JP2937689B2 - Heat-reflecting UV-absorbing transparent body - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is mainly used as a window material for vehicles such as automobiles, buildings, etc., by shielding heat rays (IR) caused by sunlight in a car or a room to reduce heat and the like. Prevents sunburn of people and interior materials by shielding ultraviolet rays (UV), and presents a neutral reflection color with a stunned appearance.
The present invention relates to a useful heat ray reflection ultraviolet ray absorbing transparent body.

[0002] The transparent body can be widely used not only for the above-mentioned vehicles or buildings, but also for window glasses of ships and aircrafts, covers of various lamps and displays, and the like.

[0003]

2. Description of the Related Art In recent years, various infrared and ultraviolet shielding transparent bodies have been proposed for transparent window materials capable of freely controlling sunlight energy. The most popular one is a heat ray reflective glass mainly for the purpose of energy saving such as a reduction in cooling load, and various kinds of transparent thin film coating materials such as metals and oxides have been proposed.

As for the shielding of ultraviolet rays, there has been proposed a method of mixing and blending an ultraviolet absorbent into a transparent material such as glass or resin film, or a method of coating a substrate with a ZnOx thin film. Further, for example, as a method of simultaneously imparting heat ray reflectivity and ultraviolet ray absorbability to a transparent body such as a glass substrate, first, a mixture obtained by mixing and adding an ultraviolet ray absorbing compound to a transparent body is used, and a heat ray reflective film is formed on the surface. how to,
In addition, a method in which a laminated film containing an ultraviolet absorbing compound is sandwiched by a transparent body coated with a heat ray reflective film to form a laminated glass, and further, an ultraviolet absorbing film is coated on the surface of the transparent body, and a heat ray reflective film is laminated and formed by a PVD method. (For example, see Japanese Unexamined Patent Publication
No. 133004).

[0005]

As described above, for example, in the case of only the above-mentioned glass having a heat ray reflective thin film, durability such as abrasion resistance, chemical resistance or abrasion resistance which is not necessarily used as a single plate. Is not only excellent, sometimes it is necessary to make a laminated glass or double-glazed glass, and because the shielding effect against ultraviolet rays is not sufficient,
Laminated glass had to be used to provide an ultraviolet shielding effect.

For example, since an ultraviolet absorbing substrate has no effect of heat ray reflection or the like, it is necessary to laminate various reflective films on the substrate in order to provide these effects, which is not suitable for small-quantity multi-product production. However, it does not cut ultraviolet rays into a sharp shape, and is not necessarily excellent in durability such as abrasion resistance, chemical resistance and abrasion resistance, and is difficult to use as a single plate.

Further, for example, in the above laminated glass,
It is hard to say that the shape correspondence is always good, and it may not be in line with the trend toward weight reduction. Although the safety is improved, it is difficult to make all of the laminated glass. Furthermore, for example, in the method disclosed in Japanese Patent Application Laid-Open No. 4-133004 or the like, in order to provide ultraviolet shielding performance with a ZnOx film, the film has a very complicated multilayer structure having both moisture resistance and protection of the film. Laminated glass or double-glazed glass is more practical for construction and vehicles, because it is expensive and has poor durability.

[0008] The development of a method for easily imparting the ultraviolet ray shielding performance to the heat ray reflective film is also important for the future of human beings who are concerned about the influence of depletion of the ozone layer by chlorofluorocarbons.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems, and has been developed from a metal, an oxide, a nitride, a nitrogen oxide and the like having a sufficient heat ray shielding performance. An acrylic resin containing, for example, a silicone component and a silicone hard coating resin having a specific ultraviolet shielding property are skillfully laminated and combined on the underlayer of the laminated film body using at least an appropriate film, and the underlayer is provided with, for example, a mask. By coating without causing damage, there is a protective effect of obtaining an excellent one having significantly improved durability such as the above-mentioned problems of chemical resistance, abrasion resistance and abrasion resistance, and veneer or veneer. It can be used as an exterior, and has sufficient heat and ultraviolet shielding performance that could not be obtained with each configuration Can, in particular obtained by shielding a sharp UV around 400 nm, or the like is also Niyutoraru effect of reflected color, for architectural and vehicle, there is provided a particularly useful heat reflecting ultraviolet absorbing transparent body.

[0010] That is, the present invention provides a method for producing a transparent base material comprising:
A heat ray reflective film is formed as a base layer, and then a synthetic resin-based primer coating solution obtained by dissolving and adding a fluorescent whitening agent and an ultraviolet absorber is applied and cured by heating to form an ultraviolet absorbing thin film. There is a heat-reflecting ultraviolet absorbing transparent body, characterized in that to form a protective film and heat-cured by applying a silicone hard coating solution formed by dissolving in an organic solvent.

[0011] Incidentally, the synthetic resin-based primer coating solution is preferably an acrylic primer coating solution containing the silicone component. Here, under
The heat ray reflection film formed as a stratum has various heat ray shielding functions.
And color tone, and adhesion or strength of the film itself
And various other functions such as radio wave functions
Metals, oxides, nitrides, carbides, nitrogen oxides, and the like can be used for the purpose .

The reason why a synthetic resin-based primer coating solution obtained by dissolving and adding a fluorescent whitening agent and an ultraviolet absorber is applied and cured by heating to form an ultraviolet absorbing thin film is particularly at the boundary between the ultraviolet / visible region. Applying a fluorescent whitening agent to the coating composition to cut very sharply without coloring, while using a synthetic resin-based primer with good adhesion to glass substrates, especially transparent substrates, especially silicone components This is because, by dissolving and adding to an acrylic primer coating solution containing the resin and coexisting with an ultraviolet absorber, the fluorescent light is absorbed, and a coating film with inconspicuous fluorescent light can be formed at a relatively low temperature.

As a fluorescent whitening agent, it absorbs in the ultraviolet region,
It emits fluorescence in the visible region and can be dissolved and added to a synthetic resin primer, especially an acrylic primer coating agent. Moreover, it has moderate heat resistance, and its absorption wavelength is in the ultraviolet / visible region boundary (for example, 400n
For example, Uvitex-OB (2,5 bis (5'-tert-butylbenzoxazolyl) thiophene, manufactured by Ciba Geigy) or EB-501 (manufactured by Mitsui Toatsu Dye) .

[0014] Examples of the ultraviolet absorber to be coexistent include benzophenone, benzotriazole, cyanoacrylate and salicylate. The molar ratio of the fluorescent whitening agent to the ultraviolet absorber is about 1: 0.5 to 1:10, and preferably about 1: 4. However, when the amount is too small, a desired ultraviolet absorbing power cannot be obtained.

Further, in the case of a synthetic resin primer, in particular, an acrylic primer, it is necessary to sufficiently dissolve the above-mentioned fluorescent whitening agent and the ultraviolet absorber, so that diacetone alcohol is added to an ether alcohol-based solvent such as ethyl cellosolve. It is preferable to use a mixed solvent in which a heat ray reflective transparent substrate is not affected by combining a ketone alcohol solvent such as ketone, ether, or an aromatic solvent. In particular, when the transparent substrate is a glass plate or the like, it is preferable to use a ketone-based solvent such as cyclohexanone having a dissolving power.

The synthetic resin for the primer is, for example, an acrylic resin, a urethane-based resin, a fluorine-based resin or a polyester-based resin.
The concentration, viscosity or film thickness may be adjusted using BR resin (manufactured by Mitsubishi Rayon) or the like. The resin concentration is about 1 to 15 wt%, and the total concentration of fluorescent brightener and ultraviolet absorber is 0.5 ~ 2wt%, viscosity 10
The thickness is preferably about 800 cP, and more preferably about 1 to 10 μm.

In particular, in order to further improve the adhesiveness, a silicone compound such as a silane coupling agent is often used. For example, OS808A (acrylic modified silicone manufactured by Daihachi Chemical, solid content: about 30 wt%, main solvent: cellosolve acetate)
It is preferable to add such as about １ ／ to 4 times the resin component concentration. Too little is ineffective and too much is uneconomical.

Further, the UV-absorbing synthetic resin primer prepared as described above, particularly the UV-absorbing acrylic primer, has a uniform thickness.
For example, it is applied by dipping, spraying, flow coating, printing, or the like to form a film, and is dried by heating at about 80 ° C. or more for about 1 hour, for example, and if it is insufficiently heated, it is a silicone hard coat. The primer component is easily eluted into the protective film, for example, clouding or cracks are easily developed, and if the heating is excessive, the adhesion of the protective film, which is a silicone-based hard coat, deteriorates.

The silicone-based hard coating solution is preferably a solution based on an alcohol solution of a siloxane prepolymer obtained by hydrolyzing an organoalkoxysilane, for example, as proposed by the present applicant. Those containing colloidal silica, such as the coating composition described in JP-A-62-220531, are also excellent in abrasion resistance and are more preferable. For commercial products, for example, Tosgard 510 (made by Toshiba Silicone) or Si coat 2
(Made by Daihachi Chemical) can be used. The resin content in the solution is about 10 to 50%, the viscosity is about 15 to 5000 cP,
Further, the thickness is preferably about 1 to 6 μm.

Further, as an application environment, for example, a temperature of about
A temperature of about 15 to 25 ° C., a humidity of about 40 to 50 RH%, and a cleanness of about 10,000 or less are preferred from the viewpoint of preventing coating film defects. In addition, as the coating method, like the ultraviolet absorbing synthetic resin primer, particularly the ultraviolet absorbing acrylic primer,
For example, a dipping method, a spray method, a flow coating method, a printing method, or the like can be used so as to obtain a uniform film thickness. The film thickness is more preferably about 2 to 5 μm. When the film thickness is thin, the effect of the surface protective film is lost, and when the film thickness is thick, cracks are easily developed during heat drying and curing. Further, a temperature of about 80 ° C. or more is preferable for the heat drying and curing. In particular, when the transparent substrate is a glass plate or the like, a treatment at about 150 ° C. for about 2 hours is preferable for increasing the surface hardness.

It is needless to say that a flow improver or a rheology control agent may be appropriately added in order to improve the coating performance of the above-mentioned ultraviolet absorbing acrylic primer or silicone hard coating solution. Furthermore, as the transparent substrate,
For example, any material having a heat resistance of about 80 ° C. or more may be used, preferably inorganic glass, or PC or PM.
Resin glass such as MA, PET, etc., whether inorganic or organic, is not particularly limited in shape, etc., in various shapes and sizes, such as bent sheet glass, as well as various tempered glass and strength It goes without saying that it can be used as an up-glass, a flat plate or a single plate, and also as a double-layer glass or a laminated glass.

[0022]

As described above, according to the present invention, a primer solution in which a fluorescent whitening agent and an ultraviolet absorber coexist with a heat ray reflective thin film layer made of a metal, an oxide, a nitride or a nitrogen oxide as an underlayer. Since it is a transparent body covered with a coating film with a unique structure and excellent ultraviolet shielding properties and a sufficient protective film, it acts as a neutral without impairing the heat ray shielding properties, and makes the fluorescence of the fluorescent whitening agent ultraviolet rays. The film can be formed at a relatively low temperature as an inconspicuous film absorbed by an absorbent, and its surface becomes a hard coat. In particular, the boundary of the ultraviolet / visible region can be extremely sharply cut at around 400 nm, and the adhesiveness, Excellent in chemical resistance, scratch resistance or durability, can be used for veneer and exterior, and can be a useful heat ray shielding and ultraviolet ray shielding window etc. The clear heat-reflecting ultraviolet absorbing transparent body, it can be obtained easily and cheaply by a simple coating process and the film formation by sputter method or the like.

[0023]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to such an embodiment. (Preparation of UV-absorbing acrylic primer) [For glass coating] 350 g of cyclohexanone and 493 g of propylene glycol monomethyl ether as solvents are put into a 1000 ml round bottom flask equipped with a stirrer and a reflux condenser, and acrylic BR-88 is stirred at room temperature. 52g of resin (Mitsubishi Rayon). Add 2g of fluorescent brightener UVITEX-OB (made by Ciba-Geigy) and 8g of UV absorber TINUVIN327 (made by Ciba-Geigy) while continuing stirring, and take about 30 minutes in an oil bath.
After heating to about 95 ℃, keep it for about 30 minutes to completely dissolve. Then, the heating was stopped, and the temperature was lowered to room temperature. Then, 95 g of an acrylic modified silicone resin OS-808A was added and dissolved by stirring to obtain an ultraviolet absorbing acrylic primer for glass application.

The UV-absorbing acrylic primer solution was transparent and had a solid content of about 8.5% and a viscosity of about 550 cP. (Preparation of Silicone Hard Coating Solution) 100 g of methyltriethoxysilane and 10 g of 3-glycidoxypropyltrimethoxysilane are put into a 500 ml round bottom flask equipped with a stirrer and a circulator, and 0.04 g of phthalic anhydride is added. Heat to about 40 ° C to dissolve, then weakly basic colloidal silica aqueous solution Snowtex C (manufactured by Nissan Chemical Industries, average particle size about 15 μm, SiO ₂ content about 20%)
Add 100g and react at about 40 ℃ for about 5 days.
Number average molecular weight about 1100 by C (Tosoh, ULC802A)
A composition having a solid content of about 29% was obtained. To this, 145 g of isopropyl alcohol was added, and the mixture was concentrated with an ultrafilter having a cut-off molecular weight of 1000 (manufactured by Nippon Millipore) to obtain a composition having a number average molecular weight of about 1200 by GPC and a solid content of about 20%. About 0.1 part of dicyandiamide as a curing catalyst was added to the composition to obtain a silicone-based hard coating solution.

(Performance evaluation method) Heat ray reflection ultraviolet absorption: Absorption spectrum pattern was measured with an ultraviolet / visible / infrared spectrophotometer. (Hitachi-U4000 type) Surface hardness: Conforms to ASTM D1044, wear wheel CS-
FH (haze) value (%) after 10F, 500 rotations.

Adhesion: According to JIS K5400, the number of tape peeling (1 mm square) tape peeling remaining is indicated by / 100. Chemical resistance: acid ---- 24hr at 25wt% H ₂ SO ₄ infusion test. Base: 4 hours in 5wt% NaOH drip test. Solvent --- 100% ethanol 4 hours in a drip test.

[0027] Weather resistance: According to JIS D0205, time until visual abnormality (film crack, peeling, remarkable yellowing) is observed with a sunshine carbon weather meter. (However, glass surface irradiation) Traverse test: 100 g with a traverse abrasion tester
After 30 reciprocations / min, 1000 reciprocations at a load of / cm ² ,
Judge by looking at the film state visually.

Example 1 A clear float glass substrate having a size of about 300 mm x 300 mm and a thickness of about 3 mm was washed with a neutral detergent, water rinse, and isopropyl alcohol successively, dried, and then vacuumed by a DC magnetron sputtering apparatus. The tank is set so as to be able to reciprocate upward facing the target of Ti set in the tank, and then the inside of the tank is evacuated to about 5 × 10 ⁻⁶ Torr or less with a vacuum pump. Gas and N ₂ gas (Ar gas and N ₂ gas
The gas flow ratio may be in the range of 0: 100 to 50:50) to maintain the degree of vacuum at about 2 × 10 ^-3 Torr,
The power of about 1.0kw is applied to Ti of Tagetsuto, through the DC magnetron reactive sputter by N ₂ gas, TiNx about 35nm thickness by conveying the glass substrate at a speed of about 85 mm / min in the Ti Tagetsuto upper A thin film was formed. After the film formation is completed, the application to the Ti target and the supply of the gas are stopped.

The uncoated surface of the obtained glass substrate with a heat ray reflective film is subjected to film masking, immersed in the above prepared ultraviolet absorbing acrylic primer solution for glass coating, and at a speed of about 0.1 cm / sec. Raised, about 120
The resultant was dried at about 0.degree. C. for about 0.5 hour to form an ultraviolet absorbing film having a thickness of about 7 .mu.m. Then, the heat ray reflective glass substrate with the ultraviolet absorbing film is immersed in the prepared silicone hard coating solution described above, pulled up at a speed of about 1 cm / sec, and about 120 ° C. for about 0.5 hour and about 150 ° C.
After drying for about 0.5 hours, a protective film having a thickness of about 4 μm was formed.

The obtained glass substrate, which is a heat-reflection ultraviolet-absorbing transparent body, was evaluated according to the above-described performance evaluation method. As a result, as shown in FIG. 1, the boundary between the ultraviolet and visible regions can be cut extremely sharply with sufficient transparency without coloring at around 400 nm, as compared with the conventional example in which only the heat ray reflective film is used. The light transmittance in the infrared region is also improved by about 5%. In particular, the light transmittance up in the visible range shows the appearance of the TiNx thin film in a neutralized color tone.

The surface hardness and the haze value (ΔH) after the Taber test are about 5, which are excellent in abrasion resistance. Not only peeling after the traverse test but also no noticeable scratching are observed, and the improvement is better than that of the TiNx thin film itself. there were. The heat resistance was 1000 hours or more without any visual abnormality, and the chemical resistance was improved without any abnormalities especially in the acid resistance in 24 hours. The heat-ray-reflecting ultraviolet-absorbing transparent body had excellent durability.

Example 2 Using the same clear float glass substrate as in Example 1,
Set so that it can reciprocate upwards facing the target of Zn and SUS (stainless steel) set in the vacuum chamber of the DC magnetron sputtering apparatus, and then the inside of the chamber is about 5 × 10 ^-6 Torr or less with a vacuum pump. After degassing, Ar gas and O ₂ gas (however, the flow ratio of Ar gas and O ₂ gas may be in the range of 0: 100 to 50:50) is introduced into the vacuum chamber, and the vacuum chamber is evacuated. The temperature was maintained at about 2 × 10 ⁻³ Torr, and a power of about 1.0 kw was applied to the Zn target, and the glass was passed through the DC magnetron reaction sputter with O ₂ gas at a speed of about 1300 mm / min above the Zn target. By transporting the substrate, a ZnOx thin film having a thickness of about 10 nm was formed as a first layer. After the film formation is completed, the application to the Zn target and the supply of the gas are stopped.

Next, while the glass substrate is placed in the vacuum chamber, Ar gas is introduced into the vacuum chamber to reduce the degree of vacuum to about 2 ×.
While maintaining the pressure at 10 ^-3 Torr, a power of about 0.15 kw was applied to the SUS target, and the speed of the DC magnetron reaction spatter with Ar gas was increased above the SUS target.
By transporting the glass substrate at 2000 mm / min, a SUS thin film having a thickness of about 3.5 nm was formed as a second layer on the ZnOx film-formed surface of the glass substrate. After film formation is completed, SUS
The application of the target and the supply of the gas are stopped.

Next, while the glass substrate is kept in the vacuum chamber, Ar gas and O ₂ gas (however, the flow ratio of O ₂ gas and Ar gas is in the range of 100: 0 to 50:50) in the vacuum chamber. , A vacuum of about 2 × 10 ^-3 Torr is applied, a power of about 1.0 kw is applied to the Zn target, and the Zn target is passed through a DC magnetron reaction sputter with O ₂ gas. By transporting the glass substrate above at a speed of about 1300 mm / min, a ZnOx thin film having a thickness of about 10 nm was formed as a third layer on the SUS film-formed surface of the glass substrate. After the film formation is completed, the application to the Zn target and the supply of the gas are stopped.

On the obtained glass substrate with a heat ray reflective film, a similar UV absorbing film having a thickness of about 6 μ was formed by using the same primer solution as in Example 1 and by the same film forming method. Next, the heat ray reflective glass substrate with the ultraviolet absorbing film is immersed in the prepared silicone-based hard coating solution and pulled up at a speed of about 1 cm / sec.
The coating was dried and cured at about 120 ° C. for about 0.5 hours and at about 150 ° C. for about 0.5 hours to form a protective film having a thickness of about 3 μm.

The obtained glass substrate, which is a heat-reflection ultraviolet-absorbing transparent body, was evaluated according to the above-described performance evaluation method. As a result, especially in the vicinity of 400 nm, the boundary between the ultraviolet / visible regions can be cut very sharply with sufficient transparency without coloring, and the light transmittance in the visible region and the infrared region is improved by about 5%. The transmittance up shows the appearance in a neutralized color tone.

The surface hardness and the haze value (.DELTA.H) after the Taber test are about 6, which are excellent in abrasion resistance, not only peeling off after the traverse test but also with almost no noticeable scratches, and are sufficiently improved, and the weather resistance is also 1000. It was a heat-reflection ultraviolet-absorbing transparent body having no visual abnormality and no abnormal chemical resistance over a period of time, and excellent durability.

[0038]

As described above, according to the present invention,
Reflects heat rays and blocks ultraviolet rays without impairing the optical characteristics and heat ray shielding performance. In particular, it can block ultraviolet rays very sharply around the ultraviolet / visible region at around 400 nm, and has excellent adhesion, chemical resistance, Excellent scratch resistance or durability, it can be used as a veneer or exterior,
The present invention can easily and inexpensively provide a useful heat-ray-reflecting ultraviolet-absorbing transparent body that can be widely used in various fields such as buildings, houses, and vehicles.

[Brief description of the drawings]

FIG. 1 shows the transmittance in the ultraviolet / visible spectral curve of the glass which is a heat ray reflective ultraviolet absorbing transparent body of Example 1 of the present invention and the glass coated with only the conventional heat ray reflective film shown in Example 1; FIG.

Continuation of the front page (51) Int.Cl. ⁶ identification code FI C08J 7/04 C08J 7/04 M E06B 5/00 E06B 5/00 Z (58) Field surveyed (Int.Cl. ⁶ , DB name) C03C 17/38 C03C 17/42

Claims (1)

(57) [Claims] 1. A heat-reflection film is formed as an underlayer on the surface of a transparent substrate, and then a synthetic resin primer coating solution obtained by dissolving and adding a fluorescent whitening agent and an ultraviolet absorber is applied and cured by heating. After forming the UV absorbing thin film,
A heat ray-reflecting ultraviolet absorbing transparent body, characterized in that a silicone-based hard coating solution in which a siloxane prepolymer is dissolved in an organic solvent is applied and cured by heating to form a protective thin film.