JP2020034766A - Transmission screen laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transmissive screen laminate which has good visibility of an image projected from a projector and which does not cause a frame-like water permeation trace on a side surface portion of a transmissive screen when water-bonded to a substrate to be adhered. provide. A light-diffusing layer containing light-diffusing fine particles and acetoacetyl-modified polyvinyl alcohol, a transparent adhesive layer, and a separate substrate are provided on at least one surface of a light-transmitting support. [Selection diagram] Figure 1

Description

  The present invention relates to a transmission screen laminate. In detail, the transparency of the image projected from the projector is good, and there is no trace of water penetration on the side surface of the transmission screen when it is applied to the substrate to be adhered such as glass or plastic plate. About the body.

  At present, so-called rear projection type transmissive screens, in which images projected by a projector are viewed from the opposite side of the projector across the screen, are becoming popular instead of conventional advertising media such as posters, signs, and signboards. is there. In recent years, digital signage, which does not require replacement and can be changed immediately and requires not only static but also dynamic posting, has attracted much attention as a digital signage that can be projected on a large screen.

  In particular, many shop show windows face the road where customers pass, and if they can be replaced with digital signage using windows as a large screen screen, they will be very useful as advertising media. There is a growing need for a so-called transmissive screen for a window display of a sticking type.

  As such a transmissive screen capable of seeing through, the transparent resin binder has an average particle diameter of 1.0 to 10 μm, and the relative refractive index n with respect to the refractive index of the transparent resin binder is 0.91 <n <1.09 (where, n (1) A screen provided with a light scattering layer containing spherical fine particles (for example, Patent Literatures 1 and 2) has been proposed. In recent years, a screen that has both higher transparency and visibility of an image projected from a projector has been achieved. Transmission screens having a light diffusion layer containing light diffusion fine particles and xerogel (for example, Patent Documents 3 and 4) have been proposed.

  As a transmission screen suitable for the window display application described above, for example, Patent Document 5 discloses that a light-diffusing layer containing light-diffusing fine particles and xerogel on one surface of a light-transmitting support, and a light-diffusing layer on the light-diffusing layer. A transmission screen having a protected base material and having an adhesive layer on the other surface of the light-transmitting support is described. Such a transmission screen is preferably obtained by spraying water containing a surfactant onto both surfaces of the pressure-sensitive adhesive layer of the transmission screen and the surface of the window (substrate to be adhered), and then bringing the two into close contact with each other. The surface of the protective substrate provided on the light diffusion layer is rubbed with a squeegee or the like to scrape off the water, and is bonded to the window by so-called water bonding, but prevents the surface of the light diffusion layer from being damaged at that time. It is.

JP 2001-242546 A JP 2007-034324 A JP 2013-182141 A JP 2013-210454 A JP 2014-126783 A

  An object of the present invention is to provide an image projected from a projector with good visibility and, when water-adhered to a substrate to be adhered such as a glass or plastic plate, a frame-shaped permeation trace of water on a side surface of a transmission screen. The object of the present invention is to provide a transmissive screen laminate in which no problem occurs.

The above object is achieved by the following invention.
A transmissive screen laminate, wherein a light diffusing layer containing light diffusing fine particles and acetoacetyl-modified polyvinyl alcohol, a transparent adhesive layer, and a separate substrate are sequentially laminated on at least one surface of the light transmissive support. body.

  According to the present invention, there is provided a transmission type screen laminate in which the visibility of an image projected from a projector is good, and a frame-shaped water penetration mark is not generated when water is applied to a substrate to be bonded such as glass or a plastic plate. Can be provided.

1 is a schematic cross-sectional view showing one embodiment of a transmission screen laminate of the present invention.

Hereinafter, the present invention will be described in detail.
FIG. 1 is a schematic sectional view showing one embodiment of the transmission type screen laminate of the present invention. As shown in FIG. 1 (before water application), the transmission type screen laminate 1 according to the present invention has a light diffusion layer 3 containing light diffusion fine particles 2 on one surface of a light transmission support 4, a transparent adhesive layer. 5 and a separate substrate 6.

FIG. 1 also shows a form after application (after application with water) using the transmission type screen laminate 1. This construction form uses the above-mentioned transmission type screen laminate 1,
1. A film construction liquid containing a surfactant and the like is sprayed on the surface of the transparent adhesive layer 5 exposed by peeling the separate base material 6 of the transmission screen laminate 1,
2. Also, the same film construction liquid is sprayed on the surface of the substrate 7 to be bonded,
3. Adhere the surfaces sprayed with both of these film construction liquids,
4. Rubbing the other surface of the light-transmitting support having no light-diffusing layer with a squeegee (not shown) to scrape out the air mixed between the substrate 7 to be adhered and the transparent adhesive layer 5 together with the film construction liquid. Obtained by

The “transmission type” of the transmission type screen laminate of the present invention means “all rays defined by JIS-K7361-1 in a state where the above-mentioned separate base material is removed from the transmission type screen laminate (transmission type screen). It means that the transmittance exceeds 50%. More preferably, it exceeds 65%. When the transmission screen included in the transmission screen laminate of the present invention requires transparency, the haze value of the transmission screen is preferably 60% or less. A more preferred haze value is 50% or less. The haze value is a value defined below in JIS-K7105, and the lower the value, the better the transparency.
H = (Td / Tt) × 100 (%)
H: Haze value Td: Diffuse light transmittance Tt: Total light transmittance

  The light diffusion layer of the transmission screen laminate of the present invention contains light diffusing fine particles and acetoacetyl-modified polyvinyl alcohol.

  The light-diffusing fine particles contained in the light-diffusing layer in the present invention can be used irrespective of organic fine particles and inorganic fine particles as long as they have the ability to diffuse light. It is preferable to use so-called single-particle-dispersible organic or inorganic fine particles having no particle diameter, or single-particle-dispersible organic / inorganic composite fine particles. The shape of the light diffusing fine particles is preferably a true sphere.

  The light diffusing property of the light diffusing layer depends on the relative refractive index of the light diffusing fine particles and the binder component of the light diffusing layer, and, in addition to the relative refractive index, the light diffusing fine particles per unit area of the transmission screen. Depends on surface area. The surface area of the light diffusing fine particles per unit area of the transmission screen can be calculated from the specific surface area and the blending amount of the light diffusing fine particles, and the specific surface area of the light diffusing fine particles depends on the average primary particle diameter of the light diffusing fine particles. In the case of single-particle-dispersible fine particles, it can be easily calculated from the average primary particle diameter and the specific gravity.

  The average primary particle diameter of the light diffusing fine particles is preferably 20 μm or less, more preferably 8.5 μm or less, and further preferably 2.75 μm or less. When light diffusing fine particles having an average primary particle size of 2.75 μm or less are used, particularly excellent transparency can be obtained. The lower limit is preferably at least 0.2 μm. The average primary particle diameter in the present invention can be measured by photography with a transmission electron microscope. In the case of light diffusing fine particles having no secondary aggregated particle diameter, a laser scattering particle size distribution meter ( For example, the number median diameter can also be measured using LA910 manufactured by Horiba, Ltd.).

  Further, the refractive index of the light diffusing fine particles is preferably 1.30 or more, and more preferably 1.40 or more.

  As the organic fine particles, for example, acrylic polymer, styrene-acryl copolymer, vinyl acetate-acryl copolymer, vinyl acetate polymer, ethylene-vinyl acetate copolymer, chlorinated polyolefin polymer, ethylene-vinyl acetate- Multi-component copolymers such as acrylic, SBR, NBR, MBR, carboxylated SBR, carboxylated NBR, carboxylated MBR, polyvinyl chloride, polyvinylidene chloride, polyester, polyolefin, polyurethane, polymethacrylate, polytetrafluoroethylene, polymethacryl It can be widely selected from conventionally known ones such as methyl acid, polycarbonate, polyvinyl acetal resin, rosin ester resin, episulfide resin, epoxy resin, silicone resin, silicone-acrylic resin, and melamine resin. . In addition, a fine particle surface such as a melamine resin or an acrylic resin such as an acrylic polymer coated with inorganic fine particles such as silica can be used. Further, even when composite particles composed of such organic fine particles and a small amount of inorganic fine particles (the ratio of the inorganic fine particles is less than 50% by mass) are used, they can be regarded as substantially organic fine particles and used. Those in which a sulfur atom is introduced into the monomer of these polymers for the purpose of increasing the refractive index, and those in which a fluorine substituent is introduced for improving the weather resistance or lowering the refractive index can be used.

  As inorganic fine particles, silica, alumina, rutile-type titanium dioxide, anatase-type titanium dioxide, zinc oxide, zinc sulfide, lead white, antimony oxides, zinc antimonate, lead titanate, potassium titanate, zirconium oxide, cerium oxide, There are oxide glasses such as hafnium oxide, tantalum pentoxide, niobium pentoxide, yttrium oxide, chromium oxide, tin oxide, molybdenum oxide, ATO, ITO, silicate glass, phosphate glass, borate glass, and the like. These composite oxides or composite sulfides can also be widely used. Further, in the case of inorganic fine particles having photocatalytic activity such as titanium dioxide and zinc oxide, those having an extremely thin surface coated with silica, alumina, boron or the like can be used. Even when composite particles composed of inorganic fine particles and a small amount of an organic polymer (the ratio of the organic fine particles is less than 50% by mass) are used, they can be regarded as inorganic fine particles and used. Further, the inorganic fine particles used as the light diffusing fine particles are preferably inorganic fine particles having single particle dispersibility.

  In the present invention, the organic fine particles and the inorganic fine particles used as the light-diffusing fine particles can be used alone or in combination of two or more, or both the organic fine particles and the inorganic fine particles can be used in combination. is there.

The content of the light diffusing fine particles in the light diffusing layer is not particularly limited, and when the transmissive screen laminate of the present invention requires transparency, it is preferable that the haze value of the entire screen is 60% or less. . The content of the light diffusing fine particles in that case varies depending on the relative refractive index of the light diffusing fine particles and the specific surface area per unit mass of the light diffusing fine particles calculated from the average primary particle diameter and the specific gravity. was to 5.0 g / ^{m 2,} preferably not 0.01~3.0g / ^{m 2,} more preferably a 0.03~2.0g / ^{m 2.}

  In the present invention, the light diffusion layer contains acetoacetyl-modified polyvinyl alcohol for the purpose of retaining the light diffusion fine particles contained in the light diffusion layer and further improving the frame-shaped trace of water penetration when applied with water. The acetoacetyl-modified polyvinyl alcohol can be produced by a known method such as a reaction between polyvinyl alcohol and diketene. The degree of acetoacetylation is preferably from 0.1 to 20 mol%, more preferably from 1 to 15 mol%. The degree of saponification is preferably at least 80 mol%, more preferably at least 85 mol%. The degree of polymerization is preferably from 500 to 5,000, more preferably from 2,000 to 4,500. As such an acetoacetyl-modified polyvinyl alcohol, a commercially available product can be obtained and used. For example, it is commercially available from Nippon Synthetic Chemical Industry Co., Ltd. as GOHSENX (registered trademark) Z series.

  In the present invention, other known resin binders may be used in addition to the acetoacetyl-modified polyvinyl alcohol. For example, polyvinyl alcohol other than acetoacetyl-modified polyvinyl alcohol, gelatin, polyethylene oxide, polyvinylpyrrolidone, polyacrylic acid, polyacrylamide, polyurethane, dextran, dextrin, carrageenan (κ, ι, λ, etc.), agar, pullulan, water-soluble polyvinyl Butyral, hydroxyethylcellulose, carboxymethylcellulose and the like can be used in combination as needed. Further, various latexes may be used in combination as a binder resin.

  When using another polymer binder together, it is preferable to use a polymer binder having high compatibility with acetoacetyl-modified polyvinyl alcohol. As a polymer binder having high compatibility with acetoacetyl-modified polyvinyl alcohol, polyvinyl alcohol other than acetoacetyl-modified polyvinyl alcohol is preferable, and for example, completely or partially saponified polyvinyl alcohol or cation-modified polyvinyl alcohol is preferable. In particular, those having a saponification degree of 80 mol% or more and an average polymerization degree of 200 to 5,000 can be preferably used. The content of the other polymer binder is preferably less than 100% by mass based on the acetoacetyl-modified polyvinyl alcohol.

  In the present invention, the light diffusing fine particles are preferably supported on xerogel. The xerogel in the present invention refers to a gel having a network structure having voids due to loss of an internal solvent due to evaporation or the like. In general, in a structure in which the light diffusing fine particles are simply included in the resin binder, the refractive index of the resin binder and the light diffusing fine particles are generally around 1.50, and therefore, the light diffusing fine particles with respect to the resin binder. Is generally in the range of 0.91 <n <1.09 (however, n ≠ 1) as in Patent Documents 1 and 2, and efficient light diffusion is unlikely to occur. However, by supporting the light diffusing fine particles on the xerogel, voids of the xerogel (air having a refractive index of 1.0) are present on the surface of the light diffusing fine particles, and the relative refractive index of the light diffusing fine particles with respect to air is extremely high. Since the height is increased, efficient light diffusion of the light diffusing fine particles becomes possible, and both high transparency and visibility of an image projected from the projector can be achieved at a high level, which is preferable.

The porosity of the light diffusing layer in which the light diffusing fine particles are held by the xerogel is preferably 50% or more, more preferably 60% or more. The porosity is defined by the following equation. Here, the void volume V is the cumulative pore volume (ml / g) of the light diffusion layer with a pore radius of 3 nm to 400 nm, which was measured and processed using a mercury porosimeter (Autopore II 9220, a manufacturer of micromeritics instrument corporation). Is multiplied by the dry solid content (g / square meter) of the light diffusion layer to obtain a value per unit area (square meter). Further, the coating layer thickness T can be obtained by photographing the cross section of the light diffusion layer with an electron microscope and measuring the length.
P = (V / T) × 100 (%)
P: Porosity (%)
V: void volume (ml / m ² )
T: Coating layer thickness (μm)

  In forming the above xerogel, the light diffusion layer preferably contains xerogel formed of inorganic fine particles and acetoacetyl-modified polyvinyl alcohol, and the xerogel has an inorganic fine particle having an average primary particle diameter of 18 nm or less and acetoacetyl-modified polyvinyl alcohol. More preferably, it is formed by alcohol. If the average primary particle size exceeds 18 nm, the transparency of the light diffusion layer may be reduced, and sufficient transparency may not be obtained. Further, the inorganic fine particles constituting the xerogel preferably have a secondary aggregated particle diameter of 500 nm or less in average secondary particle diameter. If the average secondary particle size exceeds 500 nm, the transparency of the light diffusion layer may be reduced, and sufficient transparency may not be obtained. In the case of inorganic fine particles having a secondary aggregated particle diameter, the average primary particle diameter in the present invention can be measured by photographing with a transmission electron microscope, and the average secondary particle diameter is determined by a laser scattering particle size. The number median diameter can be measured using a distribution meter (for example, LA910 manufactured by Horiba, Ltd.).

  Examples of the inorganic fine particles used for forming the xerogel include various known fine particles such as amorphous synthetic silica, alumina, alumina hydrate, calcium carbonate, magnesium carbonate, and titanium dioxide. Crystalline synthetic silica, alumina or alumina hydrate is preferred.

  Amorphous synthetic silica can be broadly classified into wet silica, fumed silica, and others depending on the production method. The wet method silica is further classified into a precipitation method silica, a gel method silica, and a sol method silica depending on the production method. Precipitated silica is produced by reacting sodium silicate and sulfuric acid under alkaline conditions. The silica particles that have grown are aggregated and sedimented, and then are commercialized through filtration, washing, drying, pulverization and classification. Precipitated silica is commercially available, for example, as Nipsil (registered trademark) from Tosoh Silica Co., Ltd. and as Tokusil (registered trademark) from Tokuyama Corporation. Gel silica is produced by reacting sodium silicate and sulfuric acid under acidic conditions. During aging, the fine particles dissolve and re-precipitate to bind the other primary particles together, so that distinct primary particles disappear and form relatively hard aggregated particles having an internal void structure. For example, it is commercially available as Nipgel (registered trademark) from Tosoh Silica Co., Ltd., and as Syroid (registered trademark) and Shirojet (registered trademark) from Grace Japan Co., Ltd. The sol method silica is also called colloidal silica, and is obtained by heating and aging a silica sol obtained by double decomposition of sodium silicate with an acid or the like through an ion-exchange resin layer, for example, Snowtex (registered trademark) from Nissan Chemical Industries, Ltd. It is commercially available as

  The fumed silica is also called a dry method with respect to a wet method, and is generally produced by a flame hydrolysis method. Specifically, a method of burning silicon tetrachloride with hydrogen and oxygen is generally known, but instead of silicon tetrachloride, silanes such as methyltrichlorosilane and trichlorosilane can be used alone or in combination with silicon tetrachloride. And can be used in a mixed state. The fumed silica is commercially available as Aerosil (registered trademark) from Nippon Aerosil Co., Ltd. and QS type from Tokuyama Corporation.

In the present invention, fumed silica can be preferably used. The average primary particle diameter of the fumed silica is preferably 18 nm or less, and in order to obtain higher transparency, the average primary particle diameter is 3 to 15 nm and the specific surface area by the BET method is 200 m ² / g or more. Is to use something. In the present invention, the average primary particle diameter is obtained by observing the fine particles by electron microscopy and determining the average particle diameter by using the diameter of a circle equal to the projected area of each of the 100 primary particles present in a certain area as the particle diameter. In the present invention, the BET method is one of the methods for measuring the surface area of a powder by a gas phase adsorption method, and is a method for determining the total surface area of 1 g of a sample, that is, the specific surface area, from an adsorption isotherm. Usually, nitrogen gas is often used as the adsorption gas, and a method of measuring the amount of adsorption from the pressure or volume change of the gas to be adsorbed is most often used. The most prominent one for expressing the isotherm of multimolecular adsorption is the Brunauer, Emmett, Teller equation, which is called the BET equation and is widely used for determining the surface area. The amount of adsorption is determined based on the BET equation, and the surface area is obtained by multiplying the area occupied by one adsorbed molecule on the surface.

  The fumed silica is preferably dispersed in the presence of a cationic compound. As a result, a light diffusion layer having a high porosity can be obtained, and an effect having excellent visibility can be obtained. As the dispersion method, the gas phase silica and the dispersion medium are premixed by ordinary propeller stirring, turbine stirring, homomixer stirring, etc., and then a ball mill, a bead mill, a media mill such as a sand grinder, a high pressure homogenizer, an ultra high pressure It is preferable to perform dispersion using a pressure type disperser such as a homogenizer, an ultrasonic disperser, a thin film revolving type disperser, or the like.

  In the present invention, wet-process silica pulverized to an average secondary particle diameter of 500 nm or less can also be preferably used. As the wet process silica used here, precipitated silica or gel process silica is preferable. As the wet process silica particles used in the present invention, wet process silica particles having an average primary particle size of 18 nm or less and an average agglomerated particle size of 5 to 50 μm are preferable, and these are pulverized in the presence of a cationic compound. It is preferable to use wet process silica fine particles.

  As the alumina used in the present invention, γ-alumina which is a γ-type crystal of aluminum oxide is preferable, and among them, δ group crystal is preferable. Although γ-alumina can reduce the primary particles to about 10 nm, secondary particles having a size of several thousand to several tens of thousands nm are usually averaged by ultrasonic waves, a high-pressure homogenizer, an opposed collision type jet pulverizer, or the like. Those having a particle diameter of 500 nm or less, preferably about 20 to 300 nm can be used.

The alumina hydrate of the present invention is represented by a constitutive formula of Al ₂ O ₃ .nH ₂ O (n = 1 to 3). Alumina hydrate can be obtained by a known production method such as hydrolysis of aluminum alkoxide such as aluminum isopropoxide, neutralization of aluminum salt with alkali, and hydrolysis of aluminate.

  The above-mentioned alumina and alumina hydrate used in the present invention are used in the form of a dispersion liquid dispersed by a known dispersant such as acetic acid, lactic acid, formic acid, and nitric acid.

  Two or more kinds of inorganic fine particles can be used in combination from the above-mentioned inorganic fine particles. For example, a combination of pulverized wet silica and fumed silica, a combination of finely pulverized wet silica and alumina or alumina hydrate, and a combination of pulverized silica and alumina or alumina hydrate are exemplified. . The ratio in the case of this combination is preferably in the range of 7: 3 to 3: 7 in any aspect. The light diffusion layer in the present invention preferably contains the above-mentioned inorganic fine particles in an amount of 50% by mass or more, more preferably 70% by mass or more based on the total solid content of the light diffusion layer and the light diffusion layer.

  The content of the acetoacetyl-modified polyvinyl alcohol when the light diffusing fine particles are supported on xerogel is preferably 3 to 100% by mass, more preferably 3 to 85% by mass, based on the inorganic fine particles constituting the xerogel. It is more preferably 5 to 50% by mass, and particularly preferably 8 to 30% by mass. By coating a coating solution containing inorganic fine particles and acetoacetyl-modified polyvinyl alcohol at such a ratio on a light-transmitting support and drying, a porous layer having fine voids (xerogel containing a large amount of air) ) Can be easily formed. The light diffusing fine particles described above are preferably 0.1 to 40% by mass, and preferably 0.3 to 20% by mass, based on the inorganic fine particles constituting xerogel, and have high transparency and excellent image quality. This is particularly preferable because the visibility of the sphere can be compatible with higher dimensions.

  In the present invention, the light diffusion layer preferably contains a crosslinking agent. As the crosslinking agent, those known as crosslinking agents for acetoacetyl-modified polyvinyl alcohol can be used, for example, boron compounds, aldehyde group-containing compounds, polyvalent metal compounds, amine compounds, hydrazine compounds, silane compounds, methylol group-containing compounds, Epoxy compounds, thiol compounds, isocyanate compounds, polyamide resins and the like can be mentioned. Particularly, a boron compound, an aldehyde group-containing compound, a polyvalent metal compound, a hydrazine compound, and an amine compound are preferable.

  Such boron compounds include orthoboric acid, metaboric acid, hypoboric acid, and their sodium, potassium, and ammonium salts.

  Examples of such aldehyde group-containing compounds include glyoxylates, formaldehyde, acetaldehyde, propionaldehyde, crotonaldehyde, monoaldehydes such as benzaldehyde, glyoxal, glutaraldehyde, malondialdehyde, terephthalaldehyde, dialdehyde starch and the like. Among them, glyoxylate is preferably used. The glyoxylates include metal salts and amine salts of glyoxylic acid.Examples of the metal salts include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium and calcium, titanium, zirconium, and chromium. Transition metals such as manganese, iron, cobalt, nickel and copper, and other metals such as zinc and aluminum and metal salts of glyoxylic acid, and amine salts such as ammonia, monomethylamine, dimethylamine and amines such as trimethylamine Glyoxylic acid salts. Metal salts, particularly salts of alkali metals and alkaline earth metals, are preferably used from the viewpoint that a crosslinked polymer having excellent water resistance can be obtained.

  Examples of the polyvalent metal compound include a compound containing an aluminum atom, a zinc atom, an iron atom, a zirconium atom, a titanium atom, a gallium atom, an indium atom, a ruthenium atom, and a hafnium atom, and in particular, a compound having a zirconium atom. Is preferred.

  Such a compound having a zirconium atom may be any of a single salt and a double salt of an inorganic acid or an organic acid, an organic metal compound, a metal complex, an oxide compound (zirconyl compound), and the like. Zirconium, zirconium chloride, zirconium bromide, zirconate, zirconate, zirconyl chloride (“Zirconol (registered trademark) ZC” manufactured by Daiichi Kagaku Kagaku Kogyo Co., Ltd.), basic zirconyl chloride (made by Daiichi Kagaku Kagaku Kogyo Co., Ltd.) “Zircosol ZC-2”), zirconyl sulfate, zirconyl nitrate (“Zircosol ZN” manufactured by Daiichi Kagaku Kagaku Kogyo Co., Ltd.), zirconyl carbonate, ammonium zirconium carbonate (“Zircosol AC-7” manufactured by Daiichi Kagaku Kagaku Kogyo Co., Ltd.) , Potassium zirconium carbonate, zirconyl acetate, zirconyl stearate, zirconyl octylate, Zirconyl enoate, zirconyl lactate, zirconyl oxalate, zirconyl phosphate, zirconium tetraacetylacetonate (“Orgatics (registered trademark) ZC-150” manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium monoacetylacetonate (“Orga manufactured by Matsumoto Fine Chemical Co., Ltd.” Chix ZC-540 "), zirconium bisacetylacetonate (Matsumoto Fine Chemical Co., Ltd." Orgatics ZC-550 "), zirconium monoethylacetonate (Matsumoto Fine Chemical Co., Ltd." Orgatics ZC-560 "), zirconium acetate (Matsumoto Fine Chemical) "Orgatics ZC-115"), zirconium acylate (Matsumoto Fine Chemical Co., Ltd. "Orgatics ZB-126") and the like. That.

  Among these compounds containing a zirconium atom, zirconyl ammonium carbonate, potassium zirconium carbonate, zirconyl acetate, basic zirconyl chloride, zirconyl chloride, zirconyl compounds such as zirconyl nitrate are preferable, and particularly basic zirconyl chloride and zirconyl nitrate of the present invention. It is preferably used in that the purpose can be remarkably exhibited.

  Further, the compound having a titanium atom may be any of a single salt and a double salt of an inorganic acid or an organic acid, an organic metal compound, a metal complex, an oxide compound, and the like.Specific examples include titanium acetyl acetate, Examples include triethanolamine titanate, titanium ammonium lactate, titanium lactate, and the like.

  Examples of the hydrazine compound include hydrazine, inorganic acid salts such as hydrochloric acid, sulfuric acid, nitric acid, sulfurous acid, phosphoric acid, thiocyanic acid, and carbonic acid of hydrazine, and organic acid salts such as formic acid and oxalic acid; methyl and ethyl hydrazine; Monosubstituted propyl, butyl, allyl and the like, hydrazine derivatives such as asymmetric disubstituted 1,1-dimethyl, 1,1-diethyl and the like, carbohydrazide, oxalic dihydrazide, malonic dihydrazide, glutaric dihydrazide, succinic dihydrazide , Adipic dihydrazide, azelaic dihydrazide, sebacic dihydrazide, dodecane diacid dihydrazide, maleic dihydrazide, fumaric dihydrazide, diglycolic dihydrazide, tartaric dihydrazide, malic dihydrazide, isophthalic dihydrazide, Zide, trihydrazide citrate, 1,3-bis (hydrazinocarbonoethyl) -5-isopropylhydantoin ("Amicure (registered trademark) VDH" manufactured by Ajinomoto Fine Techno Co., Ltd.), 7,11-octadecadien-1 And hydrazide compounds such as polyacrylic acid hydrazide and the like, and particularly, adipic acid dihydrazide and 1,3-bis (hydrazinocarbonoethyl). ) A polyvalent hydrazide compound such as -5-isopropylhydantoin is preferably used since the object of the present invention can be remarkably exhibited.

  Examples of the amine compound include ethylenediamine, hexamethylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, N-aminoethylpiperazine, 1,4-bis (3-aminopropyl) piperazine, and trimethylhexaamine. Aliphatic polyamines such as methylenediamine (a mixture of 2,2,4-, 2,4,4-) and polyoxypropylenediamine, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'- Alicyclic polyamines such as diaminodicyclohexylmethane, isophoronediamine, 1,3-bisaminomethylcyclohexane, norbornanediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, diaminodiphenylsul , M-phenylenediamine, 2,4-diaminotoluene, aromatic diamines such as m-xylylenediamine, amino group-modified polyvinyl alcohol resins, polyvinylamine, polyallylamine, amino group-containing water-soluble polymers such as polyethyleneimine. In particular, 1,3-bisaminomethylcyclohexane, m-xylylenediamine, an amino group-modified polyvinyl alcohol-based resin, polyethyleneimine, and the like are suitably used because the object of the present invention can be remarkably exhibited.

  Further, as the methylolated amino resin, methylol melamine (“SUMIMALM-30W” manufactured by Sumitomo Chemical Co., Ltd.), butyl etherified melamine, methyl etherified melamine, and the like, a part or all of the methylol group of methylol melamine is methanol, ethanol, propanol, butanol. And melamine resins modified with one or more monohydric alcohols such as octyl alcohol and 2-ethylhexyl alcohol.

  The content of the crosslinking agent is preferably from 0.1 to 50% by mass, more preferably from 1 to 30% by mass, based on the acetoacetyl-modified polyvinyl alcohol. When two or more crosslinking agents are used in combination, the total content of each crosslinking agent may be within the above range. The crosslinking agent may be added to the coating solution after application and drying, in addition to being included in the coating solution for the light diffusion layer. For example, to form a coating film having an excellent degree of crosslinking without impairing the viscosity stability of the coating solution by applying a light-diffusing layer coating solution containing boric acid, drying and forming a coating film, and then applying another crosslinking agent. Is preferred because

Dry solid coating amount of the light diffusing layer is preferably in the range of 1 to 50 g / ^{m 2,} more preferably in the range of 3~40g / ^{m 2,} in particular in the range of 5 to 30 g / ^{m 2} is preferred. The light diffusion layer further includes a cationic polymer, a preservative, a surfactant, a coloring dye, a coloring pigment, an ultraviolet absorber, an antioxidant, a pigment dispersant, an antifoaming agent, a leveling agent, a fluorescent whitening agent, and a viscosity. Stabilizers, pH adjusters and the like can also be added.

  The light diffusion layer may be composed of two or more layers. In this case, the configurations of the light diffusion layers may be the same or different from each other. When there are a plurality of light diffusing layers, the light diffusing fine particles can be contained in at least one light diffusing layer.

  In the present invention, as a coating method used for coating the light diffusion layer, various known coating methods can be used. For example, there are a slide bead method, a slide curtain method, an extrusion method, a slot die method, a gravure roll method, an air knife method, a blade coating method, a rod bar coating method, and the like.

  The light-transmitting support of the transmission type screen laminate of the present invention is not particularly limited as long as it has light-transmitting properties. A layer provided with a light-transmitting layer such as the light diffusion layer described above can be used. The type of glass is not particularly limited, but generally, oxidized glass such as silicate glass, phosphate glass, and borate glass is practical, and in particular, silicate glass and alkali silicate glass And silicate glass such as soda lime glass, potassium lime glass, lead glass, barium glass, and borosilicate glass. As the plastic, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polypropylene, polyethylene, polyarylate, acryl, acetylcellulose, polyvinyl chloride, and the like can be used. It is preferable because the mechanical strength is improved. The haze value of the light-transmitting support is preferably 30% or less.

  The thickness of the light-transmitting support of the present invention can be appropriately selected depending on the applied material, but is generally about 10 μm to 30 mm, preferably about 20 μm to 20 mm. Further, on the surface of the light-transmitting support, for the purpose of improving the adhesion between the light-diffusing layer and the light-transmitting support, or for the purpose of improving the adhesion between the transparent adhesive layer and the light-diffusing support described below. An easy adhesion treatment may be performed, or an easy adhesion layer may be separately provided.

  The transmission type screen laminate of the present invention has a transparent adhesive layer on the above-mentioned light diffusion layer. In order to protect the transparent adhesive layer, a known separate substrate such as a film or paper is provided on the transparent adhesive layer. When the transmission screen laminate is used as a transmission screen, the separate substrate is peeled off, and the transparent substrate is adhered to a substrate to be bonded via a transparent adhesive layer.

  The transparent adhesive layer is not particularly limited, but is preferably one that does not hinder transparency when used as a transmission screen. In addition, such a transparent adhesive layer can use a generally used acrylic resin, silicone resin, urethane resin, a synthetic resin adhesive such as a rubber resin, and a separate base material, for example, a silicone resin or the like on the surface. Films of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polypropylene, polyethylene, polyarylate, acryl, acetylcellulose, polyvinyl chloride, etc., which have been subjected to a release treatment, and kraft paper can be used.

  The transmission screen included in the transmission screen laminate of the present invention may include a known antireflection layer having a performance of canceling reflected light by utilizing light interference caused by a layer interface. Thus, the image projected from the projector can be clearly recognized. As the antireflection layer, for example, a single layer provided with a highly transparent low refractive index layer such as silicon oxide or lithium fluoride to be an optical thin film having a quarter of the main wavelength, A layer in which a high refractive index layer such as titanium oxide or zinc oxide is appropriately laminated on a low refractive index layer can be used.

Hereinafter, the present invention will be described in detail with reference to examples, but the contents of the present invention are not limited to the examples. In addition, a part represents the mass part of a solid content or a substantial component.

(Example 1)
One side of a 100 μm thick transparent polyethylene terephthalate film (haze value 4%) was coated with a light diffusion layer coating solution 1 having the following composition using a slide bead coating apparatus so that the solid content was 18.5 g / m ^2. And dried by blowing hot air of 10 ° C. and 50 ° C. sequentially. In addition, when the void volume was measured using a mercury porosimeter (a measuring instrument name: Autopore II 9220, micromeritics instrument corporation), the thickness was 17 ml / m ² , and the thickness of the cross section of the light-diffusing layer was 27 μm by observation with an electron microscope. Porosity was 63%. The surface area of the light diffusing fine particles per screen unit area calculated from the average primary particle diameter, the specific gravity, and the blending amount of the light diffusing fine particles was 0.6 m ² / m ² .

<Preparation of silica dispersion liquid 1>
After adding 4 parts of dimethyldiallylammonium chloride homopolymer (molecular weight 9,000) and 100 parts of fumed silica (average primary particle diameter 7 nm, specific surface area 300 m ² / g) to water to prepare a preliminary dispersion, a high-pressure homogenizer To produce a silica dispersion having a solid content concentration of 20% by mass. The average secondary particle diameter was 80 nm when measured using LA910 manufactured by Horiba, Ltd.

<Light diffusion layer coating liquid 1>
Silica dispersion liquid 1 (as silica solid content) 100 parts Acetoacetyl-modified polyvinyl alcohol 23 parts (Gohsenx Z-410: manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
Adipic dihydrazide 1 part Nonionic surfactant 0.3 part (polyoxyethylene alkyl ether)
0.74 parts of light diffusing fine particles (Optobeads (registered trademark) 500S: manufactured by Nissan Chemical Industries, Ltd., silica, melamine resin composite fine particles (mainly melamine resin), average primary particle diameter 0.5 μm, true specific gravity 2.2) , Refractive index 1.65)
Water was adjusted so that the total solid content concentration was 12% by mass.

  Subsequently, the following adhesive layer coating solution was applied and dried on the light diffusion layer to a dry coating thickness of 10 μm. On the transparent adhesive layer surface, a transparent polyethylene terephthalate film (haze value: 3%) having a thickness of 25 μm, which had been subjected to a release treatment by silicone resin processing as a separate base material, was closely adhered to protect the transparent adhesive layer. Subsequently, the resultant was heated in an environment of 35 ° C. and 50% RH for 4 days to obtain a transmission screen laminate of Example 1. When the haze value after separation of the separate base material was measured using Nippon Denshoku Industries NDH-7000, the haze value was 41%. In addition, in this transmission screen laminate, the total light transmittance before bonding the separate base material was 85%.

<Adhesive layer coating liquid>
Acrylic copolymer resin 100 parts Crosslinker 4 parts (hexamethylene diisocyanate)
It was adjusted with toluene so that the total solid concentration was 30% by mass.

(Example 2)
One side of a 100 μm thick transparent polyethylene terephthalate film (haze value 4%) was coated with a light diffusion layer coating solution 2 having the following composition using a slide bead coating device so that the solid content was 18.5 g / m ^2. And dried by blowing hot air of 10 ° C. and 50 ° C. sequentially. Further, a cross-linking agent coating solution having the following composition was applied by a coating device using a diagonal gravure roll, and dried by blowing hot air at 45 ° C. to provide a light diffusion layer of Example 2. The wet coating amount of the cross-linking agent coating liquid was adjusted to 15 ml / m ² (0.14 g / m ^{2 in} terms of solid content) by adjusting the number of rotations of the oblique gravure roll. The porosity measured in the same manner as in Example 1 was 63%, and the surface area of the light diffusing fine particles per unit area of the screen was 0.6 m ² / m ² . Subsequently, a transparent adhesive layer was formed on the light diffusion layer in the same manner as in Example 1, and a separate base material was adhered and adhered on the light diffusion layer in the same manner as in Example 1. A screen laminate was produced. The haze value after separation of the separate substrate was 43%. In addition, in this transmission screen laminate, the total light transmittance before bonding the separate base material was 85%.

<Light diffusion layer coating liquid 2>
Silica dispersion liquid 1 (as silica solid content) 100 parts Acetoacetyl-modified polyvinyl alcohol 23 parts (Gohsenx Z-410: manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
Boric acid 4 parts Nonionic surfactant 0.3 parts (polyoxyethylene alkyl ether)
0.76 parts of light diffusing fine particles (Optobead 500S)
Water was adjusted so that the total solid content concentration was 12% by mass.

<Crosslinking agent coating liquid>
Sodium glyoxylate Water was adjusted so that the solid content of the coating solution was 0.93% by mass.

(Comparative Example 1)
A transmission screen laminate of Comparative Example 1 was produced in the same manner as in Example 1 except that the light diffusion layer coating liquid 1 of Example 1 was changed to the following light diffusion layer coating liquid 3. The porosity measured in the same manner as in Example 1 was 63%, the surface area of the light diffusing fine particles per unit area of the screen was 0.6 m ² / m ² , and the haze value after peeling the separate base material was 38%. Was.

<Light diffusion layer coating liquid 3>
Silica dispersion liquid 1 (as silica solid content) 100 parts Polyvinyl alcohol 23 parts (Saponification degree 88%, average polymerization degree 3500)
Boric acid 4 parts Nonionic surfactant 0.3 parts (polyoxyethylene alkyl ether)
0.76 parts of light diffusing fine particles (Optobead 500S)
Water was adjusted so that the total solid content concentration was 12% by mass.

(Comparative Example 2)
A transmission screen laminate of Comparative Example 2 was produced in the same manner as in Example 1 except that the light diffusion layer coating solution 1 of Example 1 was changed to the following light diffusion layer coating solution 4. The porosity measured in the same manner as in Example 1 was 0%, the surface area of the light diffusing fine particles per unit area of the screen was 0.8 m ² / m ² , and the haze value after peeling the separate base material was 13%. Was.

<Light diffusion layer coating liquid 4>
Acrylic emulsion 100 parts Nonionic surfactant 0.3 part (polyoxyethylene alkyl ether)
0.76 parts of light diffusing fine particles (Optobead 500S)
Water was adjusted so that the total solid content concentration was 12% by mass.

<Evaluation of trace of water penetration after applying water>
A 5 mm thick transparent acrylic plate is prepared as a substrate to be adhered, and a 3M film working solution (nonionic surfactant) is applied to the surface of the acrylic plate and the transparent adhesive layer of the transmission screen laminate from which the separate substrate has been peeled off. ) Was sprayed with a 50-fold diluted solution of water (containing the agent), and both were brought into close contact with each other. After that, the diluting liquid of the same film construction liquid is sprayed on the surface of the light-transmitting support having the light-transmitting support having no light-diffusing layer, and the surface is rubbed with a squeegee, and the substrate to be adhered and the transmission-type screen are laminated. The air between the screens was scraped out together with the film application liquid, and both were completely adhered. After drying all day and night, the edge of the transmission screen bonded to the transparent acrylic plate was visually observed and evaluated according to the following criteria.
：: There is no trace of penetration of the construction liquid or there is no problem.
×: Permeation trace of construction liquid is observed.

<Evaluation of the visibility of the image when projecting the projector>
The visibility of the image at the time of projector projection can be measured by using a digital projector (PJ WX4141N, manufactured by Ricoh Co., Ltd.) to actually project the image on a transmissive screen pasted on an acrylic plate and project it on the screen from the opposite side of the projector. The visibility of the resulting images was visually evaluated according to the following evaluation criteria. In addition, the projector irradiated the light at an angle of about 30 degrees with respect to the perpendicular of the screen, and the evaluator visually evaluated the image at a position directly facing the screen.
：: The luminance of the image is high and the visibility is good.
Δ: Visibility of the image is inferior to the above-mentioned ○ level, but is a practically acceptable level.
X: The image brightness is low and the visibility is poor.

  From the results in Table 1, it can be seen that the transmission screen laminate of the present invention has a wide viewing angle of an image projected from the projector, and has a side surface of the transmission screen when water-adhered to a substrate to be adhered such as a glass or plastic plate. It can be seen that a transmission screen laminate having no frame-shaped trace of water penetration in the portion can be obtained.

REFERENCE SIGNS LIST 1 transmissive screen laminate 2 light diffusing fine particles 3 light diffusing layer 4 light transmissive support 5 transparent adhesive layer 6 separate substrate 7 adhered substrate

Claims (1)

  A transmissive screen laminate, wherein a light diffusing layer containing light diffusing fine particles and acetoacetyl-modified polyvinyl alcohol, a transparent adhesive layer, and a separate substrate are sequentially laminated on at least one surface of the light transmissive support. body.