JP3791549B1 - COMPOSITE MATERIAL, COATING LIQUID AND METHOD FOR PRODUCING COMPOSITE MATERIAL - Google Patents

Abstract

The present invention provides a composite material that maintains the design of a base material and is excellent in chemical resistance even when an external force is applied.
In the present invention, a base material and a coating part provided on the base material are provided, and the coating part is composed of (A) silica or an average composition formula R _p SiO _{(4-p) / 2} (wherein R is a hydrogen atom, a fluorine atom or a monovalent organic group, p is a number satisfying 0 <p <4), (B) fluororesin particles, (C) It contains a Zr element-containing compound, the content of the fluororesin particles in the coating part is 1% by weight or more and less than 20% by weight, and the weight ratio of (A) and (C) is The composite material is characterized in that the weight part of the component (C) in terms of ZrO ₂ is 0.5 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the component (A) in terms of SiO _2. I will provide a.
[Selection] Figure 4

Description

  The present invention relates to a composite material that maintains the design of a base material and is excellent in chemical resistance even when an external force is applied.

  In recent years, means for applying a protective coating to the surface of various base materials and preventing the designability from being damaged by the occurrence of scratches on the base material has been proposed.

A stainless steel sink (for example, see Patent Document 1) in which a metal oxide film is formed and scratch resistance is improved, an antifouling product (for example, see Patent Document 2) in which a glaze layer is formed on a stainless steel surface, and plastic. A molded body in which a coating layer made of colloidal silica and an epoxy group-containing silicon compound is formed on the lens surface (for example, see Patent Document 3), a method for forming a SiO ₂ ceramic coating (for example, see Patent Document 4), and the like. It is disclosed.

JP-A-2004-76071 JP 2001-152367 A JP-A-7-27896 JP-A-8-99061

  However, in the stainless steel sink in which the metal oxide film described in Patent Document 1 is formed, the surface hardness is improved to some extent, but, for example, in contact with ceramics made of fired metal oxide, scratches are still generated. It occurred easily and scratch resistance was not sufficient.

  Moreover, in the antifouling product in which the glaze layer described in Patent Document 2 is formed, it is necessary to bake at a temperature of 800 ° C. or higher in order to form the glaze layer by firing, which is limited to a base material having heat resistance. There was a problem, and when a metal was used for the base material, the surface was oxidized and discolored, and the appearance was impaired, so it was necessary to form a colored opaque glaze layer, and inevitably the base material There was a problem that the texture of was lost.

  Further, in the molded body in which the coating layer made of colloidal silica and the epoxy group-containing silicon compound described in Patent Document 3 has been improved to some extent, for example, pottery made of a fired metal oxide, etc. In contact with the metal, the colloidal silica dropped off and scratches were easily generated, and the scratch resistance was not sufficient.

In addition, in the method of forming a SiO ₂ ceramic coating described in Patent Document 4, although a ceramic coating can be formed on the surface of various base materials by an inexpensive method, for example, pottery made of a fired metal oxide and the like In this contact, scratches were easily generated and the scratch resistance was not sufficient, and the film was peeled and deteriorated by contact with an alkaline detergent or the like, so that the chemical resistance was not sufficient.

  The present invention has been made to solve the above-described problems, and is to provide a composite material that maintains the design of the base material and is excellent in chemical resistance even when an external force is applied.

In order to solve the above problems, the present invention has a base material and a coating portion provided on the base material, and the coating portion is composed of (A) silica or an average composition formula R _p SiO _{(4- p) / 2} (wherein R is a hydrogen atom, a fluorine atom or a monovalent organic group, p is a number satisfying 0 <p <4), (B) fluorine Resin particles, comprising (C) a Zr element-containing compound, wherein the content of the fluororesin particles in the coating portion is 1 wt% or more and less than 20 wt%, and (A) and (C) The weight ratio of the component (C) in terms of ZrO ₂ is 0.5 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the component (A) in terms of SiO _2. To provide a composite material.

In the preferable aspect of this invention, the film thickness of the said coating | coated part shall be 0.3-20 micrometers.
In a further preferred aspect of the present invention, the coating portion has a thickness of 0.3 to 8 μm.

In a preferred embodiment of the present invention, the fluororesin particles have an average particle size of 0.1 to 20 μm.
In a further preferred aspect of the present invention, the fluororesin particles have an average particle size of 0.1 to 8 μm.

  In a preferred aspect of the present invention, the covering portion is substantially transparent.

In a preferred embodiment of the present invention, the base material is a ductile base material.
In a further preferred aspect of the present invention, the ductile substrate is stainless steel or aluminum.

  In a preferred aspect of the present invention, the ductile substrate is a sink and / or a counter, and at least a part on the use surface side is provided with any of the above-described covering portions.

In the present invention, fluorine resin particles and (D) a compound represented by the following structural formula [— (SiR1R2) — (NR3) —] _n (wherein R1, R2, and R3 are each independently a hydrogen atom, alkyl A group, 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, wherein the group directly connected to silicon and nitrogen in the main chain is carbon, n is an integer ) And (E) a Zr element-containing compound, which is applied to a substrate and cured by heating to form a coating portion on the substrate, which contains the fluorine resin particles The amount is 1% by weight or more and less than 20% by weight, and the weight ratio of (D) and (E) is based on ZrO _{2 with} respect to 100 parts by weight of the component (D) in terms of SiO _2. (E) Component weight ratio Providing a coating liquid, wherein 20 parts by weight or less than 0.5 part by weight.

In a preferred embodiment of the present invention, the fluororesin particles have an average particle size of 0.1 to 20 μm.
In a further preferred aspect of the present invention, the fluororesin particles have an average particle size of 0.1 to 8 μm.

In the present invention, fluorine resin particles and (F) (F-1) a compound represented by the following general formula (1), R _a Si (OR ₄ ) _4-a (1) (where R Is a hydrogen atom, a fluorine atom or a monovalent organic group, R4 is a monovalent organic group, a is an integer of 1 to 2.) (F-2) A compound represented by the following general formula (2) and Si (OR5) ₄ (2) (wherein R5 represents a monovalent organic group) (F-3) a compound represented by the following general formula (3) R6 _b (R7O) _{3− b Si- (R10) d -Si (} OR8) 3-c R9 c ····· (3) wherein, R6 ～R9 each a monovalent organic group, b-c is an integer of 0 to 2, R10 represents an oxygen atom, a phenylene group or a group represented by — (CH ₂ ) _m — (wherein m is an integer of 1 to 6), and d represents 0 or 1. ] It contains at least one compound selected from the group of the above, or a hydrolyzate thereof, and (E) a Zr element-containing compound. A coating liquid for forming a coating portion, wherein the content of the fluororesin particles is 1% by weight or more and less than 20% by weight, and the weight ratio of (F) and (E) is the SiO ₂ equivalent The coating liquid is characterized in that the weight ratio of the component (E) in terms of ZrO ₂ is 0.5 to 20 parts by weight with respect to 100 parts by weight of the component (F).

In a preferred embodiment of the present invention, the fluororesin particles have an average particle size of 0.1 to 20 μm.
In a further preferred aspect of the present invention, the fluororesin particles have an average particle size of 0.1 to 8 μm.

In the present invention, fluorine resin particles and (D) a compound represented by the following structural formula [— (SiR1R2) — (NR3) —] _n (wherein R1, R2, and R3 are each independently a hydrogen atom, alkyl A group, 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, wherein the group directly connected to silicon and nitrogen in the main chain is carbon, n is an integer ) And (E) a Zr element-containing compound, which is applied to a substrate and cured by heating to form a coating portion on the substrate, which contains the fluorine resin particles The amount is 1% by weight or more and less than 20% by weight, and the weight ratio of (D) and (E) is based on ZrO _{2 with} respect to 100 parts by weight of the component (D) in terms of SiO _2. (E) Component weight ratio After coating the coating liquid characterized by being 0.5 parts by weight or more and 20 parts by weight or less, the coating liquid is cured by heating together with the base material, and (A) silica or average Compositional formula R _p SiO _{(4-p) / 2} (wherein R is a hydrogen atom, fluorine atom or monovalent organic group, p is a number satisfying 0 <p <4) Provided is a method for producing a composite material, characterized in that a coating portion containing at least one kind of (B) fluorine resin particles and (C) a Zr element-containing compound is formed.

In the present invention, fluororesin particles and (F) (F-1) a compound represented by the following general formula (1), R _a Si (OR ₄ ) _4-a (1) (1) ( In the formula, R represents a hydrogen atom, a fluorine atom, or a monovalent organic group, R4 represents a monovalent organic group, and a represents an integer of 1 to 2.) (F-2) Represented by the following general formula (2) And Si (OR5) ₄ (2) (wherein R5 represents a monovalent organic group) (F-3) a compound represented by the following general formula (3) R6 _b ( _{R7O) 3-b Si- (R10} ) d -Si (OR8) 3-c R9 c ····· (3) [wherein, R6 ~R9 each a monovalent organic group, b-c is 0 2 integer, R10 is an oxygen atom, a phenylene group or - (CH _{2) m} - group represented by (wherein, m is an integer from 1 to 6), d represents 0 or 1. ] It contains at least one compound selected from the group of the above, or a hydrolyzate thereof, and (E) a Zr element-containing compound. A coating liquid for forming a coating portion, wherein the content of the fluororesin particles is 1% by weight or more and less than 20% by weight, and the weight ratio of (F) and (E) is the SiO ₂ equivalent After applying the coating liquid, wherein the weight ratio of the component (E) in terms of ZrO ₂ is from 0.5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the component (F), The coating liquid is cured by heating, and (A) silica, or an average composition formula R _p SiO _{(4-p) / 2} (wherein R is a hydrogen atom, a fluorine atom, or a monovalent organic) Group p is a number satisfying 0 <p <4 And (C) a covering portion containing a fluorine resin particle and (C) a Zr element-containing compound is formed.

In the present invention, after the ductile base material is drawn into a sink and / or counter shape, fluorine resin particles and (D) a compound represented by the following structural formula [-(SiR1R2)-(NR3) —] _N (wherein R 1, R 2 and R 3 are each independently a hydrogen atom, alkyl group, alkenyl group, cycloalkenyl group, amino group, alkylamino group, alkylsilyl group, alkoxy group, or other than these groups) A group in which the group directly bonded to silicon and nitrogen in the main chain is carbon, and n is an integer), and (E) a Zr element-containing compound is applied to a substrate and cured by heating. A coating liquid for forming a coating on a substrate, wherein the content of the fluororesin particles is 1% by weight or more and less than 20% by weight, and the weight ratio of (D) to (E) is SiO 2 ₂ conversion With respect to the component (D) of the parts 100, by applying a coating solution weight ratios of the (E) component in terms of ZrO ₂ is equal to or less than 20 parts by weight or more 0.5 part by weight, based on Provided is a method for producing a composite material, wherein the coating liquid is cured by heating the whole material.

In the present invention, after the ductile base material is drawn into a sink and / or counter shape, fluorine resin particles and (F) (F-1) a compound represented by the following general formula (1), R _a Si (OR4) _4-a (1) (wherein R is a hydrogen atom, a fluorine atom or a monovalent organic group, R4 is a monovalent organic group, a is an integer of 1 to 2) (F-2) A compound represented by the following general formula (2) and Si (OR5) ₄ (2) (wherein R5 represents a monovalent organic group) (F -3) a compound represented by the following general formula _{(3) R6 b (R7O)} 3-b Si- (R10) d -Si (OR8) 3-c R9 c ····· (3) wherein, R6 ～R9 each a monovalent organic group, b-c is an integer of 0 to 2, R10 is an oxygen atom, a phenylene group or - (CH _{2) m} - group represented by (wherein m is an integer from 1 to 6), d represents 0 or 1. ] It contains at least one compound selected from the group of the above, or a hydrolyzate thereof, and (E) a Zr element-containing compound. A coating liquid for forming a coating portion, wherein the content of the fluororesin particles is 1% by weight or more and less than 20% by weight, and the weight ratio of (F) and (E) is the SiO ₂ equivalent (F) The coating solution, wherein the weight ratio of the component (E) in terms of ZrO ₂ is 0.5 to 20 parts by weight with respect to 100 parts by weight of the component (F), and the coating Provided is a method for producing a composite material, wherein the liquid is cured by heating.

In the present invention, fluorine resin particles and (D) a compound represented by the following structural formula [-(SiR1R2)-(NR3)-] _n (wherein R1, R2, R3 are each independently A group in which a hydrogen atom, an alkyl group, 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 directly bonded to silicon and nitrogen in the main chain is carbon, n Is an integer) and (E) a Zr element-containing compound, which is applied to the substrate and cured by heating to form a coating on the substrate, the fluorine-containing coating solution The content of the resin particles is 1% by weight or more and less than 20% by weight, and the weight ratio of (D) to (E) is ZrO with respect to 100 parts by weight of the component (D) in terms of SiO _2. the _two terms of (E) formed The coating solution is characterized in that the weight ratio is 0.5 parts by weight or more and 20 parts by weight or less, and the coating liquid is cured by heating together with the base material, and then into a sink and / or counter shape. A method for producing a composite material characterized by drawing.

In the present invention, fluorine resin particles and (F) (F-1) a compound represented by the following general formula (1), R _a Si (OR ₄ ) _4-a (1) (1) ( In the formula, R represents a hydrogen atom, a fluorine atom, or a monovalent organic group, R4 represents a monovalent organic group, and a represents an integer of 1 to 2.) (F-2) Represented by the following general formula (2) And Si (OR5) ₄ (2) (wherein R5 represents a monovalent organic group) (F-3) a compound represented by the following general formula (3) R6 _b ( _{R7O) 3-b Si- (R10} ) d -Si (OR8) 3-c R9 c ····· (3) [wherein, R6 ~R9 each a monovalent organic group, b-c is 0 2 integer, R10 is an oxygen atom, a phenylene group or - (CH _{2) m} - group represented by (wherein, m is an integer from 1 to 6), d represents 0 or 1. ] It contains at least one compound selected from the group of the above, or a hydrolyzate thereof, and (E) a Zr element-containing compound. A coating liquid for forming a coating portion, wherein the content of the fluororesin particles is 1% by weight or more and less than 20% by weight, and the weight ratio of (F) and (E) is the SiO ₂ equivalent (F) The coating solution, wherein the weight ratio of the component (E) in terms of ZrO ₂ is 0.5 to 20 parts by weight with respect to 100 parts by weight of the component (F), and the coating Provided is a method for producing a composite material, wherein the liquid is cured by heating and then drawn into a sink and / or counter shape.

  According to the present invention, even when an external force is applied, it is possible to provide a composite material that maintains the design of the base material and is excellent in chemical resistance.

The best mode of the present invention will be described below.
One embodiment of the present invention includes a base material and a covering portion provided on the base material, and the covering portion is (A) silica or an average composition formula R _p SiO _{(4-p) / 2.} (Wherein R is a hydrogen atom, a fluorine atom or a monovalent organic group, p is a number satisfying 0 <p <4), (B) fluororesin particles, ( C) It contains a Zr element-containing compound, the content of the fluororesin particles in the coating part is 1 wt% or more and less than 20 wt%, and the weight ratio of (A) to (C) is The weight part of the component (C) converted to ZrO ₂ is 0.5 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the component (A) converted to SiO ₂ . By doing so, even when an external force is applied, it is possible to provide a composite material that maintains the design of the base material and is excellent in chemical resistance.

Here, the weight ratio of the component (A) to the component (C) is 0.5 parts by weight of the component (C) in terms of ZrO _{2 with} respect to 100 parts by weight of the component (A) in terms of SiO _2. When the amount is less than parts by weight, chemical resistance is not exhibited. When the amount is more than 20 parts by weight, the effect of maintaining the design of the substrate is significantly reduced even when an external force is applied.

Here, (A) silica, or average composition formula R _p SiO _{(4-p) / 2} (wherein R is a hydrogen atom, a fluorine atom or a monovalent organic group, p satisfies 0 <p <4) At least one selected from the group of (which is a number of) to build a three-dimensional network structure on the substrate, and some unreacted residues that do not form a three-dimensional network structure may exist. .
Silica may contain a trace amount of metal, nitrogen, and hydrogen, including so-called water glass.

  Here, the (C) Zr element-containing compound, together with (A), has a three-dimensional network structure on the base material and exhibits an effect of improving chemical resistance, particularly alkali resistance. There may be unreacted residues that do not form the original network structure.

Here, since the fluororesin particles have good sliding properties and low surface energy, even when an external force is applied, the effect of maintaining the design properties of the substrate is exhibited well.
In addition, since the fluororesin particles have plasticity, the followability to the base material is improved even when an external force is applied to impart a certain degree of flexibility to the covering portion, and the design property of the base material is maintained. Good performance.
If the surface of the covering part has a concavo-convex structure having protrusions corresponding to the self-shape of the fluororesin particles, the contact area with the covering part is reduced when an external force is applied. This is desirable because the effect of maintaining the properties is satisfactorily exhibited.

  When the content of the fluororesin particles is less than 1% by weight, the effect of maintaining the design properties of the base material is not sufficiently exhibited when an external force is applied. Since the network structure is coarse, the effect of maintaining the design of the substrate is not sufficiently exhibited when an external force is applied.

Here, the content of the fluorine resin particles in the coating portion is a weight ratio of the fluorine resin particles to the total weight of the coating portion, and (A) silica or an average composition formula R _p SiO _{(4-p) / 2.} (Wherein R is a hydrogen atom, a fluorine atom or a monovalent organic group, p is a number satisfying 0 <p <4), the weight is a SiO ₂ equivalent weight, and (C) a Zr element-containing compound The weight of is the weight in terms of ZrO ₂ .

In this invention, it is preferable that the film thickness of the said coating | coated part is 0.3-20 micrometers.
Here, the film thickness in the present invention is a film thickness of a three-dimensional network structure, and when the fluororesin particles are partially exposed, it means the thickness of a portion not including the exposed portion, such as a scanning electron microscope It can be measured by cross-sectional observation.
If the film thickness is smaller than 0.3 μm, the effect of maintaining the design of the base material is not sufficiently exhibited when an external force is applied, and if the thickness exceeds 20 μm, cracks will occur in the coated part. When applied, the effect of maintaining the design of the substrate is not sufficiently exhibited.

In the present invention, it is more preferable that the thickness of the covering portion is 0.3 to 8 μm.
When the film thickness is 8 μm or less, the coating part can be easily formed using various coating methods, and the appearance of the coating part is also improved.

In the present invention, the fluororesin particles have an average particle size of 0.1 to 20 μm.
When the average particle size is smaller than 0.1 μm, the effect of maintaining the design property of the substrate is lowered when an external force is applied, and when it is larger than 20 μm, the design property of the substrate is impaired.

In the present invention, the fluororesin particles have an average particle size of 0.1 to 8 μm.
When the average particle size is 8 μm or less, the coating part can be easily formed using various coating methods, and the appearance of the coating part is also improved.

In the present invention, more preferably, the substrate is a ductile substrate.
Ductile substrates are used as various industrial products because of their excellent workability. For example, metals such as stainless steel and aluminum are typical examples, and are used in cooking utensils, kitchen sinks, kitchen counters, etc. . However, due to its characteristics, the ductile base material has the disadvantages of low surface hardness and poor scratch resistance. However, by forming the coating portion of the present invention, an external force is applied while maintaining the ductility of the ductile base material. When it does, the effect that the designability of a base material is maintained is acquired.

  Since the covering portion of the present invention contains fluororesin particles, the covering portion is provided with flexibility and has excellent followability corresponding to the deformation of the base material, so that the ductility of the ductile base material is maintained. The effect of maintaining the design properties of the substrate can be obtained.

  The composite material in which the ductile base material is a sink and / or a counter and the covering portion of the present invention is provided on at least a part of the use surface side is an external force such as sliding wear due to contact with tableware or the like When is applied, an effect of maintaining the design property of the substrate is obtained, and the design property of the substrate is maintained.

  Further, in the sink and / or the counter, stress is generated in the base material and the coating portion due to falling heavy objects or hot water, but since the coating portion of the present invention contains fluororesin particles, a certain amount of the coating portion Therefore, even when a heavy object falls or when temperature changes occur in the base material due to continuous application of hot water and cold water, followability to the base material is demonstrated. Further, peeling and dropping off of the covering portion are suppressed.

As a coating liquid for forming the coating portion of the present invention, fluorine resin particles and (D) a compound represented by the following structural formula [— (SiR1R2) — (NR3) —] _n (wherein R1, R2 , R3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkenyl group, an amino group, an alkylamino group, an alkylsilyl group, an alkoxy group, or a group directly connected to silicon and nitrogen in the main chain other than these groups Is a carbon group, n is an integer) and (E) a Zr element-containing compound, applied to the substrate, and cured by heating to form a coating on the substrate The content of the fluororesin particles is 1% by weight or more and less than 20% by weight, and the weight ratio of (D) and (E) is the weight of the component (D) in terms of SiO ₂ Part 100 Te, the coating solution above in terms of ZrO ₂ (E) the weight ratio of the components is equal to or less than 20 parts by weight or more 0.5 part by weight is preferably used.
The coating liquid may contain a diluting solvent.

As a coating liquid for forming the coating portion of the present invention, fluororesin particles and (F) (F-1) a compound represented by the following general formula (1), R _a Si (OR ₄ ) _4-a. (1) (wherein, R represents a hydrogen atom, a fluorine atom or a monovalent organic group, R4 represents a monovalent organic group, and a represents an integer of 1 to 2) (F-2) The compound represented by (2) and Si (OR5) ₄ (2) (wherein R5 represents a monovalent organic group) (F-3) represented by the following general formula (3) the compound _{R6 b (R7O) 3-b} Si- (R10) d -Si (OR8) 3-c R9 c ····· (3) wherein, R6 ～R9 each a monovalent organic group, b~c is an integer of 0 to 2, R10 is an oxygen atom, a phenylene group or - (CH _{2) m} - group represented by (wherein, m is an integer from 1 to 6), d is 0 or It represents 1. ] It contains at least one compound selected from the group of the above, or a hydrolyzate thereof, and (E) a Zr element-containing compound. A coating liquid for forming a coating portion, wherein the content of the fluororesin particles is 1% by weight or more and less than 20% by weight, and the weight ratio of (F) and (E) is the SiO ₂ equivalent A coating liquid characterized in that the weight ratio of the component (E) in terms of ZrO ₂ is 0.5 to 20 parts by weight with respect to 100 parts by weight of the component (F) is also preferably used. it can.
It may be a compound, a hydrolyzate thereof, or a mixture of these appropriately.
The coating liquid may contain a diluting solvent.

In a further preferred aspect of the coating liquid of the present invention, the fluororesin particles have an average particle size of 0.1 to 20 μm.
Here, in the present invention, the average particle diameter is a dispersed particle diameter in a liquid, and can be measured using a laser diffraction particle size distribution analyzer or the like.
When the average particle size is smaller than 0.1 μm, the effect of maintaining the design property of the substrate is lowered when an external force is applied, and when it is larger than 20 μm, the design property of the substrate is impaired.

In a further preferred aspect of the coating liquid of the present invention, the fluororesin particles have an average particle size of 0.1 to 8 μm.
When the average particle size is 8 μm or less, the coating part can be easily formed using various coating methods, the dispersion stability of the fluororesin particles in the coating liquid is improved, and the appearance of the coating part is also improved. improves.

As a preferable method for producing the composite material of the present invention, a fluororesin particle and (D) 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, an alkenyl group, a cycloalkenyl group, an amino group, an alkylamino group, an alkylsilyl group, an alkoxy group, or directly connected to the main chain silicon and nitrogen other than these groups. A group in which the group is carbon, and n is an integer), and (E) a Zr element-containing compound is applied to the substrate and cured by heating to form a coating portion on the substrate. a coating liquid, wherein a content of less than 1% by weight or more and 20 wt% of fluorine resin particles, the weight ratio of the said and (D) (E) is, said SiO ₂ in terms of the component (D) For 100 parts by weight After applying the coating solution weight ratios of the (E) component in terms of ZrO ₂ is equal to or less than 20 parts by weight or more 0.5 part by weight, curing the coating solution by heating each substrate On the substrate, (A) silica, or average composition formula R _p SiO _{(4-p) / 2} (wherein R is a hydrogen atom, a fluorine atom or a monovalent organic group, p is 0 <p < 4 is a number satisfying 4), and there is a method of forming a covering portion containing at least one selected from the group of (B) fluorine resin particles and (C) a Zr element-containing compound.

Here, (D) a compound represented by the following structural formula [— (SiR1R2) — (NR3) —] _n (wherein R1, R2, R3 are each independently a hydrogen atom, an alkyl group, 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, and n is an integer) is heated to silica Conversion occurs and cures to form a three-dimensional network structure on the substrate.
In order to cause silica conversion, it is desirable to heat at 100 ° C. or higher, and heating at 200 ° C. or higher is preferable because the conversion reaction is further promoted.

Moreover, when a heating temperature becomes high, the base material which can be used is limited from the heat resistance of a base material. Further, for example, in the case of a metal, although it has heat resistance, discoloration due to oxidation of the metal surface occurs at 400 ° C. or higher, so that design properties are impaired.
Moreover, it is more preferable that it is 350 degrees C or less from the heat resistance of a fluororesin particle.

As a preferable method for producing the composite material of the present invention, fluororesin particles and (F) (F-1) a compound represented by the following general formula (1), R _a Si (OR ₄ ) _4-a · (1) (wherein R represents a hydrogen atom, a fluorine atom or a monovalent organic group, R4 represents a monovalent organic group, and a represents an integer of 1 to 2) (F-2) Compound represented by the general formula (2) and Si (OR5) ₄ (2) (wherein R5 represents a monovalent organic group) (F-3) The following general formula (3) compound represented by _{R6 b (R7O) 3-b} Si- (R10) d -Si (OR8) 3-c R9 c ····· (3) wherein, R6 ~R9 each a monovalent organic group, b-c is an integer of 0 to 2, R10 is an oxygen atom, a phenylene group or - (CH _{2) m} - group represented by (wherein, m is an integer from 1 to 6), d is 0 Also Shows the 1. ] It contains at least one compound selected from the group of the above, or a hydrolyzate thereof, and (E) a Zr element-containing compound. A coating liquid for forming a coating portion, wherein the content of the fluororesin particles is 1% by weight or more and less than 20% by weight, and the weight ratio of (F) and (E) is the SiO ₂ equivalent After applying the coating liquid, wherein the weight ratio of the component (E) in terms of ZrO ₂ is from 0.5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the component (F), The coating liquid is cured by heating, and (A) silica, or an average composition formula R _p SiO _{(4-p) / 2} (wherein R is a hydrogen atom, a fluorine atom, or a monovalent organic) The group p is a number satisfying 0 <p <4 And (C) a method of forming a covering portion containing (B) fluorine resin particles and (C) a Zr element-containing compound.

To the substrate, fluorine resin particles and (D) a compound represented by the following structural formula [— (SiR1R2) — (NR3) —] _n (wherein R1, R2, R3 are each independently a hydrogen atom, an alkyl A group, 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, wherein the group directly connected to silicon and nitrogen in the main chain is carbon, n is an integer ) And (E) a Zr element-containing compound, which is applied to a substrate and cured by heating to form a coating portion on the substrate, which contains the fluorine resin particles The amount is 1% by weight or more and less than 20% by weight, and the weight ratio of (D) and (E) is based on ZrO _{2 with} respect to 100 parts by weight of the component (D) in terms of SiO _2. The weight ratio of component (E) is 0. After coating a coating liquid characterized by being 5 parts by weight or more and 20 parts by weight or less, the coating liquid is cured by heating together with the base material, and (A) silica or an average composition formula on the base material R _p SiO _{(4-p) / 2} (wherein R is a hydrogen atom, a fluorine atom or a monovalent organic group, and p is a number satisfying 0 <p <4). According to the method of forming the coating part containing the seed, (B) fluororesin particles, and (C) the Zr element-containing compound, the shrinkage is caused because a three-dimensional network structure is formed by the conversion of Si—N to Si—O. Since a small and denser covering portion is formed, the effect of maintaining the design of the base material is satisfactorily exhibited when more external force is applied.

The ductile base material of the present invention is a sink and / or a counter, and at least a part on the use surface side includes (A) silica, or an average composition formula R _p SiO _{(4-p) / 2} (wherein R is Hydrogen atom, fluorine atom or monovalent organic group, p is a number satisfying 0 <p <4), (B) fluorine resin particles, (C) Zr element-containing compound As another method for producing a composite material provided with a coating portion characterized by containing a ductile base material fluororesin particles after drawing a ductile base material into a sink and / or counter shape, (D) Compound represented by the following structural formula [— (SiR1R2) — (NR3) —] _n (wherein R1, R2, R3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkenyl group) , Amino group, alkyl A mino group, an alkylsilyl group, an alkoxy group, or a group other than these groups in which the groups directly connected to silicon and nitrogen in the main chain are carbon, n is an integer), and (E) a Zr element-containing compound And a coating liquid that forms a coating on the substrate by being applied to the substrate and cured by heating, wherein the content of the fluororesin particles is 1% by weight or more and less than 20% by weight. The weight ratio of (D) and (E) is 0.5 parts by weight of the component (E) in terms of ZrO _{2 with} respect to 100 parts by weight of the component (D) in terms of SiO _2. A method of curing the coating liquid by applying a coating liquid characterized by being 20 parts by weight or less and heating the whole substrate is exemplified.

The ductile base material of the present invention is a sink and / or a counter, and at least a part on the use surface side includes (A) silica, or an average composition formula R _p SiO _{(4-p) / 2} (wherein R is Hydrogen atom, fluorine atom or monovalent organic group, p is a number satisfying 0 <p <4), (B) fluorine resin particles, (C) Zr element-containing compound As another method of manufacturing a composite material provided with a coating portion characterized by containing a ductile base material, the ductile base material is drawn into a sink and / or counter shape, and then the fluororesin particles are applied to the ductile base material. And (F) (F-1) a compound represented by the following general formula (1), R _a Si (OR ₄ ) _4-a (1) (wherein R is a hydrogen atom, a fluorine atom or A monovalent organic group, R4 is a monovalent organic group, and a is an integer of 1 to 2. (F-2) a compound represented by the following general formula (2) and Si (OR @ 5) ₄ · · · · · (2) (wherein, R5 represents a monovalent organic group.) (F-3) compound _{R6 b (R7O) 3-b} Si- (R10) d -Si (OR8) 3-c R9 c ····· (3) wherein represented by the following general formula (3), R6 ~R9 each monovalent organic group, b-c is an integer of 0 to 2 is, R10 is an oxygen atom, a phenylene group or - (CH _{2) m} - group represented by (wherein, m is in integer of 1 to 6 D) represents 0 or 1. ] It contains at least one compound selected from the group of the above, or a hydrolyzate thereof, and (E) a Zr element-containing compound. A coating liquid for forming a coating portion, wherein the content of the fluororesin particles is 1% by weight or more and less than 20% by weight, and the weight ratio of (F) and (E) is the SiO ₂ equivalent Applying a coating liquid, wherein the weight ratio of the component (E) in terms of ZrO ₂ is 0.5 to 20 parts by weight with respect to 100 parts by weight of the component (F), The method of hardening the said coating liquid by heating the whole is mentioned.

  According to the method of forming the coating portion after drawing the ductile base material into a sink and / or counter shape, the residual stress on the coating portion can be reduced, so that when the external force is applied more, the design of the base material The effect of maintaining the property is exhibited well.

The ductile base material of the present invention is a sink and / or a counter, and at least a part on the use surface side includes (A) silica, or an average composition formula R _p SiO _{(4-p) / 2} (wherein R is Hydrogen atom, fluorine atom or monovalent organic group, p is a number satisfying 0 <p <4), (B) fluorine resin particles, (C) Zr element-containing compound As another method for producing a composite material provided with a coating portion characterized by containing fluorinated resin particles and (D) a compound represented by the following structural formula [-( SiR1R2)-(NR3)-] _n (wherein R1, R2, R3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkenyl group, an amino group, an alkylamino group, an alkylsilyl group, an alkoxy group, Or other than these groups A group in which the group directly connected to silicon and nitrogen in the chain is carbon, and n is an integer) and (E) a Zr element-containing compound, applied to a substrate, and cured by heating to form a group A coating liquid for forming a covering portion on a material, wherein the content of the fluororesin particles is 1% by weight or more and less than 20% by weight, and the weight ratio of (D) to (E) is SiO _2. A coating liquid characterized by having a weight ratio of the component (E) in terms of ZrO ₂ to 0.5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the component (D) in terms of conversion was applied. after curing the coating solution by heating each substrate, on the substrate, (a) silica or in the average composition formula _{R p SiO (4-p)} / 2 ( wherein,, R is a hydrogen atom, a fluorine Atomic or monovalent organic group, p satisfies 0 <p <4 After forming a coating portion containing at least one selected from the group of (a), (B) fluorine resin particles, and (C) a Zr element-containing compound, the ductile substrate is drawn into a sink and / or counter shape The method of doing is mentioned.

The ductile base material of the present invention is a sink and / or a counter, and at least a part on the use surface side includes (A) silica, or an average composition formula R _p SiO _{(4-p) / 2} (wherein R is Hydrogen atom, fluorine atom or monovalent organic group, p is a number satisfying 0 <p <4), (B) fluorine resin particles, (C) Zr element-containing compound As another manufacturing method of the composite material provided with the coating portion characterized by containing fluorinated resin particles and (F) (F-1) in the following general formula (1), Compound represented by: R _a Si (OR ₄ ) _4-a (1) (wherein R is a hydrogen atom, a fluorine atom or a monovalent organic group, R 4 is a monovalent organic group, a is Represents an integer of 1 to 2) (F-2) a compound represented by the following general formula (2) and Si (OR5) ₄ (2) (wherein R5 represents a monovalent organic group) (F-3) a compound represented by the following general formula (3) R6 _b (R7O) _3-b Si— (R10) in _{d -Si (OR8) 3-c} R9 c ····· (3) [wherein, R6 ~R9 each a monovalent organic group, b-c is an integer of 0 to 2, R10 is oxygen An atom, a phenylene group or a group represented by — (CH ₂ ) _m — (wherein m is an integer of 1 to 6), d represents 0 or 1; ] It contains at least one compound selected from the group of the above, or a hydrolyzate thereof, and (E) a Zr element-containing compound. A coating liquid for forming a coating portion, wherein the content of the fluororesin particles is 1% by weight or more and less than 20% by weight, and the weight ratio of (F) and (E) is the SiO ₂ equivalent After applying the coating liquid, wherein the weight ratio of the component (E) in terms of ZrO ₂ is from 0.5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the component (F), The coating liquid is cured by heating, and (A) silica, or an average composition formula R _p SiO _{(4-p) / 2} (wherein R is a hydrogen atom, a fluorine atom, or a monovalent organic) The group p is a number satisfying 0 <p <4 After forming a coating portion containing at least one selected from the group of (B), fluorine resin particles, and (C) a Zr element-containing compound, the ductile substrate is drawn into a sink and / or counter shape A method is mentioned.

After forming the coating, the method of drawing the ductile substrate into a sink and / or counter shape makes it easier to apply the coating liquid before it is processed into a complex sink and / or counter shape. The ductile base material is a sink and / or a counter, and at least a part on the use surface side includes (A) silica, or an average composition formula R _p SiO _{(4-p) / 2} (wherein R is a hydrogen atom, A fluorine atom or a monovalent organic group, p is a number satisfying 0 <p <4), (B) a fluorine resin particle, and (C) a Zr element-containing compound. It is possible to manufacture a composite material provided with a covering portion.

Hereinafter, the composite material of the present invention and the method for producing the composite material will be specifically described.
In the present invention, as the base material, metal materials such as iron, aluminum, and stainless steel, glass, ceramics, plastic, wood, stone, cement, concrete, combinations thereof, laminates thereof, and the like are used.

In the present invention, (A) silica, or average composition formula R _p SiO _{(4-p) / 2} (wherein R is a hydrogen atom, a fluorine atom or a monovalent organic group, p is 0 <p <4 At least one selected from the group of (a number satisfying the above) forms a three-dimensional network structure on the surface of the substrate to form a covering portion.

  In the present invention, the fluororesin particle means a fluororesin granular material, the fluororesin particle is preferable, the dispersibility in the coating is good, and it is difficult for the particle to fall off when an external force is applied. Spherical ones are preferred.

  Next, the fluororesin particles include polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene. Copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, perfluorocyclopolymer, vinyl ether-fluoroolefin copolymer, vinyl ester-fluoroolefin copolymer, tetrafluoroethylene-vinyl ether copolymer, chlorotrifluoroethylene-vinyl ether copolymer, tetrafluoroethylene urethane cross-linked Body, tetrafluoroethylene epoxy crosslinked body, tetrafluoro Chiren'akuriru crosslinked include polymers containing tetrafluoroethylene melamine crosslinked body and the like fluoro groups.

In the present invention, (A) silica or an average composition formula R _p SiO _{(4-p) / 2} (wherein R is a hydrogen atom, a fluorine atom or a monovalent organic group, p is 0 <p <4 The coating portion comprising at least one selected from the group of (a satisfying number), (B) fluorine resin particles, and (C) a Zr element-containing compound has fluorine resin particles dispersed in a three-dimensional network structure. Alternatively, a concavo-convex structure having a convex portion corresponding to the self-shape of the fluororesin particles may be formed.

  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 and / or a counter, it means an action that suppresses the occurrence of scratches caused by sliding of tableware or the like and the deterioration of the design.

  In the present invention, the ductile substrate means a substrate having a property that the substance is stretched without breaking beyond the limit of elasticity, and particularly as a material rich in ductility, such as steel, copper, aluminum, stainless steel, etc. Examples include metal materials.

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.

  In the present invention, the ductile base material is a sink and / or a counter, and the composite material provided with the coating portion of the present invention at least on a part of the use surface is the use surface side of the sink and / or the counter. In addition, the cover may be formed near the center of the bottom of the sink where contact with tableware or the like is particularly significant, or only at the periphery of the sink of the counter, and of course, the cover is formed on the entire use surface side. Also good.

In the present invention, (D) 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, wherein the group directly connected to silicon and nitrogen in the main chain is carbon, and n is an integer) Examples of the group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl and the like. Examples of the alkenyl group include vinyl, allyl, brenyl, pentenyl, hexenyl, butynyl, octenyl, decenyl and the like. Examples of the aryl group include phenyl, tolyl, xylyl, naphthyl and the like.

In the present invention, (F) (F-1) a compound represented by the following general formula (1), R _a Si (OR ₄ ) _4-a (1) (wherein R is a hydrogen atom, A fluorine atom or a monovalent organic group, R4 is a monovalent organic group, a is an integer of 1 to 2.) (F-2) A compound represented by the following general formula (2) and Si (OR5) ₄ (2) (wherein R5 represents a monovalent organic group.) (F-3) Compound represented by the following general formula (3) R6 _b (R7O) _3-b Si— ( _{R10) d -Si (OR8) 3} -c R9 c ····· (3) wherein, R6 ~R9 each a monovalent organic group, b-c is an integer of 0 to 2, R10 represents an oxygen atom , A phenylene group or a group represented by — (CH ₂ ) _m — (wherein m is an integer of 1 to 6), d represents 0 or 1. In the at least one compound selected from the group or a hydrolyzate thereof, specific examples of the compound represented by the general formula (1) include trimethoxysilane, triethoxysilane, and tri-n-propoxy. Silane, tri-iso-propoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, tri-tert-butoxysilane, triphenoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxy Silane, fluorotri-iso-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec-butoxysilane, fluorotri-tert-butoxysilane, fluorotriphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri- n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri- n-propoxysilane, vinyltri-iso-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, vinyltri-tert Butoxysilane, vinyltriphenoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane, n-propyltri-n-butoxy Silane, n-propyltri-sec-butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltri-n- Propoxysilane, i-propyltri-iso-propoxysilane, i-propyltri-n-butoxysilane, i-propyltri-sec-butoxysilane, i-propyltri-tert-butoxysilane, i-propyltriphenoxysilane, n-butyl Trimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri -Tert-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butyltriethoxysilane, sec-butyl-tri-n-propoxysilane, sec-butyl-tri-iso-propoxysilane, sec -Butyl-tri-n-butoxysilane, sec-butyl-tri-sec-butoxysilane, sec-butyl-tri-tert-butoxysilane, sec-butyl-triphenoxysilane, t-butyltrimethoxysilane, t-butyl Triethoxy Lan, t-butyltri-n-propoxysilane, t-butyltri-iso-propoxysilane, t-butyltri-n-butoxysilane, t-butyltri-sec-butoxysilane, t-butyltri-tert-butoxysilane, t-butyl Triphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-tert -Butoxysilane, phenyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltri Toxisilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyl-di-n-propoxysilane, dimethyl- Di-iso-propoxysilane, dimethyl-di-n-butoxysilane, dimethyl-di-sec-butoxysilane, dimethyl-di-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyl- Di-n-propoxysilane, diethyl-di-iso-propoxysilane, diethyl-di-n-butoxysilane, diethyl-di-sec-butoxysilane, diethyl-di-tert-butoxysilane, diethyldiphenoxy Sisilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyl-di-n-propoxysilane, di-n-propyl-di-iso-propoxysilane, di-n-propyl -Di-n-butoxysilane, di-n-propyl-di-sec-butoxysilane, di-n-propyl-di-tert-butoxysilane, di-n-propyl-di-phenoxysilane, di-iso-propyl Dimethoxysilane, di-iso-propyldiethoxysilane, di-iso-propyl-di-n-propoxysilane, di-iso-propyl-di-iso-propoxysilane, di-iso-propyl-di-n-butoxysilane Di-iso-propyl-di-sec-butoxysilane, di-iso-propyl-di-tert-butoxysila Di-iso-propyl-di-phenoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyl-di-n-propoxysilane, di-n-butyl-di- iso-propoxysilane, di-n-butyl-di-n-butoxysilane, di-n-butyl-di-sec-butoxysilane, di-n-butyl-di-tert-butoxysilane, di-n-butyl- Di-phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyl-di-n-propoxysilane, di-sec-butyl-di-iso-propoxysilane, di- sec-butyl-di-n-butoxysilane, di-sec-butyl-di-sec-butoxysilane, di-sec-butyl-di-tert-but Sisilane, di-sec-butyl-di-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyl-di-n-propoxysilane, di-tert-butyl-di -Iso-propoxysilane, di-tert-butyl-di-n-butoxysilane, di-tert-butyl-di-sec-butoxysilane, di-tert-butyl-di-tert-butoxysilane, di-tert-butyl -Di-phenoxysilane, diphenyldimethoxysilane, diphenyl-di-ethoxysilane, diphenyl-di-n-propoxysilane, diphenyl-di-iso-propoxysilane, diphenyl-di-n-butoxysilane, diphenyl-di-sec- Butoxysilane, diphenyl-di-tert-but Examples include xylsilane, diphenyldiphenoxysilane, and divinyltrimethoxysilane.

  In the present invention, specific examples of the compound represented by the general formula (2) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra- Examples include sec-butoxysilane, tetra-tert-butoxysilane, and tetraphenoxysilane.

  In the present invention, specific examples of the compound represented by the general formula (3) include hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane, 1,1,1,3,3-pentamethoxy-3- Methyldisiloxane, 1,1,1,3,3-pentaethoxy-3-methyldisiloxane, 1,1,1,3,3-pentaphenoxy-3-methyldisiloxane, 1,1,1,3 3-pentamethoxy-3-ethyldisiloxane, 1,1,1,3,3-pentaethoxy-3-ethyldisiloxane, 1,1,1,3,3-pentaphenoxy-3-ethyldisiloxane, 1,1,1,3,3-pentamethoxy-3-phenyldisiloxane, 1,1,1,3,3-pentaethoxy-3-phenyldisiloxane, 1,1,1,3,3-pentafe Xyl-3-phenyldisiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1, 3,3-tetraphenoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-diethyl Disiloxane, 1,1,3,3-tetraphenoxy-1,3-diethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,1,3,3-tetra Ethoxy-1,3-diphenyldisiloxane, 1,1,3,3-tetraphenoxy-1,3-diphenyldisiloxane, 1,1,3-trimethoxy-1,3,3-trimethyldisiloxane, , 1,3-triethoxy-1,3,3-trimethyldisiloxane, 1,1,3-triphenoxy-1,3,3-trimethyldisiloxane, 1,1,3-trimethoxy-1,3,3- Triethyldisiloxane, 1,1,3-triethoxy-1,3,3-triethyldisiloxane, 1,1,3-triphenoxy-1,3,3-triethyldisiloxane, 1,1,3- Trimethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triphenoxy-1,3,3-triphenyldisiloxane Siloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diphenoxy-1,1, 3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetraethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraethyldisiloxane, 1,3-diphenoxy -1,1,3,3-tetraethyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane 1,3-diphenoxy-1,1,3,3-tetraphenyldisiloxane, hexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane, 1,1,1,2,2-pentamethoxy-2-methyldisilane, 1,1,1,2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentaphenoxy-2-methyldisilane, 1,1 1,2,2-pentamethoxy-2-ethyldisilane, 1,1,1,2,2-pentaethoxy-2-ethyldisilane, 1,1,1,2,2-pentaphenoxy-2-ethyldisilane, 1,1,1,2,2-pentamethoxy-2-phenyldisilane, 1,1,1,2,2-pentaethoxy-2-phenyldisilane, 1,1,1,2,2-pentaphenoxy-2 -Phenyldisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraphenoxy -1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-diethyldisilane, 1,1,2,2-tetraethoxy-1,2-diethyldisilane, 1,1,2, 2-Tetraphenoxy , 2-diethyldisilane, 1,1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,1,2,2- Tetraphenoxy-1,2-diphenyldisilane, 1,1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,1,2- Triphenoxy-1,2,2-trimethyldisilane, 1,1,2-trimethoxy-1,2,2-triethyldisilane, 1,1,2-triethoxy-1,2,2-triethyldisilane, 1, 1,2-triphenoxy-1,2,2-triethyldisilane, 1,1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1,2-triethoxy-1,2,2-tri Phenyldisilane, 1,1,2-triphenoxy-1,2,2-triphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1 , 2,2-tetramethyldisilane, 1,2-diphenoxy-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraethyldisilane, 1,2-diethoxy- 1,1,2,2-tetraethyldisilane, 1,2-diphenoxy-1,1,2,2-tetraethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2- Diethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diphenoxy-1,1,2,2-tetraphenyldisilane, bis (trimethoxysilyl) methane, bis (triethoxy Silyl) methane, bis (tri-n-propoxysilyl) methane, bis (tri-i-propoxysilyl) methane, bis (tri-n-butoxysilyl) methane, bis (tri-sec-butoxysilyl) methane, bis ( Tri-t-butoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1,2-bis (tri-n-propoxysilyl) ethane, 1, 2-bis (tri-i-propoxysilyl) ethane, 1,2-bis (tri-n-butoxysilyl) ethane, 1,2-bis (tri-sec-butoxysilyl) ethane, 1,2-bis (tri -T-butoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (tri Toxisilyl) methane, 1- (di-n-propoxymethylsilyl) -1- (tri-n-propoxysilyl) methane, 1- (di-i-propoxymethylsilyl) -1- (tri-i-propoxysilyl) Methane, 1- (di-n-butoxymethylsilyl) -1- (tri-n-butoxysilyl) methane, 1- (di-sec-butoxymethylsilyl) -1- (tri-sec-butoxysilyl) methane, 1- (di-t-butoxymethylsilyl) -1- (tri-t-butoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethoxysilyl) ethane, 1- (diethoxymethylsilyl)- 2- (triethoxysilyl) ethane, 1- (di-n-propoxymethylsilyl) -2- (tri-n-propoxysilyl) ethane, 1- (di-i-propoxy) Methylsilyl) -2- (tri-i-propoxysilyl) ethane, 1- (di-n-butoxymethylsilyl) -2- (tri-n-butoxysilyl) ethane, 1- (di-sec-butoxymethylsilyl) 2- (tri-sec-butoxysilyl) ethane, 1- (di-t-butoxymethylsilyl) -2- (tri-t-butoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethyl) Silyl) methane, bis (di-n-propoxymethylsilyl) methane, bis (di-i-propoxymethylsilyl) methane, bis (di-n-butoxymethylsilyl) methane, bis (di-sec-butoxymethylsilyl) Methane, bis (di-t-butoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (di Toximethylsilyl) ethane, 1,2-bis (di-n-propoxymethylsilyl) ethane, 1,2-bis (di-i-propoxymethylsilyl) ethane, 1,2-bis (di-n-butoxymethyl) Silyl) ethane, 1,2-bis (di-sec-butoxymethylsilyl) ethane, 1,2-bis (di-t-butoxymethylsilyl) ethane, 1,2-bis (trimethoxysilyl) benzene, 1, 2-bis (triethoxysilyl) benzene, 1,2-bis (tri-n-propoxysilyl) benzene, 1,2-bis (tri-i-propoxysilyl) benzene, 1,2-bis (tri-n- Butoxysilyl) benzene, 1,2-bis (tri-sec-butoxysilyl) benzene, 1,2-bis (tri-t-butoxysilyl) benzene, 1,3-bis (trimethoxy) Ryl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,3-bis (tri-n-propoxysilyl) benzene, 1,3-bis (tri-i-propoxysilyl) benzene, 1,3- Bis (tri-n-butoxysilyl) benzene, 1,3-bis (tri-sec-butoxysilyl) benzene, 1,3-bis (tri-t-butoxysilyl) benzene, 1,4-bis (trimethoxysilyl) ) Benzene, 1,4-bis (triethoxysilyl) benzene, 1,4-bis (tri-n-propoxysilyl) benzene, 1,4-bis (tri-i-propoxysilyl) benzene, 1,4-bis (Tri-n-butoxysilyl) benzene, 1,4-bis (tri-sec-butoxysilyl) benzene, 1,4-bis (tri-t-butoxysilyl) benzene It can be mentioned.

  Zr element-containing compounds include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra n-propoxide, zirconium tetraisopropoxide, zirconium tetra n-butoxide, zirconium tetra t-butoxide, zirconium tetraoctinate, zirconium tetraacetate , Zirconium tetraacetylacetonate, zirconium butoxymonoacetylacetonate, zirconium butoxymonoacetylacetonate bisethyl acetate, zirconium isopropoxide monoacetylacetonate, zirconium isopropoxide bisacetylacetonate, zirconium isopropoxide triacetylacetonate , Zirconium t-butoxy monoacetylacetonate, zirconium Zirconium alkoxides such as sopropoxide monobenzoyl acetonate, zirconium isopropoxide bisbenzoyl acetonate, zirconium isopropoxide tribenzoyl acetonate, zirconium acetate, zirconium chelate compounds, zirconium acylate compounds and partial hydrolysates thereof, A partially hydrolyzed polycondensate can be mentioned.

In the present invention, as a coating liquid coating method, for example, known coating means such as 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 can be appropriately employed. . The film thickness can be controlled by changing the pulling speed in the dipping method, the substrate rotation speed in the spin coating method, and the like, and changing the concentration and viscosity of the coating solution.

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

  1, 2 and 3 are cross-sectional views of various patterns of composites of the present invention.

A covering portion 2 is provided on a ductile substrate 1, and the covering portion 2 includes a three-dimensional network structure 3 and fluorine resin particles 4, and the covering portion 2 has a certain degree of flexibility in the covering portion. Therefore, even when an external force is applied, the effect of maintaining the design of the substrate is exhibited.
The three-dimensional network structure contains a Zr element-containing compound and exhibits alkali resistance.

  Such a composite material can maintain the design of the base material even when an external force is applied due to, for example, sliding of tableware or the like, and is in contact with an alkaline detergent such as a bleaching agent. In this case, alkali resistance can be exhibited.

The fluororesin particles 4 contained in the covering portion 2 may be dispersed in the three-dimensional network structure 3 as shown in FIG. 1, and a part of the fluororesin particles 4 as shown in FIG. It may be exposed, or the three-dimensional network structure 3 may cover the convex portions formed by the self-shape of the fluororesin particles 4 as shown in FIG.
When the concavo-convex structure having the convex portion corresponding to the self-shape of the fluororesin particles is formed on the surface of the covering portion, the plasticity of the fluororesin particles is more significantly exhibited, and when external force is applied, Since the convex part corresponding to the self-shape of the fluororesin particles suppresses the propagation of the external force to the three-dimensional network structure, when the external force is applied, the effect of maintaining the design property of the substrate is remarkably exhibited.

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

A scanning electron microscope S4100 manufactured by Hitachi, Ltd. was used for observing the coating portion of the composite material of the present invention.
The film thickness of the covering portion is examined by cross-sectional observation. The film thickness of the covering portion is the thickness of the three-dimensional network structure 3 (indicated by Δt in the figure), and does not include the thickness of the convex portion due to the fluororesin particles.
The dispersion state of the fluororesin particles in the coating part was observed from the surface.
Moreover, about the uneven | corrugated structure of a coating | coated part, it observed from the surface and the diagonal, and it confirmed that the fluororesin had formed the convex part.

  The particle diameter of the fluororesin particles of the present invention is measured using a laser diffraction particle size distribution analyzer SALD7000 manufactured by Shimadzu Corporation, and the average particle diameter means the 50% central particle diameter of the volume distribution.

Example 1
As the substrate, a SUS304 stainless steel plate used in a counter was used. As a pretreatment of the substrate, the substrate surface was thoroughly washed with hexane and further washed with acetone.
After the coating liquid having the composition shown in Table 1 was applied to the substrate by spray coating, it was heated at 250 ° C. for 60 minutes to form a coating portion in which the fluororesin particles were dispersed.
The average particle diameter of the used fluororesin particles was 5 μm.
The content of the fluororesin particles in the non-volatile content in the coating liquid (the non-volatile content of the polysilazane liquid is the SiO ₂ equivalent concentration and the non-volatile content of the octylate zirconyl liquid is the ZrO ₂ equivalent concentration) was 4.7% by weight.
The non-volatile ZrO ₂ equivalent concentration of the zirconyl octylate solution was 0.86 parts by weight relative to the non-volatile SiO ₂ equivalent concentration of 100 parts by weight of the polysilazane liquid.
The film thickness of the coating part was 2.0 μm.

(Example 2)
The same substrate as in Example 1 was used.
After the coating liquid having the composition shown in Table 2 was applied to the substrate by spray coating, it was heated at 250 ° C. for 60 minutes to form a coating portion in which the fluororesin particles were dispersed.
The average particle diameter of the used fluororesin particles was 5 μm.
The content of the fluororesin particles in the non-volatile content in the coating liquid (the non-volatile content of the polysilazane liquid is the SiO ₂ equivalent concentration and the non-volatile content of the octylate zirconyl liquid is the ZrO ₂ equivalent concentration) was 4.7% by weight.
The non-volatile ZrO ₂ equivalent concentration of the zirconyl octylate solution was 2.2 parts by weight relative to the non-volatile SiO ₂ equivalent concentration of 100 parts by weight of the polysilazane liquid.
The film thickness of the coating part was 2.0 μm.

Example 3
The same substrate as in Example 1 was used.
After the coating liquid having the composition shown in Table 3 was applied to the substrate by spray coating, it was heated at 250 ° C. for 60 minutes to form a coating portion in which the fluororesin particles were dispersed.
The average particle diameter of the used fluororesin particles was 5 μm.
The content of the fluororesin particles in the non-volatile content in the coating liquid (the non-volatile content of the polysilazane liquid is the SiO ₂ equivalent concentration and the non-volatile content of the octylate zirconyl liquid is the ZrO ₂ equivalent concentration) was 4.4% by weight.
The non-volatile ZrO ₂ equivalent concentration of the zirconyl octylate solution was 8.6 parts by weight relative to the non-volatile SiO ₂ equivalent concentration of 100 parts by weight of the polysilazane liquid.
The film thickness of the coating part was 2.0 μm.

(Example 4)
The same substrate as in Example 1 was used.
After the coating liquid having the composition shown in Table 4 was applied to the substrate by spray coating, it was heated at 250 ° C. for 60 minutes to form a coating portion in which the fluororesin particles were dispersed.
The average particle diameter of the used fluororesin particles was 10 μm.
The content of the fluororesin particles in the non-volatile content in the coating liquid (the non-volatile content of the polysilazane liquid is the SiO ₂ equivalent concentration and the non-volatile content of the octylate zirconyl liquid is the ZrO ₂ equivalent concentration) was 4.7% by weight.
The non-volatile ZrO ₂ equivalent concentration of the zirconyl octylate solution was 2.2 parts by weight relative to the non-volatile SiO ₂ equivalent concentration of 100 parts by weight of the polysilazane liquid.
The film thickness of the coating part was 2.0 μm.

(Example 5)
The same substrate as in Example 1 was used.
After the coating liquid having the composition shown in Table 5 was applied to the substrate by spray coating, it was heated at 250 ° C. for 60 minutes to form a coating portion in which the fluororesin particles were dispersed.
The average particle diameter of the used fluororesin particles was 10 μm.
The content of the fluororesin particles in the non-volatile content in the coating liquid (the non-volatile content of the polysilazane liquid is the SiO ₂ equivalent concentration, and the non-volatile content of the octylate zirconyl liquid is the ZrO ₂ equivalent concentration) was 12.8% by weight.
The non-volatile ZrO ₂ equivalent concentration of the zirconyl octylate solution was 2.2 parts by weight relative to the non-volatile SiO ₂ equivalent concentration of 100 parts by weight of the polysilazane liquid.
The film thickness of the coating part was 2.0 μm.

(Example 6)
The same substrate as in Example 1 was used.
After the coating liquid having the composition shown in Table 6 was applied to the substrate by spray coating, it was heated at 250 ° C. for 60 minutes to form a coating portion in which the fluororesin particles were dispersed.
The average particle diameter of the used fluororesin particles was 22 μm.
The content of the fluororesin particles in the non-volatile content in the coating liquid (the non-volatile content of the polysilazane liquid is the SiO ₂ equivalent concentration and the non-volatile content of the octylate zirconyl liquid is the ZrO ₂ equivalent concentration) was 4.7% by weight.
The non-volatile ZrO ₂ equivalent concentration of the zirconyl octylate solution was 2.2 parts by weight relative to the non-volatile SiO ₂ equivalent concentration of 100 parts by weight of the polysilazane liquid.
The film thickness of the coating part was 2.0 μm.

(Comparative Example 1)
A SUS304 stainless steel plate was used as a comparative example.

(Comparative Example 2)
A covering portion was formed as the covering portion in the same manner as in Example 1 except that the fluororesin particles were removed from the coating liquid of Example 1.
The film thickness of the coating part was 2.0 μm.

(Comparative Example 3)
A covering portion was formed in the same manner as in Example 1 except that the zirconyl octylate solution was removed from the coating solution of Example 1.
The film thickness of the coating part was 2.0 μm.

(Comparative Example 4)
The same substrate as in Example 1 was used.
After the coating liquid having the composition shown in Table 7 was applied to the substrate by spray coating, it was heated at 250 ° C. for 60 minutes to form a coating portion in which the fluororesin particles were dispersed.
The average particle diameter of the used fluororesin particles was 5 μm.
The content of the fluororesin particles in the non-volatile content in the coating liquid (the non-volatile content of the polysilazane liquid is the SiO ₂ equivalent concentration and the non-volatile content of the octylate zirconyl liquid is the ZrO ₂ equivalent concentration) was 0.1% by weight.
The non-volatile ZrO ₂ equivalent concentration of the zirconyl octylate solution was 2.2 parts by weight relative to the non-volatile SiO ₂ equivalent concentration of 100 parts by weight of the polysilazane liquid.
The film thickness of the coating part was 2.0 μm.

(Comparative Example 5)
The same substrate as in Example 1 was used.
After the coating liquid having the composition shown in Table 8 was applied to the substrate by spray coating, it was heated at 250 ° C. for 60 minutes to form a coating portion in which the fluororesin particles were dispersed.
The average particle diameter of the used fluororesin particles was 5 μm.
The content of the fluororesin particles in the non-volatile content in the coating liquid (the non-volatile content of the polysilazane liquid is the SiO ₂ equivalent concentration and the non-volatile content of the octylate zirconyl liquid is the ZrO ₂ equivalent concentration) was 4.7% by weight.
The non-volatile ZrO ₂ equivalent concentration of the zirconyl octylate solution was 21 parts by weight with respect to the non-volatile SiO ₂ equivalent concentration of 100 parts by weight of the polysilazane liquid.
The film thickness of the coating part was 2.0 μm.

(Comparative Example 6)
The same substrate as in Example 1 was used.
After the coating liquid having the composition shown in Table 9 was applied to the substrate by spray coating, it was heated at 250 ° C. for 60 minutes to form a coating portion in which the fluororesin particles were dispersed.
The average particle diameter of the used fluororesin particles was 10 μm.
The content of the fluororesin particles in the non-volatile content in the coating liquid (the non-volatile content of the polysilazane liquid is the SiO ₂ equivalent concentration and the non-volatile content of the zirconyl octylate solution is the ZrO ₂ equivalent concentration) was 22.7% by weight.
The non-volatile ZrO ₂ equivalent concentration of the zirconyl octylate solution was 2.2 parts by weight relative to the non-volatile SiO ₂ equivalent concentration of 100 parts by weight of the polysilazane liquid.
The film thickness of the coating part was 1.0 μm.

(Comparative Example 7)
As a comparative example, a stainless steel enamel with a glaze layer formed on the stainless steel surface was used.

(Evaluation methods)
(1) Appearance The appearance of the composite material was visually evaluated.
Judgment criteria ○: The design property of the base material is completely maintained. △: The design property of the base material is slightly lowered, but the design of the base material can be confirmed. ×: The design property of the base material is remarkably impaired. The design of the base material cannot be confirmed. (2) Ductile evaluation The test was conducted according to the bending test method for metal materials defined in JIS Z 2248. The test piece used was 100 mm × 60 mm.
The span of the support jig was 80 mm, and it was bent until it bent by 20 mm with a metal fitting. After the test, defects such as salients and scratches on the outside of the curved portion were observed.
Judgment criteria ○: No defects Δ: Defects that can be determined with a 50 × microscope, defects such as scratches ×: Defects that can be visually determined, defects such as scratches (3) Design properties of the substrate when an external force is applied Evaluation of the maintainability of the steel The evaluation was made only for the good appearance and ductility evaluation results.
What cut out 20x20mm earthenware tile 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 for each of 100 g and 500 g, and the number of sliding was 100. For a load of 100 g, a contact with a heavy object such as a mug was assumed, and for a load of 500 g, a contact with a heavy object such as a clay pot was assumed.
Even in the case of assuming contact with a heavy object of an earthenware pot, evaluation was performed only when the designability was maintained and when the number of sliding was further increased to 400 times.
Judgment criteria ◎: No flaws and no change in design properties ○: Although fine flaws occur, the design properties are maintained △: Scratches occur and the design properties are slightly lowered ×: Remarkably flaws are generated, and the design properties are remarkably increased (4) Detergent resistance evaluation Only those having good appearance and ductility evaluation results were evaluated.
After immersing in a commercially available cleaning agent for drainage pipes (alkaline, NaOH 3.5%) for 24 hours, the maintainability of the design of the substrate when an external force was applied was evaluated. What cut out 20x20mm earthenware tile 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 500 g and the number of sliding times was 100 times.
Judgment criteria ◎: No flaws and no change in design properties ○: Although fine flaws occur, the design properties are maintained △: Scratches occur and the design properties are slightly lowered ×: Remarkably flaws are generated, and the design properties are remarkably increased (5) Exposure evaluation Only Examples 1 to 6 and Comparative Example 1 were evaluated.
After exposure for 3 months in the kitchen of a family of four, the appearance after normal cleaning with an abrasive sponge was visually evaluated.
Judgment criteria ○: Designability almost the same as that before exposure was maintained. △: Slightly soiled or slightly damaged by washing. The design is markedly damaged by cleaning and the design is significantly impaired.

(Evaluation results)
Table 10 shows the evaluation results.

FIG. 4 is an observation photograph from the surface of the covering portion of Example 2. In Examples 1 to 6 of the present invention, as a result of observation by a scanning electron microscope from the oblique direction, fluorine resin particles are dispersed in the covering portion, and the surface of the covering portion is caused by the self-shape of the fluorine resin particles. It was confirmed that convex portions were formed.
In Examples 1 to 5 of the present invention, the design of the base material was completely maintained even after the covering portion was formed. In Example 6, although the transparency was slightly inferior to Examples 1 to 5, the design properties of the substrate could be confirmed.
In all of Examples 1 to 6 of the present invention, no defects such as cracks were observed in the bent portion even after the bending test, and the ductility was maintained. Moreover, the stress-strain characteristic at the time of a bending test was the same as that of a base material, and the change was not seen.
In Examples 1 to 6 of the present invention, the design properties of the base material are maintained even when an external force is applied assuming contact with a heavy object of about a clay pot.
In the composite materials of Examples 1, 2, 4, and 5, the design properties of the base material were completely maintained even when the number of sliding operations was further increased.
Moreover, also about detergent resistance, even if Example 1-6 of this invention has all contact with detergent, the effect | action which maintains the design property of a base material is exhibited when external force is applied. In particular, in Examples 2 to 6, even after contact with the detergent, it is completely the same as before contact, and when the external force is applied, the effect of maintaining the design property of the substrate is exhibited extremely well. It was.

As is clear from Table 10, the stainless steel enamel of Comparative Example 7 in which the glaze layer was formed did not allow the design of the base material to be confirmed, and cracks occurred in the bent portion by a bending test. In particular, the glaze completely peeled from the substrate at the end of the test piece.
The SUS304 stainless steel plate of Comparative Example 1 was significantly damaged even when applied with an external force of about 100 g 100 times, and the design properties of the substrate were significantly impaired.
In Comparative Example 2 that does not contain fluororesin particles and in Comparative Example 4 in which the content of fluororesin particles is 0.1% by weight, the design maintainability when a slight external force is applied is exhibited as compared with Comparative Example 1. However, even when an external force of about 100 g 100 times was applied, the designability was deteriorated. When a load of 500 g was applied, the scratches were remarkably generated and the designability of the substrate was remarkably impaired.
In Comparative Example 6 in which the content of fluororesin particles is 22.7% by weight, the appearance is slightly inferior in transparency, and the design maintainability when a slight external force is applied is exhibited as compared with Comparative Example 1. Even when an external force of about 100 g 100 times was applied, the designability was reduced. When a load of 500 g was applied, the scratches were remarkably generated and the designability of the substrate was remarkably impaired.
In Comparative Example 3, the design property of the base material was completely maintained even when an external force was applied that assumed contact with a heavy object such as a clay pot. However, since the Zr element-containing compound was not contained, the action was When the external force which assumed the contact with the heavy article about a clay pot was applied after contacting with a detergent, the damage | wound generate | occur | produced and the design property of the base material fell.
In Comparative Example 5 containing 21 parts by weight of the non-volatile component ZrO ₂ of the octylate zirconyl liquid with respect to 100 parts by weight of the non-volatile component SiO ₂ of the polysilazane liquid, the Zr element-containing compound is excessively contained. Even when an external force of about 100 g 100 times was applied, the designability was reduced. When a load of 500 g was applied, the scratches were remarkably generated and the designability of the substrate was remarkably impaired.

In addition, as a result of the exposure evaluation, all of them were found to be white so-called dirt. In Examples 1 to 6 of the present invention, the adhesion of dirt was slight as compared with Comparative Example 1. Thereafter, by cleaning, all the stains were easily removed completely, and no scratches were generated by the cleaning, and the same designability as before the exposure was maintained.
In Comparative Example 1, even if washing was performed, the stain was not removed, and the substrate was scratched before the stain was removed. The stain and the scratch that were not removed resulted in the appearance being significantly impaired.

  FIG. 5 is a schematic view of a kitchen having a sink with the composite of the present invention.

  The sink 5 comprising the composite material of the present invention and the counter 7 are joined, and the sink is provided with a faucet 8. The water discharged from the faucet 8 is used to wash dishes in the sink 5. The water can be discharged from the drain port 9.

  FIG. 6 is an enlarged view of the sink 5 portion of the kitchen of FIG. 5, 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. 6, 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 6 on the bottom surface side in the sink 5 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 6 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 6 on the bottom surface side, scratches may occur, but in this embodiment, the covering portion 2 is formed on the use surface 6 on the bottom surface side. As a result, scratches do not occur and the design of the substrate is maintained.
Here, in the present invention, the use surface side of the sink is the side surface side or the bottom surface side as shown in FIG. 5, and specifically, the 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 5 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.

  As another embodiment, there are a counter 7 with a part of the cover as shown in FIG. 8 and a part of the counter 7 with a cover as shown in FIG.

  As another embodiment, as shown in FIG. 10, there is one in which covering portions are formed on both the sink 5 and the counter 7.

Here, the usability of this embodiment in which the covering portions are formed on both the sink 5 and the counter 7 will be described.
The user puts tableware or the like on the use surface 6 on the bottom surface side in the sink 5 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 6 on the bottom side is picked up, moved sideways in the sink 5 or placed on the counter 7. At that time, when the tableware is rubbed against the use surface 6 or the counter 7 on the bottom side, scratches may occur, but in this embodiment, the use surface 6 on the bottom side and the counter 7 Since the coating | coated part 2 is formed, a damage | wound does not generate | occur | produce and the designability of a base material is maintained.

  Subsequently, the composite material in which the ductile base material is a sink and the covering portion is formed on the entire bottom surface portion shown in FIG. 7 will be described with a specific example.

(Example 7)
The same substrate as in Example 1 was used. After the base material was drawn into a sink shape, the base material surface was thoroughly washed, and the same coating liquid as in Example 2 was spray coated, and then heated at 250 ° C. for 60 minutes, and the ductile base material was a sink. The composite material characterized by having a coating | coated part in the whole surface of the bottom face part shown in FIG.

(Example 8)
The same substrate as in Example 1 was used. The substrate surface was washed thoroughly and spray-coated with the same coating liquid as in Example 2. After heating at 250 ° C. for 60 minutes, the substrate was drawn into a sink shape, and the ductile substrate was a sink. The composite material characterized by having a coating | coated part in the whole surface of the bottom face part shown in FIG.

(Comparative Example 8)
A commercially available stainless steel sink was used as a comparative example.

(Evaluation methods)
(1) Appearance The appearance of the composite material was visually evaluated.
Judgment criteria ○: The design property of the base material is completely maintained. △: The design property of the base material is slightly lowered, but the design of the base material can be confirmed. ×: The design property of the base material is remarkably impaired. The design of the base material cannot be confirmed. (2) Evaluation of the maintainability of the design property of the base material when an external force is applied After the clay pot is reciprocated 100 times and 400 times in the sink, the design change of the base material is changed. Judgment was made visually.
Judgment criteria ◎: No flaws and no change in design properties ○: Although fine flaws occur, the design properties are maintained △: Scratches occur and the design properties are slightly lowered ×: Remarkably flaws are generated, and the design properties are remarkably increased (3) Evaluation of change in covering portion when heavy object is dropped The presence or absence of peeling or dropping of the covering portion when a 300 g iron ball is dropped from a height of 20 cm was visually determined.
Judgment criteria ○: No change Δ: Partially peeled or dropped ×: Completely peeled off or dropped (4) Evaluation of changes in the covered portion due to repeated hot water and cold water 90 ° C hot water for 1 minute, 20 The presence or absence of peeling and dropping off of the coating after 1000 minutes of spraying of cold water at 1 ° C. was repeated 1000 times.
Judgment criteria ○: No change △: Partially peeled off or dropped out ×: Completely peeled off or dropped out of cover

(Evaluation results)
The evaluation results are shown in Table 11.

As is apparent from Table 11, in Examples 7 and 8 of the present invention, the design properties of the base material were completely maintained even after the covering portion was formed.
In Examples 7 and 8 of the present invention, even when the earthenware pot was slid back and forth 400 times, no scratch was generated and the design was not changed.
In the stainless steel sink of Comparative Example 8, the scratches were remarkably generated and the designability was significantly impaired.
Moreover, although a ductile base material deform | transformed by heavy-weight fall, the change to a coating | coated part was not seen but the followability to a base material was confirmed.
Moreover, although the ductile base material repeated expansion and contraction intermittently by repeated hot water and cold water, no change was observed in the covering portion, and followability to the base material was confirmed.

It is sectional drawing of the composite material of this invention. It is sectional drawing of the composite material of this invention. It is sectional drawing of the composite material of this invention. It is the surface observation photograph of the coating part of the composite material of Example 2 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. It is the schematic of the counter which provided the composite material in a part of bottom face part of this invention. It is the schematic of the counter provided with the composite material in the bottom face whole surface of the present invention. It is the schematic of the sink and counter which provided the composite material in the whole surface of the sink and the counter of this invention.

Explanation of symbols

1: Ductile base material 2: Covering part 3: Three-dimensional network structure 4: Fluorine resin particle 5: Sink 6: Use surface 7: Counter 8: Water tap 9: Drain port

Claims (21)

A base material and a coating portion provided on the base material, wherein the coating portion is (A) silica or an average composition formula R _p SiO _{(4-p) / 2} (wherein R is hydrogen) An atom, a fluorine atom or a monovalent organic group, p is a number satisfying 0 <p <4), (B) a fluorine resin particle, and (C) a Zr element-containing compound. and also contains the a fluorine content in the coating of the resin particles is less than 1 wt% or more and 20 wt%, the weight ratio of said (a) wherein the (C) is, said terms of SiO ₂ (a The composite material is characterized in that the weight part of the component (C) in terms of ZrO ₂ is 0.5 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the component. The film thickness of the said coating | coated part is 0.3-20 micrometers, The composite material of Claim 1 characterized by the above-mentioned. The film thickness of the said coating | coated part is 0.3-8 micrometers, The composite material of Claim 2 characterized by the above-mentioned. The composite material according to any one of claims 1 to 3, wherein an average particle diameter of the fluororesin particles is 0.1 to 20 µm. The composite material according to claim 4, wherein an average particle diameter of the fluororesin particles is 0.1 to 8 μm. The composite material according to claim 1, wherein the covering portion is substantially transparent. The composite material according to claim 1, wherein the base material is a ductile base material. The composite material according to claim 7, wherein the ductile base material is stainless steel or aluminum. The composite according to claim 7 or 8, wherein the ductile substrate is a sink and / or a counter, and the covering portion is provided on a part of at least a use surface side of the sink and / or the counter. Wood. Fluorine resin particles and (D) a compound represented by the following structural formula [— (SiR1R2) — (NR3) —] _n (wherein R1, R2, R3 are each independently a hydrogen atom, an alkyl group, 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, n is an integer), E) a coating solution containing a Zr element-containing compound, applied to a substrate, and cured by heating to form a coating portion on the substrate, wherein the content of the fluororesin particles is 1 wt. % And less than 20% by weight, and the weight ratio of (D) and (E) is 100 parts by weight of the (D) component in terms of SiO ₂ , and the component (E) in terms of ZrO ₂ The weight ratio of 0.5 is A coating liquid characterized by being no less than 20 parts by weight and no more than 20 parts by weight. The coating liquid according to claim 10, wherein an average particle diameter of the fluororesin particles is 0.1 to 20 μm. The coating liquid according to claim 11, wherein an average particle diameter of the fluororesin particles is 0.1 to 8 μm. Fluororesin particles and (F) (F-1) a compound represented by the following general formula (1), R _a Si (OR ₄ ) _4-a (1) (wherein R is a hydrogen atom, A fluorine atom or a monovalent organic group, R4 is a monovalent organic group, a is an integer of 1 to 2.) (F-2) A compound represented by the following general formula (2) and Si (OR5) ₄ (2) (wherein R5 represents a monovalent organic group.) (F-3) Compound represented by the following general formula (3) R6 _b (R7O) _3-b Si— ( _{R10) d -Si (OR8) 3} -c R9 c ····· (3) wherein, R6 ~R9 each a monovalent organic group, b-c is an integer of 0 to 2, R10 represents an oxygen atom , A phenylene group or a group represented by — (CH ₂ ) _m — (wherein m is an integer of 1 to 6), d represents 0 or 1. ] It contains at least one compound selected from the group of the above, or a hydrolyzate thereof, and (E) a Zr element-containing compound. A coating liquid for forming a coating portion, wherein the content of the fluororesin particles is 1% by weight or more and less than 20% by weight, and the weight ratio of (F) and (E) is the SiO ₂ equivalent (F) the component of the weight portion 100, a coating liquid wherein the terms of ZrO ₂ (E) the weight ratio of the components is equal to or less than 20 parts by weight or more 0.5 part by weight. The coating liquid according to claim 13, wherein the fluororesin particles have an average particle size of 0.1 to 20 μm. The coating liquid according to claim 14, wherein the fluororesin particles have an average particle size of 0.1 to 8 μm. After apply | coating the coating liquid of any one of Claims 10 thru | or 12 to a base material, the said coating liquid is hardened by heating the whole base material, (A) Silica or an average composition on a base material. At least selected from the group of the formula R _p SiO _{(4-p) / 2} wherein R is a hydrogen atom, a fluorine atom or a monovalent organic group, and p is a number satisfying 0 <p <4. A method for producing a composite material comprising forming a coating portion containing one type, (B) fluorine resin particles, and (C) a Zr element-containing compound. To a substrate, after applying the coating liquid according to any one of claims 13 to 15, is cured by heating the coating liquid, onto a substrate, (A) silica or average composition formula R _p, At least one selected from the group of SiO 2 _{(4-p) / 2} (wherein R is a hydrogen atom, a fluorine atom or a monovalent organic group, and p is a number satisfying 0 <p <4), (B) The manufacturing method of the composite material characterized by forming the coating | coated part containing a fluororesin particle and (C) Zr element containing compound. After the ductile base material is drawn into a sink and / or counter shape, the coating liquid according to any one of claims 10 to 12 is applied to the ductile base material, and the whole base material is heated to apply the coating liquid. A method for producing a composite material, characterized by curing. After the ductile base material is drawn into a sink and / or counter shape, the coating liquid according to any one of claims 13 to 15 is applied to the ductile base material, and the coating liquid is cured by heating. A method for producing a composite material characterized by the above. Applying the coating liquid according to any one of claims 10 to 12 to a ductile base material, curing the coating liquid by heating the whole base material, and then drawing into a sink and / or counter shape. A method for manufacturing a composite material. The coating liquid according to any one of claims 13 to 15 is applied to a ductile substrate, the coating liquid is cured by heating, and then drawn into a sink and / or counter shape. A method of manufacturing a composite material.

Images