JPS61151258A - Transparent shielding material - Google Patents

Abstract

PURPOSE:To provide the titled material which is transparent in the visible light region and has excellent mechanical strength and resistance to chemicals, heat, marring and arc, consisting of a cured molding contg. a polyol polyallyl carbonate and a specified material. CONSTITUTION:A polyol polyallyl carbonate of formula I (wherein R is a residue of a polyol; n is at least 2), 5-30wt% (meth)acrylate ester and 0.001-1wt% at least one material selected from among an ultraviolet screening agent (e.g. benzophenone) and a near-infrared screening agent of formula II (wherein X is S, O; Y is a quaternary ammonium group; each of rings A and B may be substituted with halogen such as Cl or may be a condensed ring such as a naphthalene ring) are blended together. The mixture is polymerized and cured in the presence of a radical initiator. Alternatively, an electromagnetic wave shielding material composed of an electrical conductive net of 80-250 meshes is placed at nearly the center of the molding.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a transparent shielding material, more specifically, it is substantially transparent to visible light, yet resistant to ultraviolet, near-infrared, and electromagnetic waves. It also relates to a material that has a barrier property against one type of material, and has excellent mechanical strength and various resistances.

Background of the Invention and Prior Art In recent years, due to the development of industrial equipment and technology, such as electric and lightning equipment, functions that were not required in the past have become available.
A growing number of pigeon coops require materials that have a combination of multiple functions or a combination of functionality and decoration. 1. Against infrared, electromagnetic, waves, etc. There is a need for materials that have selective blocking properties.

Acrylic resin containing methyl methacrylate as the main component has been known for some time as an organic material with excellent transparency. has been known to be lightweight and easy to form, but this material has poor organic solvent resistance and heat resistance, is easily scratched on the surface, and has poor arc resistance. It was extremely difficult to use it for the above-mentioned multi-functional applications due to various durability issues.

Purpose of the Invention Accordingly, the purpose of the present invention is to provide transparent to visible light, but at least 1 to 100% of ultraviolet rays, near infrared rays, and electromagnetic waves.
The object of the present invention is to provide a transparent shielding material that has selective barrier properties against species.

Another object of the present invention is to provide a transparent shielding material which overcomes the above-mentioned drawbacks of conventional acrylic resins and which has excellent chemical resistance, heat resistance, scratch resistance, arc resistance and other resistance.

Structure of the Invention According to the present invention, a material containing a substance having a property of selectively blocking the transmission of at least one of ultraviolet rays, near infrared rays, and electromagnetic waves, and a base material whose main component is polyol polyallyl carbonate. A transparent #brush material is provided, characterized in that it consists of a cured molded article.

Preferred Embodiments of the Invention The preferred embodiments of the present invention will be explained in detail below.

Group M polyol polyallyl carbonate used in the present invention,
In the following general formula, nFi is a positive integer of 2 or more, preferably 2 or 5, and the group R is a polyol residue. The polyol components constituting the monomer of general formula (1) above include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, glycerin, and trimethylol. Examples include bronokun, pentaerythritol, and dipentaerythritol. The polyol polyallyl carbonate used may be a mixture of monomers containing multiple types of polyol components. A particularly suitable monomer for the purpose of the present invention is glycol diallyl carbonate. 4. A preferred compound is diethylene glycol bisallyl carbonate.

51 The monomer used in the present invention has a characteristic that it has a plurality of allyl groups in the molecule and can form a three-dimensional networked thermosetting polycarbonate through 1-polymerization and curing.

Because of this feature, the molded product of the present invention using this as a base material is
It not only has excellent mechanical properties such as strength and heat resistance, but also chemical resistance, abrasion resistance, scratch resistance, arc resistance,
This material is extremely excellent in various resistances such as radiation resistance and weather resistance.

Furthermore, the above-mentioned thermosetting polycarbonate has two advantages: it is essentially colorless and has outstanding transparency.

The present invention uses this polyol polyallyl carbonate as a base material and combines it with a substance that selectively blocks the transmission of at least one of ultraviolet rays, near infrared rays, and electromagnetic waves to form a molded article. This book provides a transparent shielding material that has excellent transparency and has a selective blocking effect against the ultraviolet rays, etc.;-2.

In the present invention, substances that react quickly to ultraviolet rays, near infrared rays, or electromagnetic waves can be incorporated in various forms into the molded product within a range that does not substantially impair the transparency of the molded product. For example, these substances can be uniformly dispersed and contained in the base material of the molded article, or can be contained in the molded article in the form of an intermediate layer and/or a surface coating layer. The coexistence form of these blocking substances depends on the type and properties of the blocking substances.

Any UV absorber can be used as the UV blocking substance, but it is preferable to use a polyol polyallyl carbonate cured molded product because it absorbs or reflects UV rays with a wavelength of 270 nm (mena meter) or less. It is preferable to use a substance having an ability to absorb ultraviolet rays having a wavelength of 270 to 400 nm, particularly a benzophenone-based or benzotriazole-based ultraviolet absorbing substance.

These benzophenone-based or benzotriazole-based ultraviolet absorbers have a drawback of poor solubility or compatibility with monomers such as diethylene glycol bisallyl carbonate.

One preferred embodiment of the present invention! ! In case 4, 1. By using an ethylenically unsaturated monomer that is soluble in diethylene glycol biscarbonate and compatible with diethylene glycol biscarbonate, etc., in the base material of the ultraviolet absorber. The desired blocking effect can be obtained while maintaining transparency. Comonomers useful for this purpose include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, looptyl methacrylate, benzyl methacrylate, glycidyl methacrylate, and methyl acrylate, ethyl acrylate, n-butyl acrylate. These comonomers were found to be acrylic esters such as
In general, it is preferable to use Fi in an amount of 5% by weight or more based on allyl carbonate monomer, and 30% by weight or less, preferably 15% by weight or less, most preferably 10% by weight or less, based on allyl carbonate monomer. Using these comonomers in amounts greater than the above range will have a negative impact on chemical resistance and other resistances, so use within a range that allows for dissolution and uniform mixing in the base material. It is best to use the minimum necessary amount.

Suitable examples of benzophenone-based and benzotriazole-based ultraviolet absorbing substances include, but are not limited to, the following.

2.2'-dihydroxy-4-methoxybenzophenone, 2.2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2 (2'-hydroxy-5' -methylphenyl)benzotriazole, 2(2'-hydroxy-3'-tertbutyl-5'-
methylphenyl)-5-chlorobenzotriazole, 2
(2'-Hydroxy-47-ocdoxyphenyl)benzotriazole, 2(2'-hydroxy-3't5/-ditartbutyl)benzotriazole.

These ultraviolet absorbing substances are O, n01 to 1 per base material.
It is added in an amount ranging from 5% to 0.5% by weight, most preferably from 0.05% to 0.5% by weight.

When producing a molded article, the above-mentioned ultraviolet absorber is dissolved in an acrylic or methacrylic comonomer, and this liquid is mixed with an allyl carbonate monomer and a radical initiator to prepare a molding composition. This molding composition is subjected to treatments such as defoaming, if necessary, and then filled into a mold, and polymerized and cured, if necessary, under heating.

The radical initiator and 1 to 1 are t-butyl hydroperoxide, cumene hydroperoxide, g-butyl peroxide, butyl peroxybenzoate, lauroyl fluoride, diisopropyl peroxydicarbonate,
Peroxides such as methyl ethyl ketone peroxide and azo compounds such as azobisisobutyronitrile and azobismethylisovaleronitrile are used. The content of these radical initiators is 0.1 to 5% by weight, especially 1% by weight per monomer.
It would be desirable to be able to rebuild it with four to four bones. These radical initiators can be used in combination with accelerators such as various amines and metal soaps.

Polymerization curing is generally initiated by heat or radiation, and the above-mentioned molding composition may contain compounding agents known per se within a range that does not impede the object of the present invention. .

Near-infrared blocking In another embodiment of the present invention, in order to impart the ability to block near-infrared rays to a molded article, a substance capable of absorbing near-infrared rays is added to the molded article.
It may be dispersed in the base material or provided as an intermediate layer and/or surface layer of a molded article made of the base material.

Suitable examples of near-infrared absorbing substances include, but are not limited to, the following formula, where Xid represents a sulfur atom or an oxygen atom, and Y is a quaternary
The compound represented by represents an ammonium group, each of rings A and R may be substituted with a halogen atom such as chlorine, or may have a condensed ring such as an otanaphthalene ring, specifically Specifically, bis(1,2,4-1 dichloro-5,6-cythiophenol/-to)nickel(II)-tetra-butylammonium, bis(1,4-dichloro-5,6-dithiophenol) −g)
Nickel (+1) tetra-rubutylammonium, bis(1,', 3,4-tetrachloro5゜6-sithioferto)nickel (Il'l, tetra-rubutylammonium, bis(1-thio-2- naphthrate) nickel (I)・
Tetra-rubutylammonium, etc. can be mentioned.

In a preferred embodiment of the present invention, the above-mentioned near-infrared absorbing substance is dissolved and dispersed in a transparent thermoplastic resin solution,
This solution is applied to at least one surface of the cured molded product made of the base material described above to form a coating layer having near-infrared absorbing ability. Dissolves near-infrared absorbing substances,
As the resin to be dispersed, from the viewpoint of optical transparency and adhesion to the polyol polyallyl carbonate cured product,
Cellulose ester resins such as cellulose acetate butyrate and acrylic resins such as polymethyl methacrylate are suitable. The thickness of the coating layer is 1 to 5
The range of μm is appropriate, and the coating amount of near-infrared absorber Fi
0.02 to 0.08 k/drr? A range of is appropriate.

Electromagnetic wave blocking In yet another aspect of the present invention, the electromagnetic wave blocking substance is
It is contained in the molded product so that the transparency of the molded product is not substantially impaired.

Conventionally, it has been reported that electromagnetic shielding function can be imparted to plastics by imparting conductivity to them. Coating (b) Directly dispersing carbon and metal fine powder into the molding material and molding (C) Vapor-depositing metal on the surface of the molded product, etc. However, the major drawbacks are transparency and visible light transmission. This cannot be said to be the preferred method.

In the present invention, by locating a conductive mesh as an intermediate layer almost at the center of the molded product, transparency can be maintained while maintaining 1. It is also possible to obtain an electromagnetic wave shielding effect. In this case, the openness of the conductive mesh is expressed by the Tyler standard mesh: 1. generally 80 to 250 meshes, especially 80 meshes
It is important that it is within the range of 150 meters. That is, if this mesh number is smaller than the above range,
If the electromagnetic wave shielding effect is within the above range, it will be inferior, while if it is larger than the above range, transparency will be impaired.

As the conductive mesh, a wire mesh, especially a wire mesh having a copper plating layer, is used. Most preferably, a metal plating or coating layer, especially a copper coating layer, is used on polyethylene terephthalate (polyester) fibers. A conductive mesh having a The latter net has particularly good resistance to cured molded products of polyol polyallyl carbonate.

In this electromagnetic continuous molded body, the conductive network is positioned at a position that should be approximately the center plane of the final molded product in the mold, the base material is supplied in a sandwiched manner 11, and the base material is polymerized. easily obtained by curing and integrating;
Ru.

Alternatively, two pre-cured parts, e.g. sheets, may be made from the polyol polyallyl carbonate, 1-1 these two parts may be stacked together with a conductive mesh between them, and an organic peroxide or further A desired molded article can also be obtained by adhering and integrating these with an acrylic resin syrup containing a polymerization accelerator.

Effects and Applications As mentioned above, the molded product of the present invention has excellent transparency, as well as various resistance properties such as mechanical strength, chemical resistance, heat resistance, abrasion resistance, and scratch resistance. It has the characteristics of a transparent shield that effectively blocks ultraviolet rays, near-infrared rays, or electromagnetic waves without any intrusion or leakage. It has the advantage of being easy to mold into the shape and dimensions of.

Because of these properties, the materials of the present invention can be used not only in optical applications, but also as shielding materials or structural materials for windows, covers, casings, etc. of various devices.

In particular, this material is useful as a protective or shielding material that can be monitored visually or by sensors.

The invention is illustrated by the following example.

Example 1 The following component (2) methyl methacrylate z2 # was prepared, and component (3) was first dissolved in component (2), and then mixed with components (1) and (4) to prepare a molding composition. did.

In FIG. 1 of the accompanying drawings, an electromagnetic shielding material 1 made of 100 mesh polyester fiber gauze with copper and a nickel plating layer provided thereon is placed in the center of two glass plates 2.2, and a soft vinyl chloride tube 6 or a soft vinyl chloride tube 6 or A flexible spacer member f that can follow shrinkage during polymerization and curing was fixed and sealed.

Injecting the molding composition into the space 4 of the glass plates 2, 2 1-
1 Polymerization and curing were carried out under the following temperature conditions to obtain a sheet-like molded article with a wall thickness of 3 mm. In this molded product, the conductive network was located on the center surface of the molded product, and the resin was completely integrated through the network.

Although the visible light transmittance of the obtained molded product decreased by about 40 cm due to the filling of the mesh, the transparency was sufficient and the visible light transmittance was reduced by about 400 nm.
The following ultraviolet rays were almost 100 times cut.

Example 2 Mixed solvent of bis(1,2,4-trichloro-5,6-sithioferto)nickel(II) tetra-n-butylammonium filter 2, polymethyl methacrylate 121, acetone 45, and toluene 40f Dissolved in 1./,
This solution was applied to one side of the molded product of Example 1 using a gravure coating machine so that the dry film thickness would be ')ltm, dried, and near-infrared absorbed! A coating layer with Y ability was formed.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram for explaining the molding method of Example 1. Patent applicant Fukubi Chemical Industry Co., Ltd.-18 = Figure 1 Wa 7A

Claims (5)

[Claims] (1) A cured molded product containing a substance that selectively blocks the transmission of at least one of ultraviolet rays, near infrared rays, and electromagnetic waves, and a base material whose main component is polyol polyallyl carbonate. Characteristic transparent shielding material. (2) The material according to claim 1, wherein the polyol polyallyl carbonate is diethylene glycol bisallyl carbonate. (3) The ultraviolet blocking substance is a benzophenone-based or benzotriazole-based ultraviolet absorbing substance, and the base material is capable of dissolving the ultraviolet absorbing substance in the base material, but in an amount of 30% by weight or less per polyol polyallyl carbonate. The material according to claim 1, which contains a methacrylic ester and/or an acrylic ester. (4) As substances that block near-infrared rays, there are the following formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (2) In the formula, X represents a sulfur atom or an oxygen atom, and Y represents a quaternary ammonium group. , each of rings A and B may be substituted with a halogen atom such as chlorine, and may have a condensed ring such as a naphthalene ring. Claim 1 contains a compound represented by: Materials listed. (5) The material according to claim 1, wherein the electromagnetic wave shielding material is a conductive net of 80 to 250 mesh provided approximately at the center surface of the molded product.