JPH1160290A - Laminated glass and intermediate film therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare an intermediate film which can hold the adhesive strength between the intermediate film and glass in an appropriate range throughout from the initial time till after passage of time and gives a laminated glass having excellent shock absorbing properties and penetration resistance by compounding a plasticized polyvinyl acetal resin film with a metal salt of a carboxylic acid having a specific carbon number and finely pulverized silica. SOLUTION: This intermediate film is composed by compounding a plasticized polyvinyl acetal resin film with a metal salt of a 5-28C carboxylic acid, preferably Mg salt of a 5-10C carboxylic acid, preferably in an amount of 0.01-0.5 pts.wt. based on 100 pts.wt. of the polyvinyl acetal resin and finely pulverized silica preferably in such an amount that the total of the surfaces of the silica becomes >=1/10 of the total surface area of the intermediate film. It is preferable that the polyvinyl acetal resin is produced from a PVA having an average degree of polymerization of 1000-2500 and a degree of saponification of >=70 mol.%, and a 3-10C aldehyde; and the resultant resin has an average acetal degree of 40-75 mol.%. The laminated glass obtained by using this film scarcely has whitening phenomenon at the peripheral parts under high humidity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an interlayer film for laminated glass and a laminated glass using the interlayer film.

[0002]

2. Description of the Related Art Conventionally, laminated glass has been widely used for windshields and side glasses of automobiles, window glasses of buildings, and the like. As a typical example of the laminated glass, an interlayer film for a laminated glass made of a plasticized polyvinyl acetal resin such as a plasticized polyvinyl butyral resin is interposed between at least two sheets of glass, and integrated. And those produced.

[0003] In such a laminated glass, when an impact is applied thereto, the glass is broken, but the interlayer film interposed between the glass is not easily broken, and the glass is adhered to the interlayer film even after the glass is broken. Since it is still worn, the shards are less likely to scatter, and thus have the function of preventing the human body inside the car or building from being injured by the shards of glass.

In this case, in order to sufficiently satisfy the function as a laminated glass, the higher the adhesive strength between the interlayer film and the glass, the better it is not, the better. The adhesive strength is adjusted within a certain appropriate range. It is necessary.

The above-mentioned adjustment of the adhesive force within an appropriate range is necessary, for example, in a car accident or the like, in order to absorb a shock or prevent penetration when a driver or a passenger collides with glass. In a building, it is necessary to prevent penetration of a flying object from outside and to prevent scattering of glass.

That is, when the adhesive strength between the interlayer and the glass is small, the glass peels off from the interlayer and the fragments are liable to be scattered, and conversely, the adhesive strength between the interlayer and the glass occurs. When the value is large, the glass and the intermediate film are simultaneously damaged, and there is a problem that a human body or a flying object from the outside easily penetrates.

On the other hand, when the adhesive strength between the interlayer and the glass is within an appropriate range, the glass is damaged over a wide range and the glass is damaged, and at the same time, the partial interface between the interlayer and the glass is reduced. Since a phenomenon occurs in which separation occurs and the intermediate film is stretched, the effect of absorbing shock and the effect of preventing penetration are increased.

[0008] In view of the above, various types of adhesive force modifiers for interlayer films have been studied in the past in order to adjust the adhesive force between the interlayer film and glass within an appropriate range.

For example, Japanese Patent Publication No. 44-32185 discloses that "a monocarboxylic acid containing 0.1 to 0.8% of water and having 6 to 22 carbon atoms, a dicarboxylic acid having 4 to 12 carbon atoms, At least one organic acid selected from aliphatic monoamino monocarboxylic acids having 2 to 6 carbon atoms, aliphatic monoamino dicarboxylic acids having 4 to 5 carbon atoms, citric acid, and mixtures thereof is added in an amount of 0 to 100 parts by weight of the resin. .01-3
Weight part, an interlayer film for laminated glass made of molded polyvinyl acetal resin "has been proposed,
Japanese Patent Publication No. 48-5772 discloses that "in a glass obtained by laminating at least two pieces of glass with a plasticized polyvinyl acetal resin composition, an aliphatic carboxylic acid having 10 to 22 carbon atoms is contained in the plasticized polyvinyl acetal resin composition. Laminated glass characterized by containing a sodium metal salt of
No. 18207 discloses that “at least two glasses are formed by a plasticized polyvinyl acetal resin intermediate film containing or adhering an alkali metal salt or an alkaline earth metal salt of a monocarboxylic acid or a dicarboxylic acid and a modified silicone oil. A laminated glass characterized by being laminated "has been proposed.

In each of the above three proposals, a carboxylic acid having a relatively large number of carbon atoms or a metal salt thereof is used as an adhesive force adjusting agent because it is easily dissolved in a plasticizer contained in an intermediate film.

However, when a carboxylic acid having a large number of carbon atoms or a metal salt thereof is used as an adhesive force adjuster, there is a problem that the adhesive force between the interlayer and the glass changes with time (elapsed time). That is, even if the initial adhesive strength is appropriate, the adhesive strength gradually decreases over time, and the glass is easily peeled off when subjected to an impact. In order to prevent this decrease in adhesive strength, it is necessary to store and mature the intermediate film in an atmosphere of, for example, 40 to 50 ° C. for 1 to 2 months, but the intermediate film has tackiness, self-adhesion, and the like. Therefore, it is practically difficult to store for a long time under the above atmosphere,
Even if aging is performed, it is possible to suppress a decrease in the adhesive force with time, but it is not possible to eliminate the adhesive force, and the above problem still remains.

To cope with the above problems, Japanese Patent Laid-Open No.
No. 86250, “Polyvinyl acetal resin,
A plasticizer, an interlayer film for a laminated glass formed from a resin composition containing an alkali or alkaline earth metal salt of an aliphatic mono- or dicarboxylic acid having 12 or less carbon atoms and an organic acid, In Japanese Patent Publication No. 2-41547, "Compatible amounts of hydrolyzable esters selected from the group consisting of triethylene glycol-di-n-heptanoate and tetraethylene glycol-di-n-heptanoate are disclosed. In a polyvinyl butyral sheet plasticized and containing an adhesion modifier, the adhesion modifier consists of an alkali or alkaline earth metal formate and the sheet has less than 10 equivalents per million parts, measured by titration, of an acid. Polyvinyl butyral sheet characterized by having a concentration of In Kohyo 6-502594 discloses an intermediate film added with potassium acetate is used as the bond strength control agent in the examples.

In the above three proposals, a carboxylic acid having a relatively small number of carbon atoms or a metal salt thereof is used in order to solve the above-mentioned problem when a carboxylic acid having a large number of carbon atoms or a metal salt thereof is used as an adhesion regulator. Used.

However, when a carboxylic acid having a small number of carbon atoms or a metal salt thereof is used as the adhesive force adjuster, the problem of a decrease in the adhesive force with time between the interlayer film and the glass is solved, but the moisture resistance of the interlayer film is not sufficient. As a result, another problem occurs in that the peripheral portion (end portion) of the laminated glass is liable to cause a whitening phenomenon due to moisture absorption.

That is, since the interlayer film has a hygroscopic property under a normal atmosphere (humidity), when it is processed into a laminated glass, for example, the water content is about 0.5% by weight or less under an atmosphere of 25% RH. It is common to adjust the humidity in such a way as to perform the processing. However, since the periphery of the laminated glass is usually bare, the interlayer film absorbs moisture in a high humidity atmosphere, and the water content increases to about 2 to 3% by weight. At this time, water collects around a metal salt of a carboxylic acid having a small number of carbon atoms, such as potassium acetate, magnesium acetate, or potassium formate, which is present as fine crystals in the intermediate film, causing a whitening phenomenon. Also, if the amount of the carboxylic acid having a small number of carbon atoms or a salt thereof is reduced in order to reduce the whitening phenomenon, the adhesive strength between the interlayer and the glass deviates from an appropriate range, and the impact absorbing property of the laminated glass is reduced. The penetration resistance and the like become insufficient.

As described above, when a carboxylic acid having a large number of carbon atoms or a metal salt thereof is used as an adhesive force adjusting agent, the adhesive force between the intermediate film and the glass decreases with time, and conversely, a carboxylic acid having a small number of carbon atoms is used. Alternatively, when the metal salt is used, a whitening phenomenon occurs at the periphery of the laminated glass.

On the other hand, in recent years, the use of laminated glass has been expanding, and the use of laminated glass as a side glass for automobiles and the use of laminated glass for various buildings have been active mainly for crime prevention.

In the use of such relatively new laminated glass, the use of the laminated glass in a state where the peripheral portion is exposed is increasing, and there is an increasing demand for prevention of the whitening phenomenon.

However, as described above, the adhesive strength between the interlayer film and the glass is maintained within an appropriate range both at the initial stage and after a lapse of time, and therefore, it is necessary to provide a laminated glass having shock absorption and penetration resistance. At present, laminated glass having excellent basic performance and less occurrence of whitening even under a high humidity atmosphere has not been put to practical use.

[0020]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems, and an object of the present invention is to make it possible to obtain an adhesive force between an interlayer film and glass both at an initial stage and after a lapse of time. Within a reasonable range, and therefore
Excellent in basic performance required for laminated glass such as shock absorption and penetration resistance, and suitable for obtaining laminated glass that does not cause whitening on the periphery of laminated glass even when placed in a humid atmosphere. An object of the present invention is to provide an interlayer film for a laminated glass and a laminated glass manufactured using the interlayer film.

[0021]

An interlayer film for laminated glass according to the invention described in claim 1 (hereinafter referred to as the "first invention") is obtained by forming a plasticized polyvinyl acetal resin film on a carbonized resin having 5 to 28 carbon atoms. It is characterized by containing a metal salt of an acid and finely divided silica.

The second aspect of the present invention (hereinafter referred to as "second
The interlayer film for laminated glass according to the present invention is characterized in that, in the interlayer film for laminated glass according to the first aspect, the metal salt of a carboxylic acid is a magnesium salt of a carboxylic acid having 5 to 10 carbon atoms. .

Further, the invention according to claim 3 (hereinafter referred to as "the invention")
The interlayer film for laminated glass according to the “third invention” is
The interlayer film for laminated glass according to the first invention is characterized in that the finely divided silica is contained in such an amount that the total surface area thereof is 1/10 or more of the total surface area of the interlayer film for laminated glass.

The laminated glass according to the invention described in claim 4 (hereinafter, referred to as “fourth invention”) is a laminated glass for laminated glass according to any one of the first to third inventions described above, provided between at least a pair of glasses. It is characterized by being integrated with an intermediate film interposed.

Hereinafter, the present invention will be described in detail.

The method for preparing the polyvinyl acetal resin which is the main component of the plasticized polyvinyl acetal resin film (hereinafter simply referred to as “resin film”) constituting the interlayer film for laminated glass according to the first invention is particularly limited. Although not a specific example, for example, polyvinyl alcohol (PVA) is dissolved in warm water, and the resulting aqueous solution is cooled to a predetermined temperature, for example, 0 to 9
While maintaining the temperature at 5 ° C., the required acid catalyst and aldehyde were added, the acetalization reaction was allowed to proceed while stirring, and then the reaction was completed by raising the reaction temperature and aging, followed by neutralization, water washing and A method of drying to obtain a powder of a polyvinyl acetal resin is employed.

In the above method for preparing a polyvinyl acetal resin, the PVA may have an average degree of polymerization of 500 to 500.
0 is preferred, and those having an average degree of polymerization of 1000 to 2500 are more preferred. If the average degree of polymerization of PVA is less than 500, the strength of the resin film becomes too weak, and the penetration resistance of the obtained laminated glass may decrease.
If the average degree of polymerization of VA exceeds 5,000, molding of the resin film may be difficult, and the strength of the resin film may be too strong, resulting in a decrease in the shock absorption and penetration resistance of the obtained laminated glass. There is.

The vinyl acetate component of the polyvinyl acetal resin obtained above is preferably set at 30 mol% or less, and for this reason, a PVA having a saponification degree of 70 mol% or more is suitably used. Degree of saponification of PVA is 7
If it is less than 0 mol%, the transparency and heat resistance of the polyvinyl acetal resin may be reduced, and the reactivity may be reduced. . Here, the average degree of polymerization and the degree of saponification of PVA can be measured based on, for example, JIS K-6726 "Testing method for polyvinyl alcohol".

In the first invention, the aldehyde used to obtain the polyvinyl acetal resin is not particularly limited, but examples thereof include aldehydes having 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms. It is preferably used.

Examples of such aldehydes include, but are not particularly limited to, for example, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde, n-heptylaldehyde. , N-octylaldehyde, n-nonylaldehyde, n-decylaldehyde, benzaldehyde, cinnamaldehyde, and other aliphatic, aromatic and alicyclic aldehydes, and one or more of these are suitably used. .

If the carbon number of the aldehyde is less than 3, the moldability of the resin film may be insufficient. Conversely, if the carbon number of the aldehyde exceeds 10, the reactivity of acetalization decreases, In addition, resin blocks are likely to be generated during the reaction, and it may be difficult to synthesize the resin. Among the aldehydes having 3 to 10 carbon atoms, n having 4 to 8 carbon atoms
-Butyraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde, n-octylaldehyde, etc.
Species or two or more species are more preferably used.

Among the above aldehydes having 4 to 8 carbon atoms, those obtained by acetalization with n-butyraldehyde having 4 carbon atoms are particularly preferable. By using a polyvinyl butyral resin obtained by acetalization with n-butyraldehyde, the adhesive strength of the resin film is increased, the weather resistance is excellent, and the resin is easily manufactured.

The polyvinyl butyral resin thus obtained is composed of a vinyl butyral component, a vinyl alcohol component and a vinyl acetate component. The amounts of these components can be measured, for example, based on JIS K-6728 "Testing method for polyvinyl butyral" or nuclear magnetic resonance (NMR).

In the case of a polyvinyl acetal resin other than the polyvinyl butyral resin, the amount of the vinyl alcohol component and the amount of the vinyl acetate component are measured, and the amount of the remaining vinyl acetal component is calculated by subtracting the amounts of both components from 100. I can do it.

The average acetalization degree of the above-mentioned various polyvinyl acetal resins is generally preferably from 40 to 75 mol%. If the average degree of acetalization of the polyvinyl acetal resin is less than 40 mol%, the compatibility with the plasticizer described later is deteriorated, and it becomes difficult to mix an amount of the plasticizer necessary for securing the penetration resistance. Conversely, obtaining a resin having an average acetalization degree of more than 75 mol% requires a long reaction time, which is not preferable in terms of process.

The plasticizer used for the interlayer film for laminated glass according to the first invention may be a conventionally known plasticizer used for this type of interlayer film, and is not particularly limited. Organic plasticizers such as basic acid esters and polybasic acid esters, and phosphoric acid plasticizers such as organic phosphoric acid and organic phosphorous acid, etc., and one or more of these are preferably used. Can be

The monobasic acid ester is not particularly restricted but includes, for example, triethylene glycol and butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptanoic acid, n-octylic acid and 2-ethylhexylic acid. Glycol-based esters obtained by the reaction with organic acids such as pelargonic acid (n-nonylic acid) and decyl acid, and glycol-based esters obtained by the reaction of tetraethylene glycol and tripropylene glycol with the above-mentioned organic acids. And one or more of these are preferably used.

The polybasic acid ester is not particularly restricted but includes, for example, adipic acid, sebacic acid,
Esters obtained by reacting an organic acid such as azelaic acid with a linear or branched alcohol having 4 to 8 carbon atoms, and the like, and one or more of these are preferably used.

The organic phosphoric acid plasticizer is not particularly restricted but includes, for example, tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphite and the like. One or more of these may be used. Is preferably used.

Among the above various plasticizers, for example, triethylene glycol-di-2-ethylbutyrate (3G
H), triethylene glycol-di-2-ethylhexanoate (3GO), triethylene glycol-di-n
-Heptanoate (3G7), triethylene glycol dicaprylate, triethylene glycol di-n-octoate, tetraethylene glycol di-2-ethyl butyrate (4GH), tetraethylene glycol
Di-2-ethylhexanoate (4GO), tetraethylene glycol-di-n-heptanoate (4G7),
One or more of dihexyl adipate (DHA) and dibenzyl phthalate are more preferably used.

The amount of the plasticizer to be added to the polyvinyl acetal resin (hereinafter, referred to as “polyvinyl acetal resin including polyvinyl butyral resin”) is not particularly limited, but may be based on 100 parts by weight of the polyvinyl acetal resin. The amount of the plasticizer is preferably 20 to 60 parts by weight, and more preferably 30 to 50 parts by weight.

If the amount of the plasticizer is less than 20 parts by weight based on 100 parts by weight of the polyvinyl acetal resin, the resulting intermediate film may have poor penetration resistance.
If the amount is more than 0 parts by weight, the plasticizer may bleed, resulting in an increase in optical distortion of the obtained interlayer film or a decrease in transparency and adhesiveness.

The interlayer for laminated glass according to the first invention contains a metal salt of a carboxylic acid having 5 to 28 carbon atoms.

The carboxylic acid having 5 to 28 carbon atoms is not particularly limited, and examples thereof include aliphatic carboxylic acids such as aliphatic monocarboxylic acids and aliphatic dicarboxylic acids, aromatic monocarboxylic acids, and aromatic carboxylic acids. Salts obtained by using an aromatic carboxylic acid such as an aromatic dicarboxylic acid as an acid component and an alkali metal, an alkaline earth metal, zinc or the like as a metal component are used, and one or more of these salts are suitably used.

Specific examples of the carboxylic acid having 5 to 28 carbon atoms as the acid component include, but are not particularly limited to, linear monocarboxylic acids such as pentanoic acid, hexanoic acid, and heptanoic acid; Examples thereof include branched monocarboxylic acids such as ethylbutanoic acid and 2-ethylhexanoic acid, dicarboxylic acids such as adipic acid and sebacic acid, and monobutyladipic acid, and one or more of these are suitably used.

When the number of carbon atoms of the carboxylic acid is less than 5, the moisture resistance of the interlayer film is reduced, and a whitening phenomenon may easily occur on the peripheral portion of the obtained laminated glass. When the number of carbon atoms exceeds 28, the handleability of the obtained metal salt is remarkably reduced, and may be lacking in practicality.

Specific examples of the metal as the metal component include, but are not particularly limited to, sodium,
Examples thereof include alkali metals belonging to Group I of the periodic table such as potassium, alkaline earth metals belonging to Group II of the periodic table such as magnesium and calcium, and zinc. One or more of these are suitably used.

Among the salts obtained from the above-mentioned acid component and metal component, there is no particular limitation.
One or more of magnesium ethylbutanoate, magnesium hexanoate, potassium sebacate and the like are more preferably used.

The metal salt of a carboxylic acid having 5 to 28 carbon atoms (hereinafter referred to as a “metal salt”) with respect to the plasticized polyvinyl acetal resin film.
The amount of the “metal salt” is not particularly limited, but is preferably 0.01 to 0.5 part by weight, more preferably 0.1 to 0.5 part by weight, based on 100 parts by weight of the polyvinyl acetal resin. More preferably, the amount is from 02 to 0.2 parts by weight.

If the amount of the metal salt is less than 0.01 part by weight based on 100 parts by weight of the polyvinyl acetal resin, the effect of adjusting the adhesive strength may not be sufficiently obtained. If it exceeds, the adhesive strength of the obtained interlayer film may be too low, or the water resistance and transparency may be reduced.

The interlayer film for laminated glass according to the first invention contains finely divided silica.

The composition of the finely divided silica is not particularly limited, and the main component is silicon dioxide, which is the main component of glass, and aluminum oxide, calcium oxide,
It may contain one or two or more of various components contained in ordinary various glasses, such as magnesium oxide, sodium oxide, zirconium oxide, potassium oxide, and boron oxide.

The average particle size of the finely divided silica is not particularly limited, and is preferably 100 μm or less, more preferably 10 μm or less.

Further, the shape of the finely divided silica is not particularly limited, and may be any shape such as a sphere, a plate, and a fiber, and may be dispersed in a polyvinyl acetal resin or a plasticizer. Surface treatment may be applied to improve the properties.

By containing the finely divided silica in the interlayer film for laminated glass and uniformly dispersing the same, even when a metal salt of a carboxylic acid having a relatively large number of carbon atoms of 5 to 28 is used as an adhesive force adjuster, the adhesion can be improved. It is possible to prevent the metal salt from migrating to the interface between the intermediate film and the glass over time, and thus it is possible to prevent a decrease in the adhesive force between the intermediate film and the glass over time.

The amount of the finely divided silica added to the plasticized polyvinyl acetal resin film also depends on the average particle size of the finely divided silica, and is not particularly limited. It is preferable that the amount is 1/10 or more of the total surface area.

When the amount of the finely divided silica added is such that the total surface area thereof is less than 1/10 of the total surface area of the intermediate film, the effect of preventing the adhesive force between the intermediate film and the glass from decreasing over time is prevented. May be insufficient.

In the interlayer film for laminated glass according to the first invention, the above-mentioned polyvinyl acetal resin which is an essential component,
Other than a plasticizer, a metal salt of a carboxylic acid having 5 to 28 carbon atoms and finely divided silica, an adhesive other than the metal salt of a carboxylic acid having 5 to 28 carbon atoms may be used as needed as long as the object of the present invention is not hindered. Commonly used in interlayers for laminated glass, such as force regulators, UV absorbers and light stabilizers to improve weather resistance, antioxidants to prevent thermal degradation, surfactants, and colorants One or more known additives may be contained.

The adhesive force adjuster other than the metal salt of a carboxylic acid having 5 to 28 carbon atoms is not particularly limited, but examples thereof include those having 1 carbon atom such as formic acid, acetic acid, propanoic acid and butanoic acid. And carboxylic acid metal salt-based adhesion modifiers such as those disclosed in JP-B-55-29950, such as epoxy-modified silicone oil, ether-modified silicone oil, ester-modified silicone oil, and amine-modified silicone oil. Silicone oil-based adhesive force adjusters and the like can be mentioned, and one or more of these are suitably used.

The amount of the metal salt-based adhesion modifier of carboxylic acid having 1 to 4 carbon atoms and / or the modified silicone oil-based adhesion modifier to the polyvinyl acetal resin is not particularly limited. , 100 parts by weight of polyvinyl acetal resin, 0.0
Preferably from 0.5 to 0.5 part by weight,
More preferably, it is 0.2 parts by weight.

The ultraviolet absorber is not particularly limited, but may be a benzotriazole-based one, for example,
Ciba Geigy's trade name “Tinuvin P”, trade name “Tinuvin 320”, trade name “Tinuvin 326”, trade name “Tinuvin 328”, etc., and one or more of these are suitably used.

The light stabilizer is not particularly limited, but includes hindered amine-based light stabilizers, for example, trade name “ADK STAB LA-57” manufactured by Asahi Denka Kogyo Co., Ltd. More than one species is preferably used.

Examples of the antioxidant include, but are not particularly limited to, phenol-based antioxidants, such as “Sumilyzer BHT” (trade name, manufactured by Sumitomo Chemical Co., Ltd.) and “Irganox 1010” (trade name, manufactured by Ciba Geigy) And one or more of these are preferably used.

Examples of the surfactant include, but are not particularly limited to, sodium lauryl sulfate and sodium alkylbenzenesulfonate, and one or more of these are suitably used.

The method for producing the interlayer film for laminated glass according to the first invention is not particularly limited. For example, the above-mentioned polyvinyl acetal resin, a plasticizer,
A predetermined amount of a metal salt of a carboxylic acid having 5 to 28 carbon atoms and finely divided silica, and one or more of various additives added as necessary, are blended, and the mixture is uniformly kneaded. A plasticized polyvinyl acetal resin film may be formed into a sheet by a method, a calendering method, a pressing method, a casting method, an inflation method, or the like, and then used as an intermediate film.

The above-mentioned resin film may be used as an intermediate film in a single layer, or may be used as an intermediate film in a state where two or more films are laminated. The intermediate film may be used as a single layer, or may be used in a state where two or more sheets are stacked.

The total film thickness of the intermediate film is not particularly limited, but practically, in consideration of the minimum required shock absorption, penetration resistance, weather resistance, etc., as a laminated glass, it is practically the usual thickness. As with the thickness of the interlayer for laminated glass,
Generally, it is preferable to be in the range of 0.3 to 1.6 mm.

Next, the interlayer film for laminated glass according to the second invention is the interlayer film for laminated glass according to the first invention described above, wherein the metal salt of the carboxylic acid is a magnesium salt of a carboxylic acid having 5 to 10 carbon atoms. It is necessary.

The magnesium salt of a carboxylic acid having 5 to 10 carbon atoms is not particularly limited.
For example, magnesium pentanoate, magnesium hexanoate, magnesium heptanoate, magnesium 2-ethylbutanoate, magnesium 2-ethylhexanoate,
Examples thereof include magnesium ethyl octanoate, and one or more of these are suitably used.

The amount of the magnesium salt of a carboxylic acid having 5 to 10 carbon atoms to be added to the polyvinyl acetal resin is not particularly limited, but the amount of the magnesium salt is 0.1 to 100 parts by weight of the polyvinyl acetal resin.
It is preferably from 0.01 to 0.5 part by weight, and
More preferably, it is 0.2 parts by weight.

If the amount of the magnesium salt is less than 0.01 part by weight based on 100 parts by weight of the polyvinyl acetal resin, the effect of adjusting the adhesive strength may not be sufficiently obtained. If it exceeds, the adhesive strength of the obtained interlayer film may be too low, or the water resistance and transparency may be reduced.

Next, the interlayer film for laminated glass according to the third invention is the same as the interlayer film for laminated glass according to the first invention described above, except that the total surface area of the finely divided silica is 1/1 of the total surface area of the interlayer film for laminated glass. It must be contained in such an amount that it becomes 10 or more.

Since the total surface area of the finely divided silica varies depending on the average particle diameter and the amount of addition of the finely divided silica, in the third invention, the total of the surface area of the finely divided silica is calculated from the average particle diameter and the amount of addition of the finely divided silica. The addition amount of the finely divided silica to the plasticized polyvinyl acetal resin film is set so that the total surface area is 1/10 or more of the total surface area of the intermediate film.

The total surface area of the intermediate film or the total surface area of the finely divided silica is calculated as follows.

For example, polyvinyl acetal resin 100
consists g and a plasticizer 40 g, if the intermediate film having a thickness of 0.8 mm, the surface area of one side is 1540 cm ^2, the total surface area of the intermediate layer after being a laminated glass by the combined process is about 3100 cm ^2.

On the other hand, when 0.1 g of finely divided silica having an average particle diameter of 1 μm is added, the total surface area is 2400 c.
m ² , and when 0.1 g of finely divided silica having an average particle diameter of 0.1 μm is added, the total surface area is 24,000.
cm ² .

According to the above calculation, the addition amount of the fine silica powder is set according to the average particle diameter of the fine silica powder to be used so that the total surface area of the fine silica powder is 1/10 or more of the total surface area of the interlayer. Just do it.

When the amount of the finely divided silica added is such that the total surface area thereof is less than 1/10 of the total surface area of the interlayer, the effect of preventing the adhesive strength between the interlayer and the glass from lowering over time can be prevented. May be insufficient.

Next, in the laminated glass according to the fourth invention, the interlayer film for a laminated glass according to any of the first to third inventions described above is interposed between at least a pair of glasses,
It must be integrated.

The above glass includes not only ordinary inorganic transparent glass but also organic transparent glass such as polycarbonate plate and polymethyl methacrylate plate.

The type of the above glass is not particularly limited. For example, various types of inorganic glass such as float plate glass, polished plate glass, template glass, mesh plate glass, wire plate glass, heat ray absorbing plate glass, colored plate glass, etc. Glass or organic glass is mentioned, and one or more of these are suitably used. The thickness of the glass may be appropriately selected depending on the application, and is not particularly limited.

The manufacturing method of the laminated glass according to the fourth invention is not special, and the same manufacturing method as that of the ordinary laminated glass is employed. For example, an interlayer film for laminated glass according to any of the first to third inventions is interposed between two transparent glass plates, placed in a rubber bag, and sucked under reduced pressure at a temperature of about 70 to 110 ° C. Pre-adhesion and then using an autoclave or press at a temperature of about 120-150 ° C and about 10-15 kg /
A desired laminated glass can be obtained by performing actual bonding at a pressure of cm ² and integrating them.

[0083]

The interlayer film for laminated glass according to the first invention comprises a plasticized polyvinyl acetal resin film containing a metal salt of a carboxylic acid having a relatively large number of carbon atoms of 5 to 28 as an adhesion regulator. And, since fine silica is contained in order to prevent a decrease in the adhesive force between the intermediate film and the glass over time, the adhesive force between the intermediate film and the glass is within an appropriate range both in the initial stage and after the elapse of time. Has been retained,
Therefore, both in the initial stage and after the lapse of time, the basic performance required as a laminated glass, such as shock absorption and penetration resistance, is excellent, and the peripheral portion of the laminated glass has a whitening phenomenon even when placed in a humid atmosphere for a long period of time. It is suitable for obtaining a laminated glass that is less likely to cause cracks.

The interlayer film for laminated glass according to the second invention uses the magnesium salt of a carboxylic acid having 5 to 10 carbon atoms as the metal salt of the carboxylic acid in the interlayer film for a laminated glass according to the first invention. The present invention is suitable for obtaining a laminated glass which is more excellent in the above various properties obtained from the interlayer film for a laminated glass according to the first invention.

Further, the interlayer film for a laminated glass according to the third invention is the interlayer film for a laminated glass according to the first invention, wherein the total of the surface area of the finely divided silica is 1/10 or more of the total surface area of the interlayer film for a laminated glass. Is added in such an amount that the carbon number is 5 to 2 as an adhesion regulator.
Even if a metal salt of a carboxylic acid having a relatively large value of 8 is used, it is possible to prevent a decrease in the adhesive force between the interlayer film and the glass over time, and therefore it is possible to stably provide excellent shock absorption and penetration resistance. Suitable for obtaining laminated glass that exhibits

The laminated glass according to the fourth invention is characterized in that
Since it is produced using the interlayer film for laminated glass according to any one of the inventions to the third invention, it is excellent in basic performance required as a laminated glass such as shock absorption and penetration resistance, both in the initial stage and after aging, In addition, even if it is placed in a humid atmosphere for a long period of time, the peripheral portion is less likely to cause whitening.

[0087]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” means “parts by weight”.

(Example 1)

(1) Preparation of polyvinyl acetal resin In 2890 g of pure water, the average degree of polymerization was 1700 and the degree of saponification was 98.
275 g of 9 mol% polyvinyl alcohol was added and dissolved by heating. The temperature of the reaction system was adjusted to 12 ° C., 201 g of 35% by weight hydrochloric acid catalyst and 148 g of n-butyraldehyde were added, and the temperature was maintained to precipitate a reaction product. afterwards,
The reaction was maintained at 45 ° C. for 3 hours to complete the reaction, washed with excess water to remove unreacted n-butyraldehyde, and the hydrochloric acid catalyst was neutralized with a general-purpose neutralizing agent, sodium hydroxide aqueous solution. The mixture was further washed with excess water for 2 hours and dried to obtain a white powdery polyvinyl butyral resin.
The average degree of polymerization of the obtained polyvinyl butyral resin is 17
00, butyralization degree is 65 mol%, residual acetyl group content is 1 mol%, residual vinyl alcohol component content is 34 mol%
Met.

(2) Production of interlayer film for laminated glass For 100 parts of the polyvinyl butyral resin obtained above, 40 parts of triethylene glycol di-2-ethylbutyrate (3GH) as a plasticizer, a metal salt of carboxylic acid 0.087 parts (2.8 × 10 ^-4 mol) of magnesium 2-ethylbutanoate, 0.05 parts of finely divided silica (average particle diameter of primary particles: 12 nm) as an (adhesion modifier), an ultraviolet absorber and an antioxidant After adding the agent and stirring and mixing, 8
The two rolls heated to 0 ° C. were sufficiently melt-kneaded to obtain a polyvinyl butyral resin film having a thickness of about 0.8 mm.
Next, the obtained resin film was regulated by a spacer having a thickness of 0.76 mm and press-molded with a press molding machine heated to 120 ° C. to obtain an interlayer film for laminated glass having an average film thickness of 0.76 mm.

(3) Production of Laminated Glass The interlayer film for laminated glass obtained above was conditioned in a constant temperature and humidity chamber such that the moisture content was 0.4 to 0.5% by weight, and then float glass was used. (Thickness: 2.4 mm) It was sandwiched between two sheets and preliminarily bonded by a roll method. Next, the pre-bonded laminate was heated to 130 ° C. in an air-type autoclave.
The main bonding was performed under the condition of a pressure of 13 kg / cm ² to obtain a laminated glass.

(4) Evaluation The performances (Pummel value,
(Moisture resistance) was evaluated by the following method. The results were as shown in Table 2.

Pummel value : The laminated glass, which was allowed to stand at a temperature of −18 ± 0.6 ° C. for 16 hours and temperature-controlled, had a head of 0.1 mm .
Hitting with a 45Kg hammer, glass particle size is 6mm
Crushed until the following. Then, the degree of exposure of the interlayer film after the glass was partially peeled was determined by a preliminarily graded limit sample, and the result was expressed as a Pummel value according to the criteria shown in Table 1 below. The Pummel value was calculated as follows: (a) initial, (b) 50 ° C.-1 month later, (c) room temperature—half a year later.
The conditions were determined. The higher the Pummel value, the higher the adhesion between the interlayer and the glass, and the lower the Pummel value, the lower the adhesion between the interlayer and the glass.

[0094]

[Table 1]

Moisture resistance : Laminated glass at 50 ° C.-95%
It was left in an RH atmosphere, taken out after 2 weeks and 4 weeks, and the distance of the whitened portion (whitening distance: mm) was measured from the periphery of the laminated glass.

Example 2 In the production of an interlayer film for laminated glass, the amount of magnesium 2-ethylbutanoate (metal salt of carboxylic acid) was changed to 0.072 parts (2.8 × 10 ^-4).
(Mol), and an interlayer film for laminated glass and a laminated glass were obtained in the same manner as in Example 1.

Example 3 In the production of an interlayer film for laminated glass, 0.064 parts of magnesium pentanoate (2.8 × 10 4 parts) were used as the metal salt of carboxylic acid instead of 0.087 parts of magnesium 2-ethylbutanoate. ^-4 mol) in the same manner as in Example 1 to obtain an interlayer film for laminated glass and a laminated glass.

(Example 4) A polyvinyl butyral resin having an average degree of polymerization of 1650, a degree of butyralization of 65 mol%, a residual acetyl group content of 1 mol%, and a residual vinyl alcohol component content of 34 mol% was prepared. 100
Parts, 3GH (plasticizer) 39 parts, magnesium 2-ethyloctanoate (metal salt of carboxylic acid) 0.103 parts (2.
Intermediate for laminated glass in the same manner as in Example 1 except that 8 × 10 ⁻⁴ mol), 0.1 part of finely divided silica (average particle diameter of primary particles: 30 nm), an ultraviolet absorber and an antioxidant were used. A membrane and a laminated glass were obtained.

Example 5 A polyvinyl butyral resin having an average degree of polymerization of 1650, a degree of butyralization of 67 mol%, a residual acetyl group content of 1 mol%, and a residual vinyl alcohol component content of 32 mol% was prepared. 100
Parts, triethylene glycol-di-2-ethylheptanoate (plasticizer) 38 parts, magnesium 2-ethyloctanoate (metal salt of carboxylic acid) 0.103 parts (2.8 ×
10 ^-4 mol), finely divided silica (average particle size of primary particles 12
nm), an interlayer film for laminated glass and a laminated glass were obtained in the same manner as in Example 1 except that 0.02 part of the ultraviolet absorbent and the antioxidant were used.

Example 6 In the production of an interlayer film for laminated glass, the average particle size of primary particles was 1 as fine silica powder.
The interlayer film for laminated glass and the laminated glass were prepared in the same manner as in Example 5 except that 0.01 part of fine silica having an average primary particle diameter of 24 nm was added instead of 0.02 part of 2 nm fine silica. Obtained.

Example 7 In the production of an interlayer film for laminated glass, the average particle size of primary particles was 1 as fine silica powder.
The interlayer film for laminated glass and the laminated glass were prepared in the same manner as in Example 5 except that 0.01 part of fine silica having an average primary particle diameter of 50 nm was added instead of 0.02 part of 2 nm fine silica. Obtained.

Example 8 A polyvinyl butyral resin having an average polymerization degree of 1700, a butyralization degree of 65 mol%, a residual acetyl group content of 1 mol%, and a residual vinyl alcohol component content of 34 mol% was prepared. 100
Part, tetraethylene glycol-di-n-heptanoate (plasticizer) 39 parts, magnesium 2-ethylhexylate (metal salt of carboxylic acid) as a metal salt of carboxylic acid
0.061 part (2.0 × 10 ⁻⁴ mol) and 0.021 part (2.5 × 10 ⁻⁴ mol) of potassium formate, finely divided silica (1
An interlayer film for laminated glass and a laminated glass were obtained in the same manner as in Example 1 except that 0.05 part of an average particle diameter of the secondary particles (12 nm), an ultraviolet absorber and an antioxidant were used.

Comparative Example 1 An interlayer film for laminated glass and a laminated glass were obtained in the same manner as in Example 1 except that fine powdered silica was not added in the production of the interlayer film for laminated glass.

Comparative Example 2 In the production of an interlayer film for laminated glass, 0.040 parts of magnesium acetate (2.8 × 10 ⁻ ) was used as the metal salt of carboxylic acid instead of 0.087 parts of magnesium 2-ethylbutanoate. ⁴ moles)
Example 1 except that finely divided silica was not added
In the same manner as in the above, an interlayer film for laminated glass and a laminated glass were obtained.

(Comparative Example 3) In the production of the interlayer film for laminated glass, 0.056 parts of magnesium butanoate (2.8 × 10 4 parts) were used as the metal salt of carboxylic acid instead of 0.087 parts of magnesium 2-ethylbutanoate. ^-4 mol) and no finely divided silica was added in the same manner as in Example 1 to obtain an interlayer film for laminated glass and a laminated glass.

Comparative Example 4 An interlayer film for laminated glass and a laminated glass were obtained in the same manner as in Example 2 except that fine powdered silica was not added in the production of the interlayer film for laminated glass.

Comparative Example 5 An interlayer film for laminated glass and a laminated glass were obtained in the same manner as in Example 3 except that fine silica was not added in the production of the interlayer film for laminated glass.

Comparative Example 6 An interlayer film for laminated glass and a laminated glass were obtained in the same manner as in Example 4 except that fine silica powder was not added in the production of the interlayer film for laminated glass.

Comparative Example 7 An interlayer film for laminated glass and a laminated glass were obtained in the same manner as in Example 5 except that fine silica was not added in the production of the interlayer film for laminated glass.

Comparative Example 8 An interlayer film for laminated glass and a laminated glass were obtained in the same manner as in Example 6 except that fine silica was not added in the production of the interlayer film for laminated glass.

The performance of the 15 types of laminated glass obtained in Examples 2 to 8 and Comparative Examples 1 to 8 was evaluated in the same manner as in Example 1. The results were as shown in Table 2.

[0112]

[Table 2]

As is evident from Table 2, the laminated glasses of Examples 1 to 5 or Example 8 produced using the interlayer film for laminated glass according to the present invention are suitable both in the initial stage and after the elapse of time. The Pummel value, that is, the proper adhesive strength between the interlayer and the glass was maintained. Also, 50 ℃ -95% R
Even after leaving for 2 weeks or 4 weeks in an atmosphere of H, almost no whitening phenomenon occurred on the periphery of the laminated glass.

The laminated glass of Example 6 or 7 produced by using the interlayer film for laminated glass according to the present invention had a Pummel value after lapse of time, but was reduced to 50 ° C.-9 ° C.
Even after being left for 2 weeks or 4 weeks in an atmosphere of 5% RH, no whitening phenomenon occurred at the periphery of the laminated glass.

On the other hand, the laminated glass of Comparative Example 1 or Comparative Examples 4 to 8 produced using the interlayer film for laminated glass which did not contain the finely divided silica showed a lapse of time as compared with the initial Pummel value. Shows that the Pummel value was extremely low, indicating that the adhesive force between the interlayer and the glass was remarkably reduced with the elapse of time. Further, the laminated glass was left in an atmosphere of 50 ° C.-95% RH for 2 weeks or 4 weeks. A slight whitening phenomenon occurred at the periphery.

Further, it was produced using an interlayer film for laminated glass which contained a metal salt (magnesium salt) of a carboxylic acid having less than 5 carbon atoms as an adhesion regulator and did not contain finely divided silica. Although the laminated glass of Comparative Example 2 or Comparative Example 3 hardly reduced the Pummel value with the passage of time, the peripheral edge of the laminated glass after leaving for 2 weeks or 4 weeks in an atmosphere of 50 ° C. and 95% RH was significantly whitened. A phenomenon was observed, indicating poor moisture resistance.

[0117]

As described above, in the interlayer film for laminated glass according to the present invention, the adhesive strength between the interlayer film and the glass is maintained in an appropriate range both at the initial stage and after the lapse of time, and the moisture resistance is improved. It has excellent basic performance required for laminated glass such as shock absorption and penetration resistance,
Moreover, it is suitable for obtaining a laminated glass which hardly causes a whitening phenomenon in the peripheral portion even when it is placed in a humid atmosphere for a long time.

Further, since the laminated glass according to the present invention is produced using the interlayer film for laminated glass, it has excellent shock absorption properties and penetration resistance both in the initial stage and after the elapse of time. In addition, even if it is placed in a humid atmosphere for a long period of time, almost no whitening phenomenon occurs on the periphery. Therefore,
For automobile windshields and side glasses, or
It is suitably used for window glass of buildings and the like.

Claims (4)

[Claims] 1. A plasticized polyvinyl acetal resin film,
An interlayer film for laminated glass, comprising a metal salt of a carboxylic acid having 5 to 28 carbon atoms and finely divided silica. 2. The metal salt of a carboxylic acid has 5 to 10 carbon atoms.
2. The interlayer film for laminated glass according to claim 1, which is a magnesium salt of a carboxylic acid. 3. The laminated glass according to claim 1, wherein the finely divided silica is contained in such an amount that the total surface area is at least 1/10 of the total surface area of the interlayer film for laminated glass. Interlayer. 4. The method according to claim 1, wherein at least between the pair of glasses.
A laminated glass characterized by being integrated with the interlayer film for laminated glass according to any one of (1) to (3).