JP2015040166A - Intermediate film for laminated glass, and laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an intermediate film for a laminated glass which displays an image having high contrast by irradiation with rays, can control adhesiveness while suppressing discoloration, and has excellent humidity resistance, and a laminated glass containing the intermediate film for the laminated glass.SOLUTION: An intermediate film for a laminated glass has a light-emitting layer containing polyvinyl acetal, a light-emitting material having a terephthalic acid ester structure, a potassium salt, and a humidity resistance improver.

Description

The present invention relates to an interlayer film for laminated glass that displays an image with high contrast by being irradiated with light, can control adhesion while suppressing discoloration, and has excellent moisture resistance. Moreover, this invention relates to the laminated glass containing this intermediate film for laminated glasses.

Laminated glass is safe because it does not scatter glass fragments even if it is damaged by an external impact, so it can be used as a windshield, side glass, rear glass for vehicles such as automobiles, and window glass for aircraft, buildings, etc. Widely used. Examples of the laminated glass include a laminated glass obtained by integrating an interlayer film for laminated glass including a liquid plasticizer and a polyvinyl acetal resin between at least a pair of glasses.

2. Description of the Related Art In recent years, there has been a growing demand for a windshield for an automobile to display an instrument display such as speed information, which is automobile travel data, as a head-up display (HUD) within the same field of view as the windshield.
A number of forms have been developed as HUDs so far. By reflecting the speed information transmitted from the control unit as the most common HUD to the windshield from the display unit of the instrument panel, the driver can obtain the speed information at the same position as the windshield, that is, within the same field of view. There is a HUD that can be visually recognized.
As an interlayer film for laminated glass for HUD, for example, Patent Document 1 proposes an interlayer film for wedge-shaped laminated glass having a predetermined wedge angle, and HUD's that the instrument display looks double in laminated glass. It has been proposed to solve the drawbacks.

If the laminated glass described in patent document 1 is a partial area | region in the surface of a laminated glass, the fault of HUD that an instrument display looks double can be solved. That is, the problem that the instrument display appears double on the entire surface of the laminated glass has not been solved.
Patent Document 2 discloses a laminated glass in which an intermediate layer containing hydroxyterephthalate is laminated between two transparent plates. The laminated glass described in Patent Document 2 can display an image with high contrast when irradiated with light. However, when laminated glass is produced using an intermediate layer containing hydroxyl terephthalate, there is a problem that the intermediate layer is discolored.

Japanese National Publication No. 4-502525 International Publication No. 10/139889 Pamphlet

An object of the present invention is to provide an interlayer film for laminated glass that displays an image with high contrast by being irradiated with light, can control adhesion while suppressing discoloration, and is excellent in moisture resistance. . Another object of the present invention is to provide a laminated glass including the interlayer film for laminated glass.

The present invention is an interlayer film for laminated glass having a light emitting layer containing polyvinyl acetal, a light emitting material having a terephthalic acid ester structure, a potassium salt, and a moisture resistance improver.
The present invention is described in detail below.

The present inventors examined the use of a light-emitting material having a terephthalic acid ester structure (hereinafter also referred to as “compound A”) having excellent light-emitting properties for the light-emitting layer of the interlayer film for laminated glass. However, in order to adjust the adhesion between the interlayer film for laminated glass and the glass, when a commonly used adhesive force regulator such as a compound containing magnesium element is used in combination with the compound A, the interlayer film for laminated glass There is a problem that may change color.
The present inventors have been able to prevent discoloration of the interlayer film for laminated glass when a potassium salt is used in combination with the above compound A as an adhesion modifier, but the moisture resistance of the interlayer film for laminated glass is reduced. I found a problem. Therefore, the present inventors use polyvinyl acetal, the above compound A, potassium salt, and a moisture resistance improver, and when irradiated with light, display a high contrast image while suppressing discoloration. The inventors have found that an interlayer film for laminated glass that can control adhesiveness and is excellent in moisture resistance can be obtained, and has completed the present invention.

The interlayer film for laminated glass of the present invention has a light emitting layer containing polyvinyl acetal, the compound A, a potassium salt, and a moisture resistance improver. By using a light emitting layer containing polyvinyl acetal, the above-mentioned compound A, potassium salt, and a moisture resistance improver, not only a high contrast image can be displayed, but also the discoloration can be suppressed, and the adhesion of the interlayer film for laminated glass The moisture resistance can be increased.

The interlayer film for laminated glass of the present invention may be a single-layer interlayer film including only the light emitting layer, and includes the light emitting layer and a first resin layer disposed on one surface of the light emitting layer. It may be a multilayer interlayer film. When the interlayer film for laminated glass of the present invention is a multilayer interlayer film, the light emitting layer is preferably disposed as the outermost layer of the multilayer interlayer film. Among these, a three-layer interlayer film in which the first resin layer is sandwiched between two light emitting layers is preferable. The first resin layer preferably contains polyvinyl acetal. The first resin layer may be directly laminated on one surface of the light emitting layer.

The light emitting layer contains polyvinyl acetal.
The polyvinyl acetal is not particularly limited as long as it is a polyvinyl acetal obtained by acetalizing polyvinyl alcohol with an aldehyde, but polyvinyl butyral is preferable. Moreover, you may use together 2 or more types of polyvinyl acetal as needed.
The preferable lower limit of the degree of acetalization of the polyvinyl acetal is 40 mol%, the preferable upper limit is 85 mol%, the more preferable lower limit is 60 mol%, and the more preferable upper limit is 75 mol%.

The polyvinyl acetal has a preferred lower limit of the hydroxyl group content of 15 mol% and a preferred upper limit of 35 mol%. When the hydroxyl group amount is 15 mol% or more, the interlayer film for laminated glass can be easily molded. When the amount of hydroxyl group is 35 mol% or less, handling of the resulting interlayer film for laminated glass becomes easy.
The degree of acetalization and the amount of hydroxyl groups can be measured in accordance with, for example, JIS K6728 “Testing method for polyvinyl butyral”.

The polyvinyl acetal can be prepared by acetalizing polyvinyl alcohol with an aldehyde. The polyvinyl alcohol is usually obtained by saponifying polyvinyl acetate, and polyvinyl alcohol having a saponification degree of 70 to 99.8 mol% is generally used.
The preferable lower limit of the polymerization degree of the polyvinyl alcohol is 500, and the preferable upper limit is 4000. When the polymerization degree of the polyvinyl alcohol is 500 or more, the penetration resistance of the obtained laminated glass is increased. When the polymerization degree of the polyvinyl alcohol is 4000 or less, the interlayer film for laminated glass can be easily molded. The minimum with a more preferable polymerization degree of the said polyvinyl alcohol is 1000, and a more preferable upper limit is 3600.

The aldehyde is not particularly limited, but generally an aldehyde having 1 to 10 carbon atoms is preferably used. The aldehyde having 1 to 10 carbon atoms is not particularly limited. For example, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, n-nonylaldehyde N-decylaldehyde, formaldehyde, acetaldehyde, benzaldehyde and the like. Of these, n-butyraldehyde, n-hexylaldehyde, and n-valeraldehyde are preferable, and n-butyraldehyde is more preferable. These aldehydes may be used alone or in combination of two or more.

The light emitting layer contains the compound A.
Compound A emits light when irradiated with light. The light beam is not particularly limited as long as the compound A can be excited to emit light, and examples thereof include ultraviolet rays and infrared rays.
The compound A is preferably a compound having a structure represented by the following general formula (1).

In the general formula (1), R represents an organic group, and x is 1 or 2.
The organic group is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 10 carbon atoms, still more preferably a hydrocarbon group having 1 to 5 carbon atoms, and a carbon number. A hydrocarbon group of 1 to 3 is particularly preferred. When the hydrocarbon group has 10 or less carbon atoms, the compound A can be easily dispersed in the interlayer film for laminated glass. The hydrocarbon group is preferably an alkyl group. Further, among the hydrogen atoms of the benzene ring of the terephthalic acid ester structure of Compound A, any one hydrogen atom may be substituted with a hydroxyl group, and any two hydrogen atoms may be substituted with a hydroxyl group. .
Examples of the compound A include diethyl-2,5-dihydroxyterephthalate (manufactured by Aldrich, “diethyl 2,5-dihydroxyterephthalate”), dimethyl 2,5-dihydroxyterephthalate, and the like. Among them, the compound A is preferably diethyl-2,5-dihydroxyterephthalate (manufactured by Aldrich, “diethyl 2,5-dihydroxyterephthalate”) because an image with higher contrast can be displayed.

Although content of the said compound A is not specifically limited, The preferable minimum with respect to 100 weight part of said polyvinyl acetals is 0.001 weight part, and a preferable upper limit is 1 weight part. When the content of the compound A is 0.001 part by weight or more, an image with much higher contrast can be displayed by irradiation with light. When the content of the compound A is 1 part by weight or less, the transparency of the interlayer film for laminated glass is further increased. The more preferable lower limit of the content of the compound A is 0.005 parts by weight, the more preferable upper limit is 0.9 parts by weight, the still more preferable lower limit is 0.01 parts by weight, and the still more preferable upper limit is 0.8 parts by weight. Is 0.1 part by weight, and a particularly preferred upper limit is 0.7 part by weight.

The light emitting layer contains a potassium salt.
By including the potassium salt, it is possible not only to easily control the adhesive force between the light emitting layer and the glass, but also to prevent the light emitting layer from being discolored. Although the said potassium salt is not specifically limited, It is preferable that it is a C1-C16 organic acid potassium salt, it is more preferable that it is a C1-C16 carboxylic acid potassium salt, and a C1-C8 carboxylic acid. More preferably, it is a potassium salt of an acid. Although it does not specifically limit as said C1-C16 carboxylic acid potassium salt, For example, potassium formate, potassium acetate, potassium propionate, potassium 2-ethylbutanoate, potassium 2-ethylhexanoate etc. are mentioned. In addition, discoloration means that the YI value of the laminated glass in which the interlayer film for laminated glass is laminated between two clear glasses (thickness 2.5 mm) exceeds 20. The YI value can be measured based on JIS Z 8722 using a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, “U-4100”). The YI value is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. The YI value is preferably 0 or more.

Although content of the said potassium salt is not specifically limited, The preferable minimum with respect to 100 weight part of said polyvinyl acetals is 0.001 weight part, and a preferable upper limit is 0.5 weight part. When the content of the potassium salt is 0.001 part by weight or more, the penetration resistance of the laminated glass is increased. When the content of the potassium salt is 0.5 parts by weight or less, the transparency of the interlayer film for laminated glass increases. The minimum with more preferable content of the said potassium salt is 0.015 weight part, and a more preferable upper limit is 0.25 weight part.
Since the discoloration of the light emitting layer can be further prevented, the content of potassium element in the light emitting layer is preferably 300 ppm or less, more preferably 250 ppm or less, still more preferably 200 ppm or less, and 150 ppm. Even more preferably: Since the moisture resistance of the light emitting layer is increased, the potassium element content in the light emitting layer is particularly preferably 100 ppm or less. The potassium element may be contained as potassium derived from a potassium salt, or may be contained as potassium derived from a neutralizing agent used when synthesizing polyvinyl acetal. A preferable lower limit of the content of potassium element in the light emitting layer is 30 ppm, a particularly preferable upper limit is 90 ppm, a more preferable lower limit is 40 ppm, and a most preferable upper limit is 80 ppm.

If the said light emitting layer is a range which does not inhibit the solution of the subject of this invention, it may contain a magnesium salt. By including the magnesium salt, the adhesive force between the light emitting layer and the glass can be more easily controlled. Although the said magnesium salt is not specifically limited, It is preferable that it is a C2-C16 organic acid magnesium salt, and it is more preferable that it is a C2-C16 carboxylic acid magnesium salt. Although it does not specifically limit as said C2-C16 carboxylic acid magnesium salt, For example, magnesium acetate, magnesium propionate, 2-ethylbutanoic acid magnesium, 2-ethylhexanoic acid magnesium, etc. are mentioned.

Although content of the said magnesium salt is not specifically limited, The preferable minimum with respect to 100 weight part of said polyvinyl acetals is 0.02 weight part, and a preferable upper limit is 0.5 weight part. When the content of the magnesium salt is 0.02 parts by weight or more, the penetration resistance of the laminated glass is increased. When the content of the magnesium salt is 0.5 parts by weight or less, the transparency of the interlayer film for laminated glass increases. The minimum with more preferable content of the said magnesium salt is 0.03 weight part, and a more preferable upper limit is 0.2 weight part.
Since the adhesiveness of the interlayer film for laminated glass of the present invention can be controlled more easily and discoloration can be further suppressed, the magnesium element content in the light emitting layer is preferably 80 ppm or less. The magnesium element may be included as magnesium derived from a magnesium salt, or may be included as magnesium derived from a neutralizing agent used when synthesizing polyvinyl acetal. A preferable lower limit of the content of magnesium element in the light emitting layer is 20 ppm, a more preferable upper limit is 75 ppm, a more preferable lower limit is 30 ppm, and a still more preferable upper limit is 70 ppm. In addition, content of the said potassium element or the said magnesium element can be measured with an ICP emission spectrometer (“ICPE-9000” manufactured by Shimadzu Corporation).

Since the discoloration of the interlayer film for laminated glass can be further suppressed, the concentration of the lithium element in the light emitting layer is preferably 25 ppm or less. A preferable lower limit of the concentration of lithium element in the light emitting layer is 0 ppm, a more preferable upper limit is 20 ppm, a more preferable lower limit is 1 ppm, and a further preferable upper limit is 10 ppm or less.

The light emitting layer contains the moisture resistance improver.
In order to contain the compound A in the light emitting layer and further adjust the adhesive force between the light emitting layer and the glass, a potassium salt is contained as an adhesive strength adjusting agent. Can be adjusted. However, the interlayer film for laminated glass having the light emitting layer containing the compound A and the potassium salt is deteriorated in moisture resistance. Therefore, the light emitting layer contains a moisture resistance improver.
By using a compound that is excellent in compatibility with the potassium salt or a compound that captures the potassium salt as the moisture resistance improver, it is considered that water hardly collects around the potassium salt and the moisture resistance is improved.

Examples of the compound having excellent compatibility with the potassium salt include compounds having an anionic functional group.
Examples of the anionic functional group include a phosphoric acid (ester) group, a carboxylic acid (ester) group, and a sulfonic acid group. Among these, a phosphoric acid (ester) group is preferable because of excellent moisture resistance.
Examples of the compound having an anionic functional group include polyoxyethylene alkyl ether phosphate such as polyoxyethylene lauryl ether phosphate, polyoxyethylene tridecyl ether phosphate, polyoxyethylene lauryl ether phosphate Examples include esters.

As a compound which capture | acquires the said potassium salt, the compound etc. which have the said nonionic functional group are mentioned, for example.
Examples of the nonionic functional group include an ether group and a hydroxy group.
As the compound having a nonionic functional group, a crown ether is preferable because it is excellent in the effect of capturing an adhesive force regulator.

Specific examples of the moisture resistance improver include, for example, a phosphate ester represented by the following general formula (2) as a compound having the anionic functional group, a compound having a molecular weight of 100 or more having a carboxylic acid group, Examples of the compound that captures the potassium salt include 18-crown ether-6. These moisture resistance improvers also function as a dispersant described later.

In the general formula (2), R ¹ represents an alkyl group having 1 to 20 carbon atoms, m is 1 to 300, and n is 1 to 3.

The preferable lower limit of the content of the moisture resistance improver relative to 100 parts by weight of the polyvinyl acetal is 0.01 part by weight, and the preferable upper limit is 5 parts by weight. When the content of the moisture resistance improver is within this range, the moisture resistance of the interlayer film for laminated glass obtained can be sufficiently improved. The minimum with more preferable content of the said moisture resistance improving agent is 0.03 weight part, and a more preferable upper limit is 1 weight part.

The light emitting layer preferably further contains a dispersant. By containing the dispersant, aggregation of the compound A can be suppressed, and more uniform light emission can be obtained. The dispersant is, for example, a compound having a sulfonic acid structure such as a linear alkylbenzene sulfonate, or an ester structure such as a diester compound, a ricinoleic acid alkyl ester, a phthalic acid ester, an adipic acid ester, a sebacic acid ester, or a phosphoric acid ester. , Compounds having an ether structure such as polyoxyethylene glycol, polyoxypropylene glycol and alkylphenyl-polyoxyethylene-ether, compounds having a carboxylic acid structure such as polycarboxylic acid, laurylamine, dimethyllauryl Compounds having an amine structure such as amines, oleylpropylenediamine, secondary amines of polyoxyethylene, tertiary amines of polyoxyethylene, and diamines of polyoxyethylene, and polyalkylenepolyaminealkyleneoxy Dispersants such as compounds having a polyamine structure such as amides, compounds having an amide structure such as oleic acid diethanolamide and alkanol fatty acid amide, and compounds having a high molecular weight amide structure such as polyvinylpyrrolidone and polyester acid amide amine salts Can be used. Moreover, you may use high molecular weight dispersing agents, such as polyoxyethylene alkyl ether phosphoric acid (salt), high molecular polycarboxylic acid, and condensed ricinoleic acid ester. The high molecular weight dispersant is defined as a dispersant having a molecular weight of 10,000 or more.

When the dispersant is blended, the preferable lower limit of the content of the dispersant with respect to 100 parts by weight of the compound A in the light emitting layer is 1 part by weight, and the preferable upper limit is 50 parts by weight. When the content of the dispersant is within this range, the compound A can be uniformly dispersed in the light emitting layer. The more preferable lower limit of the content of the dispersant is 3 parts by weight, the more preferable upper limit is 30 parts by weight, the still more preferable lower limit is 5 parts by weight, and the still more preferable upper limit is 25 parts by weight.

It is preferable that the light emitting layer further contains an ultraviolet absorber. When the light emitting layer contains an ultraviolet absorber, the light resistance of the light emitting layer is increased. The light emitting layer may not contain an ultraviolet absorber. Since an interlayer film for laminated glass capable of displaying an image having a higher contrast is obtained, the preferable upper limit of the content of the ultraviolet absorber in the light emitting layer with respect to 100 parts by weight of the polyvinyl acetal is 1 part by weight, more preferably. The upper limit is 0.5 parts by weight, the more preferred upper limit is 0.2 parts by weight, and the particularly preferred upper limit is 0.1 parts by weight.

Examples of the ultraviolet absorber include a compound having a malonic ester structure, a compound having an oxalic acid anilide structure, a compound having a benzotriazole structure, a compound having a benzophenone structure, a compound having a triazine structure, a compound having a benzoate structure, and a hindered amine Examples include ultraviolet absorbers such as compounds having a structure.

The light emitting layer may further contain a plasticizer as necessary. The plasticizer is not particularly limited, and examples thereof include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, phosphoric acid plasticizers such as organic phosphoric acid plasticizers and organic phosphorous acid plasticizers, and the like. Is mentioned. The plasticizer is preferably a liquid plasticizer.

The monobasic organic acid ester is not particularly limited. For example, glycols such as triethylene glycol, tetraethylene glycol, and tripropylene glycol, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, and n-octyl Examples thereof include glycol esters obtained by reaction with monobasic organic acids such as acid, 2-ethylhexyl acid, pelargonic acid (n-nonyl acid), and decyl acid. Of these, triethylene glycol dicaproate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-n-octylate, triethylene glycol di-2-ethylhexylate and the like are preferable.

Although the said polybasic organic acid ester is not specifically limited, For example, ester compound of polybasic organic acid, such as adipic acid, sebacic acid, azelaic acid, and the alcohol which has a C4-C8 linear or branched structure Is mentioned. Of these, dibutyl sebacic acid ester, dioctyl azelaic acid ester, dibutyl carbitol adipic acid ester and the like are preferable.

The organic ester plasticizer is not particularly limited, and triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n-octanoate, Triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, tetraethylene glycol di-2-ethylhexanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethyl Butyrate, 1,3-propylene glycol di-2-ethyl butyrate, 1,4-butylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl butyrate, diethylene glycol di- -Ethyl hexanoate, dipropylene glycol di-2-ethyl butyrate, triethylene glycol di-2-ethyl pentanoate, tetraethylene glycol di-2-ethyl butyrate, diethylene glycol dicapryate, dihexyl adipate, adipine Dioctyl acid, hexyl cyclohexyl adipate, diisononyl adipate, heptylnonyl adipate, dibutyl sebacate, oil-modified sebacic acid alkyd, a mixture of phosphate ester and adipic acid ester, adipic acid ester, alkyl alcohol having 4 to 9 carbon atoms and Examples thereof include mixed adipic acid esters prepared from cyclic alcohols having 4 to 9 carbon atoms and adipic acid esters having 6 to 8 carbon atoms such as hexyl adipate.

The organophosphate plasticizer is not particularly limited, and examples thereof include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate, and the like.

Among the above plasticizers, dihexyl adipate (DHA), triethylene glycol di-2-ethylhexanoate (3GO), tetraethylene glycol di-2-ethylhexanoate (4GO), triethylene glycol di-2- Selected from the group consisting of ethyl butyrate (3GH), tetraethylene glycol di-2-ethylbutyrate (4GH), tetraethylene glycol di-n-heptanoate (4G7) and triethylene glycol di-n-heptanoate (3G7) It is preferable that it is at least one kind.

Furthermore, since it is difficult to cause hydrolysis as the plasticizer, triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethylbutyrate (3GH), tetraethylene glycol di-2- It preferably contains ethyl hexanoate (4GO) and dihexyl adipate (DHA), and tetraethylene glycol di-2-ethylhexanoate (4GO) and triethylene glycol di-2-ethylhexanoate (3GO). More preferably, it contains triethylene glycol di-2-ethylhexanoate, and even more preferably.

The content of the plasticizer in the light emitting layer is not particularly limited, but a preferable lower limit with respect to 100 parts by weight of the polyvinyl acetal is 30 parts by weight, and a preferable upper limit is 70 parts by weight. When the content of the plasticizer is 30 parts by weight or more, the melt viscosity of the laminated glass interlayer film becomes low, so that the laminated glass interlayer film can be easily formed. When the content of the plasticizer is 70 parts by weight or less, the transparency of the interlayer film for laminated glass increases. The minimum with more preferable content of the said plasticizer is 35 weight part, and a more preferable upper limit is 63 weight part.

The light emitting layer may contain additives such as an antioxidant, a light stabilizer, an antistatic agent, a blue pigment, a blue dye, a green pigment, and a green dye as necessary.

Since the outstanding light resistance can be obtained, it is preferable that the said light emitting layer contains antioxidant. The antioxidant is not particularly limited, and examples thereof include an antioxidant having a phenol structure, an antioxidant containing sulfur, and an antioxidant containing phosphorus.
The antioxidant having the phenol structure is an antioxidant having a phenol skeleton. Examples of the antioxidant having the phenol structure include 2,6-di-t-butyl-p-cresol (BHT), butylated hydroxyanisole (BHA), 2,6-di-t-butyl-4- Ethylphenol, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2′-methylenebis- (4-methyl-6-butylphenol), 2,2′-methylenebis- ( 4-ethyl-6-tert-butylphenol), 4,4′-butylidene-bis- (3-methyl-6-tert-butylphenol), 1,1,3-tris- (2-methyl-hydroxy-5-t) -Butylphenyl) butane, tetrakis [methylene-3- (3 ', 5'-butyl-4-hydroxyphenyl) propionate] methane, 1,3,3-tris- (2-methyl) 4-hydroxy-5-tert-butylphenol) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, and bis ( 3,3′-tert-butylphenol) butyric acid glycol ester, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like. The said antioxidant may be only 1 type, and may use 2 or more types together.

Although the thickness of the said light emitting layer is not specifically limited, A preferable minimum is 300 micrometers and a preferable upper limit is 2000 micrometers. When the thickness of the light emitting layer is within this range, light emission with sufficiently high contrast can be obtained when a light beam having a specific wavelength is irradiated. The more preferable lower limit of the thickness of the light emitting layer is 350 μm, and the more preferable upper limit is 1000 μm.

The said light emitting layer may be arrange | positioned in the whole surface of the intermediate film for laminated glasses of this invention, and may be arrange | positioned only in part. In the case where the light emitting layer is arranged only in part, information can be displayed only in the light emitting area, with the part as a light emitting area and the other part as a non-light emitting area.

The interlayer film for laminated glass of the present invention may be a three-layer interlayer film in which a first resin layer may be laminated on one surface of the light emitting layer, and the first resin layer is sandwiched between two light emitting layers. It is preferable that The first resin layer preferably includes polyvinyl acetal, more preferably includes polyvinyl acetal and a plasticizer, and further preferably includes polyvinyl acetal, a plasticizer, and an adhesive force regulator. Furthermore, in addition to the light emitting layer and the first resin layer, other layers may be laminated. Examples of the other layer include a layer containing a thermoplastic resin such as polyethylene terephthalate and polyvinyl acetal. The other layer may be an ultraviolet blocking layer containing an ultraviolet absorber. As the ultraviolet absorber used in the ultraviolet blocking layer, the ultraviolet absorber used in the light emitting layer described above can be used.

As the polyvinyl acetal contained in the first resin layer, the polyvinyl acetal contained in the light emitting layer can be used. The polyvinyl acetal contained in the first and second resin layers and the polyvinyl acetal contained in the light emitting layer may be the same or different. When the light emitting layer contains a plasticizer, the plasticizer contained in the first resin layer may be the same as or different from the plasticizer contained in the light emitting layer.

The first resin layer preferably contains an adhesive strength modifier. The adhesive strength modifier is not particularly limited, and is preferably a metal salt, and is preferably at least one metal salt selected from the group consisting of alkali metal salts, alkaline earth metal salts, and magnesium salts. The metal salt preferably contains at least one metal selected from potassium and magnesium. The metal salt is more preferably an alkali metal salt of an organic acid having 2 to 16 carbon atoms or an alkaline earth metal salt of an organic acid having 2 to 16 carbon atoms, and a magnesium carboxylate having 2 to 16 carbon atoms or More preferably, it is a carboxylic acid potassium salt having 2 to 16 carbon atoms. Although it does not specifically limit as said C2-C16 carboxylic acid magnesium salt and said C2-C16 carboxylic acid potassium salt, For example, magnesium acetate, potassium acetate, magnesium propionate, potassium propionate 19, 2-ethylbutane Examples include magnesium acid, potassium 2-ethylbutanoate, magnesium 2-ethylhexanoate, and potassium 2-ethylhexanoate.

The content of the adhesive strength modifier is not particularly limited, but a preferable lower limit with respect to 100 parts by weight of the polyvinyl acetal is 0.0005 parts by weight, and a preferable upper limit is 0.05 parts by weight. The penetration resistance of laminated glass becomes high as content of the said adhesive force regulator is 0.0005 weight part or more. When the content of the adhesion adjusting agent is 0.05 parts by weight or less, the transparency of the interlayer film for laminated glass is increased. The minimum with more preferable content of the said adhesive force regulator is 0.002 weight part, and a more preferable upper limit is 0.02 weight part.
Since the moisture resistance of the first resin layer is increased, the total content of alkali metal, alkaline earth metal and magnesium in the first resin layer is preferably 300 ppm or less. For example, the alkali metal, alkaline earth metal, and magnesium may be included as a metal derived from the adhesive strength adjusting agent, or may be included as a metal derived from a neutralizing agent used when synthesizing polyvinyl acetal. The total content of alkali metal, alkaline earth metal and magnesium in the first resin layer is more preferably 200 ppm or less, further preferably 150 ppm or less, and particularly preferably 100 ppm or less.

When heat-shielding property is required for the interlayer film for laminated glass of the present invention, any one layer, any two layers, or all layers of the light emitting layer and the first resin layer contain a heat ray absorbent. You may let them. Alternatively, in addition to the light emitting layer and the first resin layer, a heat ray shielding layer containing a heat ray absorbent may be further laminated.

The heat ray absorber is not particularly limited as long as it has the ability to shield infrared rays, but tin-doped indium oxide (ITO) particles, antimony-doped tin oxide (ATO) particles, aluminum-doped zinc oxide (AZO) particles, indium-doped At least one selected from the group consisting of zinc oxide (IZO) particles, tin-doped zinc oxide particles, silicon-doped zinc oxide particles, lanthanum hexaboride particles and cerium hexaboride particles is preferred.

The interlayer film for laminated glass of the present invention may further have a sound insulation layer for the purpose of improving the sound insulation performance. Sound insulation may be imparted to any one of the light emitting layer and the first resin layer to form a sound insulation layer, and a sound insulation layer may be further laminated in addition to the light emitting layer and the first resin layer.
Examples of the sound insulation layer include a layer containing 50 to 80 parts by weight of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal. The sound insulation layer preferably contains polyvinyl acetal, and more preferably contains polyvinyl butyral. The polyvinyl acetal contained in the sound insulation layer preferably has a hydroxyl group content in the range of 20 to 28 mol%. The polyvinyl acetal contained in the sound insulation layer is polyvinyl acetal A having an acetyl group amount of 8 to 30 mol%, an acetyl group amount of more than 0 mol% and less than 5 mol%, and an acetalization degree of 70 to 85 mol%. Or polyvinyl acetal C having an acetyl group amount of 5 mol% or more and less than 8 mol% and an acetalization degree of 65 to 80 mol%.

Since the interlayer film for laminated glass of the present invention has the light emitting layer, it emits light when irradiated with light having a specific wavelength. By utilizing this property, it is possible to display information with higher contrast than HUD.
As an apparatus for irradiating the light beam having the specific wavelength, for example, a spot light source (“Hamamatsu Photonics Co.,“ LC-8 ”), a xenon flash lamp (Heraeus Co.,“ CW lamp ”), a black light (Iuchi Seieido Co., Ltd., “Carry Hand”).

The laminated glass in which the interlayer film for laminated glass of the present invention is laminated between a pair of glass plates is also one aspect of the present invention.
The said glass plate can use the transparent plate glass generally used. Examples thereof include inorganic glass such as float plate glass, polished plate glass, template glass, netted glass, wire-containing plate glass, colored plate glass, heat ray absorbing glass, heat ray reflecting glass, and green glass. Further, an ultraviolet shielding glass having an ultraviolet shielding coating layer formed on the glass surface can also be used. Furthermore, organic plastics plates such as polyethylene terephthalate, polycarbonate, and polyacrylate can also be used.
Two or more types of glass plates may be used as the glass plate. For example, the laminated glass which laminated | stacked the intermediate film for laminated glasses of this invention between transparent float plate glass and colored glass plates like green glass is mentioned. Moreover, you may use the glass plate from which 2 or more types of thickness differs as said glass plate.

According to the present invention, it is possible to provide an interlayer film for laminated glass that displays an image with high contrast and is capable of controlling adhesion while suppressing discoloration and having excellent moisture resistance when irradiated with light. Moreover, according to this invention, the laminated glass containing this intermediate film for laminated glasses 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) The structure represented by the general formula (1) as a light-emitting material having a terephthalic acid ester structure is added to 40 parts by weight of a resin composition triethylene glycol di-2-ethylhexanoate (3GO) forming a light-emitting layer. 0.55 part by weight of diethyl-2,5-dihydroxylterephthalate (manufactured by Aldrich, “diethyl 2,5-dihydroxyterephthalate”), 0.051 part by weight of potassium formate as a potassium salt, and moisture resistance As an improver, 0.13 part by weight of polyoxyethylene lauryl ether phosphate (Daiichi Kogyo Seiyaku Co., Ltd., “Plisurf A208B”) was added to prepare a luminescent plasticizer solution. Polyvinyl butyral obtained by acetalizing polyvinyl alcohol having a polymerization degree of 1700 with n-butyraldehyde (acetyl group content 0.9 mol%, hydroxyl group content 30.6 mol) %, Butyralization degree 68.5 mol%) was sufficiently kneaded with a mixing roll to prepare a resin composition for forming a light emitting layer.

(2) Acetalization of 60 parts by weight of the resin composition triethylene glycol di-2-ethylhexanoate (3GO) forming the first resin layer and polyvinyl alcohol having a polymerization degree of 2300 with n-butyraldehyde 100 parts by weight of polyvinyl butyral (13 mol% acetyl group, 23 mol% hydroxyl group, 64 mol% degree of butyralization) obtained in this manner was sufficiently kneaded with a mixing roll to form a first resin layer A resin composition was prepared.

(3) Production of interlayer film for laminated glass The resin composition forming the light emitting layer and the resin composition forming the first resin layer are coextruded using an extruder, and the first resin is formed by the two light emitting layers. An interlayer film for laminated glass (length 30 cm × width 15 cm) in which the layers were sandwiched was obtained. Each of the light emitting layers had a thickness of 350 μm, and the first resin layer had a thickness of 100 μm.

(4) Manufacture of laminated glass The obtained interlayer film for laminated glass was laminated between a pair of clear glass (thickness 2.5 mm) measuring 30 cm in length and 15 cm in width to obtain a laminate. 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.

(Examples 2-5, Comparative Examples 1-3)
Except having changed into the composition of Table 1, it carried out similarly to Example 1, and obtained the intermediate film for laminated glasses, and the laminated glass.

(Evaluation)
About each laminated glass obtained by the Example and the comparative example, it evaluated by the following method. The results are shown in Table 1.

(1) High Power xenon light source (“REX-250” manufactured by Asahi Spectroscopic Co., Ltd., irradiation wavelength: 405 nm) placed at a position 10 cm away from the surface of the obtained laminated glass in a direction perpendicular to the surface of the obtained laminated glass Luminance is measured with a luminance meter ("Top-3 Techno House", "SR-3AR") placed at a position 35cm away from the surface of the laminated glass irradiated with light at an angle of 45 degrees. It was measured.

(2) Initial yellow index value of the obtained laminated glass (5 cm long × 5 cm wide) in accordance with JIS Z 8722 using a color change spectrophotometer (manufactured by Hitachi High-Technologies Corporation, “U-4100”) (Initial YI value) was measured.

(3) Adhesiveness (measurement of Pummel value of interlayer film for laminated glass)
The obtained laminated glass was allowed to stand for 16 hours in an environment of −18 ° C. ± 0.6 ° C. The center of this laminated glass (length 150 mm × width 150 mm) was hammered with a head of 0.45 kg. The glass was pulverized until the particle size of the glass became 6 mm or less, and the degree of exposure of the film after the glass partially peeled was measured.

(4) Moisture resistance The obtained laminated glass was allowed to stand in an environment of 50 ° C. and a humidity of 95% RH for 8 weeks, and then the whitening distance from the central part of each periphery of the laminated glass was measured. Table 1 shows the maximum value of the whitening distance among the whitening distances from the central part of each periphery of the laminated glass.

According to the present invention, it is possible to provide an interlayer film for laminated glass that displays an image with high contrast and is capable of controlling adhesion while suppressing discoloration and having excellent moisture resistance when irradiated with light. Moreover, according to this invention, the laminated glass containing this intermediate film for laminated glasses can be provided.

Claims (6)

An interlayer film for laminated glass comprising a light emitting layer containing polyvinyl acetal, a light emitting material having a terephthalic acid ester structure, a potassium salt, and a moisture resistance improver. The interlayer film for laminated glass according to claim 1, wherein the light-emitting material having a terephthalic acid ester structure is a compound having a structure represented by the following general formula (1).

In general formula (1), R represents an organic group, and x is 1 or 2. 3. The interlayer film for laminated glass according to claim 1, wherein the light emitting layer contains 0.001 to 1 part by weight of a light emitting material having a terephthalic acid ester structure with respect to 100 parts by weight of polyvinyl acetal. The interlayer film for laminated glass according to claim 1, 2, or 3, wherein the content of potassium element in the light emitting layer is 300 ppm or less. 5. The interlayer film for laminated glass according to claim 1, wherein the light emitting layer contains a magnesium element, and the content of the magnesium element is 80 ppm or less. A laminated glass, wherein the interlayer film for laminated glass according to claim 1, 2, 3, 4 or 5 is laminated between a pair of glass plates.