JP2017186488A - Fluorescent pigment and white laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorescent pigment dispersion capable of changing color of white derived from a white pigment and enhancing whiteness and high in heat resistance and a laminate containing a phosphor layer consisting of the fluorescent pigment dispersion.SOLUTION: There is provided a fluorescent pigment dispersion containing a blue color inorganic phosphor having main absorption region in a wavelength range of 400 nm or less and a luminescence peak in a wavelength region in a wavelength range of 430 nm to 480 nm respectively and emitting blue color fluorescence and a silicone resin. There is provided a white laminate containing a white layer containing an inorganic white pigment and a phosphor layer formed by laminating on a single sided surface of the white layer and using the fluorescent pigment dispersion.SELECTED DRAWING: None

Description

  The present invention relates to a fluorescent pigment dispersion and a white laminate including a phosphor layer formed from the fluorescent pigment dispersion.

  For touch panel displays such as smartphones, tablet terminals, and electronic notebooks, for example, a capacitive display in which a liquid crystal display, a glass plate on which a touch sensor is formed, and a glass plate for a cover are sequentially stacked is used. It has been. The touch sensor is formed, for example, by printing a circuit pattern on the surface of a glass plate using a transparent conductive paint and baking it at a high temperature exceeding 200 ° C. And in order to protect the liquid crystal display and touch sensor and conceal various sensors and speakers arranged in the vicinity from the outside, it is called a bezel layer so as to surround the touch sensor along the periphery of the touch sensor. A black or white strip layer is provided. The white bezel layer is formed using, for example, a pigment dispersion containing an inorganic oxide-based white pigment such as titanium oxide.

  Compared to the conventional touch panel system as described above, touch sensors are directly formed on the inner surface of the cover glass plate without using a touch sensor forming glass plate for the purpose of further thinning and weight reduction of smartphones and the like. One Glass Solution (hereinafter sometimes referred to as “OGS”) has been proposed. In OGS, it is required to simultaneously form the touch sensor and the bezel layer on the inner surface of the glass plate for the cover in order to save the process, and the material constituting the bezel layer needs to have high heat resistance. .

  Inorganic oxide-based white pigments such as titanium oxide (hereinafter, sometimes simply referred to as “inorganic-based white pigments” unless otherwise specified) have high heat resistance and exceed 200 ° C. when forming a circuit for a touch sensor. Even when exposed to such a high temperature, there is almost no change in whiteness before and after heating, and it can also be used for OGS. However, as the demand for designability and freedom of product design increases based on the diversification of modern tastes, not only the white color of inorganic white pigments but also the whiteness level is higher. White variations such as high white, reddish white, and bluish white are required.

  For example, if the thickness of the white layer is increased, the reflectance of light increases and the L * value increases, but the yellowness and the like also increase. In addition, increasing the thickness of the white layer is contrary to the trend toward thinner and lighter smartphones in the industrial field such as smartphones.

  Patent Document 1 includes a white layer made of an inorganic white pigment, and a light shielding layer made of a silver-white metal such as Al, Ti, Mo, Ag, Cr, or an alloy thereof laminated on the white layer. A white bezel layer is proposed. However, it is necessary to use a vapor deposition method, an atomic layer deposition layer, a sol-gel method, or the like for forming the light shielding layer, and cannot be said to be a technique suitable for OGS whose purpose is to save labor of the process.

  Patent Document 2 discloses a white bezel in which two white layers made of an inorganic white pigment are laminated via a transparent resin layer made of one or more selected from the group consisting of an acrylic resin, a silicone resin, and an epoxy resin. Suggest a layer. The white bezel layer of Patent Document 2 is a technique for increasing white variation by utilizing a change in refractive index due to a transparent resin layer. The technique of Patent Document 2 has a problem that the number of processes required for manufacturing increases.

  On the other hand, Patent Document 3 discloses a coated body for an outer plate of an automobile in which a white coating film, a blue fluorescent coating film, and a top coat film are sequentially formed on the surface of a metal substrate. The white coating film is a cured layer of a resin composition containing an inorganic white pigment, and the resin composition includes a hydroxyl group-containing resin selected from a hydroxyl group-containing acrylic resin and a hydroxyl group-containing polyester resin, a compound having an isocyanate group, And is cured by crosslinking by a urethanization reaction at a temperature of about room temperature to about 140 ° C. to become a urethane resin. The blue fluorescent coating is a urethane resin layer that is a cross-linked cured product of a resin composition that includes a blue inorganic phosphor that converts ultraviolet rays into blue visible light and emits it. The white layer of patent document 3 consists of a white coating film and a blue fluorescent coating film.

JP 2014-093070 A Japanese Patent Laying-Open No. 2015-076095 JP 2012-096213 A

  Patent Document 3 is a technique related to painting of an automobile or the like, and is not a technique for forming a bezel layer of a smartphone or the like. The present inventors examined the application of the laminate of the white coating film and the blue fluorescent coating film disclosed in Patent Document 3 to a white bezel layer such as a smartphone. As a result, when the blue fluorescent coating film of Patent Document 3 is exposed to a high temperature exceeding 200 ° C. at the time of circuit formation for touch panels, the thermal deterioration of the urethane resin, which is the matrix resin of the blue fluorescent coating film, is likely to proceed. The resin absorbs light having a wavelength of 400 nm or less, such as ultraviolet light, and lowers the luminous efficiency of the blue inorganic phosphor. It has been found that the effect of changing is insufficient.

  In addition, when organic pigments such as phthalocyanine and quinacridone are used, a white having a different color is obtained before heating. However, since organic pigments do not have sufficient heat resistance, after heating at high temperatures, The color tone fades and becomes white, and the whiteness is remarkably lowered. In addition, organic phosphors, like organic pigments, are severely discolored by heating at high temperatures, and a satisfactory effect for improving the whiteness of the white bezel layer in OGS cannot be obtained. Further, generally used inorganic pigments such as iron oxide and cobalt blue have better heat resistance than organic pigments, but have a low L value and cannot improve whiteness.

  The purpose of the present invention is to increase the white variation by changing the color of the white layer made of an inorganic white pigment and to further increase the whiteness of the white layer even after being exposed to a high temperature exceeding 200 ° C. And a laminate including a fluorescent pigment dispersion and a phosphor layer made of the fluorescent pigment dispersion.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have a blue system that emits blue fluorescence having a main absorption region at 400 nm or less and an emission peak in the range of 430 nm to 480 nm. A fluorescent pigment dispersion containing an inorganic phosphor and a silicone resin has been found. Furthermore, the present inventors changed the color of the white layer by laminating the phosphor layer made of the above-mentioned fluorescent pigment dispersion on the surface of the white layer made of an inorganic white pigment such as titanium oxide. It is possible to increase the white variation and increase the whiteness of the white layer, and to change the color and increase the whiteness even after being exposed to the same high temperature as when forming a touch sensor in OGS. The present inventors have found that it can be maintained at the same level as before being exposed to a high temperature, and have completed the present invention.

That is, the present invention provides fluorescent pigment dispersions [1] to [5] below and white laminates [6] to [7] below.
[1] A blue inorganic phosphor that has a main absorption region in a wavelength range of 400 nm or less and an emission peak in a wavelength range of 430 nm to 480 nm and emits blue fluorescence, and a silicone resin, Fluorescent pigment dispersion.
[2] The fluorescent pigment dispersion according to [1], including 5 to 200 parts by weight of a silicone resin with respect to 100 parts by weight of the blue inorganic phosphor.
[3] The fluorescence of [1] or [2], wherein the blue inorganic phosphor is at least one selected from the group consisting of a europium activated halophosphate phosphor and a europium activated aluminate phosphor. Pigment dispersion.
[4] Europium activated halophosphate phosphor
General formula (1): (Sr, Ca) _a (Ba) _b (Eu) _c (PO ₄ ) _d (Cl) _{e wherein} a and b are a + b = 5-c and 0.12 ≦ { b / (a + b)} ≦ 0.4. 0.3 ≦ c ≦ 1.2, 2.7 ≦ d ≦ 3.3, and 0.9 ≦ e ≦ 1. ] A phosphor (1) represented by
General formula (2): (Sr _1-xy Ba _x Ca _y ) ₅ (PO ₄ ) ₃ (Cl) (Eu) [wherein 0 ≦ x <0.5, 0 ≦ y <0.1] phosphors (2), and general formula _{(3) :( Sr 1-xyz} M x Ca y Eu z) 5 (PO 4) 3 (Cl) wherein, x and y are as defined above. M represents Ba and / or Mg. 0.005 <z <0.1. ]
The fluorescent pigment dispersion of the above [3], which is at least one selected from the group consisting of the phosphor (3) represented by:
[5] The europium activated aluminate phosphor is an alkaline earth metal aluminate phosphor, and the alkaline earth metal aluminate phosphor is
Phosphor (4) represented by the general formula (4): BaMgAl ₁₀ O ₁₇ : Eu,
Phosphor (5) represented by the general formula (5): (Ba, Sr) MgAl ₁₀ O ₁₇ : Eu,
Formula _{(6): Ba 1-p} MgAl 10 O 17: in Eu _p [Formula is 0.03 ≦ p ≦ 0.2. And a phosphor (6) represented by
General formula (7): Ba _1-pq M _q MgAl ₁₀ O ₁₇ : Eu _p [wherein p is the same as defined above. M represents Sr and / or Ca. 0.1 ≦ q ≦ 0. ] The fluorescent pigment dispersion according to the above [3], which is at least one selected from the group consisting of phosphors (7) represented by
[6] A white layer containing an inorganic white pigment, a phosphor layer laminated on one surface of the white layer and formed using the fluorescent pigment dispersion according to any one of [1] to [5], White laminate containing
[7] The white laminate according to [6], further including a transparent substrate layer, which is a laminate of the transparent substrate layer, the phosphor layer, and the white layer in this order.

  According to the present invention, by laminating on the surface of a white layer composed of an inorganic white pigment, the color of the white layer is changed to increase white variations and to increase the whiteness of the white layer, thereby exposing to a high temperature. Provided is a fluorescent pigment dispersion that can form a phosphor layer that can maintain the function of changing the color and increasing the whiteness even after being applied.

It is a graph which shows the relationship between the a * value and b * value of the white laminated body of Example 1 and Comparative Examples 1-3. It is a graph which shows the L * value of the white laminated body of Example 1 and Comparative Examples 1-3. It is a graph which shows the relationship between the a * value of the white laminated body of Examples 2-4 and the comparative example 4, and b * value.

<Fluorescent pigment dispersion>
The fluorescent pigment dispersion of the present invention is a blue inorganic phosphor that has a main ultraviolet absorption region at 400 nm or less and emits blue fluorescence having a blue emission peak in the range of 430 nm to 480 nm (hereinafter simply referred to as “blue inorganic phosphor”). And a silicone resin, which may be referred to as “blue inorganic phosphor”.

  A layer formed from the fluorescent pigment dispersion of the present invention (a cured layer of the fluorescent pigment dispersion of the present invention, hereinafter sometimes referred to as “phosphor layer”) is a white layer made of an inorganic white pigment. By laminating on the surface on the incident side, the white color derived from the inorganic white pigment is changed, the white variation is increased, and the whiteness of the white layer is further increased. Even after being exposed to a high temperature exceeding 1, the above effect can be maintained at a high level. According to the present invention, the blue inorganic phosphor is dispersed in a layer mainly composed of a silicone resin, thereby suppressing or preventing deterioration or alteration of the blue inorganic phosphor due to heat, and the white color of the blue inorganic phosphor. It is considered that the effect of changing the color to the pigment and the effect of improving the whiteness can be sufficiently exhibited even after being exposed to a high temperature. The fluorescent pigment dispersion of the present invention can also be used as various inks and ink raw materials.

  When the phosphor layer comprising the fluorescent pigment dispersion of the present invention is applied to the formation of a white bezel layer such as a smartphone, for example, pre-baking heating (for example, 230 ° C. × 30 minutes) for forming the phosphor layer itself And withstands at least two high-temperature heating, such as heating for forming a white layer and a touch panel circuit (for example, 250 ° C. × 120 minutes), and even when subjected to high-temperature heating in other processes, an inorganic white pigment It is necessary to change the color of the white layer made of and to increase its whiteness.

  This visually reduces the yellowness peculiar to inorganic white pigments, or changes the yellowishness to another color, and increases the apparent whiteness. In terms of instrumental analysis, the values of a * value, b * value, and L * value are in a specific range. The a * value and b * value are indicators of color, and the L * value is an indicator of color brightness. In this specification, the a * value and b * value are mainly white. Since the whiteness of the white color appears higher as the brightness of the color increases, the L * value is expressed as the whiteness of the whiteness. Shown as an indicator.

  In the present invention, in consideration of using the white laminate of the present invention as a white bezel layer of a smartphone, heating for 30 minutes or more at a high temperature exceeding 200 ° C. (preferably 30 minutes at a temperature of 230 to 250 ° C. The a * value of the white laminate after performing twice (heating for ~ 120 minutes) is preferably -0.5 to 5, more preferably -0.45 to 5, more preferably -0.45. 1, particularly preferably in the range of -0.35 to 1, and the b * value is preferably -2 to -5, more preferably -2.2 to -5, still more preferably -2.5 to -5. The L * value of the white laminate is preferably 88 or more, more preferably 88.5 or more.

  The fluorescent pigment dispersion of the present invention contains a blue-based inorganic phosphor and a silicone resin as essential components as described above, and, as will be described later, further conventionally known additives for pigment dispersion are added. One kind or two or more kinds of agents may be contained as optional components. Hereinafter, essential and optional components will be described in detail.

  The blue-based inorganic phosphor is a phosphor made of an inorganic compound and absorbing blue light and emitting blue light, and various types have been conventionally known. In the present invention, among such blue inorganic phosphors, the ultraviolet absorption region is mainly in the wavelength range of 400 nm or less, and the emission peak of the emission region that emits blue light is 430 nm to 480 nm, preferably 450 nm to Those in the wavelength range of 470 nm are used. The blue inorganic phosphor used in the present invention may absorb ultraviolet rays up to about 410 nm. When the wavelength at which the emission peak exists is less than 430 nm and exceeds 480 nm, the yellowish white color derived from the white pigment may not be changed or the whiteness may not be increased. In the present invention, the blue inorganic phosphors having the absorption region and the emission peak wavelength range can be used alone or in combination of two or more different types.

  In the present invention, any blue-based inorganic phosphor having the above-described absorption region and emission peak wavelength range can be used without particular limitation, but among them, from the viewpoint of increasing the whiteness of the white layer obtained by the inorganic white pigment. Preferably, at least one selected from the group consisting of a europium activated halophosphate phosphor and a europium activated aluminate phosphor.

  The europium-activated halophosphate phosphor is not particularly limited as long as it has the aforementioned absorption region and emission peak wavelength range, but a europium-activated halophosphate phosphor containing an alkaline earth metal is preferable. Specific examples include phosphors (1) to (3) represented by the following general formulas (1) to (3), respectively. The phosphors (1) to (3) can be used alone or in combination of two or more.

Phosphor (1): (Sr, Ca) _a (Ba) _b (Eu) _c (PO ₄ ) _d (Cl) _{e wherein} a and b are a + b = 5-c and 0.12 ≦ { b / (a + b)} ≦ 0.4. 0.3 ≦ c ≦ 1.2, 2.7 ≦ d ≦ 3.3, and 0.9 ≦ e ≦ 1. ]
The phosphor (1) is described in, for example, International Publication No. 2012/114640.

Specific examples of the phosphor (1) include, for example, Eu _0.50 Sr _4.05 Ba _0.45 (PO ₄ ) ₃ Cl, Eu _0.50 Sr _3.83 Ba _0.57 (PO ₄ ) ₃ Cl, Eu _0.50 Sr _3.78 Ba _0.72 (PO ₄ ) ₃ Cl, Eu _0.50 Sr _3.42 Ba _1.08 (PO ₄ ) ₃ Cl, Eu _0.50 Sr _2.97 Ba _1.53 (PO ₄ ) ₃ Cl, Eu _0.45 Sr _3.40 Ba _0.65 (PO ₄ ) ₃ Cl, Eu _0.55 Sr _3.74 Ba _0.71 (PO ₄ ) ₃ Cl, Eu _0.65 Sr _3.65 Ba _0.70 (PO ₄ ) ₃ Cl, Eu _0.32 Sr _3.74 Ba _0.94 (PO ₄ ) ₃ Cl, Eu _0.38 Sr _3.70 Ba _0.92 (PO ₄ ) ₃ Cl, Eu _0.95 Sr _3.24 Ba _0.81 ( PO ₄ ) ₃ Cl, Eu _0.50 Sr _3.60 Ba _0.45 Ca _0.45 (PO ₄ ) ₃ Cl, and the like. The phosphor (1) can be used alone or in combination of two or more.

Phosphor (2): (Sr _1-xy Ba _x Ca _y ) ₅ (PO ₄ ) ₃ (Cl) (Eu) [where 0 ≦ x <0.5, 0 ≦ y <0.1]
The phosphor (2) is described in, for example, JP2013-229539A.

Specific examples of the phosphor (2) include, for example, Sr ₅ (PO ₄ ) ₃ Cl: Eu, (Sr _0.88 Ba _0.12 ) ₅ (PO ₄ ) ₃ Cl: Eu, (Sr _0.79 Ba _0.21 ) ₅ (PO ₄ ) ₃ Cl: Eu, and the like. For example, Sr ₅ (PO ₄ ) ₃ Cl: Eu is commercially available from Nemotomi Material Co., Ltd., Nichia Corporation and the like. In the present specification, the same type of phosphor (2) is also included in the phosphor (2). Here, the same kind as the phosphor (2) is a blue phosphor containing at least 1 mol of Eu and further containing PO ₄ , Cl and an alkaline earth metal. Specific examples of the blue phosphor include, for example, (Sr, Ca, Ba ₂ , Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Sr, Ca, Ba) ₅ (PO ₄ ) ₃ Cl: Eu, (Ba, Ca) ₅ (PO ₄ ) ₃ Cl: Eu, (Ca, Sr, Ba) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu and the like. The phosphor (2) and the same type of blue phosphor can be used singly or in combination of two or more.

Phosphor _{(3) :( Sr 1-xyz} M x Ca y Eu z) 5 (PO 4) 3 (Cl) wherein, x and y are as defined above. M represents Ba and / or Mg. 0.005 <z <0.1. ]
The phosphor (3) is described in, for example, Japanese Patent Application Laid-Open No. 2004-253747, Japanese Patent Application Laid-Open No. 2014-197707, International Publication No. 2009/141982, and the like.

Specific examples of the phosphor (3) include, for example, (Sr _0.9 Eu _0.1 ) ₅ (PO ₄ ) ₃ Cl, (Sr _0.8 Eu _0.2 ) ₅ (PO ₄ ) ₃ Cl, (Sr _0.7 Eu _0.3 ) ₅ (PO ₄ ) ₃ Cl, (Sr _0.6 Eu _0.4 ) ₅ (PO ₄ ) ₃ Cl, (Sr _0.4 Eu _0.6 ) ₅ (PO ₄ ) ₃ Cl, (Sr _0.99 Eu _0.01 ) ₅ (PO ₄ ) ₃ Cl, (Sr _0.1 Eu _0.9 ) ₅ (PO ₄ ) ₃ Cl, (Sr _0.98 Eu _0.02 ) ₅ (PO ₄ ) ₃ Cl, (Sr _0.8 Ba _0.19 Eu _0.01 ) ₅ (PO ₄ ) ₃ Cl, (Sr _0.8 Ca _0.19 Eu _0.01 ) ₅ (PO ₄ ) ₃ Cl, (Sr _0.85 Ba _0.01 Ca _0.09 Eu _0.05 ) ₅ (PO ₄ ) ₃ Cl, (Sr _0.894 Ba _0.1 Eu _0.006 ) ₅ (PO ₄ ) ₃ Cl, (Sr _0.42 Ba _0.48 Ca _0.01 Eu _{0.09 ) 5 (PO 4) 3 Cl} 2, (Sr 0.85 Ba 0.01 Ca 0.09 Eu 0.05) 5 (PO 4) 3 Cl, ( _{r 0.44 Ba 0.49 Ca 0.02 Eu 0.05} ) 5 (PO 4) 3 Cl , and the like. A fluorescent substance (3) can be used individually by 1 type or in combination of 2 or more types.

  The europium activated aluminate phosphor is not particularly limited as long as it has the aforementioned absorption region and emission peak wavelength range. For example, a europium activated aluminate phosphor containing an alkaline earth metal is preferable. Specific examples thereof include phosphors (4) to (7) represented by the following general formulas (4) to (7), respectively. The phosphors (4) to (7) can be used singly or in combination of two or more.

Phosphor (4): BaMgAl ₁₀ O ₁₇ : Eu
Phosphor (5): (Ba, Sr) MgAl ₁₀ O ₁₇ : Eu
The phosphors (4) and (5) are described in many patent documents and are commercially available from, for example, Nemotomi Material Co., Ltd. The phosphor (5) is preferably configured to contain 5 to 15 mol% of Eu with respect to the total molar amount of (Ba, Sr) and Eu.

Phosphor (6): Ba _1-p MgAl ₁₀ O ₁₇ : Eu _p [wherein, 0.03 ≦ p ≦ 0.2. ]
Phosphor (7): Ba _{1 -pq} M _q MgAl ₁₀ O ₁₇ : Eu _p [wherein p is the same as defined above. M represents Sr or Ca. 0.1 ≦ q ≦ 0. ]
The phosphors (6) and (7) are described in, for example, JP-A-2005-340155, JP-A-2008-181886, JP-A-2010-248525, and the like. In addition,

Specific examples of the phosphor (6) and the phosphor (7) include, for example, Ba _0.97 MgAl ₁₀ O ₁₇ : Eu _0.03 , Ba _0.95 MgAl ₁₀ O ₁₇ : Eu _0.05 , Ba _0.9 MgAl ₁₀ O ₁₇ : Eu _0.1 , Ba _0.8 MgAl ₁₀ O ₁₇ : Eu _0.2 , Ba _0.87 Sr _0.1 MgAl ₁₀ O ₁₇ : Eu _0.03 , Ba _0.6 Sr _0.3 MgAl ₁₀ O ₁₇ : Eu _0.1 , Ba _0.4 Sr _0.5 MgAl ₁₀ O ₁₇ : Eu _0.1 , Ba _0.5 Sr _0.3 MgAl ₁₀ O ₁₇ : Eu _0.2 , Ba _0.8 Sr _0.1 MgAl ₁₀ O ₁₇ : Eu _{0.1 and the} like. A fluorescent substance (6) and a fluorescent substance (7) can be used individually by 1 type or in combination of 2 or more types, respectively.

  Considering the further improvement of the whiteness of the white layer made of an inorganic white pigment by the phosphor layer and the heat resistance of the phosphor layer itself, among the above, the phosphors (1), (2), (4 ) And (5) are preferred, phosphors (2), (4) and (5) are more preferred, and phosphor (2) is more preferred. In addition, as a blue-type inorganic fluorescent substance, if it has the above-mentioned absorption region and the wavelength range of an emission peak, various commercial items can also be used.

The particle size of the blue inorganic phosphor is not particularly limited, but considering application to a white bezel layer, etc., it is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm, still more preferably 0.2 to 1 μm. Particularly preferred is 0.2 to 0.8 μm. The particle diameter here is a 50% cumulative volume average particle diameter (D ₅₀ ) measured by a light scattering method.

  The silicone resin used as an essential component together with the blue inorganic phosphor becomes, for example, a matrix resin that holds the blue inorganic phosphor in the phosphor layer, and protects the blue inorganic phosphor from high temperatures. Even if the white bezel layer is exposed to high temperatures due to OGS, the blue inorganic phosphor is prevented from being altered or deteriorated by heat, and the effect of changing the color of the inorganic inorganic pigment in the blue inorganic phosphor is improved and the whiteness is improved. It is thought that the effect can be maintained, and thus it is possible to cope with diversified designs and improve the degree of design freedom of products.

  As the silicone resin, those having a main chain containing a plurality of siloxane bonds (—Si—O—) and having or not having an organic functional group in the side chain can be used without particular limitation. From the viewpoint of suppressing deterioration and deterioration due to heat, a silicone resin having one or more organic functional groups in the side chain is preferred. The organic functional group is substituted by 0 to 2 for one Si atom, and may be substituted for all silicon atoms contained in the silicone resin or may not be substituted. Here, as the organic functional group, for example, a linear or branched alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, etc. , Methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, tert-butoxy, etc., linear or branched alkoxy groups having 1 to 4 carbon atoms, aromatic hydrocarbon groups such as phenyl groups Etc. Among these organic functional groups, a linear alkyl group and an aromatic hydrocarbon group are preferable, and a methyl group and a phenyl group are more preferable.

  The silicone resin includes a chain silicone resin, a modified chain silicone resin in which an organic group is introduced into the side chain and / or the terminal of the chain silicone resin, one silicon atom in the chain silicone resin, and another silicon. Examples thereof include a crosslinked silicone resin in which atoms are crosslinked by a divalent group, and a cyclic silicone resin (cyclic polysiloxane). Among these, a chain silicone resin, a modified chain silicone resin, and the like are preferable from the viewpoint of suppressing or preventing deterioration and deterioration of the blue inorganic phosphor due to heat.

  Among the chain silicone resins, for example, a chain silicone resin in which a linear alkyl group and / or a phenyl group are substituted on at least a part of all silicon atoms is preferable, and a methyl silicone resin, a methyl phenyl silicone resin, and the like are more preferable. As the modified chain silicone resin, for example, a monomer obtained by reacting an acrylic monomer such as an acrylic modified silicone resin, a polyester modified silicone resin, an epoxy modified silicone resin, or acrylic acid with a silane compound is polymerized or copolymerized with another acrylic monomer. Similar to acrylic resin-modified silicone resin, polyester resin-modified silicone resin in which silane compound is reacted with hydroxyl group of polyester, epoxy resin-modified silicone resin in which epoxy-containing silane compound is reacted with amino group residue of resin, alkyne resin Examples thereof include alkyd resin-modified silicone resins modified with reactive silane compounds, and rubber-based silicone resins that form a covalent bond directly with the resin using an oxime-based initiator.

A commercially available product may be used as the silicone resin. Examples of the commercially available product include KR-112, KR-211, KR-212, KR-255, KR-271, KR-272, and KR.
-282, KR-300, KR-311, KR-2621-1, X-40-2667A,
KR-480, KR-220L, KR-220LP, KR-242A, KR-251 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), TSR116, TSR117, TSR144,
TSR145, TSR1452, TSR165, TSR180, TSR194, XR32
-901, XR-32-901, XR32-A1612, XR3303, YR47, YR
3370 (all trade names, manufactured by Momentive Performance Materials Japan GK), 804 RESIN, 805 RESIN, 806 ARESIN, 840 RES
IN, SR2400 (both are trade names, manufactured by Toray Dow Corning Co., Ltd.) and the like.

  The molecular weight of the silicone resin can be appropriately selected from a wide range according to the type and content of the blue inorganic phosphor, the use of the fluorescent pigment dispersion, etc.For example, to improve the whiteness of the bezel layer containing a white pigment, etc. When used, the number average molecular weight is preferably 1000 to 1000000, more preferably 2000 to 800000, and further preferably 2500 to 500000 from the viewpoint of film formability.

  In the fluorescent pigment dispersion of the present invention, since the silicone resin is present, deterioration and deterioration of the blue inorganic phosphor due to heat are remarkably suppressed, so the blending amount of the silicone resin is not particularly limited, and the blue color used Depending on the type and particle size of the inorganic phosphor, the type of silicone resin, the use of the white laminate of the present invention including the phosphor layer, the storage stability as a paint, coating properties, handling properties, and after curing A suitable range may be selected as appropriate in consideration of the mechanical strength and durability of the phosphor layer. For example, when used to cancel yellowness of a bezel layer containing an inorganic white pigment or improve whiteness, a blue inorganic phosphor is used from the viewpoint of suppressing or preventing deterioration or alteration of the blue inorganic phosphor due to heat. Preferably it is 5-200 weight part with respect to 100 weight part.

  Moreover, the fluorescent pigment dispersion of the present invention may be used as it is immediately after production, or may be used after being diluted with silicone resin or the like after production. When the product immediately after production is used as it is, the compounding amount of the silicone resin is more preferably 65 to 200 parts by weight, and further preferably 80 to 150 parts by weight with respect to 100 parts by weight of the blue inorganic phosphor. When used, the blending amount of the silicone resin is more preferably 5 to 50 parts by weight, still more preferably 10 to 20 parts by weight with respect to 100 parts by weight of the blue inorganic phosphor.

  The fluorescent pigment dispersion of the present invention preferably contains an organic solvent in addition to the two essential components described above. The organic solvent is a dispersion and storage stability of the blue inorganic phosphor and silicone resin in the fluorescent pigment dispersion of the present invention (especially preventing aggregation and precipitation of the blue inorganic phosphor), and a blue inorganic fluorescence in the phosphor layer. It is useful for improving the uniform dispersibility of the body, the handling property, the coating property and the like of the fluorescent pigment dispersion of the present invention.

  The organic solvent is not particularly limited, and is appropriately selected according to various conditions such as the types of blue-based inorganic phosphors and silicone resins, the blending amounts thereof, the use of the obtained phosphor pigment dispersion, Aromatic solvents, aliphatic solvents, ketone solvents, ester solvents, glycol ether solvents, alcohol solvents and the like can be mentioned. Among these, aromatic solvents, ketone solvents, ester solvents, glycol ether agents and the like are preferable from the viewpoint of compatibility with silicone resins. One organic solvent may be used alone, or two or more organic solvents may be used in combination if possible.

Examples of the aromatic solvent include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene.
Examples of the aliphatic solvent include aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane.
Examples of the ketone solvent include methyl ethyl ketone, methyl inbutyl ketone, diin butyl ketone, acetone, acetylacetone, isophorone, acetophenone, and cyclohexanone.

Examples of the ester solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, impropyl acetate, methyl propionate, 3-methoxybutyl acetate, ethyl glycol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether. Acetate, 3-methyl-3-methoxybutyl acetate,
Methyl monochloroacetate, ethyl monochloroacetate, butyl monochloroacetate, methyl acetoacetate, ethyl acetoacetate, butyl carbitol acetate, butyl lactate, ethyl-3-ethoxypropionate, ethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, propyl acetate 1,3-butylene glycol diacetate and the like.

  Examples of the glycol ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, and ethylene glycol mono-iso-propyl ether. , Diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol mono-tert-butyl ether, 1- Methyl-1-methoxybutanol, pro Lenglycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-tert-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Water-soluble glycol ethers such as dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-iso-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, ethylene glycol monohexyl ether , Ethylene glycol-2-ethylhexyl ether, ethylene glycol phenyl ether, Water-insoluble glycol ethers such as ethylene glycol-n-hexyl ether, diethylene glycol-2-ethylhexyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, dipropylene glycol propyl ether, propylene glycol methyl ether propionate, etc. Can be mentioned.

  Examples of the alcohol solvent include C1-C4 alkyl alcohols such as ethanol, methanol, n-butanol, n-propanol, and inpropanol, ethylene glycol, propylene glycol, diethylene glycol, pentamethylene glycol, trimethylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, tripropylene glycol, polyethylene glycol having a molecular weight of 2000 or less, 1,3-propylene glycol, impylene glycol , Inbutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, menoerythritol, pentaerythritol Lumpur, and the like.

  In the fluorescent pigment dispersion of the present invention containing an organic solvent, the solid content of the blue inorganic phosphor and the silicone resin is such that the dispersibility and storage stability of the blue inorganic phosphor and the silicone resin in the dispersion are reduced. From the viewpoint of the handling property and coating property of the dispersion, it is preferably 50 to 90% by weight, more preferably 55 to 75% by weight of the total amount of the dispersion.

  The fluorescent pigment dispersion of the present invention may contain one or more general additives used in the pigment dispersion, if necessary, in addition to the two essential components and the organic solvent. it can. Examples of the additive include a dispersion aid, a pH adjuster, an antioxidant, an ultraviolet absorber, an antiseptic, an antifungal agent, a fluorine-based organic compound, a surfactant, an adhesion promoter, an aggregation inhibitor, and a surface conditioner. Agents (leveling agents) and the like. Although the content of the additive in the fluorescent pigment dispersion of the present invention is not particularly limited, for example, it is appropriately selected from the range of 0.01 to 10% by weight of the total amount of the fluorescent pigment dispersion.

  The fluorescent pigment dispersion of the present invention can be produced, for example, by mixing a blue inorganic phosphor, a silicone resin, and, if necessary, an additive. However, the dispersibility of the blue inorganic phosphor is increased. For this purpose, the dispersion may be produced by mixing a dispersion obtained by dispersing a blue inorganic phosphor in an organic solvent, a silicone resin or an organic solvent solution thereof, and an additive as necessary. For dispersion of the blue inorganic phosphor in the organic solvent, various dispersion methods used for dispersing fine particles in the organic solvent can be used without any particular limitation.

<White laminate>
The white laminate of the present invention includes a white layer containing an inorganic white pigment and a phosphor layer formed on the one surface of the white layer and formed from the phosphor pigment dispersion of the present invention (the phosphor of the present invention). A hardened layer of the pigment dispersion). That is, the white laminate of the present invention is a laminate of a white layer and a phosphor layer. Moreover, the preferable form of the white laminated body of this invention is the laminated body laminated | stacked in this order with the transparent base material layer, the fluorescent substance layer, and the white layer.

  In a preferred embodiment of the present invention, a sheet-like material made of a transparent material can be used for the transparent substrate layer. Although it does not specifically limit as a transparent material, For example, thermoplastic materials, such as ceramic materials, such as glass, polyethylene terephthalate, polycarbonate, polyethylene naphthalate, polyethersulfone, polymethylmethacrylate, an acrylic resin, and a cyclic olefin copolymer, epoxy Examples thereof include resin materials such as resins and thermosetting resin materials such as silicone resins. The thickness of the transparent substrate layer is not particularly limited, and is appropriately selected according to the use of the white laminate of the present invention. When the white laminate of the present invention is used as a bezel layer in a display unit such as a smartphone, for example. Is preferably 50 μm to 3 mm, more preferably 100 μm to 1 mm, still more preferably 100 μm to 500 μm, and particularly preferably 200 μm to 500 μm.

  A phosphor layer is formed in a predetermined region on one surface of the transparent substrate layer. The phosphor layer is formed by applying the fluorescent pigment dispersion of the present invention to a predetermined region on the surface of the transparent substrate layer, treating the dispersion by natural curing or heat curing, and forming a cured layer. Moreover, a photopolymerizable material may be added to the fluorescent pigment dispersion of the present invention, and the cured layer may be formed by irradiating the coating film with light. Further, a radical polymerizable material or a radical polymerization initiator is added to the fluorescent pigment dispersion of the present invention, and when the coating film is heated, the radical polymerizable material is polymerized to form a cured layer. Good. The method for applying the fluorescent pigment dispersion is not particularly limited, and any known application (or printing) method can be adopted. For example, methods such as roll coating, spin coating, slot coating, and screen printing can be preferably used.

  The coating film of the fluorescent pigment dispersion applied to the surface of the transparent substrate layer is cured, for example, by heating or light irradiation. For the heat curing of the coating film, only pre-baking heating may be performed, pre-baking heating and subsequent main heating may be performed, or only main heating may be performed. In the case of only pre-baking heating, when the white layer is laminated on the phosphor layer, the main heating of the phosphor layer is simultaneously performed by heating the white layer. In these heating, the heating temperature and the heating time are appropriately selected according to the kind of silicone resin and organic solvent contained in the fluorescent pigment dispersion, but the prebaking is performed at a temperature of about 80 to 120 ° C., for example. The heating is completed in about 1 to 30 minutes, and the main heating is performed at a temperature of about 200 to 250 ° C., for example, and is completed in about 20 to 60 minutes. The thickness of the phosphor layer is not particularly limited, but for example, when the obtained white laminate is used for a touch panel such as a smartphone, it is preferably about 1 to 20 μm, more preferably about 2 to 15 μm, still more preferably. It is about 3 to 10 μm.

  A white layer is formed on the surface of the phosphor layer. The white layer contains an inorganic white pigment, a resin material, and an organic solvent, and further, if necessary, a white paste similar to the conventional one that may contain various pigments for color correction is applied to the phosphor layer surface, It can produce by heat-curing the obtained white coating film. The coating method can use the same method as the phosphor pigment dispersion. In the heat curing of the white coating film, the heating temperature and the heating time are appropriately selected according to the type of resin material and organic solvent described later, but the heat curing of the white coating film is preferably 200 to 300 ° C., more preferably. Is carried out at a temperature of 230 to 290 ° C. and is preferably completed in 20 to 150 minutes, more preferably 30 to 120 minutes. The thickness of the white layer is not particularly limited, but is preferably 2 to 100 μm, more preferably 5 to 50 μm, considering the hiding power of the white layer.

  Here, the white inorganic pigment is not particularly limited and known ones can be used. For example, metal oxides such as titanium oxide, alumina, silica, zinc oxide, magnesium oxide, zirconium oxide, and antimony oxide can be preferably used. . The particle size of the white inorganic pigment is not particularly limited, but the primary particle size is preferably 100 to 400 nm, more preferably 200 to 300 nm.

  As the resin material and the organic solvent, the same resin material and organic solvent as those used for the transparent substrate layer and the phosphor layer can be appropriately selected and used. In addition, the color correction pigment is not particularly limited. For example, inorganic pigments such as transparent iron oxide pigments and composite oxide pigments such as titanium yellow; azo pigments, quinacridone pigments, diketopyrrolopyrrole pigments Perylene pigments, perinone pigments, benzimidazolone pigments, isoindoline pigments, isoindolinone pigments, metal chelate azo pigments, phthalocyanine pigments, indanthrone pigments, dioxazine pigments, selenium pigments, indigo And organic pigments such as pigments. In addition, since the organic pigment may be deteriorated or deteriorated when exposed to a high temperature as described above, it is necessary to pay attention to this point.

  In addition, when using the obtained white laminated body as touch panels etc., such as a smart phone, it is transparent conductive paste on the same surface as the fluorescent substance layer and white layer of a transparent base material layer being laminated | stacked simultaneously with a white layer. The OGS method can be easily adopted by printing the circuit by, for example, and simultaneously heating and curing the white layer and the circuit.

  The white laminate of the present invention has a high whiteness because the phosphor layer has high heat resistance, and the phosphor layer changes the color of the white layer, further improves the whiteness and has a high quality white. Can be suitably used for the production of a coating film that requires a white color or the like that is different from the white color derived from the property or inorganic white pigment, and more particularly for the production of a coating film including a process of heating at a high temperature. It can be used suitably. For example, when the touch panel of a multifunctional portable terminal is manufactured by a technique such as OGS that requires higher heat resistance than before, the white laminate of the present invention can be used very suitably as a white bezel layer. When the white laminate of the present invention is used as a white bezel layer in a display screen, the display method of the combined display screen is not particularly limited, for example, a liquid crystal display method, an electroluminescence display method, a plasma display display method, a laser display method, A field emission display (FED) system and the like can be given.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, unless otherwise specified, both “%” and “part” are based on weight.

Example 1
(1) Preparation of Fluorescent Pigment Dispersion of the Present Invention As the blue inorganic phosphor, the formula: Sr ₅ (PO ₄ ) ₃ Cl: Eu (trade name; D1231, manufactured by Nemotolmi Materials Co., Ltd.) was used. This blue inorganic phosphor has a lower limit of an ultraviolet absorption region of about 400 nm and an emission peak of 446 nm.
Blue phosphor (D1231) / silicone resin (trade name: KR-300, manufactured by Shin-Etsu Silicone Co., Ltd.) / Xylene (solvent) = 36/24 (solid content) / 40 (weight ratio) 1 mm glass beads were added to the resulting mixture in an amount 1.5 times the amount of mill base and stirred and dispersed for 0.5 hours to prepare the fluorescent pigment dispersion of the present invention.

  The obtained fluorescent pigment dispersion was applied to the surface of a 0.7 mm thick glass plate (trade name: Eagle XG, manufactured by Toray Dow Corning Co., Ltd.) with a spin coater, and heated and cured at 230 ° C. for 120 minutes. A phosphor layer of the present invention having a thickness of 5 μm was produced. (L * value, a * value, b * value) of the obtained phosphor layer was measured with a spectrocolorimeter (trade name: CM-3600d, D65 light source, manufactured by Konica Minolta Co., Ltd.). The measured values obtained here are used in Comparative Example 2 and Comparative Example 3.

(2) Preparation of White Paste A As a white pigment dispersion, trade name: SF WHITE AD4299, manufactured by Sanyo Dye Co., Ltd. was used. The dispersion is made of titanium oxide (trade name: CR-93, manufactured by Ishihara Sangyo Co., Ltd.) / Acrylic dispersant (trade name: Solsperse 36000, manufactured by Nippon Lubrizol Co., Ltd.) / PMA (propylene glycol monomethyl ether acetate). , Solvent) = 70/3 (solid content) / 27 (weight ratio), and 0.5 mm zirconia beads were added to the resulting mixture twice as much as the mill base and stirred and dispersed for 1 hour.
The white pigment dispersion / silicone resin (KR-300) was mixed at a ratio (weight ratio) of 5 / 3.35 (solid content) to prepare a white paste A.

(3) Production of the white laminate of the present invention The fluorescent pigment dispersion of the present invention obtained above was applied to the surface of a 0.7 mm thick glass plate with a spin coater, and the resulting coating film was applied at 90 ° C. Pre-baked for 5 minutes to form a phosphor layer having a thickness of 5 μm. Furthermore, the white paste A obtained above was applied to the surface of the phosphor layer with a spin coater, and the obtained coating film was heat-cured at 230 ° C. for 30 minutes to form a white layer having a thickness of 15 μm. A white laminate (total thickness: 20 μm) of the present invention was produced. In order to confirm the heat resistance of the obtained white laminate, this white laminate was reheated at 250 ° C. for 120 minutes.

  About the present invention obtained above and the white laminate after reheating, the hue (a * value, b * value) and whiteness (L * value) from the glass plate side of the white layer were measured with a spectrocolorimeter (CM3600d). SCI D65 light source, ultraviolet light was not cut). The results are shown in FIGS.

  FIG. 1 is a graph showing the relationship between the a * value and the b * value of the white laminates of Example 1 and Comparative Examples 1 to 3. In FIG. 1, two measured values are spotted for each of Example 1 (●), Comparative Example 1 (■), Comparative Example 2 (♦), and Comparative Example 3 (▲), and the spot on the right side of the paper is reheated. The measured value of the white laminated body which has not been shown is shown, and the spot on the left side of the paper shows the measured value of the white laminated body after reheating.

  FIG. 2 is a graph showing L * values of the white laminates of Example 1 and Comparative Examples 1 to 3. In FIG. 2, two bar graphs are displayed side by side for each of Example 1 and Comparative Examples 1 to 3, and the black bar graph on the left side of the paper shows the L * value of the white laminate that has not been reheated. A white bar graph shows the L * value of the white laminate after reheating.

(Comparative Example 1)
The white paste A obtained in (2) of Example 1 was applied to the surface of a 0.7 mm thick glass plate with a spin coater, and the obtained coating film was cured by heating at 230 ° C. for 30 minutes to obtain a thickness. A white layer of 15 μm was formed to produce a white laminate of Comparative Example 1. This white laminate was reheated at 250 ° C. for 120 minutes. The hue (a * value, b * value) and whiteness (L * value) of Comparative Example 1 and the white laminate after reheating were measured in the same manner as in Example 1. The results are shown in FIGS.

(Comparative Example 2)
(1) Preparation of toning agent A C.I. I. Pigment Violet 37 (trade name: Chromophthal Violet D5700, manufactured by BASF Japan Ltd., hereinafter referred to as “PV37”) / C.I. I. Pigment Red 122 (trade name: Chromofine Magenta 6887, manufactured by Dainichi Seika Kogyo Co., Ltd., hereinafter referred to as “PR122”) / acrylic dispersant (trade name: Disperbyk-LPN6919, manufactured by Big Chemie Japan Co., Ltd.) / Propylene glycol monomethyl ether acetate (PMA, solvent) is mixed at a ratio of 8/2/5/85 (weight ratio), 4 times the amount of 0.5 mm zirconia beads is added to the mill base, and the mixture is stirred and dispersed for 1.5 hours. Colorant A was prepared.

(2) Preparation of White Paste B To the white paste A obtained in (2) of Example 1, the hue (a *, b *) of the heat-cured layer was the hue of the phosphor layer obtained in Example 1 ( The toning agent A obtained above was added and mixed so as to coincide with a *, b *) to prepare a white paste B.

(3) Production of White Laminate A white layer having a thickness of 15 μm was formed in the same manner as Comparative Example 1 except that the white paste B obtained above was used instead of the white paste A, and the white laminate of Comparative Example 2 was formed. The body was made. This white laminate was reheated at 250 ° C. for 120 minutes. The hue (a * value and b * value) and whiteness (L * value) of Comparative Example 2 and the white laminate after reheating were measured in the same manner as in Example 1. The results are shown in FIGS.

(Comparative Example 3)
(1) Preparation of toning agent B PV37 / C.I. I. Pigment Blue 15: 6 (trade name: EP-207, manufactured by DIC Corporation, hereinafter referred to as “PB15: 6”) / C, I. Pigment Red 177 (trade name: SR4C, hereinafter referred to as “PR177”) / C.I. I Pigment Violet 23 (trade name: Fast Violet 2382, manufactured by Sanyo Dye Co., Ltd., hereinafter referred to as “PV23}”) / acrylic dispersant (Disperbyk-LPN6919) /PMA=6/1.1/0.1/0 Mixing at a ratio of 8/4/88 (weight ratio), adding 4 times the amount of 0.5 mm zirconia beads to the mill base and stirring and dispersing for 1.5 hours, toning agent B was prepared.

(2) Preparation of white paste C The phosphor layer obtained in Example 1 in which the hue (L *, a *, b *) of the heat-cured layer was added to the white paste A obtained in (2) of Example 1. The toning agent B obtained above was added and mixed so as to match the hues (L *, a *, b *) of the above to prepare a white paste C.

(3) Production of white laminate Using the white paste C obtained above instead of the white paste A, the L * value from the glass plate side of the white layer after curing is L * of the white laminate of Comparative Example 2. The coating amount of the white paste C was adjusted so as to substantially match the value, and the obtained coating film was heated and cured at 230 ° C. for 30 minutes to form a white layer having a thickness of about 20 μm. A white laminate was produced. This white laminate was reheated at 250 ° C. for 120 minutes. The hue (a * value, b * value) and whiteness (L * value) of Comparative Example 3 and the white laminate after reheating were measured in the same manner as in Example 1. The results are shown in FIGS.

  1 to 2, the white laminate of Example 1 has an a * value and b * value which are indicators of hue, and the a * value before heating is −0.2 which is very close to “0”. The b * value is close to −2.5, the fluctuation range of the a * value and the b * value is small even after reheating, and the L * value, which is an index of whiteness, is approximately similar to 89.0 before and after reheating. It can be seen that the white laminate is stable at the measured values and has very high heat resistance. Further, regarding the color change with respect to the yellowishness, although it is not sufficiently clear by mechanical measurement, according to visual observation, Example 1 has a very light yellowishness as compared with Comparative Example 1, and whiteness It was revealed that the white color was high, particularly pure white with a remarkable whiteness under sunlight.

  In Comparative Example 1, since all fluctuations of the a * value, the b * value, and the L * value are small before and after the reheating, it can be confirmed that the white pigment has high heat resistance, and the L * value is carried out. Since it is almost the same as Example 1, it can also be confirmed that the whiteness is high, but the a * value and the b * value are significantly larger than Example 1 regardless of before and after the reheating, which is yellowish. This is considered to be one of the causes of whiteness. Moreover, it became clear by the visual comparison with Example 1 mentioned above and the comparative example 1 that the comparative example 1 exhibits yellowish white.

  Comparative Example 2 to which an organic pigment was added was greatly inferior to Example 1 before and after reheating with respect to the L * value, and smaller than Example 1 before reheating with respect to the a * value and b * value, Although it is a good value, after reheating, the decrease in the a * value and the increase in the b * value are more significant than in Example 1, the whiteness of the white pigment is impaired by the addition of the organic pigment, and The low heat resistance of the organic pigment was confirmed.

  Comparative Example 3 in which an organic pigment was added so as to adjust the whiteness showed a value close to that of Example 1 even though it could not be said to be the same level as Example 1 before and after reheating with respect to the L * value. Regarding the * value and the b * value, the level before the reheating was almost the same as that in Example 1, but the decrease in the a * value and the increase in the b * value after the reheating were extremely remarkable. The low heat resistance of the organic pigment was confirmed.

(Examples 2 to 4 and Comparative Example 4)
Example 2 uses BaMgAl ₁₀ O ₁₇ (trade name: PDB-B (H), manufactured by Nemotomi Material Co., Ltd.) instead of Sr ₅ (PO ₄ ) ₃ Cl: Eu as a blue inorganic phosphor. 3 uses Sr ₅ (PO ₄ ) ₃ Cl: Eu as the blue inorganic phosphor, and Example 4 uses BaMgAl ₁₀ O ₁₇ (trade name: in place of Sr ₅ (PO ₄ ) ₃ Cl: Eu as the blue inorganic phosphor. Comparative Example 4 was replaced with a blue inorganic phosphor as a red inorganic phosphor (Y ₂ O ₂ S: Eu, trade name: D1124, manufactured by Nemotomi Material Co., Ltd.). In the same manner as in Example 1, except that 230 ° C. × 30 minutes + 250 ° C. × 120 minutes is employed as the heat curing condition, and the thickness of the phosphor layer is 2 μm or 5 μm. Two types of white laminate with different thickness It was produced.

  For each of the two types of white laminates obtained in Example 2 (▲), Example 3 (■), Example 4 (♦), and Comparative Example 4 (●), the hue was determined in the same manner as in Example 1 and the like. (A * value, b * value) were measured. The results are shown in FIG. In FIG. 3, among the two spots in each example, each spot on the right side of the drawing shows a case where the thickness of the phosphor layer is 10 μm, and a spot on the left side of the drawing shows a case where the thickness of the phosphor layer is 5 μm. Show. From FIG. 3, it can be seen that the white laminates of Examples 2 to 4 have high whiteness at any film thickness. Moreover, according to visual observation, the white laminated body of Examples 2-4 became large in the color change effect with respect to the yellowishness derived from a white pigment, and exhibited white with high whiteness.

  On the other hand, the white laminate of Comparative Example 4 using the red inorganic phosphor has a low a * value and a high b * value, and thus the whiteness is further lost when the film thickness is increased. I know that. Moreover, according to visual observation, the white laminated body of the comparative example 4 was exhibiting yellowish green.

Claims (7)

  A fluorescent pigment dispersion containing a blue inorganic phosphor that has a main absorption region in a wavelength range of 400 nm or less and an emission peak in a wavelength range of 430 nm to 480 nm and emits blue fluorescence, and a silicone resin body.   The fluorescent pigment dispersion according to claim 1, comprising 5 to 200 parts by weight of the silicone resin with respect to 100 parts by weight of the blue inorganic phosphor.   The fluorescent pigment dispersion according to claim 1 or 2, wherein the blue inorganic phosphor is at least one selected from the group consisting of a europium activated halophosphate phosphor and a europium activated aluminate phosphor. . The europium activated halophosphate phosphor is
General formula (1): (Sr, Ca) _a (Ba) _b (Eu) _c (PO ₄ ) _d (Cl) _{e wherein} a and b are a + b = 5-c and 0.12 ≦ { b / (a + b)} ≦ 0.4. 0.3 ≦ c ≦ 1.2, 2.7 ≦ d ≦ 3.3, and 0.9 ≦ e ≦ 1. ] A phosphor (1) represented by
General formula (2): (Sr _1-xy Ba _x Ca _y ) ₅ (PO ₄ ) ₃ (Cl) (Eu) [wherein 0 ≦ x <0.5, 0 ≦ y <0.1] phosphors (2), and general formula _{(3) :( Sr 1-xyz} M x Ca y Eu z) 5 (PO 4) 3 (Cl) wherein, x and y are as defined above. M represents Ba and / or Mg. 0.005 <z <0.1. ]
The fluorescent pigment dispersion according to claim 3, which is at least one selected from the group consisting of phosphors (3) represented by: The europium activated aluminate phosphor is an alkaline earth metal aluminate phosphor, and the alkaline earth metal aluminate phosphor is
Phosphor (4) represented by the general formula (4): BaMgAl ₁₀ O ₁₇ : Eu,
Phosphor (5) represented by the general formula (5): (Ba, Sr) MgAl ₁₀ O ₁₇ : Eu,
Formula _{(6): Ba 1-p} MgAl 10 O 17: in Eu _p [Formula is 0.03 ≦ p ≦ 0.2. And a phosphor (6) represented by
General formula (7): Ba _1-pq M _q MgAl ₁₀ O ₁₇ : Eu _p [wherein p is the same as defined above. M represents Sr and / or Ca. 0.1 ≦ q ≦ 0. The fluorescent pigment dispersion according to claim 3, which is at least one selected from the group consisting of phosphors represented by the formula (7):   A white layer containing an inorganic white pigment, and a phosphor layer laminated on one surface of the white layer and formed using the phosphor pigment dispersion according to any one of claims 1 to 5. Contains white laminate.   The white laminate according to claim 6, further comprising a transparent substrate layer, wherein the transparent substrate layer, the phosphor layer, and the white layer are laminated in this order.

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