JPH09254325A - Film laminate for protection of cathode ray tube - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film laminate for protection of a cathode ray tube which is excellent in adhesion to the surface of the cathode ray tube, optical characteristics wherein distinctness provided to the cathode ray tube is not impaired, scratch resistance, etc. SOLUTION: In this cathod ray tube protecting film laminate, a surface hardened layer (B) to one side surface, and a pressure sensitive adhesive layer (C) are respectively provided to the other side surface via laminate films (A), (A') provided on both sides of a polyester film. In this case a thickness of the polyester film is 100-200μm, and the laminate films (A), (A') contain a water dispersive polyester resin of 10-40 deg.C glass transition temperature and a melamine base crosslinking agent. The water dispersive polyester resin has a carboxylic acid and/or its salt on its side chain. The pencil hardness of the surface hardened layer (B) is 3H or higher. Total light transmittance as the laminate is 80-99.5%, and haze is 0.1-3%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film laminate for protecting cathode ray tubes, and more specifically, a surface hardening layer is provided on one surface and a pressure-sensitive adhesive layer is provided on the other surface of a base polyester film with a laminated film interposed therebetween. And a film laminate for protecting a cathode ray tube.

[0002]

2. Description of the Related Art In order to improve the adhesiveness of a polyester film, various polyester resins, urethane resins, etc. may be provided on the polyester film.
It is known from Japanese Patent No. 15825, Japanese Patent Laid-Open No. 58-78761, Japanese Patent Laid-Open No. 60-248232, and the like. Further, JP-A-62-263237, JP-A-63-147798, and the like are known as methods for providing a surface-hardened layer on various types of easy-adhesion films.

However, when these are used for protection of cathode ray tubes, sufficient optical properties and durability have not been obtained.

[0004]

The cause of this may be as follows. That is, it is important to provide a surface-hardened layer and at the same time make the film have a certain thickness in order to provide a sufficient protection function, in order to provide good protection of the cathode ray tube. is there.

However, if the film is made too thick, the sharpness of the cathode ray tube will be impaired, which is not necessarily optically desirable. On the other hand, if the film is made too thin, the workability during film production will be poor. However, there is a problem such as durability, which is not desirable either.

In particular, when the film laminate for protecting a cathode ray tube is viewed as a whole, it can be adhered to the surface of the cathode ray tube, has the optical characteristics that do not substantially impair the sharpness inherent in the cathode ray tube, and has scratch resistance. Good characteristics are important characteristics.

In view of the above-mentioned problems and required characteristics, the present invention has an object of providing a film laminate for protecting a cathode ray tube which is excellent in adhesion, optical property, scratch resistance and the like.

[0008]

The cathode ray tube protective film laminate of the present invention which achieves the above-mentioned object has the following constitution. That is, the film laminate for protecting a cathode ray tube of the present invention has a surface cured layer (B) on one side and an adhesive on the other side via the laminated films (A) and (A ′) provided on both sides of a polyester film. In the cathode ray tube protective film laminate provided with the layer (C), the polyester film has a thickness of 100 to 200 μm, and the laminate films (A) and (A ′) have a glass transition temperature of 10 to 40 ° C. Including a dispersible polyester resin and a melamine-based crosslinking agent,
The water-dispersible polyester resin has a carboxylic acid and / or a salt thereof in the side chain, the surface hardened layer (B) has a pencil hardness of 3H or more, and the total light transmittance as a laminate is 80 to 99.
5% and haze are 0.1% to 3%.

Further, in a preferred embodiment of the film laminate for protecting a cathode ray tube of the present invention, the surface-cured layer (B) comprises a monomer having three or more (meth) acryloyloxy groups in one molecule. Actinic radiation curing containing an actinic radiation-curable monomer mixture, which is a main constituent, of at least one species and at least one monomer having 1 to 2 ethylenically unsaturated double bonds in one molecule. In a preferred embodiment, in the film laminate for protecting a cathode ray tube of the present invention, the pressure-sensitive adhesive layer (C) is a main constituent component of an actinic ray curable monomer mixture. And an actinic radiation cured product.

As one more preferable embodiment, the above-mentioned cathode ray tube protecting film laminate is used, and the surface-hardened layer (B) of the film laminate is provided on the side opposite to the side where the polyester film is present. A film laminate for protecting a cathode ray tube, which has a light reflection preventing film formed on the surface thereof and has a total light transmittance of 60 to 99.5% and a haze of 0.1% to 3% as the whole laminate. Is.

Further, in this embodiment, the light antireflection film is preferably a cathode ray tube protection film laminate including at least a light absorption layer, and more preferably, the light antireflection film is at least In this embodiment, the cathode ray tube protection film laminate is configured to include a dielectric layer, a conductor layer, and a light absorption layer.

In the present invention, the adhesion to the surface of the cathode ray tube as the cathode ray tube protective film laminate is mainly brought about by providing the laminated films (A) and (A '), which the cathode ray tube originally has. The optical characteristics that do not impair the sharpness are mainly brought about by the total light transmittance of the laminate as 80 to 99.5% and the haze of 0.1% to 3%, and the improvement of scratch resistance. Is mainly brought about by the pencil hardness of the surface hardened layer being 3H or more.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The cathode ray tube protective film laminate of the present invention has a surface cured layer (B) on one side and an adhesive layer (on the other side) via the laminated films (A) and (A ′) provided on both sides of a polyester film. C) is provided as a basic structure of a laminated structure, and the features thereof are firstly that the polyester film has a thickness of 100 to 200 μm, and secondly, the laminated film (A) and (A). ′) Is composed of a water-dispersible polyester resin having a glass transition temperature of 10 to 40 ° C. and a melamine-based crosslinking agent, and the water-dispersible polyester resin has a carboxylic acid and / or a salt thereof in a side chain. is there. And thirdly, the pencil hardness of the surface hardened layer is 3
It is H or more, the total light transmittance of the laminate is 80% or more, and the haze is 3% or less.

According to the knowledge of the present inventors, when the total light transmittance of the laminate is less than 80%, or when the haze is more than 3%, the CRT definition is insufficient. Not preferable. According to the findings of the present inventors, the upper limit of the total light transmittance is about 99.5% and the lower limit of the haze is about 0.1%. It is a typical range.

The polyester of the polyester film used in the present invention is a generic term for polymers having an ester bond as a main bonding chain, and preferred polyesters are ethylene terephthalate and ethylene-2,6. -It is preferable to use one having as a main constituent at least one constituent selected from naphthalate, butylene terephthalate, ethylene-α, β-bis (2-chlorophenoxy) ethane-4,4-dicarboxylate and the like. it can. These constituent components may be used alone or in combination of two or more, and any of them may be used. Among them, a polyester containing ethylene terephthalate as a main constituent component is comprehensively judged from the viewpoint of quality, economy and the like. Is particularly preferably used.

Further, in the polyester, if necessary, various additives such as an antioxidant, a heat resistance stabilizer, a weather resistance stabilizer, an ultraviolet absorber, an organic lubricant, a pigment, a dye,
Organic or inorganic fine particles, a filler, an antistatic agent, a nucleating agent, etc. may be added within a range that does not impair the effects of the present invention.

The intrinsic viscosity of the above-mentioned polyester (25 ° C.
Measured in o-chlorophenol) of 0.4-1.2.
dl / g is preferred, more preferably 0.5-0.8d
Those in the range of 1 / g are suitable for the present invention.

From the viewpoint of further improving the adhesion to the laminated film, the amount of carboxyl terminal groups of the base polyester film is preferably 37 equivalents / ton or more, more preferably 40 equivalents / ton or more. . According to the knowledge of the present inventors, most preferably, the amount of the carboxyl end group is in the range of 40 to 55 equivalent / ton.

The polyester film using the above polyester is preferably biaxially oriented when the laminated film is provided. Biaxially oriented polyester film means an unstretched polyester sheet or film in the longitudinal direction and the width direction, respectively.
It is a product which has been stretched by about 5 times and then heat-treated to complete the crystal orientation, and which shows a biaxial orientation pattern by wide-angle X-ray diffraction.

Although the thickness of the polyester film is not particularly limited, it is 100 to 2 from the viewpoint of processing suitability as a film for protecting cathode ray tubes and explosion proof.
It is important to set the thickness in the range of 00 μm.

Membranes (A) and (A ') are laminated on both sides of the polyester film. The laminated membranes (A) and (A') are composed of a water-dispersible polyester resin and melamine as constituent components. Contains a system crosslinking agent. This polyester resin has an ester bond in the main chain or side chain and has a carboxylic acid and / or its salt in the side chain. Such a polyester resin can be obtained by copolymerizing a polyvalent carboxylic acid with a polyester resin obtained by polycondensing a dicarboxylic acid and a diol.

The laminated films (A) and (A ') are as follows.
They may have the same composition as each other, but may have different compositions.

As the carboxylic acid component constituting the polyester resin, aromatic, aliphatic, or alicyclic dicarboxylic acid, trivalent or higher polyvalent carboxylic acid and the like can be used. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 2,5-dimethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2. −
Bisphenoxyethane-p, p'-dicarboxylic acid, phenylindanedicarboxylic acid and the like can be used. From the viewpoint of strength and heat resistance of the laminated film, it is desirable that these aromatic dicarboxylic acids account for 30 mol% or more, preferably 35 mol% or more, and more preferably 40 mol% or more of the total dicarboxylic acid components. According to the findings of the present inventors,
Most preferably, it is in the range of 60 to 100 mol%.

Examples of the aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1, 4-Cyclohexanedicarboxylic acid and the like and their ester-forming derivatives can be used.

As the glycol component of the polyester resin, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3
-Butanediol, 1,4-butanediol, 1,5-
Pentanediol, 1,6-hexanediol, 1,7
-Heptanediol, 1,8-octanediol, 1,
9-nonanediol, 1,10-decanediol, 2,
4-dimethyl-2-ethylhexane-1,3-diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 3 -Methyl-1,5
-Pentanediol, 2,2,4-trimethyl-1,6
-Hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-
Cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4'-thiodiphenol, bisphenol A, 4,4'-methylenediphenol, 4,4 '-(2 -Norbornylidene)
Diphenol, 4,4'-dihydroxybiphenol,
o-, m-, and p-dihydroxybenzene, 4,
4'-isopropylidenephenol, 4,4'-isopropylidenebindiol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol and the like can be used.

As the polycarboxylic acid, for example, trimellitic acid, trimellitic anhydride, pyromellitic acid,
Pyromellitic dianhydride, 4-methylcyclohexene-1,
2,3-tricarboxylic acid, trimesic acid, 1,2,3
4-Putanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, 5- (2,5-dioxotetrahydrofurfuryl) -3 -Methyl-3-cyclohexene-1,2-dicarboxylic acid, 5- (2,5-dioxotetrahydrofurfuryl) -3-cyclohexene-1,2-
Dicarboxylic acid, cyclopentanetetracarboxylic acid, 2,
3,6,7-naphthalenetetracarboxylic acid, 1,2,
5,6-naphthalenetetracarboxylic acid, ethylene glycol bistrimellitate, 2,2 ', 3,3'-diphenyltetracarboxylic acid, thiophene-2,3,4,5-
Tetracarboxylic acid, ethylene tetracarboxylic acid, etc. or their alkali metal salts, alkaline earth metal salts, ammonium salts, etc. can be used, but are not limited thereto.

The polyester resin obtained by these copolymers has a glass transition temperature of 40 ° C. or lower, 10 ° C.
It is necessary to be above. Preferably 35 ° C or lower, 10 ° C
It is above, more preferably 30 ° C or lower, and 15 ° C or higher. When the glass transition temperature is within the above range, the adhesion with the base film and the coating is improved.

The polyester resin can be manufactured by various manufacturing techniques. Further, as a method for obtaining a polyester resin having a large amount of carboxylic acid at the terminal and / or side chain, JP-A-54-46294, JP-A-60-209073, and JP-A-62-240318 are known.
JP-A-53-26828, JP-A-53-28828
26829, JP-A-53-98336, JP-A-56-116718, and JP-A-61-1246.
It can be produced by a resin obtained by copolymerizing a polyvalent carboxylic acid having a valence of 3 or more, as described in JP-A-84, JP-A-62-240318, etc., but other methods may be used.

In the present invention, the laminated films (A) and (A ')
The melamine-based cross-linking agent used as a constituent component is not particularly limited, but is partially or partially reacted with melamine, a methylolated melamine derivative obtained by condensing melamine and formaldehyde, and a lower alcohol to methylolated melamine. Completely etherified compounds and mixtures thereof can be used.

The melamine-based cross-linking agent may be either a monomer or a condensate composed of a dimer or higher polymer, or a mixture thereof.

As the lower alcohol used for the etherification, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like can be preferably used. As a functional group,
Those having an imino group, a methylol group, or an alkoxymethyl group such as a methoxymethyl group or a butoxymethyl group in one molecule, and imino group-type methylated melamine resin, methylol group-type melamine resin, methylol group-type methylated melamine resin, Complete alkyl type methylated melamine resin and the like can be used. Among them, the methylolated melamine resin is the most preferable. Furthermore, an acidic catalyst such as p-toluenesulfonic acid may be used to accelerate the thermal curing of the melamine-based crosslinking agent.

The polyester resin and the melamine-based cross-linking agent may be mixed and used in an arbitrary ratio, but in order to bring out the effect of the present invention more remarkably, the following ratio (solid content weight ratio) is used.
Mix with. That is, polyester resin 100
The melamine-based cross-linking agent is preferably 0.5 to 100 parts by weight.
40 parts by weight, more preferably 1 to 30 parts by weight, most preferably 2 to 20 parts by weight.

In the present invention, the laminated films (A) and (A ')
Is a coating composition containing the above-mentioned two components as the main components,
It is dried and heat treated. The main component means that the above two kinds occupy 50% by weight or more in the laminated film. However, it is preferable that the two kinds account for 80% by weight or more, and most preferably 90% by weight or more.

In the laminated films (A) and (A '), other resins, for example, polyester resins other than the above-mentioned polyesters used in the present invention, and acrylic resins may be used within the range that the effects of the present invention are not impaired. , Urethane resin, epoxy resin,
Silicone resin, urea resin, phenol resin, etc. may be blended.

Further, in the laminated films (A) and (A '), various additives such as antioxidants, heat resistance stabilizers, weather resistance stabilizers, and ultraviolet absorbers are used as long as the effects of the present invention are not impaired. , Organic lubricants, pigments, dyes, organic or inorganic fine particles, fillers, antistatic agents, nucleating agents and the like may be used in combination. In particular, those obtained by adding and blending inorganic particles and / or organic particles in the coating agent and biaxially stretching are more preferable because the slipperiness is improved.

The inorganic particles to be added include silica, colloidal silica, alumina, alumina sol, kaolin,
Talc, mica, calcium carbonate and the like can be used as typical ones. As the organic particles, acrylic particles, styrene particles, olefin particles, imide particles, etc. can be used. The particles have an average particle size of 0.01 to 1
It is preferable to use one having a thickness of 0 μm, more preferably 0.05 to 5 μm, and most preferably 0.08 to 2 μm.
It is better to use the one. Moreover, the compounding ratio to the solid content in the coating material is not particularly limited, but is 0.05 to 8 by weight ratio.
It is preferable to use parts by weight, and more preferably 0.1 to
3 parts by weight.

A preferable method for providing a laminated film in producing the film laminate for protecting a cathode ray tube according to the present invention is to apply a laminated film component during the production process of the polyester film and stretch it together with the base film. Is most preferred. For example, a melt-extruded polyester film before crystal orientation is 2.5 to 5 in the longitudinal direction.
It is stretched about twice, and the surface to be coated is subjected to corona discharge treatment, and the coating agent is continuously applied to the treated surface. The film thus coated is dried while being passed through a stepwise heated zone, and stretched in the width direction by about 2.5 to 5 times. Further, the laminated film can be provided by a method of continuously leading to a heating zone of 150 to 250 ° C. to complete the crystal orientation.

At this time, the thickness of the coating film is not particularly limited, but normally, a range of about 0.01 to 0.3 μm is desirable. This is because if the thickness of the laminated film is too thin, the adhesion may be poor.

As the method of coating on the substrate film, various coating methods such as reverse coating method, gravure coating method, rod coating method, bar coating method, die coating method, spray coating method and the like can be used.

The surface hardened layer (B) provided on one surface side of the laminated film may be made of an acrylic type, urethane type, melamine type, organic silicate, silicone type, metal oxide or the like. The surface hardened layer (B)
Requires a pencil hardness of 3H or more. This is because when the pencil hardness is less than 3H, it is inferior in practicality as a protective film for a cathode ray tube because it is easily scratched.

In particular, in terms of hardness, durability, etc., the surface-cured layer (B) is preferably a silicone-based or acrylic-based one, and an acrylic-based one, particularly a curable, flexible and productive one. Actinic ray curable acrylic type is preferable.
The actinic ray curable acrylic system contains an acryl oligomer and a reactive diluent as actinic ray polymerization components, and may further contain a photoinitiator, a photosensitizer, and a modifier as required. Is.

Here, as the acrylic oligomer, polyester acryl, urethane acryl, epoxy acryl, polyether acryl, etc. can be used, including those in which a reactive acryl group is bonded to an acryl-based resin skeleton. A rigid skeleton such as melamine or isocyanuric acid to which an acrylic group is bonded can be used, but the skeleton is not limited thereto. Further, the reactive diluent has a function as a solvent in a coating step as a medium of a coating agent, and also has a group which itself reacts with a monofunctional or polyfunctional acrylic oligomer,
It serves as a copolymerization component of the coating film.

Further, particularly in the case of crosslinking by ultraviolet rays,
Since the light energy is small, it is preferable to add a photopolymerization initiator and / or a sensitizer in order to promote conversion or initiation of light energy.

Specific examples of these acrylic oligomers, reactive diluents, photopolymerization initiators, sensitizers, crosslinking devices, etc. are as follows:
"Crosslinking Agent Handbook", pages 267 to 275,
Pages 562 to 593 (edited by Shinzo Yamashita, Tosuke Kaneko, published by Taiseisha in 1981) can be referred to, but not limited thereto. Examples of commercially available polyfunctional acrylic UV-curable coatings include Mitsubishi Rayon Co., Ltd., Fujikura Kasei Co., Ltd., Dainichi Seika Kogyo Co., Ltd., Dainippon Ink and Chemicals Co., Ltd., Toagosei Kagaku Kogyo Co., Ltd. , Nitto Kasei Co., Ltd. and other products can be used, but are not limited thereto.

As a modifier for the surface hardened layer (B),
Applicability improvers, defoamers, thickeners, antistatic agents, inorganic particles, organic particles, organic lubricants, organic polymers, dyes, pigments, stabilizers, etc. can be used, and these are active. It can be used as a composition of a coating layer within a range that does not inhibit the reaction due to rays, and the characteristics of the surface-hardened layer (B) can be improved depending on the application.

Further, the composition of the surface-hardened layer used in the present invention has an organic content within the range that does not impair the effects of the present invention for the purpose of improving the workability during coating and controlling the coating film thickness. A solvent can be added.

Among these, particularly at least one kind of monomer having three or more (meth) acryloyloxy groups in one molecule and 1 to 2 ethylenically unsaturated double bonds in one molecule. A surface-cured layer made of an actinic radiation-cured product containing, as a main component, an actinic radiation-curable monomer mixture composed of at least one kind of a monomer having
It is preferable because it is excellent in abrasion resistance and flexibility.

In the present invention, three or more (meth) acryloyloxy groups in one molecule (however, in the present invention, "(meth) acryloyloxy group" is abbreviated to acryloyloxy group and methacryloyloxy group). As a monomer) having 3 or more alcoholic hydroxyl groups in one molecule, the hydroxyl groups of the polyhydric alcohol are esterified products of 3 or more (meth) acrylic acid. Existing compounds can be used.

Specifically, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate. , Dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate and the like can be used. These monomers may be used alone or in combination of two or more.

The proportion of the monomer having 3 or more (meth) acryloyloxy groups in one molecule is preferably 20 to 90% by weight based on the total amount of the polymerizable monomers, It is preferable to use 30 to 80% by weight, and most preferably about 30 to 70% by weight.

If the amount of the above-mentioned monomer used is less than 20% by weight, it tends to be inferior in that a cured coating having sufficient abrasion resistance is obtained, and if it exceeds 90% by weight. However, the shrinkage due to the polymerization becomes large, so that the cured film may be distorted, the flexibility of the film may be deteriorated, and the cured film may be greatly curled, which is not preferable.

As the monomer having 1 to 2 ethylenically unsaturated double bonds in one molecule as used in the present invention, any ordinary radical polymerizable monomer may be used without particular limitation. be able to.

As the compound having two ethylenically unsaturated double bonds in the molecule, the following (meth) acrylates (a) to (f) can be used.

That is, (a) (meth) acrylic acid diesters of alkylene glycol having 2 to 12 carbon atoms: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth )
Acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, etc.

(B) Polyoxyalkylene glycol (meth) acrylate diesters: diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, etc.

(C) Polyester (meth) acrylic acid diesters: pentaerythritol di (meth) acrylate, etc.

(D) (Meth) acrylic acid diesters of bisphenol A or hydrides of bisphenol A with ethylene oxide and propylene oxide adducts:
2,2'-bis (4-acryloxyethoxyphenyl)
Propane, 2,2'-bis (4-acryloxypropoxyphenyl) propane, etc.

(E) In the molecule obtained by further reacting the terminal isocyanate group-containing compound obtained by previously reacting the diisocyanate compound with two or more alcoholic hydroxyl group-containing compounds with the alcoholic hydroxyl group-containing (meth) acrylate. Urethane (meth) acrylates having two or more (meth) acryloyloxy groups,

(F) Epoxy (meth) acrylate having two or more (meth) acryloyloxy groups in the molecule, which is obtained by reacting a compound having two or more epoxy groups in the molecule with acrylic acid or methacrylic acid. And so on.

Examples of the compound having one ethylenically unsaturated double bond in the molecule include methyl (meth) acrylate, ethyl (meth) acrylate, n- and i-propyl (meth) acrylate, n- and sec-. , And t
-Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, polyethylene glycol Mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-hydroxyethyl (meth)
Acrylamide, N-vinylpyrrolidone, N-vinyl-
3-Methylpyrrolidone, N-vinyl-5-methylpyrrolidone or the like can be used. These monomers are 1
You may use it in mixture of 2 or more types.

The proportion of the monomer having 1 to 2 ethylenically unsaturated double bonds in one molecule is preferably 10 to 80% by weight with respect to the total amount of the monomers. It is preferably 20 to 70% by weight.

When the proportion of the above-mentioned monomer used exceeds 80% by weight, it is not preferable from the viewpoint of obtaining a cured coating having sufficient abrasion resistance, which is not preferable. Further, if the usage ratio is less than 10% by weight, there arises inconveniences such as a decrease in flexibility of the coating film and a decrease in adhesion with the laminated film provided on the base polyester film. It is not preferable because it comes.

In the present invention, a method of curing the actinic radiation curable composition includes, for example, a method of irradiating with ultraviolet rays. In this method, a photopolymerization initiator may be added to the composition. desirable. Specific examples of the photopolymerization initiator include acetophenone, 2,2-getoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-
Chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone,
Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methyl benzoyl formate,
Carbonyl compounds such as p-isopropyl-α-hydroxyisobutylphenone, α-hydroxyisobutylphenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, thioxanthone , Sulfur compounds such as 2-chlorothioxanthone and 2-methylthioxanthone, and peroxide compounds such as benzoyl peroxide and di-t-butyl peroxide. These photopolymerization initiators may be used alone or in combination of two or more.

The amount of the photopolymerization initiator used is appropriately 0.01 to 10 parts by weight based on 100 parts by weight of the polymerizable monomer composition. However, when electron rays or gamma rays are used as the curing means, it is not always necessary to add a polymerization initiator.

The actinic radiation-curable composition used in the present invention contains hydroquinone, hydroquinone monomethyl ether, 2,5-t-butyl hydroquinone, etc. in order to prevent thermal polymerization during production and dark reaction during storage. It is desirable to add various thermal polymerization inhibitors. The addition amount is preferably in the range of 0.005 to 0.05% by weight based on the total weight of the polymerizable compound.

The actinic radiation-curable composition used in the present invention is used within the range in which the effects of the present invention are not impaired for the purpose of improving workability during coating and improving controllability of coating thickness. An organic solvent can be added. Examples of the organic solvent include those having a boiling point of 50 to 150 ° C.
Easy to use in terms of workability during coating and drying before and after curing. Specific examples include alcohol solvents such as methanol, ethanol and isopropyl alcohol, acetic ester solvents such as methyl acetate, ethyl acetate and butyl acetate, ketone solvents such as acetone and methyl ethyl ketone, aromatic solvents such as toluene. A cyclic ether solvent such as dioxane or the like can be used. These solvents may be used alone or in admixture of two or more.

Various additives may be added to the actinic radiation-curable composition, if necessary, within a range that does not impair the effects of the present invention. For example, an antioxidant, a light stabilizer, a stabilizer such as an ultraviolet absorber, a surfactant, a leveling agent, an antistatic agent and the like can be added.

Further, the actinic ray curable composition contains silicon oxide particles or organic particles within the range where the effect of the present invention is not impaired, for the purpose of reducing the brightness and clarity of the reflected image of an external light source. A matting agent such as a filler can be blended, and the surface of the surface-hardened layer can be provided with an uneven surface structure by, for example, an embossing method or a sand mat method.

As a means for applying the actinic radiation curable composition,
Conventional coating methods such as brush coating, dip coating, knife coating, roll coating, spray coating, flow coating, spin coating (spinner, whaler, etc.) can be used. Each of these methods has features, and a specific coating method can be appropriately selected depending on the required characteristics of the surface-cured film, the intended use, and the like.

In the present invention, actinic radiation means electromagnetic waves such as ultraviolet rays, electron rays, radiation (α rays, β rays, γ rays, etc.) for polymerizing acrylic vinyl groups, and in practice, ultraviolet rays are convenient. And is preferable. As the ultraviolet ray source, an ultraviolet fluorescent lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc lamp or the like can be used. Further, the electron beam method is advantageous in that the device is expensive and needs to be operated under an inert gas, but it is not necessary to include a photopolymerization initiator or a photosensitizer in the coating layer. is there.

In constructing the cathode ray tube protective film laminate of the present invention, the thickness of the surface-hardened layer (B) may be appropriately determined depending on the application, but is usually 0.5 μm to 1
It is preferably within the range of 0 μm, more preferably 1
μm to 8 μm. When the thickness of the surface-hardened layer is less than 0.5 μm, the surface hardness is insufficient and scratches are likely to occur. On the other hand, when it exceeds 10 μm, the cured film tends to be brittle and the surface-cured film is bent. Sometimes the cured film is apt to crack, which is not preferable.

As described above, the cathode ray tube protective film laminate of the present invention comprises a polyester film, laminated films (A) and (A ') provided on both surfaces thereof, and a surface hardened layer (B) on one surface thereof. ), The pressure-sensitive adhesive layer (C) is provided on the other surface, and it is preferable that the surface of the surface-hardened layer is further subjected to an antireflection treatment or an antifouling treatment. That is, this is a mode in which a light antireflection film or an antifouling treatment film is formed on the surface of the surface-cured layer (B) of the cathode ray tube protection film laminate opposite to the side where the polyester film is present.

As a method of performing such a light reflection preventing treatment or an antifouling treatment, wet coating, sputtering, chemical vapor deposition method, etc. can be used, but not limited thereto.

As the substance to be treated, a layer of a low refractive index compound or an inorganic substance such as magnesium fluoride or silicon oxide is used for preventing light reflection, and a silicone resin or a fluorine resin is used for antifouling treatment. be able to.

In particular, there are various kinds of structures of the light antireflection film, but it is practical that at least the light absorption layer is included. For example, vapor deposition in the following configuration including at least a dielectric layer, a conductor layer, and a light absorption layer,
It can also be formed using a vacuum thin film forming technique such as sputtering. Configuration examples are shown in Tables 1 to 3.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

In the film constitutions shown in Tables 1 to 3 above,
Particularly, as the high refractive index film material, TiO ₂ , ZrO ₂ , I
TO, SnO ₂ , Y ₂ O ₃ or the like can be selected, and the low refractive index material can be selected from SiO ₂ , MgF ₂ or the like. In addition, ITO, SnO ₂ , ZnO and the like can serve both as a conductive film and a high refractive index film.

As the light absorption film, TiNx, Au, A
It is also possible to interpose a film of g, NiOx or the like as a constituent element when forming a λ / 2 film or a λ / 4 film as a composite film, and various film configurations are conceivable. This does not impair the effects of the present invention.

It is possible to adjust and control the total light transmittance of the cathode ray tube protection film laminate by adjusting the thickness and the like of the above-mentioned light absorbing film, and especially according to the knowledge of the present inventors. For example, in a CRT application, the total light transmittance of the CRT protective film laminate is 60%.
As described above, the haze is preferably 0.1% to 3%.

The pressure-sensitive adhesive layer (C) in the present invention is not particularly limited as long as it adheres two objects by its pressure-sensitive adhesive action, and the pressure-sensitive adhesive may be a rubber-based, acrylic-based, silicone-based or polyvinyl ether-based adhesive. And the like can be used. Among them, rubber type is common,
Silicone type has good heat resistance and adheres to fluororesin, but it is expensive. Acrylic resins are preferred because they also have heat resistance, have a large adhesive strength, and do not have the oxidative deterioration of rubber.

Further, the pressure-sensitive adhesive is roughly classified into a solvent-type pressure-sensitive adhesive and a solventless pressure-sensitive adhesive. Solvent-based pressure-sensitive adhesives that are excellent in dryability, productivity, and raw processing are still mainstream,
In recent years, in view of pollution, energy saving, resource saving, safety, etc., a solventless adhesive is being changed. Of these, an actinic ray-curable pressure-sensitive adhesive, which is a pressure-sensitive adhesive that is cured in seconds by irradiation with actinic radiation and has excellent properties such as flexibility, adhesion, and chemical resistance, is preferable.

In order to produce a film laminate for protecting a cathode ray tube according to the present invention, for example, an actinic ray-curable monomer mixture is a main constituent between the laminated polyester film which has been subjected to the easy-adhesion treatment and the cathode ray tube. After the layer is provided, by irradiating the layer with actinic radiation, it is possible to take a means for attaching the polyester film and the cathode ray tube at once. By adopting such means, there are advantages that the process is simplified and dust is less mixed at the time of bonding, and the productivity is further improved, which is preferable.

The actinic ray-curable adhesive, especially the actinic ray-curable acrylic adhesive, contains an acrylic oligomer and a reactive diluent as the actinic ray-polymerizing components, and optionally contains a photoinitiator and a photosensitizer. You may use what contained the sensitizer and the modifier. For each of these components, the above-mentioned acrylic oligomer, reactive diluent, photoinitiator, photosensitizer, modifier and the like can be used.

For specific examples of the actinic ray curable acrylic pressure-sensitive adhesive, reference can be made to "Adhesives Data Book" edited by The Japan Adhesive Society, page 83 to page 88, published by Nikkan Kogyo Shimbun in 1990. However, it is not limited to this. Hitachi Chemical Polymer Co., Ltd., Toho Kasei Kogyo Co., Ltd.
Products such as Three Bond Co., Ltd., Toagosei Kagaku Kogyo Co., Ltd., and Cemedine Co., Ltd. can be used, but are not limited thereto.

In the present invention, the cathode ray tube is a so-called cathode ray tube (CRT) for converting an electric signal into an optical image.
ray tube), which creates an electron beam in a vacuum-sealed glass tube and changes its direction according to a signal applied from the outside, such as TV, computer display, oscilloscope, radar. Is a generic term for those used for display screens such as.

In order to obtain the total light transmittance of the laminate of 80% or more and the haze of 3% or less, the film is produced by using it while minimizing the amount of various organic or inorganic particles added to the film. Can be achieved, particularly preferably by substantially adding no additives. In addition, especially as described above, the total light transmittance is 60%.
In order to reduce the above and lower limit values, as described above, the light reflection preventing film may be formed on the surface of the surface hardened layer opposite to the polyester film side.

Next, the method for producing the film laminate for protecting a cathode ray tube of the present invention will be described, but the present invention is not limited to this. That is, for example, polyethylene terephthalate (PET) pellets are sufficiently vacuum dried, then supplied to an extruder, melt-extruded into a sheet at about 280 ° C., and cooled and solidified to prepare an unstretched PET sheet. This sheet is stretched 2.5 to 5 times in the longitudinal direction with a roll heated to 70 to 120 ° C. to obtain a uniaxially oriented PET film. Corona discharge treatment is applied to both sides of this film as required, and the treated surface is coated with the water-based coating agent of the present invention in a predetermined concentration. After the application, the end portion of the film is gripped with a clip and guided to a hot air zone heated to 70 to 150 ° C., dried, and then stretched 2.5 to 5 times in the width direction. Then, it is introduced into a heat treatment zone of 160 to 250 ° C. and heat treatment is performed for 1 to 30 seconds to complete the crystal orientation. During this heat treatment process, 0 to 0 in the width direction or the longitudinal direction as required.
12% relaxation treatment or contraction treatment may be performed. In this case, the coating solution to be used is preferably an aqueous solution in view of environmental pollution and explosion-proof properties.

The film laminate according to the present invention can be obtained by providing a surface-hardened layer on the laminated film of the above laminated polyester film. The surface-hardened layer is formed by applying a composition having an actinic ray-curable monomer mixture as a main component.
It can be obtained by drying if necessary and then curing with actinic radiation.

Further, a composition containing an actinic ray-curable monomer mixture as a main constituent is applied onto a cathode ray tube or film, and dried if necessary, and then the surface-cured layer of the laminate becomes a surface layer. Thus, the cathode ray tube and the laminated polyester film are adhered to each other via the pressure-sensitive adhesive layer by sticking together and curing with actinic radiation. In this way,
It can have a constitution of cathode ray tube / adhesive layer / laminated polyester film / cured surface layer.

In the above example, the base film on which the laminated film is provided can also contain at least one selected from melamine resins and polyester resins. In this case, there is also an effect such that the easy adhesion between the laminated film and the base film is improved, and / or the slipperiness of the laminated polyester film is improved. When containing a melamine resin or a polyester resin,
The amount added is 5 ppm or more and less than 20% by weight.
It is preferable in terms of easy adhesion and slipperiness. Of course, the melamine-based resin and the polyester resin may be a coating composition or a regenerated pellet that constitutes a laminated film provided on the base film.

The laminate thus obtained provided on a cathode ray tube has high surface hardness and excellent abrasion resistance, and at the same time, excellent durability of the surface-hardened layer and the pressure-sensitive adhesive layer. Further, since the laminated body made of the polyester film is provided on the cathode ray tube made of glass, it is possible to obtain a safe cathode ray tube in which glass is not scattered even when it is broken.

[Method of measuring characteristics and method of evaluating effects]
The method of measuring characteristics and the method of evaluating effects in the present invention are as follows. (1) Thickness of coating layer It was determined from a photograph obtained by observing a cross section of a biaxially oriented polyester film provided with a laminated film using a transmission electron microscope HU-12 manufactured by Hitachi, Ltd. Thickness is 30 within the field of view
The average value was used.

(2) Adhesiveness-1 100 crosscuts of 1 mm ² were put in the surface hardened layer,
Nichiban Co., Ltd. cellophane tape was pasted on it, pressed firmly with fingers, and then rapidly peeled in the direction of 90 degrees,
Four-level evaluation based on the number of remaining (◎: 100 remaining,
◯: 80 to 99 remaining, Δ: 50 to 79 remaining, ×: 0
˜49 remained). (⊚) and (∘) have good adhesion and excellent durability.

(3) Adhesiveness-2 AGR-100 manufactured by Nippon Kayaku Co., Ltd. was applied as a pressure-sensitive adhesive on a glass plate to a thickness of about 100 μm, and after laminating the laminate, an ultraviolet (UV) irradiator was used. Then, an energy of 1000 mJ / cm ² is applied to cure the material with ultraviolet rays. The laminate was peeled from the horizontally placed glass surface in the direction of 90 degrees, and the peeled state was observed, and evaluated according to the following criteria. (○)
Has good adhesion and excellent durability. ◯: Peeled between the glass / UV adhesive layer Δ: Peeled between both the glass / UV adhesive layer and the base film / UV adhesive layer X: Between the base film / UV adhesive layer What is peeled off

(4) Pencil Hardness In accordance with JIS-K5400, pencils of various hardness were vertically applied to the surface of the surface-hardened layer, scratched with a load of 1 kg, and the hardness of the pencil when scratched was displayed.

(5) Glass transition temperature (Tg) Using DSCII manufactured by Perkin Elmer, 10 mg was sampled and measured at a heating rate of 20 ° C./min.

(6) Screen sharpness A good color of the screen color to which the protective film was attached was evaluated as ◯, and a slightly dull one was evaluated as x.

[0100]

Next, the present invention will be specifically described based on examples. Example 1 PET substantially free of particles (intrinsic viscosity 0.65 dl
/ G) After vacuum drying the pellet to a moisture content of 25 ppm,
The mixture was supplied to an extruder heated at 280 ° C., extruded in a sheet form from a T-shaped die, and wound around a mirror-casting drum having a surface temperature of 30 ° C. by an electrostatic applied casting method to be cooled and solidified. This unstretched film was stretched 3.1 times in the longitudinal direction while passing through a group of heating rolls at 95 ° C.,
The film was a uniaxially oriented film. Both sides of this film were subjected to corona discharge treatment, and the treated surface was coated with the following water-based coating agent. The coated uniaxially stretched film is guided to a preheating zone while being held by a clip, dried at 110 ° C., continuously stretched 3.3 times in a width direction at a heating zone of 125 ° C., and further at a heating zone of 225 ° C. Heat-treated, base material P
ET film thickness is 188 μm, laminated film thickness is 0.1
A laminated PET film of 5 μm was obtained.

Water-based coating agent: (A), (A '): Polyester resin-acid component terephthalic acid: 28 mol% isophthalic acid: 9 mol% trimellitic acid: 10 mol% sebacic acid: 3 mol% -glycol component ethylene Glycol: 15 mol% Neopentyl glycol: 18 mol% 1,4-butanediol: 17 mol% An ammonium salt type aqueous dispersion of a polyester resin (Tg: 20 ° C.) comprising the above acid component and glycol component. (B): Methylolated melamine resin (B) with respect to 100 parts by weight of the solid content of (A) and (A ').
Was mixed in a solid content ratio of 5 parts by weight to obtain a laminated film forming coating agent.

Then, 70 parts by weight of dipentaerythritol hexaacrylate and N were placed on the laminated PET film.
-Using a bar coater, a composition obtained by stirring and mixing 30 parts by weight of vinylpyrrolidone and 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone has a film thickness of 3 μm after curing.
Was applied uniformly. 9 cm from the coated surface
Was irradiated with ultraviolet rays for 15 seconds with a high pressure mercury lamp having an irradiation intensity of 80 W / cm set to the height of 1 to obtain a laminate having a surface-cured layer on the laminated PET film.
Further, AGR-100 manufactured by Nippon Kayaku Co., Ltd. was used as a pressure-sensitive adhesive on the surface on which the surface-hardened layer was not provided, and after bonding it to a cathode ray tube, it was irradiated with ultraviolet rays at an energy of 1000 mJ / cm ² . The results are shown in Table 4.

Example 2 A laminated body was obtained in the same manner as in Example 1 except that the thickness of the laminated film was adjusted to 0.08 μm using the coating material of Example 1. The results are shown in Table 4.

Comparative Example 1 A laminate was obtained in the same manner as in Example 1 except that the coating material of Example 1 was used without adding a melamine-based crosslinking agent. The results are shown in Table 4.

Comparative Example 2 A laminate was obtained in the same manner as in Example 1 except that the polyester resin of the coating material of Example 1 was replaced by the copolymerized polyester resin of the following components. The results are shown in Table 4.・ Acid component terephthalic acid: 42 mol% 5-sodium sulfoisophthalic acid: 8 mol% ・ Glycol component ethylene glycol: 47 mol% diethylene glycol: 3 mol% Containing a carboxylic acid in the side chain consisting of the above acid component and glycol component Aqueous dispersion of polyester resin (Tg: 72 ° C).

Example 3 The same as Example 1 except that the film thickness was 125 μm.

Comparative Example 3 The same as Example 1 except that the film thickness was 50 μm. The film was wavy when pasted, and the screen appeared to be distorted, so the sharpness was marked as "x".

Comparative Example 4 The same as Example 1 except that the film thickness was 500 μm. The film was cloudy and the screen sharpness was insufficient.

[0109]

[Table 4]

Examples 4, 5 and Comparative Example 5 The same laminate as in Example 3 having a surface-hardened layer on a PET film was used, and vapor deposition was performed on the surface-hardened layer.
Alternatively, an antireflection film layer was formed from the dielectric layer and the metal layer with the structure shown in Table 5 by the sputtering method. In Example 5, the Al metal layer is used as a constituent film of the antireflection layer and also has a role as a light absorption layer. In some cases, glass having a transmittance of glass material used for a cathode ray tube panel reduced to 70 to 90% is used. In that case, the transmittance of the panel glass is 90%.
It is possible to obtain the same effect as using the glass having the transmittance of 70 to 90% by making the antireflection film layer have the light absorptivity while keeping the content of at least 100%. The results are shown in Table 6. In addition, in Table 6, in addition to the evaluation items shown in Table 4, the results of visually determining the screen brightness and the contrast ratio between the screen brightness and the external light reflection were added.

[0111]

[Table 5]

[0112]

[Table 6]

[0113]

As described in detail above, according to the present invention,
It is possible to obtain a film laminate for protecting a cathode ray tube, which has excellent adhesion to the surface of the cathode ray tube, optical characteristics that do not impair the sharpness of the cathode ray tube, scratch resistance and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number for FI Technical indication H04N 5/65 H04N 5/65 (72) Inventor Kikuo Tagano 1-1-Sonoyama, Otsu City, Shiga Prefecture No. 1 Toray Co., Ltd. Shiga Plant (72) Inventor Tsunesei Saito 6-735 Kita-Shinagawa, Shinagawa-ku, Tokyo Inside Sony Corporation (72) Inventor Shiro 6-7 Kita-Shinagawa, Shinagawa-ku, Tokyo No. 35 Sony Corporation

Claims (6)

[Claims] 1. A surface-cured layer (B) is provided on one side and a pressure-sensitive adhesive layer (C) is provided on the other side via the laminated films (A) and (A ') provided on both sides of a polyester film. In the cathode ray tube protective film laminate, the polyester film has a thickness of 100 to 200 μm, and the laminate films (A) and (A ′) have a glass transition temperature of 10 to 40 ° C. and a water-dispersible polyester resin and melamine-based cross-linking. Including the agent,
The water-dispersible polyester resin has a carboxylic acid and / or a salt thereof in the side chain, the surface hardened layer (B) has a pencil hardness of 3H or more, and the total light transmittance as a laminate is 80 to 99.
5%, haze is 0.1% to 3%, a film laminate for protecting a CRT. 2. The surface-cured layer (B) comprises at least one kind of a monomer having 3 or more (meth) acryloyloxy groups in one molecule and 1 to 2 ethylenic monomers in one molecule. 2. An actinic radiation-cured product containing, as a main component, an actinic radiation-curable monomer mixture containing at least one monomer having a saturated double bond, and protecting the cathode ray tube according to claim 1. Film laminate. 3. The film for protecting a cathode ray tube according to claim 1, wherein the pressure-sensitive adhesive layer (C) is composed of an actinic radiation cured product containing an actinic radiation curable monomer mixture as a main constituent. Laminate. 4. The film laminate for protecting a cathode ray tube according to claim 1, 2 or 3 is used, and the film laminate on the side opposite to the side where the polyester film is present in the surface-hardened layer (B). A light reflection preventing film is formed on the surface, and the total light transmittance of the laminated body as a whole is 60 to 99.5.
%, Haze is 0.1% to 3%, a film laminate for protecting a CRT. 5. The cathode ray tube protective film laminate according to claim 4, wherein the light antireflection film contains at least a light absorbing layer. 6. The light antireflection film comprises at least a dielectric layer,
The cathode ray tube protective film laminate according to claim 4, comprising a conductor layer and a light absorbing layer.