is transparent enough to confirm the design of the base material in appearance.
For example, a composite material with a coating on a stainless steel substrate means that the gloss, texture, and color tone of stainless steel can be confirmed. When there is a pattern such as a pattern on the substrate, the pattern and pattern can be confirmed. Means transparency.

  The polysilazane used in the present invention is a compound represented by the following structural formula [— (SiR1R2) — (NR3) —] n (wherein R1, R2, and R3 each independently represent a hydrogen atom, an alkyl group, an alkenyl A group, a cycloalkenyl group, an amino group, an alkylamino group, an alkylsilyl group, an alkoxy group, or a group other than these groups that is directly connected to silicon and nitrogen of the main chain is a carbon), a chain, Of those having a cyclic structure, a crosslinked structure, or those having a plurality of these structures in the molecule, any of them may be used alone or as a mixture.

In the present invention, silica conversion means that a polysilazane film formed on a ductile base material is converted into silica or an average composition formula R _p SiO _{(4-p) / 2} (wherein R Is converted into at least one selected from the group of organic groups, halogens and nitrogen-containing groups, and p is a number satisfying 0 <p <4) to form a siloxane network It is something to be made.
In order to cause silica conversion, it is desirable to heat at 120 ° C. or higher, and heating at 160 ° C. or higher is preferable because the conversion reaction is further promoted.

  Further, for example, in the case of a metal that is representative of a ductile base material, although it has heat resistance, discoloration due to oxidation of the metal surface occurs by heating. For example, in the case of stainless steel, discoloration due to surface oxidation at a temperature higher than 450 ° C. Therefore, the designability is impaired.

In the present invention, the grain boundary means a boundary between crystal grains.
If there is a grain boundary in the covering part, when an external force is applied, the covering part is easy to peel off from the grain boundary, and it is difficult to maintain the design of the substrate. Since there is no grain boundary in the covering portion in the present invention, a covering portion having the design properties of the substrate can be easily obtained even when an external force is applied.
When a granular material is used as a starting material, there are grain boundaries in the coating, which is not preferable. In order to obtain a coating part having no grain boundary, a sol-gel method in a broad sense is generally used. For example, it is preferable to use a polysilazane-containing liquid.

  In the present invention, since a silica conversion can be caused at a lower temperature by using a catalyst, when a metal is used as the ductile substrate, it may be heated to a temperature at which discoloration due to oxidation of the metal surface does not occur, It is easy to maintain the design of the substrate.

  The catalyst used in the present invention is a compound represented by the following structural formula [-(SiR1R2)-(NR3)-] n (wherein R1, R2, and R3 are each independently a hydrogen atom, an alkyl group, or an alkenyl. Group, a cycloalkenyl group, an amino group, an alkylamino group, an alkylsilyl group, an alkoxy group, or a group other than these groups in which the group directly connected to silicon and nitrogen in the main chain is carbon). Specifically, 1-methylpiperazine, 1-methylpiperidine, 4,4′-trimethylenedipiperidine, 4,4′-trimethylenebis (1-methylpiperidine), diazabicyclo- [2, 2,2] octane, cis-2,6-dimethylpiperazine, 4- (4-methylpiperidine) pyridine, pyridine, dipyridine, α-picoline, β-picoline, γ- Choline, piperidine, lutidine, pyrimidine, pyridazine, 4,4'-trimethylenedipyridine, 2- (methylamino) pyridine, pyrazine, quinoline, quinoxaline, triazine, pyrrole, 3-pyrroline, imidazole, triazole, tetrazole, 1- N-heterocyclic compounds such as methylpyrrolidine; methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, pentylamine, dipentylamine, tri Pentylamine, hexylamine, dihexylamine, trihexylamine, heptylamine, diheptylamine, octylamine, dioctylamine, trioctylamine Amines such as amine, phenylamine, diphenylamine, triphenylamine; DBU (1,8-diazabicyclo [5,4,0] 7-undecene), DBN (1,5-diazabicyclo [4,3,0] 5 -Nonene), 1,5,9-triazacyclododecane, 1,4,7-triazacyclononane and the like.

Organic acids, inorganic acids, metal carboxylates, acetylacetona complexes, and metal fine particles are also preferable catalysts. Organic acids include acetic acid, propionic acid, butyric acid, valeric acid, maleic acid, stearic acid, and inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrogen peroxide, chloric acid, hypochlorous acid, etc. Is mentioned. The metal carboxylate is represented by the formula: (RCOO) _n M [wherein R represents an aliphatic group or an alicyclic group and represents one having 1 to 22 carbon atoms, and M represents Ni, Ti, Pt, Rh. Represents at least one metal selected from the group consisting of Co, Fe, Ru, Os, Pd, Ir, and Al, and n is the valence of M. It is a compound represented by. The metal carboxylate may be an anhydride or a hydrate. The acetylacetona complex is a complex in which an anion acac ′ generated by acid dissociation from acetylacetone (2,4-pentadione) is coordinated to a metal atom, and generally has the formula (CH ₃ COCHCOCH ₃ ) _n M [Wherein M represents a metal having an ionic value of n. Suitable metals M include, for example, nickel, platinum, palladium, aluminum, rhodium and the like. As the metal fine particles, Au, Ag, Pd, and Ni are preferable, and Ag is particularly preferable. The particle diameter of the metal fine particles is preferably smaller than 0.5 μm, more preferably 0.1 μm or less, and further preferably smaller than 0.05 μm. In addition to these, organic metal compounds such as peroxide, metal chloride, ferrocene, zirconocene, and the like can also be used.

  In the present invention, as a method for forming a polysilazane film on a ductile substrate, for example, a polysilazane-containing liquid is a dipping method, a spin coating method, a spray method, a printing method, a flow coating method, a roll coating method, and a combination thereof. Known application means can be appropriately employed.

The solvent used in the present invention may be any solvent as long as it can dissolve polysilazane and the catalyst. Petroleum solvents such as mineral spirits, paraffinic solvents, aromatic solvents, cycloaliphatics. Examples thereof include solvents, ethers, and halogenated hydrocarbons.
Specifically, as paraffins, C8 octane, 2,2,3-trimethylpentane, C9 nonane, 2,2,5-trimethylhexane, C10 decane, C11 n-undecane, etc. are aromatic. Examples of the solvent include C8 xylene, C9 cumene, mesitylene, C10 naphthalene, tetrahydronaphthalene, butylbenzene, p-cymene, diethylbenzene, tetramethylbenzene, C11 pentylbenzene, and the like. C7 methylcyclohexane, C8 ethylcyclohexane, C10 p-menthane, α-pinene, dipentene, decalin, etc., and ethers such as dimethyl ether, diethyl ether, dibutyl ether, polyglycol ether, tetrahydrofuran, etc. are halogenated. Charcoal The hydrogen can be exemplified dichloromethane, dichloroethane, chloroform, chlorobenzene and the like.

  In the present invention, the sink provided with the covering portion of the present invention at least on a part of the use surface side, the covering portion is formed only in the vicinity of the center of the bottom surface portion where contact with tableware or the like is particularly remarkable among the bottom surface portions of the sink. Of course, the covering portion may be formed on the entire bottom surface. In addition, it is more preferable that it is also formed on the elevation surface portion, since the occurrence of scratches on the elevation surface portion due to sliding or the like at the time of cleaning with a scrubbing or the like in the sink is also suppressed.

As a method for manufacturing a sink provided with a coating portion in the present invention, after processing a ductile base material into a sink shape, a polysilazane-containing liquid may be applied to the sink, and the polysilazane may be converted to silica to form a coating portion. And you may affix the composite material provided with the coating | coated part of this invention to a part of at least use surface side of a sink.
When the external force is applied because the method using a polysilazane-containing liquid can prevent cracks from being generated in the coating due to the application of external force for processing into a sink shape, and can reduce residual stress on the coating. Moreover, the effect | action which maintains the designability of a base material is exhibited favorably.

  The present invention will be described more specifically with reference to the following examples.

  A covering portion is provided on the ductile substrate, and the covering portion exhibits an effect of maintaining the design of the substrate even when an external force is applied.

  Such a composite material can maintain the design of the base material even when an external force is applied, for example, by sliding of tableware or the like.

  Next, a preferred method for producing a composite material will be described based on experimental results.

Example 1
A 100 × 100 mm SUS304 stainless steel plate was used as the substrate. As a pretreatment of the substrate, ultrasonic cleaning was performed in hexane for 10 minutes, and then ultrasonic cleaning was further performed in acetone for 10 minutes to clean the substrate surface.
A polysilazane-containing liquid containing a palladium-based catalyst {NL110A-10, manufactured by AZ Electronic Materials Co., Ltd.} is applied to a substrate by a flow coating method, and then heated at 250 ° C. for 60 minutes to have a coating material having a coating portion Got.

(Example 2)
The same substrate as in Example 1 was used.
The polysilazane-containing liquid {NL110A-10} was applied to the substrate by a flow coating method, and then heated at 200 ° C. for 60 minutes to obtain a composite material having a coating portion.

(Example 3)
The same substrate as in Example 1 was used.
After applying the polysilazane-containing liquid {NL110A-10} to the base material by a flow coating method, it was heated at 150 ° C. for 60 minutes to obtain a composite material having a coating portion.

Example 4
The same substrate as in Example 1 was used.
After applying a polysilazane-containing liquid without catalyst (NN110A-10, manufactured by AZ Electronic Materials Co., Ltd.) to the base material by the flow coating method, the composite material having a coating portion is heated at 400 ° C. for 60 minutes. Obtained.

(Example 5)
The same substrate as in Example 1 was used.
The polysilazane-containing liquid {NN110A-10} was applied to the substrate by the flow coating method, and then heated at 250 ° C. for 60 minutes to obtain a composite material having a coating portion.

(Comparative Example 1)
The same substrate as in Example 1 was used.
The polysilazane-containing liquid {NL110A-10} was applied to the substrate by a flow coating method, and then heated at 100 ° C. for 60 minutes to obtain a composite material having a coating portion.

(Comparative Example 2)
The same substrate as in Example 1 was used.
After applying the polysilazane-containing liquid {NL110A-10} to the base material by a flow coating method, it was dried at room temperature to obtain a composite material having a coating portion.

(Comparative Example 3)
The same substrate as in Example 1 was used.
The polysilazane-containing liquid {NN110A-10} was applied to the substrate by a flow coating method, and then heated at 500 ° C. for 60 minutes to obtain a composite material having a coating portion.

(Comparative Example 4)
The same substrate as in Example 1 was used.
A polysiloxane solution {Glaska T2202, manufactured by JSR Co., Ltd.} was applied to a substrate by a flow coating method, and then heated at 150 ° C. for 30 minutes to obtain a composite material having a coating portion.

(Evaluation methods)
(1) Presence / absence of grain boundaries The presence / absence of grain boundaries in the coating of the composite material was evaluated.
The composite material was cut into a 15 × 15 mm flat plate shape, and the coated portion was observed at a magnification of 10,000 times with a scanning electron microscope S-4100 manufactured by Hitachi High-Technologies Corporation to determine the presence or absence of grain boundaries.
(2) Density The density of the coating part of the composite material was measured.
The composite material was cut into a flat plate of 50 × 50 mm, and measured with a semiconductor density / film thickness measuring device SMAT212 manufactured by Technos. The X-ray slit was 10 mm, the measurement start angle was 0.1 deg, the measurement end angle was 0.25 deg, and an average density in the range of 10 × 10 mm was measured.
(3) Appearance The appearance of the composite material was visually evaluated.
Judgment criteria ○: The design property of the base material is completely maintained. △: Some cloudiness occurs, but the design property of the base material is maintained. ×: The design property of the base material is remarkably impaired, and the design of the base material cannot be confirmed. (4) Evaluation of maintainability of design properties of base material when external force is applied A ceramic tile cut out to 20 × 20 mm was used as a slider. In a state where a load was further applied, the substrate was reciprocated on the surface of the substrate, and then the design change of the substrate was visually determined.
The load was evaluated at 100 g, and the number of sliding was 200. At a load of 100 g, it was set assuming contact with a heavy object of about a mug.
Judgment criteria ◎: No flaws and no change in design properties ○: Although fine flaws occur, the design properties are maintained △: Flaws are generated and the design properties are deteriorated ×: Remarkably flaws are generated and the design properties are remarkably improved Spoil

(Evaluation results)
The evaluation results are shown in Table 1.

  There were no grain boundaries in the coated portions of Examples 1 to 5 of the present invention.

The average density of the coating portions of Examples 1, 2 and 4 of the present invention was 2.19 g / cm ³ .
The average density of the coating portion of Example 3 of the present invention was 2.13 g / cm ³ .
The average density of the coating portion of Example 5 of the present invention was 2.01 g / cm ³ .

In Examples 1 to 3 and Example 5 of the present invention, the design of the base material was maintained even after the covering portion was formed.
In Example 4, since the heating temperature at the time of forming the covering portion was high, the substrate was slightly clouded after the covering portion was formed, but the design of the substrate was maintained.

In Example 1, Example 2, and Example 4 of the present invention, the design of the base material was maintained even when an external force was applied. Almost a density of 2.2 g / cm ³ of the quartz glass is of comparable density 2.19 g / cm ^3, since the dense film is formed, but also by applying an external force to maintain the design property of the base material did it.
In Examples 3 and 5, even when an external force was applied, the design properties of the base material were maintained, although fine scratches were present.

In Example 1 and Example 2 using a polysilazane-containing liquid containing a catalyst and heated to 160 ° C. or higher, the appearance is indistinguishable from the base material itself, and the design is also achieved by applying external force. Maintained.
By using a polysilazane-containing liquid containing a catalyst, the average density of the coated portion can be 2.19 g / cm ³ even when heated at a relatively low temperature without causing the substrate to change color and impair the design. A good balance between appearance and scratch resistance.

The average density of the coating portion of Comparative Example 1 of the present invention was 1.87 g / cm ³ .
There were no grain boundaries in the coated portion of Comparative Example 1.
In Comparative Example 1, the design properties of the base material were completely maintained even after the covering portion was formed. However, in Comparative Example 1, remarkable scratches were observed when an external force was applied, and the design of the base material was significantly impaired.

The average density of the coating portion of Comparative Example 2 of the present invention was 1.53 g / cm ³ .
There was no grain boundary in the coating portion of Comparative Example 2.
In Comparative Example 2, the design properties of the base material were completely maintained even after the covering portion was formed. However, in Comparative Example 2, significant scratches were observed when an external force was applied, and the design properties of the substrate were significantly impaired.

The average density of the coating portion of Comparative Example 3 of the present invention was 2.19 g / cm ³ .
There were no grain boundaries in the coated portion of Comparative Example 3.
Since the heating temperature at the time of forming the coating part in Comparative Example 3 was high, the discoloration of the base material was remarkable, and the designability of the base material was significantly impaired. In Comparative Example 3, no scratches were generated due to the application of external force.

The average density of the coating portion of Comparative Example 4 of the present invention was 1.62 g / cm ³ .
There were no grain boundaries in the coated portion of Comparative Example 4.
In Comparative Example 4, the design properties of the base material were completely maintained even after the covering portion was formed. However, in Comparative Example 4, remarkable scratches were observed when an external force was applied, and the design properties of the substrate were significantly impaired.

  As in the above results, the design was maintained in Example 4 and the design was damaged in Comparative Example 3 due to the formation of the covering portion. In order to maintain the appearance, heating was performed at a temperature of 450 ° C. or lower. It was necessary to do.

In Comparative Example 1, Comparative Example 2, and Comparative Example 4, the design properties of the substrate were significantly impaired by the application of external force. In Examples 1 to 5, the design properties of the substrate were not affected even when an external force was applied. Maintained. That is, when the average density of the covering portion of the present invention is 1.9 g / cm ³ or more, the effect of maintaining the design properties of the base material when an external force is applied is dramatically improved. The effect | action which maintains a design property more that the average density of the coating | coated part was 2.15 g / cm < ³ > or more was acquired. When heated at a temperature of 120 ° C. or higher, the average density of the coating was 1.9 g / cm ³ or higher, and the design of the substrate was maintained even when an external force was applied.

  FIG. 2 is a schematic view of a kitchen having a sink with the composite of the present invention.

  The sink 3 provided with the composite material of the present invention and the counter 5 are joined, and the sink is provided with a faucet 6. The water discharged from the faucet 6 can wash dishes in the sink 3. The water is drained from the drain port 7.

  FIG. 3 is an enlarged view of the sink 3 portion of the kitchen of FIG. 2, and the covering portion 2 is formed on a part (shaded display portion) of the sink bottom surface portion.

  In the present embodiment, as shown in FIG. 3, the covering portion 2 is formed on a part of the bottom surface of the sink.

Next, usability of the present embodiment will be described.
The user puts tableware or the like on the use surface 4 on the bottom surface side in the sink 3 of the present embodiment, and performs the cleaning operation of the tableware. When washing a plurality of tableware, the tableware once placed on the use surface 4 on the bottom side is picked up or moved sideways in the sink. At that time, when the tableware is rubbed against the use surface 4 on the bottom surface side, scratches may occur. In this embodiment, the covering portion 2 is formed on the use surface 4 on the bottom surface side. Therefore, no scratches are generated and the design of the base material is maintained.
Here, in the present invention, the use surface side of the sink is a side surface side or a bottom surface side, as shown in FIG. 2, and specifically, a surface side used as a kitchen sink. The back side which is not illustrated, for example, is hidden in the cabinet, is not the use surface side.

  In another embodiment, the bottom surface of the sink 3 has a covering portion formed on the entire surface as shown in FIG. In this case, a step difference between the end portion of the covering portion and the non-covering portion is not formed, and it is more preferable that the end portion of the covering portion is not conspicuous due to light reflection.

  The composite material of the present invention can be used for a kitchen sink or the like.

It is sectional drawing of the composite material of this invention. It is the schematic of the kitchen provided with the sink of this invention. It is the schematic of the sink provided with the composite material in a part of bottom face part of this invention. It is the schematic of the sink provided with the composite material in the bottom face part whole surface of this invention.

Explanation of symbols

1: Ductile base material 2: Covering part 3: Sink 4: Use surface 5: Counter 6: Faucet 7: Drain port

Claims (6)

A ductile substrate and a coating provided on the ductile substrate, the coating being silica, or an average composition formula R _p SiO _{(4-p) / 2 where} R is an organic group, At least one selected from the group of halogen and nitrogen-containing groups, and p is a number satisfying 0 <p <4), and the average density is 1.9 g / cm ³ or more A composite material characterized by being substantially transparent. The composite material according to claim 1, wherein the covering portion is formed by converting a polysilazane-containing liquid applied to a ductile base material into silica. The composite material according to claim 1, wherein the covering portion is formed by heating a polysilazane-containing liquid applied to a ductile base material in a temperature range of 450 ° C. or less together with the base material. The composite material according to claim 1, wherein the covering portion does not include a grain boundary. The composite material according to claim 2, wherein the polysilazane-containing liquid contains a catalyst. A sink provided with the composite material according to any one of claims 1 to 5 at least at a part on a use surface side.

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