JP2003306087A - Antifouling vehicle interior material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antifouling treatment making it hard for odor and contamination to attach to a vehicle interior material and, even if the odor and contamination are adhered thereto, capable of rather easily eliminating the odor and contamination, in the interior material of cars and electric cars. <P>SOLUTION: In this interior material of vehicles, a hydrophilic treatment is applied to the surface of the interior material, and an antifouling agent layer is painted on the hydrophilic-treated surface. The hydrophilic treatment is first applied to the interior material, and an intermediate layer formed of amorphous titanium peroxide without a photocatalyst or, the case may be, a mixture with the amorphous titanium peroxide and an antifouling agent layer formed of a photocatalyst body having a water system photocatalyst function which is an anatase titanium oxide having a photocatalyst function are formed. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to interior materials (dashboards, doors, armrests, seats, etc.) of automobiles, trains, etc. (hereinafter referred to as vehicles) and their antifouling technology.

[0002]

2. Description of the Related Art Tobacco smoke produces odors and stains on vehicle interior materials and stains such as hand marks after long-term use. The removal of these stains is extremely time-consuming, and it is difficult to simply wipe them off with a cloth. Depending on the type and degree of stains, you can use water wipes, detergents, etc., but this also does not completely remove the stains. It was In particular, the odor cannot be easily removed, and it is necessary to use a deodorant or the like together with a means for removing stains.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been invented in view of such conventional techniques, and it is difficult for odors and stains to be attached to vehicle interior materials, and even if these are attached, odors can be relatively easily generated. The present invention provides an antifouling treatment capable of removing dirt.

[0004]

An object of the present invention is to provide an interior material for a vehicle or the like, wherein the surface of the interior material is subjected to hydrophilic treatment, and an antifouling agent layer is applied on the hydrophilic treated surface. The vehicle interior material is an antifouling vehicle interior material in which the vehicle interior material is a plastic selected from PP, PE, vinyl chloride, and acrylic resin. The antifouling agent layer is a photocatalyst having an aqueous photocatalytic ability, such as anatase type titanium oxide having photocatalytic ability, and may contain amorphous titanium peroxide. An intermediate layer is provided between the exposed surface and the antifouling agent layer. The intermediate layer is composed of amorphous titanium peroxide having no photocatalytic activity, and may be a mixture with amorphous titanium oxide. Furthermore, the intermediate layer contains a surfactant and / or a hydrophilic agent. It may be.

And, as a hydrophilic treatment means for the exterior material,
Corona discharge treatment, plasma discharge treatment, ultraviolet treatment, ozone treatment, which improves the wetting property and / or reactivity with respect to the antifouling agent layer and the intermediate layer.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be further described below, in which a photocatalyst layer (antifouling agent layer) is formed on the surface of a vehicle interior material, and oxide particles having a photocatalytic activity are brought into contact with the outside air to form an organic substance. A surface layer is formed that provides resolution and hydrophilicity. Therefore, odors and stains (mainly organic substances) attached to the vehicle interior material are decomposed and can be easily removed by wiping with cloth or the like.

It is particularly preferable to form an intermediate layer on the interior material in advance before applying the photocatalyst layer (antifouling agent layer), and the main structure of the intermediate layer is amorphous titanium peroxide TiO ₃ or amorphous titanium oxide. TiO ₂ , which does not have a photocatalytic function, unlike anatase-type titanium oxide and rutile-type titanium oxide, which have photocatalytic activity when photoexcited by ultraviolet rays. Among these amorphous titanium oxides having no photocatalytic function, amorphous titanium peroxide sol using water as a solvent is preferable from the viewpoint of film forming property and the like.

Further, as the surfactant constituting the intermediate layer, there are nonionic surfactants and anionic surfactants, and as the hydrophilic agent, silicon dioxide such as n-methylpyrrolidone and colloidal silica, and siloxane compounds. , Water glass and other silicon oxide containing agents.

As an example of the production of the amorphous titanium peroxide sol for the intermediate layer, for example, an amorphous hydroxide produced by adding an alkali such as sodium hydroxide to an aqueous solution of titanium salt such as titanium tetrachloride TiCl ₄ is used. Titanium Ti
After (OH) ₄ is washed and separated, it is treated with hydrogen peroxide solution to obtain an amorphous titanium peroxide solution. The above amorphous type titanium peroxide sol is in an amorphous state at room temperature and has not yet been crystallized in anatase type titanium oxide, so that it has excellent adhesion, high film-forming property, and can form a uniform and flat thin film, and can be dried. In addition to the property that the film is not soluble in water, it has hydrophilic properties and is stable to the photocatalyst.

A photocatalyst layer is provided on the intermediate layer in order to exhibit an antifouling function. The layer containing a photocatalyst having photocatalytic activity has an excellent hydrophilic function and an antifouling function due to a photocatalyst when irradiated with ultraviolet rays, and an antifouling function due to a photocatalyst cannot be exhibited when not irradiated with ultraviolet rays, but an excellent hydrophilic property. It has the feature of having a function.

Here, the photocatalyst is a conduction electron due to the excitation of electrons in the valence band when irradiated with light having an energy larger than the energy gap between the conduction band and the valence band of the crystal. A substance capable of generating holes. The activated photocatalyst produces active oxygen from moisture and oxygen in the air, and the active oxygen reacts with organic substances and inorganic gas in the air. As the photocatalyst oxide, oxides such as anatase type titanium oxide, rutile type titanium oxide, zinc oxide, tin oxide and nibismuth trioxide are used. Of these, sol-like anatase type titanium oxide TiO ₂ is preferable. This is because the sol-like material forms an extremely smooth surface if the contacting side is hydrophilic.

Therefore, by forming a photocatalyst layer containing a photocatalyst on the surface of the vehicle interior material, the photocatalyst of the photocatalyst layer activated by being photoexcited by sunlight (ultraviolet rays) is mainly an organic substance. The substance is decomposed by reacting with the source or the stain, and this can be easily removed by wiping with water or the like.

As a material for the photocatalyst layer, a photocatalyst containing anatase type titanium oxide or rutile type titanium oxide having a photocatalytic function is used, but an amorphous titanium peroxide sol having no photocatalytic function is used. ,
It may contain a mixture with the above-mentioned photocatalyst having a photocatalytic function.

As the light source used for photoexcitation of the photocatalyst, sunlight can be used as it is. And, in order to make the surface of the base material hydrophilic in response to photoexcitation, the illuminance of the excitation light is 0.00
1 mw / cm ² or more, preferably 0.01 mw / cm ²
More preferably, it is 0.1 mw / cm ² or more.

As for the thicknesses of the intermediate layer and the antifouling agent layer (surface layer), the former (TiO3 protective layer) is
0.02-4.0 μm, preferably 0.1-2.0 μm
m, more preferably 0.2-0.5 μm thick, the latter layer being the anatase TiO 2 layer as a photocatalyst,
0.02-4.0 μm, preferably 0.1-2.0 μm
m, and more preferably 0.3 to 1.0 μm.
If they are too thin, defects such as coating defects such as pinholes are likely to occur, and if they are too thick, defects in appearance due to light interference occur. In addition, Ag and C are added to these layers.
u, a metal such as Zn can be added,
This also brings about an antibacterial effect. Pt,
Platinum group metals such as Pd, Ru, Rh, and R can also be added, and in this case, the redox activity of the photocatalyst is enhanced, resulting in decomposition of stains and decomposition of harmful gas and malodor.

Here, the photocatalyst layer having a hydrophilic property, which is exposed so that the photocatalytic oxide particles are in contact with the outside air, will be described. Basically, the photocatalyst layer is formed by fixing the coating composition to the surface of the intermediate layer. As a method for applying the coating composition, known methods such as a spray method, a dip method, a flow coating method, a roll method, and a brush coating method are adopted.

When the surface of the interior material and the intermediate layer are laminated,
Both must be completely performed, but the surface of the interior material is subjected to corona discharge treatment, ultraviolet treatment, plasma treatment, ozone treatment, etc. to make it hydrophilic, and in particular to the intermediate layer wetting characteristics and / or Alternatively, it is preferable to improve the reactivity.

In order to make the surface hydrophilic by the corona discharge treatment or the like, the contact angle of water is preferably about 10 to 40 degrees. When it is 40 degrees or more, it becomes difficult to repel the aqueous solution applied thereon to obtain a uniform coating film, while when it is 10 degrees or more, the aqueous solution can be sufficiently coated.

Here, the corona discharge treatment will be described. That is,
Corona discharge treatment is performed on the surface of an interior material such as a vehicle, which is an object to be treated. The surface to be treated is usually a resin layer, and highly reactive active groups are generated by the action of electrons or secondary ozone or ultraviolet rays generated by corona discharge.
The wettability and reactivity of the treated surface can be improved.

As shown in FIG. 1, the corona discharge treatment device 20 has a surface 10 to be treated of the interior material (object to be treated) 10.
A first electrode 21 installed close to S and a second electrode installed close to the first electrode 21 on the same side as the first electrode 21 and the workpiece 10. A high-voltage generator 23 including a high-frequency oscillator 23A and a high-voltage transformer 23B is applied between the electrodes 22 and 22 to generate a high-frequency high-frequency voltage to generate corona discharge between the electrodes 21 and 22. Specifically, the first electrode 21 is a roll-shaped covering member 24 that moves while rotating the surface to be processed 10S.
It is composed of a stainless steel rod coated with. or,
The second electrode 22 is composed of a flat plate made of stainless steel, and moves on the surface 10S to be processed while maintaining a predetermined distance from the first electrode 21 as the covering member 24 rotates. Therefore, the corona discharge is generated between the first electrode 21 and the second electrode, and the first electrode 21 and the second electrode are moved along the surface 10S to be processed, Corona discharge treatment can be performed uniformly on 10S. In addition, you may use the corona discharge treatment apparatus of the type which installs a to-be-processed object between the discharge electrodes and counter electrodes which oppose each other.

Next, an intermediate layer and a photocatalyst layer (antifouling agent layer) are formed on the surface to be treated which has been subjected to the corona discharge treatment. In the present invention, it is recommended that the photocatalyst layer be formed by using an aqueous compound containing water and titanium oxide.

As the intermediate layer and the photocatalyst layer, a titanium peroxide layer (intermediate layer) formed on the surface to be treated which has been hydrophilized by the corona discharge treatment, and an oxidation formed on the titanium peroxide layer. It is composed of a titanium layer (photocatalyst layer). That is, the titanium peroxide layer is composed of amorphous titanium peroxide having no photocatalytic activity, and in some cases, contains a mixture with amorphous titanium oxide and does not have a photocatalytic function.
₃ ) and may contain a surfactant and / or a hydrophilic agent. On the other hand, the titanium oxide layer is formed from a photocatalyst such as an anatase type titanium oxide having a photocatalytic function (TiO ₂₎ and rutile titanium oxide (TiO _2), and Amorufuasu titanium peroxide sol and the like having no photocatalytic function Alternatively, it may contain a mixture with the above-mentioned photocatalyst having a photocatalytic function.

FIG. 2 is a sectional view of the obtained interior material 50, in which the surface of a resin base material 51 (in some cases, an organic resin coating film layer 52 such as an acrylic resin is formed) is hydrophilized by corona discharge treatment. After the treatment, the intermediate layer 53 and the photocatalyst layer (antifouling agent layer) 54 are formed on this surface. The layer 54 formed by coating after such corona discharge treatment has high wettability and a small contact angle with water, so that an excellent antifouling effect can be obtained.

The second surface treatment in the present invention is to make the surface to be treated hydrophilic by performing an ultraviolet treatment, and the wavelength of the ultraviolet rays is preferably 150 to 365 nm. This is because ultraviolet rays having a wavelength of 365 nm or more cannot sufficiently hydrophilize the surface to be treated, while it is difficult to obtain a wavelength of 150 nm or less from an ultraviolet ray lamp used in a wide range. Furthermore, when performing the above-mentioned ultraviolet treatment, it is preferable to carry out in an atmosphere of air, water vapor, and ozone, and by reacting oxygen, ozone, and water in the air,
This is because by forming a carbonyl group, a carboxyl group, a hydroxyl group or the like on the surface to be treated and making the surface to be treated hydrophilic, the water-based paint can be applied uniformly and firmly. In particular, if water is adhered to the surface to be treated and UV treatment is carried out, the hydrophilicity of the surface can be increased.

The UV treatment is preferably carried out after cleaning the surface to be treated. Since the active group having high reactivity is generated on the surface to be treated due to collision of electrons due to the UV treatment, wettability and reactivity are improved. You will be able to Therefore, the adhesiveness is extremely improved.

A low-pressure ultraviolet lamp is preferable as the ultraviolet light source used in the ultraviolet processing apparatus. This is because the low-pressure ultraviolet lamp is mainly composed of light of 254 nm and 184.9 nm, has a short wavelength, and has a very large irradiation energy, and is suitable for making the base material hydrophilic. That is, the surface to be processed can be uniformly processed by irradiating the surface to be processed with ultraviolet rays while maintaining a predetermined distance.

The surface to be treated has improved wettability and reactivity as in the corona discharge treatment. The same applies to the contact angle of water. Needless to say, the formation of the intermediate layer and the photocatalyst layer (antifouling agent layer) described above can be performed in the same manner as in the previous example.

As the third surface treatment means of the present invention, plasma discharge treatment is adopted. In this case, it is preferable to perform it in an active gas species, and the gas species are Ar, 0 ₂ , CO, CO ₂ ,
N ₂ , NO, NO ₂ , NH ₃ , air (0 ₂ + CO ₂ + N ₂
Etc. are used and there is no particular limitation as long as a polar group can be introduced on the surface. Desirably, Ar, O ₂ and N ₂ are good. The degree of vacuum in the chamber during plasma processing is 1
It is 0 to 0.1 torr, preferably 1 to 0.1 torr. As a result, the surface to be processed can be uniformly processed. The processing time is 1 to 60 minutes.

It consists of free electrons due to the electrons of the ionized gas generated when the arc discharge occurs, cations due to the electrons, and neutral gas that has not been ionized, and the positive and negative charges have the same density. The gas in the neutral state is called plasma, but the surface to be treated has a highly reactive active group due to the collision of electrons due to this plasma discharge treatment and the action of the gas contained in the treatment atmosphere. It is possible to improve the property. Thereby,
Similar to the treatment of the previous example, the adhesion with the surface layer formed on this layer is extremely improved.

An outline of the plasma discharge treatment is as follows. When the surface of the interior material to be treated is subjected to the plasma discharge treatment, it is highly reactive due to the collision of electrons due to the plasma discharge and the action of secondary ozone or ultraviolet rays. Since the active groups are generated, the wettability and reactivity of the surface to be treated can be improved. The relationship of the contact angle of water is the same as in the above example. Of course,
It goes without saying that the intermediate layer and the photocatalyst layer (antifouling agent layer) are also formed in the same manner as described above.

FIG. 3 also shows an outline of the plasma discharge processing apparatus 40. The first electrode 42 installed in the chamber 41 in the vicinity of the surface 10S to be processed, the first electrode 42 and the surface to be processed. It is provided with a second electrode 43 installed on the opposite side of 10S and a power supply device 45 having a high voltage transformer 44. The chamber 41 is equipped with a vacuum pump 46 and a gas cylinder 47 to replace the atmospheric gas inside the chamber 41. A high voltage is applied between the electrodes 42 and 43 to generate plasma discharge between the electrodes 42 and 43. It is generated to activate the gas and uniformly process the surface 10S to be processed. The same applies to the formation of the coating layer on the surface 10S to be processed.

Although the ozone treatment is not particularly mentioned, the surface to be treated is treated by using an ozonizer having an appropriate capacity, and the treatment is performed so that the contact angle of water has the above relationship.

As for the thickness of the intermediate layer and the photocatalyst layer (antifouling agent layer), the former layer (TiO3 protective layer) is used.
Is 0.02-4.0 μm, preferably 0.1-2.0
The thickness of the anatase-type TiO2 layer as the photocatalyst, which is the latter layer, is:
0.02-4.0 μm, preferably 0.1-2.0 μm
m, and more preferably 0.3 to 1.0 μm.
If they are too thin, defects such as coating defects such as pinholes are likely to occur, and if they are too thick, defects in appearance due to light interference occur. In addition, Ag and C are added to these layers.
Metals such as u and Zn can be added, which also brings about an antibacterial effect. Pt, P
Platinum group metals such as d, Ru, Rh, and r can also be added, and in this case, the redox activity of the photocatalyst is enhanced, resulting in decomposition of stains and decomposition of harmful gas and malodor.

In the conventional photocatalyst layer (antifouling agent layer), a coating layer in which anatase-type TiO ₂ particles are dispersed in silicon or the like is directly applied to the surface of an organic substance, but TiO ₂ is a base material. Since it decomposed, the problem was large, and the duration of photocatalytic activity was relatively short. However, in the case of the present invention, for example, by performing corona discharge treatment, the adhesiveness with the base material becomes extremely good, and the intermediate layer has almost no function of decomposing the base material. Due to the interposition, the optical resolution of the surface layer is not likely to decompose the base material,
Since these coating layers are not deteriorated, hydrophilicity and optical resolution are maintained for a long time.

The contact angle of water on the surface of the interior material for exhibiting the antifouling effect is 40 degrees or less, preferably 25 degrees or less, and more preferably 10 degrees or less. If it is greater than 40 degrees, stains may remain in areas where it is difficult to wash, such as uneven portions of the interior material, and a sufficient antifouling effect cannot be obtained.

[0036]

EXAMPLES The features of the present invention will be further described below with reference to examples. (Example of Corona Discharge Treatment) As the interior material 50, a dashboard 51 of a thermoplastic resin (manufactured by ABS) was used, and its surface was subjected to corona discharge treatment. Thereafter, as the intermediate layer 53, amorphous titanium peroxide sol (TK-100, 0.8
Aqueous solution containing 5% by weight of titanium peroxide (TAO)
Was evenly spray-coated and dried at room temperature, and this was repeated 3 times. Further, as the surface layer (photocatalyst layer) 54, a mixture of an amorphous type titanium peroxide sol and anatase type titanium oxide (TAK-70, an aqueous solution containing 1.70% by weight of titanium oxide and titanium peroxide, titanium oxide: titanium peroxide = 7). : 3 (manufactured by TAO)) was uniformly sprayed and dried at room temperature, and this was repeated 3 times. Then 1 at 140 ℃
A time-baked dashboard 50 was obtained. The contact angle of water after the corona discharge treatment was 20 degrees.

As a comparative example, an interior material whose surface is not subjected to corona discharge treatment has a water contact angle of 60 degrees.
Even if the above-mentioned intermediate layer and surface layer were applied, they were repelled and a film could not be formed.

(Evaluation-1) The dashboard thus treated was mounted on an actual vehicle and observed and evaluated after 3 months, 6 months and 12 months. Almost no dirt is attached, and the effect is as good as new when it is new.

(Evaluation-2) Next, the treated dashboard surface was soiled with coffee, chocolate, juice and lipstick, and wiped off with water after 1 hour and after 24 hours. I was able to.

(Evaluation: 3) It was confirmed that the cigarette odor and the formaldehyde concentration inside the vehicle were significantly reduced, and the deodorizing effect of the photocatalyst coating layer was confirmed. A gas (10 liters) having a concentration of 1.0 ppm was prepared as an initial gas.
The dashboard of this example was tested for formaldehyde decomposition. The irradiated UV lamp is UPL
Use AND-UVM-28 to set the distance to the sample to 5
It was kept at 0 mm and irradiated for 1 hour. On the other hand, it was left in a formaldehyde atmosphere for 1 hour without being irradiated with ultraviolet rays.

As a result of the measurement, the concentration of formaldehyde was 0.0 ppm in the former case, but the concentration of the latter was 0.6 ppm. The latter test shows that 0.4 ppm is absorbed by the sample, but it is proved that the difference from the former, that is, 0.6 ppm of formaldehyde was decomposed by irradiating the sample with ultraviolet rays.
The resolution of such atmospheric gases is not only the smell of cigarettes,
This shows that it is possible to decompose gas bodies such as NO _x , SO _x , ammonia, and trimethylamine which are said to be harmful to the human body.

(Example of plasma discharge treatment) As an example,
Plasma discharge treatment was applied to the surface of the dashboard. That is, the interior material is degreased with ethanol and placed in a chamber, the chamber is evacuated, and then O ₂ , N ₂ and Ar gas are filled respectively to a pressure of 1 torr and a voltage of 100 W to 1
Plasma discharge treatment was performed for 0 minutes.

The contact angles of water on the surface of the treated interior material were 23 °, 32 ° and 35 °, respectively. TiO that is the surface layer
The coatability of ₂ is easy.

(Example of UV Treatment) As an example, the surface of the dashboard was subjected to UV treatment. That is, the interior material surface was degreased with ethanol, and the distance between the treated surface and the low-pressure ultraviolet lamp was 1.5 cm using 110 W low-pressure ultraviolet lamp SUVllOGS-36 manufactured by Sen Engineering Co., Ltd.
Then, UV treatment was carried out at normal pressure for 5 minutes. The contact angle of water was 25 degrees. It was easy to form each coating layer.

[0045]

Industrial Applicability According to the present invention, a titanium oxide TiO ₂ layer applied to the surface of a vehicle interior material is firmly adhered, and the substance adhered by this surface layer is decomposed by a photocatalyst and exhibits hydrophilicity. Due to the formation of dirt, the dirt does not stick to the surface of the vehicle interior material, and it is possible to easily maintain a clean state by washing with water, and its utility value is extremely high.

[Brief description of drawings]

FIG. 1 is a diagram showing a configuration of a corona discharge treatment device of the present invention.

FIG. 2 is a view showing a cross section of a vehicle interior material.

FIG. 3 is a diagram showing a configuration of a plasma discharge treatment apparatus of the present invention.

[Explanation of symbols]

10 ... Base material 10S: Processing surface, 20. Corona discharge treatment device, 21 ... the first electrode, 22 ... second electrode, 23. High voltage generator, 24 ... Roll-shaped covering member, 40 ... Plasma discharge treatment device, 41 ... Chamber, 42 ... the first electrode, 43 ... the second electrode, 44: High voltage transformer, 45: power supply, 46 ... vacuum pump, 47 ... Gas cylinder, 50: Interior materials, 51 ... Interior material base material (10), 52 ... Organic resin layer, 53 ... the middle layer, 54 ... Photocatalyst layer (antifouling material layer).

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 3D023 BA01 BA08 BB01 BE02 BE11                 4D075 BB44Y BB46Y BB49Y BB70Y                       CA13 CA34 CA37 DA06 DA23                       DB35 DB36 DB37 DB38 DB43                       DC13 EA06 EA07 EA12 EB02                       EB43 EC02 EC07 EC35

Claims (13)

[Claims] 1. An antifouling vehicle interior material, which is an interior material for a vehicle or the like, wherein the surface of the interior material is subjected to a hydrophilic treatment, and an antifouling agent layer is applied on the hydrophilic treated surface. . 2. The antifouling vehicle interior material according to claim 1, wherein the vehicle interior material is plastic. 3. The antifouling vehicle interior material according to claim 2, wherein the plastic is selected from PP, PE, vinyl chloride and acrylic resin. 4. The antifouling vehicle interior material according to any one of claims 1 to 3, wherein the antifouling agent layer is a water-based photocatalyst having photocatalytic activity. 5. The antifouling vehicle interior material according to claim 4, wherein the photocatalyst having photocatalytic activity is anatase type titanium oxide. 6. The antifouling vehicle interior material according to claim 5, wherein the photocatalyst body contains amorphous titanium peroxide. 7. The antifouling vehicle interior material according to claim 1, wherein an intermediate layer is provided between the surface subjected to the hydrophilic treatment and the antifouling agent layer. 8. The antifouling vehicle interior material according to claim 7, wherein the intermediate layer is an amorphous type titanium peroxide having no photocatalytic activity. 9. The antifouling vehicle interior material according to claim 1, wherein the intermediate layer contains a surfactant and / or a hydrophilic agent. 10. The antifouling vehicle interior material according to any one of claims 1 to 9, wherein the hydrophilic treatment is corona discharge treatment. 11. The antifouling vehicle interior material according to claim 1, wherein the hydrophilic treatment is plasma discharge treatment. 12. The antifouling vehicle interior material according to claim 1, wherein the hydrophilic treatment is an ultraviolet treatment. 13. The antifouling vehicle interior material according to any one of claims 1 to 9, wherein the hydrophilic treatment is ozone treatment.