JP2003183016A - Method for producing silica-coated molded product, and silica-coated molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silica-coated molded product which is suitable for the use in the plumbing of housing equipment, to which dirt hardly attaches (dirt- proof properties), and from which dirt attached thereto is easily cleaned (easiness of cleaning). <P>SOLUTION: This silica-coated molded product is prepared by coating a substrate with a silane coupling agent to form a solid film, then coating the solid film with a polysilazane-containing solution, and heating thus coated substrate (two-liquid, two-bake) or by coating a substrate with a solution containing both a polysilazane and a silane coupling agent without coating with a silane coupling agent alone and then heating the coated substrate (one-liquid, one-bake). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to equipment for housing equipment around water such as bathtubs, washing areas (waterproof pans) and washbasins.
The present invention relates to a method for producing a silica film-coated molded article that can be suitably used for equipment and a silica film-coated molded article obtained by the production method.

[0002]

2. Description of the Related Art Since resin molded products are lightweight and suitable for mass production, housing equipment such as bathtubs, bathtub aprons, washrooms (waterproof pans), bathroom walls, washbasins, washroom counters, dishes, wall materials, flooring materials, etc. In addition to equipment (or building materials), it is widely used in a wide range of product fields such as automobile parts and electric / electronic parts. On the other hand, resin moldings have the drawback that they are easily soiled and difficult to remove (contamination / difficulty cleaning) and that they are inferior in heat resistance and abrasion resistance. Therefore, in order to improve these properties, resin moldings There are several known methods for forming a film of an inorganic oxide (such as a silica film) on the surface.

In the field of housing equipment, a method for forming a layer containing photocatalyst particles such as anatase type titanium oxide on the surface of a resin molding around water, for example, the surface of a bath to make the surface of the bath hydrophilic (Japanese Patent Laid-Open No. 10-225393). No. gazette) is known.

Further, in the field of electric / electronic parts, when inorganic polysilazane is applied to the surface of resin and heat-treated at 100 to 200 ° C. to form a cured film (or the applied material is subjected to electron beam treatment to form a cured film). The heat resistance of the resin molding.
It is known to improve wear resistance and chemical resistance (Japanese Patent Laid-Open No. 8-143689 / Japanese Patent No. 313641).
No. 2). In addition, when a coating composition containing a glycidol-added polysilazane obtained by reacting polysilazane and glycidol with heating is applied onto a substrate and baked at 50 ° C. or higher, or kept at less than 50 ° C., heat resistance It is also known that a ceramic film having excellent wear resistance and corrosion resistance can be obtained (JP-A-6-122852).

[0005]

However, regarding the above-mentioned housing equipment, the method of forming a photocatalyst particle-containing layer of anatase type titanium oxide or the like to hydrophilize the photocatalyst particle-containing layer (membrane ) Has a difficulty in durability. At present, most of the resin moldings around the water of the housing facility such as a bathtub are resin moldings that are not subjected to hydrophilic treatment (that is, do not have a film of inorganic oxide).

[0006] The present invention is a molded article suitable for use in equipment and equipment used around the water of residential equipment. It is difficult for dirt to adhere (anti-contamination) or dirt that adheres is easy to remove (easy cleaning). The present invention provides a method for producing a silica film-coated molded article, and a silica film-coated molded article produced by the method.

[0007]

The surface of a resin molded body, which is an organic polymer, is usually water repellent, and it is necessary to coat the surface with a hydrophilic film in order to make it hydrophilic. However, the combination of a base resin (organic polymer) and a hydrophilic film-forming material (usually an inorganic material) often results in poor adhesion due to the difference in the organic / inorganic nature and physical properties of the two. It is important to solve

The present inventors, in the process of variously studying the hydrophilic film forming material and the film forming conditions for coating the base resin, undercoat a silane coupling agent on the resin base material (resin substrate). After forming a solid film, a layer of a polysilazane-containing liquid is formed on the solid film and then heated to cause a silica conversion reaction (that is, 2 liquids and 2 baking), or a mixed liquid of polysilazane and a silane coupling agent. When a silica conversion reaction is performed using (1 liquid 1 bake), a silica film-coated resin molded product that has high adhesion, hydrophilicity and stain resistance, and is hard and wear-resistant is stable. The present invention has been completed and the present invention has been completed.

That is, according to the method of the present invention, after a silane coupling agent is undercoated on a substrate (substrate) to form a solid film, a layer of a polysilazane-containing solution (varnish) is formed on the solid film and silica conversion is performed. It is a method for producing a silica film-covered molded product (2 liquid, 2 bake), which is characterized by performing a reaction treatment.

A liquid (varnish) containing both a polysilazane and a silane coupling agent is formed in a layer on the base material in advance without undercoating the silane coupling agent on the base material and subjected to a silica conversion reaction treatment. Good (1 liquid 1 bake).

Perhydropolysilazane is preferably used as the polysilazane.

The temperature and time for the above silica conversion reaction treatment are as follows: "SiH absorbance" / "SiO absorbance" (absorbance at 2400 cm ^-1 when the surface of the molded article after the reaction is analyzed by infrared absorption spectroscopy). It is advisable to determine that the ratio of (baseline) is 3.0 or less. Insufficient or excessive treatment (heating and time) can be prevented, and energy can be saved.

The temperature of the above silica conversion reaction treatment is preferably 100 to 200 ° C., more preferably 120 to 170 ° C., in order to accelerate the reaction.

The present invention also provides a silica film-coated molded product manufactured by the above-mentioned manufacturing method, wherein the surface of the molded product is any one or more of the following (a) to (f) (preferably:
It also relates to a silica film-coated molded product having the characteristics of (all items). (A) Contact angle with water: 50 ° or less (b) When the surface is analyzed by infrared absorption spectroscopy,
"Absorbance of SiH" / "Absorbance of SiO" (2400c
Ratio of the absorbance at m ⁻¹ as a baseline): 3.
0 or less. The smaller this ratio is, the more the silica conversion is advanced. (C) Abrasion resistance: 1,000 times or more (d) Adhesion: "No peeling" when tested by the tape test method (e) Surface hardness: 3H or more as pencil strength (f) Hot water resistance: 50h or more Each test method will be described later.

The silica-coated molded article can be preferably applied to equipment / equipment (or building material) for housing equipment.

The present invention also discloses a method of evaluating a silica film when a polysilazane-containing liquid is subjected to a silica conversion reaction to form a silica film (a film containing silica as a main component, which contains crosslinked polysilazane). "SiH absorbance" / "SiO absorbance" measured by infrared absorption spectroscopy
The ratio (Z) of (the absorbance at 2400 cm ⁻¹ is the baseline) is evaluated as an index of the degree of silica conversion.

As the infrared absorption spectrum method, a general KBr method can be used, but an attenuated total reflection (ATR) infrared absorption spectrum method is preferable. This is because the silica film formed on the surface of the base material can be directly analyzed.

[0018]

[Function] The silane coupling agent, which is an undercoat on the surface of the base material that is an organic polymer, has an affinity for the base material because it contains an organic functional group. It is thought to act as a material (which improves the adhesion to the inorganic components of the material). Also, when a liquid (varnish) containing both polysilazane and a silane coupling agent is applied onto a substrate instead of undercoating the silane coupling agent, the silane coupling agent has the same action as the "primer". it seems to do. Therefore, as compared with the case of using a polysilazane solution containing no silane coupling agent, the adhesiveness (particularly, the adhesiveness evaluated by hot water resistance) is excellent.

When the polysilazane applied as a layer on the surface of the base material is heated in an oxidizing atmosphere in the presence of a curing agent and / or a catalyst, the crosslinking reaction proceeds and oxygen replaces the nitrogen atoms in the network. Atoms are taken in and converted to silica with an increase in weight (silica conversion reaction).
Shrinkage during the silica conversion reaction is smaller than that in the silica conversion such as the sol-gel method, and cracks are less likely to occur. It is easy to form a relatively thick film.

Furthermore, since the highly hydrophilic silica film is formed in close contact with the surface of the molded product produced by the present invention, the contact angle with water is higher than that of the surface of the molded product without the silica film. Small and naturally highly hydrophilic. That is, greasy dirt, soap residue (metal soap), etc. are unlikely to adhere to the surface of the silica film-coated molded article of the present invention, and even if they do, they can be easily washed off with water. That is, the stain resistance (easy cleaning) is high.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Base material (substrate) used in the present invention
Examples of the resin include polypropylene, polyethylene, polycarbonate, polyimide, polyethylene terephthalate, nylon, acrylic, polyvinyl chloride, polystyrene, unsaturated polyester, epoxy, polyurethane, phenolic resin and ABS resin. It may be a resin (or molded body) obtained by reaction injection molding using dicyclopentadiene as a raw material. Further, a resin (or a molded body) which is press-molded using a molding die (mostly made of metal) using a plastic molding material such as SMC or BMC may be used. In addition to resins, organic polymer materials such as wood can also be used.
Considering that the base material may be heated to accelerate the reaction after the layer of the polysilazane-containing liquid is formed on the surface, a material capable of withstanding the heating is preferable. The softening point of the resin is preferably 100 ° C. or higher (more preferably 130 ° C. or higher).

The polysilazane-containing liquid used in the present invention is a liquid substance (varnish) containing polysilazane. Here, the polysilazane is an oligomer or polymer having the repeating unit of the following chemical formula 1, and may be a cyclic polysilazane, a chain polysilazane, or a polysilazane having both a cyclic structure and a chain structure.

[0023]

[Chemical 1]

In the chemical formula 1, R represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, an alkoxy group or the like, and three Rs are the same or different. Good.

One of the preferable polysilazanes is that R in the above chemical formula 1 is all hydrogen atoms, has a chain portion and a cyclic portion in the molecule, and has a molecular weight (number average molecular weight) of 100 to 100.
It is 50,000 perhydropolysilazane.

Further, the above polysilazane is added to a tertiary amine such as a trialkylamine, a secondary amine having a sterically hindering substituent, or a basic solvent such as phosphine,
Alternatively, a molecular weight of 200 to 50 obtained by performing a dehydrogenative condensation reaction in a solvent of non-basic hydrocarbons
Those of 10,000 can also be used.

Alternatively, it is obtained by a modification reaction of inorganic polysilazane, and has a cross-linking bond —NH— or —NH—N.
H-, N / Si ratio of 0.8 or more molecular weight 200 ~
Those of 50,000 can also be used. The composition formula is (RSiH
NH) _X [(RSiH) _1.5 N] _Y (where R is as defined in Chemical Formula 1, Y is 1-X, and 0.4 <
X <1. ) Polyorganohydrosilazane represented by

Further, polysiloxazane containing oxygen, polymetallosilazane obtained by reacting a metal alkoxide, or polyborosilazane obtained by reacting an organic boron compound can be used. The above-mentioned various polysilazanes are usually liquid or solid at room temperature.

The polysilazane used in the present invention is
In terms of adhesion to the base material, a material having a high ratio of active hydrogen atoms bonded to silicon or nitrogen is preferable. The number of active hydrogen atoms is preferably 90 or more, and more preferably 100 to 1 with respect to the total number of silicon atoms and nitrogen atoms of 100.
50 (150 for perhydropolysilazane).

The polysilazane may include organic amine, carboxylic acid anhydride, isocyanate, thiol,
A curing agent such as carbodiimide, metal alkoxide, metal halide or the like can be added. In order to convert silica at a low temperature, it is possible to use a catalyst such as nickel, platinum, palladium, aluminum and amines. Further, if necessary, metal powder, ceramic powder, defoaming agent, surfactant, ultraviolet absorber, leveling agent, antistatic agent, dispersant, pigment, thixotropic agent, etc. may be added.

The silane coupling agent used in the present invention is
It is a compound represented by the general formula XSiQ ₃ . Where X
Is a functional group capable of reacting with an organic group, and Q is a hydrolyzable functional group. More specifically, X is a vinyl group, a methacryloxy group, an epoxy group, an amino group, an isocyanate group, a mercapto group, or a halogen, and Q is an alkoxy group such as a methoxy group or an ethoxy group, or a halogen. . Some of these are commercially available. Appropriately select and use.

The amount of the silane coupling agent used may be determined in consideration of its "primer" action. The (final) ratio of silane coupling agent / polysilazane is preferably 10/90 to 90/10 (weight ratio).

When the silane coupling agent is used as the "primer" for the undercoat, it is diluted with an alcohol such as methanol, ethanol, propanol or butanol to about 0.1 to 50% by weight. This is applied on the base material and 70 to 1
A film (base film) is formed by heating at a temperature of about 30 ° C. for 5 to 20 minutes.

Next, a polysilazane (varnish) containing a curing agent and / or a catalyst is appropriately diluted with a solvent and coated on a substrate. At this time, the thickness of the polysilazane layer is set within a range that does not impair stain resistance, abrasion resistance, and hot water resistance. The thickness of the coated solid film is preferably 0.5 μm to 5.0.
μm, and more preferably 1.0 μm to 2.0 μm. If the film thickness is too thin, the wear resistance tends to decrease, and if it is too thick, cracks tend to occur.

Examples of the polysilazane diluting solvent include an aliphatic hydrocarbon solvent, a halogenated hydrocarbon solvent, an alicyclic hydrocarbon solvent, an aromatic hydrocarbon solvent and an ether solvent, which may be used alone or Use a mixture of two or more.

Next, a silica film is formed by heating in an oxidizing atmosphere (air may be used) for a predetermined time. The heating temperature and the heating time at this time are, as described above, the "absorbance of SiH" when the surface of the molded body is analyzed by the infrared absorption spectrum method.
The ratio of "/ absorbance of SiO" (based on the absorbance at 2400 cm ^-1 ) can be determined to be 3.0 or less, and workability and melting point (or decomposition point) of the base resin can be determined. Etc. can be taken into consideration when deciding. When the base material is SMC (polyester resin), preferably 1
The temperature is from 00 to 200 ° C, more preferably from 120 to 170 ° C. The heating time is preferably about 30 minutes to 2 hours. By this treatment, a silica film (a film containing silica as a main component, including a crosslinked polysilazane film) is formed. In addition,
In order to increase the hydrophilicity of the coated surface, it may be further treated with weak alkaline water (pH 9 to 12) or hot water (however, bath tubs for bathrooms, waterproof pans, etc. should be treated with hot water at the time of use). I'm not exposed to this, so I don't dare to do this).

The silane coupling agent or the polysilazane-containing liquid can be coated by a known method such as spray coating, spin coating, dip coating or flow coating.

Instead of undercoating the substrate with the silane coupling agent, a liquid (varnish) containing both the polysilazane and the silane coupling agent is formed in a layer on the substrate and heated to cause a silica conversion reaction. Good (1 liquid 1 bake). In this case, the ratio of polysilazane and silane coupling agent is 10/90 to 90/10 (weight ratio).
The mixed liquid is used so that the mixed liquid is diluted to a concentration of about 0.1 to 50% by weight with a solvent.

This mixed solution is applied to a base material and heated. The temperature and time at this time are the same as the above-mentioned conditions.

The treatment temperature after applying the silane coupling agent, the treatment temperature after applying the polysilazane-containing solution thereafter, or the treatment temperature after applying the mixed solution of the silane coupling agent and polysilazane is room temperature (0 -30 ° C). It is also possible to use a suitable temperature between 30 and 100 ° C. In the silica conversion reaction, the lower the treatment temperature is, the longer the time (days) is required for the silica conversion reaction. In other words, the ratio (Z) of “SiH absorbance” / “SiO absorbance” measured by infrared absorption spectroscopy. Is required to be 3.0 or less, but it is particularly effective in the case of bathroom reforming or the like that the silica conversion reaction can be performed at less than 100 ° C.

FIG. 1 shows that 5% polysilazane NP-1 was used as the base material.
It is a chart which shows the change of the infrared absorption spectrum when 00 (xylene solvent) (made by Clariant Japan Co., Ltd.) is coated and left at room temperature (4 h and 96 h). With the passage of time at room temperature, the absorbance of SiH decreases and the absorbance of SiO increases, so
It can be seen from this chart that the silica conversion proceeds while the ratio (Z) of "absorbance of SiH" / "absorbance of SiO" decreases.

Thus, a molded article coated with the hydrophilic silica film is obtained. The use of the silica film-coated molded article is as follows:
Bathtub, bathtub apron, wash floor (waterproof pan), bathroom wall,
There are household equipment and equipment (or building materials) such as wash bowls, wash counters, kitchen counters, kitchen cabinet components, tableware, wall materials and floor materials. In addition, it can be applied to automobile parts.

Applications include bathtubs, bathtub aprons, wash floors (waterproof pans), bathroom walls such as bathroom walls, kitchen counters,
When the main purpose is to add antifouling functions to household equipment and equipment around water such as washbasins, by making the surface of the coating film highly hydrophilic, it is possible to remove soap residue, oil stains, etc. Greatly improve.

[0044]

The present invention will be described in more detail with reference to the following examples. The base material (molded plate) is an SMC molded plate using an unsaturated polyester resin, and each evaluation method is as follows. In the text,% means% by weight unless otherwise specified. <Contact angle with water> Kyowa Interface Science Co., Ltd. contact angle meter "G
A-X150 type "was used. The smaller the contact angle, the higher the hydrophilicity of the surface of the plastic molded product.

<Abrasion resistance> Using a commercially available sponge (urethane) with a net for a bath, a dry load was applied with a load of 49 N, and the film was abraded, and the presence or absence of peeling of the film after abrasion was checked. Fifty,
100, 200, 300, 400, 500, 1000
(Times), after every 500 times, visually check 10,000 times
Went up to times.

<Adhesion> The tape test method (JIS-K-5400) evaluated. ◯: No peeling Δ: 0 to 10 ×: 10 or more

<Surface hardness> Pencil hardness (JIS-K-54
It evaluated by 00). <Hard coat property (HC property)> Hard coat property (HC property
Property) uses steel wool at a pressure of 10 kPa for 10
0 reciprocating rubbing, evaluated by the number of scratches after rubbing ○: 0 to 2 △: 3 to 10 ×: 10 or more

<Anti-fouling property> When sodium laurate is dissolved in warm water and calcium chloride is added, fatty acid calcium (scum) similar to soap dregs is produced. The test piece was put into and taken out of the cup in which the scum was floated 10 times, the scum was forcibly adhered to the surface of the test piece, and then the stain and gloss when washed off with a shower were visually observed. ◯: Almost no (dirt) Δ: A little left ×: Most left

<Hot water resistance> The test piece was completely immersed in distilled water at 80 ° C., taken out every 4 hours, and taken out and rubbed with a wet paper towel 20 times with a force of about 20 N to check the appearance and the contact angle (contact). The test is continued if the angle is less than 50 ° as passing. Time to deteriorate appearance or contact angle with water is 50 °
The above time was evaluated as hot water resistance.

<Infrared absorption spectrum> Attenuated total reflection (A
TR) Measured by infrared absorption spectroscopy.

Example 1 (pretreatment with silane coupling agent + coating with polysilazane; 2 liquid / 2 bake) 5% silane coupling agent A-1100 (isopropyl alcohol solution) (Nihon Unicar Co., Ltd.) (Made by the company) is applied with a spray coat, and 100
It was dried in a drying oven at 0 ° C for 10 minutes. Next, 5% of polysilazane NL-110 (xylene solvent) (manufactured by Clariant Japan Co., Ltd.) was applied by spray coating, and 14
It was dried (crosslinked) for 60 minutes in a drying oven at 0 ° C. afterwards,
It was treated with a 0.02% aqueous sodium hydroxide solution. Regarding the properties of the formed film (Table 1), the contact angle with water is 25.
At o, the abrasion resistance, the adhesion, the pencil hardness, the stainproofing property and the drying property were good, and the hot water resistance did not peel the film up to 100 hours.

Example 2 (Application of mixed solution of polysilazane + silane coupling agent; 1 liquid 1 bake) 5% polysilazane NL-110 (xylene solvent) (Clariant Japan KK) and 2% silane coupling agent A mixed solution (xylene solvent) with A-1100 was used as a coating material. This was spray-coated on a substrate that had been degreased in advance, and dried (crosslinked) for 60 minutes in a drying oven at 140 ° C. Then, it was treated with a 0.02% aqueous sodium hydroxide solution. Regarding the properties of the formed film (Table 1), the contact angle with water is 35 °, abrasion resistance, adhesion, pencil hardness, stain resistance and dryness are good, and hot water resistance is 1
There was no peeling of the film until 00 hours.

Comparative Example 1 (Coating with polysilazane; 1 liquid, 1 bake) 5% polysilazane NL-1 was applied to a substrate that had been degreased in advance.
10 (xylene solvent) (manufactured by Clariant Japan Co., Ltd.) was applied by spray coating, and then dried (crosslinked) in a drying oven at 140 ° C. for 60 minutes. Then, it was treated with a 0.02% aqueous sodium hydroxide solution. Regarding the properties of the formed film (Table 1), the contact angle with water is 25 °, wear resistance,
Adhesion, pencil hardness, stain resistance and dryness were good. In the hot water resistance test (total immersion in distilled water at 80 ° C.), no peeling of the film was observed for up to 20 hours, which was inferior to Examples 1 and 2.

Comparative Example 2 For comparison, the properties of the substrate alone (without silica film) are also shown in Table 1.

[0055]

[Table 1] Item Example 1 Example 2 Comparative Example 1 Comparative Example 2 Contact angle with water 25 35 25 75 Abrasion resistance> 10,000 times> 10,000 times> 10,000 times-Adhesion ○ ○ ○ -Pencil hardness 3-4H 3-4H 3-4H 2H Contamination resistance ○ ○ ○ × Hot water resistance 100h 100h 20h-

Experimental Examples 1 to 95 Using 5% of polysilazane NL-110 (xylene solvent) or polysilazane NP-110 (xylene solvent) (both manufactured by Clariant Japan Co., Ltd.), this was degreased as a base material. It was applied by spray coating and treated under various temperature conditions and times (days) to prepare various silica film-coated molded products (film thickness 1.0 to 2.0 μm). The relationship between the ratio (Z) of “absorbance of SiH” / “absorbance of SiO” when measured by an attenuated total reflection (ATR) infrared absorption spectrum method on this surface, and antifouling property, adhesion and hard coat property Examined.

No. 1: 5% of polysilazane NP-110 (xylene solvent) was applied by spray coating to a base material that had been degreased in advance, and then left for 1 hour in an environment of 30 ° C. and 50% RH (relative humidity). No. 2: In addition to the above-mentioned No. 2 except that the time (days) after application was left for 4 days. Same as 1. No. 3: Other than leaving for 10 days after application for 10 days. Same as 1. No. 4: No. 4 except that the heating temperature after coating was 120 ° C. and the heating time (leaving time) was 10 minutes. Same as 1.

No. 5: 5% of polysilazane NL-110 (xylene solvent) was applied by spray coating to the base material that had been degreased in advance, and then 2 in an environment of 30 ° C. and 50% RH.
It was left for 4 hours. No. 6: After application (2 at 30 ° C, 50% RH environment
Instead of leaving for 4 hours) heating temperature at 140 ° C, 60
Heated for minutes. Others are the above No. Same as 5. No. 7: After coating, the coating was heated at a temperature of 140 ° C. for 60 minutes and then left standing in an environment of 30 ° C. and 50% RH for 7 days. Others are the above No. Same as 5.

No. 8: 5% polysilazane NP-110 (xylene solvent) was applied by spray coating to the base material that had been degreased in advance, and then 1 at 30 ° C. and 50% RH.
It was left for 0 minutes. No. 9: 5% polysilazane N on the base material which was previously degreased
L-110 (xylene solvent) was applied by spray coating and then left in an environment of 30 ° C. and 50% RH for 10 minutes.

[0060]

[Table 2] Item Experimental example 1 Experimental example 2 Experimental example 3 Experimental example 4 Ratio (Z) 0.85 0.15 0.09 0.14 Contamination resistance ○ ○ ○ ○ Adhesion × ○ ○ ○ HC property × △ ○ ○

[0061]

[Table 3] Item Experimental example 5 Experimental example 6 Experimental example 7 Experimental example 8 Experimental example 9 Ratio (Z) 2.8 0.42 0.04 3.5 4.0 Antifouling property ○ ○ ○ × × Adhesion △ ○ ○ × × HC property × ○ ○ × ×

The results of this experiment show that the ratio (Z) is preferably 3.0 or less, more preferably 0.7 or less, depending on the type of polysilazane.

[0063]

EFFECTS OF THE INVENTION According to the present invention, a molded product such as a resin molded product used around the water of a residential facility is less likely to be soiled (anti-staining property) or is easily removed (easy cleaning property). A silica film-covered molded product can be easily manufactured. In addition, the processing temperature for the silica conversion reaction is room temperature (0 to 30 ° C).
It is also possible to use a suitable temperature between 30 and 100 ° C. In this case, the lower the treatment temperature is, the longer the time (days) is required for the silica conversion reaction, but this is an effective method in the case of bathroom reforming and the like.

Since the silica film-coated molded product of the present invention is coated with the hydrophilic silica film, the contact angle with water is 50 °.
It can be: Therefore, even if dirt such as greasy dirt or soap residue is attached, it can be easily removed by simply rinsing it with water, and it has excellent stain resistance. Further, even if water adheres to the surface, the droplets spread due to its hydrophilic property, and the surface easily dries quickly. The silica film has excellent adhesion, hot water resistance, abrasion resistance, and hard coat properties.

According to the silica film evaluation method disclosed in the present invention, it is possible to easily set the conditions for producing a film having an optimum degree of silica conversion, and to omit excessive treatment (heating and time). The type of base material can be selected from many materials.

[Brief description of drawings]

FIG. 1 is a chart of an infrared absorption spectrum when a substrate is coated with polysilazane and left at room temperature (4 h and 96 h).

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08J 7/04 CER C08J 7/04 CERE CEZ CEZ C09D 1/00 C09D 1/00 183/16 183/16 / / C08L 101: 00 C08L 101: 00 F term (reference) 4D075 AE15 BB26Y BB26Z BB93Z BB95Z CA02 CA13 CA18 CA33 CA37 CA38 CA44 DA06 DB21 DB35 DB36 DB37 DB38 DB43 DB46 DB47 DB48 DB49 DB50 DB53 DB61 DC02 DC13 DC18 DC45 EA07 EB42 EB42 EB07 4F006 AA11 AA31 AB39 AB67 BA01 BA10 DA05 EA05 4F100 AA20C AB11B AR00B AT00A BA03 BA07 BA10A BA10C GB08 JK09 JK12 JL06 JL11B YY00C 4G072 AA25 BB09 GG03 HH28 MM01 RR12 4J038 AA011 DL172 HA441 JC32 JC34 JC35 JC36 KA03 NA04 NA05 NA06 NA11 NA12 NA14 PA11 PA18 PA19 PB02 PB05 PB06

Claims (10)

[Claims] 1. A method for producing a silica film-covered molded product, comprising forming a solid film by undercoating a silane coupling agent on a substrate, forming a layer of a polysilazane-containing liquid on the solid film, and subjecting the layer to a silica conversion reaction. . 2. The production method according to claim 1, wherein perhydropolysilazane is used as polysilazane. 3. The temperature and time of the silica conversion reaction are such that the ratio of "absorbance of SiH" / "absorbance of SiO" when the surface of the molded article after the reaction is analyzed by infrared absorption spectroscopy is 3.
The manufacturing method according to claim 1 or 2, wherein the manufacturing method is determined to be 0 or less. 4. The temperature of the silica conversion reaction is 100 to 200 ° C.
The method according to any one of claims 1 to 3, wherein 5. A layer of a liquid containing polysilazane and a silane coupling agent is formed on a substrate, and a silica conversion reaction is performed.
A method for producing a silica film-coated molded product. 6. The method according to claim 5, wherein perhydropolysilazane is used as polysilazane. 7. The temperature and time of the silica conversion reaction are such that the ratio of "absorbance of SiH" / "absorbance of SiO" when the surface of the molded article after the reaction is analyzed by infrared absorption spectroscopy is 3.
The manufacturing method according to claim 5 or 6, which is determined so as to be 0 or less. 8. The reaction temperature of the silica conversion reaction is 100 to 20.
The method according to any one of claims 5 to 7, which is 0 ° C. 9. A silica film-coated molded article produced by the method according to any one of claims 1 to 8, the surface of which has one or more of the following characteristics (a) to (f). A silica film-coated molded article having the same. (A) Contact angle with water: 50 ° or less (b) When the surface is analyzed by infrared absorption spectroscopy,
"Absorbance of SiH" / "Absorbance of SiO" (2400c
Ratio of the absorbance at m ⁻¹ as a baseline): 3.
0 or less (c) Abrasion resistance: 1,000 times or more (d) Adhesion: "No peeling" when tested by the tape test method (e) Surface hardness: 3H or more as pencil strength (f) Hot water resistance: 50h or more 10. A silica-coated molded article according to claim 9, wherein:
Silica film coated molding for housing equipment and equipment.