JP2000191348A - Intermediate film for sandwich glass and sandwich glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an intermediate film for sandwich glass which has good moisture resistance and does not give rise to whitening, obviates the degradation in adhesive power in peripheral parts under a high-humidity atmosphere and has excellent transparency, moisture resistance and adhesiveness and excellent sound shieldability by decreasing the compounding amount of magnesium carboxylate salt which is an adhesive power control agent as far as possible. SOLUTION: The polyvinyl acetal resin film (A1) of >=2 layers of the laminated resin films laminated with two kinds of the polyvinyl acetal resin films (A1) and (B) consists of a polyvinyl acetal resin which is obtained by acetalyzing polyvinyl alcohol with a 4-6C aldehyde and contains 5 to 8 mol% vinyl acetate component and a plasticizer. The polyvinyl acetal resin film (B) consists of a polyvinyl acetal resin which is obtained by acetalyzing polyvinyl alcohol with a 3 or 4c aldehyde and contains <=4 mol% vinyl acetate component and a plasticizer.

Description

DETAILED DESCRIPTION OF THE INVENTION

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

[0001]

[Prior art]

2. Description of the Related Art Conventionally, laminated glass has been used for automobiles,
Widely used for construction and so on. This laminated glass is
A typical example is a laminate obtained by sandwiching an intermediate film made of plasticized polyvinyl acetal resin between two sheets of glass. In such laminated glass, when an external shock is applied, the glass is broken, but the interlayer film interposed between the glass is not easily broken, and the glass is not damaged even after the breakage. Shards are less likely to scatter,
It serves to prevent people in transit or buildings from being injured by broken glass.

However, in order to satisfy the function as a laminated glass, the higher the adhesive strength between the glass and the interlayer, the better it is not, and it is necessary to adjust it within a certain range. This is for the purpose of absorbing shock and preventing penetration when a driver or a passenger collides with the glass in the case of an automobile, and preventing penetration of a foreign object and scattering of glass fragments in the case of a building. This is for prevention. That is, if the adhesive force between the glass and the intermediate film is too small, the glass is peeled off and scattered from the intermediate film, and if the adhesive force is too large, the glass and the intermediate film are simultaneously broken and penetrated. . If the adhesive strength is within an appropriate range, three types of destruction occur: glass cracking occurs in a wide range, and at the same time, the glass breaks, and at the same time, interfacial separation between the glass and the interlayer occurs, and the interlayer extends. Energy is greatly absorbed, which is effective in preventing penetration.

[0003] The adhesive strength between the interlayer film and the glass is different in the degree of penetration resistance required for an automobile windshield, an automobile side glass, and a building. Since high penetration resistance is required for automotive windshields, the adhesion is adjusted by adding an adhesion regulator, but for automotive side glasses and construction, penetration resistance is as large as that for automobile windshields. Since penetration resistance is not required, no study has been made to improve penetration resistance by adjusting the amount of an adhesion regulator such as a metal carboxylate. This is because the use of an adhesive force adjuster tends to cause problems such as foaming in the laminated glass.

Further, when an interlayer containing a metal carboxylate is used for laminated glass, there is a problem that whitening occurs in the peripheral portion. This is because the interlayer film has a high hygroscopicity and absorbs moisture under a normal atmosphere (humidity). When an actual laminated glass is manufactured, the water content is about 0.45%. As described above, the processing is performed by adjusting the humidity at a relative humidity of 25%. However, the edges of the laminated glass for automobile side glass and architectural use are usually exposed, and in a high-humidity atmosphere, the surrounding area contains water. Rate is 2-3%
To rise.

[0005] In order to suppress such whitening of the peripheral portion and further reduction of the adhesive strength, it is most effective to reduce the blending amount of the metal carboxylate. However,
If the amount of the metal carboxylate is reduced, the impact resistance and penetration resistance of the obtained laminated glass are excessively reduced, so that the amount of the metal carboxylate cannot be simply reduced.

By the way, this kind of laminated glass is excellent in safety because glass fragments do not scatter when broken.
Generally inferior in sound insulation. In particular, in the middle and high frequency range around the frequency of 2000 Hz, the sound transmission loss is reduced due to the coincidence effect, and the sound insulation is reduced. The coincidence effect is a phenomenon in which when a sound wave is incident on glass, a transverse wave is conducted on the glass surface due to the rigidity and inertia of the glass, and the transverse wave resonates with the incident sound to cause sound transmission.

[0007] In recent years, the demand for sound insulation has been increasing more and more. In particular, in the case of architectural window glass, in addition to the fact that glass shards are not scattered when broken, excellent sound insulation performance is exhibited. Is required. As such a sound insulating interlayer for laminated glass and laminated glass, using two types of plasticized polyvinyl acetal resin films,
A laminated glass using at least two layers of an interlayer film for sound insulating laminated glass constituted by laminating them has been proposed (see JP-A-4-254444).

Here, the one resin film is made of a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with an aldehyde having 6 to 10 carbon atoms and a plasticizer. The other resin film is formed of a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with an aldehyde having 1 to 4 carbon atoms and a plasticizer.

[0009] As described above, the interlayer for laminated glass used for architectural and automotive side glass does not need to have the same penetration resistance as the interlayer for automotive windshield, but has the moisture resistance, adhesiveness, and the like. Good performance such as sound insulation has been demanded.

[0010]

DISCLOSURE OF THE INVENTION The present invention aims to improve the moisture resistance and prevent the occurrence of whitening by reducing the amount of magnesium carboxylate as an adhesion regulator as much as possible. An object of the present invention is to provide an interlayer film for laminated glass and a laminated glass which are excellent in transparency, moisture resistance, adhesiveness, and sound insulation without causing a decrease in the adhesive strength at the peripheral portion.

[0011]

The interlayer film for laminated glass of the invention according to claim 1 of the present invention (hereinafter referred to as "first invention") comprises two types of polyvinyl acetal resin films (A1) and (B). Is a laminated resin film of two or more layers, wherein the polyvinyl acetal resin film (A1) is obtained by acetalizing polyvinyl alcohol with an aldehyde having 4 to 6 carbon atoms, and has a vinyl acetate component content of 5 to 8 mol. % Of a polyvinyl acetal resin (a1) and a plasticizer, the polyvinyl acetal resin film (B) is obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or 4 carbon atoms, and a vinyl acetate component having a vinyl acetate content of 4 mol% or less. Consisting of a polyvinyl acetal resin (b) and a plasticizer,
Among the polyvinyl acetal resin films (A1) and (B), at least the polyvinyl acetal resin film which is in contact with glass contains 0.0005 to 5 parts by weight of magnesium carboxylate having 1 to 28 carbon atoms with respect to 100 parts by weight of the polyvinyl acetal resin. 0.5 parts by weight.

In the first invention, the polyvinyl alcohol used in the preparation of the polyvinyl acetal resins (a1) and (b) may have a low average polymerization degree, which may lower the penetration resistance of the laminated glass. Is high, the resin film is difficult to mold or the strength of the resin film may be too strong, so that the average degree of polymerization is 500 to 3000.
And more preferably an average degree of polymerization of 1000
~ 2500.

The degree of saponification of the polyvinyl alcohol is preferably from 5 to 8 mol% in the preparation of the polyvinyl acetal resin (a1), so that the saponification degree is preferably from 92 to 95 mol%. Used. On the other hand, in the preparation of the resin (b), the vinyl acetate component must be set to 4 mol% or less.
Those having a saponification degree of 96 mol% or more are suitably used.

Here, the average degree of polymerization and saponification degree of polyvinyl alcohol can be measured, for example, according to JIS K 6726 "Testing method for polyvinyl alcohol".

If the number of carbon atoms of the aldehyde used in the preparation of the polyvinyl acetal resin (a1) is 3 or less, sufficient sound insulating properties cannot be obtained in the laminated glass, and if the number of carbon atoms of the aldehyde used is 7 or more,
The reactivity of acetalization is reduced, and the sound insulating performance of the laminated glass at around room temperature is not sufficiently exhibited.

The aldehyde having 4 to 6 carbon atoms includes:
For example, n-butyraldehyde, isobutyraldehyde, valeraldehyde, n-hexylaldehyde, 2-
Ethyl butyraldehyde and the like, which may be used alone or in combination of two or more. Among them, n-butyraldehyde, isobutyraldehyde, n
-Hexyl aldehyde is preferably used alone or in combination of two or more.

When the number of carbon atoms of the aldehyde used in the preparation of the polyvinyl acetal resin (b) is 2 or less, the moldability of the polyvinyl acetal resin film (B) deteriorates. And the sound insulation performance near room temperature is not sufficiently exhibited.

The above aldehyde having 3 or 4 carbon atoms includes, for example, propionaldehyde, n-butyraldehyde, isobutyraldehyde and the like, and these may be used alone or in combination of two or more. Among them, single or a combination of two or more of n-butyraldehyde and isobutyraldehyde is preferable.

In particular, the polyvinyl acetal resin (a
Both 1) and (b) are preferably those obtained by acetalization with n-butyraldehyde having 4 carbon atoms. n
By using a resin acetalized with butyraldehyde, the adhesive strength of each resin film is enhanced, the weather resistance is excellent, and the production of a polyvinyl acetal resin film is facilitated.

The polyvinyl acetal resins (a1) and (b) are composed of a vinyl acetal component, a vinyl alcohol component and a vinyl acetate component. The amounts of these components can be measured based on, for example, JIS K 6728 "Polyvinyl butyral test method".

When the content of the vinyl acetate component in the polyvinyl acetal resin (a1) is too small, the resulting laminated glass cannot exhibit sound insulation performance sufficiently.
If the content increases, blocking occurs during the production of the resin, so the content is 5 to 8 mol%, preferably 6 to 8 mol%.

As the content of the vinyl acetate component in the polyvinyl acetal resin (b) increases, the viscoelastic properties of the resulting polyvinyl acetal resin films (A1) and (B) become similar, and the polyvinyl acetal resin films (A1) and (B) have similar viscoelastic properties. Is not sufficiently exhibited, the content is 4 mol% or less.
Preferably it is 0-2 mol%.

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. can do.

The degree of acetalization of the polyvinyl acetal resins (a1) and (b) can also be measured based on the above test method. If the degree of acetalization of the polyvinyl acetal resin (a1) is low, the compatibility between the polyvinyl acetal resin (a1) and the plasticizer is reduced, so that it is difficult to contain a plasticizer in an amount necessary for exhibiting sound insulation performance. , 40 mol% or more, more preferably 50 mol% or more.

When the degree of acetalization of the polyvinyl acetal resin (b) is low, the compatibility between the polyvinyl acetal resin (b) and the plasticizer is reduced, and it becomes difficult to contain the plasticizer in an amount necessary for ensuring the penetration resistance. Therefore, 50 mol%
The above is preferred.

The method for preparing the polyvinyl acetal resins (a1) and (b) is not particularly limited, and any known method may be used. For example, a polyvinyl alcohol is dissolved in warm water, and the resulting aqueous solution is dissolved. While maintaining the temperature at a predetermined temperature, for example, 0 to 95 ° C., the required acid catalyst and aldehyde are added, the acetalization reaction is allowed to proceed with stirring, and then the reaction temperature is raised to ripen and complete the reaction. , Neutralization, washing and drying to obtain polyvinyl acetal resin (a1) and (b) powder.

The polyvinyl acetal resins (a1) and (b) thus prepared are each mixed with a predetermined amount of a plasticizer, and formed into a sheet by extrusion, calendering, pressing or the like. Thus, polyvinyl acetal resin films (A1) and (B) are obtained. The polyvinyl acetal resin films (A1) and (B) can also be obtained by blending a predetermined amount of a plasticizer with the polyvinyl acetal resins (a1) and (b), and integrally molding the same by a multilayer extrusion method. can get.

The plasticizer used in the first invention is not particularly limited, and known plasticizers used for this kind of interlayer film, for example, ester plasticizers such as monobasic acid ester and polybasic acid ester. Agents: Phosphoric plasticizers such as organic phosphoric acid and organic phosphorous acid.

As the above monobasic acid ester, for example,
Triethylene glycol, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptanoic acid, n-octylic acid,
-Ethylhexylic acid, pelargonic acid (n-nonylic acid),
Glycol esters obtained by reaction with an organic acid such as decyl acid are exemplified. In addition, esters of the above-mentioned organic acids with tetraethylene glycol, tripropylene glycol or the like are also used.

The polybasic acid ester includes, for example,
Esters of organic acids such as adipic acid, sebacic acid and azelaic acid with linear or branched alcohols having 4 to 8 carbon atoms can be mentioned. Examples of the phosphate plasticizer include, for example,
Tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphite and the like can be mentioned.

Among these plasticizers, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, and triethylene glycol diester
n-octoate, triethylene glycol di-n-heptoate, tetraethylene glycol di-n-heptoate, dibutyl sebacate, dioctyl azelate,
Dibutyl carbitol adipate and the like are particularly preferably used.

If the amount of the above plasticizer to be added to the polyvinyl acetal resin (a1) is too small, it is difficult to obtain sufficient sound insulation of the laminated glass, and if it is too large, the plasticizer bleeds and the transparency of the laminated glass and the glass plate. Since the adhesiveness to the interlayer may be impaired, 55 to 70 parts by weight of the polyvinyl acetal resin (a1) is used.
The amount is preferably 0 parts by weight, more preferably 55 to 65 parts by weight.

The blending amount of the above plasticizer with respect to the polyvinyl acetal resin (b) is substantially the same as the amount of the plasticizer used in an intermediate film made of a general plasticized polyvinyl butyral resin. The penetration resistance may decrease, and if the amount increases, the plasticizer bleeds and the transparency of the laminated glass and the adhesion between the glass plate and the interlayer may be impaired. Therefore, 100 parts by weight of the polyvinyl acetal resin (b) The amount is preferably 25 to 55 parts by weight, more preferably 30 to 45 parts by weight.

Resin (a1) used in the first invention
And the resin (b) have 1 to 2 carbon atoms as an adhesive force adjuster.
8 magnesium carboxylate is blended. The magnesium carboxylate is not particularly limited as long as it has 1 to 28 carbon atoms. For example, magnesium acetate,
Examples thereof include magnesium propionate, magnesium 2-ethylbutanoate, and magnesium 2-ethylhexanoate. These magnesium carboxylate salts may be used alone or in combination of two or more.

When the amount of the magnesium carboxylate is too small, the adhesive strength at the periphery of the laminated glass in a high-humidity atmosphere is reduced. When the amount is too large, the adhesive strength of the interlayer is too low and the transparency is lowered. Therefore, 0.0005 to 0.5 parts by weight based on 100 parts by weight of the polyvinyl acetal resin.
Parts by weight, preferably 0.001 to 0.2 parts by weight.

In the first invention, a modified silicone oil such as an ether-modified silicone oil, an epoxy-modified silicone oil, an ester-modified silicone oil, an amine-modified silicone oil or the like is used in addition to the above-mentioned magnesium carboxylate as an adhesion regulator. You may. The amount of the modified silicone oil is preferably 0.001 to 0.5 part by weight, more preferably 0.005 to 0.1 part by weight, based on 100 parts by weight of the polyvinyl acetal resin.

In the polyvinyl acetal resins (a1) and (b) used in the first invention, in addition to the above-mentioned adhesive force modifier, an ultraviolet absorber, a light stabilizer, an antioxidant, a surfactant, a coloring agent A well-known additive used for an interlayer for a laminated glass may be blended.

Examples of the ultraviolet absorber include Tinuvin P (trade name) and Tinuvin 320 manufactured by Ciba Geigy.
(Trade name), Tinuvin 326 (trade name), Tinuvin 32
8 (trade name). Examples of the light stabilizer include hindered amine-based light stabilizers such as ADK STAB LA-57 (trade name) manufactured by Asahi Denka Co., Ltd. Examples of the antioxidant include phenol-based antioxidants such as Sumilizer BHT (trade name) manufactured by Sumitomo Chemical Co., Ltd. and Irganox 1010 (trade name) manufactured by Ciba Geigy Co., Ltd. Examples of the surfactant include sodium lauryl sulfate and alkylbenzene sulfonic acid.

As described above, the interlayer film for laminated glass of the first invention is a method of integrally forming the polyvinyl acetal resin films (A1) and (B) by a multilayer extrusion method, and a method of separately forming the polyvinyl acetal resin film (A1). And (B)
And a method in which the polyvinyl acetal resin films (A1) and (B) are stacked between two glass plates and heated and pressurized to form an integrated body and simultaneously with the production of a laminated glass. And so on.

The method for producing a laminated glass using the interlayer film for a laminated glass of the first invention is not particularly limited. For example, an intermediate film or a polyvinyl acetal resin film (before lamination) between two transparent glass plates is used. A1) and (B)
And put it in a rubber bag for about 7
Pre-adhesion at 0-110 ° C., then using an autoclave or using a press, about 120-150 ° C., about 1
A method of manufacturing by performing actual bonding at a pressure of 0 to 15 kg / cm ² is exemplified.

The laminated structure of the polyvinyl acetal resin films (A1) and (B) includes, for example, the following structure. -Two-layer laminated structure of resin film (A1) / resin film (B)-Resin film (A1) / resin film (B) / resin film (A1) or resin film (B) / resin film (A1) / 3 of resin film (B)
Four-layer laminated structure of resin film (A1) / resin film (B) / resin film (A1) / resin film (B) Note that in the laminated structure, for example, resin film (A
Resin films of the same type such as 1) / resin film (A1) and resin film (B) / resin film (B) may be stacked one upon another.

In any of the above-mentioned lamination structures, it is preferable to laminate the resin films (B) so as to be disposed on the outermost layers on both sides. With this arrangement, good workability comparable to that of a normal polyvinyl butyral intermediate film can be obtained when the glass plate and the intermediate film are combined, and the conventional combination processing technology can be used as it is. Further, it is also preferable in terms of the adhesion between the glass plate and the interlayer and the weather resistance.

The thickness of the polyvinyl butyral resin films (A) and (B) is preferably not less than 0.05 mm because the thinner the film thickness, the more difficult it is to obtain good sound insulation performance and weather resistance. In addition, although the sound insulation performance becomes better as the thickness of the entire intermediate film increases, the thickness of the entire intermediate film is generally 0.3 to 1.6 mm, similarly to the thickness of a general interlayer film for laminated glass. It is preferable to be within the range.

The glass plate used in manufacturing the laminated glass is not particularly limited, and not only an inorganic glass plate but also an organic glass plate such as a polycarbonate plate and a polymethyl methacrylate plate can be used.

When the laminated glass is placed under high humidity, the water content of the interlayer usually increases to several% in the peripheral portion.
When magnesium carboxylate is not present in the interlayer, the adhesive force monotonously decreases with an increase in the water content in the interlayer. Therefore, when the water content increases to several percent, the adhesive force between the interlayer and the glass is reduced. Almost disappears and peeling occurs. On the other hand, when the magnesium carboxylate is added, a minimum point of the adhesive force is present at around 1% with an increase in the water content, and the adhesive force is increased above the minimum. As described above, since the relationship between the water content and the adhesive strength is greatly changed by the addition of the magnesium carboxylate, it is possible to improve the peeling at the peripheral portion of the laminated glass by adding a small amount of the magnesium carboxylate. That is, in the first invention, the magnesium carboxylate is used not for the purpose of adjusting the adhesive force, which is the usual purpose, but for increasing the adhesive force at the periphery of the laminated glass.

Further, whitening of the laminated glass occurs when the magnesium carboxylate is dispersed in the plasticizer without being dissolved, because water is collected in the crystal part and the visible light is scattered. It is generally considered. Therefore, if the size of the crystal of the magnesium carboxylate decreases or the total amount of the crystal decreases, the whitening can be suppressed. The interlayer film for a laminated glass according to the first invention is used for an application for which the necessity of adjusting an adhesive force for an automobile side glass, an architectural use, etc. is not higher than that for an automobile windshield. Since it is not necessary to add a large amount of a metal carboxylate to the glass, whitening of the laminated glass can be suppressed.

The interlayer film for laminated glass according to the second aspect of the present invention (hereinafter referred to as the "second invention") comprises a laminate of two types of polyvinyl acetal resin films (A2) and (B). The polyvinyl acetal resin film (A2), which is a laminated resin film having two or more layers, is obtained by acetalizing polyvinyl alcohol with an aldehyde having 4 to 6 carbon atoms, and a polyvinyl acetal resin having a vinyl acetate component of 8 to 30 mol% ( a2) and a plasticizer, the polyvinyl acetal resin film (B) is obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or 4 carbon atoms, and a polyvinyl acetal resin (b) having a vinyl acetate component of 4 mol% or less. At least one of the polyvinyl acetal resin films (A2) and (B) The acetal resin film, carbon atoms relative to 100 parts by weight of the polyvinyl acetal resin 1-2
0.0005 to 0.5 of magnesium carboxylate
Parts by weight are included.

The degree of saponification of the polyvinyl alcohol used in the preparation of the polyvinyl acetal resin (a2) must be set to 8 to 30 mol% of the vinyl acetate component in the polyvinyl acetal resin (a2).
Those having a saponification degree of 70 to 92 mol% are suitably used.

When the content of the vinyl acetate component in the polyvinyl acetal resin (a2) is small, the sound insulation performance in a temperature range higher than room temperature is good, but the sound insulation performance near room temperature cannot be sufficiently obtained. Although the sound insulation performance in the temperature range lower than room temperature is good, the sound insulation performance near room temperature cannot be sufficiently obtained, so that the content is 8 to 30 mol%, preferably 12 to 24 mol%.

Examples of the plasticizer used in the second invention include the same plasticizers used in the first invention. When the compounding amount of the plasticizer with respect to the polyvinyl acetal resin (a2) is too small, it is difficult to obtain a sufficient sound insulating performance of the laminated glass. Of the polyvinyl acetal resin (a2) in an amount of 30 to
It is preferably 70 parts by weight, more preferably 35 to 65 parts by weight.

In the interlayer film for laminated glass of the second invention, the other components, the amounts thereof, and the production method are the same as those of the first invention.

The interlayer film for laminated glass of the invention according to claim 3 of the present invention (hereinafter referred to as "third invention") comprises a laminate of two types of polyvinyl acetal resin films (A3) and (B). A multilayer resin film of at least one layer, wherein the polyvinyl acetal resin film (A3) is obtained by acetalizing polyvinyl alcohol with an aldehyde having 6 to 10 carbon atoms,
The polyvinyl acetal resin (a3) having a vinyl acetate component of 4 mol% or less and a plasticizer, and the polyvinyl acetal resin film (B) is obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or 4 carbon atoms. The polyvinyl acetal resin (b) whose component is 4 mol% or less and a plasticizer, and at least one of the polyvinyl acetal resin films (A3) and (B) that come into contact with glass have a polyvinyl acetal resin 100 1 to 2 carbons per part by weight
0.0005 to 0.5 of magnesium carboxylate
An interlayer film for laminated glass, characterized by being contained in parts by weight.

The degree of saponification of the polyvinyl alcohol used in the preparation of the polyvinyl acetal resin (a3) must be set to 4 mol% or less in the polyvinyl acetal resin (a3), so that the saponification degree is 96 mol% or more. Is preferably used.

The aldehyde having 6 to 10 carbon atoms used in the preparation of the polyvinyl acetal resin (a3) includes, for example, n-hexylaldehyde, n-octylaldehyde, benzaldehyde, n-heptylaldehyde, 2-ethylbutyraldehyde, Cinnamaldehyde and the like, which may be used alone or 2
More than one species may be used in combination. Among them, n-hexyl aldehyde, n-octyl aldehyde, and 2-ethyl butyraldehyde are preferably used alone or in combination of two or more.

When the content of the vinyl acetate component in the polyvinyl acetal resin (a3) is too small, the synthesis of the polyvinyl acetal resin (a3) becomes difficult, so that the content is 4 mol% or less.

In the third invention, the blending amount of the plasticizer with respect to the polyvinyl acetal resins (a3) and (b) may decrease if the amount is small, and the plasticizer may bleed when the amount is too large. Of the polyvinyl acetal resin (a3) and (b) 10
The amount is preferably 30 to 60 parts by weight, more preferably 45 to 50 parts by weight, based on 100 parts by weight of the polyvinyl acetal resin (a3), and 35 to 40 parts by weight based on 100 parts by weight of the polyvinyl acetal resin (b). is there.

The other components and amounts of the interlayer in the interlayer film for laminated glass according to the third invention, and the manufacturing method thereof are the same as those of the first invention.

[0058]

Hereinafter, the present invention will be described in more detail by showing Examples and Comparative Examples of the present invention. Note that “parts” means “parts by weight”.

Example 1 <Preparation of polyvinyl butyral resin film (A1)> A butyralization degree of 63 mol%, a vinyl acetate component of 7 mol%,
To 100 parts of polyvinyl butyral resin (a1) having a polymerization degree of 1700 with 30 mol% of residual vinyl alcohol, 60 parts of triethylene glycol di-2-ethyl butyrate, 0.013 parts of magnesium acetate (magnesium concentration of 15 p
pm), an ultraviolet absorber, and an antioxidant, and the mixture was sufficiently melt-kneaded with a mixing roll and then press-formed at 150 ° C. for 30 minutes using a press-forming machine to obtain a thickness of 0.2 m.
m of a polyvinyl butyral resin film (A1) was obtained.

<Preparation of Polyvinyl Butyral Resin Film (B)> 100 parts of polyvinyl butyral resin (b) having a degree of butyralization of 66 mol%, a vinyl acetate component of 1 mol%, a residual vinyl alcohol of 33 mol%, and a polymerization degree of 1700, After adding 40 parts of triethylene glycol di-2-ethyl butyrate, 0.013 parts of magnesium acetate (magnesium concentration 15 ppm), an ultraviolet absorber, and an antioxidant, the mixture was sufficiently melted and kneaded with a mixing roll.
Press molding was performed at 150 ° C. for 30 minutes using a press molding machine to obtain a polyvinyl butyral resin film (B) having a thickness of 0.2 mm.

<Production of Laminated Glass> The polyvinyl butyral resin films (A1) and (B) obtained had a water content of 0.1%.
It is adjusted in a constant temperature and humidity chamber so as to be 4 to 0.5%, and is superposed in the order of resin film (B) / resin film (A1) / resin film (B), and has a thickness of 2.4 mm from both sides. After sandwiching with a transparent float glass, the obtained sandwich is put in a rubber bag, deaerated at a degree of vacuum of 20 torr for 20 minutes, and then transferred to a 90 ° C. oven in a deaerated state at 90 ° C. It was further vacuum pressed for 30 minutes. The laminated glass thus preliminarily bonded is placed in an air-type autoclave at a temperature of 140 ° C.
Main bonding was performed at 13 ° C. and a pressure of 13 kg / cm ² for 20 minutes to obtain a laminated glass.

When the CSS of the obtained laminated glass was measured, it was 19.2 N / sqmm. In addition, temperature 5
When a moisture resistance test was performed for 4 weeks in an atmosphere of 0 ° C. and a humidity of 95%, whitening of the peripheral portion was 0.5 mm.
No peeling of the peripheral portion was observed. In addition, these evaluations were performed by the following methods.

<CSS Measuring Method> A test piece was cut out from the obtained laminated glass into a disk having a diameter of 23 mm, and measured at a temperature of 20 ° C. (68 F) and a crosshead speed of 10 mm / min using a glass fixing jig. , A compression test was performed, and the maximum load value was calculated by dividing the obtained maximum load value by the test piece area (φ23 mm).

<Moisture resistance test>
After being left for 4 weeks in an atmosphere at a temperature of 50 ° C. and a relative humidity of 95%, the whitening state of the end was visually observed. In addition, whitening was shown by the distance from the periphery.

<Peripheral Part Peeling Test> The obtained laminated glass was left in an atmosphere at a temperature of 50 ° C. and a relative humidity of 95% for 4 weeks, and then the presence or absence of peeling at the peripheral part was visually observed.

Examples 2 and 3 and Comparative Examples 1 to 4 Laminated glass was produced in the same manner as in Example 1 except that the kind and the amount of magnesium carboxylate were changed.
Evaluation was performed in the same manner as in Example 1. Table 1 shows the obtained results.

[0067]

[Table 1]

Example 4 <Preparation of Polyvinyl Butyral Resin Film (A2)> A degree of butyralization of 60 mol%, a vinyl acetate component of 12 mol%, a residual vinyl alcohol of 28 mol%, and a polymerization degree of 170
100 parts of polyvinyl butyral resin (a2), 50 parts of triethylene glycol di-2-ethyl butyrate
Parts, 0.013 parts of magnesium acetate (magnesium concentration 15 ppm), an ultraviolet absorber, and an antioxidant,
This was sufficiently melt-kneaded with a mixing roll, and then press-formed at 150 ° C. for 30 minutes using a press-forming machine to obtain a polyvinyl butyral resin film (A2) having a thickness of 0.2 mm.

<Preparation of Polyvinyl Butyral Resin Film (B)> 100 parts of polyvinyl butyral resin (b) having a degree of butyralization of 66 mol%, a vinyl acetate component of 1 mol%, a residual vinyl alcohol of 33 mol%, and a polymerization degree of 1700, After adding 40 parts of triethylene glycol di-2-ethyl butyrate, 0.013 parts of magnesium acetate (magnesium concentration 15 ppm), an ultraviolet absorber, and an antioxidant, the mixture was sufficiently melted and kneaded with a mixing roll.
Press molding was performed at 150 ° C. for 30 minutes using a press molding machine to obtain a resin film (B) having a thickness of 0.2 mm.

<Manufacture of Laminated Glass> The obtained resin films (A2) and (B) were adjusted in a constant temperature and humidity chamber so that the water content was 0.4 to 0.5%. B) / resin film (A2) / resin film (B) in this order, sandwiched from both sides with a transparent float glass having a thickness of 2.4 mm, put the obtained sandwiched body in a rubber bag and vacuum After deaeration at a temperature of 20 torr for 20 minutes, the substrate was transferred into an oven at 90 ° C. in a deaerated state, and further vacuum-pressed at 90 ° C. for 30 minutes. The laminated glass thus preliminarily bonded is heated in an air-type autoclave at a temperature of 140 ° C. and a pressure of 13 kg / c.
This was adhered for 20 minutes at m ² to obtain a laminated glass.

When the obtained laminated glass was evaluated in the same manner as in Example 1, the CSS was 17.8 N / sq.
mm, whitening of the peripheral part was 0.5 mm, and peeling of the peripheral part was not recognized.

Examples 5 and 6 and Comparative Examples 5 to 8 Laminated glass was produced in the same manner as in Example 4 except that the kind and the amount of magnesium carboxylate were changed.
evaluated. Table 2 shows the obtained results.

[0073]

[Table 2]

Example 7 <Preparation of Polyvinyl Butyral Resin Film (A3)> The degree of acetalization was 67.5 mol%, the vinyl acetate component was 1 mol%, the residual vinyl alcohol was 31.5 mol%, and the degree of polymerization was 1
To 100 parts of a 700 polyvinyl acetal resin (a3), 50 parts of triethylene glycol di-2-ethyl butyrate, 0.013 part of magnesium acetate (magnesium concentration 15 ppm), an ultraviolet absorber, and an antioxidant were added, and this was added. After sufficiently melting and kneading with the mixing roll,
Press molding was performed at 150 ° C. for 30 minutes using a press molding machine to obtain a polyvinyl butyral resin film (A2) having a thickness of 0.2 mm. In addition, n-hexyl aldehyde was used for acetalization of the polyvinyl acetal resin (a3).

<Preparation of Polyvinyl Butyral Resin Film (B)> 100 parts of polyvinyl butyral resin (b) having a degree of polymerization of 1700 and a degree of butyralization of 66 mol%, a vinyl acetate component of 1 mol% and a residual vinyl alcohol of 33 mol% After adding 40 parts of triethylene glycol di-2-ethyl butyrate, 0.013 parts of magnesium acetate (magnesium concentration 15 ppm), an ultraviolet absorber, and an antioxidant, the mixture was sufficiently melted and kneaded with a mixing roll.
Press molding was performed at 150 ° C. for 30 minutes using a press molding machine to obtain a resin film (B) having a thickness of 0.2 mm.

<Manufacture of Laminated Glass> The obtained resin films (A3) and (B) were adjusted in a constant temperature and humidity chamber so that the water content became 0.4 to 0.5%. B) / resin film (A3) / resin film (B) in this order, sandwiched from both sides with a transparent float glass having a thickness of 2.4 mm, and the obtained sandwiched body was placed in a rubber bag and vacuumed. After deaeration at a temperature of 20 torr for 20 minutes, the substrate was transferred into an oven at 90 ° C. in a deaerated state, and further vacuum-pressed at 90 ° C. for 30 minutes. The laminated glass thus preliminarily bonded is heated in an air-type autoclave at a temperature of 140 ° C. and a pressure of 13 kg / c.
This was adhered for 20 minutes at m ² to obtain a laminated glass.

When the obtained laminated glass was evaluated in the same manner as in Example 1, the CSS was 19.0 N / sq.
mm, whitening of the peripheral part was 0.5 mm, and peeling of the peripheral part was not recognized.

Examples 8 and 9 and Comparative Examples 9 to 12 Laminated glass was produced in the same manner as in Example 7 except that the kind and the amount of magnesium carboxylate were changed.
evaluated. Table 3 shows the obtained results.

[0079]

[Table 3]

[0080]

The interlayer film for laminated glass and the laminated glass according to the present invention have transparency,
The sound insulation performance due to the coincidence effect is maintained, the whitening in a high humidity atmosphere is suppressed, and the peeling of the peripheral portion is also prevented. That is, by blending a specific small amount of magnesium carboxylate, each of the above performances is stably maintained over a long period of time.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a glass fixing jig used in CSS measurement.

Claims (4)

[Claims] Claims: 1. A polyvinyl acetal resin film (A)
1) and (B) are laminated resin films of two or more layers, wherein the polyvinyl acetal resin film (A1) is obtained by acetalizing polyvinyl alcohol with an aldehyde having 4 to 6 carbon atoms, and vinyl acetate The polyvinyl acetal resin (a1) having a component of 5 to 8 mol% and a plasticizer, and the polyvinyl acetal resin film (B) is obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or 4 carbon atoms, and a vinyl acetate component. Consists of a polyvinyl acetal resin (b) of not more than 4 mol% and a plasticizer, and among the polyvinyl acetal resin films (A1) and (B), at least the polyvinyl acetal resin film which is in contact with glass has a polyvinyl acetal resin weight of 100% The magnesium carboxylate having 1 to 28 carbon atoms is 0.0005 to 0 Intermediate film for laminated glass, characterized in that 5 contained parts. 2. A polyvinyl acetal resin film (A)
2) and (B) are laminated resin films of two or more layers, wherein the polyvinyl acetal resin film (A2) is obtained by acetalizing polyvinyl alcohol with an aldehyde having 4 to 6 carbon atoms, and vinyl acetate 8 to 30 components
A polyvinyl acetal resin (a2) and a plasticizer, and the polyvinyl acetal resin film (B) is obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or 4 carbon atoms, and the vinyl acetate component contains 4 mol%.
The following polyvinyl acetal resin (b) and a plasticizer comprise a polyvinyl acetal resin film (A2) and (B)
Among them, at least the polyvinyl acetal resin film in contact with the glass contains 0.0005 to 0.5 parts by weight of a magnesium carboxylate having 1 to 28 carbon atoms with respect to 100 parts by weight of the polyvinyl acetal resin. Characteristic interlayer film for laminated glass. 3. A polyvinyl acetal resin film (A)
3) and (B) are laminated resin films of two or more layers, wherein the polyvinyl acetal resin film (A3) is obtained by acetalizing polyvinyl alcohol with an aldehyde having 6 to 10 carbon atoms, and vinyl acetate The component comprises a polyvinyl acetal resin (a3) having a content of 4 mol% or less and a plasticizer, and the polyvinyl acetal resin film (B) is obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or 4 carbon atoms. 4 mol%
A polyvinyl acetal resin film (A3) comprising the following polyvinyl acetal resin (b) and a plasticizer, and (B)
Among them, at least the polyvinyl acetal resin film in contact with the glass contains 0.0005 to 0.5 parts by weight of a magnesium carboxylate having 1 to 28 carbon atoms with respect to 100 parts by weight of the polyvinyl acetal resin. Characteristic interlayer film for laminated glass. 4. A laminated glass, wherein the interlayer film for laminated glass according to claim 1 is sandwiched between two transparent glass plates.