JPH07138052A - Picture image-containing laminated glass - Google Patents

Abstract

PURPOSE:To obtain a picture image-containing laminated glass having high image picture concentration, excellent revolving power and improved weather resistance by sandwiching a picture image layer formed from a coloring layer between intermediate films for a laminated glass, further laying both the surfaces of the intermediate films between glass plates. CONSTITUTION:A coloring layer comprising a photopolymerizable resin composition consisting essentially of a photopolymerizable resin and a colored pigment is exposed to light and developed to give an picture image layer, which is sandwiched between two intermediate films for a laminated glass and further both the surfaces of the intermediate films are laid between two glass plates to give the objective laminated glass. The photopolymerizable resin generally comprises a linear copolymer, a photopolymerizable unsaturated compound and a photopolymerization initiator. The linear polymer is preferably a linear polymer soluble or swellable with an alkali aqueous solution. For example, a polymer comprising an alpha,beta-unsaturated ethylenic monomer containing a carboxyl group and an alpha,beta-unsaturated ethylenic monomer not containing a carboxyl group as constituent components may be cited as the linear polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated glass for vehicles, buildings, etc., and an image-containing laminated glass used for decoration, display, etc.

[0002]

2. Description of the Related Art As an image-containing laminated glass, the conventional interlayer film for laminated glass is improved in the drawback that the film surface is too sticky and difficult to print. Form an image by offset printing, gravure printing, screen printing, etc.
What is sandwiched between two pieces of glass is disclosed in Japanese Patent Publication No. 59-46903.

As another image-containing laminated glass, polyethylene terephthalate printed by various printing methods is used.
Japanese Patent Application Laid-Open No. 60-226436 discloses a laminate in which a laminated film is sandwiched between two interlayer films for laminated glass, and two glasses are bonded to both sides of the laminate.

The laminated glass containing an image using the interlayer film for laminated glass subjected to the offset printing described above is suitable for multicolor printing at a high speed of image formation, but since the thickness of the ink cannot be increased, an image can be formed with transmitted light. In the application of laminated glass containing an image to be viewed, there is a drawback that the color density is low.

As a method of increasing the color density, there is a method of printing on an interlayer film for laminated glass by gravure printing or screen printing. However, when the color density is increased, the viscosity of the ink increases and the resolution of the obtained image is increased. Therefore, as long as the conventional printing method is used, there is a problem that it is difficult to manufacture an image-containing laminated glass having high color density and high resolution.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks. It uses an interlayer film for laminated glass and has a high image density, excellent resolution, and weather resistance. It is also intended to provide a laminated glass with an excellent image.

[0007]

The laminated glass with an image of the present invention has an image layer obtained by exposing and developing a colored layer comprising a photopolymerizable resin composition containing a photopolymerizable resin and a coloring pigment as main components. It is sandwiched between two sheets of interlayer film for laminated glass, and then sandwiched between two sheets of glass.

The photopolymerizable resin composition used in the present invention contains a photopolymerizable resin and a coloring pigment as main components. The photopolymerizable resin generally comprises a linear copolymer, a photopolymerizable unsaturated compound, and a photopolymerization initiator.

The above linear copolymer is preferably one which is soluble or swellable in an alkaline aqueous solution.
Examples thereof include a polymer having an α, β-unsaturated ethylenic monomer containing a carboxyl group and an α, β-unsaturated ethylenic monomer not containing a carboxyl group as constituent components.

Examples of the α, β-unsaturated ethylenic monomer containing a carboxyl group include unsaturated compounds such as (meth) acrylic acid, crotonic acid, maleic acid (anhydride), fumaric acid and itaconic acid. Examples thereof include carboxylic acids, which may be used alone or in combination of two or more kinds.

Α, β-containing no carboxyl group
The unsaturated ethylene-based monomer may be any one that can be copolymerized with the α-, β-unsaturated ethylene-based monomer containing a carboxyl group, such as styrene, o-methylstyrene and m-methylstyrene. , P-methylstyrene, α
-Styrenes such as methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-hexylstyrene, p-octylstyrene, p-methoxystyrene, p-phenylstyrene and 3,4-dimethylchlorostyrene; α- Vinylnaphthalene or other vinylnaphthalene; ethylene, propylene, butylene or C _{5 to} C ₃₀
And higher α-olefins; vinyl halides such as vinyl chloride, vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate; methyl (meth) acrylate, (meth ) Ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, -2- (meth) acrylate Ethylhexyl, 2-chloroethyl (meth) acrylate, methyl α-chloro (meth) acrylate, phenyl (meth) acrylate,
(Meth) acrylic acid esters such as dimethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, and dicyclopentanyl (meth) acrylate; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether; vinyl Vinyl ketones such as methyl ketone and vinyl ethyl ketone; N-vinyl compounds such as N-vinyl pyrrole and N-vinyl indole; (meth) acrylonitrile and (meth) acrylic acid amides. The above may be used in combination.

When the amount of the portion corresponding to the α, β-unsaturated ethylenic monomer containing a carboxyl group in the constituents of the linear copolymer becomes small, it becomes insoluble in the alkaline aqueous solution, and the amount thereof depends on the alkaline aqueous solution. Since the developability will decrease,
If the amount is too large, the compatibility with the coating solvent or other components is reduced, and the resolution of the obtained image is reduced.
The amount is preferably 15% by weight, more preferably 15 to 35% by weight, and the α, β-unsaturated ethylenic monomer containing no carboxyl group is preferably 60 to 90% by weight.

When the weight-average molecular weight of the linear copolymer becomes small, a colored layer is formed on the support, and when it is rolled and stored, the colored layer causes cold flow to form a colored layer. If wrinkles easily form and become large, the solubility in an alkaline aqueous solution decreases and the developability decreases, so 20,000 to 5
It is preferably 0,000, more preferably 50,000 to 300,000.

The photopolymerizable unsaturated compound may be a monomer that is liquid at room temperature and can be cured by a photopolymerization reaction. For example, triethylene glycol (meth) acrylate,
Tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol -Ruzi (meth) acrylate, nonapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, dipentaerythritol lupenta (meth) acrylate, dipentaerythritol, ruhexa (meth) acrylate, tho, trimethylolpropane tri (meth) acrylate, 2,2-bis [4- (Acryloxydiethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy) Rokishijietokishi) phenyl] propane, 3-phenoxy-2-propanoyl acrylate les -
, Polyfunctional monomers such as 1,6-bis [3-acryloxy-2-hydroxypropyl] hexyl ether; methyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl ( Monofunctional monomers such as (meth) acrylate; urethane and polyester acrylates
Examples thereof include a oligomer and the like, and they may be used alone or in combination of two or more kinds.

When the amount of the photopolymerizable unsaturated compound added is small, the surface hardness of the image layer after exposure and development is insufficient, and when it is large, the coloring layer used for forming the image layer is deformed during storage. Since cold flow is likely to occur, it is 10 to 2 with respect to 100 parts by weight of the linear copolymer.
The amount is preferably 00 parts by weight, more preferably 30 to 150 parts by weight.

The photopolymerization initiator may be any one having a property of initiating the polymerization of the photopolymerizable unsaturated compound with an actinic ray, and examples thereof include sodium methyldithiocarbamate sulfide and tetramethyl. Sulfides such as thiuram monosulfide, diphenyl monosulfide, dibenzothiazoyl monosulfide and disulfide; thioxanthone derivatives such as thioxanthone, ethylthioxanthone, 2-chlorothioxanthone, diethylthioxanthone, diisopropylthioxanthone; hydrazone, azoisobutyronitrile, benzene Diazo compounds such as diazonium; benzoin,
Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, dimethylaminobenzophenone, Michler's ketone,
Benzyl anthraquinone, t-butyl anthraquinone,
Aromatic carbonyl compounds such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-aminoanthraquinone, 2-chloroanthraquinone, benzyldimethylketol and methylphenylglyoxylate; 4- (2
-Hydroxyethoxy) phenyl (2-hydroxy-2
-Propyl) ketone, α-hydroxy-α, α'-dimethyl-acetophenone, acetophenone derivatives such as 2,2-diethoxyacetophenone and 2,2-dimethoxyacetophenone; methyl p-dimethylaminobenzoate;
Dialkylaminobenzoic acid esters such as ethyl p-dimethylaminobenzoate, butyl p-dimethylaminobenzoate and isopropyl p-diethylaminobenzoate; benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, cumene hydro Peroxides such as peroxides; 9-phenylacridine, 9
Acridine derivatives such as -p-methoxyphenylacridine, 9-acetylaminoacridine and benzacridine; phenazine derivatives such as 9,10-dimethylbenzphenazine, 9-methylbenzphenazine and 10-methoxybenzphenazine; 6,4 ', 4 ”-Quinoxaline derivative such as trimethoxy-2,3-diphenylquinoxaline; 2,4,5-triphenylimidazoyl dimer; halogenated ketone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, acylphosphine oxide, acylphosphona -Such as acylated phosphorus compounds such as -to initiate polymerization of the above-mentioned photopolymerizable unsaturated compound with ultraviolet rays, 2-nitrofluorene, 2,4,
Examples thereof include those that initiate polymerization with visible light such as 6-tris (trichloromethyl) -1,3,5-triazine, 3,3′-carbonylbiscoumarin and thiomihira-ketone.

When the amount of the photopolymerization initiator added is small, it takes a long time to cure the colored layer, resulting in insufficient curing.
When the image forming property is lowered and increases, the image layer becomes yellowed or becomes brittle. Therefore, the linear copolymer 100 described above is used.
0.1 to 10 parts by weight is preferable with respect to parts by weight.

The above-mentioned coloring pigments are used for making the coloring layer have a predetermined hue, and conventionally known pigments can be used. For example, typical pigments are yellow, magenta, cyan, and And four types of black type are used.

Examples of the yellow pigments include Hansa yellow, benzidine yellow, cadmium yellow, yellow lead G, zinc chromate, lemon yellow, strocian yellow, indian yellow, isoindolinone yellow and the like. As the magenta pigment, for example, Rhodamine B lake, cadmium red, red iron oxide, chrome bar million, pyrazolone red, lisole red, red lead, watching red, quinacridone red, and the like, cyan Examples of the pigments include ultramarine bulls, prussian bulls, cobalt bulls, ceruleans bulls, manganis bulls, phthalocyanines bulls, and the like, and examples of black pigments include titanium black and calcite. -Bonblack and the like.

If the amount of the above-mentioned coloring pigment added decreases,
When the image density becomes low and the coloring becomes insufficient and becomes large,
Since the image layer becomes brittle, 0.1 to 300 parts by weight is preferable with respect to 100 parts by weight of the linear copolymer.

The photopolymerizable resin coloring composition used in the present invention is as described above, but if necessary, dioctyl phthalate, triethylene glycol diacetate, p-toluene sulfonamide, N-ethyl. A plasticizer such as toluenesulfonamide; a thermal polymerization inhibitor such as hydroquinone or p-methoxyphenol; a stabilizer; an ultraviolet absorber; an antioxidant or the like may be added.

The interlayer film for laminated glass used in the present invention is
Any transparent resin film or sheet that can be bonded to glass by heating may be used. For example, polyvinyl butyral obtained by reacting polyvinyl alcohol commonly used as an interlayer film for laminated glass with butyraldehyde. -Based resin, polyvinyl chloride-based resin, ethylene-vinyl acetate-based resin, ethylene-acrylic acid-based resin, ethylene-
Examples thereof include a film or sheet of a resin whose main component is a thermoplastic resin such as an acrylate resin, a urethane resin or an acrylic resin.

In the polyvinyl butyral resin, triethylene glycol di-2-ethyl butyrate, an antioxidant, a stabilizer, an ultraviolet absorber, and a plasticizer may be added as needed, as long as transparency is not impaired. Lubricants, colorants and the like may be added.

Examples of the polyvinyl butyral-based resin intermediate film include Sekisui Chemical's interlayer film for laminated glass, "ESREC Film ST", and the polyvinyl chloride-based interlayer film for laminated glass is mentioned. , For example, vinyl chloride-ethylene-glycidyl methacrylate copolymer interlayer film, and commercial products include Sekisui Chemical Co., Ltd. interlayer film for laminated glass "Eslec neomute film", ethylene-acetic acid. As a commercial product of the vinyl-based resin intermediate film, an intermediate film for laminated glass “EVASAFE” manufactured by Bridgestone is cited.

The method for producing a laminated glass with an image of the present invention includes, for example, dissolving and dispersing a photopolymerizable resin coloring composition in a solvent, coating it on a support film, drying and forming an image having a coloring layer. A sheet is produced, exposed on a colored layer through a halftone dot negative mask, an unexposed portion is dissolved and removed with an alkaline aqueous solution to form an image layer, and then an image forming sheet on which the image layer is formed is formed. -A sandwich is sandwiched between two sheets of interlayer film for humidity-controlled laminated glass, and the sandwich is sandwiched between two sheets of glass plates to form a laminate, and the mixture is passed through a pressure roll. A method of wrapping the same with a rubber bag and temporarily adhering it by a method of decompressing the inside, and then finally adhering it with an oil type or air type autoclave or the like can be mentioned.

Another method for producing an image-containing laminated glass of the present invention is to dissolve and disperse a photopolymerizable resin coloring composition in a solvent, coat it on a support film, and dry it to form an image forming sheet having a coloring layer. On the colored layer, exposed through a halftone dot negative mask, the unexposed portion is dissolved and removed with an alkaline aqueous solution to form an image layer, and the image layer is transferred onto a support film to form a transferred layer. The formed transfer film is laminated so as to be in contact with the transfer layer, and then the support film of the image forming sheet is peeled off and transferred to produce a laminate composed of the image layer and the transfer film. .

Next, the above laminated body is sandwiched between two sheets of interlayer film for laminated glass whose humidity has been adjusted, and further sandwiched between two glass plates to form a laminated body, and a pressure roll is provided. And a method of wrapping the laminated body in a rubber bag and depressurizing the inside, and then temporarily adhering the laminated body with an oil-type or air-type autoclave to produce a laminated glass with an image.

The conditions for the main adhesion should be appropriately determined depending on the interlayer film for laminated glass to be used. For example, the maximum temperature is 120 to 150 ° C., the holding time at the maximum temperature is 20 to 40 minutes, and the pressure is 10. It is preferable to carry out at about 15 Kg / cm ² .

The image layer of the image-containing laminated glass of the present invention can be a multi-layer image layer. For example, a photopolymerizable resin coloring composition is dissolved and dispersed in a solvent, coated on a support film, and dried. Black, magenta, cyan, yellow
To produce an image forming sheet having a colored layer for each hue of
An image forming sheet of a color is selected, and the colored layer is exposed through a halftone negative mask and the unexposed portion is dissolved and removed with an aqueous alkaline solution to form an image layer. The image layer is a support film. The transfer film having the transfer layer formed thereon is laminated so as to be in contact with the transfer layer, and then the support film of the image forming sheet is peeled off and transferred to form the image layer and the transfer film. Obtain a laminate.

Then, in the same manner as described above, an image-forming sheet having a second-color image layer formed thereon is obtained, and the image layer of the obtained image-forming sheet is the image layer of the above-mentioned laminate. And the support film of the image forming sheet is peeled off to obtain a laminate in which the first and second color image layers are laminated.

At this time, the layer to be transferred protrudes from the image layer of the first color and the image layers of the first and second colors are adhered.

Further, an adhesive layer may be laminated on the image layer for more firm adhesion, or a heat fusion layer may be provided between the colored layer and the support film to transfer the image layer, The image layer and the heat fusion layer may be transferred together.

The above heat-sealing layer is formed from a heat-sealing layer composition, and the heat-sealing layer composition is, for example, a photopolymerization comprising an organic polymer, a photopolymerizable unsaturated compound, and a photopolymerization initiator. Examples of the resin composition include thermoplastic resin compositions and thermoplastic resin compositions.

The above organic polymer may be any solvent-soluble resin, and examples thereof include those similar to the linear copolymer used in the photopolymerizable resin coloring composition.

Examples of the photopolymerizable unsaturated compound and photopolymerization initiator include the same as the photopolymerizable unsaturated compound and photopolymerization initiator used in the photopolymerizable resin coloring composition. .

The thermoplastic resin composition may be a resin soluble in a solvent or water, such as polyamide,
Examples thereof include polymethylmethacrylate.

The above thermoplastic resin composition contains rosin (manufactured by Arakawa Chemical Industry Co., Ltd .; trade name: KR-61) for the purpose of improving adhesiveness.
0) may be added.

Further, the image layers of the third color and the fourth color are laminated to form a laminate in which the image layers of the four colors are laminated.

The multi-layer image layer can be a full color image layer in which the hue of the image forming sheet used is four colors of black, yellow, magenta and cyan.

Then, the four image layers are laminated so that the transfer layers of the transfer film are in contact with each other.
A laminate having a structure of 4 image layers / transferred film is produced.

In order to produce an image-containing laminated glass by using the above-mentioned laminated body composed of four image layers and a transfer-receiving film, the same method as the above-mentioned method for producing an image-containing laminated glass using the image layer and the transfer-receiving film is used. Can be produced by the method described above to obtain a full-color laminated glass.

As another manufacturing method, for example, the image forming sheet for the first color used in the present invention is laminated on the transfer layer of the transfer film, and a halftone dot negative mask is applied from the support side of the image forming sheet. Through exposure, the support film of the image forming sheet is peeled off, the colored layer is transferred onto the transferred layer, the unexposed portion is dissolved and removed with an alkaline aqueous solution to form an image layer, and then the image layer is formed thereon. The second, third, and fourth color image forming sheets are respectively laminated on the transferred layer, and each time the layers are laminated,
From the support side of the image forming sheet, exposed through a halftone negative mask, peeling the support film of the image forming sheet,
Examples include a method of transferring onto the transferred layer, dissolving and removing the unexposed portion with an alkaline aqueous solution to form an image layer, and forming a multilayer image layer on the transferred film.

Image laminated glass can be produced from the above-mentioned multi-layer image layer in the same manner as in the method for producing image-containing laminated glass.

As the solvent, any solvent capable of dissolving the resin component of the photopolymerizable resin coloring composition may be used, and for example, polar solvents such as methyl ethyl ketone (MEK), ethyl acetate and methanol are suitable.

The thickness of the colored layer is not particularly limited,
When the thickness becomes thin, the handling becomes difficult, and the color density of the obtained image becomes low. When the thickness becomes thick, the coloring layer is easily peeled off from the support film, and the developing accuracy is lowered, so that it is 0.5 to 0.5.
The range of 20 μm is preferable.

It is also possible to change the gradation of light and shade by setting the color density per sheet of the image forming sheet to be low and adjusting the number of sheets to be overlapped.

The support film of the image forming sheet may be a transparent film, for example, a polyethylene terephthalate film, a biaxially stretched polyethylene terephthalate film, a stretched polypropylene film (OPP).
And so on.

When the support film is used without being peeled off, a thermoplastic resin is provided on the surface on which the colored layer is provided,
An adhesive layer containing a photopolymerizable resin, a thermopolymerizable resin or the like may be provided to form a support film.

When the support film is peeled off and used, it may be subjected to a silicone treatment or a release treatment with a fluororesin coat or the like. If the thickness is reduced, it becomes difficult to handle. When the thickness is increased, the light-transmitting property and the followability when the image layer is transferred to the transfer target film are deteriorated.
μm is preferred.

The colored layer may be provided with a protective layer which is soluble in an alkaline aqueous solution in order to prevent scratches and adhesion of dust in the manufacturing process, and examples thereof include those formed from a resin composition containing polyvinyl alcohol. To be

The halftone dot negative mask is prepared by color-separating an original image into a hue similar to that of the coloring layer to be used by a color separation machine.

The light source for exposing and curing the colored layer is not particularly limited, and for example, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are preferably used.

As the alkaline aqueous solution for dissolving and removing the unexposed portion of the colored layer, for example, a 1 wt% sodium carbonate aqueous solution can be used.

The transfer layer is a surface on which an image layer is laminated,
In order to prevent air bubbles from being mixed in during laminating on the surface in contact with the support film, it is preferable that the pressure-sensitive adhesive property is not exhibited at room temperature, and the adhesive property is exhibited by heating. It is formed from a saturated compound, a photopolymerizable resin composition containing a photopolymerization initiator, a thermoplastic resin, and the like.

Examples of the organic polymer include those similar to the linear copolymer used in the photopolymerizable resin coloring composition. Examples of the photopolymerizable unsaturated compound and the polymerization initiator include: Examples thereof include the same photopolymerizable unsaturated compounds and polymerization initiators used in the photopolymerizable resin coloring composition.

The support film constituting the transfer film can be the same as the support film of the image forming sheet, and the transfer film is the surface on which the transfer layer of the support film is laminated. In addition, the transfer layer and the support film can be used as one body without peeling the support film by subjecting it to an anchor treatment such as a primer treatment or a corona treatment, or a release treatment such as a silicon treatment or a fluorine treatment. Then, the support film may be removed and used after laminating the image layer.

The thickness of the transferred layer is not particularly limited, but if it becomes thin, the adhesiveness to the image layer is poor and it becomes difficult to handle, and if it becomes thick, thermal distortion occurs during the production of laminated glass. Transparency may decrease, so
500 μm is preferable.

[0058]

EXAMPLES Examples of the present invention will be described below. Hereinafter, "part" means "part by weight".

(Example 1) (Production of image-forming sheet) Methyl methacrylate / butyl methacrylate / 2-ethylhexyl acrylate having a predetermined weight average molecular weight of 100,000 shown in Table 1 / Methacrylic acid copolymer (weight ratio 31: 31: 13: 25), pentaerythritol tetraacrylate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (B
ASF's "Lucirin TPO"), yellow pigments (Dainichi Seika's "FPF-27E ero"), magenta pigments (Dainichi Seika's "FPF-96Q red"), cyan pigments (Dainichi Seika) "FPF-CP2 blue"), a black pigment ("FPF-40S Black" manufactured by Dainichiseika Co., Ltd.), and methyl ethyl ketone are mixed to obtain a photopolymerizable resin coloring composition having a hue of yellow, magenta, cyan and black. A coating liquid was obtained.

75 μm thick polyethylene terephthalate
Alcohol soluble polyamide (Toray; C
M-8000) 90 parts, stabilized ultra-light color rosin (Arakawa Chemical Industry Co., Ltd .; KR-610) 10 parts, and a coating solution of a heat-sealing resin composition consisting of 900 parts of methanol at 100 ° C. It was dried for 2 minutes to obtain a support film having a heat fusion layer having a thickness of 4 μm. On the obtained support film, a coating liquid of the photopolymerizable resin coloring composition of each hue described above was applied,
An image-forming sheet having a yellow, magenta, cyan, and black coloring layer having a thickness of 4 μm, which was dried at 0 ° C. for 2 minutes.
Got

Polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry; Goshenol GL) was formed on the colored layers of the yellow, magenta, cyan and black image forming sheets.
-05) A composition comprising 10 parts, 97 parts of water and 3 parts of methanol was applied and dried at 105 ° C. for 2 minutes to form a protective layer having a thickness of 1 μm.

[0062]

[Table 1]

(Production of Transferred Film) 100 parts of saturated copolyester resin (manufactured by Toray; Chemit R-99),
A coating solution of a thermoplastic resin composition consisting of 100 parts of methyl ethyl ketone and 300 parts of toluene is produced to have a thickness of 75 μm.
Of polyethylene terephthalate film (manufactured by Teijin; Tetron film SC type) that has been subjected to anchor treatment by corona discharge, and dried at 100 ° C. for 2 minutes to form a transfer layer made of a thermoplastic resin having a thickness of 25 μm. A transfer film having the above was produced.

(Formation of image) The original image is color-separated into yellow, magenta, cyan and black by a color separation machine and converted into halftone dots, and the shade of the color is converted into the size of halftone dots, yellow, magenta, Cyan and black halftone negative masks were prepared.

A halftone dot negative mask corresponding to the black image was placed in contact with the protective layer of the image forming sheet of black hue, and 400 mJ / cm ² of light was irradiated through the halftone dot negative mask by an ultrahigh pressure mercury lamp. The exposed portion is cured, and the unexposed portion is spray-developed at 25 ° C. with a 1 wt% sodium carbonate aqueous solution at a discharge pressure of 2 kg / cm ² for 45 seconds to dissolve and remove the unexposed portion and the protective layer. An image forming sheet having a black image layer of halftone dots corresponding to a halftone negative mask was obtained.

Then, image forming sheets having respective hues of cyan, magenta and yellow are used, and an image forming sheet having image layers of halftone dots corresponding to cyan, magenta and yellow is used in the same manner as above. -I got it.

(Transfer of Image Layer to Transfer Target Film) The black image layer was superposed so as to be in contact with the transfer target layer of the transfer target film, and a pressure of 5 kg was applied using a laminator roll.
/ Cm ² Pressurize, heat at a temperature of 120 ° C., peel the polyethylene terephthalate film of the image forming sheet while fusing the black image layer and the transferred layer at a line speed of 1.2 m / min. The black image layer and the heat fusion layer were transferred onto the transfer target film.

Next, the cyan image layer is laminated so that the protective layer is in contact with the heat-fusion layer, and the cyan image layer and the heat-fusion layer are fused in the same manner as above, while the image forming sheet of the cyan image layer is formed. Peel off the polyethylene terephthalate film of
The cyan image layer and the heat fusion layer were transferred.

In the same manner, the magenta image layer and the yellow image layer are transferred, and the transferred film / black image layer / heat fusion layer / cyan image layer / heat fusion layer / magenta image layer / heat fusion layer / A laminate having a layer structure of yellow-image layer / heat-sealing layer was obtained.

The transfer film was laminated on the heat-sealing layer of the obtained laminate so that the transfer layer was in contact with the heat-fusible layer to obtain a laminated image layer.

(Production of laminated glass with image) Polyvinyl butyral-based interlayer film for laminated glass (manufactured by Sekisui Chemical;
"S-REC Film ST") is prepared by cutting two sheets of the laminated image layer, each having a size of 1 cm at both ends, and cutting the laminated interlayer film for laminated glass at a temperature of 20 ° C and a relative humidity of 20% RH. The laminated image layer was sandwiched between two sheets of interlayer film for laminated glass and further sandwiched between two sheets of glass, by allowing the laminated image layer to stand for 4 hours in a chamber for humidity control.

Then, air existing between the sandwiched glass and the interlayer film and between the interlayer film and the laminated film is expelled, the glass end is sealed with a rubber ring, and the pressure is reduced from the gap between the seals. Then, the mixture was heated at 90 ° C. for 5 minutes, and the pressure was increased to 12 kg / cm ² with an autoclave over 5 minutes.
When the pressure during pressurization reached 7.2 Kg / cm ² , the temperature started to rise to 130 ° C. over 10 minutes, and then the pressure 12
Kg / cm ² , temperature 130 ° C. for 30 minutes, then
After gradually cooling over 10 minutes or more, when the temperature reached 45 ° C., the pressure was released to produce an image-containing laminated glass.

(Example 2) (Production of image-forming sheet) Copolymer of methyl methacrylate / butyl methacrylate / 2-ethylhexyl acrylate / methacrylic acid having a weight average molecular weight of 100,000 ( Weight ratio 31: 31: 13: 25,) 60 parts, pentaerythritol tetraacrylate 40 parts, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BAS
8 parts of "Lucirin TPO" manufactured by Company F, 10 parts of yellow pigment ("FPF-27E ero" manufactured by Dainichiseika) and 10 parts of cyan pigment ("FPF-CP2 Bull-" manufactured by Dainichiseika). Dissolved in 400 parts of methyl ethyl ketone, a coating liquid of a photopolymerizable resin coloring composition having a green hue was prepared.

38 μm thick polyethylene terephthalate
The coating solution of the above photopolymerizable resin coloring composition is applied to the coating film and dried at 90 ° C. for 2 minutes to provide a colored layer having a thickness of 4 μm, and polyvinyl alcohol (Nippon Synthetic Chemical Industry) is further formed on the colored layer. Industrial; Go-Cenol GL-05) 10 parts water 9
Dissolved in a mixed solvent consisting of 7 parts and 3 parts of methanol,
The obtained composition is applied and dried at 105 ° C. for 2 minutes to provide a protective layer having a thickness of 1 μm, and an image forming sheet having the protective layer.
Got

(Formation of halftone dot image) A halftone dot negative mask is prepared in which the original image is color-separated and the shade of green is converted into halftone dots.
A halftone dot negative mask was superposed so as to be in contact with the protective layer on the photopolymerizable resin colored layer of the obtained image-forming sheet, and 400 mJ / cm ² light irradiation was performed by an ultra-high pressure mercury lamp to cure, and then 25 ° C. 2 with 1% by weight aqueous sodium carbonate solution
Spray development was carried out for 45 seconds at a discharge pressure of kg / cm ² , and the unexposed portion was dissolved and removed to obtain an image forming sheet having an image layer corresponding to a halftone negative mask.

(Production of Laminated Glass with Image) Thickness 0.
4mm ethylene-vinyl acetate copolymer system laminated glass interlayer film (manufactured by Bridgestone, trade name; EVASAF
E), an image forming sheet having the image image layer obtained above.
To form an image having an image image layer while being kept in a humidity controlling chamber at a temperature of 20 ° C. and a relative humidity of 20% for 4 hours to control the humidity, and then taking care to prevent dust from entering in the constant temperature and humidity chamber. The sheet is sandwiched between two humidity-controlled interlayer films for laminated glass, which is further sandwiched between two glass flat plates, and then glass and interlayer films for laminated glass and glass and laminated glass. Air existing between the intermediate film and the image forming sheet having the image image layer was expelled to perform temporary adhesion.

For the temporary adhesion, the glass end is sealed with a rubber ring, degassed from the gap of the seal at a pressure reduction degree of 700 mmHg, depressurized, heated at 90 ° C. for 5 minutes, and then opened.
The pressure was increased to 12 Kg / cm ^{2 with a} Toclave over 5 minutes, and after 3 minutes from the start of pressure increase, when the pressure reached 7.2 Kg / cm ² , the temperature started to rise to 130 ° C. over 10 minutes and the pressure was 12 Kg. / Cm ² , the temperature was kept at 130 ° C for 30 minutes, and then gradually cooled over 10 minutes, and when the temperature reached 45 ° C, the pressure was released to obtain a laminated glass having an image.

[0078]

[Comparative Example 1] Vinyl chloride / ethylene / glycidyl methacrylate copolymer (weight ratio 93: 5: 2), dioctyl phthalate 40 parts, tin antioxidant 3 parts, and ultraviolet absorber 0.3 part. Mix and knead to form a film with an extruder, thickness 0.7 mm
An interlayer film for laminated glass was obtained, and the original image of Example 1 was color-separated on one side to prepare an offset plate, and 30 parts of phenol resin, 4 parts of rosin-modified phenol resin, and linseed oil 10 were obtained.
Parts, 30 parts of ink oil (organic solvent), 1 part of manganese octanoate and 25 parts of the yellow, magenta, cyan and black pigments used in Example 1 are mixed and dispersed to obtain yellow, magenta, cyan and An offset printing ink having a black hue is prepared, and four colors of image layers each having a thickness of 2 μm of one color are overlaid with each other by using an offset printing machine to perform multicolor printing, and an intermediate image for laminated glass having an image obtained. The film was sandwiched between two pieces of glass, heated and pressed, and laminated with the glass to produce an image-containing laminated glass.

[0079]

[Comparative Example 2] Gravure printing was used as offset printing, and 10 parts of vinyl chloride / ethylene / glycidyl methacrylate copolymer (weight ratio 93: 5: 2) and plasticizer (DOP) 4 were used.
Part, ethyl acetate 76 parts, and the same yellow, magenta, cyan, and black pigments as those used in Example 1 respectively.
0 parts were mixed and dispersed, and the same yellow, magenta, and
An image-containing laminated glass was manufactured in the same manner as in Comparative Example 1 except that inks for gravure printing of cyan and black hues were prepared and the thickness of the image of one color was set to 8 μm using these inks.

[0080]

[Comparative Example 3] An image-containing laminated glass was produced in the same manner as Comparative Example 1 except that "ESREC Film ST" manufactured by Sekisui Chemical Co., Ltd. was used as the interlayer film for laminated glass.

COMPARATIVE EXAMPLE 4 A corona-treated polyethylene terephthalate film having a thickness of 38 μm was ink-printed with the same yellow, magenta, cyan, and black hues as in Comparative Example 1, and four colors of offset printing were overprinted. An image-containing laminated glass was produced in the same manner as in Example 2 except that the obtained one was used as an image layer.

(Comparative Example 5) An image-containing laminated glass was produced in the same manner as in Comparative Example 4 except that the offset printing in Comparative Example 4 was changed to gravure printing and the same gravure printing ink as in Comparative Example 2 was used. .

Image densities and image resolutions of the image-containing laminated glass produced in Examples 1 and 2 and Comparative Examples 1 to 5 were measured, and the results are shown in Table 2.

Image weather resistance of the image-containing laminated glass produced in Examples 1 and 2 and Comparative Examples 1, 2, 4, and 5 was evaluated, and all were good with no fading.

The above measurement was carried out by the following method. (Image density) Solid area of each color image layer (area ratio of non-dot area:
0%) as a transmission densitometer (manufactured by Dainippon Screen, DM-5)
50). For the measurement, filters other than black are used, yellow is B, magenta is G, cyan is R,
For black, the value of W was used as the measured value.

(Weather resistance test) Using a fader according to JIS K-5400 "General test method for paints", the distance from the light source was 150 mm, and the fading property after 500 hours was visually observed. .

(Measurement of Resolution) The ratio of the halftone dot area of the obtained image to the halftone dot area of the halftone negative mask was measured, and the non-halftone dot area ratio was measured when the value was within 100 ± 3%. The minimum value is adopted in the shadow part and the maximum value is adopted in the highlight part. When the shadow part is 5% or less and the highlight part is 95% or more, the resolution is reproducing the original image.

The halftone dot negative mask has a linear density of 15
0 / inch and 200 / inch were used.

[0089]

[Table 2]

[0090]

According to the constitution of the laminated glass with an image of the present invention, since the image layer formed of the colored layer is provided between the two adhesive intermediate films as described above, it is directly printed on the conventional intermediate film. Compared with the method, it has a high image density and an excellent image resolution, and can be used as a laminated glass containing an image for decoration for vehicles, construction, etc .;

Claims (1)

[Claims] 1. An image layer obtained by exposing and developing a colored layer composed of a photopolymerizable resin composition containing a photopolymerizable resin and a color pigment as main components is sandwiched by two interlayer films for laminated glass. Is
Furthermore, an image-containing laminated glass, characterized in that both surfaces thereof are sandwiched between two pieces of glass.