JP2000007386A - Interlayer for laminated glass and laminated glass - Google Patents

Abstract

(57) [Summary] [Problem] The adhesive strength between an interlayer film and glass is maintained within an appropriate range both at an initial stage and after a lapse of time, and therefore, as a laminated glass having shock absorption and penetration resistance. In addition to having the required basic performance, it has excellent moisture resistance, and hardly causes whitening on the periphery (end) of the laminated glass even when left for a long time in a humid atmosphere.
And, an interlayer film for laminated glass suitable for obtaining a laminated glass exhibiting excellent reflectivity or absorptivity to light rays having a specific wavelength such as heat rays, ultraviolet rays, near infrared rays, infrared rays, and the like, and using the interlayer film It is an object of the present invention to provide a laminated glass manufactured by the above method. SOLUTION: The plasticized polyvinyl acetal resin film has
A metal salt of a carboxylic acid having 1 to 12 carbon atoms, a carboxyl-modified or amine-modified silicone oil, and an interlayer film for laminated glass, which is characterized by containing wavelength-selective particles, and at least between a pair of glasses, Laminated glass characterized by being integrated with an interlayer for laminated glass interposed therebetween.

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 rear 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.

[0009] For example, 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, the plasticized polyvinyl acetal resin composition contains 10 to 10 carbon atoms.
22. A laminated glass characterized by containing a sodium metal salt of an aliphatic carboxylic acid of No. 22 has been proposed, and JP-B-53-18207 discloses an alkali metal salt of a monocarboxylic acid or a dicarboxylic acid. Or a laminated glass characterized in that at least two glasses are bonded by a plasticized polyvinyl acetal resin interlayer containing or attached to an alkaline earth metal salt and a modified silicone oil. Further, JP-A-5-186250 discloses a resin composition containing a polyvinyl acetal resin, a plasticizer, an alkali or alkaline earth metal salt of an aliphatic mono- or dicarboxylic acid having 12 or less carbon atoms, and an organic acid. An interlayer film for laminated glass formed by the above method has been proposed.

In each of the above three proposals, a metal salt of a carboxylic acid is used as an adhesive force regulator.

However, as proposed in Japanese Patent Publication No. 48-5772, when a metal salt of a carboxylic acid having a relatively large number of carbon atoms is used as an adhesive force regulator, the adhesive force between the interlayer and the glass is reduced. There is a problem that it changes with the passage of time (time). In other words, even if the initial adhesive strength is appropriate, the adhesive strength gradually decreases or increases over time,
The glass is easily peeled off when subjected to an impact, or on the contrary, the adhesive strength becomes too high and the penetration resistance is reduced. In order to prevent this change in adhesive strength, it is necessary to store and ripen the interlayer under an atmosphere of, for example, 40 to 50 ° C. for 1 to 2 months, but the interlayer has tackiness, self-adhesion, and the like. Therefore, it is practically difficult to store for a long time under the above atmosphere, and even if aging is performed, it is possible to suppress the change over time of the adhesive force, but it is impossible to eliminate it at all. I ca n’t,
The above problems remain.

Further, as proposed in Japanese Patent Application Laid-Open No. 5-186250, when a metal salt of a carboxylic acid having a relatively small number of carbon atoms is used as an adhesive force adjusting agent, the adhesive force between the interlayer and the glass can be measured with time. Although the problem of the change is eliminated, the moisture resistance of the interlayer film becomes insufficient, and 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 high hygroscopic property under a normal atmosphere (humidity), when it is processed into a laminated glass, for example, the water content is 0.1% under an atmosphere having a relative humidity of 25% (25% RH). It is common practice to adjust the humidity so as to be about 45% by weight and to perform the processing. However, since the periphery (end) of the laminated glass is usually bare, the interlayer film absorbs moisture in a high humidity atmosphere, and the moisture content is 2 to 2.
It rises to about 3% by weight. At this time, water collects around a metal salt of a carboxylic acid having a relatively 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.

In practice, however, especially in the case of laminated glass for automobiles, safety (adhesion) is emphasized, and even if a slight whitening phenomenon occurs, the number of carbon atoms capable of suppressing a change with time in the adhesive force is relatively small. Metal salts of carboxylic acids have been used.

On the other hand, in recent years, there has been a movement to use heat ray reflecting glass, heat ray absorbing glass and the like for automobiles from the viewpoint of energy saving. In particular, the heat ray reflective glass has a large energy saving effect. However, heat-reflective or heat-absorbing glass is generally produced by coating a glass surface with a multilayer coating of a raw material or material that reflects or absorbs a specific wavelength by vacuum deposition, which is costly,
There is a problem that its use is limited to luxury cars and the like.

One way to address the above problems is to:
A transparent film, such as a polyethylene terephthalate film (PET film), in which particles reflecting or absorbing a specific wavelength (hereinafter referred to as “wavelength-selective particles”) are kneaded in advance, is attached to the glass surface with an adhesive. Heat ray reflective or heat ray absorbing glass of the configuration is being considered.

However, the heat ray reflecting glass or the heat ray absorbing glass having the above structure has a limit in the durability of the adhesive.
With the passage of time, the edge of the transparent film is peeled off from the glass surface, or a phenomenon such as generation of a rough surface such as wrinkles on the transparent film surface occurs. Therefore, there is a problem that the transparent film has to be replaced in several months to several years. . Also, the windshield of an automobile has a curved surface, but it is difficult to apply the transparent film tightly along the curved surface with an adhesive without causing a phenomenon such as wrinkling. However, it is difficult to use it on a flat surface, and there is also a problem that the application is limited to only a flat portion.

As another method corresponding to the problem of the above-mentioned vacuum evaporation type or the above-mentioned transparent film pasting type heat ray reflection or heat ray absorption glass, a method of kneading the wavelength-selective particles into the intermediate film itself has also been studied. However, if the wavelength-selective particles are contained in the interlayer, the adhesive strength between the interlayer and the glass becomes too high, so that the adhesive strength between the interlayer and the glass is in an appropriate range both at the initial stage and after aging. In order to maintain the adhesive strength within the above range, it is necessary to contain a large amount of the above-mentioned metal salt-based adhesion modifier of carboxylic acid or a modified silicone oil-based adhesion modifier as disclosed in JP-B-53-18207. Occurs.

In this case, if a large amount of the metal salt-based adhesion modifier of carboxylic acid is contained, the occurrence of whitening phenomenon becomes severe, and if a large amount of the modified silicone oil-based adhesion modifier is contained, an interlayer film is produced. The problem that the change with time of the adhesive force between the glass and the glass increases.

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 the elapse of time, and is excellent in moisture resistance and left in a high humidity atmosphere for a long period of time. At present, an interlayer film for laminated glass and a laminated glass suitable for obtaining a laminated glass with less occurrence of a whitening phenomenon have not been put to practical use.

[0021]

SUMMARY OF THE INVENTION In order to solve the above-mentioned conventional problems, the present invention maintains the adhesive strength between the interlayer film and the glass within an appropriate range both in the initial stage and after the elapse of time. Therefore, it excels in basic performance required for laminated glass such as shock absorption and penetration resistance, and also has excellent moisture resistance, and even when left in a humid atmosphere for a long period of time, it can be applied to the edge (end) of the laminated glass. Almost no whitening phenomenon, and heat rays, ultraviolet rays, near infrared rays, interlayer film for laminated glass suitable for obtaining a laminated glass exhibiting excellent reflectivity or absorptivity to light rays having specific wavelengths such as infrared rays, Another object is to provide a laminated glass manufactured using the intermediate film.

[0022]

An interlayer film for laminated glass according to the invention described in claim 1 (hereinafter referred to as "first invention") is obtained by adding a plasticized polyvinyl acetal resin film to a carboxyl group having 1 to 12 carbon atoms. It is characterized by comprising a metal salt of an acid, a carboxyl-modified or amine-modified silicone oil and wavelength-selective particles.

The invention according to claim 2 (hereinafter referred to as “second
The laminated glass according to the "invention") is characterized in that the interlayer film for a laminated glass according to the first invention is interposed between at least a pair of glasses and integrated.

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 average degree of polymerization is 500 to 500 as PVA.
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 as described above is preferably set at 30 mol% or less. For this reason, 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. The average degree of polymerization and the degree of saponification of the PVA can be measured, for example, according to 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, preferably 4 to 8 carbon atoms. Are preferably used.

Examples of such aldehydes include, but are not limited to, 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 the respective components can be measured, for example, in accordance with 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 below is reduced, and it may be difficult to mix an amount of the plasticizer necessary for securing the penetration resistance. Conversely, to obtain a resin having an average acetalization degree exceeding 75 mol%, a long reaction time may be required, 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-based plasticizer is not particularly limited, and examples thereof include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphite, and the like. Is preferably used.

Among the above various plasticizers, for example, triethylene glycol-di-2-ethyl butyrate (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 containing polyvinyl butyral resin”) is not particularly limited, but is 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 reduced penetration resistance.
When the amount is more than the weight part, the plasticizer bleeds out, and the optical distortion of the obtained intermediate film may increase, or the transparency and the adhesive strength may decrease.

The interlayer film for laminated glass according to the first invention comprises:
In the plasticized polyvinyl acetal resin film composed of the above-mentioned polyvinyl acetal resin and a plasticizer, a metal salt of a carboxylic acid having 1 to 12 carbon atoms and a carboxyl-modified or amine-modified silicone oil as an adhesion regulator, and Contains wavelength-selective particles for imparting reflectivity or absorptivity to light rays having a specific wavelength such as heat rays, ultraviolet rays, near infrared rays, infrared rays, etc. (hereinafter, simply referred to as “light rays having a specific wavelength”). Become.

The metal salt of a carboxylic acid having 1 to 12 carbon atoms used as the above-mentioned adhesive force modifier is not particularly limited, but examples thereof include aliphatic monocarboxylic acids and aliphatic dicarboxylic acids. Salts obtained by using an aromatic carboxylic acid such as a carboxylic acid, an aromatic monocarboxylic acid, or an aromatic dicarboxylic acid as an acid component, and an alkali metal or an alkaline earth metal as a metal component are listed. More than one species is preferably used.

Specific examples of the carboxylic acid having 1 to 12 carbon atoms as the acid component are not particularly limited.
Linear monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, capric acid, and succinic acid;
Examples thereof include branched monocarboxylic acids such as 2-ethylbutyric acid and 2-ethylcaproic acid, dicarboxylic acids such as adipic acid and sebacic acid, and monobutyladipic acid, and are preferably used. Ethyl butyric acid and the like are more preferably used.

When the carboxylic acid has more than 12 carbon atoms, the resulting interlayer has good moisture resistance, but the adhesive strength between the interlayer and the glass changes over time, and the initial adhesive strength is not appropriate. However, the adhesive force gradually decreases or increases with the passage of time, so that the glass is easily peeled off when subjected to an impact, or hardly peeled off.

Specific examples of the metal component include, but are not particularly limited to, alkali metals such as potassium and sodium, and alkaline earth metals such as magnesium and calcium. Among them, potassium, magnesium and the like are more preferably used.

Specific examples of the metal salt of a carboxylic acid having 1 to 12 carbon atoms obtained from the carboxylic acid having 1 to 12 carbon atoms as the acid component and the metal component are not particularly limited. , Potassium acetate, magnesium acetate, potassium propionate, sodium propionate,
Magnesium propionate, potassium butyrate, sodium butyrate, magnesium butyrate, sodium caproate, magnesium caproate, sodium 2-ethylcaproate, magnesium 2-ethylcaproate, sodium caprylate, magnesium caprylate, sodium caprate, magnesium caprate And sodium succinate, magnesium succinate, sodium adipate, magnesium adipate, and the like, and are preferably used. Among them, potassium salts and magnesium salts are more preferably used, and among them, potassium acetate and magnesium acetate are preferred. Particularly preferably used.

The metal salt of a carboxylic acid having 1 to 12 carbon atoms may be used alone or in combination of two or more.

The amount of the metal salt of a carboxylic acid having 1 to 12 carbon atoms to be added to the plasticized polyvinyl acetal resin film is not particularly limited, but may be 1 to 12 parts by weight based on 100 parts by weight of the polyvinyl acetal resin. Is preferably 0.01 to 0.5 part by weight, more preferably 0.02 to 0.2 part by weight.

If the amount of the metal salt of a carboxylic acid having 1 to 12 carbon atoms is less than 0.01 part by weight per 100 parts by weight of the polyvinyl acetal resin, the effect of adjusting the adhesive strength may not be sufficiently obtained. If the amount of the metal salt of a carboxylic acid having 1 to 12 carbon atoms with respect to 100 parts by weight of the polyvinyl acetal resin exceeds 0.5 part by weight, the adhesive strength of the obtained intermediate film may be too low, or the water resistance or transparency may be reduced. Etc. may decrease.

The carboxyl-modified or amine-modified silicone oil also used as an adhesion regulator is not particularly limited. For example, a polysiloxane and a compound having a carboxyl group or an amine group to be introduced into the polysiloxane may be used. And generally a pale yellow transparent viscous liquid obtained by deriving from polysiloxane by reacting

The above-mentioned carboxyl-modified or amine-modified silicone oil may have an appropriately adjusted modification rate in order to adjust the compatibility with the plasticizer contained in the plasticized polyvinyl acetal resin film. preferable.

The above carboxyl-modified or amine-modified silicone oil may be used alone or in combination of two or more.

The amount of the above-mentioned carboxyl-modified or amine-modified silicone oil to be added to the plasticized polyvinyl acetal resin film is not particularly limited. 00
Preferably from 0.5 to 0.5 part by weight, and from 0.01 to 0.5 part by weight.
More preferably, it is 0.2 parts by weight.

If the amount of the carboxyl-modified or amine-modified silicone oil is less than 0.0005 parts by weight per 100 parts by weight of the polyvinyl acetal resin, the effect of containing the carboxyl-modified or amine-modified silicone oil becomes insufficient, and If the adhesive strength between the film and the glass becomes too high, and if the amount of the carboxyl-modified or amine-modified silicone oil added to 100 parts by weight of the polyvinyl acetal resin exceeds 0.5 part by weight, the adhesive strength between the interlayer and the glass will become too high. The decrease with time increases. In this case, if the amount of the metal salt of the carboxylic acid is increased in order to adjust the adhesive force between the intermediate film and the glass to an appropriate range, the water resistance and transparency of the intermediate film and the laminated glass are reduced.

In the interlayer film for laminated glass according to the first invention, the above-mentioned C 1 -C 12 is used as an adhesive force regulator.
It is necessary that the metal salt of a carboxylic acid and the above-mentioned carboxyl-modified or amine-modified silicone oil be used in combination.

When only a metal salt of a carboxylic acid having 1 to 12 carbon atoms is contained and no carboxyl-modified or amine-modified silicone oil is contained, the adhesive strength between the intermediate film and the glass, particularly the wavelength selectivity described later The effect of adjusting the adhesive force between the interlayer film containing the particles and the glass cannot be sufficiently obtained, and conversely, it contains only a carboxyl-modified or amine-modified silicone oil and contains a metal salt of a carboxylic acid having 1 to 12 carbon atoms. If not, a larger amount of a carboxyl-modified or amine-modified silicone oil is required than in the past, and the change over time in the adhesive force between the interlayer and the glass becomes large.

In the interlayer film for laminated glass according to the first invention,
The wavelength-selective particles contained to impart reflectivity or absorptivity to light having the specific wavelength are not particularly limited, but include, for example, metals, metal oxides, metal sulfides, metals, and the like. And are preferably used.

Specific examples of the above-mentioned wavelength-selective particles are not particularly limited. Examples thereof include titanium oxide, zinc oxide, tin oxide, bismuth oxide, tungsten oxide, indium oxide, zirconium oxide, and mixtures thereof. Metal oxides; doped metals such as tin-doped indium, antimony-doped tin oxide, and antimony-doped zinc oxide;
Metal sulfides such as zinc sulfide; metals such as gold, silver, copper, tin, aluminum, nickel, palladium, and alloys thereof; and the like are preferably used. Among them, metals having a good balance between performance and cost Oxides are more preferably used, and among them, titanium oxide and zinc oxide are particularly preferably used.

The wavelength-selective particles may be used alone or in combination of two or more.

The average particle diameter of the wavelength-selective particles is not particularly limited, but is preferably 0.2 μm or less in order to prevent irregular reflection of visible light.

The amount of the wavelength-selective particles to be added to the plasticized polyvinyl acetal resin film is not particularly limited depending on the degree of need for reflectivity or absorptivity for light having a specific wavelength. For 100 parts by weight of the acetal resin, 0.0
It is preferably 1 to 5 parts by weight, more preferably 0.05 to 1 part by weight.

If the amount of the wavelength-selective particles is less than 0.01 part by weight based on 100 parts by weight of the polyvinyl acetal resin, sufficient reflectivity or absorptivity to light having a specific wavelength may not be obtained. If the addition amount of the wavelength-selective particles to 100 parts by weight of the polyvinyl acetal resin exceeds 5 parts by weight, the addition is excessive, and the reflection or absorption of light having a specific wavelength is no longer improved. It is necessary to greatly increase the amount of the force adjusting agent, and the adhesion between the interlayer and the glass may be poor.

The interlayer film for laminated glass according to the first invention comprises, as essential components, polyvinyl acetal resin, plasticizer, metal salt of carboxylic acid having 1 to 12 carbon atoms, carboxyl-modified or amine-modified silicone oil, and wavelength-selective particles. In addition, if necessary, a modified silicone oil such as ether-modified silicone oil, ester-modified silicone oil, epoxy-modified silicone oil other than carboxyl-modified or amine-modified silicone oil may be used as long as the object of the present invention is not hindered. One of various additives such as an adhesion regulator, an ultraviolet absorber and a light stabilizer for improving weather resistance, for example, an antioxidant for preventing thermal deterioration in an extruder, a surfactant, and a colorant. Species or two or more species may be contained.

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.

Examples of the light stabilizer include, but are not particularly limited to, 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 "Ilganox 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 alkylbenzene sulfonate, 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, a polyvinyl acetal resin, a plasticizer, a metal salt of a carboxylic acid having 1 to 12 carbon atoms, which are essential components, After mixing predetermined amounts of the carboxyl-modified or amine-modified silicone oil and the wavelength-selective particles with one or more predetermined amounts of various additives to be added as necessary, and uniformly kneading them. Extrusion, calendaring, pressing, casting, inflation, etc. to form a sheet into a plasticized polyvinyl acetal resin film,
This may be used as an intermediate film.

The plasticized polyvinyl acetal resin film may be used as an intermediate film in a single layer or 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 above intermediate film is not particularly limited, but it is necessary to consider the minimum required shock absorption, penetration resistance, weather resistance, heat ray reflection or heat ray absorption as laminated glass. Then, in practice, the film thickness is generally 0.3 to 1.6 in the same manner as the film thickness of the usual interlayer film for laminated glass.
mm.

Next, the laminated glass according to the second invention is formed by interposing the above-mentioned interlayer film for a laminated glass according to the first invention between at least a pair of glasses.

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, float glass, polished glass, template glass, meshed glass, wire glass, heat reflective or heat absorbing glass, colored glass Various types of inorganic glass or organic glass such as plate glass are exemplified, 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 second invention is not special, and the same manufacturing method as in the case of ordinary laminated glass is employed. For example, an interlayer film for laminated glass according to the first invention is interposed between two transparent glass plates, placed in a rubber bag, and preliminarily bonded at a temperature of about 70 to 110 ° C. while suctioning under reduced pressure. Or using a press, about 120-150 ° C
At this temperature, the main bonding is performed at a pressure of about 10 to 15 kg / cm ² , and a desired laminated glass can be obtained by integrating them.

[0076]

The interlayer film for laminated glass according to the first invention is formed by bonding a metal salt of a carboxylic acid having 1 to 12 carbon atoms and a carboxyl-modified or amine-modified silicone oil to a plasticized polyvinyl acetal resin film as an adhesion regulator. Is contained in a state used together, and, since the wavelength-selective particles are contained, the adhesive force between the interlayer film and the glass is maintained within an appropriate range both in the initial stage and after the elapse of time, Therefore, it excels in basic performance required for laminated glass such as shock absorption and penetration resistance, and also has excellent moisture resistance, and even when left in a humid atmosphere for a long period of time, it can be applied to the edge (end) of the laminated glass. Synthetic gas that hardly causes whitening and exhibits excellent reflectivity or absorptivity to light having a specific wavelength such as heat rays, ultraviolet rays, near infrared rays, infrared rays, etc. Suitable to get a scan.

Further, since the laminated glass according to the second invention is produced using the interlayer film for a laminated glass according to the first invention, the laminated glass has excellent basic performances required as a laminated glass such as shock absorption and penetration resistance. Even when left in a humid atmosphere for a long period of time, almost no whitening phenomenon occurs at the peripheral portion (end portion), and it exhibits excellent reflectivity or absorptivity to light having the specific wavelength.

[0078]

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, an adhesive force adjuster 0.03 part of magnesium acetate (carbon number 2) as a metal salt of a carboxylic acid having 1 to 12 carbon atoms, 0.05 part of a carboxyl-modified silicone oil as an adhesive force modifier,
After adding 0.2 parts of titanium oxide (average particle size: 0.2 μm) and an antioxidant as wavelength-selective particles for imparting reflectivity or absorptivity to light having a specific wavelength, and stirring and mixing, Kneading with two rolls heated to ℃
A plasticized polyvinyl butyral resin film having a thickness of about 0.8 mm was formed. Next, the plasticized polyvinyl butyral resin film obtained above was coated with a thickness of 0.76 mm.
The mixture was heated and pressurized with a press heated to 120 ° C. to obtain a 0.76 mm-thick interlayer film for laminated glass.

(3) Production of laminated glass The interlayer film for laminated glass obtained above is adjusted to have a water content of 0.4 to 0.5% by weight in a constant temperature and humidity chamber (20 ° C.-65% RH). After humidification, the float glass (thickness 2.
4 mm) and sandwiched between two sheets, preliminarily bonded by a roll method and laminated. Next, the preliminarily bonded laminate was fully bonded in an autoclave at a temperature of 130 ° C. and a pressure of 13 kg / cm ² to obtain a laminated glass.

(4) Evaluation The performances (Pummel value,
Penetration resistance, moisture resistance, ultraviolet cut rate) were evaluated by the following methods. The results were as shown in Table 2.

Pummel value: The laminated glass which had been left to stand at a temperature of −18 ± 0.6 ° C. for 16 hours and was conditioned had a head of 0.1 mm.
Hitting with a 45kg hammer, the 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. In addition, Pummel values are initial and 5
Two conditions after leaving at 0 ° C. for 4 weeks 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.

[0085]

[Table 1]

[0086] Penetration resistance: 2.26 kg in weight from above, with the end of the laminated glass (test piece) cut into 300 mm x 300 mm fixed to a support frame and held horizontally.
Using a device that allows the steel ball to fall freely into the center of the test piece, the drop height of the steel ball is changed in 0.5m units, and a repeated drop ball test is performed. 50% of the test pieces pass through the steel ball. The falling ball height (m) that can prevent the occurrence of the falling ball was measured. The higher the falling ball height, the better the penetration resistance.

Moisture resistance: Laminated glass at 50 ° C.-95%
After being left for two weeks in an atmosphere of RH, it was taken out and the distance of the whitened portion (whitening distance: mm) was measured from the periphery (end) of the laminated glass. The smaller the whitening distance, the better the moisture resistance.

UV cut rate: The spectral transmittance curve of the laminated glass was measured, and the UV cut rate (%) was determined based on DIN 67507.

Example 2 In the production of an interlayer film for laminated glass, potassium acetate (C 2) was used as a metal salt of a carboxylic acid having 1 to 12 carbon atoms as an adhesion regulator.
In the same manner as in Example 1 except that 5 parts, and also 0.02 part of an amine-modified silicone oil as an adhesive force adjuster and 0.2 part of zinc oxide (average particle diameter: 0.1 μm) as wavelength-selective particles were added. Thus, an interlayer film for laminated glass and a laminated glass were obtained.

(Comparative Example 1) In the production of the interlayer for laminated glass, the procedure was carried out except that 0.03 part of polyether-modified silicone oil was added instead of 0.05 part of carboxyl-modified silicone oil as the modified silicone oil. In the same manner as in Example 1, an interlayer film for laminated glass and a laminated glass were obtained.

Comparative Example 2 In the production of an interlayer film for laminated glass, the addition amount of magnesium acetate (2 carbon atoms) was 0.1 part and the modified silicone oil was 0.05 part of carboxyl-modified silicone oil. Instead, an interlayer film for laminated glass and a laminated glass were obtained in the same manner as in Example 1 except that 0.03 part of a polyether-modified silicone oil was added.

(Comparative Example 3) In the production of an interlayer film for laminated glass, the procedure was carried out except that 0.03 part of a polyether-modified silicone oil was added instead of 0.02 part of an amine-modified silicone oil as a modified silicone oil. In the same manner as in Example 2, an interlayer film for laminated glass and a laminated glass were obtained.

Comparative Example 4 An interlayer film for laminated glass and a laminated glass were obtained in the same manner as in Example 1 except that no wavelength-selective particles were added in the production of the interlayer film for laminated glass.

(Comparative Example 5) In the production of an interlayer for laminated glass, 0.03 part of a polyether-modified silicone oil was added instead of 0.05 part of a carboxyl-modified silicone oil as a modified silicone oil, and
An interlayer film for laminated glass and a laminated glass were obtained in the same manner as in Example 1 except that the wavelength-selective particles were not added.

(Comparative Example 6) In the production of the interlayer for laminated glass, the procedure was carried out except that 0.2 parts of polyether-modified silicone oil was added instead of 0.05 parts of carboxyl-modified silicone oil as the modified silicone oil. In the same manner as in Example 1, an interlayer film for laminated glass and a laminated glass were obtained.

The performances (Pummel value, penetration resistance, moisture resistance, UV cut rate) of the seven types of laminated glass obtained in Example 2 and Comparative Examples 1 to 6 were the same as in Example 1. evaluated. The results were as shown in Table 2.

[0097]

[Table 2]

As is evident from Table 2, the laminated glasses of Examples 1 and 2 produced using the interlayer films for laminated glass of Examples 1 and 2 according to the present invention were initially and at 50 ° C.
After 4 weeks, the Pummel value, that is, the adhesive force between the interlayer and the glass, is maintained at an appropriate value, and the basic performance required as a laminated glass such as penetration resistance and moisture resistance is excellent. And the UV cut rate was also high.

On the other hand, Comparative Examples 1 and 3 containing the modified silicone oils (polyether-modified silicone oils) other than the carboxyl-modified or amine-modified silicone oils were used. Laminated glasses 1 and 3 were inferior in penetration resistance.

Further, a modified silicone oil (polyether-modified silicone oil) other than the carboxyl-modified or amine-modified silicone oil was contained, and was produced using the interlayer film for laminated glass of Comparative Example 2 in which the amount of magnesium acetate added was large. The obtained laminated glass of Comparative Example 2 was inferior in moisture resistance.

Further, the laminated glass of Comparative Examples 4 and 5 produced using the interlayer films for laminated glass of Comparative Examples 4 and 5, which did not contain the wavelength-selective particles, had a low ultraviolet ray cut rate.

Furthermore, Comparative Example 6 produced using the interlayer for laminated glass of Comparative Example 6 in which the amount of the modified silicone oil (polyether-modified silicone oil) other than the carboxyl-modified or amine-modified silicone oil was large. In the laminated glass of No. 4, the Pummel value significantly decreased after 50 ° C. for 4 weeks, indicating that the adhesive force between the interlayer film and the glass was extremely reduced with time.

[0103]

As described above, the interlayer film for laminated glass according to the present invention has excellent basic properties required for laminated glass, such as shock absorption and penetration resistance, both at the initial stage and after aging, and has a high moisture resistance. Excellent in properties, hardly causes whitening on the edge (end) of the laminated glass even when left in a humid atmosphere for a long time, and has a specific wavelength such as heat rays, ultraviolet rays, near infrared rays, infrared rays, etc. It is suitable for obtaining a laminated glass exhibiting excellent reflectivity or absorptivity to a light ray having the following.

Further, since the laminated glass according to the present invention is produced using the above-mentioned interlayer film for laminated glass, the basic performance required as a laminated glass, such as shock absorption and penetration resistance, both initially and after aging. It has excellent moisture resistance, hardly causes whitening on the periphery (edge) even when left in a humid atmosphere for a long time, and has excellent reflectivity to light having the above specific wavelength. Or it exhibits absorbency. Therefore, it is suitably used for a windshield of an automobile, a side glass, a rear glass, a window glass of a building, and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // (C08L 29/14 83:04)

Claims (2)

[Claims] 1. A plasticized polyvinyl acetal resin film,
An interlayer film for laminated glass, comprising a metal salt of a carboxylic acid having 1 to 12 carbon atoms, a carboxyl-modified or amine-modified silicone oil, and wavelength-selective particles. 2. The method according to claim 1, further comprising: at least a pair of glasses.
A laminated glass characterized by being integrated with an interlayer film for laminated glass as described in 1 above.