WO1986000313A1

WO1986000313A1 - Ultraviolet ray-absorbing plastic plate

Info

Publication number: WO1986000313A1
Application number: PCT/JP1985/000330
Authority: WO
Inventors: Kotaro Ono; Kenji Sumida; Kazunori Kagei; Kazuhide Takai
Original assignee: Washi Kosan Co., Ltd.
Priority date: 1984-06-25
Filing date: 1985-06-13
Publication date: 1986-01-16

Abstract

An ultraviolet ray-absorbing plastic plate which cuts off ultraviolet rays for extended periods of time to protect objects of art from ultraviolet rays and mechanical damage. The ultraviolet ray-absorbing plastic plate is obtained by polymerizing a polymerizable mixture which consists of a radical polymerizable compound containing at least one radical polymerizable monomer which has two or more alpha-beta unsaturated double bonds such as diethylene glycol bisallyl carbonate, a benzophenone-type ultraviolet ray-absorbing agent, and a radical polymerization initiator. The ultraviolet ray-absorbing plastic plate of the invention has a crosslinked structure, does not permit the ultraviolet ray-absorbing agent to bleed out of the surface of the plastic plate even after it has been used for extended periods of time, exhibits excellent properties such as great mechanical strength and heat resistance, and is transparent. Therefore, the plastic plate of the invention is used for protecting eyes and objects of art from the ultraviolet rays, i.e., used as an ultraviolet ray-shielding plate being installed in front of, for instance, a CRT display, as a member for protecting a picture frame, and as a member for cutting off ultraviolet rays generated from a source of light such as lighting apparatus.

Description

Small

Description UV-absorbing plastic material

- 〖 Technical field ]

TECHNICAL FIELD The present invention relates to an ultraviolet bran-absorbing plastic plate material used as a protective member for works of art and the like.

[Background technology]

Ultraviolet rays have large enough energy to break open the compounds of the known compounds, so when ultraviolet rays are radiated on the human body or artworks, fatigue eyes, conjunctivitis, sun Burning, skin cancer, etc. may occur, and in arts such as paintings, beverages, foods, etc., discoloration or deterioration of the contents may occur. In addition, rubber-based plastics and the like deteriorate over the years and cannot maintain their initial performance.

Therefore, it is necessary to protect the human body and works of art from ultraviolet rays that are contained in sunlight bran and artificially generated from water lamps, brown tube displays, and the like. It protects the human body, especially the eyes, by cutting off ultraviolet rays from people who work during long-term rushes, especially under strong sunlight or around equipment that emits ultraviolet light. There is a strong demand for materials that protect art objects and other objects.

On the other hand, as an ultraviolet-blocking resin composition that blocks ultraviolet rays, Various transparent resins to which colored titanium oxide fine powder is added (Japanese Patent Application Laid-Open No. 58-166432), and a method for producing a resin material having improved ultraviolet blocking properties. A method of impregnating a vinyl resin or a vinylidene monomer containing an ultraviolet absorber and a polymerization initiator into a polymer of a refrigerated polymer (Japanese Unexamined Patent Application Publication No. 1982-782) is also known.

However, in the former case, since the colored titanium oxide fine powder is added, the resin composition is colored and lacks transparency, and thus requires transparency. There are drawbacks that cannot be applied to applications.

In the latter method, the polymer particles are impregnated with the above-mentioned monomer in an aqueous suspension and polymerized in the aqueous suspension, so that as the polymerization reaction proceeds, The polymer particles condensed, making it difficult to carry out the polymerization reaction smoothly, and in addition to requiring an impregnation step, there was a drawback that workability was poor. In addition, the obtained resin material is mainly made of an aged refin-based polymer, so that not only properties such as mechanical strength and heat resistance are small, but also it includes The disadvantage is that it is not enough to prevent the immersion of the UV absorber from escaping, and therefore it is not possible to maintain UV-blocking properties over a long period of time. It was.

In order to prevent the polymer from being deteriorated by ultraviolet rays, generally, esters of salicylic acid, benzotriazole, benzof: L-non-substituted, Ultraviolet absorbers such as acrylonitrile are used in the minimum amount necessary to prevent resin deterioration However, the UV absorber added to these polymers exudes to the surface of the polymer according to 絰, and the UV absorbability is deteriorated. In particular, when the compatibility between the ultraviolet absorber and the polymer is poor, the oozing of the ultraviolet absorber is remarkable. Therefore, these polymers cannot completely block ultraviolet rays having a wavelength of 380 nB or less over a long period of time. Also, if the amount of the UV absorber used is greatly increased in order to completely block the UV light, these polymers will be significantly colored, and the mechanical strength and heat resistance of the polymer, etc. However, there was a drawback that it became so low that it could not be put to practical use.

An object of the present invention is to provide an ultraviolet bran-absorbing plastic which is capable of almost completely shielding ultraviolet rays having a wavelength of 380 riB or less for a long period of time, is transparent, has little coloring, and has excellent mechanical strength and the like. May provide plate material _α

[DISCLOSURE OF THE INVENTION]

The present invention provides a plastic plate material having a crosslinked structure and containing an ultraviolet absorber, that is, a radial plate having at least two or more α-3 unsaturated double bonds. A polymerizable monomer or a radical polymerizable compound containing at least one of these prepolymers; an ultraviolet absorber; a radical polymerization initiator; The above-mentioned conventional problems are solved by the ultraviolet-absorbing plastic plate obtained by polymerizing the radical polymerizable mixture of the present invention. In the case of the base plate, the radical polymerizable compound has at least 2 or more c / 3 unsaturated double bonds. However, since the obtained plastic plate has a cross-linked structure, even if the amount of the ultraviolet absorbent used is large, the ultraviolet absorbent can ooze out over a long period of time. There is no. Therefore, ultraviolet rays having a wavelength of 380 nm or less can be completely blocked over a long period of time.

Further, since the ultraviolet-absorbing plastic plate material of the present invention has a crosslinked structure, it has remarkably excellent properties such as mechanical strength and ripening resistance.

Further, the plastic plate material has excellent transparency and is not colored, so that it can be used for various purposes.

In the terms used below, the term "plate material" is not limited to a flat plate shape, but also includes a curved plate shape having a constant thickness, such as a lens having a thick bulging shape as a whole, such as a lens. Used for meanings that do not include.

[Brief description of drawings]

FIGS. 1 to 7 are diagrams each showing an application example of the ultraviolet-absorbing plastic plate material of the present invention.

Fig. 1 is an exploded perspective view of a picture frame, Fig. 2 is a side sectional view of an exhibition room for artworks, etc., Fig. 3 is a sectional view of a lighting fixture, Fig. 4 is a perspective view of a storage cabinet, and FIG. 5 is a cross-sectional view showing a suction mechanism for a front glass, FIG. 6 is a cross-sectional perspective view of another lighting device, and FIG. 7 is a perspective view of a hat.

FIG. 8 is a diagram showing the ultraviolet absorption characteristics of the ultraviolet-absorbing plastic plate material of the present invention. [Best mode for carrying out the invention]

Hereinafter, the present invention will be described in detail.

The ultraviolet-absorbing plastic material of the present invention comprises a radically polymerizable monomonomer having at least two or more α-3 unsaturated double bonds, or a prepolymer thereof. A polymer obtained by polymerizing a polymerizable mixture of a radical polymerizable compound containing at least one polymer, an ultraviolet absorbing agent, and a radical polymerization initiator. .

Examples of the radical polymerizable compound include an aryl-based monomer, an acryl-based monomer, and a styrene having two or more α-3 unsaturated double bonds. Radical polymerizable monomers, such as system-based monomers, and their prepolymers, which are used for ultraviolet-absorbing plastic materials, One or two or more are used depending on the mechanical properties.

Examples of the above-mentioned aryl-based monomers include polyethylene glycol, bisphenol-based car components, gary phthalates, and tri-alias. Examples include compounds having two or more aryl groups such as Louisiana Nurate.

Acryl-based monomers include ethyl-cole-collectors, ethylene-coal-recycles, and propylene-gels. Multi-functional devices such as multi-metacreate, neopentylglycolate, trimethylolpropane, and trimethacrylate There are relays and meta-relays. Styrene-based monomers include divinyl benzene.

Among these radically polymerizable monomers having at least two or more α-3 unsaturated double bonds, from the viewpoint of polymerizability, an arylyl-based monomer, Acrylic monomers are preferred, and among them, those containing polyethylene glycol, bis-glycerol carbonate, because of their transparency and low coloration. Is preferred.

The prepolymer of the radical polymerizable monomer can be prepared by adding a predetermined amount of a radical polymerization initiator to these monomers according to a conventional method. And one or more prepolymers of a radical polymerizable monomer having two or more α--3 unsaturated double bonds, which is a viscous liquid obtained by the above method. It's okay,

The above-mentioned radical polymerizable compounds having two or more α-unsaturated double bonds include various kinds of radical polymerizable compounds having one α-i3 unsaturated double bond. It can be used in combination with these prepolymers.

(Examples of various radically polymerizable compounds having one X-β unsaturated double bond include acrylic acid, methacrylic acid, and methacrylic acid. Methyl acrylate, methyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, butyl acrylate, acryl Acrylates, methacrylates, phenylmethacrylates, and acrylates having an alkyl group having 1 to 18 carbon atoms such as acid laurel; Relonitrile, Acryl Amid, etc. Acrylic monomers, styrene, 0-chlor styrene, 4-pole styrene, and other styrene monomers, and more Examples include vinyl pyrrolidone, maleic anhydride, itaconic acid, and the like.

Among these radically polymerizable compounds having one α — 3 unsaturated double bond, those having transparency and rigidity are preferred, and acrylic monomer is preferred. In particular, methyl methacrylate is preferred.In this case, methyl methacrylate is used in combination with the diethyl alcohol bisulfur carbonate. This makes it possible to arbitrarily adjust mechanical strength, transparency, and the like, which is preferable.

Radical polymerizable monomers and prepolymers having two or more α-3 unsaturated double bonds are at least 25% by weight, especially from the viewpoint of mechanical strength and optical properties. If used in an amount of 50% by weight, if it is less than 25% by weight, not only the above-mentioned properties are deteriorated, but also the ultraviolet absorbent cannot be contained and held for a long period of time. In addition, as the amount of the radical polymerizable monomer having two or more a-β unsaturated double bonds and the amount of the prepolymer increased, the ultraviolet-absorbing plastic was increased. The properties such as the mechanical strength and shochu maturity of the board material are significantly increased.

As the ultraviolet absorber, various types such as salicylate ester type, benzotriazole type, and substituted acrylonitrile type can be used. When a benzophenone UV absorber or a fluorescent whitening agent is used, these are contained and retained in the polymer for a long time, and the UV absorbability is maintained for a long time. It is possible It is preferable because there is no coloring of the plastic material.

Benzofenon-based UV absorbers include, for example, 2.

4 -Hydroxy benzophenone, 2 -Hydroxy 41 -Methoxy benzophenone, 2 -Hydroxy 4 -Hydroxy benzene Zofenon, 2-hydroxy-4-dodecyl Kishibenzofenon, 2.2 1-Hydroxy-4-methoxybenzofenone, 2.2.11 Hydroxy 4.4.2-Dimethoxy xybenzophenone, 2.2'.4.4.11 Tetrahydroxybenzopheno , 2.4-benzene resorcinol, etc.

The amount of the benzophenone-based UV absorber used depends on the thickness of the UV-absorbing plastic plate and the type of the benzophenone-based UV absorber used. Although markedly different, the transmittance of light having a wavelength of 380 nm is less than 10% to shield ultraviolet rays, and the light in the visible region of wavelength 440 nm or less is used to avoid coloring. The transmittance is 85% or more as a whole! ) It is necessary to add an amount that satisfies the conditions.

For example, when the thickness of the plastic plate is 2 mm and 2-hydroxy 4 is used as the ultraviolet absorber, it is used as a UV absorber. As shown in FIG. 8, the range of the amount used is 0.03 to 0.05% by weight. In addition, benzophenon-based UV absorbers can satisfy the above-mentioned conditions with a usage amount of 0.01 to 5% by weight of the enclosure.

In addition, those using a fluorescent brightener as an ultraviolet absorber are not suitable. Even if a material having a yellowish tinge is used, a brighter color can be provided by the whitening effect, and ultraviolet light can be absorbed.

Examples of such optical brighteners include 2.5 bis (5 'tertiary chillbenzo kisazoril) and chi phen (chipagagi). And OBEX OB>, and the amount used is preferably 0.0001 to 0.1% by weight.

If the amount is less than 0.0001%, the ultraviolet ray absorption and whitening effects are not sufficient. If the amount exceeds 0.1%, it is not economical, and the above-mentioned effects are not significantly improved.

The above-described fluorescent whitening agent is used by being added to and mixed with the above-mentioned various polymer mixtures by a usual method because of its good solubility. The above-mentioned fluorescent whitening agent may be added together with the above-mentioned fluorescent whitening agent to increase the whiteness by adding a blue tint to the plastic plate material. When added to the above-mentioned benzofu-Xonone-based UV absorber, the benzofuenonone-based UV absorber increases the robustness of the fluorescent whitening agent. UV absorption can be further enhanced.

As the radical polymerization initiator used for obtaining the ultraviolet-absorbing plastic plate material of the present invention, a usual polymerization initiator can be used, but from the viewpoint of the polymerization temperature, Selection 10-hour half-life The following organic oxides with a temperature of 80 are preferred.

Examples of these are Jisopropirper Kissika components and Ginomalpropiperper Kissisi carbonate. Ji-ri-Stir-Pil-Kishi-Ki-Porter, Ji-Ki-H-Ki-L-Pi-L-Ki-S-Pi-K-Pi-N, Ji- (2-ethyl-kil) Peri-Ki-Shi-Ki-Kar Pocket, tertiary chill pupil, cinema decano unit, tertiary butyl per liter, chip pallet, radio roll kid, tar 2-year-old kexanolate, benzoylperoxylate, etc.

Selection of BiJ 5C1 10 The half-life temperature of 80 hours is 80, and the use amount of the following organic oxides is preferably 2 to 5% by weight. If the amount is less than 2% by weight, the polymerization time will increase significantly, or the hardness of the obtained plastic plate will decrease. If the content is more than 5% by weight, excessive use is caused, which is not economical, and also causes cracks in the plastic plate, which is not preferable.

In addition, in order to complete the polymerization and remarkably improve the hardness of the plastic plate material in the post-polymerization, it is necessary to select the 10-hour half-life temperature of 90 hours together with the above-mentioned polymerization initiator. As described above, it is preferable to use an organic peroxide at 110 ° C. or lower in combination.

Examples of these organic conductive oxides include, for example, 1.1 bis (tertiary butyl), 3.3.5 — trimethylsilyl chloride. Kisane, 1.1-vis (Tertiary butyl persimmon) Shik Mouth Hexane, Ta-cis butyl perperimon, 2.2 vis ( Tarsia Chill Perpetual Kiss, Tachary Cripple Percentage Kisset, 2.2-Vis (Tarly Chill Perpetual Kiss) Tang, tertiary chill pel per year, and more.

Further, the amount used is preferably 0.05 to 5% by weight. If the amount is less than 0.05% by weight, the hardness cannot be sufficiently improved, and if the amount is more than 5% by weight, the hardness increases but cracks are formed or brittle. It's not easy to crack.

The polymerizable mixture having the above-mentioned composition preferably has a viscosity of 45 to 300 cps from the viewpoint of workability and the like.

In addition, additives such as antioxidants, fillers, pigments, dyes and the like may be added as long as the polymerizability is not impaired.

The polymerization conditions for the above polymerizable mixture can be appropriately selected. That is, the polymerizable mixture can be polymerized by various polymerization methods according to the use of the ultraviolet-absorbing plastic plate material, etc., to obtain a member having a refractive portion and the like. In order to obtain a plate-like product, it is preferable to use the batch casting polymerization method for continuous polymerization, and to use the continuous casting polymerization method for polymerization.

The polymerization temperature in the above polymerization method can be arbitrarily selected depending on the type of the polymerizable compound, the cleavage temperature of the radical polymerization initiator, and the like. From the viewpoint of coloring of the plate material, it is preferable to polymerize at room temperature to 120, especially 90 or less, then ripen to 100D or more, and perform post-polymerization. In order to heat at 100 or more, a heating medium having a boiling point of 100 ° C or more such as various oils may be used. In order to prevent the plastic plate from being colored by an oxidation reaction or the like, the polymerization reaction is preferably carried out in a state substantially free of oxygen by a nitrogen substitution or the like. Yes.

Further, in the case of obtaining a flat plate-shaped material having a smooth and uniform thickness, the polymerizable mixture may be polymerized under pressure. In this case, two endless belts running in parallel in the same direction at a predetermined speed and at a constant speed around the circumference, and running in contact with both leg ends of the endless belts, The polymerizable mixture is injected from the starting end of the endless belt into a gap formed by a gasket that seals a space between the dressing belts, and the polymerization reaction is performed. It is preferable to continuously obtain the ultraviolet-absorbing plastic plate material by carrying out the process. In particular, it is a liquid tank provided from the start end to the end of the endless belt, and a plurality of polymerization liquid tanks arranged in parallel in the running direction of the belt. It is preferable that the plate material after the polymerization is passed through a liquid tank composed of a cooling liquid tank for cooling if it is preferable to carry out the polymerization.

According to this method, a liquid pressure is applied to the polymerizable mixture between the belts by the liquid in the liquid tank via the belts, and the polymerization reaction is performed in a state where oxygen is substantially absent. As a result, it is possible to continuously produce a plate material having a high transparency, a non-colored smooth and uniform thickness, and which can be applied to a wide range of applications.

Further, the heat of polymerization can be easily removed by the liquid in the plurality of polymerization liquid tanks, and the polymerization reaction can be smoothly carried out. Therefore, a polymerizable compound having a large degree of polymerization, especially an α-3 unsaturated double bond, It is suitable for the polymerization of a polymerizable mixture containing two or more of the above polymerizable compounds.

The ultraviolet-absorbing plastic plate materials of various shapes obtained as described above have no coloring, high transparency, are smooth, have excellent scratch resistance, and have high ultraviolet-absorbing properties.

Further enhance the antireflection effect you good beauty surface hardness, to widen the application of the ultraviolet ray absorbent plus switch click plate of the present invention, the surface of the bra scan switch click plate, M _g F 9, AI 2 _{0 3, Z n 0 2 Z} n S , etc. of the metal compound vacuum deposition, Ri to form a spa jitter-ring, I O amplifier les over Te I ing a by Ri coating which film forming means, co chromatography It is preferable that a coating of a silicone resin is formed by the tent.

For example, the metal compound may be deposited by ripening and depositing the metal compound in a vacuum state of about ⁴ × 10 -4 mmHg, and attaching the metal compound to the plastic plate. . In addition, in the case of ion plating, since the kinetic energy given to the vapor of the metal compound is large, a very strong film having excellent adhesion can be obtained.

The UV-absorbing plastic plate of the present invention has a crosslinked structure and a remarkably low vapor pressure, so that unlike the conventional plastic plate, the UV-absorbing plastic plate is different from the conventional plastic plate. -A coating can be easily formed even by using the denting method.

Also, it is sufficient that at least one kind of the above-mentioned metal compounds is formed on the surface of the plastic plate material, and the coating is not limited to one genus. Even if it is formed of two or more layers Okay. The coating is preferably formed of two or more layers in order to increase the anti-reflection effect and the surface hardness.

A plastic plate with a metal compound-silicone resin film formed on the surface of the plastic plate material does not cause damage due to dust or friction. Therefore, the obtained plastic plate material can be applied to a wider range of uses.

In addition, due to errors in the formulation or polymerization operation, etc., the obtained plastic material may have insufficient UV shielding properties, or the plastic plate material may be colored. In such a case, it is preferable to stain with a fluorescent whitening dye, especially a whitening dye-based dispersed fluorescent whitening dye having a whitening silver ring. By staining, ultraviolet rays of 400 nm or less, particularly 380 nm or less, can be shielded. In this case, it is preferable that the dye is dyed so as to block at least 90% of ultraviolet rays and transmit at least 80% of visible light. In addition, a flat plastic plate is particularly easy to dye uniformly.

Various methods can be used as the dyeing method, and a high-temperature high-pressure dyeing method in which dyeing is performed under high temperature and high pressure even under weak acidity, and a normal pressure carrier dyeing method which is performed under normal pressure. Is preferred. The hot and pressure dyeing method is carried out at a temperature of 100 to 150 and a pressure of 2 to 10 ° by using various acidic compounds such as acetic acid and hydrochloric acid. The normal pressure carrier dyeing method is carried out under a neutral condition within a range of 50 to 100.

Since the plastic plate thus dyed contains an ultraviolet absorber, the discoloration of the dispersion type fluorescent whitening dye is considered to be due to the fact that the plastic plate contains an ultraviolet absorber. The ultraviolet absorption and the dispersible fluorescent whitening dye both maintain the ultraviolet absorption over a long period of time.

In addition, the above-mentioned dyeing method may be applied to a plastic plate material containing no ultraviolet absorbent to block ultraviolet rays and allow visible light to pass therethrough.

In this case, for example, a synthetic resin plate polymerized and formed with the above-mentioned radical polymerizable monomer and 3% of a polymerization initiator is subjected to 0.1 / Acetic acid (98%) at a low concentration and a dispersive fluorescent dye were mixed, poured into a solution having a bath ratio of 1:20, and dyed under conditions of 135 and 2 for 30 minutes. A transparent synthetic resin plate having an ultraviolet transmittance of 390 nm or less of 0% and a transmittance of around 400 nm of 10% or less can be obtained. In addition, the same synthetic resin plate as above is dyed by throwing it into a neutral solution with a bath ratio of 1:10, as in the case of the normal pressure carrier method. As a result, a synthetic resin plate having the same characteristics as above can be obtained.

The ultraviolet-absorbing plastic plate of the present invention is obtained by polymerizing a specific radical polymerizable compound in the presence of an ultraviolet absorber, and the plastic plate has a crosslinked structure. Excellent in various properties such as mechanical strength and heat resistance.The contained ultraviolet absorber does not ooze out of the surface of the plastic plate, and has a long-term ultraviolet shielding effect. Can be maintained. Further, the ultraviolet-absorbing plastic plate material of the present invention almost completely blocks ultraviolet light having a wavelength of 380 nm or less, without having the inherent properties of resin, and is visible. Light penetration rate is low and coloring is low.

Due to the above properties, the ultraviolet-absorbing plastic material of the present invention is suitably used for shielding ultraviolet rays.

The UV-absorbing plastic material of the present invention is obtained by preliminarily polymerizing into a shape suitable for the application by a casting polymerization method, or by obtaining a plate-like plastic or the like. Although it can be applied to various applications by forming and processing a plastic plate material by compression molding, etc., the plastic plate material has a cross-linked structure, and its mechanical strength and heat resistance are large. However, the former is preferred.

The use of the ultraviolet-absorbing plastic plate material of the present invention will be described below.

When the ultraviolet-absorbing plastic plate obtained by the present invention is in the form of a flat plate, it is suitable for the following uses.

It is suitable as an ultraviolet shielding plate disposed on the front of a brown tube display such as a television and a word processor. When used as such a shielding plate, the ultraviolet absorbing plate material completely blocks harmful ultraviolet rays. In addition, even if the brightness of the brown tube is large and the work is performed for a long time, the eyes are less fatigued and do not adversely affect the human body.

Also, disposing the ultraviolet-absorbing plate of the present invention in the vicinity of or in a shielded state with respect to art objects such as fc paintings, hanging scrolls, ornamental carpets, etc. prevents the fading and deterioration of the art objects. it can .

For example, as shown in FIG. 1, the outer frame 1 having a flat rectangular shape and having a fitting concave portion on the back side fits the fitting concave portion of the outer frame 1. In a picture frame composed of an inner frame 2 and a back cover 3 of a given size, a sign 4 such as a painting is interposed in a garden of the inner frame 2 and the back cover 3. . The front of the sign 4, for example, between the outer frame 1 and the inner frame 2, or between the inner frame 2 and the sign 4, has a size suitable for the back of the outer frame 1. The ultraviolet-absorbing plate member 5 is disposed in a state of being fitted to the outer frame 1.

In such a frame, the ultraviolet light entering from the front of the outer frame 1 is absorbed and blocked by the ultraviolet absorbing plate 5 provided on the front of the sign 4. Therefore, it is possible to protect articles such as paintings from ultraviolet rays.

The inner frame 2 of the picture frame is not always necessary.

Further, a transparent plate such as an inorganic glass which is usually used may be used together with the inside or outside of the ultraviolet absorbing plate. When the transparent plate is used, the plate may be disposed close to the transparent plate via an attaching means such as an adsorbing member. In the case where the plate material is arranged by the attachment means in this way, it can be easily attached to the conventional frame.

Also, in the above-mentioned frame, in order to prevent discoloration of a document or the like due to a change in humidity, a processing element having a moisture absorbing function or the like may be provided on the frame or the back cover. I like it.

In the example shown in FIG. 1, a processing layer 6 composed of a composite layer of a first processing layer 7 and a second processing layer 8 is provided on one surface of the inner frame 2. A processing layer 6 similar to the above is provided on the inner surface of the back cover 3. In addition, the processing elements are two layers, or three or more layers. It is better to have multiple layers

The above-mentioned first processing layer is described in JP-A-57-271176, JP-A-57-151616, and JP-A-57-17443. That disclosed in No. 57 is preferably used. That is, the first treatment layer 7 is made of a paint having hygroscopicity and ripeness. This paint has a moisture-absorbing function such as starch-acrylic acid graft polymer. Water-absorbing polymer, acrylic acid ester, ethylene monovinyl acetate, SBR Various binders such as latex and other emulsions, water-soluble resins, oil-soluble resins soluble in various organic solvents, porous fillers such as diatomaceous earth, and coloring agents And various additives such as a solvent such as water and an organic solvent, and a shockproofing agent such as magnesium orthophosphate. The above-mentioned paint contains a water-absorbing polymer or various emulsions and a small amount of a porous filler, and has both functions of absorbing moisture and releasing moisture. A structured one is preferred.

The binder should use the minimum amount necessary to disperse the coloring agent and the like without preventing the obtained dried coating film from absorbing and releasing water. Preferably, it is sufficient that mpd is an amount necessary to bind the water-absorbing polymer emulsion. Further, the water-absorbing polymer and the emulsion may be used in combination or may be used alone.

Since the above diatomaceous earth is porous and hydrophilic, it has the property of absorbing and releasing moisture in response to environmental humidity.

The amount of the above-mentioned porous filler used depends on the water-absorbing polymer, 250 phr to 500 phr is preferred for marsion. If the amount is less than 250 phr, the absorption and release of water will not be sufficient, and if it exceeds 500 hours, the toughness of the obtained coating film will be lacking.

In order to impart heat insulation to the first treatment layer, the binder may be a moisture-curing type as disclosed in Japanese Patent Application Laid-Open No. 57-271176. Use a one-pack type polyurethane foam composition.

The paint with the above composition is 0.2 inn depending on the environmental humidity etc. An appropriate thickness such as about 2 mm is applied to the frame of the frame by a suitable means such as a sprayer or a brush.

Further, the second treatment layer 8 has a water absorbing property, a moisture absorbing property or a decorative property.

The second treatment step 8 is preferably made of a hydrophilic material that absorbs water by capillary action or easily adsorbs water. These materials are, for example, those obtained by planting fine fibers by electric flocking or the like by attaching fine fibers such as velvet. Good hygroscopicity is good. In addition, fc, woven fabric, knitted fabric, Japanese paper, etc. may be used as the material.In this case, in order to enhance the decorative effect of the design, woven fabric, knitted fabric, Japanese paper, etc. May be attached.

When the picture frame provided with the above-mentioned treatment layer is attached to a wall surface where dew condensation or the like is generated, if the dew condensation is large, the second treatment layer causes the moisture to be removed by the second treatment layer. As the water is absorbed, the water absorbed in the second processing layer is more rapidly absorbed by the first processing layer. Because it is contained, it is possible to prevent discoloration of paintings and the like due to changes in humidity. When the humidity is low, moisture is released from the first and second treatment layers according to the environmental humidity, so that the environment can be maintained under a constant humidity condition. . Furthermore, the ultraviolet-absorbing plate material of the present invention has high mechanical strength and heat resistance, and therefore, unlike conventional inorganic glass, can protect artworks from external impacts and the like. it can .

As another example of the use of protecting artworks, the ultraviolet absorbing material of the present invention is hung on the front of a hanging shaft or used on the floor to protect a hanging shaft between floors or the like. An ultraviolet-absorbing plate may be sandwiched between the concave support parts of the mounting table, etc.

Further, in an exhibition room of an art museum or the like, the ultraviolet absorbing material of the present invention may be used in order to protect works of art from ultraviolet rays generated from lighting members.

In other words, as shown in Fig. 2, it is provided at the corner of the upper part of the transparent glass plate 12 and the ceiling 16 arranged in front of the exhibition room 10 of an art museum or the like. In order to shield the ultraviolet light generated from the illuminated lighting member 11 and to protect the signage 14 such as a painting, it is necessary to obliquely surround the illuminating member 11 according to the present invention. It is sufficient to dispose the lumber 15. The upper and lower ends of the plate 15 are fixed to the upper part of the transparent glass plate 12 and the ceiling 16 by holding and fixing members 13, but there are appropriate means for attaching the plate. Can be adopted. Further, if the material of the present invention is used instead of the transparent glass plate, the ultraviolet shielding effect can be further improved. Great. Further, as a mode for surrounding the lighting member, the lighting member may be surrounded by a UV-absorbing plate material having a curved cross-sectional plate shape and a lighting device to be described later.

In this way, not only the discoloration and fading of the pigments in paintings and hanging art can be prevented, but also the yellowing and deterioration of paper as a base material can be prevented over a long period of time. Therefore, protection and management of artworks that require strict management can be easily performed.

Further, it is also suitable as an ultraviolet shielding material of a lighting device using a fluorescent lamp, a white lamp or the like that emits ultraviolet light. In this case, it is possible to prevent discoloration of the artwork due to ultraviolet rays and to protect eyes in reading and the like.

Also, when used as an ultraviolet shielding material for medical lighting equipment used in surgery, etc., harmful ultraviolet rays are not applied to the irradiated body such as the human body, and the incised internal organs can be protected. In addition, since the eyes of the practitioner can be protected, the procedure of the operation is efficient.

An example of such an operation is a surgical lighting device 20 as shown in FIG. The luminaire 20 includes a box-shaped frame 21 having an opening, a member 25 for shielding the opening of the frame 21, and a code 24 positioned inside the frame rest 21. A light source 23 such as a white ripe lamp mounted on a socket 22 to which the UV-absorbing plate of the present invention is used. Projecting pieces 26 are provided on both sides of the frame body 21, and the projecting pieces 26 are supported by holding members 27 so as to be rotatable at the sides so that the light irradiation angle can be changed. In addition, the plate member 25 is provided with an opening of the frame 21. It is attached by screw 28 at the end of the part.

The ultraviolet-absorbing plate material of the present invention is not limited to the above-described attaching means, but may be attached by any suitable means such as adhesion, fitting, and hooking. Further, in a lighting fixture having a plurality of openings through which light passes, the plurality of openings may be shielded by the plate material as described above.

Further, the surface of the plate material does not need to be smooth, and the surface may be provided with an uneven pattern or the like.

Also, at stores and museums, it deteriorates due to ultraviolet rays such as cases where arts and crafts, calligraphy, textile products, dolls, etc. are displayed and stored, and chemicals, foods, dyes, etc. When the ultraviolet ray absorbing material of the present invention is disposed in place of the light transmissive part in the storage cabinet for storage of easy-to-use articles, that is, in place of the inorganic glass used in the related art, the exhibition is made. In addition to preventing discoloration and deterioration of the product, it can also protect against external mechanical damage.

For example, the open-type closet 30 shown in FIG. 4 includes a closet main body 31 on which shelves 32 for storing articles are placed, and an open-closed main body 31 divided into two. It is made of a plate material 35 for shielding the closed part, and one end of the plate material 35 is supported at the upper and lower ends of the opening side end of the closet body so as to be opened and closed independently. Further, at the other end of the plate member 35 and at the opening / closing center of the closet main body 31 corresponding to this end, magnets 33, 34 are attached, respectively. In addition, the material 35 can be magnetically adsorbed. The ultraviolet absorbing plate of the present invention is used as the plate 35. In a case, a cabinet for storing articles, and the like, the material of the present invention is not limited to a door-door type, but may be a sliding-type cabinet or the like. You can install it.

In this case, if the same treatment layer (the first treatment layer and the second treatment layer) as described in (1) above is provided in an appropriate place, such as a case or the inside lower surface of a closet, the humidity changes. Deterioration and deterioration can be more effectively prevented ο

It is also suitable as a material for a blind curtain. That is, in a blind-shaped curtain that receives or blocks light by operations such as rotation and vertical movement, the present invention is used as a component of a looper as a light blocking member. The use of UV-absorbing plate material only blocks ultraviolet bran when blocking, protects indoor household items and furnishings from light, especially ultraviolet light, and prevents deterioration and discoloration. And the transparency is good, so you can see through the outside scenery

Therefore, the use of the ultraviolet absorbing plate material of the present invention for the looper of the blind-shaped curtain as described above can improve the compatibility of the room atmosphere. You will feel the spaciousness of the room, providing a comfortable and relaxing space.

The use of colored or dyed plate materials can enhance the decorative effect of design. The loopers may be arranged in parallel or radially, or the loopers may be arranged vertically.

In addition, vehicles such as automobiles, buildings, or aircraft window glasses When the ultraviolet ray absorbing plate material of the present invention is attached to the inside of a window glass or by a suitable means as appropriate, various articles in a car or a building can be protected from ultraviolet rays. In addition, it is possible to protect the driver's eyes from ultraviolet bran when driving the vehicle. In particular, when the ultraviolet-absorbing plastic plate material of the present invention is provided for a window glass of an aircraft flying in a layer having a lot of ultraviolet rays or in the vicinity of the window glass, the pilot can use the glass. It can effectively protect the eyes from ultraviolet rays. Further, since the plate material of the present invention has a crosslinked structure and is excellent in mechanical strength, heat resistance, impact resistance, etc., the ultraviolet absorbing material of the present invention is used in place of the window glass. Thus, in addition to the above effects, various articles in the car and the building can be protected from mechanical damage and the like.

When the member of the present invention is attached to a window glass close to the window glass, the member can be attached to an appropriate place such as a window glass, but can be freely rotated by a suitable means with respect to a sunvisor in the vehicle. It is preferable to use the one attached to the front glass or the one attached to the front glass via a suction mechanism such as a suction cup.

In addition, as shown in FIG. 5, the suction mechanism for attaching a plate material to a front glass or the like of a vehicle includes, as shown in FIG. 5, a suction section 40 having a suction concave surface, and an outwardly extending suction section. It is preferable that the suction member 43 has a tube portion 42 having a hole 41 communicating with the outside at the center of the protrusion, and in this suction member 43, the outside protruding end of the tube portion 42 is preferable. Is closed with a stopper 44 and the projecting end of the tube section 42 can be braned with a cap nut 46 via a zipper 47. It has been made.

Such an adsorbing member 43 is formed by passing the pipe 42 through a hole provided at an appropriate position such as an end of an ultraviolet absorbing plate 45, and plugging the external protruding end of the pipe 42. The suction member 43 can be attached to the plate member 45 by closing with a cap nut 46. In this way, the stopper 44 can be prevented from falling off, and the suction portion 40 can be pressed against the front glass to form a vacuum space with the suction concave surface. Thus, the plate material 45 can be easily attached. Also, removing the plate 45 from the front glass or the like simply requires removing the plug 44 and sending air to the vacuum portion, and thus the detachment of the plate 45 is extremely easy.

The above-mentioned adsorption mechanism is also suitable for attaching the ultraviolet absorbing plate material of the present invention in other applications such as an inorganic glass or a window glass of the frame. It is.

Further, when the ultraviolet-absorbing plastic plate material of the present invention is in the form of a curved plate having a substantially constant thickness, the ultraviolet-absorbing plastic member of the present invention is suitable as a shielding member for lighting equipment suitable for the following uses. When the flexible plastic plate is used, it is possible to prevent discoloration and deterioration of various articles due to ultraviolet rays generated from the light source of the lighting fixture, similarly to the lighting fixture.

As such an example, there is a lighting device 50 as shown in FIG. In the lighting device 50, a light source 51 such as a fluorescent lamp that generates ultraviolet light is separated from the reflecting plate 52 located on the rear side of the light source 51 by a predetermined distance. Sockets at both ends in the longitudinal direction It is attached to 56. Reference numeral 57 denotes a storage unit for codes and the like.

Since the reflector 52 surrounds the light source 51 in a shielded state with the ultraviolet-absorbing plastic plate 55 of the present invention, the both ends are engaged with both ends 54 of the plate 55. It has part 53. That is, the ultraviolet-absorbing plastic plate material 55 that engages with the engagement portion 53 of the reflection plate 52 has a U-shaped cross section, and both leg ends 54 are curved inward. The plastic member 55 is shaped so as to engage with the engaging portion 53 of the reflecting plate 52, and the plastic member 55 is in a state of being held by the engaging portions 53 at both ends of the reflecting plate 52. Is engaged.

The ultraviolet-absorbing plastic material of the present invention is not limited to the above-mentioned engaging means, but may be attached by any suitable means such as fitting and engaging means.

Further, it is also suitable as a member for a head covering such as a hat for shielding direct sunlight and preventing sunburn on the face and fatigue of eyes.

In this case, as shown in FIG. 7, the hat 60 has an attachment means 61 attached to the head and a collar portion 62 connected to the attachment means 61. It consists of 65. The attaching means 61 is formed of a member having a certain degree of elasticity in order to increase the degree of adhesion to the head when it is put on the head, or a flexible fastener on the back of the head. It is better to use a device so that it can be adjusted appropriately when worn.

The collar 65 may be provided so as to be connected to the attaching means 61, and in particular, to be pivotally supported by itself. In this example, the collar 65 is composed of a forked portion 62 and a forked portion 63, 64 connected to the forked portion 62. Also, at the ends of the portions 63 and 64, the attachment means 61 is pivotally supported by fixing screws 66 and 67. And, as the aforementioned step 65, the ultraviolet absorbing plastic plate material of the present invention is used.

Such a head covering, especially in the case of strong sunlight, can be stopped by stopping the collar and turning around a screw or the like and setting it at a position covering the face. In addition to preventing sunburn on the face, including the above, the visible light transmittance of the plastic plate also increases the visual field of the front face.

Even if it is used for golf, etc., since the plate is rotatable, there is no trouble in swinging. Furthermore, if the wood is colored, it can act as a sagittarius, further preventing eye fatigue. It should be noted that the same effect can be obtained not only in the shape of the sun visor as described above but also in a shape suitable for various uses such as goggles.

It is also suitable as a storage container for medicines, foods, dyes, etc., for example, as a container material such as a tube or a pot. When the plastic plate material of the present invention is used as such a container material, it is not necessary to color it brown or store it in a cool and dark place as in the conventional case. Further, the container is transparent, lightweight, has heat resistance and impact resistance, and absorbs and blocks ultraviolet rays, so that the contents can be easily checked, and storage and handling are easy.

[Industrial Applicability]

The ultraviolet absorbing plastic material of the present invention has a crosslinked structure. In addition to having high mechanical strength such as tensile strength and toughness, it is excellent in impact resistance, heat resistance, etc., it is not colored, it is transparent, and the UV absorber contained is Since it does not exude to the surface of the plastic plate material, it has ultraviolet absorbing properties over a long period of time and has a high visible light transmittance. Therefore, the ultraviolet-absorbing plastic plate material of the present invention is suitable for use in blocking ultraviolet rays and protecting various articles from mechanical damage and the like.

Claims

Scope of Claim: A plastic obtained by polymerizing a radically polymerizable mixture comprising a radically polymerizable compound, an ultraviolet absorber, and a radical polymerization initiator. A board material, wherein the radically polymerizable compound is a radically polymerizable monomer having two or more α- / 3 unsaturated double bonds, or a mixture thereof. An ultraviolet-absorbing plastic plate characterized by containing at least one prepolymer. The radical polymerizable compound is an aryl-based monomer or a The ultraviolet absorption according to claim 1, which contains at least one kind of a acryl-based monomer, a styrene-based monomer, or a prepolymer thereof. Plastic plate material.

Claim 1 wherein the radically polymerizable compound is a diethyl glycol bis-carbyl carbonate or a prepolymer thereof. Is a UV-absorbing plastic plate material as described in Paragraph 2.

The radically polymerizable compound is composed of a diethylene glycol bisaryl carbonate or its prepolymer and methyl methacrylate or methyl methacrylate. 3. The ultraviolet-absorbing plastic plate material according to claim 1, which is a mixture of methyl methacrylate and a prepolymer.

Claims wherein the radically polymerizable compound contains at least 25% by weight of a radically polymerizable monomer having two or more 13 unsaturated double bonds. The ultraviolet absorption described in paragraph 1 or 4 Yield plastic plate material.

6. The amount of the ultraviolet absorber is such that the transmittance of light having a wavelength of 380 nm is 10% or less and the transmittance of the visible region having a wavelength of 440ηπι or more is 85% or more as a whole. The ultraviolet-absorbing plastic plate material according to claim 1.

7. The ultraviolet-absorbing plastic plate material according to claim 1 or 6, wherein the ultraviolet absorber is a benzophenone-based ultraviolet absorber.

8. The ultraviolet absorbent plastic material according to claim 6 or 7, wherein the amount of the benzofunonone-based ultraviolet absorbent is 0.01 to 5% by weight.

9. Claims 1 or 6 in which the ultraviolet absorber is 2.5 bis (5.1 tert-butyl benzoxazole) thiophene. The UV-absorbing plastic plate material described.

10.2.5 Claims or claim 6 wherein the amount of bis (5-tert-butyl pentazole) is 0.0001 to 0.1% by weight. Item 9. The ultraviolet-absorbing plastic plate material according to item 9.

11. The ultraviolet-absorbing plastic according to claim 1, wherein the selected radical polymerization initiator is a 10-hour and half-life, and the temperature is 80 ° C or less. Board material.

12. The ultraviolet absorbing plastic according to claim 11, wherein the amount of the radical polymerization initiator having a half-life temperature of not more than 80 ° G at 10:00 is 2 to 5% by weight. Board material.

13. Radical polymerization initiator selected, 10-hour half-life temperature is 801; Radical polymerization initiator below, and selected 10-hour half-life temperature, 90-110 The ultraviolet-absorbing plastic plate material according to claim 1, which is made of an agent.

14. Selection of 2 to 5% by weight of the following radical polymerization initiator at a half-life temperature of 10 o'clock of 10:00 and a radical polymerization initiator of ~ 110 ° G at a 10-hour half-life temperature of 0.05: 0.05 14. The ultraviolet absorbing plastic plate material according to claim 13, wherein the weight of the plastic plate is from 96 to 5 weight.

_{15. M g F 2, AI 2} 0 3, Z n 0 2, Z n least for the even one range of coating claims formed on the surface of the plus switch click plate of metal compounds S 2. The ultraviolet-absorbing plastic plate material according to item 1.

16. The ultraviolet-absorbing plastic plate according to claim 1, wherein a silicone resin film is formed on the surface of the plastic plate.

17. The ultraviolet-absorbing plastic plate material according to claim 1, dyed with a dispersion-type fluorescent whitening dye.

18. The ultraviolet-absorbing plastic material according to claim 1, which is an ultraviolet-shielding plate disposed on the front surface of the brown tube display.

19. The ultraviolet-absorbing plastic plate material according to claim 1 or 6, which is an ultraviolet shielding member disposed on a front surface of a protected article such as a work of art.

20. An outer frame, a back lid attached to the back of the outer frame, and the outer frame and the back Claims that are protective members disposed in front of the artistic notice in a frame composed of an artistic notice such as a picture interposed between the lid and the artistic notice. Item 1. The ultraviolet-absorbing plastic plate according to item 1 or 19.

7. The ultraviolet-absorbing plastic material according to claim 1 or 6, which is an ultraviolet-shielding material disposed so as to shield a light source of a lighting device.

The ultraviolet-absorbing plastic plate material α according to any one of claims 1, 6, and 19, which is a material for a light-transmitting portion of a case.

The ultraviolet absorbing material described in any of claims 1, 6 or 19, which is a material for a light-transmitting part in the opening / closing part of an article storage cabinet. Plastic board material. -. The UV-absorbing plastic plate material according to claim 1 or 6, which is a material for a looper 'in a planed curtain. .

The ultraviolet-absorbing plastic plate material according to paragraph 1 or 6 of the patent request, which is a material for window glass of buildings, vehicles, aircraft, and the like.

The ultraviolet-absorbing plastic according to claim 1 or 6, which is an ultraviolet-shielding member disposed close to a window glass of a building, a vehicle, an aircraft, or the like. Board material.

The ultraviolet-absorbing plastic according to claim 1, wherein the ultraviolet-absorbing plastic is a material for a collar or a sampler for a head covering such as a hat. Chipboard material.

28. The ultraviolet-absorbing plastic plate material according to claim 1, which is a material for a storage container for a substance that is deteriorated or deteriorated by ultraviolet light.