WO2012176627A1 - 光学反射フィルム - Google Patents
光学反射フィルム Download PDFInfo
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- WO2012176627A1 WO2012176627A1 PCT/JP2012/064717 JP2012064717W WO2012176627A1 WO 2012176627 A1 WO2012176627 A1 WO 2012176627A1 JP 2012064717 W JP2012064717 W JP 2012064717W WO 2012176627 A1 WO2012176627 A1 WO 2012176627A1
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- refractive index
- index layer
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- low refractive
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/26—Reflecting filters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
- G02B5/0891—Ultraviolet [UV] mirrors
Definitions
- the present invention relates to an optical reflective film formed by alternately laminating layers having different refractive indexes by simultaneous multilayer coating, and relates to a film that can be suitably used for a metallic glossy film, a visible light colored film, and a thermal barrier film.
- a film in which layers having different refractive indexes are alternately laminated can be designed to reflect visible light by adjusting the optical film thickness.
- Patent Document 1 after forming SiO 2 layers and Si layers alternately by sputtering, annealing is performed and oxygen (O) is diffused to form a mixed layer, thereby forming 3 layers by sputtering. It is disclosed that a layer (O diffusion layer) configuration can be realized. In the manufacturing method using sputtering, the cost can be reduced because it can be reduced from three layers to two layers. However, providing two layers of sputter layers with a large area is clearly less expensive than simultaneous multilayer coating. Become high.
- an alternating laminated film of a specific polyester component A and a specific polyester component B having different refractive indexes is formed by melt extrusion, and further biaxially stretched to reflect in a wavelength band of 400 to 1400 nm. It is disclosed that a film having a rate peak can be obtained.
- a thin film having a thickness of about several tens of nanometers per layer is required, the stretching ratio increases, and film thickness unevenness occurs.
- the sample surface of film thickness unevenness due to the absence of a mixed region between layers The influence on the reflectance unevenness in the visible light region becomes large, and the optical characteristics are not sufficient.
- Patent Document 3 discloses that a high refractive index layer coating liquid in which a thermosetting silicone resin or an ultraviolet curable acrylic resin containing metal oxide or metal compound fine particles is dispersed in an organic solvent is wet using a bar coater. A method of forming a transparent laminate by coating on a substrate by a coating method is known. However, in the disclosed method, the optical characteristics are not sufficient because there is no mixed region between layers as described above.
- an object of the present invention is to obtain an optical reflection film that is low in manufacturing cost, can be increased in area, and has both productivity and optical characteristics with reduced reflectance unevenness in the visible light region.
- a film comprising a water-soluble polymer and metal oxide particles in at least one of a high refractive index layer and a low refractive index layer, wherein the high refractive index layer and the low refractive index layer are alternately laminated.
- the optical reflection film having at least one on the support, By simultaneously coating the high refractive index layer and the low refractive index layer, the high refractive index layer and the low refractive index layer are mixed between the high refractive index layer and the low refractive index layer.
- An optical reflective film having a region, and having a region having an average reflectance of 30% or more and 100% or less in at least one region of a visible light wavelength region.
- optical reflective film as described in 1 above, wherein at least one of the high refractive index layer and the low refractive index layer includes a layer having a dry film thickness of 600 nm or more and 1200 nm or less.
- optical reflection film according to 1 or 2 wherein the optical reflection film has two or more types of units having different optical film thicknesses, in which high refractive index layers and low refractive index layers are alternately laminated.
- optical reflection film as described in 3 above, wherein the two or more units include at least one unit that mainly reflects visible light and at least one unit that mainly reflects near-infrared light.
- an optical reflection film that is low in manufacturing cost, can be increased in area, and has both productivity and optical characteristics with reduced reflectance unevenness in the visible light region.
- an infrared reflective film is constituted by an alternating laminated unit composed of a high refractive index layer A (refractive index nA) and a low refractive index layer C (refractive index nC)
- a layer B having a refractive index of 0.5 and different layers B are laminated in the order of ABCB together with the high refractive index layer A and the low refractive index layer C, and each layer is an optical film.
- a laminate of polymer films having alternating lamination units set so that the thickness ratio is A1 / 3, B1 / 6, and C1 / 3 is known (for example, Japanese Patent No. 3067863).
- the present invention basically adopts such a configuration, the region (mixed region) where both the high refractive index material in the high refractive index layer and the low refractive index material in the low refractive index layer exist is present.
- a mixed region in which the high refractive index layer and the low refractive index layer are mixed is provided between the high refractive index layer (high refractive index region) and the low refractive layer (low refractive index region). It is what.
- the optical reflective film of the present invention contains a water-soluble polymer and metal oxide particles in at least one of a high refractive index layer and a low refractive index layer, and the high refractive index layer and the low refractive index layer.
- the optical reflection film having at least one unit (hereinafter also referred to as “alternate lamination unit”) laminated on a film support (for example, a resin film), the high refractive index layer, the low refractive index layer,
- a film support for example, a resin film
- the high refractive index layer, the low refractive index layer By simultaneously applying multiple layers, a mixed region of the high refractive index layer and the low refractive index layer is provided between the high refractive index layer and the low refractive index layer.
- the mixed region by simultaneous multi-layer coating, the number of layers required for coating can be reduced to 1 ⁇ 2 compared to a method in which the layer B is separately installed, and the cost can be greatly reduced.
- each component of the coating solution (high refractive index material and low refractive index material) mixes in the time until set, resulting in an interface.
- a mixed region in which the ratio between the high refractive index material and the low refractive index material continuously changes can be formed. That is, in one embodiment of the present invention, the refractive index change in the mixed region is continuous.
- the alternating lamination is formed by simultaneous multilayer coating using the high refractive index layer coating liquid A (refractive index nA) and the low refractive index layer coating liquid C (refractive index nC) as described above, the respective layers are formed.
- the mixed region mixed region
- the position where the maximum refractive index ⁇ n / 3 with respect to the refractive index is 0.9 / 3 to 1.1 from the maximum refractive index point with respect to the width (layer thickness) from the maximum refractive index to the minimum refractive index. / 3, and for the minimum refractive index, the position where the minimum refractive index + ⁇ n / 3 is from the minimum refractive index point to the width (layer thickness) from the maximum refractive index to the minimum refractive index. It is preferable to have a continuous refractive index profile so as to be in the range of 0.9 / 3 to 1.1 / 3.
- the refractive index profile of the mixed region preferably exhibits a sine curve.
- each layer is not clearly laminated in the order of ABCB, but the high refractive index layer coating solution and the low refractive index layer coating solution are simultaneously stacked.
- the laminated body has a structure in which the refractive index continuously changes in the mixed region from the high refractive index layer (high refractive region) to the low refractive region.
- the state in which the refractive index continuously changes can be determined, for example, by observing a metal oxide concentration profile described later.
- the width (layer thickness) T is set to T / 4 each. It is desirable to satisfy ( ⁇ n / 16) ⁇ ⁇ S ⁇ ( ⁇ n / 2), where ⁇ S is the minimum value of the refractive index difference in any T / 4 section.
- ⁇ n is a difference between the maximum refractive index and the minimum refractive index.
- ⁇ S has a refractive index difference ( ⁇ n / 16) of a predetermined value or more.
- the average reflectance and further the average visible light reflectance described later can be improved, and reflection unevenness can be suppressed. it can.
- These configurations according to the present invention can be obtained by simultaneous multilayer coating of a high refractive index layer coating solution and a low refractive index layer coating solution, have good productivity, can be produced in a large area, Even if there is a variation in film thickness, the optical reflection property is highly robust. Especially, an optical reflection film that has excellent optical properties in the visible light region, which requires a thin film thickness of about several tens of nanometers and is easily affected by film thickness variation. Can be obtained.
- the refractive index profile is a high refractive index material and a low refractive index material in the film thickness direction of these laminated films. This can be determined by measuring the concentration profile. That is, the refractive index can be converted into the refractive index by the composition from the concentration profile of the materials (high refractive index material and low refractive index material) in the film thickness direction of the laminated film.
- the refractive index profile can be known by measuring the metal oxide concentration profile in the film thickness direction of these laminated films. Can do.
- the metal oxide when used as the high refractive index material and the low refractive index material, for example, high refractive index
- the refractive index layer contains titanium oxide as a high refractive index material and the low refractive index layer contains silicon oxide as a low refractive index material
- the metal oxide concentration profile in the film thickness direction of these laminated films You can know by measuring. And it can convert into a refractive index with a composition from the metal oxide density
- the metal oxide concentration profile of the laminated film is sputtered from the surface in the depth direction using a sputtering method, and is sputtered at a rate of 0.5 nm / min using the XPS surface analyzer with the outermost surface being 0 nm. It can be observed by measuring the atomic composition ratio.
- the XPS surface analyzer is not particularly limited, and any model can be used.
- ESCALAB-200R manufactured by VG Scientific is used.
- Mg is used for the X-ray anode, and measurement is performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA).
- the difference in refractive index between at least two adjacent layers is preferably 0.2 or more, more preferably 0.3 or more.
- the upper limit is not particularly limited, but is usually 1.4 or less.
- the alternating layered unit of the present invention has a mixed region at the boundary between the high refractive index layer and the low refractive index layer, but is produced by simultaneously applying the high refractive index layer and the low refractive index layer. This is explained in terms of two layers.
- the refractive index difference between the high refractive index layer and the low refractive index layer is actually the difference between the maximum refractive index point in the high refractive index region and the lowest refractive index point in the low refractive index region.
- n ⁇ d wavelength / 4 when viewed as a single layer film
- the reflected light is controlled to be strengthened by the phase difference.
- the reflectance can be increased.
- n is the refractive index
- d is the physical film thickness of the layer
- n ⁇ d is the optical film thickness.
- this relationship is used to control the refractive index and film thickness of each layer to control the reflection of visible light and near infrared light. That is, the reflectance in a specific wavelength region is increased by the refractive index of each layer, the film thickness of each layer, and the way of stacking each layer.
- the present invention is characterized in that a region having an average reflectance of 30% or more and 100% or less is provided in at least one region of the visible light wavelength region.
- the average reflectance is preferably 40 to 100%, more preferably 50 to 100%.
- the said structure can be obtained by controlling the refractive index and physical film thickness of each layer which comprise an alternately laminated unit as mentioned above.
- the average reflectivity is 2 nm in the wavelength region from wavelength 1 to wavelength 2 with a 5 ° reflection unit attached to a spectrophotometer (Hitachi, Ltd. U-4000 type) and the surface side of the optical reflection layer as the measurement surface.
- the reflectance is measured at (wavelength 2 ⁇ wavelength 1) / 2 + 1 points at intervals, and the value obtained by adding all the obtained reflectances is divided by (wavelength 2 ⁇ wavelength 1) / 2 + 1.
- the average reflectance when the wavelength 1 is 400 nm and the wavelength 2 is 700 nm that is, the average reflectance of the entire visible light wavelength region (400 to 700 nm) is equal to the following average visible light reflectance.
- the average visible light reflectance is a spectrophotometer (U-4000 type, manufactured by Hitachi, Ltd.) with a 5 ° reflection unit, and the surface side of the optical reflection layer is taken as the measurement surface. Then, the reflectance at 151 points is measured, and the value obtained by adding all the obtained reflectances is divided by 151 to measure.
- the preferred refractive index of the high refractive index layer is 1.70 to 2.50, more preferably 1.80 to 2.20.
- the preferable refractive index of the low refractive index layer is 1.10 to 1.60, more preferably 1.30 to 1.55.
- a thick film layer having a thickness of 600 nm to 1200 nm can be preferably used for any one layer. That is, in one embodiment of the present invention, at least one of the high refractive index layer and the low refractive index layer includes a layer having a dry film thickness of 600 to 1200 nm. More preferably, only one of the high-refractive index layer and the low-refractive index layer includes a layer having a dry film thickness of 600 to 1,200 nm, and more preferably visible light, because it is easier to handle by reducing the total dry film thickness.
- a layer having a dry film thickness of 600 to 1200 nm is included in the low refractive index layer from the viewpoint of efficiently reflecting visible light by widening the bandwidth of the light reflection band in the region.
- This thick film layer (1) can broaden the reflected wavelength range, (2) when used in a layer adjacent to the support, it can improve the adhesion to the support, (3) the thick film can relieve stress This has the effect of improving the physical properties of the film with a laminated film. More preferably, the dry film thickness is 700 nm to 1000 nm.
- a plurality of alternately laminated units can be used. That is, one embodiment of the present invention has two or more types of units having different optical film thicknesses, in which high refractive index layers and low refractive index layers are alternately laminated.
- the unit from which an optical film thickness differs means that the optical film thickness of the layer which comprises a certain alternating lamination unit differs from the optical film thickness of the layer which comprises another alternating lamination unit.
- the optical film thickness of a high refractive index layer constituting a certain alternating laminated unit is different from the optical film thickness of a high refractive index layer constituting another alternating laminated unit, (2) an alternating laminated unit
- the optical film thickness of the low-refractive index layer constituting the optical film is different from the optical film thickness of the low-refractive index layer constituting the other alternately laminated unit, or (3) the high refractive index layer and the low refractive index constituting the alternate laminated unit
- the optical film thickness of each layer is different from the optical film thicknesses of the high refractive index layer and the low refractive index layer constituting the other alternately laminated units.
- the optical film thickness (product n ⁇ d of refractive index n and physical film thickness d) is a material (high refractive index material and low refractive index layer and low refractive index layer) constituting the alternately laminated unit (at least one of high refractive index layer and low refractive index layer). It can be controlled by changing at least one of the refractive index material) and / or the film thickness.
- the optical film thickness for each unit (1) the reflected wavelength range can be broadened, (2) the band edge can be sharpened, (3) ripple can be reduced, (4) higher order Reflection can be suppressed, (5) the band shift can be reduced by changing the incident angle, and (6) the optical reflection characteristics can be suppressed from being changed due to different polarizations.
- the optical reflective film of the present invention is composed of at least one high refractive index layer and a low refractive index alternating lamination unit, and the total number of the high refractive index layer and the low refractive index layer in the optical reflective film is n.
- the total film thickness of the constituent layer (also referred to as the lower layer region) on the base material side is ⁇ d1, based on the position of n / 2, that is, the position of 1/2 the total number of layers (boundary region), and the reference position
- the film thickness ratio ⁇ d1 / ⁇ d2 is preferably 1.05 or more and 1.80 or less.
- the boundary region between the lower layer region from layer 1 to layer n / 2 and the upper layer region from layer n / 2 + 1 to layer n is the layer n / 2 and layer n It becomes an interface with / 2 + 1.
- the boundary region (n + 1/2) is defined on the lower layer side of the layer corresponding to the boundary region (n + 1/2) on the basis of the layer corresponding to the boundary region (n + 1/2).
- the total film thickness of the constituent layers up to the base material excluding the layer corresponding to n + 1/2) is ⁇ d1, and the boundary region (n + 1/2) on the upper layer side corresponding to the boundary region (n + 1/2)
- the total film thickness of the constituent layers up to the outermost layer excluding the layer corresponding to is defined as ⁇ d2.
- Each of the high refractive index layer and the low refractive index layer is composed of a high refractive index material and a low refractive index material and, if necessary, a water-soluble polymer as a binder, a curing agent, an amino acid, and various additives described later.
- a water-soluble polymer as a binder, a curing agent, an amino acid, and various additives described later.
- examples of the high refractive index material and the low refractive index material include metal oxide particles, metal fine particles, a high refractive index polymer, and a low refractive index polymer.
- a water-soluble polymer can be used as a high refractive index material or a low refractive index material.
- At least one of the high refractive index layer and the low refractive index layer contains a water-soluble polymer and metal oxide particles. That is, both the high refractive index layer and the low refractive index layer may contain a water-soluble polymer and metal oxide particles. Alternatively, only one of the high refractive index layer and the low refractive index layer may contain a water-soluble polymer and metal oxide particles. In the latter case, the configuration of the other layer may include a form containing a water-soluble polymer and no metal oxide particles, or a form in which other known compounds having different refractive indexes coexist.
- water-soluble polymer In the refractive index layer (low refractive index layer, high refractive index layer) according to the present invention, since each layer coating solution is prepared and laminated by simultaneous multilayering, synthetic polymers such as polyvinyl alcohol, gelatin, thickening are used as binders. At least one water-soluble polymer selected from the group consisting of polysaccharides and the like can be used. In particular, it is preferable to use gelatin.
- water-soluble polymer means a G2 glass filter (maximum pores 40 to 40) when dissolved in water at a concentration of 0.5% by mass at the temperature at which the water-soluble polymer is most dissolved. 50 mass), the mass of the insoluble matter that is filtered off when filtered at 50 ⁇ m) is within 50 mass% of the added water-soluble polymer.
- the weight average molecular weight of the water-soluble polymer is preferably 1,000 or more and 200,000 or less. Furthermore, 2,000 or more and 150,000 or less are more preferable, and 3,000 or more and 40,000 or less are more preferable.
- the value measured using gel permeation chromatography (GPC) is employ
- Synthetic polymers applicable to the present invention include, for example, polyvinyl alcohols, polyvinyl pyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate-acrylonitrile copolymer, vinyl acetate-acrylic acid.
- Acrylic resins such as ester copolymers or acrylic acid-acrylic acid ester copolymers, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylic acid ester copolymers, styrene -Styrene acrylic resin such as ⁇ -methylstyrene-acrylic acid copolymer or styrene- ⁇ -methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-sodium styrenesulfonate copolymer, styrene-2- Hydroxyethyl acrylate copolymer Styrene-2-hydroxyethyl acrylate-potassium styrene sulfonate copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride cop
- the polyvinyl alcohol preferably used in the present invention includes, in addition to ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate, modified polyvinyl alcohol such as polyvinyl alcohol having a cation-modified terminal and anion-modified polyvinyl alcohol having an anionic group. Alcohol is also included.
- the polyvinyl alcohol obtained by hydrolyzing vinyl acetate preferably has an average degree of polymerization of 1,000 or more, and particularly preferably has an average degree of polymerization of 1,500 to 5,000.
- the degree of saponification is preferably 70 to 100%, particularly preferably 80 to 99.5%.
- Examples of the cation-modified polyvinyl alcohol include primary to tertiary amino groups and quaternary ammonium groups in the main chain or side chain of the polyvinyl alcohol described in JP-A-61-10383. It is obtained by saponifying a copolymer of an ethylenically unsaturated monomer having a cationic group and vinyl acetate.
- Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl- (2-acrylamido-2,2-dimethylethyl) ammonium chloride and trimethyl- (3-acrylamido-3,3-dimethylpropyl) ammonium chloride.
- the ratio of the cation-modified group-containing monomer in the cation-modified polyvinyl alcohol is 0.1 to 10 mol%, preferably 0.2 to 5 mol%, relative to vinyl acetate.
- Anion-modified polyvinyl alcohol is, for example, polyvinyl alcohol having an anionic group as described in JP-A-1-206088, as described in JP-A-61-237681 and JP-A-63-307979, Examples thereof include a copolymer of vinyl alcohol and a vinyl compound having a water-soluble group, and modified polyvinyl alcohol having a water-soluble group as described in JP-A-7-285265.
- Nonionic modified polyvinyl alcohols include, for example, polyvinyl alcohol derivatives obtained by adding a polyalkylene oxide group to a part of vinyl alcohol as described in JP-A-7-9758, and described in JP-A-8-25795. And a block copolymer of a vinyl compound having a hydrophobic group and vinyl alcohol.
- Polyvinyl alcohol can be used in combination of two or more, such as the degree of polymerization and the type of modification.
- the content of the synthetic polymer in the refractive index layer is preferably 5% by mass or more and 20% by mass or more with respect to the total mass (100% by mass) of the refractive index layer. More preferred.
- the content of the synthetic polymer is 5% by mass or more, a strong film can be formed, and when the content is 20% by mass or more, it becomes more remarkable because it becomes remarkable.
- the content of the synthetic polymer is preferably 80% by mass or less.
- the refractive index layer in the above range can be produced by adjusting the concentration of the synthetic polymer with respect to the entire solid content in the coating solution.
- gelatin water-swellable polymer
- acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme-decomposed product can also be used.
- gelatin water-swellable polymer
- These water-swellable polymers may be used alone or in a plurality of types.
- the low molecular weight gelatin: high molecular weight gelatin is preferably from 3: 7 to 7: 3 from the viewpoint of coating solution viscosity stability.
- the content of gelatin in the refractive index layer is preferably 5% by mass or more, and more preferably 20% by mass or more with respect to the total mass (100% by mass) of the refractive index layer. . If the gelatin content is 5% by mass or more, a strong film can be formed, and if it is 20% by mass or more, it becomes more prominent because it becomes remarkable. On the other hand, from the viewpoint of refractive index control, the gelatin content is preferably 80% by mass or less.
- a refractive index layer in the above range can be prepared by adjusting the gelatin concentration relative to the entire solid content in the coating solution.
- thickening polysaccharide examples include generally known natural polysaccharides, natural complex polysaccharides, synthetic simple polysaccharides, and synthetic complex polysaccharides. For details, reference can be made to “Biochemical Encyclopedia (2nd edition), Tokyo Chemical Doujinshi”, “Food Industry”, Vol. 31 (1988), p. 21.
- the thickening polysaccharide referred to in the present invention is a polymer of saccharides and has many hydrogen bonding groups in the molecule, and the viscosity at low temperature and the viscosity at high temperature due to the difference in hydrogen bonding force between molecules depending on the temperature. It is a polysaccharide with a large difference in characteristics, and when adding metal oxide fine particles, it causes a viscosity increase that seems to be due to hydrogen bonding with the metal oxide fine particles at a low temperature. It is a polysaccharide that causes a viscosity increase at 40 ° C. of 1.0 mPa ⁇ s or more by addition, preferably 5.0 mPa ⁇ s or more, more preferably 10.0 mPa ⁇ s or more. Polysaccharides.
- thickening polysaccharide examples include ⁇ 1-4 glucan (eg, carboxymethylcellulose, carboxyethylcellulose, etc.), galactan (eg, agarose, agaropectin, etc.), galactomannoglycan (eg, locust bean gum).
- glucan eg, carboxymethylcellulose, carboxyethylcellulose, etc.
- galactan eg, agarose, agaropectin, etc.
- galactomannoglycan eg, locust bean gum
- xyloglucan eg, tamarind gum, etc.
- glucomannoglycan eg, salmon mannan, wood-derived glucomannan, xanthan gum, etc.
- galactoglucomannoglycan eg, softwood-derived glycan
- arabino Galactoglycans for example, soybean-derived glycans, microorganism-derived glycans, etc.
- gluconamnoglycans for example, gellan gum
- glycosaminoglycans for example, hyaluronic acid, keratan sulfate, etc.
- alginic acid and alginate agar Examples include natural polymer polysaccharides derived from red algae such as ⁇ -carrageenan, ⁇ -carrageenan, ⁇ -carrageenan, and fercelerane, and are preferable from the viewpoint of not reducing the dispersion stability of the metal oxide
- the structural unit preferably has no carboxylic acid group or sulfonic acid group.
- polysaccharides include, for example, pentoses such as L-arabitose, D-ribose, 2-deoxyribose, and D-xylose, and hexoses such as D-glucose, D-fructose, D-mannose, and D-galactose only. It is preferable that it is a polysaccharide.
- tamarind seed gum known as xyloglucan whose main chain is glucose and side chain is xylose
- guar gum known as galactomannan whose main chain is mannose and side chain is galactose
- locust bean gum Tara gum or arabinogalactan whose main chain is galactose and whose side chain is arabinose
- xyloglucan whose main chain is glucose and side chain is xylose
- galactomannan whose main chain is mannose and side chain is galactose
- locust bean gum Tara gum or arabinogalactan whose main chain is galactose and whose side chain is arabinose
- two or more thickening polysaccharides may be used in combination.
- each refractive index layer (low refractive index layer, high refractive index layer) containing a thickening polysaccharide
- 5 mass% or more and 50 mass% or less are preferable, and 10 mass% or more and 40 mass% or less are more. preferable.
- it may be contained in an amount of 2% by mass or more.
- the content is 50% by mass or less, the relative content of the metal oxide becomes appropriate, and it becomes easy to increase the difference in refractive index between the high refractive index layer and the low refractive index layer.
- the refractive index layer (low refractive index layer, high refractive index layer) according to the present invention preferably contains a curing agent.
- the curing agent applicable to the present invention is not particularly limited as long as it causes a curing reaction with a water-soluble polymer, and generally a compound having a group capable of reacting with a water-soluble polymer or a water-soluble polymer. Is a compound that promotes the reaction between different groups, and is appropriately selected according to the type of water-soluble polymer.
- the water-soluble polymer is polyvinyl alcohol
- boric acid and its salt are preferable.
- known ones can be used.
- the curing agent include, for example, epoxy curing agents (diglycidyl ethyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6 -Diglycidylcyclohexane, N, N-diglycidyl-4-glycidyloxyaniline, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, etc.), aldehyde curing agents (formaldehyde, glycoxal, etc.), active halogen curing agents (2,4- Dichloro-4-hydroxy-1,3,5-s-triazine, etc.), active vinyl compounds (1,3,5-tris-acryloyl-hexahydro-s-triazine, bisvinylsulfate,
- water-soluble polymer is gelatin
- organic hardeners such as vinylsulfone compounds, urea-formalin condensates, melanin-formalin condensates, epoxy compounds, aziridine compounds, active olefins, isocyanate compounds, etc.
- Inorganic polyvalent metal salts such as chromium, aluminum and zirconium.
- water-soluble polymer is a thickening polysaccharide
- examples thereof include an epoxy compound and an aldehyde compound.
- the total amount of the curing agent used is preferably 1 to 600 mg per 1 g of the water-soluble polymer, and more preferably 100 to 600 mg per 1 g of the water-soluble polymer.
- the metal oxide particles are used when constituting the low refractive index layer or the high refractive index layer.
- the metal oxide used for the above purpose include titanium dioxide, zirconium oxide, zinc oxide, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, lead titanate, red lead, yellow lead, zinc yellow, Examples thereof include chromium oxide, ferric oxide, iron black, copper oxide, magnesium oxide, magnesium hydroxide, strontium titanate, yttrium oxide, niobium oxide, europium oxide, lanthanum oxide, zircon, and tin oxide.
- metal oxide particles it is preferable to use solid fine particles selected from titanium dioxide, silicon dioxide, and alumina.
- Alumina or alumina hydrate may be crystalline or amorphous, and any shape such as amorphous particles, spherical particles, and acicular particles can be used.
- One kind of metal oxide particles in each refractive index layer may be used alone, or two or more kinds may be used in combination.
- the average particle diameter of the metal oxide particles is determined by observing the particles themselves or the particles appearing on the cross section or surface of the refractive index layer (low refractive index layer, high refractive index layer) with an electron microscope, and 1,000 arbitrary particles The particle size is measured as a simple average value (number average).
- the particle diameter of each particle is represented by a diameter assuming a circle equal to the projected area.
- the metal oxide particles preferably have a particle size of 100 nm or less, more preferably 4 to 50 nm, and still more preferably 4 to 35 nm.
- the content of the metal oxide particles in the refractive index layer is preferably 30% by mass or more, and 40% by mass or more with respect to the total mass (100% by mass) of the refractive index layer. Is more preferable.
- the content of the metal oxide particles is 30% by mass or more, the function as a low refractive index layer or a high refractive index layer can be exhibited.
- the content of the metal oxide particles is preferably 95% by mass or less in order to ensure the binding property between the metal oxides and form a coating film.
- silicon dioxide (silica) is preferably used as the metal oxide, and acidic colloidal silica sol is particularly preferably used.
- silicon dioxide As silicon dioxide (silica) that can be used in the present invention, silica synthesized by an ordinary wet method, colloidal silica, silica synthesized by a gas phase method, or the like is preferably used, but is particularly preferably used in the present invention.
- the fine particle silica colloidal silica or fine particle silica synthesized by a gas phase method is preferable. Among them, fine particle silica synthesized by a gas phase method is preferable because coarse aggregates are difficult to be formed when added to a cationic polymer. .
- the metal oxide particles are preferably in a state where the fine particle dispersion before mixing with the cationic polymer is dispersed to the primary particles.
- the type and content of the metal oxide particles may be appropriately determined so that desired refractive indexes of the high refractive index layer and the low refractive index layer can be obtained.
- silicon dioxide silicon dioxide
- acidic colloidal silica sol acidic colloidal silica sol
- silicon dioxide As silicon dioxide (silica) that can be used in the present invention, silica synthesized by an ordinary wet method, colloidal silica, silica synthesized by a gas phase method (gas phase method fine particle silica), or the like is preferably used.
- gas phase method gas phase method fine particle silica
- particulate silica particularly preferably used in the present invention colloidal silica or particulate silica synthesized by a vapor phase method (vapor phase particulate silica) is preferable.
- the average particle size (particle size in the dispersion state before coating) of the metal oxide particles dispersed in the primary particle state is 100 nm or less. More preferably, it is 4 to 50 nm, and most preferably 4 to 20 nm.
- Aerosil manufactured by Nippon Aerosil Co., Ltd. is commercially available as the silica synthesized by the gas phase method in which the average particle size of primary particles is 4 to 20 nm.
- the vapor phase fine particle silica can be dispersed to primary particles relatively easily by being sucked and dispersed in water, for example, by a jet stream inductor mixer manufactured by Mitamura Riken Kogyo Co., Ltd.
- the colloidal silica preferably used in the present invention is obtained by heating and aging a silica sol obtained by metathesis with an acid of sodium silicate or passing through an ion exchange resin layer, and this colloidal silica is used for ink jet recording paper.
- a silica sol obtained by metathesis with an acid of sodium silicate or passing through an ion exchange resin layer is used for ink jet recording paper.
- the preferred average particle size of colloidal silica is usually 5 to 100 nm, but an average particle size of 7 to 30 nm is particularly preferable.
- Silica synthesized by the gas phase method (gas phase method fine particle silica) and colloidal silica may be those whose surfaces are cation-modified, and those treated with Al, Ca, Mg, Ba, etc. There may be.
- colloidal silica composite emulsion can also be used as a metal oxide in the low refractive index layer.
- the colloidal silica composite emulsion preferably used in the present invention has a central part of a particle mainly composed of a polymer or copolymer, and is described in JP-A-59-71316 and JP-A-60-127371. It is obtained by polymerizing a monomer having an ethylenically unsaturated bond in the presence of colloidal silica which has been conventionally known by an emulsion polymerization method.
- the particle diameter of colloidal silica applied to the composite emulsion is preferably less than 40 nm.
- the colloidal silica used for the preparation of this composite emulsion usually includes primary particles of 2 to 100 nm.
- the ethylenic monomer include (meth) acrylic acid ester having 1 to 18 carbon atoms, aryl group, or allyl group, styrene, ⁇ -methylstyrene, vinyl toluene, acrylonitrile, vinyl chloride, vinylidene chloride. , Vinyl acetate, vinyl propionate, acrylamide, N-methylol acrylamide, ethylene, butadiene, and other materials known in the latex industry, and if necessary, vinyl trimethoate is used to improve compatibility with colloidal silica.
- Vinyl silanes such as oxysilane, vinyltriethoxysilane, ⁇ -methacrylooxypropyltrimethoxysilane, etc. are also used to stabilize the dispersion of (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid.
- Anionic monomers such as -Is used as an auxiliary agent.
- two or more types of ethylenic monomers can be used together as necessary.
- the ratio of ethylenic monomer / colloidal silica in the emulsion polymerization is preferably 100/1 to 200 in terms of solid content.
- colloidal silica composite emulsions used in the present invention those having a glass transition point in the range of ⁇ 30 to 30 ° C. are preferable.
- compositions include ethylenic monomers such as acrylic acid esters and methacrylic acid esters, and particularly preferred are copolymers of (meth) acrylic acid esters and styrene, alkyl (meth) acrylates.
- ethylenic monomers such as acrylic acid esters and methacrylic acid esters
- copolymers of (meth) acrylic acid esters and styrene, alkyl (meth) acrylates examples thereof include a copolymer of ester and (meth) acrylic acid aralkyl ester, and a (meth) acrylic acid alkyl ester and (meth) acrylic acid aryl ester copolymer.
- emulsifiers used in emulsion polymerization include alkyl allyl polyether sulfonic acid soda salt, lauryl sulfonic acid soda salt, alkyl benzene sulfonic acid soda salt, polyoxyethylene nonylphenyl ether sodium nitrate salt, alkyl allyl sulfosuccinate soda salt, sulfo Examples include propyl maleic acid monoalkyl ester soda salt.
- Preferred particle diameters are 10 nm or less for primary particles and 30 nm or less for secondary particles, and have low haze and excellent visible light permeability.
- TiO 2 , ZnO, and ZrO 2 are preferable, and TiO 2 is used from the viewpoint of the stability of the metal oxide particle-containing composition described later for forming the high refractive index layer.
- (Titanium dioxide) sol is more preferable.
- TiO 2 rutile type is more preferable than anatase type because the high refractive index layer and the adjacent layer have high weather resistance due to low catalytic activity, and the refractive index is high. That is, in one embodiment of the present invention, the metal oxide particles are rutile titanium dioxide.
- the first step in the method for producing rutile type fine particle titanium dioxide is at least one selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides. This is a step (Step 1) of treatment with a basic compound.
- Titanium dioxide hydrate can be obtained by hydrolysis of water-soluble titanium compounds such as titanium sulfate and titanium chloride.
- the method of hydrolysis is not particularly limited, and a known method can be applied. Among them, it is preferable to be obtained by thermal hydrolysis of titanium sulfate.
- the step (1) can be performed, for example, by adding the basic compound to an aqueous suspension of the titanium dioxide hydrate and treating (reacting) it under a predetermined temperature condition for a predetermined time. it can.
- the method for preparing the titanium dioxide hydrate as an aqueous suspension is not particularly limited, and can be performed by adding the titanium dioxide hydrate to water and stirring.
- the concentration of the suspension is not particularly limited.
- the concentration of TiO 2 is 30 to 150 g / L in the suspension. By setting it within the above range, the reaction (treatment) can proceed efficiently.
- the at least one basic compound selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides used in the step (1) is not particularly limited. Examples include potassium, magnesium hydroxide, calcium hydroxide, and the like.
- the amount of the basic compound added in the step (1) is preferably 30 to 300 g / L in terms of the basic compound concentration in the reaction (treatment) suspension.
- the above step (1) is preferably performed at a reaction (treatment) temperature of 60 to 120 ° C.
- the reaction (treatment) time varies depending on the reaction (treatment) temperature, but is preferably 2 to 10 hours.
- the reaction (treatment) is preferably performed by adding an aqueous solution of sodium hydroxide, potassium hydroxide, magnesium hydroxide, or calcium hydroxide to a suspension of titanium dioxide hydrate. After the reaction (treatment), the reaction (treatment) mixture is cooled, neutralized with an inorganic acid such as hydrochloric acid as necessary, and then filtered and washed with water to obtain fine particle titanium dioxide hydrate.
- the compound obtained in step (1) may be treated with a carboxylic acid group-containing compound and an inorganic acid.
- the method of treating the compound obtained in the above step (1) with an inorganic acid in the production of rutile fine particle titanium dioxide is a known method, but in addition to the inorganic acid or in place of the inorganic acid, a carboxylic acid group-containing compound is used. It can be used to adjust the particle size.
- the carboxylic acid group-containing compound is an organic compound having a —COOH group.
- the carboxylic acid group-containing compound is preferably a polycarboxylic acid having 2 or more, more preferably 2 or more and 4 or less carboxylic acid groups. Since the polycarboxylic acid has a coordination ability to a metal atom, it is presumed that agglomeration between fine particles can be suppressed by coordination, whereby rutile type fine particle titanium dioxide can be suitably obtained.
- the carboxylic acid group-containing compound is not particularly limited, and examples thereof include dicarboxylic acids such as succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, propylmalonic acid, and maleic acid; hydroxys such as malic acid, tartaric acid, and citric acid.
- dicarboxylic acids such as succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, propylmalonic acid, and maleic acid
- hydroxys such as malic acid, tartaric acid, and citric acid.
- two or more compounds may be used in combination.
- carboxylic acid group-containing compound may be a neutralized product of an organic compound having a —COOH group (for example, an organic compound having a —COONa group or the like).
- the inorganic acid is not particularly limited, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid and the like.
- the inorganic acid may be added so that the concentration in the reaction (treatment) solution is 0.5 to 2.5 mol / L, more preferably 0.8 to 1.4 mol / L.
- the step (2) is preferably performed by suspending the compound obtained in the step (1) in pure water and heating it with stirring as necessary.
- the carboxylic acid group-containing compound and the inorganic acid may be added simultaneously or sequentially, but it is preferable to add them sequentially.
- the addition may be to add an inorganic acid after the addition of the carboxylic acid group-containing compound, or to add the carboxylic acid group-containing compound after the addition of the inorganic acid.
- a carboxyl group-containing compound is added to the suspension of the compound obtained by the above step (1), heating is started, and the inorganic acid is added when the liquid temperature is 60 ° C. or higher, preferably 90 ° C. or higher. Adding and maintaining the liquid temperature, preferably stirring for 15 minutes to 5 hours, more preferably 2 to 3 hours (Method 1); heating the suspension of the compound obtained by the above step (1)
- an inorganic acid is added when the liquid temperature is 60 ° C. or higher, preferably 90 ° C. or higher, and a carboxylic acid group-containing compound is added 10 to 15 minutes after the inorganic acid addition, and the liquid temperature is preferably maintained.
- a method of stirring for 15 minutes to 5 hours, more preferably 2 to 3 hours (Method 2).
- the carboxylic acid group-containing compound is preferably used in an amount of 0.25 to 1.5 mol% with respect to 100 mol% of TiO 2 , and 0.4 to More preferably, it is used at a ratio of 0.8 mol%.
- the addition amount of the carboxylic acid group-containing compound is less than 0.25 mol%, there is a possibility that particle growth proceeds and particles having the target particle size may not be obtained.
- the amount is more than 5 mol%, rutile conversion of the particles does not proceed and anatase particles may be formed.
- the carboxylic acid group-containing compound is preferably used in an amount of 1.6 to 4.0 mol% with respect to 100 mol% of TiO 2 , and is preferably 2.0 to It is more preferable to use it at a ratio of 2.4 mol%.
- the addition amount of the carboxylic acid group-containing compound is less than 1.6 mol%, there is a possibility that the particle growth proceeds and particles having the target particle size may not be obtained, and the addition amount of the carboxylic acid group-containing compound is 4. If the amount is more than 0 mol%, the rutile conversion of the particles may not proceed and anatase particles may be formed. Even if the amount of the carboxylic acid group-containing compound exceeds 4.0 mol%, the effect will be good. It is economically disadvantageous. Further, if the addition of the carboxylic acid group-containing compound is performed in less than 10 minutes after the addition of the inorganic acid, there is a possibility that the rutileization will not proceed and anatase-type particles may be formed. In some cases, the particle growth proceeds excessively, and particles having a target particle size cannot be obtained.
- step (2) it is preferable to cool after completion of the reaction (treatment) and further neutralize so that the pH becomes 5.0 to 10.0.
- the neutralization can be performed with an alkaline compound such as an aqueous sodium hydroxide solution or aqueous ammonia.
- the target rutile type fine particle titanium dioxide can be separated by filtering and washing with water after neutralization.
- titanium dioxide fine particles As a method for producing titanium dioxide fine particles, a known method described in “Titanium oxide—physical properties and applied technology” (Kagino Kiyono, pp 255-258 (2000) Gihodo Publishing Co., Ltd.) can be used.
- the preferred primary particle diameter of the titanium dioxide fine particles is 4 to 50 nm, more preferably 4 to 35 nm.
- amino acids may be added to each refractive index layer (low refractive index layer, high refractive index layer) for the purpose of further improving the dispersibility of the metal oxide.
- the amino acid as used in the present invention is a compound having an amino group and a carboxyl group in the same molecule, and may be any type of amino acid such as ⁇ -, ⁇ -, ⁇ -, but has an isoelectric point of 6.5 or less. It is preferably an amino acid.
- Some amino acids have optical isomers, but in the present invention, there is no difference in effect due to optical isomers, and any isomer having an isoelectric point of 6.5 or less is used alone or in racemic form. be able to.
- preferred amino acids include glycine, alanine, valine, ⁇ -aminobutyric acid, ⁇ -aminobutyric acid, ⁇ -alanine, serine, ⁇ -amino-n-caproic acid, leucine, norleucine, phenylalanine, threonine, asparagine, asparagine.
- examples include acid, histidine, lysine, glutamine, cysteine, methionine, proline, hydroxyproline, etc.
- the solubility at the isoelectric point is preferably 3 g or more with respect to 100 g of water.
- Glycine, alanine, serine, histidine, lysine, glutamine, cysteine, methionine, proline, hydroxyproline, etc. are preferably used, and from the viewpoint that the metal oxide particles have a gentle hydrogen bond with the binder, serine, It is more preferable to use a mud hydroxyproline.
- the high refractive index layer and the low refractive index layer according to the present invention can contain various additives as necessary.
- ultraviolet absorbers described in JP-A-57-74193, JP-A-57-87988 and JP-A-62-261476, JP-A-57-74192, JP-A-57-87989, and JP-A-60-72785 No. 61-146591, JP-A-1-95091 and JP-A-3-13376, etc., various surfactants such as anti-fading agents, anions, cations or nonions, No. 42993, No. 59-52689, No. 62-280069, No.
- whitening agents such as sulfuric acid, phosphoric acid, acetic acid, PH adjusters such as citric acid, sodium hydroxide, potassium hydroxide and potassium carbonate, antifoaming agents, lubricants such as diethylene glycol, preservatives Antistatic agents, can also contain various known additives such as a matting agent.
- the optical reflective film of the present invention has at least one alternate lamination unit as described above on a film support.
- the film support is not particularly limited as long as it can support the alternately laminated unit.
- polyester films polyethylene terephthalate, polyethylene naphthalate, etc.
- polyvinyl chloride polyvinyl chloride
- cellulose acetate etc.
- polyester film it does not specifically limit as a polyester film (henceforth polyester), It is preferable that it is polyester which has the film formation property which has a dicarboxylic acid component and a diol component as main structural components.
- the main component dicarboxylic acid component includes terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic acid, Examples thereof include cyclohexane dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl thioether dicarboxylic acid, diphenyl ketone dicarboxylic acid, and phenylindane dicarboxylic acid.
- diol component examples include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis ( 4-Hydroxyphenyl) sulfone, bisphenol fluorene hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol and the like.
- polyesters having these as main components from the viewpoints of transparency, mechanical strength, dimensional stability, etc., dicarboxylic acid components such as terephthalic acid, 2,6-naphthalenedicarboxylic acid, diol components such as ethylene glycol and 1 Polyester having 1,4-cyclohexanedimethanol as the main constituent is preferred.
- polyesters mainly composed of polyethylene terephthalate and polyethylene naphthalate, copolymerized polyesters composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and mixtures of two or more of these polyesters are mainly used. Polyester as a constituent component is preferable.
- the thickness of the film support used in the present invention is preferably 10 to 300 ⁇ m, particularly 20 to 150 ⁇ m.
- the film support of the present invention may be a laminate of two sheets. In this case, the type may be the same or different.
- the optical reflective film of the present invention comprises a plurality of constituent layers including a high-refractive index layer and a low-refractive index layer, which are appropriately selected from known coating methods, and are simultaneously coated in water on a support, and then set and dried. Can be manufactured. Due to the simultaneous multi-layering, a certain amount of mixing occurs at the boundary of each layer before each coating solution is set, and the mixed region can be formed. Further, the refractive index can be continuously changed from the high refractive region to the low refractive region in the mixed region.
- Examples of the coating method include a roll coating method, a rod bar coating method, an air knife coating method, a spray coating method, a curtain coating method, or US Pat. Nos. 2,761,419 and 2,761,791.
- a slide bead coating method using an hopper, an extrusion coating method, or the like is preferably used.
- mass ratio (F) of the said water-soluble polymer (B) and the said metal oxide particle (F) in each layer coating liquid is preferably in the range of 0.3 to 10, more preferably 0.5 to 5.
- the preferred concentration of the water-soluble polymer is 0.3 to 3% by mass, more preferably 0.35 to 2% by mass.
- each refractive index layer coating solution is preferably 4 to 9, and more preferably 5 to 8. In such a case, a coating solution having high temporal stability can be obtained.
- the pH can be adjusted by adding a pH adjusting agent or an acid and / or base to the coating solution.
- the set time is adjusted by adjusting the viscosity according to the concentration of metal oxide fine particles and other components.
- the set time is adjusted by adjusting the binder mass ratio and various known types such as gelatin, pectin, agar, carrageenan, gellan gum, etc.
- the gelling agent can be added, adjusted or the like.
- set refers to a process of increasing the viscosity of the coating composition by lowering the temperature by applying cold air or the like to the coating film and reducing the material fluidity in each layer and in each layer.
- the time from setting to setting refers to the time at which the finger is stuck on the surface when cold air is applied to the coating film from the surface and the finger is pressed against the surface.
- a temperature condition when using cold air, 25 ° C. or less is preferable, and 15 ° C. or less is more preferable.
- the time for which the coating film is exposed to the cold air is preferably 10 seconds or more and 120 seconds or less, although it depends on the coating conveyance speed.
- the time from the simultaneous multilayer coating of the high refractive index layer and the low refractive index layer to the sol-gel transition and setting is within 5 minutes, preferably within 2 minutes. Moreover, it is preferable to take time of 45 seconds or more.
- the position where the refractive index becomes the maximum refractive index ⁇ n / 3 is in the range of 0.9 / 3 to 1.1 / 3 from the maximum refractive index point with respect to the width (layer thickness) from the maximum refractive index to the minimum refractive index.
- the minimum refractive index the position where the minimum refractive index + ⁇ n / 3 is 0.9 / from the minimum refractive index point with respect to the width (layer thickness) from the maximum refractive index to the minimum refractive index. This is because the laminated film has a refractive index profile so as to be in the range of 3 to 1.1 / 3. If the time to set is too short, mixing of preferable components may not occur. Further, if the set time is lengthened, the mixing of the layers proceeds and the required refractive index difference may not be obtained.
- the viscosity at the time of applying each coating solution when performing simultaneous multilayer coating is preferably in the range of 5 to 100 mPa ⁇ s, more preferably in the range of 10 to 50 mPa ⁇ s. .
- the range of 5 to 1200 mPa ⁇ s is preferable, and the range of 25 to 500 mPa ⁇ s is more preferable.
- the viscosity of the coating solution at 15 ° C. is preferably 100 mPa ⁇ s or more, more preferably 100 to 30,000 mPa ⁇ s, still more preferably 3,000 to 30,000 mPa ⁇ s, and most preferably 10 , 30,000 to 30,000 mPa ⁇ s.
- the coating liquid is heated to 30 ° C. or higher and coated, and then the temperature of the formed coating film is once cooled to 1 to 15 ° C. and dried at 10 ° C. or higher. More preferably, the drying conditions are a wet bulb temperature of 5 to 50 ° C. and a film surface temperature of 10 to 50 ° C. Moreover, as a cooling method immediately after application
- optical reflection film When the optical reflective film of the present invention is used as a heat shielding film, a multilayer film is formed by laminating films having different refractive indexes on a polymer film by simultaneous multilayer coating, and the visible light region shown in JIS R3106-1998 is formed. It is preferable to design the optical film thickness and unit so that the transmittance is 50% or more and the region having a wavelength of 900 nm to 1400 nm has a region exceeding the reflectance of 40%.
- the infrared region of the incident spectrum of direct sunlight is related to the increase in indoor temperature, and by blocking this, the increase in indoor temperature can be suppressed.
- the cumulative energy ratio from the shortest infrared wavelength (760 nm) to the longest wavelength 3200 nm based on the weight coefficient described in Japanese Industrial Standard JIS R3106-1998 the infrared from the wavelength 760 nm to the longest wavelength 3200 nm
- the cumulative energy from 760 nm to each wavelength when the total energy of the entire region is 100
- the total energy from 760 nm to 1300 nm occupies about 75% of the entire infrared region. Therefore, shielding the wavelength region up to 1300 nm has the most efficient energy saving effect by heat ray shielding.
- the reflectance in the near-infrared region (760 to 1300 nm) is about 80% or more at the maximum peak value
- a decrease in the sensory temperature is obtained by sensory evaluation.
- the temperature at the window facing southeast in the morning of August showed a clear difference when the reflectance in the near infrared region was shielded to about 80% at the maximum peak value.
- the reflectance does not reach 60% when the number of stacked layers is 4. However, when there are 6 layers, a reflectance of about 80% can be obtained.
- the wavelength of the reflected light can be controlled by changing the optical film thickness in this way, in the unit in which the high refractive index layer and the low refractive index layer are alternately laminated, the high refractive index layer and the low refractive index layer Heat-shielding film that reflects not only the near-infrared but also part of the infrared or visible light region by expanding the range of reflected light by configuring multiple units with different optical film thickness. It can be.
- the optical reflective film has two or more units having different optical film thicknesses, in which high refractive index layers and low refractive index layers are alternately laminated.
- the unit includes at least one unit that mainly reflects visible light and at least one unit that mainly reflects near-infrared light.
- mainly reflecting visible light means giving a maximum reflection wavelength in a wavelength band of 400 to 700 nm.
- mainly reflecting near-infrared light means giving a maximum reflection wavelength at a wavelength band of 780 to 1300 nm.
- optical reflective film of the present invention can be applied to a wide range of fields.
- film for window pasting such as heat ray reflecting film that gives heat ray reflection effect, film for agricultural greenhouses, etc. Etc., mainly for the purpose of improving the weather resistance.
- the optical external reflection film according to the present invention can be suitably used for a member that is bonded to a substrate such as glass or a glass substitute resin directly or via an adhesive (adhesive layer).
- the adhesive should be installed so that the near-infrared reflective film is on the sunlight (heat ray) incident surface side when pasted on a window glass or the like. Further, when the near-infrared reflective film is sandwiched between the window glass and the base material, it can be sealed from ambient gas such as moisture, which is preferable for durability. Even if the near-infrared reflective film of the present invention is installed outdoors or outside the vehicle (for external application), it is preferable because of environmental durability.
- an adhesive (adhesive layer) applicable to the present invention, an adhesive mainly composed of a photocurable or thermosetting resin can be used.
- the adhesive preferably has durability against ultraviolet rays, and is preferably an acrylic adhesive or a silicone adhesive. Furthermore, an acrylic adhesive is preferable from the viewpoint of adhesive properties and cost. In particular, since the peel strength can be easily controlled, a solvent system is preferable among the solvent system and the emulsion system in the acrylic adhesive. When a solution polymerization polymer is used as the acrylic solvent-based pressure-sensitive adhesive, known monomers can be used as the monomer.
- polyvinyl butyral resin or ethylene-vinyl acetate copolymer resin used as an intermediate layer of laminated glass may be used as an adhesive (adhesive layer).
- plastic polyvinyl butyral manufactured by Sekisui Chemical Co., Ltd., Mitsubishi Monsanto Co., Ltd.
- ethylene-vinyl acetate copolymer manufactured by DuPont Co., Ltd., Takeda Pharmaceutical Co., Ltd., duramin]
- a metal oxide can be used as a light absorbing material that absorbs light other than the reflection band.
- metal oxides include tin oxide, indium oxide, zinc oxide, cadmium oxide, antimony doped tin oxide (ATO), fluorine doped tin oxide (FTO), tin doped indium oxide (ITO) and aluminum doped zinc oxide (AZO).
- ATO and ITO are particularly preferable.
- Example 1 (Sample 1: Comparative example)
- the resin A polyethylene terephthalate (inherent viscosity 0.65, melting point 255 ° C., Toray F20S) was used.
- the resin B a polyethylene terephthalate copolymer (copolymerization of intrinsic viscosity 0.72, cyclohexanedicarboxylic acid component 29 mol%, spiroglycol component 20 mol%), PBT (Toraycon, Toray), PET (Toray), and ADK STAB A resin obtained by mixing (ASKA manufactured by ADEKA) at a mass ratio of 69.9 / 20/10 / 0.1 and melt-kneading and solidifying the resin was used.
- a laminated body of layers is produced, and then stretched 3.3 times in the transverse direction at a temperature of 110 ° C., further subjected to a relaxation treatment of 5% in the same temperature and in the same direction, cooled to room temperature, and a total film thickness of 40 ⁇ m.
- the optical reflection film of Comparative Example 1 was prepared.
- Example 2 Comparative example
- the following composition was dispersed with a ball mill for 4 hours to prepare a dispersion of titanium oxide having a dispersed particle diameter of D50 and 20 nm.
- Isopropanol 100 parts by mass Pyridine 3 parts by mass Ethyl silicate (manufactured by Colcoat, active ingredient 30% by mass) 5 parts by mass Rutile-type titanium oxide particles (volume average particle size 15 nm) 10 parts by mass UV dispersion binder (Shin-Etsu) X-12-2400 manufactured by Kagaku Kogyo Co., Ltd., 1.5 parts by mass of active ingredient 30% by mass) and 0.15 part by mass of catalyst (DX-2400 manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed and dispersed for 1 hour in a ball mill. Gave a titanium oxide-containing high refractive index layer coating solution 1 having a D50 of 16 nm.
- the coating solution is applied onto a polyethylene terephthalate film having a thickness of 50 ⁇ m using a spin coat under the condition that the dry film thickness is 75 nm, dried at 100 ° C., irradiated with ultraviolet rays, cured, and then applied onto the substrate.
- a titanium oxide-containing high refractive index layer 1 was formed.
- the low-refractive index layer coating solution 1 is the above-described high-refractive index layer coating solution except that the rutile titanium oxide particles are changed to silica organosols (average primary particle size: 10 to 20 nm, manufactured by Nissan Chemical Co., Ltd., XBA-ST).
- silica organosols average primary particle size: 10 to 20 nm, manufactured by Nissan Chemical Co., Ltd., XBA-ST.
- the obtained silica-containing low refractive index layer coating solution 1 was applied by a wet coating method using spin coating on the titanium oxide-containing high refractive index layer 1 under the condition that the dry film thickness was 78 nm.
- the silica-containing low refractive index layer 1 was formed by drying and thermosetting in the same manner as the titanium oxide-containing high refractive index layer 2.
- the same operation was repeated to produce an optical reflective film of Comparative Example 2 having 12 units composed of titanium oxide-containing high refractive index layer 1 / silica-containing low refractive index layer 1 and a total of 24 layers.
- Example 3 the present invention
- the following additives 1) to 5) were added and mixed in this order to prepare a high refractive index layer coating solution 2.
- This preparation method is referred to as preparation pattern A.
- the following additives 1) to 5) were added and mixed in this order to prepare a low refractive index layer coating solution 2.
- colloidal silica average particle size 6 nm, manufactured by Nissan Chemical Co., Ltd., Snowtex AK
- low molecular weight gelatin was added and stirred for 10 minutes.
- high molecular weight gelatin and 4) pure water were added and stirred for 10 minutes, and 5) a low refractive index layer coating solution 2 was prepared using Preparation Pattern A in which a surfactant was added.
- GelL1 is a low molecular weight gelatin having a weight average molecular weight of 20,000 hydrolyzed by alkali treatment
- GelH1 is an acid-treated gelatin (high molecular weight gelatin) having a weight average molecular weight of 130,000.
- the coating solution was stagnated for 56 hours while keeping the prepared high refractive index layer coating solution 2 and low refractive index layer coating solution 2 at 45 ° C., respectively. Then, using a slide hopper, the high refractive index layer coating solution 2 and the low refractive index layer coating solution 2 are alternately arranged on a 50 ⁇ m thick polyethylene terephthalate film so that the dry film thickness is 78 nm. After coating, and then setting by blowing cold air for 1 minute under the condition that the film surface is 15 ° C. or less, it is dried by blowing hot air of 80 ° C., and 12 layers of high refractive index layer and low refractive index layer respectively. An optical reflection film composed of (total 24 layers) was produced.
- the film surface pH was adjusted to 7.2. Acetic acid and aqueous ammonia were used to adjust the pH.
- the viscosities at the time of application of the high refractive index layer coating solution 2 and the low refractive index layer coating solution 2 were 12 mPa ⁇ s and 18 mPa ⁇ s, respectively, and the viscosities at 15 ° C. were 2500 mPa ⁇ s and 20000 mPa ⁇ s, respectively. .
- Example 4 the present invention
- the high refractive index layer coating solution 2 and the low refractive index layer coating solution 2 excluding gelatin and the same amount of polyvinyl alcohol (hereinafter also referred to as PVA) as the gelatin mass (low molecular weight gelatin + high molecular weight gelatin).
- PVA polyvinyl alcohol
- the film surface pH was adjusted to 5.0 using boric acid / borax, and the optical reflective film of Sample 4 was similarly prepared.
- the viscosities at the time of application of the high refractive index layer coating solution and the low refractive index layer coating solution were 13 mPa ⁇ s and 20 mPa ⁇ s, respectively, and the viscosities at 15 ° C. were 3500 mPa ⁇ s and 19000 mPa ⁇ s, respectively.
- Example 5 the present invention
- tamarind seed gum TG-500, manufactured by MRC Polysaccharide Co., Ltd.
- MRC Polysaccharide Co., Ltd. MRC Polysaccharide Co., Ltd.
- Samples 6 to 14 were prepared in the same manner as Sample 4 except that the film thickness and layer structure of Sample 4 are shown in Table 1.
- the high refractive index layer H1 and the low refractive index layer L1 formed in each sample respectively, have an (optical) film thickness (nm). It was produced instead.
- Table 1 also shows the layer structure of the sample.
- (H1 / L1) 200 is (H1 / L1) (H1 / L1)... (H1 / L1) / base material, and H1 / L1 is repeatedly laminated 200 times. It means that.
- Samples 9 to 14 are formed to include a layer having a dry film thickness of 600 nm or more and 1200 nm or less.
- FIG. 1 shows a reflection spectrum of Sample 9 as a representative example. It can be seen that it has reflection characteristics in the visible light region. Similarly, the other samples also detected a reflection band in the visible light region.
- H1 / L1, H2 / L2, and H3 / L3 units function as units that mainly reflect visible light.
- the maximum refractive index ⁇ n / 3 means the position where the refractive index is the maximum refractive index ⁇ n / 3 with respect to the maximum refractive index, the width from the maximum refractive index to the minimum refractive index (layer It is expressed as a ratio of the position from the maximum refractive index point to (thickness).
- the minimum refractive index + ⁇ n / 3 is the minimum relative to the width (layer thickness) from the maximum refractive index to the minimum refractive index. This is expressed as a ratio from the refractive index point.
- ⁇ S indicates refractive index change continuity, and when the thickness (layer thickness) T from the maximum refractive index to the minimum refractive index in the film thickness direction profile of the refractive index described above is divided into T / 4 units, This is the minimum value of the refractive index difference in an arbitrary section.
- the configuration satisfying the present invention has a continuous mixed region of Ti and Si elements between the layers by XPS analysis, and the appearance is colored, has a reflection characteristic in the visible light region, and has excellent reflectance unevenness.
- Ti and Si each have a stepped distribution, and no mixed region was detected.
- the average visible light reflectance was reduced by 62% from Tables 1 and 2, but a mixed region was detected, and the unevenness in reflectance had the same tendency. It turns out that there is.
- Sample 15 was prepared as follows and evaluated in the same manner.
- Example 15 Comparative example
- the high refractive index layer coating solution 1 and the low refractive index coating solution of Sample 2 were mixed at a volume ratio of 1: 1 to prepare a medium refractive index coating solution 1.
- Sample 15 having a medium refractive index layer of 23 layers and a total of 47 layers was prepared in the same manner as Sample 2, except that the intermediate refractive index layer was applied at a dry film thickness of 39 nm between the high refractive index layer and the low refractive index layer. .
- the refractive index of the middle refractive index layer (the created middle refractive index layer is M1) is 1.67, the Ti and Si distribution by XPS analysis is stepped, the average visible light reflectance is 28%, the reflection The unevenness evaluation was 5. It can be seen that the optical characteristics of the continuous ahead index distribution of the present invention are superior to the refractive index distribution that changes stepwise.
- H4 / L4 functions as a unit that mainly reflects near infrared light.
- the mixture layer comprising the ATO (antimony-doped tin oxide) / poly (vinyl alcohol) 4/6 by volume
- a sample 17 (visible light absorption layer) having a thickness of 8 ⁇ m was formed between the base material and the (H4 / L4) 24 layer.
- the solar heat gain rate of sample 17 was 51%, which was equivalent to sample 16.
- the sample 16 and the sample 17 were attached to the window glass through the adhesive layer so as to have a configuration of window glass / adhesive layer / coating film / base material, and a practical test was performed by applying sunlight. Although the sample 17 cracked the window glass in about two months, no damage to the window glass of the sample 16 was observed, and the visible light portion of the present invention also provided a reflective film that did not absorb heat. The configuration was found to be excellent against thermal cracking.
- Example 3 In the sample 9 of Example 1, an optical reflective film was produced in the same manner except that the layer configuration was changed to ((H1 / L1) 4 (H1 / L2) (H1 / L1) 4 (H1 / L2)) 10 . . The average visible light reflectance was 99.5%, and an optical reflective film having a metallic luster appearance was obtained.
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Abstract
Description
前記高屈折率層と前記低屈折率層とを同時重層塗布することにより、前記高屈折率層と前記低屈折率層との間に、前記高屈折率層と前記低屈折率層との混合領域を設け、可視光波長領域の少なくとも1つの領域に平均反射率が30%以上100%以下である領域を有する光学反射フィルム。
本発明においては、少なくとも隣接した2層(高屈折率層及び低屈折率層)の屈折率差が、0.2以上が好ましく、より好ましくは0.3以上である。また、上限には特に制限はないが通常1.4以下である。本発明の交互積層ユニットは、高屈折率層及び低屈折率層の境界が混合領域となっているが、高屈折率層および低屈折率層を同時重層塗布して作製するので、便宜的に2層ということで説明している。ここで高屈折率層と低屈折率層との屈折率差は、実際には高屈折領域の最大屈折率点と低屈折率領域の最低屈折率点との差である。
高屈折率層および低屈折率層はそれぞれ、高屈折率材料および低屈折率材料ならびに必要に応じてバインダーとしての水溶性高分子、硬化剤、アミノ酸、後述する各種の添加剤を含んで構成される。なお、高屈折率材料および低屈折率材料としては金属酸化物粒子、金属微粒子、高屈折率ポリマー、低屈折率ポリマー等が挙げられる。また、場合によっては、水溶性高分子を高屈折率材料または低屈折率材料として用いることができる。
本発明に係る屈折率層(低屈折率層、高屈折率層)においては、各層塗布液を調製して同時重層により積層を行うため、バインダーとしてポリビニルアルコール等の合成高分子、ゼラチン、増粘多糖類等からなる群から選択される少なくとも1種の水溶性高分子を用いることができる。特に、ゼラチンを用いることが好ましい。
本発明に適用可能な合成高分子としては、例えば、ポリビニルアルコール類、ポリビニルピロリドン類、ポリアクリル酸、アクリル酸-アクリルニトリル共重合体、アクリル酸カリウム-アクリルニトリル共重合体、酢酸ビニル-アクリル酸エステル共重合体、若しくはアクリル酸-アクリル酸エステル共重合体などのアクリル系樹脂、スチレン-アクリル酸共重合体、スチレン-メタクリル酸共重合体、スチレン-メタクリル酸-アクリル酸エステル共重合体、スチレン-α-メチルスチレン-アクリル酸共重合体、若しくはスチレン-α-メチルスチレン-アクリル酸-アクリル酸エステル共重合体などのスチレンアクリル酸樹脂、スチレン-スチレンスルホン酸ナトリウム共重合体、スチレン-2-ヒドロキシエチルアクリレート共重合体、スチレン-2-ヒドロキシエチルアクリレート-スチレンスルホン酸カリウム共重合体、スチレン-マレイン酸共重合体、スチレン-無水マレイン酸共重合体、ビニルナフタレン-アクリル酸共重合体、ビニルナフタレン-マレイン酸共重合体、酢酸ビニル-マレイン酸エステル共重合体、酢酸ビニル-クロトン酸共重合体、酢酸ビニル-アクリル酸共重合体などの酢酸ビニル系共重合体及びそれらの塩が挙げられる。これらの中で、特に好ましい例としては、ポリビニルアルコール、ポリビニルピロリドン類及びそれを含有する共重合体が挙げられる。
本発明に適用可能なゼラチン(水膨潤性高分子)としては、石灰処理ゼラチンのほか、酸処理ゼラチンを使用してもよく、さらにゼラチンの加水分解物、ゼラチンの酵素分解物を用いることもできる。これらの水膨潤性高分子は、単独で用いても複数の種類を用いても良い。
本発明で用いることのできる増粘多糖類としては、例えば、一般に知られている天然単純多糖類、天然複合多糖類、合成単純多糖類及び合成複合多糖類に挙げることができ、これら多糖類の詳細については、「生化学事典(第2版),東京化学同人出版」、「食品工業」第31巻(1988)21頁等を参照することができる。
本発明においては、バインダーである水溶性高分子を硬化させるため、硬化剤を使用することが好ましい。すなわち、本発明に係る屈折率層(低屈折率層、高屈折率層)は硬化剤を含むことが好ましい。
本発明において金属酸化物粒子は、上記低屈折率層または高屈折率層を構成するときに用いられる。上記目的で使用される金属酸化物としては、例えば、二酸化チタン、酸化ジルコニウム、酸化亜鉛、合成非晶質シリカ、コロイダルシリカ、アルミナ、コロイダルアルミナ、チタン酸鉛、鉛丹、黄鉛、亜鉛黄、酸化クロム、酸化第二鉄、鉄黒、酸化銅、酸化マグネシウム、水酸化マグネシウム、チタン酸ストロンチウム、酸化イットリウム、酸化ニオブ、酸化ユーロピウム、酸化ランタン、ジルコン、酸化スズ、等を挙げることができる。中でも、金属酸化物粒子として、二酸化チタン、二酸化ケイ素、及びアルミナから選ばれた固体微粒子を用いることが好ましい。また、アルミナまたはアルミナ水和物は、結晶性であっても非晶質であってもよく、また不定形粒子、球状粒子、針状粒子など任意の形状のものを使用することができる。各屈折率層における金属酸化物粒子はそれぞれ1種を単独で使用してもよいし、2種以上を組み合わせて使用してもよい。
本発明で用いることのできる二酸化ケイ素(シリカ)としては、通常の湿式法で合成されたシリカ、コロイダルシリカ或いは気相法で合成されたシリカ等が好ましく用いられるが、本発明において特に好ましく用いられる微粒子シリカとしては、コロイダルシリカまたは気相法で合成された微粒子シリカが好ましく、中でも気相法により合成された微粒子シリカは、カチオン性ポリマーに添加したときに、粗大凝集体が形成されにくいので好ましい。
本発明で用いることのできる二酸化ケイ素(シリカ)としては、通常の湿式法で合成されたシリカ、コロイダルシリカ或いは気相法で合成されたシリカ(気相法微粒子シリカ)等が好ましく用いられる。本発明において特に好ましく用いられる微粒子シリカとしては、コロイダルシリカまたは気相法で合成された微粒子シリカ(気相法微粒子シリカ)が好ましい。
二酸化チタンゾルの製造方法
ルチル型微粒子二酸化チタンの製造方法における第1の工程は、二酸化チタン水和物をアルカリ金属の水酸化物及びアルカリ土類金属の水酸化物からなる群から選択される少なくとも1種の塩基性化合物で処理する工程(工程1)である。
本発明においては、各屈折率層(低屈折率層、高屈折率層)において、更に、金属酸化物の分散性を向上させる目的で、アミノ酸を添加してもよい。
本発明に係る高屈折率層と低屈折率層には、必要に応じて各種の添加剤を含有させることができる。
本発明の光学反射フィルムは少なくとも一つの上述した交互積層ユニットをフィルム支持体上に有する。フィルム支持体は交互積層ユニットを支持できる限り特に制限されない。
本発明の光学反射フィルムは、高屈折率層、低屈折率層を含む複数の構成層を、公知の塗布方式から適宜選択して、支持体上に水系で同時重層塗布した後、セット、乾燥して製造することができる。同時重層により、各塗布液がセットするまでの間に各層境界において混合がある程度生じ、前記混合領域が形成することができる。また、当該混合領域において高屈折領域から低屈折領域へと屈折率を連続的に変化させることができる。
本発明の光学反射フィルムを遮熱フィルムに用いる場合は、高分子フィルムに互いに屈折率が異なる膜を同時重層塗布により積層させた多層膜を形成し、JIS R3106-1998で示される可視光領域の透過率が50%以上で、かつ、波長900nm~1400nmの領域に反射率40%を超える領域を有する様に光学膜厚とユニットを設計することが好ましい。
本発明の光学反射フィルムは、幅広い分野に応用することができる。例えば、建物の屋外の窓や自動車窓等長期間太陽光に晒らされる設備(基体)に貼り合せ、熱線反射効果を付与する熱線反射フィルム等の窓貼用フィルム、農業用ビニールハウス用フィルム等として、主として耐候性を高める目的で用いられる。特に、本発明に係る光学外反射フィルムが直接もしくは接着剤(接着層)を介してガラスもしくはガラス代替樹脂等の基体に貼合されている部材には好適に使用されうる。
(試料1:比較例)
樹脂Aとしてポリエチレンテレフタレート(固有粘度0.65、融点255℃、東レ製F20S)を使用した。また、樹脂Bとしてポリエチレンテレフタレート共重合体(固有粘度0.72、シクロヘキサンジカルボン酸成分29mol%、スピログリコール成分20mol%の共重合)、PBT(トレコン、東レ製)、PET(東レ製)、およびアデカスタブ(ADEKA製AS36)を69.9/20/10/0.1の質量比率で混合して溶融混練して固化させた樹脂を用いた。樹脂A、樹脂Bをそれぞれ押出機にて270℃の溶融状態とし、ギアポンプにて樹脂A/樹脂B=1.2/1になる様に量を測りながらスリット間を押し出し、総積層数が400層の積層体を作製し、その後、110℃の温度で横方向に3.3倍延伸し、さらに同温度、同方向で5%の弛緩処理を施し、室温まで冷却して、全膜厚40μmの比較例1の光学反射フィルムを作製した。
下記組成物をボールミルにて4時間分散させ、分散粒子径がD50で20nmの酸化チタンの分散液を作製した。
ピリジン 3質量部
エチルシリケート(コルコート製、有効成分30質量%) 5質量部
ルチル型酸化チタン粒子(体積平均粒子径15nm) 10質量部
得られた分散液に、紫外線硬化バインダー(信越化学工業製X-12-2400、有効成分30質量%)1.5質量部、触媒(信越化学工業製DX-2400)0.15質量部配合し、ボールミルにて1時間分散させ、分散粒子径がD50で16nmの酸化チタン含有高屈折率層塗布液1を得た。該塗布液を、厚さ50μmのポリエチレンテレフタレートフィルム上に、乾燥膜厚が75nmとなる条件で、スピンコートを用いて塗布し、100℃乾燥後、紫外線を照射し、硬化させ、基材上に酸化チタン含有高屈折率層1を形成した。
下記の添加物1)~5)をこの順序で添加、混合して、高屈折率層塗布液2を調製した。はじめに1)酸化チタン粒子ゾルを攪拌しながら50℃まで昇温した後、2)低分子量ゼラチンを添加して30分間攪拌して、酸化チタン粒子表面を低分子量ゼラチンで被覆した。次いで、3)高分子量ゼラチンおよび4)純水を添加し、90分間攪拌した後、5)界面活性剤を添加して、高屈折率層塗布液2を調製した。この調製方法を、調製パターンAと称す。
2)5.0質量%低分子量ゼラチン(GelL1)水溶液 125g
3)5.0質量%高分子量ゼラチン(GelH1)水溶液 100g
4)純水 150g
5)5.0質量%界面活性剤水溶液(コータミン24P、4級アンモニウム塩系カチオン性界面活性剤、花王社製) 0.45g
GelL1はアルカリ処理により加水分解を施した重量平均分子量が2万の低分子量ゼラチン(新田ゼラチン株式会社製HBC-P20)であり、GelH1は重量平均分子量が13万の酸処理ゼラチン(高分子量ゼラチン)(株式会社ニッピ製AP-270)である。
2)5.0質量%低分子量ゼラチン(GelL1)水溶液 180g
3)5.0質量%高分子量ゼラチン(GelH1)水溶液 100g
4)純水 240g
5)5.0質量%界面活性剤水溶液(コータミン24P、4級アンモニウム塩系カチオン性界面活性剤、花王社製) 0.64g
GelL1はアルカリ処理により加水分解を施した重量平均分子量が2万の低分子量ゼラチンであり、GelH1は重量平均分子量が13万の酸処理ゼラチン(高分子量ゼラチン)である。
上記試料3の作製において、高屈折率層塗布液2、低屈折率層塗布液2ともゼラチンを除き、ゼラチン質量(低分子量ゼラチン+高分子量ゼラチン)と同量のポリビニルアルコール(以下、PVAとも称する)(ポリビニルアルコール235、クラレ社製;重量平均分子量:14万)に変更し、ホウ酸/硼砂を用いて膜面pHを5.0に調整した以外は同様にして、試料4の光学反射フィルムを作製した。なお、高屈折率層塗布液、低屈折率層塗布液の塗布時の粘度はそれぞれ13mPa・s、20mPa・sであり、15℃における粘度はそれぞれ3500mPa・s、19000mPa・sであった。
上記試料4の高屈折率層塗布液2に、タマリンドシードガム(MRCポリサッカライド株式会社製 TG-500)を金属酸化物粒子体積に対して15%(質量に対して4%)添加した以外同様にして、試料5の光学反射フィルムを作製した。尚、膜面pHはホウ酸/硼砂を用いてPH5.5に調整した。また、なお、高屈折率層塗布液の塗布時の粘度は21mPa・sであり、15℃における粘度は5500mPa・sであった。
試料4の膜厚と層構成を表1に示す以外は全く試料4と同様にして、試料6~試料14を作製した。
(各層の屈折率の測定)
基材(石英ガラス)上に屈折率を測定する対象層(高屈折率層、低屈折率層)をそれぞれ単層で塗設したサンプルを作成し、下記の方法に従って、各高屈折率層及び低屈折率層の屈折率を求めた。分光光度計として、U-4000型(日立製作所社製)を用いて、各サンプルの測定側の裏面を粗面化処理したのち、黒色のスプレーで光吸収処理を行って裏面での光の反射を防止して、5度正反射の条件にて可視光領域(400nm~700nm)の反射スペクトルの測定を行い、該反射スペクトルのカーブフィッテングにより屈折率を求めた。
層間の混合領域は、積層膜を切断して切断面をXPS表面分析装置で高屈折率材料(TiO2)および低屈折率材料(SiO2)の金属元素(TiおよびSi)の存在量を測定しデプスプロファイルを求めた。
分光光度計(日立製作所社製 U-4000型)に5°反射ユニットを付け、付属の鏡でベースライン補正したのち、光学反射層の面側を測定面にして、400~700nmの領域で、2nm間隔で151点の反射率を測定し、得られた反射率を全て足し合わせた値を、151で除することで平均可視光反射率とした。各塗布試料を20cm×20cm用意し、これを2cm間隔の計100個のグリッドに分割し、各グリッド内の前記平均可視光反射率を測定により求めて、その最大値から最小値を減じた値を、反射率ムラの評価尺度にした。
2:最大値-最小値が1%以上4%未満
3:最大値-最小値が4%以上8%未満
4:最大値-最小値が8%以上12%未満
5:最大値-最小値が12%以上
図1に代表例として、試料9の反射スペクトルを示す。可視光域に反射特性を有していることが判る。その他の試料も同様に、可視光域に反射バンドを検出した。
試料2の高屈折率層塗布液1と低屈折率塗布液とを1:1の体積比で混合し、中屈折率塗布液1を作製した。高屈折率層と低屈折率層との間に中屈折率層を乾燥膜厚39nmで塗布した以外は試料2と同様にして、中屈折率層23層、トータル47層の試料15を作製した。中屈折率層(作成した中屈折率層をM1とする)の屈折率は1.67、XPS分析によるTi,Si分布は、階段状になっており、平均可視光反射率は28%、反射ムラ評価は5であった。階段状変化する屈折率分布より、本発明の連続的な屈折率分布の方が、光学特性が優れているのが判る。
実施例1の試料8において、新たにH4=130nm、L4=170nmを追加し、層構成を変えた以外は試料8と同様にして、(H1/L1)6(H2/L2)3(H3/L3)3(H4/L4)24の構成を有する光学反射フィルム(試料16)を作製した。反射率を測定したところ、可視光域の平均可視光反射率が31%、さらに近赤外領域にも反射バンドを検出し、本光学反射フィルムが、可視光~近赤外域の広い波長範囲に反射特性を有することが判った。JIS R3106を用いて求めた日射熱取得率は51%であり、反射バンドのみで遮蔽性の高い遮熱フィルムが得られた。
実施例1の試料9において、層構成を((H1/L1)4(H1/L2)(H1/L1)4(H1/L2))10に変更した以外は同様にして光学反射フィルムを作製した。平均可視光反射率は99.5%であり、金属光沢の外観を有する光学反射フィルムが得られた。
Claims (7)
- 水溶性高分子と金属酸化物粒子とを、高屈折率層および低屈折率層の少なくとも1層に含有し、前記高屈折率層と前記低屈折率層とを交互に積層させたユニットをフィルム支持体上に少なくとも一つ有する光学反射フィルムにおいて、
前記高屈折率層と前記低屈折率層とを同時重層塗布することにより、前記高屈折率層と前記低屈折率層との間に、前記高屈折率層と前記低屈折率層との混合領域を設け、可視光波長領域の少なくとも1つの領域に平均反射率が30%以上100%以下である領域を有する光学反射フィルム。 - 前記高屈折率層および前記低屈折率層の少なくとも一方が、乾燥膜厚600nm以上、1200nm以下の層を含む、請求項1に記載の光学反射フィルム。
- 前記光学反射フィルムが、高屈折率層と低屈折率層とを交互に積層させた、光学膜厚の異なる2種以上のユニットを有する、請求項1または2に記載の光学反射フィルム。
- 2種以上の前記ユニットが、可視光を主反射するユニットを1種以上、および、近赤外光を主反射するユニットを1種以上含む、請求項3に記載の光学反射フィルム。
- 前記水溶性高分子が、ゼラチン、ポリビニルアルコール、および増粘多糖類からなる群から選ばれる少なくとも1種である、請求項1~4のいずれか1項に記載の光学反射フィルム。
- 前記金属酸化物粒子がルチル型二酸化チタンである、請求項1~5のいずれか1項に記載の光学反射フィルム。
- 前記混合領域における屈折率の変化が連続的である、請求項1~6のいずれか1項に記載の光学反射フィルム。
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CN201280031146.1A CN103635838B (zh) | 2011-06-24 | 2012-06-07 | 光学反射膜 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103786380A (zh) * | 2014-01-10 | 2014-05-14 | 福建农林大学 | 一种汽车魔芋贴膜及其制备方法 |
JP2016224334A (ja) * | 2015-06-02 | 2016-12-28 | コニカミノルタ株式会社 | 光学フィルムの製造方法 |
WO2023189317A1 (ja) * | 2022-03-28 | 2023-10-05 | 東レ株式会社 | 積層フィルム |
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EP2725395A1 (en) | 2014-04-30 |
EP2725395A4 (en) | 2014-12-10 |
US20140192413A1 (en) | 2014-07-10 |
CN103635838B (zh) | 2016-08-10 |
CN103635838A (zh) | 2014-03-12 |
JP6070550B2 (ja) | 2017-02-01 |
JPWO2012176627A1 (ja) | 2015-02-23 |
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