JP2018172253A - Intermediate film for laminated glass, and laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an intermediate film for laminated glass which can display an image with high contrast while securing safety by application of an up-conversion function, and can maintain the up-conversion function over a long period of time, and to provide a laminated glass.SOLUTION: An intermediate film for laminated glass contains lanthanoid-containing inorganic fine particles having an up-conversion function and a binder resin, where the lanthanoid-containing inorganic fine particles having the up-conversion function have a coating layer with a thickness of 10-1,500 nm.SELECTED DRAWING: None

Description

The present invention provides a laminated glass capable of displaying a high-contrast image or the like while ensuring safety by providing an up-conversion function and maintaining the up-conversion function for a long period of time. The present invention relates to an interlayer film and laminated glass.

Inorganic fine particles having an “up-conversion” function for converting long-wavelength light such as infrared light into short-wavelength light such as visible light and ultraviolet light are expected to be applied to medical uses such as biomarkers. In recent years, highly functional materials having an up-conversion function by dispersing such inorganic fine particles in a matrix material have attracted attention.
As inorganic fine particles having an upconversion function, those containing mainly lanthanoid elements are known, and a phenomenon called “multiphoton excitation” due to the energy level difference of these elements is used.

On the other hand, it is known that upconversion fluorescence can be generated in the visible region on the short wavelength side by irradiating glass containing a lanthanoid element with infrared rays. For example, Patent Document 1 discloses that an upconversion glass containing heavy metal oxides such as TeO ₂ , Ga ₂ O ₃ , PbO, Bi ₂ O ₃ , GeO _{2 and the} like and Er ₂ O ₃ as a rare earth element oxide is 560 to 565 nm. It is described that light emission having a peak in the vicinity can be obtained.
Patent Document 2 discloses a laminated glass in which an intermediate layer containing hydroxyterephthalate is laminated between two transparent plates. In such a laminated glass, information can be displayed by irradiating specific light.
However, there is a problem in safety because an excitation ultraviolet laser is used as irradiation light.

JP-A-3-295828 International Publication WO2010 / 139889 Pamphlet

In view of the above situation, the present invention can display a high-contrast image or the like while ensuring safety by providing an up-conversion function, and maintain the up-conversion function for a long period of time. An object is to provide an interlayer film for laminated glass and a laminated glass.

The present invention includes a lanthanoid-containing inorganic fine particle having an up-conversion function and a binder resin, and the lanthanoid-containing inorganic fine particle having an up-conversion function is an interlayer film for laminated glass having a coating layer having a thickness of 10 to 1500 nm. is there.
The present invention is described in detail below.

By adding lanthanoid-containing inorganic fine particles having an upconversion function to the interlayer film for laminated glass, the present inventors can impart an upconversion function, and as a result, while ensuring safety, It has been found that a contrast image can be displayed.
On the other hand, when only the lanthanoid-containing inorganic fine particles having an up-conversion function are added, there is a problem that the light intensity after wavelength conversion decreases when used for a long time.
On the other hand, the present inventors have found that the upconversion function can be maintained over a long period of time by using the lanthanoid-containing inorganic fine particles having a coating layer having a predetermined thickness. It came to complete.

The interlayer film for laminated glass of the present invention contains lanthanoid-containing inorganic fine particles having an up-conversion function. The lanthanoid-containing inorganic fine particles having the up-conversion function have a coating layer (hereinafter, the lanthanoid-containing inorganic fine particles having a coating layer are also referred to as up-conversion-coated inorganic fine particles).
By including the above-mentioned upconversion-coated inorganic fine particles, the interlayer film for laminated glass of the present invention has an “upconversion” function for converting long-wavelength light such as infrared light into short-wavelength light such as visible light and ultraviolet light. Is granted. This makes it possible to generate short-wavelength light by using high-safety infrared light or the like without using ultraviolet rays or the like, and as a result, display a high-contrast image or the like on the laminated glass. It becomes possible.
In the present invention, the “up-conversion function” refers to a function of converting long-wavelength light such as infrared light into short-wavelength light such as visible light or ultraviolet light.
In addition, by having the coating layer, the upconversion-coated inorganic fine particles become extremely durable particles, and as a result, the upconversion function can be maintained for a long period of time.

The interlayer film for laminated glass of the present invention may have a multilayer structure as long as it contains upconversion-coated inorganic fine particles and a binder resin. For example, a multilayer structure containing an upconversion layer containing upconversion-coated inorganic fine particles and a binder resin and a first resin layer containing a thermoplastic resin may be used. By having other layers such as the first resin layer in addition to the up-conversion layer, it is possible to impart other functions to the interlayer film for laminated glass while maintaining high-contrast light emission. .
The interlayer film for laminated glass of the present invention includes a first resin layer containing a thermoplastic resin, an upconversion layer containing upconversion-coated inorganic fine particles having an upconversion function and a binder resin, and a second resin containing a thermoplastic resin. The resin layers are preferably laminated in this order in the thickness direction. By laminating the first resin layer, the up-conversion layer, and the second resin layer in this order in the thickness direction, the adhesiveness to the glass is moderately maintained while maintaining high-contrast light emission. The laminated glass which can be adjusted and was excellent in scattering prevention property can be obtained.

The coating layer preferably contains a metal oxide. Especially, since the refractive index difference with a resin layer can be made small, it is preferable to contain a silicon oxide.
Examples of the silicon oxide include silica, a silica compound obtained from a silica precursor such as TEOS (tetraethyl orthosilicate), an alkoxysilane such as tetramethoxysilane and tetraethoxysilane, and polysilazane, a hydrolysis catalyst composition, a liquid Examples thereof include a silica compound obtained by hydrolysis / condensation from a solvent and water.

The coating layer may contain an organic component. The organic component preferably contains a polymer, particularly preferably an amphiphilic polymer.
Examples of the amphiphilic polymer include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl acetal, cellulose, cellulose derivatives, polyamylamine, and polyvinylamine. Among these, an amphiphilic polymer having a hydrogen bonding functional group is preferable, and polyvinyl pyrrolidone is particularly preferable.

The preferable lower limit of the average molecular weight of the amphiphilic polymer is 5000, and the preferable upper limit is 1,000,000. Aggregation between particles can be prevented when the molecular weight is 5000 or more.

The lower limit of the thickness of the coating layer is 10 nm, and the upper limit is 1500 nm. When the thickness of the coating layer is 10 nm or more, the up-conversion function can be maintained over a long period of time, and when the thickness of the coating layer is 1500 nm or less, the up-conversion function itself is deteriorated. Can be prevented.
The preferable lower limit of the thickness of the coating layer is 20 nm, and the preferable upper limit is 1000 nm.

As the particle size of the lanthanoid-containing inorganic fine particles having an up-conversion function before coating, the preferable lower limit of the average particle size of the primary particles is 10 nm, and the preferable upper limit is 1000 nm. When the average particle diameter is 10 nm or more, it is possible to suitably prepare up-conversion-coated inorganic fine particles, and when it is 1000 nm or less, it is possible to maintain transparency.
The “average particle diameter” indicates a volume average particle diameter. The volume average particle diameter can be measured using, for example, a particle size distribution analyzer (“UPA-EX150” manufactured by Nikkiso Co., Ltd.), a dynamic light scattering analyzer (manufactured by PSS-NICOMP, 380DLS), and the like.

The coating layer may contain conventionally known additives such as an antioxidant, a light stabilizer, a surfactant, a flame retardant, an antistatic agent, a moisture resistant agent, a heat ray reflective agent, and a heat ray absorbent.

The lanthanoid constituting the upconversion-coated inorganic fine particle is not particularly limited as long as it is a rare earth element that can be excited by light having a wavelength within a predetermined range and can emit upconversion, for example, erbium. (Er), holmium (Ho), praseodymium (Pr), thulium (Tm), neodymium (Nd), gadolinium (Gd), europium (Eu), ytterbium (Yb), samarium (Sm), cerium (Ce), etc. Can be mentioned. These lanthanoids may be used alone or in combination of two or more.
Especially, each combination of erbium, holmium, thulium, and ytterbium whose wavelength obtained is a visible light region is preferable. Among them, a combination of ytterbium having strong absorption in the vicinity of 10000 cm ⁻¹ and at least one selected from erbium, holmium, and thulium, which emits light upon receiving energy transfer from ytterbium, and whose wavelength is in the visible light region. Is preferred.

When the upconversion-coated inorganic fine particles contain ytterbium and at least one selected from erbium, holmium, and thulium, the ytterbium content (A) in the upconversion-coated inorganic fine particles, erbium, holmium, and thulium The ratio (A / B) to at least one selected content (B) is preferably 1 in terms of atomic composition ratio, more preferably 5 in the lower limit, 50 in the preferred upper limit, and 40 in the more preferred upper limit. The ratio (A / B) of the ytterbium content (A) in the up-conversion-coated inorganic fine particles and at least one content (B) selected from erbium, holmium and thulium is not less than the preferred lower limit, and When the ytterbium is used in combination with at least one lanthanoid selected from erbium, holmium and thulium, the energy absorbed by the ytterbium is uniformly and uniformly within the upconversion-coated inorganic fine particles. Since it can move to at least one lanthanoid selected from erbium, holmium, and thulium, the efficiency of the obtained up-conversion light emission is high.

As the particle size of the upconversion-coated inorganic fine particles, a preferable lower limit of an average particle size of primary particles is 15 nm, and a preferable upper limit is 2500 nm. The “average particle diameter” indicates a volume average particle diameter. The volume average particle diameter can be measured using a particle size distribution measuring device (“UPA-EX150” manufactured by Nikkiso Co., Ltd.), a dynamic light scattering analyzer (manufactured by PSS-NICOMP, 380DLS), and the like.

The content of the upconversion-coated inorganic fine particles in the interlayer film for laminated glass of the present invention is not particularly limited, but the preferred lower limit of the content of the upconversion-coated inorganic fine particles is 0.0001 with respect to 100 parts by mass of the binder resin. A mass part, a more preferable minimum is 0.01 mass part, a preferable upper limit is 20 mass parts, and a more preferable upper limit is 10 mass parts. When the content of the upconversion-coated inorganic fine particles is within the preferable range, light having a sufficiently high contrast can be obtained when light having a specific wavelength is irradiated.
Further, in 100% by mass of the interlayer film for laminated glass of the present invention, the content of the upconversion-coated inorganic fine particles is preferably 0.00007% by mass or more, more preferably 0.007% by mass or more, preferably 12.5% by mass. % Or less, more preferably 6.7% by mass or less. When the content of the upconversion-coated inorganic fine particles in the interlayer film for laminated glass of the present invention is within the above preferable range, light emission with sufficiently high contrast can be obtained when light of a specific wavelength is irradiated.

In addition, the upconversion-coated inorganic fine particles may contain an element having an ionic radius similar to that of the lanthanoid or a crystallization structure or a compound thereof. The compound of an element having an ionic radius similar to that of the lanthanoid or a structure at the time of crystallization is preferably an oxide or a halide. Examples of the element having an ionic radius similar to that of the lanthanoid and a structure upon crystallization include rare earth elements other than the lanthanoid, and examples of the compound include oxides and halides of rare earth elements other than the lanthanoid. Examples of the rare earth element other than the lanthanoid include yttrium (Y) and scandium (Sc). Examples of the rare earth element compound other than the lanthanoid include oxides or halides of yttrium (Y) and scandium (Sc).
Among them, the upconversion-coated inorganic fine particles can be expected to have high efficiency in terms of energy transfer between lanthanoids and can be expected to improve luminous efficiency. Therefore, the upconversion-coated inorganic fine particles include yttrium (Y), yttrium oxide, or yttrium. It is preferable that the halide of this is included. The yttrium oxide is preferably Y ₂ O ₃ , and the yttrium halide is preferably NaYF ₄ .

The upconversion-coated inorganic fine particles contain Y ₂ O ₃ or NaYF ₄ as a compound of an element having an ionic radius similar to that of the lanthanoid or a structure upon crystallization, and ytterbium, erbium, holmium and It is preferable to contain at least one selected from the group consisting of thulium.

The total content of lanthanoids constituting the upconversion-coated inorganic fine particles is the atomic composition of the lanthanoid contained in the upconversion-coated inorganic fine particles and an element having an ionic radius similar to that of the lanthanoid and a structure at the time of crystallization. It is preferably 2 atomic% or more, more preferably 2.5 atomic% or more, preferably 50 atomic% or less, and 25 atomic% or less with respect to a total of 100 atomic% with respect to the ratio. Is more preferable. When the total content of lanthanoids constituting the upconversion-coated inorganic fine particles is not less than the preferred lower limit and not more than the preferred upper limit, the lanthanoid in the upconversion-coated inorganic fine particles has an ionic radius similar to that of the lanthanoid, Since substitution and doping can be performed without destroying the crystal structure composed of the element having the structure at the time of crystallization, the efficiency of energy transfer in the upconversion-coated inorganic fine particles can be maintained. The content of the lanthanoid constituting the upconversion-coated inorganic fine particles can be measured using, for example, a fluorescent X-ray analyzer (manufactured by Shimadzu Corporation, EDX-800HS).

The content of an element having an ionic radius similar to that of the lanthanoid or a structure at the time of crystallization has the lanthanoid contained in the upconversion-coated inorganic fine particles and an ionic radius similar to that of the lanthanoid or a structure at the time of crystallization. It is preferably 5 atomic% or more, more preferably 10 atomic% or more, preferably 98 atomic% or less, and preferably 80 atomic% or less with respect to 100 atomic% in total with the atomic composition ratio of the element. More preferably. When the content of an element having an ionic radius similar to that of the lanthanoid or a structure at the time of crystallization is not less than the preferable lower limit and not more than the preferable upper limit, the ordered arrangement of the crystal structure as a host material for doping the lanthanoid A structure can be formed, the efficiency of energy transfer in the upconversion-coated inorganic fine particles can be increased, and the luminous efficiency is improved. The content of an element having an ionic radius similar to that of the lanthanoid and a structure at the time of crystallization can be measured using, for example, a fluorescent X-ray analyzer (manufactured by Shimadzu Corporation, EDX-800HS).

The interlayer film for laminated glass of the present invention contains a binder resin.
The binder resin is preferably a thermoplastic resin, and specific examples include polyvinyl acetal resin, ethylene-vinyl acetate copolymer, ethylene-acrylic copolymer, polyurethane resin, polyvinyl alcohol resin, and polyester resin. Moreover, you may use thermoplastic resins other than these.
Especially, as said binder resin, since versatility is high, polyvinyl acetal resin is preferable. Further, when the interlayer film for laminated glass of the present invention has a multilayer structure and contains the upconversion layer, the binder resin contained in the upconversion layer is preferably a polyvinyl acetal resin or a polyester resin. . If the binder resin contained in the upconversion layer is a polyvinyl acetal resin, the adhesion with other layers other than the upconversion layer is improved. Moreover, if the binder resin which the said up conversion layer contains is a polyester resin, the long-term stability of an up conversion layer will improve.

The polyvinyl acetal resin can be produced, for example, by acetalizing polyvinyl alcohol with an aldehyde. The polyvinyl alcohol can be obtained, for example, by saponifying polyvinyl acetate. The degree of saponification of the polyvinyl alcohol is generally in the range of 80 to 99.8 mol%.

The preferable lower limit of the polymerization degree of the polyvinyl alcohol is 200, the more preferable lower limit is 500, the preferable upper limit is 3,000, and the more preferable upper limit is 2,500. When the polymerization degree is 200 or more, the penetration resistance of the laminated glass can be improved. When the polymerization degree is 3,000 or less, the moldability of the interlayer film for laminated glass is improved.

The aldehyde is not particularly limited. In general, an aldehyde having 1 to 10 carbon atoms is preferably used as the aldehyde. Examples of the aldehyde having 1 to 10 carbon atoms include propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, and n-nonylaldehyde. , N-decylaldehyde, formaldehyde, acetaldehyde, benzaldehyde and the like. Among these, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexylaldehyde or n-valeraldehyde is preferable, propionaldehyde, n-butyraldehyde or isobutyraldehyde is more preferable, and n-butyraldehyde is still more preferable. As for the said aldehyde, only 1 type may be used and 2 or more types may be used together.

From the viewpoint of further enhancing the adhesive strength of the interlayer film for laminated glass of the present invention, the content of hydroxyl groups (hydroxyl content) in the polyvinyl acetal resin is preferably in the range of 15 to 40 mol%. The more preferable lower limit of the hydroxyl group content is 18 mol%, and the more preferable upper limit is 35 mol%. Adhesive force can be improved more as the said hydroxyl group is 15 mol% or more. Further, when the hydroxyl group is 40 mol% or less, the flexibility of the interlayer film for laminated glass is enhanced, and the handling is improved.
The hydroxyl group content of the polyvinyl acetal resin is a value indicating the mole fraction obtained by dividing the amount of ethylene groups to which the hydroxyl group is bonded by the total amount of ethylene groups in the main chain, as a percentage. The amount of ethylene group to which the hydroxyl group is bonded can be determined, for example, by measuring the amount of ethylene group to which the hydroxyl group of polyvinyl alcohol as a raw material is bonded in accordance with JIS K6726 “Testing method for polyvinyl alcohol”. it can.

The preferable lower limit of the degree of acetylation (acetyl group amount) of the polyvinyl acetal resin is 0.1 mol%, the more preferable lower limit is 0.3 mol%, the still more preferable lower limit is 0.5 mol%, and the preferable upper limit is 30 mol%. A more preferable upper limit is 25 mol%, and a further preferable upper limit is 20 mol%.
When the degree of acetylation is 0.1 mol% or more, the compatibility between the polyvinyl acetal resin and the plasticizer can be enhanced. When the acetylation degree is 30 mol% or less, the moisture resistance of the interlayer film is increased.
The degree of acetylation is obtained by subtracting the amount of ethylene groups to which acetal groups are bonded and the amount of ethylene groups to which hydroxyl groups are bonded from the total amount of ethylene groups of the main chain, It is a value indicating the mole fraction obtained by dividing by the percentage. The amount of ethylene group to which the acetal group is bonded can be measured, for example, according to JIS K6728 “Testing method for polyvinyl butyral”.

The preferable lower limit of the degree of acetalization of the polyvinyl acetal resin (the degree of butyralization in the case of polyvinyl butyral resin) is 60 mol%, the more preferable lower limit is 63 mol%, the preferable upper limit is 85 mol%, and the more preferable upper limit is 75 mol%. A more preferred upper limit is 70 mol%.
When the degree of acetalization is 60 mol% or more, the compatibility between the polyvinyl acetal resin and the plasticizer increases. The reaction time required in order to manufacture polyvinyl acetal resin as the said acetalization degree is 85 mol% or less can be shortened. The degree of acetalization is a value indicating the mole fraction obtained by dividing the amount of ethylene groups to which acetal groups are bonded by the total amount of ethylene groups in the main chain, as a percentage.
The degree of acetalization was determined by measuring the degree of acetylation (acetyl group content) and the hydroxyl group content (vinyl alcohol content) according to JIS K6728 “Testing methods for polyvinyl butyral”. The fraction can be calculated and then calculated by subtracting the degree of acetylation and the hydroxyl content from 100 mol%.
When the polyvinyl acetal resin is a polyvinyl butyral resin, the acetalization degree (butyralization degree) and acetylation degree (acetyl group amount) were measured by a method in accordance with JIS K6728 “Testing methods for polyvinyl butyral”. It can be calculated from the result.

Examples of the polyester resin include polyalkylene terephthalate resin and polyalkylene naphthalate resin. Examples of the polyalkylene terephthalate resin include polyethylene terephthalate, polybutylene terephthalate, and poly-1,4-cyclohexanedimethylene terephthalate. Among them, the polyalkylene terephthalate resin is preferably a polyethylene terephthalate resin because it is chemically stable and the long-term stability when the upconversion-coated inorganic fine particles are dispersed is further enhanced. Examples of the polyalkylene naphthalate resin include polyethylene naphthalate and polybutylene naphthalate.

Moreover, when the interlayer film for laminated glass of the present invention has a multilayer structure and contains the first resin layer and the second resin layer, the first resin layer and the second resin layer are As a thermoplastic resin to contain, the resin similar to the thermoplastic resin illustrated in the above-mentioned binder resin can be used. In particular, the thermoplastic resin contained in the first resin layer and the second resin layer can be obtained by appropriately adjusting the adhesion to the glass and obtaining a laminated glass excellent in scattering prevention. Is preferably a polyvinyl acetal resin.

The interlayer film for laminated glass of the present invention may further contain a plasticizer.
The plasticizer is not particularly limited as long as it is usually used for a polyvinyl acetal resin, and a known plasticizer generally used as a plasticizer for an intermediate film can be used. Organic plasticizers such as organic organic acid esters and polybasic organic acid esters; and phosphoric acid plasticizers such as organic phosphoric acid and organic phosphorous acid. These plasticizers may be used alone or in combination of two or more, and are used properly according to the type of the polyvinyl acetal resin in consideration of compatibility with the resin.

The monobasic organic acid ester plasticizer is not particularly limited. For example, glycol such as triethylene glycol, tetraethylene glycol or tripropylene glycol, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid And glycol esters obtained by reaction with monobasic organic acids such as n-octylic acid, 2-ethylhexyl acid, pelargonic acid (n-nonyl acid) or decyl acid. Among them, triethylene glycol-dicaproate, triethylene glycol-di-2-ethylbutyrate, triethylene glycol-di-n-octylate, triethylene glycol-di-2-ethylhexyl ester, etc. A monobasic organic acid ester of glycol is preferably used.

The polybasic organic acid ester plasticizer is not particularly limited. For example, a polybasic organic acid such as adipic acid, sebacic acid or azelaic acid, and a linear or branched alcohol having 4 to 8 carbon atoms. And esters. Of these, dibutyl sebacic acid ester, dioctyl azelaic acid ester, dibutyl carbitol adipic acid ester and the like are preferably used.
The organophosphate plasticizer is not particularly limited, and examples thereof include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate, and the like.

Among these, triethylene glycol-di-ethyl butyrate, triethylene glycol-di-ethyl hexoate, triethylene glycol-di-butyl sebacate and the like are preferably used as the plasticizer.

The amount of the plasticizer is preferably 20 to 60 parts by mass with respect to 100 parts by mass of the binder resin. By setting it as 20 mass parts or more, the obtained intermediate film and laminated glass are excellent in impact absorption. By setting it as 60 mass parts or less, the optical film of the intermediate film or laminated glass obtained by bleeding out the plasticizer is obtained. It is possible to prevent the distortion from becoming large and the transparency and the adhesion between the glass and the intermediate film from being impaired. More preferably, it is 30-50 mass parts.

The interlayer film for laminated glass of the present invention may contain a dispersant such as glycerin ester or polycarboxylic acid for the purpose of improving the dispersibility of the upconversion-coated inorganic fine particles. The glycerin ester is not particularly limited. For example, decaglycerin monostearic acid ester, decaglycerin tristearic acid ester, decaglycerin decastearic acid ester, hexaglycerin monostearic acid ester, hexaglycerin distearic acid ester, hexaglycerin tristearic acid Ester, hexaglycerin pentastearate, tetraglyceryl monostearate, tetraglyceryl tristearate, tetraglycerin pentastearate, polyglyceryl stearate, glycerol monostearate, decaglycerin monooleate, decaglycerin Decaoleate, hexaglycerin monooleate, hexaglycerin pen Oleic acid ester, tetraglycerin monooleic acid ester, tetraglycerin pentaoleic acid ester, polyglycerin oleic acid ester, glycerol monooleate, 2-ethylhexanoic acid triglyceride, capric acid monoglyceride, capric acid triglyceride, myristic acid monoglyceride, myristic acid Triglyceride, decaglycerin monocaprylate, polyglycerin caprylate, caprylic triglyceride, decaglycerin monolaurate, hexaglycerin monolaurate, tetraglycerin monolaurate, polyglyceryl laurate, decaglycerine heptabehenic acid Esters, decaglycerin dodecavehenate, polyglycerin Henin esters, decaglycerol erucic acid ester, polyglycerol erucic acid esters, tetraglycerol condensed ricinoleate, hexaglycerol condensed ricinoleate, polyglycerol condensed ricinoleic acid ester and the like.
Among the glycerin esters, commercially available products include, for example, SY Glycer CR-ED (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., condensed ricinoleic acid polyglyceric acid ester), SY Glyster PO-5S (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., oleic acid hexaglycerin penta). Ester) and the like.
The polycarboxylic acid is not particularly limited, and examples thereof include a polycarboxylic acid polymer obtained by grafting polyoxyalkylene to a polymer having a carboxyl group in the main chain skeleton.
Among the polycarboxylic acids, commercially available products include, for example, Mariarim series (AFB-0561, AKM-0531, AFB-1521, AEM-3511, AAB-0851, AWS-0851, AKM-1511-60, manufactured by NOF Corporation. Etc.).

The content of the dispersant in the interlayer film for laminated glass of the present invention is preferably 1 part by mass, preferably 10,000 parts by mass, and more preferably 10 parts by mass with respect to 100 parts by mass of the upconversion-coated inorganic fine particles. The more preferred upper limit is 1000 parts by mass, the still more preferred lower limit is 30 parts by mass, and the still more preferred upper limit is 300 parts by mass. When the content of the dispersant is within the above range, the dispersibility of the upconversion-coated inorganic fine particles is improved, so that the transparency of the interlayer film for laminated glass is increased.

The interlayer film for laminated glass of the present invention preferably contains an ultraviolet shielding agent. The ultraviolet shielding agent includes an ultraviolet absorber. Conventionally known general ultraviolet shielding agents include, for example, metal ultraviolet shielding agents, metal oxide ultraviolet shielding agents, benzotriazole ultraviolet shielding agents, benzophenone ultraviolet shielding agents, triazine ultraviolet shielding agents, Examples thereof include benzoate-based ultraviolet shielding agents, malonic ester-based ultraviolet shielding agents, and oxalic acid anilide-based ultraviolet shielding agents.

Examples of the metallic ultraviolet shielding agent include platinum particles, particles in which the surface of the platinum particles is coated with silica, palladium particles, particles in which the surface of the palladium particles is coated with silica, and the like. The ultraviolet shielding agent is preferably not a heat shielding particle. The ultraviolet shielding agent is preferably a benzotriazole ultraviolet shielding agent, a benzophenone ultraviolet shielding agent, a triazine ultraviolet shielding agent or a benzoate ultraviolet shielding agent, and more preferably a benzotriazole ultraviolet shielding agent.

Examples of the metal oxide ultraviolet shielding agent include zinc oxide, titanium oxide, and cerium oxide. Furthermore, the surface may be coat | covered as said metal oxide type ultraviolet-ray shielding agent. Examples of the coating material on the surface of the metal oxide ultraviolet shielding agent include insulating metal oxides, hydrolyzable organosilicon compounds, and silicone compounds.
Examples of the insulating metal oxide include silica, alumina and zirconia. The insulating metal oxide has a band gap energy of 5.0 eV or more, for example.
Examples of the benzotriazole-based ultraviolet shielding agent include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole (“TinvinP” manufactured by BASF), 2- (2′-hydroxy-3 ′, 5 ′). -Di-t-butylphenyl) benzotriazole ("Tinvin 320" manufactured by BASF), 2- (2'-hydroxy-3'-t-butyl-5-methylphenyl) -5-chlorobenzotriazole (manufactured by BASF " Tinuvin 326 ") and 2- (2'-hydroxy-3 ', 5'-di-amylphenyl) benzotriazole (" Tinvin 328 "manufactured by BASF) and the like. The ultraviolet shielding agent is preferably a benzotriazole-based ultraviolet shielding agent containing a halogen atom, more preferably a benzotriazole-based ultraviolet shielding agent containing a chlorine atom, because of its excellent performance of absorbing ultraviolet rays.
Examples of the benzophenone-based ultraviolet shielding agent include octabenzone (“Chimasorb 81” manufactured by BASF).
Examples of the triazine-based ultraviolet shielding agent include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol (manufactured by BASF Corporation, “Tinuvin 1577FF”). ]) And the like.
Examples of the benzoate-based ultraviolet shielding agent include 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (manufactured by BASF, “tinuvin 120”).
Examples of the malonic ester-based ultraviolet shielding agent include malonic acid [(4-methoxyphenyl) -methylene] -dimethyl ester (manufactured by Clariant Japan, Hostavin).
PR-25) and the like.
Examples of the oxalic acid anilide ultraviolet shielding agent include 2-ethyl 2′-ethoxy-oxalanilide (manufactured by Clariant Japan, Sanduvor V SU).

The interlayer film for laminated glass of the present invention may contain heat ray shielding particles.
Although it does not specifically limit as said heat ray shielding particle, For example, a tin dope indium oxide (ITO) fine particle, an antimony dope tin oxide (ATO) fine particle, an aluminum dope zinc oxide (AZO) fine particle, an indium dope zinc oxide (IZO) fine particle, silicon At least one selected from the group consisting of doped zinc oxide fine particles, anhydrous zinc antimonate fine particles and lanthanum hexaboride fine particles is preferred.

As a compounding quantity of the said heat ray shielding particle, a preferable minimum is 0.005 mass part with respect to 100 mass parts of binder resin, and a preferable upper limit is 3 mass parts. By being 0.005 parts by mass or more, the infrared shielding effect can be sufficiently exerted, and the obtained interlayer film for laminated glass and laminated glass have sufficient heat shielding properties, and by being 3 parts by mass or less. The visible light transmittance of the obtained interlayer film for laminated glass and laminated glass is increased, and the haze can be reduced.

The interlayer film for laminated glass of the present invention comprises an organic or inorganic acid alkali metal salt or alkaline earth metal salt, an adhesive strength modifier such as a modified silicone oil; an antioxidant, a light stabilizer, a surfactant, a flame retardant. In addition, conventionally known additives such as an antistatic agent, a moisture-resistant agent, a heat ray reflective agent, and a heat ray absorbent may be contained.

The method for producing the interlayer film for laminated glass of the present invention is not particularly limited.For example, after performing the step of producing the upconversion-coated inorganic fine particles, the obtained upconversion-coated inorganic fine particles, the polyvinyl acetal resin, and Various additives to be added as necessary are kneaded using an extruder, plastograph, kneader, Banbury mixer, calender roll, etc., and this is subjected to ordinary film forming methods such as an extrusion method, a calender method, a press method, etc. Examples include a method of forming a film into a sheet.

In the step of preparing the upconversion-coated inorganic fine particles, for example, it is preferable to perform the coating step after first performing the step of preparing the lanthanoid-containing inorganic fine particles having an upconversion function.

Examples of the method for producing the lanthanoid-containing inorganic fine particles having the upconversion function include, for example, a precipitation step in which an alkali solution is added to a metal salt solution containing a lanthanoid to precipitate lanthanoid-containing hydroxide fine particles, and the lanthanoid-containing water. It is preferable to use a method having a firing step of firing oxide fine particles.

Examples of the metal salt containing the lanthanoid include, for example, lanthanoid nitrates, sulfates, phosphates, borates, silicates, vanadates and the like, lanthanoid carboxylates and sulfonates. Organic salts such as phenol salts, sulfinates, salts of 1,3-diketone compounds, thiophenol salts, oxime salts, aromatic sulfonamide salts, primary and secondary nitro compound salts, And lanthanoid chlorides.
Of these, nitrate is preferable.

The content of the metal salt containing the lanthanoid in the metal salt solution containing the lanthanoid has a preferable lower limit of 0.005 mol% and a preferable upper limit of 0.5 mol%. By setting the content to 0.005 mol% or more, the lanthanoid-containing hydroxide fine particles can be precipitated after adding the alkaline solution. By setting the amount to 0.5 mol% or less, hydroxide can be immediately deposited when the alkaline solution is dropped, and the particle size of the resulting lanthanoid-containing hydroxide fine particles can be easily controlled. The minimum with said more preferable content is 0.01 mol%, and a more preferable upper limit is 0.25 mol%.

Examples of the solvent used in the metal salt solution containing the lanthanoid include water and hydrophilic organic solvents such as alcohol. Of these, water is preferred.

Examples of the alkaline solution include those containing sodium hydroxide, calcium hydroxide, ammonia and the like.
The amount of the alkali solution added can be appropriately selected depending on the pH of the alkali solution and the type and concentration of the metal salt solution containing the lanthanoid.

In the precipitation step, it is preferable to further add a hardly thermally decomposable organic polymer. As a result, the hardly heat-decomposable organic polymer is adsorbed on the surface of the lanthanoid-containing hydroxide fine particles, so that in the subsequent firing step, the above-mentioned hardly heat-decomposable organic polymer is thermally decomposed to produce carbide. . This carbide can intervene between the fine particles to prevent coalescence of the fine particles obtained after the firing step.

Examples of the hardly heat decomposable organic polymer include soluble polymer compounds. Specifically, for example, polyvinyl alcohol, polycarboxylic acid, polycarboxylic anhydride, polyvinyl pyrrolidone, polyvinyl acetate, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, a copolymer of vinyl pyrrolidone and vinyl acetate, styrene and maleic anhydride And a copolymer with a product. Moreover, as said polycarboxylic acid and polycarboxylic acid anhydride, the comb-shaped polycarboxylic acid and comb-shaped polycarboxylic acid anhydride in which many linear branched chains exist with respect to the principal chain in the shape of a comb are preferable. By using the polycarboxylic acid and the polycarboxylic acid anhydride, it becomes easier to adsorb on the surface of the lanthanoid-containing hydroxide fine particles. As the comb-shaped polycarboxylic acid and the comb-shaped polycarboxylic acid anhydride, the polyoxyalkylene monoalkyl ether unit, the maleic anhydride unit, and the styrene unit are more easily adsorbed on the surface of the lanthanoid-containing hydroxide fine particles. It is preferably a maleic anhydride copolymer. As the maleic anhydride copolymer, Mariarim AKM-1511, Marialim AKM-0531, Marialim AFB-1521 (all manufactured by NOF Corporation) are more easily adsorbed on the surface of the lanthanoid-containing hydroxide fine particles. ) Is preferred.

It is preferable that the said heat-decomposable organic polymer has at least one functional group selected from the group consisting of a carboxyl group, a carbonyl group and a hydroxyl group. Thereby, it becomes easy to adsorb | suck to the surface of a lanthanoid containing hydroxide microparticles | fine-particles, and can fully exhibit the effect of this invention.

It is preferable that the said heat-decomposable organic polymer has a weight average molecular weight of 5,000 to 500,000. By setting the weight average molecular weight to 5000 or more, a sufficient effect can be obtained by remaining as a carbide during thermal decomposition. By setting it to 500,000 or less, the volume of the hardly thermally decomposable organic polymer does not become too large, and it becomes possible to uniformly adsorb the lanthanoid-containing hydroxide fine particles. The minimum with said more preferable weight average molecular weight is 10,000, and a more preferable upper limit is 250,000.

It is preferable that the addition amount of the said heat-degradable organic polymer is 0.025-0.25 mass% with respect to the metal salt solution whole quantity containing the lanthanoid after alkali solution addition. By making the addition amount 0.025% by mass or more, the amount of carbides interposed between the fine particles increases, and a sufficient effect can be obtained. By setting it as 0.25 mass% or less, the added alkali solution can be neutralized and it can prevent inhibiting precipitation of hydroxide fine particles. The minimum with said preferable addition amount is 0.05 mass%, and a preferable upper limit is 0.2 mass%.

The firing step is not particularly limited, and examples thereof include a method of firing using a muffle furnace, a tunnel furnace, a ceramic furnace, a gas furnace, an electric furnace, and the like. Note that the firing step is preferably performed in an air atmosphere. Moreover, you may perform a drying process before performing the said baking process.
The firing temperature in the firing step is preferably 700 to 1200 ° C.
By setting the firing temperature to 700 ° C. or higher, the thermal decomposition and oxidation of the hydroxide fine particles can be made sufficient, and desired oxide fine particles can be obtained. By setting it as 1200 degrees C or less, coalescence can be prevented and the coalescence by the intervention of carbide can be further suppressed.

You may perform a crushing process after performing the said baking process.
Examples of the crushing step include a method using a bead mill, a high energy ball mill, a high-speed conductor collision type airflow type pulverizer, a collision type pulverizer, a gauge mill, a medium agitation type mill, a high hydraulic pressure pulverizer and the like.

By performing the coating step on the lanthanoid-containing inorganic fine particles having an up-conversion function thus obtained, up-conversion-coated inorganic fine particles can be obtained.
Examples of the coating step include a step of adding a silica precursor to the obtained dispersion containing lanthanoid-containing inorganic fine particles having an upconversion function, a step of adding an amphiphilic polymer, and the like.
Specifically, it is preferable to use a method of depositing up-conversion-coated inorganic particles by performing a salting out after performing the step of adding a silica precursor to the dispersion.

The silica precursor is a compound that generates silica by physical and chemical changes. Examples of the silica precursor include TEOS (tetraethyl orthosilicate), alkoxysilane such as tetramethoxysilane and tetraethoxysilane, and polysilazane. Can be mentioned.

A laminated glass in which the interlayer film for laminated glass of the present invention is sandwiched between a pair of glass plates is also one aspect of the present invention.

The glass used for the laminated glass of the present invention is not particularly limited, and a commonly used transparent plate glass can be used. For example, float plate glass, polished plate glass, template plate glass, mesh plate glass, wire plate glass, colored Various glass such as glass plate, heat ray absorbing glass, etc .: organic glass such as polycarbonate plate: polymethyl methacrylate plate, etc. These glasses may be used alone or in combination of two or more. Especially, it is preferable to use heat ray absorption glass.
In addition, the laminated glass of this invention can be manufactured by a conventionally well-known method using the intermediate film for laminated glasses of this invention.

The use of the laminated glass of the present invention is not particularly limited, and examples thereof include an automobile windshield, a side glass, a rear glass, a roof glass; a glass part of a vehicle such as an aircraft or a train, and an architectural glass. Among these, it is particularly suitable for applications in which an image displayed during driving can be visually recognized, such as a windshield of an automobile.

According to the present invention, by providing an upconversion function, it is possible to display a high-contrast image or the like while ensuring safety and to maintain the upconversion function for a long period of time. An interlayer film for glass and a laminated glass can be provided.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
(1) Preparation of lanthanoid-containing inorganic fine particles 2.98 g of yttrium nitrate and ytterbium nitrate in an aqueous solution containing 0.1% by mass of comb-shaped polycarboxylic acid (maleic anhydride copolymer, Marialim AFB-1521, weight average molecular weight 50000) 0 .83 g and erbium nitrate 0.09 g were dissolved to prepare a metal ion solution 150 g.
Similarly, 2.81 g of potassium hydroxide was dissolved in 50 g of an aqueous solution to which 0.1 mass% of comb-shaped polycarboxylic acid was added to prepare an alkaline solution. Hydroxide fine particles were precipitated by gradually adding an alkali solution to the metal ion solution while stirring (the concentration of the comb-shaped polycarboxylic acid after the addition of the alkali solution was 0.1% by mass).
Then, after repeating the centrifugal separator (manufactured by Hitachi Koki Co., Ltd., CR21N) and washing by ultrasonic dispersion with addition of pure water several times, the obtained hydroxide fine particle dispersion was centrifuged using the centrifugal separator. It collect | recovered and it dried on 80 degreeC and the conditions for 24 hours. Then, the lanthanoid-containing inorganic fine particles were obtained by performing a baking treatment in an air atmosphere at 1000 ° C. for 1 hour using a baking furnace (manufactured by Advantech, KM-420).

(2) Preparation of lanthanoid-containing coated inorganic fine particles 50 mg of the obtained lanthanoid-containing inorganic fine particles were added to 50 ml of ethanol, and then subjected to ultrasonic treatment for 15 minutes. Further, 400 μl of tetraethyl orthosilicate (TEOS) and 24.0 ml of an aqueous ammonia solution (28%) were added, followed by stirring at 25 ° C. for 120 minutes and centrifugation at 5000 rpm for 30 minutes. Then, it wash | cleaned 3 times with diluted ethanol (distilled water: ethanol = 1: 1), and distilled water and ethanol were evaporated by the vacuum dryer (60 degreeC), and the lanthanoid containing covering inorganic particle was obtained.

(3) Production of interlayer film for laminated glass 0.02 g of the obtained lanthanoid-containing coated inorganic fine particles was added to 8.00 g of triethylene glycol di-2-ethylhexanoate (3GO) to prepare a luminescent solution. By fully kneading the total amount of the obtained dispersion and polyvinyl butyral resin (acetyl group amount 13 mol%, hydroxyl group amount 22 mol%, average polymerization degree 2300) (hereinafter PVB1) 20.00 g, A composition was prepared.
The obtained resin composition was sandwiched between polytetrafluoroethylene (PTFE) sheets, pressed through a spacer having a thickness of 800 μm with a hot press at 150 ° C. and 100 kg / cm ² for 10 minutes, and a thickness of 800 μm. An interlayer film for laminated glass was obtained.

(4) Manufacture of laminated glass The obtained interlayer film for laminated glass was cut into a size of 5 cm in length and 5 cm in width and sandwiched and laminated with a pair of clear glasses. The obtained laminate was vacuum-pressed while being held at 90 ° C. for 30 minutes with a vacuum laminator to be pressure-bonded. After the pressure bonding, pressure bonding was performed for 20 minutes using an autoclave under conditions of 140 ° C. and 14 MPa to obtain a laminated glass.

(Example 2)
Example 1 except that in (2) Preparation of lanthanoid-containing coated inorganic fine particles in Example 1 was changed to 100 μl of tetraethyl orthosilicate (TEOS) and 6.0 ml of an aqueous ammonia solution (28%). In the same manner, lanthanoid-containing inorganic fine particles, lanthanoid-containing coated inorganic fine particles, an interlayer film for laminated glass, and laminated glass were produced.

(Example 3)
Example 1 except that “(2) Preparation of lanthanoid-containing coated inorganic fine particles” in Example 1 was changed to adding 1000 μl of tetraethyl orthosilicate (TEOS) and 60.0 ml of an aqueous ammonia solution (28%). In the same manner, lanthanoid-containing inorganic fine particles, lanthanoid-containing coated inorganic fine particles, an interlayer film for laminated glass, and laminated glass were produced.

Example 4
In “(2) Preparation of lanthanoid-containing coated inorganic fine particles” in Example 1, (1) Fluoride-based lanthanoid having a commercially available up-conversion function instead of the lanthanoid-containing inorganic fine particles prepared in the preparation of the lanthanoid-containing inorganic fine particles The lanthanoid-containing coated inorganic fine particles, the interlayer film for laminated glass, and the laminated glass were prepared in the same manner as in Example 1 except that the contained inorganic fine particles NaYF ₄ : Yb: Er (manufactured by Sigma-Aldrich, volume average particle diameter 1000 nm) were used. Produced.

(Example 5)
Example 4 is the same as Example 4 except that 800 μl of tetraethyl orthosilicate (TEOS) and 48.0 ml of an aqueous ammonia solution (28%) are added in “(2) Preparation of lanthanoid-containing coated inorganic fine particles” in Example 4. Similarly, lanthanoid-containing coated inorganic fine particles, an interlayer film for laminated glass, and laminated glass were produced.

(Comparative Example 1)
A lanthanoid-containing inorganic fine particle, an interlayer film for laminated glass, and a laminated glass were produced in the same manner as in Example 1 except that “(2) Preparation of lanthanoid-containing coated inorganic fine particles” was not performed.

(Comparative Example 2)
Example 1 except that in (2) Production of lanthanoid-containing coated inorganic fine particles in Example 1 was changed to addition of 50 μl of tetraethyl orthosilicate (TEOS) and 3.0 ml of an aqueous ammonia solution (28%). In the same manner, lanthanoid-containing inorganic fine particles, lanthanoid-containing coated inorganic fine particles, an interlayer film for laminated glass, and laminated glass were produced.

(Comparative Example 3)
In “(2) Preparation of lanthanoid-containing coated inorganic fine particles” in Example 1, 1000 μl of tetraethyl orthosilicate (TEOS) and 60.0 ml of aqueous ammonia solution (28%) were added, followed by stirring at 40 ° C. for 120 minutes. Except for the above, in the same manner as in Example 1, lanthanoid-containing inorganic fine particles, lanthanoid-containing coated inorganic fine particles, an interlayer film for laminated glass, and laminated glass were produced.

(Evaluation)
The lanthanoid-containing inorganic fine particles, the lanthanoid-containing coated inorganic fine particles, the interlayer film for laminated glass and the laminated glass obtained in Examples and Comparative Examples were evaluated by the following methods. The results are shown in Table 1.

(1) Measurement of average particle diameter The volume average particle diameter of the obtained lanthanoid-containing inorganic fine particles and lanthanoid-containing coated inorganic fine particles was measured using a dynamic light scattering analyzer (PSS-NICOMP, 380DLS).

(2) Measurement of thickness of coating layer The obtained lanthanoid-containing coated inorganic particles were photographed with a microscope using a TEM. Using the obtained TEM photograph, the thickness of any 10 coating layers of the lanthanoid-containing coated inorganic particles was measured, and the average was taken as the thickness of the coating layer.

(3) Composition analysis of lanthanoid elements About the obtained lanthanoid-containing inorganic fine particles and commercially available fluoride lanthanoid-containing inorganic fine particles having an up-conversion function, an X-ray fluorescence analyzer (manufactured by Shimadzu Corporation, EDX-800HS) is used. The composition ratios of the elements constituting the obtained lanthanoid-containing inorganic fine particles and the commercially available fluoride lanthanoid-containing inorganic fine particles having an up-conversion function were measured. In addition, it calculated by making the sum total of the composition ratio of yttrium, ytterbium, and erbium into 100 atomic%.

(4) Confirmation of up-conversion function (fluorescence intensity ratio) before and after coating For the obtained lanthanoid-containing inorganic fine particles (before coating) and lanthanoid-containing coated inorganic particles (after coating), an infrared light generator (made by THORLABS, L980P300J) was used to measure fluorescence intensity (wavelength: 662 nm) when irradiated with light having a wavelength of 980 nm and an output of 300 mW using a fluorescence spectrophotometer (U-2700, manufactured by Hitachi High-Tech).
The case where the ratio of fluorescence intensity before and after coating (after coating / before coating) was 0.7 or more was evaluated as “◯”, and the case where it was less than 0.7 was evaluated as “x”.

(5) Confirmation of up-conversion function (fluorescence intensity ratio) before and after the durability test The obtained lanthanoid-containing coated inorganic particles (after coating) were left to stand for 1000 hours under conditions of 85% humidity and 85 ° C. went. Thereafter, the fluorescence intensity (wavelength: 662 nm) when irradiated with light having a wavelength of 980 nm and an output of 300 mW using an infrared generator (THORLABS, L980P300J) as an external light source is measured with a fluorescence spectrophotometer (manufactured by Hitachi High-Tech). , U-2700).
The case where the ratio of the fluorescence intensity before and after the endurance test (after the endurance test / before the endurance test) was 0.7 or more was evaluated as “◯”, and the case where it was less than 0.7 was evaluated as “×”.

According to the present invention, by providing an up-conversion function, it is possible to display a high-contrast image or the like while ensuring safety, and it is possible to maintain the up-conversion function for a long period of time. An interlayer film for laminated glass and laminated glass can be provided.

Claims (4)

An interlayer film for laminated glass comprising a lanthanoid-containing inorganic fine particle having an up-conversion function and a binder resin, wherein the lanthanoid-containing inorganic fine particle having an up-conversion function has a coating layer having a thickness of 10 to 1500 nm. . The interlayer film for laminated glass according to claim 1, wherein the binder resin is a polyvinyl acetal resin. The interlayer film for laminated glass according to claim 1 or 2, further comprising a plasticizer. A laminated glass, wherein the interlayer film for laminated glass according to claim 1, 2 or 3 is sandwiched between a pair of glass plates.