JP3433336B2 - Method of forming CRT surface protective layer - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to a CRT (Cathod).
The present invention relates to a method of forming a surface protective layer with a film on the outermost surface of an e-ray tube).

[0002]

2. Description of the Related Art In CRT manufacturing, the glass surface has minute scratches of the order of 100 μm in manufacturing, and if it is used as it is, the quality of the displayed image deteriorates. It was Further, if necessary, an antiglare treatment or the like may be performed one by one after the mirror polishing.

[0003]

Therefore, the conventional CR
In the production of T, there is a problem in that the mirror polishing process takes time, resulting in an increase in cost, and in addition, some products become defective in the mirror polishing process, and the non-defective rate decreases. Further, when antiglare treatment or the like is performed instead of only the mirror polishing, there is a problem that the cost is further increased and the non-defective product rate is further reduced due to a defective product generated in the processing step. It was

Therefore, an object of the present invention is to solve the above problems and to provide a CRT that is excellent in quality in a short time at low cost.
It is to provide a method by which a glass surface can be provided.

[0005]

In order to achieve the above object, the CRT surface material of the present invention is a uncured ionizing radiation-curing material which is solid at room temperature and is thermoplastic on a substrate made of a transparent resin. A curable resin layer containing a flexible resin is laminated.

On the other hand, in the method for forming a surface protective layer for a CRT of the present invention, an adhesive composed of an ionizing radiation curable resin liquid is applied to the surface of a CRT glass before mirror finishing, and then the surface material for the CRT is used as the surface material. Is laminated with the curable resin layer on the front side and then irradiated with ionizing radiation to cure the curable resin layer of the adhesive and the surface material for CRT. In the above method for forming a surface protective layer for CRT, before laminating the surface material for CRT, C
It is also the one that is preformed into the shape of the RT glass surface.

The method for forming the CRT surface protective layer of the present invention will be described in detail below. FIG. 1 is a cross-sectional view showing a surface material for CRT. As shown in the figure, the CRT surface material 1 comprises a base material 2 made of a transparent resin and an uncured ionizing radiation curable resin which is solid at room temperature and is thermoplastic and is provided on the base material 2. And the curable resin layer 3 which it has.

FIG. 2 is a sectional view showing an embodiment of the CRT surface protective layer obtained by the method for forming a CRT surface protective layer of the present invention, which uses the CRT surface material 1. That is, in FIG. 2, the CRT surface material 1 is a CRT.
A cross-section of a state in which the surface material 1 for CRT is laminated on the glass 5 via an adhesive 4 made of an ionizing radiation curable resin liquid and laminated along the surface shape of the CRT glass to form the surface protective layer 1 of the CRT glass. It is a figure. As shown in the figure, C
The curable resin layer 3 of the RT surface material 1 becomes the outermost layer. Further, the scratches 6 on the surface of the CRT glass are filled with the adhesive 4.

The base material 2 of the CRT surface material 1 may be made of a resin that is transparent enough to allow the rear surface image of the surface material to be seen through and can support a curable resin layer. As such a substrate, a film-like one is usually used, for example, a polyester resin such as polyethylene terephthalate, an acrylic resin such as polymethylmethacrylate, a cellulose resin such as cellulose triacetate,
Alternatively, a known resin such as a polycarbonate resin can be used. Especially when preforming CRT surface materials,
Thermoplastic resin is good. Among these, polyethylene terephthalate, which has excellent optical properties and is excellent in strength and cost, is preferable. The thickness of the base material is usually about 50 to 400 μm, more preferably about 150 to 300 μm, in view of handleability and moldability. Further, the surface of the base material may be subjected to a known easy-adhesion treatment.

The curable resin layer 3 is solid at room temperature in an uncured state, has thermoplasticity and solvent solubility, but is apparent or hand-painted after coating and drying the solvent. It is mainly composed of an ionizing radiation-curable resin that gives a coating film that is non-fluid (touch-drying property) when touched with and is non-adhesive. Here, ionizing radiation refers to ionizing radiation composed of an electromagnetic wave or a charged particle beam having an energy quantum sufficient for crosslinking and polymerizing molecules, and there are various types, but industrially usable ones are: Ultraviolet rays or electron rays, and γ rays can also be used.

The ionizing radiation curable resin has a glass transition temperature of 0 to 250, as will be specifically described below.
There are compounds having a radical-polymerizable unsaturated group in a polymer at ° C, and compounds having a radical-polymerizable unsaturated group having a melting point of 20 to 250 ° C. Further, these may be used as a mixture, and further, a radical-polymerizable unsaturated monomer may be added to them for use. Further, in order to obtain flexibility of the cured resin product, a non-crosslinking type thermoplastic resin may be added. To do.

(1) Those having a radically polymerizable unsaturated group in a polymer having a glass transition temperature of 0 to 250 ° C .: More specifically, those obtained by polymerizing or copolymerizing the following compounds What introduced the radically polymerizable unsaturated group by the method (a)-(d) mentioned later can be used.

Monomers having hydroxyl groups: N-methylol (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3. -Phenoxypropyl (meth)
Acrylate etc.

Monomers having a carboxyl group: (meth) acrylic acid, (meth) acryloyloxyethyl monosuccinate and the like.

Monomers having epoxy groups: glycidyl (meth) acrylate and the like.

Monomers having an aziridinyl group: 2-aziridinylethyl (meth) acrylate, allyl 2-aziridinylpropionate and the like.

Monomers having amino groups: (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and the like.

Monomers having sulfone groups: 2- (meth) acrylamido-2-methylpropanesulfonic acid and the like.

Monomers having isocyanate groups: 2,
An addition product of 4-toluene diisocyanate and 2-hydroxyethyl (meth) acrylate in an amount of 1 mol to 1 mol, such as an addition product of diisocyanate and a radical-polymerizable monomer having active hydrogen.

Monomers copolymerizable with the above-mentioned monomers and other than the above-mentioned: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth). Acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth)
Acrylate etc. These are used as a copolymerization component for adjusting the glass transition point of the polymer or copolymer obtained from the above monomers (1) to (4) and the coating film strength of the curable resin layer after curing.

Next, the polymer or copolymer obtained as described above is reacted by the following methods (a) to (d) to introduce a radically polymerizable unsaturated group, )
An ionizing radiation curable resin having a radically polymerizable unsaturated group in a polymer having a glass transition temperature of 0 to 250 ° C. is obtained.

(A) In the case of a polymer or copolymer of a monomer having a hydroxyl group, the above-mentioned monomer having a carboxyl group such as (meth) acrylic acid is subjected to a condensation reaction.

(B) In the case of a polymer or copolymer of a monomer having a carboxyl group or a sulfone group, the above-mentioned monomer having a hydroxyl group is subjected to a condensation reaction.

(C) In the case of a polymer or copolymer of a monomer having an epoxy group, an isocyanate group or an aziridinyl group, the above-mentioned monomer having a hydroxyl group or a carboxyl group is subjected to an addition reaction.

(D) In the case of a polymer or copolymer of a monomer having a hydroxyl group or a carboxyl group, the above-mentioned monomer having an epoxy group or an aziridinyl group, or the diisocyanate compound and a hydroxyl group-containing acryl A monomer having an isocyanate group, such as a 1: 1 mole addition product of an acid ester monomer, is subjected to an addition reaction.

In order to carry out the above reaction, it is desirable to add a small amount of a polymerization inhibitor such as hydroquinone and to send it with dry air.

(2) A compound having a melting point of room temperature (20 ° C.) to 250 ° C. and a radically polymerizable unsaturated group:
Stearyl (meth) acrylate, triacrylic isisoannurate, cyclohexanediol di (meth) acrylate, spiroglycol diacrylate, spiroglycol (meth) acrylate and the like.

Further, it is also possible to use a mixture in which the compound of the above (1) and the compound of the above (2) are mixed, to which a radical polymerizable unsaturated monomer is added as a reactive diluent. You can also

The radical-polymerizable unsaturated monomer which serves as the reactive diluent improves the crosslink density and the heat resistance upon irradiation with ionizing radiation. , Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tetra (meth) acrylate , Pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, polyethylene glycol diglycidyl ether di (meth) acrylate,
Propylene glycol diglycidyl ether di (meth)
Acrylate, polypropylene glycol diglycidyl ether di (meth) acrylate, diglycidyl ether di (meth) acrylate, sorbitol tetraglycidyl ether tetra (meth) acrylate and the like can be used. The amount used is the compound of (1), the compound of (2), or a mixture of the compound of (1) and the compound of (2),
It is preferable to use 0.1 to 100 parts by weight based on 100 parts by weight of the solid content.

The above-mentioned ionizing radiation curable resin can be sufficiently cured by an electron beam, but when it is cured by irradiation of ultraviolet rays, benzoquinone, benzoin, benzoin ethers such as benzoin methyl ether, and halogenated acetophenones. , A known photopolymerization initiator that generates a radical upon irradiation with ultraviolet rays such as diacetyls, and, if necessary, a known photosensitizer such as amines such as n-butylamine and triethylamine, and tri-n-butylphosphine Etc. can be used.

Further, in order to adjust flexibility or to facilitate touch-drying, a non-crosslinking type thermoplastic resin which is an ionizing radiation non-curing resin in contrast to the above-mentioned ionizing radiation curable resin. 1 to 70% by weight, preferably 1 to 50% by weight can be mixed and used. As the non-crosslinking type thermoplastic resin, for example, thermoplastic resins such as urethane resin, butyral resin, cellulose resin, polyester resin, acrylic resin and the like can be used. Particularly, from the viewpoint of flexibility, cellulose resin, butyral resin, urethane Resins are preferred.

The curable resin layer containing the above-mentioned ionizing radiation curable resin and the base material made of a transparent resin as a support thereof may be colored if necessary. Also, the base material,
When the adhesive and the curable resin layer after curing have the same refractive index as the adjacent layers, for example, the CRT glass and the base material in the case of an adhesive, the optical interface at the interlayer interface is improved. Distortion can be canceled.

The curable resin layer is a coating liquid prepared by diluting the above-mentioned ionizing radiation curable resin by an appropriate method, for example, with a solvent, such as roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating. It can be obtained by coating on a substrate by a known coating means such as coat, air knife coat, kiss coat, smooth coat, comma coat and the like. The thickness of the curable resin layer is usually 2 to 20 μm, preferably 4
It is about 10 μm.

Since the curable resin layer is the outermost layer of the surface protection layer of CRT glass, the curable resin layer is
The antiglare property, the antireflection property, the antistatic property and the like may be imparted individually or in combination. Utilizing the fact that the curable resin layer is thermoplastic in order to impart antiglare properties, a shaping process using a shaping mold such as an embossing roll, a shaping film or a shaping plate (for example, laminating a shaping film The desired surface roughness pattern is formed on the surface by irradiating with ionizing radiation and curing after that, or the resin beads are placed in the ionizing radiation curable resin coating liquid for forming the resin layer. A matting agent such as silica or silica may be added. Further, in order to impart antireflection property, a known antireflection film may be formed by vapor deposition or coating. Further, in order to impart antistatic property, various functions can be obtained by adding a known antistatic agent to an ionizing radiation-curable resin coating liquid or coating an antistatic primer after forming a resin layer. A CRT surface material is obtained.

In this way, for the CRT of the present invention, the curable resin layer having the uncured ionizing radiation curable resin which is solid and is thermoplastic at room temperature is laminated on the base material made of the transparent resin. A surface material is obtained.

Then, this CRT surface material is adhered to the glass surface of the CRT with an adhesive composed of an ionizing radiation curable resin liquid, and then irradiated with ionizing radiation to cure the curable resin layer and the adhesive. Therefore, the surface material for CRT is C
It becomes a surface protective layer on the surface of the RT glass. Below, this CRT
A method for forming a CRT surface protective layer by adhering the surface material for use on the glass surface of the CRT will be described.

The adhesive for adhering the surface material for CRT to the surface of the CRT glass is not particularly limited as long as it is transparent and adheres both, but an adhesive composed of an ionizing radiation curable resin liquid is particularly preferable. As such an adhesive,
Acrylate prepolymers such as polyester acrylate, urethane acrylate, and epoxy acrylate, acrylate monomers, epoxy, cationic polymerization systems,
Known ionizing radiation curable adhesives such as polyene / thiol type can be used, but solventless adhesives made of ionizing radiation curable resin that is liquid at room temperature in the uncured state can be heat-cured or solvent-dried. Is unnecessary, and there is no generation of bubbles due to residual solvent after adhesion, which is preferable. Further, the adhesive composed of the ionizing radiation-curable resin is cured by ionizing radiation such as ultraviolet rays or electron beams, similarly to the above-mentioned curable resin layer.

The CRT surface protective layer is formed, for example, by cutting the surface of the CRT glass surface by a suitable method such as flow coating onto the surface of the CRT and cutting it to a desired size.
Laminate so that the side surface of the base material of the RT surface material abuts. Alternatively, an adhesive is applied to the side surface of the base material of the surface material for CRT, and the surface of the CRT glass is brought into contact with the adhesive to be laminated. If a roll or the like is used at the time of lamination, the adhesive agent interposed between the CRT glass surface and the CRT surface material can be spread. In addition, even if the surface of the CRT glass is scratched, the liquid adhesive fills the scratches,
It does not matter if the CRT glass surface is not mirror-polished.

If the shape of the surface of the CRT glass has a large curvature, the CRT surface material may be preformed in advance so as to correspond to the curvature.
Applicable to RT glass surface. Preforming of the surface material for CRT includes, for example, vacuum forming, pressure forming, vacuum pressure forming,
A known forming means such as press forming or drawing is used. The surface material for CRT is heated to a temperature at which desired moldability of the base material and the curable resin layer is obtained, if necessary.

Crosslinking and curing of the curable resin and the adhesive are carried out by irradiating ionizing radiation such as ultraviolet rays and electron beams from the surface material side for CRT. For example, as ultraviolet rays, ultra high pressure mercury lamp,
Ultraviolet light from light sources such as high-pressure mercury lamps, low-pressure mercury lamps, carbon arc, xenon arc, black light, and metal halide lamps, and electron beams include Cockcroft-Walton type, Handegraph type, resonance transformer type, insulating core transformer type, An electron beam having an energy in the range of 50 to 1000 keV, preferably 100 to 300 keV by various electron beam accelerators such as a linear type, a dynamitron type and a high frequency type is used. Further, by using an electron beam that is continuously irradiated in a curtain shape from a linear filament, it is possible to continuously cure the CRT glass to which the surface material for CRT that is an irradiation target is attached.

Thus, a surface protective layer made of the surface material for CRT is formed on the surface of the CRT glass before mirror finishing. Then, the unevenness due to minute scratches on the glass surface is also eliminated.

[0042]

According to the method for forming a CRT surface protective layer of the present invention,
Molding that allows the curable resin layer of the CRT surface material, which is the outermost layer after being attached to the CRT glass surface, to deform and follow the curved CRT glass surface because it is uncured and thermoplastic when attached Since it has a property, it can be laminated without causing optical distortion. Then, since the curable resin layer is cured after being attached, excellent surface properties are exhibited. Moreover, the curable resin layer is composed of a layer having an ionizing radiation curable resin, and since the ionizing radiation curable resin liquid is used for the adhesive, ionizing radiation can be used as a curing means for the CRT glass surface. The object can be cured quickly without being heated in the pasted state. Further, since the curable resin layer as the outermost layer has the ionizing radiation curable resin, excellent surface properties such as scratch resistance can be obtained. In addition, before laminating the surface material for CRT, by preforming the shape of the CRT glass surface, it is possible to laminate to a three-dimensional curved surface shape.

[0043]

EXAMPLES Next, the present invention will be described more specifically by way of Examples and Comparative Examples.

Example 1 As a substrate, one side of a transparent polyethylene terephthalate film (manufactured by Teijin Ltd.) having a thickness of 188 μm, which was subjected to easy-adhesion treatment on both sides, was coated with an ultraviolet curable resin (Mitsubishi Yuka Fine Co., Ltd.). Produced by triazine-based acrylate, LZ-075) was gravure-coated with a methylethylketone / cyclohexanone = 2/1 solution to form a curable resin layer having a thickness of 7 μm (when dry) to obtain a CRT surface material of the present invention. .

On the other hand, the laminated portion is a CR with a quadric surface.
UV-curable resin (Nippon Kayaku Co., Ltd., Kayarad ASE-01) 300 μm as an adhesive agent on the surface of T glass
The surface material for CRT obtained as described above was laminated onto the surface of the CRT, and the roll was pressure-bonded with a roll according to the shape of the glass surface such as the edge of the CRT and laminated. Then, the high-pressure mercury lamp emits an ultraviolet ray of 300 mJ / c.
The adhesive and the curable resin layer were cured by irradiation under the condition of m ² to form a CRT surface protective layer. Obtained, CR
The T surface protective layer had no distortion and satisfied the practical use for CRT.

Example 2 In Example 1, a CRT glass having a three-dimensional curved surface is used in the laminating portion, and a CRT is used.
Before attaching the surface material for the CRT to the glass surface,
A CRT surface protective layer was formed in the same manner as in Example 1 except that the glass surface shape was formed by vacuum lamination under predetermined conditions. The obtained CRT surface protective layer had no distortion and satisfied the practical use as a CRT.

Comparative Example In Example 1, the formation of the curable resin layer was carried out by using an ultraviolet curable resin (Dainichi Seika Kogyo Co., Ltd.).
Manufactured by EXG-62) is gravure-coated and then irradiated with ultraviolet rays from a high-pressure mercury lamp (irradiation condition: 160W
/ Cm, processing speed 10m / min, 4pass), thickness 7μ
The surface material for CRT has a curable resin layer that has been cured with m. Then, in the same manner as in Example 1, it was attached to the surface of the CRT glass. As a result, the obtained CRT surface protective layer did not satisfy the practical use as a CRT because optical distortion occurred in the surface material for CRT around the edge of the glass.

[0048]

As described above in detail, according to the CRT surface material and the method for forming a CRT surface protective layer of the present invention, mirror polishing of the CRT glass surface becomes unnecessary, and the curved glass surface can be processed in a short time. A CRT surface protective layer having low optical distortion and excellent surface properties such as surface hardness can be obtained at a low cost. Further, in the method for forming a CRT surface protective layer, the surface material for CRT to be used is preformed in advance into the glass surface shape of the CRT, so that the surface protective layer can be formed even if the CRT glass surface has a three-dimensional curved surface shape. Becomes In addition, the CRT surface protective layer also has an explosion-proof function, which in turn has the effect of reducing the weight of the CRT.

If it is only necessary to apply a hard protective layer to the CRT surface protective layer, a hardened resin layer may be formed on the surface material for CRT from the beginning.
The glass surface is not perfectly flat, and especially in the peripheral portion, it has a three-dimensional curved surface shape. For this reason, it is possible to use an ionizing radiation curable resin as the cured curable resin layer and provide it with some formability capable of following the curved surface shape, but optical distortion is likely to occur. On the other hand, if a thermoplastic resin layer is applied to the protective film, there is no problem in moldability and the problem of optical distortion can be solved. However, a thermoplastic resin layer cannot have surface properties such as scratch resistance as a protective film. However, in the present invention, since the resin layer is a thermoplastic resin layer during lamination and a curable resin layer after lamination, a protective layer satisfying all the properties of surface physical properties, distortion, and moldability can be obtained. Further, in the present invention, since the curable resin layer is solid at room temperature before lamination,
Unlike liquid, it has excellent handling properties for CRT surface materials.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of an example of a surface material for CRT of the present invention.

FIG. 2 is a sectional view of an example of a CRT surface protective layer obtained by the present invention.

[Explanation of symbols]

1 CRT surface material, CRT surface protection layer 2 base materials 3 Curable resin layer 4 Adhesive (layer) 5 CRT glass 6 scratches

Claims (2)

(57) [Claims] 1. A transparent CRT glass surface, which has not been mirror-finished, is coated with an adhesive composed of an ionizing radiation-curable resin liquid and then transparent.
It is a solid at room temperature and is thermoplastic on a substrate made of various resins.
Curable resin having uncured ionizing radiation curable resin
Using the CRT surface material obtained by laminating a layer was laminated and a surface of the cured resin layer of the surface material and then irradiated with ionizing radiation to cure the curable resin layer of the adhesive and the CRT surface material A method for forming a CRT surface protective layer, comprising: 2. The method for forming a CRT surface protective layer according to claim 1 , wherein the CRT surface protective layer is preformed before being laminated with the CRT surface material.