JP6660198B2 - Interlayer for laminated glass and laminated glass - Google Patents

Description

The present invention relates to an interlayer film for laminated glass and a laminated glass capable of providing an up-conversion function while displaying optical properties such as visible light transmittance and haze, and displaying an image without unevenness.

Inorganic fine particles having an "up-conversion" function of converting long-wavelength light such as infrared light into short-wavelength light such as visible light or ultraviolet light are expected to be applied to medical applications such as biomarkers. In recent years, high-performance 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 up-conversion function, those mainly containing a lanthanoid element are known, and a phenomenon called "multiphoton excitation" due to a difference in energy level between these elements is used.

On the other hand, it is known that a glass containing a lanthanoid element can be irradiated with infrared rays to generate up-conversion fluorescence in a visible region on the short wavelength side. For example, Patent Document 1 discloses that an up-conversion glass containing heavy metal oxides such as TeO ₂ , Ga ₂ O ₃ , PbO, Bi ₂ O ₃ , and GeO ₂ and Er ₂ O ₃ as a rare earth element oxide has a wavelength of 560 to 565 nm. It is described that light emission having a peak in the vicinity can be obtained.
Also, a laminated glass in which an intermediate layer containing lanthanoid-containing inorganic fine particles having an up-conversion function is laminated between two transparent plates is being studied. It is stated that such laminated glass can display information by irradiating infrared light of a specific wavelength.
However, the addition of particles causes deterioration of optical characteristics such as visible light transmittance and haze, and as another problem, the intensity of emission varies depending on the position at which information is displayed, and the image sometimes becomes uneven.

JP-A-3-295828

The present invention has been made in view of the above situation, and has an optical property such as visible light transmittance and haze, can be provided with an up-conversion function, and can display an image without unevenness. And to provide a laminated glass.

The present invention is an interlayer film for laminated glass containing lanthanoid-containing inorganic fine particles having an up-conversion function, a binder resin, and a dispersant.
Hereinafter, the present invention will be described in detail.

The interlayer film for a laminated glass of the present invention contains lanthanoid-containing inorganic fine particles having an up-conversion function.
By containing the lanthanoid-containing inorganic fine particles, the interlayer film for laminated glass of the present invention has an "up-conversion" function of converting long-wavelength light such as infrared light into short-wavelength light such as visible light or ultraviolet light. Granted. This makes it possible to generate short-wavelength light with high-safety long-wavelength light such as infrared light without using ultraviolet light or the like, thereby displaying a high-contrast image or the like on the laminated glass. It becomes possible.
Note that, 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.

The lanthanoid constituting the lanthanoid-containing inorganic fine particles 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 emit up-conversion light, and for example, yttrium ( Y), erbium (Er), holmium (Ho), praseodymium (Pr), thulium (Tm), neodymium (Nd), gadolinium (Gd), europium (Eu), ytterbium (Yb), samarium (Sm), cerium ( Ce) and the like. These lanthanoids may be used alone or in combination of two or more.
Of these, at least one selected from the group consisting of erbium, holmium, thulium, and ytterbium, whose wavelength is in the visible light range, is preferable. In addition, 10,000 cm ^-1
It is preferable to use a combination of ytterbium having a strong absorption in the vicinity and at least one selected from erbium, holmium and thulium, which emits light by receiving energy transfer from ytterbium and has a wavelength obtained in a visible light region.

When the lanthanoid-containing inorganic fine particles contain ytterbium and at least one selected from erbium, holmium and thulium, the content (A) of ytterbium in the lanthanoid inorganic fine particles and at least one selected from erbium, holmium and thulium Regarding the ratio (A / B) to one content (B), the lower limit is preferably 1, the more preferable lower limit is 5, the more preferable upper limit is 50, and the more preferable upper limit is 40 in atomic composition ratio.
The ratio (A / B) of the content (A) of ytterbium in the lanthanoid inorganic fine particles to the content (B) of at least one selected from erbium, holmium and thulium is equal to or more than the preferred lower limit and preferred. By being equal to or less than the upper limit, when using a combination of ytterbium and at least one lanthanoid selected from erbium, holmium and thulium, erbium and holmium in the lanthanoid-containing inorganic fine particles uniformly and without excess or deficiency in the energy absorbed by ytterbium. And at least one lanthanoid selected from thulium, the efficiency of the obtained up-conversion light emission is high.

The lanthanoid-containing inorganic fine particles are not particularly limited as long as they are made of a substance containing the lanthanoid. For example, those made of oxides, halides, and the like of the lanthanoid are preferable. The halide is preferably a fluoride. Further, the lanthanoid-containing inorganic fine particles are preferably a sodium salt or a potassium salt.

Regarding the particle diameter of the lanthanoid-containing inorganic fine particles, a preferable lower limit of the average particle diameter of the primary particles is 5 nm, and a preferable upper limit is 5 μm. When the average particle diameter is less than 5 nm, it may be difficult to substantially prepare the resin, and when it exceeds 5 μm, it may be difficult to maintain the transparency.
The above “average particle diameter” indicates a volume average particle diameter. The average particle size can be measured using a particle size distribution analyzer (“UPA-EX150” manufactured by Nikkiso Co., Ltd.), a dynamic light scattering analyzer (380DLS manufactured by PSS-NICOMP) or the like.

Further, the lanthanoid-containing inorganic fine particles may contain an element having a similar ionic radius or a structure at the time of crystallization, or a compound thereof, as the lanthanoid. The compound of the element having an ionic radius similar to that of the lanthanoid and a structure at the time of crystallization is preferably an oxide or a halide.
Examples of the element having an ionic radius and a structure at the time of crystallization similar to those of the lanthanoid include rare earth elements other than the lanthanoid, and examples of the compound include oxides and halides of the 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 compound of a rare earth element other than the lanthanoid include oxides and halides of yttrium (Y) and scandium (Sc). Above all, the lanthanoid-containing inorganic fine particles can be expected to have high efficiency with respect to energy transfer between lanthanoids and an improvement in luminous efficiency. Therefore, the lanthanoid-containing inorganic fine particles include yttrium (Y), yttrium oxide or yttrium halogen. It is preferable to include a compound. The oxide of yttrium is preferably Y ₂ O ₃ , and the halide of yttrium is preferably NaYF ₄ .

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

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

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

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

The interlayer film for a laminated glass of the present invention contains a binder resin.
The binder resin is preferably a thermoplastic resin, and specific examples thereof include a polyvinyl acetal resin, an ethylene-vinyl acetate copolymer, an ethylene-acrylic copolymer, a polyurethane resin, a polyvinyl alcohol resin, and a polyester resin. Further, other thermoplastic resins may be used.
Above all, polyvinyl acetal resin is preferable as the binder resin because of high versatility.

The polyvinyl acetal resin can be produced, for example, by acetalizing polyvinyl alcohol with an aldehyde. The polyvinyl alcohol is 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%.

A preferred lower limit of the degree of polymerization of the polyvinyl alcohol is 200, a more preferred lower limit is 500, a preferred upper limit is 3,000, and a more preferred upper limit is 2,500. When the degree of polymerization is 200 or more, the penetration resistance of the laminated glass can be improved. When the degree of polymerization 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 suitably used as the aldehyde. Examples of the aldehyde having 1 to 10 carbon atoms include n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, n-nonylaldehyde, and n-butylaldehyde. Decylaldehyde, formaldehyde, acetaldehyde, benzaldehyde and the like. Among them, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexylaldehyde and n-valeraldehyde are preferred, propionaldehyde, n-butyraldehyde and isobutyraldehyde are more preferred, and n-butyraldehyde is even more preferred. As the aldehyde, only one kind may be used, or two or more kinds may be used in combination.

From the viewpoint of further increasing the adhesive strength of the interlayer film for laminated glass of the present invention, the content of hydroxyl groups (the amount of hydroxyl groups) of the polyvinyl acetal resin is preferably in the range of 15 to 40 mol%. A more preferred lower limit of the hydroxyl content is 18 mol%, and a more preferred upper limit is 35 mol%. When the hydroxyl group is at least 15 mol%, the adhesive strength can be further increased. Further, when the hydroxyl group is at most 40 mol%, the flexibility of the interlayer film for laminated glass will be enhanced, and the handling will be good.
The hydroxyl group content of the polyvinyl acetal resin is a value obtained by dividing the amount of ethylene groups to which the hydroxyl groups are bonded by the total amount of ethylene groups in the main chain, and is expressed as a percentage. The amount of the ethylene group to which the hydroxyl group is bonded can be determined, for example, by measuring the amount of the ethylene group to which the hydroxyl group of the polyvinyl alcohol as a raw material is bonded in accordance with JIS K6726 “Testing method for polyvinyl alcohol”. it can.

A preferred lower limit of the acetylation degree (acetyl group content) of the polyvinyl acetal resin is 0.1 mol%, a more preferred lower limit is 0.3 mol%, a still more preferred lower limit is 0.5 mol%, and a preferred upper limit is 30 mol%. A more preferred upper limit is 25 mol%, and a still more preferred 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 increased. When the degree of acetylation is 30 mol% or less, the moisture resistance of the interlayer film is increased.
The degree of acetylation is calculated 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 in the main chain, and calculating the total amount of ethylene groups in the main chain. Is a value expressed as a percentage of the molar fraction obtained by dividing by. The amount of the ethylene group to which the acetal group is bonded can be measured, for example, according to JIS K6728 “Testing method for polyvinyl butyral”.

A preferred lower limit of the degree of acetalization of the polyvinyl acetal resin (degree of butyralization in the case of polyvinyl butyral resin) is 60 mol%, a more preferred lower limit is 63 mol%, a preferred upper limit is 85 mol%, and a more preferred upper limit is 75 mol%. The more preferable upper limit is 70 mol%.
When the acetalization degree is 60 mol% or more, the compatibility between the polyvinyl acetal resin and the plasticizer increases. When the degree of acetalization is 85 mol% or less, the reaction time required for producing a polyvinyl acetal resin can be reduced.
The degree of acetalization is a value 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 and expressing the molar fraction as a percentage.
The degree of acetalization is determined by measuring the degree of acetylation (amount of acetyl group) and the content of hydroxyl group (amount of vinyl alcohol) by a method based on JIS K6728 “Testing method for polyvinyl butyral”, and from the obtained measurement results, The fraction can be calculated by calculating the fraction, and then subtracting the degree of acetylation and the content of the hydroxyl group from 100 mol%.
In the case where the polyvinyl acetal resin is a polyvinyl butyral resin, the degree of acetalization (degree of butyralization) and the degree of acetylation (amount of acetyl group) were measured by a method based on JIS K6728 “Polyvinyl butyral test method”. It can be calculated from the result.

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 generally 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 basic 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. Depending on the compatibility with the resin and the like, these plasticizers are properly used depending on the type of the polyvinyl acetal resin.

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

The polybasic organic acid ester-based 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 the like. Among them, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate and the like are preferably used.
The organic phosphoric acid plasticizer is not particularly limited, and includes, for example, tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate and the like.

As the plasticizer, among them, triethylene glycol-di-ethyl butyrate, triethylene glycol-di-ethylhexoate, triethylene glycol-di-butyl sebacate and the like are preferably used.

The blending amount of the plasticizer is preferably 20 to 60 parts by mass with respect to 100 parts by mass of the binder resin. When the amount is less than 20 parts by mass, the resulting interlayer film or laminated glass may have insufficient shock absorption. When the amount exceeds 60 parts by mass, the plasticizer bleeds out to obtain an interlayer film or laminated glass. The optical distortion may be increased, or the transparency or the adhesion between the glass and the interlayer may be impaired. More preferably, it is 30 to 50 parts by mass.

The interlayer film for a laminated glass of the present invention contains a dispersant. Examples of the dispersant include a nonionic dispersant, an anionic dispersant, a cationic dispersant, and an amphoteric dispersant. Above all, since the interlayer film and laminated glass for laminated glass having high transparency and further suppressing unevenness of the displayed image can be obtained, the dispersant is a nonionic dispersant, an anionic dispersant and a cationic dispersant. It is preferably at least one selected from dispersants. As the nonionic dispersant, a nonionic glycerin ester is preferable. As the anionic dispersant, an anionic polycarboxylic acid, an anionic phosphate, and the like are preferable.

The nonionic glycerin ester is not particularly limited. For example, decaglycerin monostearate, decaglycerin tristearate, decaglycerin decastearate, hexaglycerin monostearate, hexaglycerin distearate, hexaglycerin tristearate Stearic acid ester, hexaglycerin pentastearate, tetraglycerin monostearate, tetraglycerin tristearate, tetraglycerin pentastearate, polyglycerin stearate, glycerol monostearate, decaglycerin monooleate, Decaglycerin decaoleate, hexaglycerin monooleate, hexaglyceride Phosphorus pentaoleate, tetraglycerin monooleate, tetraglycerin pentaoleate, polyglycerin oleate, glycerol monooleate, 2-ethylhexanoate triglyceride, capric monoglyceride, capric triglyceride, myristate monoglyceride, Myristate triglyceride, decaglycerin monocaprylate, polyglycerin caprylate, caprylate triglyceride, decaglycerin monolaurate, hexaglycerin monolaurate, tetraglycerin monolaurate, polyglycerin laurate, decaglycerin heptabehe Nitrate, decaglycerin decabehenate, poly Riserinbehenin 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 nonionic glycerin esters, commercially available products include, for example, SY Glyster CR310 (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., polyglycerin condensed ricinoleic acid ester) and Rheodol V430 (manufactured by Kao Corporation, polyoxyethylene sorbitol fatty acid ester). .

The anionic polycarboxylic acid is not particularly limited, and examples thereof include a polycarboxylic acid polymer, a polycarboxylic anhydride, a salt of a polycarboxylic acid polymer, and a salt of a polycarboxylic anhydride. Further, as the polycarboxylic acid polymer and the polycarboxylic anhydride, a comb-shaped polycarboxylic acid and a comb-shaped polycarboxylic acid anhydride in which a large number of linear branched chains having a carboxyl group with respect to the main chain are present in a comb shape. preferable. Further, as the salt of the polycarboxylic acid polymer and the salt of the polycarboxylic acid anhydride, a salt of a comb-shaped polycarboxylic acid and a comb-shaped salt in which a large number of linear branched chains having a carboxyl group with respect to the main chain are present in a comb shape. Salts of polycarboxylic anhydrides are preferred.
The comb-shaped polycarboxylic acid and the comb-shaped polycarboxylic anhydride are preferably polymers having a polyoxyalkylene monoalkyl ether unit. The salt of the comb-shaped polycarboxylic acid and the salt of the comb-shaped polycarboxylic anhydride are preferably a polymer salt having a polyoxyalkylene monoalkyl ether unit. As the salt of the polymer having a polyoxyalkylene monoalkyl ether unit, polyoxyethylene octyl ether phosphate is preferable. Among the above-mentioned polycarboxylic acids, commercially available products include, for example, NOF Mariaria Series AFB-0561, AKM-0531, AFB-1521, AEM-3511, AAB-0851, AWS-0851, AKM-1511-60, And Plysurf series M208F manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

The cationic dispersant is preferably a cationic ammonium salt, and particularly preferably a cationic quaternary ammonium salt. As the cationic quaternary ammonium salt, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, and alkylbenzyldimethylammonium chloride (benzalkonium chloride) are preferable. Commercial products of the above cationic quaternary ammonium salts include, for example, Sanizole C and Sanizol B-50 (manufactured by Kao Corporation).

The anionic dispersant is preferably an anionic phosphate, particularly preferably an anionic polyoxyethylene alkyl phosphate. Examples of the anionic polyoxyethylene alkyl phosphate include polyoxyethylene alkyl (C12, 13) ether phosphate, polyoxyethylene alkyl (C10) ether phosphate, and polyoxyethylene alkyl (C8) ether phosphate. Ester, polyoxyethylene tridecyl ether phosphate, polyoxyethylene lauryl ether phosphate, polyoxyethylene styrenated phenyl ether phosphate, and the like.

As the dispersing agent, a higher transparency, and an interlayer film and a laminated glass for a laminated glass in which unevenness of a displayed image is further suppressed are obtained, so that a nonionic glycerin ester, an anionic polycarboxylic acid and More preferably, it is at least one selected from cationic ammonium salts.

The content of the dispersant in the interlayer film for a laminated glass of the present invention is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the lanthanoid-containing inorganic fine particles. A more preferable lower limit is 0.5 part by mass, a more preferable upper limit is 80 parts by mass, a further preferable lower limit is 1 part by mass, a further preferable upper limit is 50 parts by mass, a particularly preferable lower limit is 5 parts by mass, and a particularly preferable upper limit is 30 parts by mass. is there. When the content of the dispersant is within the above range, the dispersibility of the lanthanoid-containing inorganic fine particles is improved, so that the transparency of the interlayer film for laminated glass and the dispersion of displayed images can be reduced.

Further, the content of the dispersant is preferably 0.01 to 3.2 parts by mass with respect to 100 parts by mass of the binder resin. A more preferred lower limit is 0.1 part by mass, a more preferred upper limit is 1.0 part by mass, a still more preferred lower limit is 0.2 part by mass, and a still more preferred upper limit is 0.4 part by mass. When the content of the dispersant is within the above range, an intermediate film having high transparency and having uniform light emission can be produced.

Further, the weight average molecular weight of the dispersant is desirably 100 to 8000. A more preferred lower limit is 300, a more preferred upper limit is 7000, a still more preferred lower limit is 400, and a still more preferred upper limit is 3,000. When the weight average molecular weight of the dispersant is within the above range, the dispersibility of the lanthanoid-containing inorganic fine particles is improved, so that the transparency of the interlayer film for laminated glass and the variation in the displayed image can be further reduced. it can.

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

Examples of the metal-based ultraviolet shielding agent include platinum particles, particles whose surfaces are coated with silica, palladium particles, and particles whose surfaces are coated with silica. It is preferable that the ultraviolet shielding agent is not a heat shielding particle. The ultraviolet shielding agent is preferably a benzotriazole-based ultraviolet shielding agent, a benzophenone-based ultraviolet shielding agent, a triazine-based ultraviolet shielding agent, or a benzoate-based ultraviolet shielding agent, and more preferably a benzotriazole-based ultraviolet shielding agent.

Examples of the metal oxide-based ultraviolet shielding agent include zinc oxide, titanium oxide, and cerium oxide. Furthermore, the surface may be coated as the metal oxide-based ultraviolet shielding agent. Examples of the coating material on the surface of the metal oxide-based ultraviolet shielding agent include an insulating metal oxide, a hydrolyzable organosilicon compound, and a silicone compound.
Examples of the insulating metal oxide include silica, alumina, and zirconia. The insulating metal oxide has a band gap energy of, for example, 5.0 eV or more.
Examples of the benzotriazole-based ultraviolet shielding agent include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole (“Tinuvin P” manufactured by BASF), 2- (2′-hydroxy-3 ′, 5 ′). -Di-t-butylphenyl) benzotriazole (“Tinuvin 320” manufactured by BASF), 2- (2′-hydroxy-3′-t-butyl-5-methylphenyl) -5-chlorobenzotriazole (manufactured by BASF) Tinuvin 326 "), and benzotriazole-based ultraviolet shielding agents such as 2- (2'-hydroxy-3 ', 5'-di-amylphenyl) benzotriazole (" Tinuvin 328 "manufactured by BASF). The ultraviolet ray shielding agent is preferably a benzotriazole type ultraviolet ray shielding agent containing a halogen atom, and more preferably a benzotriazole type ultraviolet ray shielding agent containing a chlorine atom, because of its excellent ability to absorb ultraviolet rays.
Examples of the benzophenone-based ultraviolet shielding agent include, for example, octabenzone (“Chimassorb 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, “Tinuvin 1577FF”). ") And the like.
Examples of the benzoate-based ultraviolet shielding agent include, for example, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (“tinuvin 120” manufactured by BASF).
As the malonic ester-based ultraviolet shielding agent, for example, malonic acid [(4-methoxyphenyl) -methylene] -dimethyl ester (manufactured by Clariant Japan, Hostavin)
PR-25) and the like.
Examples of the oxalic acid anilide-based ultraviolet shielding agent include, for example, 2-ethyl 2'-ethoxy-oxalanilide (manufactured by Clariant Japan, Sanduvor V SU).

The interlayer film for a laminated glass of the present invention may contain heat ray shielding particles.
The heat ray shielding particles are not particularly limited. For example, tin-doped indium oxide (ITO) fine particles, antimony-doped tin oxide (ATO) fine particles, aluminum-doped zinc oxide (AZO) fine particles, indium-doped zinc oxide (IZO) fine particles, silicon At least one selected from the group consisting of doped zinc oxide fine particles, anhydrous zinc antimonate and lanthanum hexaboride fine particles is preferable.

As for the compounding amount of the heat ray shielding particles, a preferable lower limit is 0.005 parts by mass and a preferable upper limit is 3 parts by mass based on 100 parts by mass of the binder resin. When the amount is less than 0.005 parts by mass, the infrared ray shielding effect is not sufficiently exhibited, and the obtained interlayer film for laminated glass or the heat shielding property of the laminated glass may not be sufficiently improved. Visible light transmittance of the interlayer film for laminated glass or laminated glass may be reduced, or haze may be increased.

The interlayer film for a laminated glass of the present invention is an adhesion modifier such as an alkali metal salt or an alkaline earth metal salt of an organic acid or an inorganic acid, and a modified silicone oil; an antioxidant, a light stabilizer, a surfactant, and a flame retardant. And a conventionally known additive such as an antistatic agent, a moisture resistant agent, a heat ray reflective agent, and a heat ray absorber.

The method for producing the interlayer film for laminated glass of the present invention is not particularly limited, for example, after performing a step of preparing lanthanoid-containing inorganic fine particles having an up-conversion function, the resulting lanthanoid-containing inorganic having an up-conversion function Fine particles, a binder resin such as a polyvinyl acetal resin, a dispersant, and various additives to be added as necessary are kneaded using an extruder, a plastograph, a kneader, a Banbury mixer, a calendar roll, and the like, and extruded. And a method of forming a film into a sheet by a normal film forming method such as a calendering method, a calendering method, and a pressing method.

In the step of producing the lanthanoid-containing inorganic fine particles having the up-conversion function, for example, an alkali solution is added to a lanthanoid-containing metal salt solution to precipitate lanthanoid-containing hydroxide fine particles, It is preferable to use a method having a firing step of firing the fine particles.

Examples of the metal salts containing the lanthanoid include lanthanoid nitrates, sulfates, phosphates, borates, silicates, vanadates and other oxyacid salts, and the lanthanoid carboxylate and sulfonates. Organic acid salts such as phenol salts, sulfinates, salts of 1,3-diketone compounds, thiophenol salts, oxime salts, salts of aromatic sulfonamides, salts of primary and secondary nitro compounds, Lanthanoid chloride and the like.
Of these, nitrates are preferred.

The preferred lower limit of the content of the lanthanoid-containing metal salt in the lanthanoid-containing metal salt solution is 0.005 mol%, and the preferred upper limit is 0.5 mol%. If the content is less than 0.005 mol%, lanthanoid-containing hydroxide fine particles may not be precipitated even when an alkali solution is added. If it exceeds 0.5 mol%, hydroxide may be immediately precipitated when the alkali solution is dropped, and it may be difficult to control the particle size of the obtained lanthanoid-containing hydroxide fine particles. A more preferred lower limit of the content is 0.01 mol%, and a more preferred upper limit is 0.25 mol%.

Examples of the solvent used for the lanthanoid-containing metal salt solution include water and hydrophilic organic solvents such as alcohols. Among them, water is preferred.

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

In the above-mentioned precipitation step, it is preferable to further add a thermally decomposable organic polymer. Thereby, since the hardly heat-decomposable organic polymer is adsorbed on the surface of the lanthanoid-containing hydroxide fine particles, in the subsequent firing step, carbides are generated by the heat-decomposable organic polymer being thermally decomposed. . By interposing the carbide between the fine particles, coalescence of the fine particles obtained after the firing step can be prevented.

Examples of the hardly thermally decomposable organic polymer include soluble polymer compounds. Specifically, for example, polyvinyl alcohol, polycarboxylic acid, polyvinyl pyrrolidone, polyvinyl acetate, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, a copolymer of vinyl pyrrolidone and vinyl acetate, a copolymer of styrene and maleic anhydride And the like. Further, as the polycarboxylic acid, a comb-shaped polycarboxylic acid is preferable.

It is preferable that the above-mentioned thermally 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 be adsorbed on the surface of the lanthanoid-containing hydroxide fine particles, and the effect of the present invention can be sufficiently exhibited.

It is preferable that the weight average molecular weight of the hardly heat decomposable organic polymer is 5,000 to 500,000. When the weight average molecular weight is less than 5,000, it is difficult to remain as a carbide at the time of thermal decomposition, and it may be difficult to obtain the effect. If it exceeds 500,000, the volume of the thermally decomposable organic polymer is so large that it may be difficult to uniformly adsorb the lanthanoid-containing hydroxide fine particles. A more preferred lower limit of the weight average molecular weight is 10,000, and a more preferred upper limit is 250,000.

The addition amount of the above-mentioned thermally decomposable organic polymer is preferably from 0.025 to 0.25% by mass based on the total amount of the lanthanoid-containing metal salt solution after the addition of the alkali solution. If the addition amount is less than 0.025% by mass, the amount of carbides interposed between the fine particles is reduced, so that a sufficient effect may not be obtained. If it exceeds 0.25% by mass, the added alkaline solution may be neutralized, which may hinder the precipitation of hydroxide fine particles. A more preferred lower limit of the addition amount is 0.05% by mass, and a more preferred upper limit is 0.2% by mass.

The firing step is not particularly limited, and examples thereof include a method of firing using a muffle furnace, a tunnel furnace, or the like, a pottery kiln, a gas furnace, an electric furnace, or the like. Note that the firing step is preferably performed in an air atmosphere. Further, a drying step may be performed before performing the above-described firing step.
The firing temperature in the firing step is preferably 700 to 1200 ° C.
When the calcination temperature is lower than 700 ° C., thermal decomposition and oxidation of the hydroxide fine particles become insufficient, so that desired oxide fine particles may not be obtained. If it exceeds 1200 ° C., coalescence is further promoted, and coalescence may not be able to be suppressed even by the presence of carbides.

After performing the above firing step, a crushing step may be performed.
Examples of the crushing step include a method using a bead mill, a high-energy ball mill, a high-speed conductor collision airflow crusher, a collision crusher, a gauge mill, a medium stirring mill, a high hydraulic crusher, and the like.

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

The glass used for the laminated glass of the present invention is not particularly limited, and generally 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 plate glass Various types of inorganic glass such as sheet glass and heat ray absorbing glass: polycarbonate plate: organic glass such as polymethyl methacrylate plate, and the like. These glasses may be used alone or in combination of two or more. Among them, it is preferable to use heat ray absorbing glass.
In addition, the laminated glass of this invention can be manufactured by the conventionally well-known method using the interlayer film for laminated glass of this invention.

The application of the laminated glass of the present invention is not particularly limited, and examples thereof include a windshield of an automobile, a side glass, a rear glass, and a roof glass; glass parts of vehicles such as aircraft and trains; and architectural glass. In particular, it is particularly suitable for applications such as a windshield of an automobile in which an image or the like displayed during driving can be visually recognized.

Advantageous Effects of Invention According to the present invention, an interlayer film for laminated glass and a laminated glass capable of providing an up-conversion function while displaying optical characteristics such as visible light transmittance and haze and displaying an image without unevenness can be provided. It is possible to provide.

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

( Reference Example 1)

(1) Production of interlayer film for laminated glass Into 10.00 g of triethylene glycol di-2-ethylhexanoate (3GO), lanthanoid-containing inorganic fine particles (Sigma Aldrich, sodium yttrium fluoride, ytterbium and erbium doped, particle size 1 to 1) 5 gm), 1.0 g of a dispersant (polyglycerin condensed ricinoleate, Sakamoto Yakuhin Kogyo, SY Glister CR310) and 30 g of zirconia beads having a particle diameter of 1 mm were added to a rocking mill RM-01DS (manufactured by Seiwa Giken Co., Ltd.). The bead mill was performed under the conditions of a speed of 8 and 30 minutes. This solution was filtered to prepare a luminescent solution. 4.42 g was weighed from the obtained luminescent solution, and polyvinyl butyral resin (PVB) (acetyl group content 0.7 mol%, hydroxyl group content 31 mol%, acetalization degree 0.7 mol%, average polymerization degree 1800) By sufficiently kneading 10.00 g, a resin composition was prepared.
The obtained resin composition is sandwiched between polytetrafluoroethylene (PTFE) sheets, and pressed with a hot press at 150 ° C. and 100 kg / cm ² for 2 minutes through a spacer having a thickness of 800 μm to form a resin having a thickness of 800 μm. An interlayer for laminated glass was obtained.
The composition ratio of each element constituting the lanthanoid-containing inorganic fine particles was measured for the lanthanoid-containing inorganic fine particles using an X-ray microanalysis system (Themo Fisher Scientific, Inc., NORAN System 7). Note that the composition ratio of each element was calculated assuming that the total atomic composition ratio of fluorine, sodium, yttrium, erbium, and ytterbium was 100 atomic%. The composition ratio of each element of the lanthanoid-containing inorganic fine particles was 62.1 atomic% of fluorine, 19.6 atomic% of sodium, 13.7 atomic% of yttrium, 1.1 atomic% of erbium, and 3.5 atomic% of ytterbium. .

(2) Production 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, sandwiched between a pair of clear glasses, and laminated. The obtained laminate was subjected to vacuum press and pressure bonding at 90 ° C. and 80 kPa for 50 seconds with a vacuum laminator. After the pressure bonding, pressure bonding was performed using an autoclave at 140 ° C. and 13 MPa for 20 minutes to obtain a laminated glass.

( Reference Example 2)
Same as Reference Example 1 except that in “(1) Production of interlayer film for laminated glass” of Reference Example 1, the content of the dispersant was changed to 0.2 g, and 4.48 g was measured and taken from the luminescent solution. In this way, an interlayer film for laminated glass and a laminated glass were produced.

( Reference Example 3)
In "(1) laminated glass production intermediate film" in the Reference Example 1, the content of the dispersing agent was changed to 0.3 g, except that O'TRI Measure 4.52g from the light-emitting solution, similarly as in Reference Example 1 In this way, an interlayer film for laminated glass and a laminated glass were produced.

( Reference Example 4)
In "(1) laminated glass production intermediate film" in the Reference Example 1, except that the content of the dispersing agent was changed to 0.4 g, was O'to take measure to 4.56g from the dispersion, the same manner as in Reference Example 1 In this way, an interlayer film for laminated glass and a laminated glass were produced.

(Comparative Example 1)
In "(1) laminated glass production intermediate film" in the Reference Example 1, except that no blending dispersant in the same manner as in Reference Example 1 to obtain a glass intermediate film, and laminated glass combined.

(Example 5)
In "(1) Production of interlayer film for laminated glass" in Reference Example 1, the type and content of the dispersant were changed to 0 (polyoxyethylene octyl ether phosphate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Plysurf M208F). 0.2 g, and an interlayer film for laminated glass and a laminated glass were produced in the same manner as in Reference Example 1 except that 4.48 g was measured from the dispersion.

(Example 6)
In “(1) Production of interlayer film for laminated glass” of Reference Example 1, the content of the lanthanoid-containing inorganic fine particles was changed to 0.1 g, and the type and content of the dispersant were changed to the dispersant (Daiichi Kogyo Seiyaku Co., Ltd.). , Plysurf M208F) was changed to 0.02 g, and an interlayer film for laminated glass and a laminated glass were produced in the same manner as in Reference Example 1 except that 4.048 g was measured and taken from the dispersion.

(Example 7)
In “(1) Production of interlayer film for laminated glass” in Reference Example 1, the content of the lanthanoid-containing inorganic fine particles was changed to 0.1 g, and the type and content of the dispersant were changed to the dispersant (Sanisol C, manufactured by Kao Corporation). : Alkylbenzyldimethylammonium chloride [alkyl C8-18]) In the same manner as in Reference Example 1, except that the dispersion was changed to 0.02 g and 4.048 g was measured from the dispersion, the interlayer film for laminated glass and the laminated glass were used. Was prepared.

(Example 8)
In "(1) Production of interlayer film for laminated glass" in Reference Example 1, the type and content of the dispersant were changed by the dispersant (Plysurf A-208S: polyoxyalkylene ether phosphate ester manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). An interlayer film for laminated glass and a laminated glass were produced in the same manner as in Reference Example 1 except that the dispersion was changed to 0.2 g and 4.48 g was measured from the dispersion.

(Example 9)
In "(1) Production of interlayer film for laminated glass" in Reference Example 1, the type and content of the dispersant were changed by using a dispersant (Daiichi Kogyo Seiyaku Co., Ltd., Plysurf A-210G: polyoxyalkylene alkylphenyl ether phosphate). Ester) An interlayer film for laminated glass and a laminated glass were produced in the same manner as in Reference Example 1 except that the amount was changed to 0.2 g and 4.48 g was measured and taken from the dispersion.

(Example 10)
In "(1) Production of interlayer film for laminated glass" in Reference Example 1, the type and content of the dispersant were changed by using a dispersant (Kanisha Co., Sanisol B-50: alkylbenzyldimethylammonium chloride [lauryl / myristyl = 2 / 1]) An interlayer film for laminated glass and a laminated glass were produced in the same manner as in Reference Example 1 except that the dispersion was changed to 0.2 g and 4.48 g was measured from the dispersion.

(Example 11)
In "(1) Production of interlayer film for laminated glass" in Reference Example 1, the type and content of the dispersant were changed to 0.2 g of the dispersant (Rhodol 430: polyoxyethylene sorbite tetraoleate) manufactured by Kao Corporation. Then, an interlayer film for laminated glass and a laminated glass were produced in the same manner as in Reference Example 1 except that 4.48 g of the dispersion liquid was measured and taken.

(Comparative Example 2)
In “(1) Production of interlayer film for laminated glass” in Reference Example 1, the content of the lanthanoid-containing inorganic fine particles was changed to 0.1 g, and 4.04 g was measured and taken from the dispersion without adding a dispersant. Except for the above, an interlayer film for laminated glass and a laminated glass were obtained in the same manner as in Reference Example 1.

(Evaluation)
The interlayer film for laminated glass and the laminated glass obtained in Examples , Reference Examples and Comparative Examples were evaluated by the following methods.
The results are shown in Tables 1 and 2. The results were compared in the case where the content of the lanthanoid-containing inorganic fine particles with respect to the binder resin was the same.

(1) Calculation of visible light transmittance About the obtained laminated glass, using a UV-visible spectrophotometer (V-670, manufactured by JASCO Corporation), a response Fast, a bandwidth of 2.0 nm, a scanning speed of 2000 nm / min, The transmittance was measured under the conditions of a start wavelength of 2500 nm, an end wavelength of 300 nm, a data acquisition interval of 1.0 nm, and a near-infrared bandwidth of 8.0 nm. The visible light transmittance was calculated from the measured spectrum according to JISR3106-1985.

(2) Measurement of haze The haze was measured using a haze meter (manufactured by Toyo Seiki, Haze Guard II). The haze at four points randomly selected from the obtained laminated glass was measured, and the average value was adopted.

(3) Luminescence The obtained laminated glass was irradiated with light in a dark room using an infrared ray generator (THORLABS, L980P300J) under the conditions of a wavelength of 980 nm and an applied current of 283.42 mA to emit visible light. Was made. The spectrum was measured using a spectrofluorometer (F-2700, manufactured by Hitachi High-Technologies Corporation) using a fluorescence start wavelength of 450 nm, a fluorescence end wavelength of 750 nm, a scan speed of 300 nm / min, an excitation side slit of 5.0 nm, and a fluorescence side slit of 5.0 nm. The measurement was performed under the condition of a photovoltaic voltage of 400 V, and the value at the peak top of 542.5 nm was recorded as emission intensity from the spectrum. This operation was performed for ten randomly selected points of the laminated glass, and the standard deviation was calculated.

(4) Measurement of Molecular Weight <br/> implementation examples 5-11, each dispersing agent used in Reference Example 1-4 was dissolved in tetrahydrofuran (THF), to prepare a 0.2 wt% solution. The obtained solution was subjected to Gel Permeation Chromatography (GPC) apparatus (APC system manufactured by Nippon Waters Co., Ltd., column: HSPgel HRMB-M 6.0 * 150 mm manufactured by Nippon Waters Detector: RI manufactured by Nippon Waters, analysis apparatus: EMPOWAR3). analyzed. The measurement was performed under the conditions of a flow rate of 0.5 ml / min, a column temperature of 40 ° C., and an injection volume of 10 μl.

As a specific measuring procedure, first, a polystyrene standard sample having a known molecular weight (Mw = 210,000, 90,000, 427000, 190,000, 37900, 18100, 5970, 2420, 500: Tosoh Corporation, for organic solvent-based size exclusion chromatography) Using a standard polystyrene kit (PStQuick series), a 0.2% by weight THF solution was prepared. The relationship between the retention time and the molecular weight was determined from the GPC measurement result of the obtained dispersant solution, and this was used as a GPC calibration curve.

Next, the dispersant was dissolved in THF to prepare a THF solution. From the results of GPC measurement of the obtained dispersant solution, the weight average molecular weight was calculated for all peaks detected from the sample, and defined as the molecular weight of the dispersant.

Advantageous Effects of Invention According to the present invention, an interlayer film for laminated glass and a laminated glass capable of providing an up-conversion function while displaying optical characteristics such as visible light transmittance and haze and displaying an image without unevenness can be provided. It is possible to provide.

Claims (8)

An interlayer film for laminated glass , comprising : lanthanoid-containing inorganic fine particles having an up-conversion function; a binder resin; and a dispersant , wherein the dispersant has a weight average molecular weight of 100 to 3,000 . 2. The interlayer for laminated glass according to claim 1, wherein the dispersant is at least one selected from nonionic glycerin esters, anionic polycarboxylic acids and cationic ammonium salts. The interlayer for laminated glass according to claim 1 or 2, wherein the dispersant is contained in an amount of 0.1 to 100 parts by mass based on 100 parts by mass of the lanthanoid-containing inorganic fine particles. 4. The interlayer film for laminated glass according to claim 1, wherein the dispersant is contained in an amount of 0.01 to 3.2 parts by mass with respect to 100 parts by mass of the binder resin. Binder resin, the interlayer film for a laminated glass according to claim 1, 2, 3 or 4, wherein the polyvinyl acetal resin. The binder resin 100 parts by weight, the interlayer film for a laminated glass according to claim 1, 2, 3, 4 or 5 wherein the lanthanide-containing inorganic fine particles, characterized by containing 0.0001 parts by weight. Further, the interlayer film for a laminated glass according to claim 2, 3, 4, 5 or 6, wherein it contains a plasticizer. Laminated glass interlayer film for a laminated glass according to claim 1,2,3,4,5,6 or 7, wherein, characterized in that is sandwiched a pair of glass plates.