JP2000319044A - Interlayer for laminated glass and laminated glass - Google Patents

Abstract

(57) [Problem] To provide an interlayer film for laminated glass and a laminated glass excellent in sound insulation and moisture resistance. The intermediate film is a laminated resin film of at least two layers composed of two types of plasticized polyvinyl acetal resin films. One of the resin films is obtained by acetalizing polyvinyl alcohol with an aldehyde having 4 to 10 carbon atoms. Obtained
The vinyl acetate component is composed of a polyvinyl acetal resin of 30 mol% or less and a plasticizer, and the sodium concentration of the resin film is 20 ppm or less. The other resin film is obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or 4 carbon atoms. And a plasticizer comprising a polyvinyl acetal resin having a vinyl acetate component of 4 mol% or less and a plasticizer, and a sodium concentration of the resin film of 15 ppm or less. Using this intermediate film, a laminated glass is obtained by an ordinary method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an interlayer film for laminated glass and a laminated glass having excellent sound insulation and moisture resistance.

[0002]

2. Description of the Related Art A laminated glass in which an intermediate film made of a plasticized polyvinyl acetal resin such as a plasticized polyvinyl butyral resin is bonded between at least two transparent glass plates has good transparency, weather resistance and adhesion. In addition, it has good penetration resistance and has basic performances required for laminated glass such that glass fragments are not easily scattered when broken, and is widely used for window glasses of automobiles and buildings, for example.

However, this kind of laminated glass has poor sound insulation. In particular, in the middle and high frequency range around the frequency of 2000 Hz, the amount of 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 by the rigidity and inertia of the glass, and the transverse wave and the incident sound resonate, so that sound transmission occurs. The demand for sound insulation is increasing more and more in recent years. In particular, in the case of architectural glazings, those which have the above-mentioned basic performance and are excellent in safety and also exhibit excellent sound insulation performance are required.

[0004] As such an interlayer film for laminated sound insulating glass and laminated glass, at least two laminated resin films composed of two types of plasticized polyvinyl acetal resin films A and B, wherein the resin film A is polyvinyl alcohol. Is obtained by acetalization with an aldehyde having 6 to 10 carbon atoms, and 100 parts by weight of a polyvinyl acetal resin (a) having a vinyl acetate component of 4 mol% or less and 30 to 60 parts by weight of a plasticizer. An intermediate for laminated glass obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or 4 carbon atoms and comprising 100 parts by weight of a polyvinyl acetal resin (b) having a vinyl acetate component of 4 mol% or less and 30 to 60 parts by weight of a plasticizer. Laminated glass using a film is known (JP-A-4-254444 and JP-A-5-3104). See No. 9).

A laminated resin film of at least two layers composed of two types of plasticized polyvinyl acetal resin films C and D, wherein the resin film C is formed of polyvinyl alcohol having 4 carbon atoms.
And vinyl acetal resin (c) having a vinyl acetate component of 8 to 30 mol% and a plasticizer. The resin film D is obtained by converting polyvinyl alcohol with an aldehyde having 3 or 4 carbon atoms. There is known a laminated glass obtained by acetalization and using an interlayer film for a laminated glass comprising a polyvinyl acetal resin (d) having a vinyl acetate component of 4 mol% or less and a plasticizer (JP-A-10-36146). reference).

A laminated resin film of at least two layers composed of two types of plasticized polyvinyl acetal resin films E and F, wherein the resin film E comprises polyvinyl alcohol having 4 carbon atoms.
And a vinyl acetate component obtained by acetalization with an aldehyde of ６6, 100 parts by weight of a polyvinyl acetal resin (e) having a vinyl acetate component of 5 to 8 mol%, and 55 to 70 parts by weight of a plasticizer. An intermediate film for laminated glass, obtained by acetalizing with an aldehyde having 3 or 4 carbon atoms and comprising 100 parts by weight of a polyvinyl acetal resin (f) having a vinyl acetate component of 4 mol% or less and 25 to 55 parts by weight of a plasticizer, is used. A laminated glass is known (see JP-A-7-206483).

[0007]

According to the above-mentioned interlayer film and laminated glass for sound insulating laminated glass, the transparency, weather resistance and adhesiveness are good, the penetration resistance is good, and glass fragments are scattered when broken. It is excellent in basic performance required for laminated glass such as difficult to perform, and furthermore, a decrease in sound insulation due to a coincidence effect is prevented, and the sound insulation performance is improved.

However, the conventional sound insulating laminated glass has insufficient moisture resistance. That is, if such a laminated glass is used for a long time in a humid or humid environment, the adhesive strength between the glass plate and the interlayer decreases with time, and the marginal glass plate and the interlayer may not be bonded to each other. There is a problem that moisture or moisture in the air intrudes inward from the interface, and the periphery of the laminated glass is whitened.

The present invention solves the above problems,
Its purpose is to have good basic performance required for laminated glass, such as good transparency, weather resistance and adhesion, and good penetration resistance, and it is difficult for glass fragments to scatter when broken.
Moreover, an object of the present invention is to provide an interlayer film for laminated glass and a laminated glass having excellent sound insulation properties and moisture resistance.

[0010]

According to the first aspect of the present invention, there is provided a laminated resin film having at least two layers of two types of plasticized polyvinyl acetal resin films A and B. The resin film A is obtained by acetalizing polyvinyl alcohol with an aldehyde having 6 to 10 carbon atoms, and 100 parts by weight of a polyvinyl acetal resin (a) having a vinyl acetate component of 4 mol% or less and a plasticizer 30 to 6 parts by weight.
The resin film B is obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or 4 carbon atoms, and 100 parts by weight of a polyvinyl acetal resin (b) having a vinyl acetate component of 4 mol% or less and a plasticizer. 30-6
In the interlayer film for laminated glass consisting of 0 parts by weight, the sodium concentration of the resin film A is 20 ppm or less,
An interlayer film for laminated glass is provided, wherein the resin film B has a sodium concentration of 15 ppm or less.

According to the second aspect of the present invention, there is provided at least a two-layer laminated resin film composed of two types of plasticized polyvinyl acetal resin films C and D, wherein the resin film C comprises polyvinyl alcohol having 4 to 4 carbon atoms. 6 is obtained by acetalization with an aldehyde having a vinyl acetate component of 8 to 30 mol% of a polyvinyl acetal resin (c) and a plasticizer. The resin film D is obtained by converting polyvinyl alcohol with an aldehyde having 3 or 4 carbon atoms. In the interlayer film for a laminated glass comprising a polyvinyl acetal resin (d) having a vinyl acetate component of 4 mol% or less and a plasticizer, the sodium concentration of the resin film C is 20 ppm or less, and the resin film D Is provided with an interlayer film for laminated glass, wherein the sodium film has a sodium concentration of 15 ppm or less.

According to the third aspect of the present invention, there is provided at least a two-layer laminated resin film composed of two types of plasticized polyvinyl acetal resin films E and F, wherein the resin film E comprises polyvinyl alcohol having 4 to 4 carbon atoms. Acetalized with the aldehyde of No. 6 and having a vinyl acetate component of 5 to 8 mol%
A resin film F is obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or 4 carbon atoms, and 100 parts by weight of a polyvinyl acetal resin (e) and 55 to 70 parts by weight of a plasticizer. % Of the polyvinyl acetal resin (f) of 100% by weight or less and a plasticizer of 25 to 55 parts by weight, the resin film E has a sodium concentration of 20 ppm or less, and the resin film F has a sodium concentration of 20 ppm or less. Is 15 ppm
There is provided an interlayer film for laminated glass characterized by the following.

Further, in the invention according to claim 4, the interlayer film for laminated glass according to any one of claims 1 to 3 is sandwiched between at least two transparent glass plates. A featured laminated glass is provided.

In the present invention, the polyvinyl acetal resins (a), (b), (c), (d), (e) and (f)
In order to manufacture the same, for example, JP-A-4-254444 and JP-A-5-310444 cited as the prior art are used.
No. 9, JP-A-10-36146 and JP-A-Hei7
The manufacturing method described in detail in JP-A-206483 or the like is employed. However, in this case, in order to reduce the sodium concentration in each resin, for example, the powdery polyvinyl acetal resin obtained by the above-described production method is mixed with, for example, 40 to 60.
A new step of washing with stirring while adding warm water of ° C. is added.

Using the polyvinyl acetal resins (a), (b), (c), (d), (e) and (f) thus produced, a predetermined amount of a plasticizer is added to each of them. This is formed into a sheet by an extrusion method, a calender method, a press method, or the like, whereby resin films A, B, C, D, E, and F are manufactured. Then, the resin films A and B, the resin films C and D, and the resin films D and F are stacked in a combination of at least two layers, and are stacked by pressing. The above resins (a), (b), (c), (d), (e) and (f) were used, and a predetermined amount of a plasticizer was mixed with each of these resins. Thereby, it is also possible to integrally mold at least two layers of the laminated resin film. The thickness of the intermediate film is determined in consideration of the penetration resistance and the like required for the laminated glass. In particular, the thickness is preferably set to 0.2 to 2 mm.

In this case, the laminated resin film is generally made of resin film A / resin film B, resin film B / resin film A / resin film B, resin film C / resin film D, resin film D / resin film C / resin film. It has a laminated structure such as the film D, the resin film E / the resin film F, and the resin film F / the resin film E / the resin film F, but is not limited thereto.

Examples of the plasticizer include known plasticizers used in this type of interlayer, for example, organic plasticizers such as monobasic acid esters and polybasic acid esters, and organic phosphoric acid and organic phosphorous acid. A phosphoric acid plasticizer such as an acid plasticizer is used.

Among the monobasic acid esters, for example, triethylene glycol and butyric acid, isobutyric acid, caproic acid,
Glycol esters obtained by reaction with organic acids such as 2-ethylbutyric acid, heptanoic acid, n-octylic acid, 2-ethylhexylic acid, pelargonic acid (n-nonylic acid) and decylic acid are preferred. In addition, esters of tetraethylene glycol and tripropylene glycol with the above organic acids are also used.

As the polybasic acid ester, for example, an ester of an organic acid such as adipic acid, sebacic acid, azelaic acid and a linear or branched alcohol having 4 to 8 carbon atoms is preferable. As the phosphoric acid plasticizer, tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphite, and the like are preferable.

In particular, triethylene glycol di-2-
Ethyl butyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n-octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n -Heptanoate, other dibutyl sebacate, 2-ethylhexyl adipate, dibutyl carbitol adipate and the like are preferably used.

If necessary, known additives used in the interlayer film for laminated glass, such as an adhesive force regulator, an ultraviolet absorber, a light stabilizer, an antioxidant, and a colorant, may be blended. Can be.

Examples of the adhesion regulator include formic acid, acetic acid, propionic acid, 2-ethylbutyric acid, octanoic acid,
Potassium salts and magnesium salts of organic carboxylic acids such as ethylhexyl acid, oxalic acid, butyric acid and benzoic acid are used. In addition, metal salts of organic acids such as hydrochloric acid and nitric acid are also used.

In particular, the above-mentioned magnesium salts of organic carboxylic acids are preferred. Such a magnesium salt is considered to suppress a decrease in the adhesive force between the glass plate and the intermediate film by attracting water molecules, thereby improving the penetration resistance of the obtained laminated glass. be able to. In addition, since these magnesium salts are distributed at a high concentration on the film surface without agglomeration in the intermediate film, a small amount of the magnesium salt exhibits an adhesive force adjusting effect. Further, the peripheral portion of the laminated glass does not excessively whiten due to moisture absorption.

Examples of the ultraviolet absorber include benzotriazole-based ones, for example, Tinuvin P (trade name), Tinuvin 320 (trade name), Tinuvin 326 (trade name), Tinuvin 328 (trade name) manufactured by Ciba Geigy. Are used. As the light stabilizer, a hindered amine-based stabilizer such as ADK STAB LA-57 (trade name) manufactured by Asahi Denka Co., Ltd. is used. Examples of the antioxidant include phenol-based antioxidants such as Sumilizer BH manufactured by Sumitomo Chemical Co., Ltd.
T (trade name), Irganox 10 manufactured by Ciba-Geigy
10 (product name) or the like is used.

According to the first aspect of the present invention,
The sodium concentration of the resin film A is set to 20 ppm or less, and the sodium concentration of the resin film B is set to 15 ppm or less. Further, in the invention according to claim 2, the sodium concentration of the resin film C is set to 20 ppm or less, and the sodium concentration of the resin film D is set to 15 ppm or less. In the third aspect of the invention, the sodium concentration of the resin film E is set to 20 ppm or less, and the sodium concentration of the resin film F is set to 15 ppm or less.

Here, the resin films A, B, C, D, E and F
Can be reduced mainly by decreasing the sodium concentration of the polyvinyl acetal resins (a), (b), (c), (d), (e) and (f). In order to reduce the sodium concentration in each resin, a method of washing each polyvinyl acetal resin in powder form obtained by a known production method while adding hot water at 40 to 60 ° C. while stirring, for example, is suitably adopted. You. This operation may be performed once or multiple times.

The inventor of the present invention disclosed in JP-A-4-254444, JP-A-5-310449, JP-A-10-36146 and JP-A-7-2, which were particularly excellent in sound insulation.
Focusing on the interlayer film and the laminated glass described in JP 064833, various studies were conducted to improve the whitening of the peripheral portion of the laminated glass under high humidity. As a result, the following findings were obtained.

That is, in the acetalization reaction of polyvinyl alcohol, the polyvinyl acetal resin that precipitates and precipitates in the form of powder is used to remove the remaining acid catalyst.
It is neutralized with an alkali neutralizing agent such as sodium hydroxide or sodium bicarbonate, and is subjected to water washing, dehydration, drying, etc., to give a polyvinyl acetal resin. In this case, an alkali neutralizing agent such as sodium hydroxide or sodium bicarbonate reacts with the acid catalyst to form a sodium salt, and the sodium or unreacted alkali neutralizing agent is used in the polyvinyl acetal resin particles. Or adhere to the particle surface. The raw material polyvinyl alcohol also contains a sodium salt derived from an alkali catalyst such as sodium hydroxide used for the synthesis.

Such sodium salts and unreacted alkali neutralizing agents can be removed to some extent by sufficiently repeating washing with water in a known production method. The alkali neutralizer in the reaction is difficult to remove. Therefore, it has been found that the interlayer film for laminated glass obtained by using such a polyvinyl acetal resin has reduced moisture resistance due to the influence of the metal component.

Therefore, in order to remove the sodium salt in the polyvinyl acetal resin, a powdery polyvinyl acetal resin obtained by a known production method is added to hot water at a temperature of 40 ° C. or higher, preferably 40 to 60 ° C. It has been found that by adding a new step of washing while stirring, the sodium salt in the polyvinyl acetal resin is effectively removed. When the temperature at the time of washing is set to 40 ° C. or higher, water-soluble metal components remaining in the resin particles are efficiently removed. However, when the temperature at the time of washing is 60 ° C. or higher, the resin in the slurry is softened and the powders and granules are likely to coalesce with each other, so that a particle having a stable particle diameter may not be obtained. Accordingly, the removal of the sodium salt is not significantly improved, so that energy is wasted.

It has been found that the sodium concentration of the resin films A, B, C, D, E and F has a great effect on the whitening of the periphery of the laminated glass.
By reducing the sodium concentration of C, D, E and F to a specific concentration or less as described above, transparency, weather resistance and adhesion are good, penetration resistance is good, and glass shards are scattered when broken. It has been found that the laminated glass is excellent in basic performance required for laminated glass such as difficulty, and also excellent in sound insulation and moisture resistance, and can prevent whitening of the peripheral portion of the laminated glass.

[0032]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Examples and comparative examples of the present invention are shown below. (Example 1) <Preparation of resin (a) and resin film A> Average polymerization degree 170
0, polyvinyl alcohol 1 having a saponification degree of 98.9 mol%
93 g was added to 2900 g of pure water and dissolved by heating. The temperature of this solution was adjusted to 28 ° C., and 201 g of a 35% hydrochloric acid catalyst was used.
And 192 g of n-hexylaldehyde were added, and the liquid temperature was 2 ° C.
And the temperature was maintained to precipitate a reaction product.

Thereafter, the reaction system was maintained at 30 ° C. for 5 hours to complete the reaction, washed with excess water to wash away unreacted n-hexylaldehyde, neutralized the hydrochloric acid catalyst, washed with water and dried. Thus, a white powdery polyvinyl acetal resin (a) was obtained. Further, the resin (a) in the form of a white powder is stirred for 30 minutes with warm water at 60 ° C. (1,000 parts by weight of hot water with respect to 100 parts by weight of the resin), and after dehydration, washing and drying,
The final white powdery polyvinyl acetal resin (a) was obtained. The resin (a) had a degree of acetalization of 67.5 mol%, a vinyl acetate component of 1.1 mol%, and a residual vinyl alcohol of 31.4 mol%.

100 parts by weight of the resin (a), 50 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer, and Irganox 101 as an antioxidant
0 (trade name) and 0.2 parts by weight of Ciba Geigy's Tinuvin P (trade name) as an ultraviolet absorber, and then sufficiently melt-kneaded with a mixing roll, followed by press molding. At 150 ° C. for 30 minutes to obtain a resin film A having a thickness of 0.20 mm.

<Preparation of Resin (b) and Resin Film B> 190 g of polyvinyl alcohol having an average degree of polymerization of 1700 and a saponification degree of 98.9 mol% was added to 2900 g of pure water and dissolved by heating. The temperature of the solution was adjusted to 20 ° C., 201 g of 35% hydrochloric acid catalyst and 124 g of n-butyraldehyde were added, the liquid temperature was lowered to 8 ° C., and this temperature was maintained to precipitate a reaction product.

Thereafter, the reaction system is maintained at 50 ° C. for 4 hours to complete the reaction, washed with excess water to wash away unreacted n-butyraldehyde, neutralized the hydrochloric acid catalyst, washed with water and dried. Thus, a white powdery polyvinyl acetal resin (b) was obtained. Further, the resin (b) in the form of a white powder is stirred for 30 minutes with warm water at 60 ° C. (1,000 parts by weight of hot water with respect to 100 parts by weight of the resin), and after dehydration, washing and drying,
The final white powdery polyvinyl acetal resin (b) was obtained. The resin (b) had a degree of acetalization of 66.0 mol%, a vinyl acetate component of 1.1 mol%, and a residual vinyl alcohol of 32.9 mol%.

100 parts by weight of the resin (b), 40 parts by weight of triethylene glycol di-2-ethylbutyrate as a plasticizer, and Irganox 101 as an antioxidant.
0 (trade name) and 0.2 parts by weight of Ciba Geigy's Tinuvin P (trade name) as an ultraviolet absorber, and then sufficiently melt-kneaded with a mixing roll, followed by press molding. At 150 ° C. for 30 minutes to obtain a resin film B having a thickness of 0.20 mm.

<Preparation of Intermediate Film and Laminated Glass> Using the above resin films A and B, these resin films were adjusted in a constant temperature and high humidity chamber so that the water content was 0.4 to 0.5% by weight. This is superposed in the order of resin film B / resin film A / resin film B, and transparent float glass (30 cm × 30 cm) is applied from both sides.
× 3 mm thick) and put it in a rubber bag for 20 minutes.
After degassing for 20 minutes at a degree of vacuum of torr, the substrate was transferred to an oven at 90 ° C. while being degassed, and further vacuum-pressed while being kept at 90 ° C. for 30 minutes.

The laminated glass preliminarily bonded in this manner is subjected to a pressure of 13 kg / cm ^{2 in} an air type autoclave.
The main bonding was performed at a temperature of 140 ° C. for 20 minutes, and the production of the interlayer film and the production of the laminated glass were simultaneously performed.

Example 2 In the preparation of the resin (a) and the resin (b), the temperature of the hot water in the washing step with hot water of 60 ° C. was changed to 50 ° C. Other than that, it carried out similarly to Example 1.

(Comparative Example 1) In the preparation of the resin (b),
The temperature of the hot water at the time of the washing process with hot water of 60 ° C. is set to 40 ° C.
Changed to Other than that, it carried out similarly to Example 1.

Comparative Example 2 In the preparation of the resin (a),
The temperature of the hot water at the time of the washing process with hot water of 60 ° C. is set to 40 ° C.
Changed to Other than that, it carried out similarly to Example 1.

(Comparative Example 3) In the preparation of the resin (a) and the resin (b), the temperature of the hot water in the washing step with hot water of 60 ° C was changed to 40 ° C. Other than that, it carried out similarly to Example 1.

(Comparative Example 4) In the preparation of the resin (a),
The washing step with hot water at 60 ° C. was not performed. Other than that, it carried out similarly to Example 1.

Comparative Example 5 In the preparation of resin (b),
The washing step with hot water at 60 ° C. was not performed. Other than that, it carried out similarly to Example 1.

(Comparative Example 6) In the preparation of the resin (a),
The temperature of the hot water at the time of the washing process with hot water of 60 ° C. is set to 40 ° C.
And in the preparation of the resin (b), the temperature of the hot water in the washing step with hot water of 60 ° C. was changed to 50 ° C. Other than that, it carried out similarly to Example 1.

(Example 3) <Preparation of resin (c) and resin film C> Average polymerization degree 170
0, polyvinyl alcohol 1 having a saponification degree of 88.0 mol%
93 g was added to 2900 g of pure water and dissolved by heating. The temperature of this solution was adjusted to 28 ° C., and 201 g of a 35% hydrochloric acid catalyst was used.
And 192 g of n-butyraldehyde, and the liquid temperature was 2 ° C.
And the temperature was maintained to precipitate a reaction product.

Thereafter, the reaction system was maintained at 30 ° C. for 5 hours to complete the reaction, washed with excess water to wash away unreacted n-butyraldehyde, neutralized the hydrochloric acid catalyst, washed with water and dried. Thus, a white powdery polyvinyl acetal resin (c) was obtained. Further, the resin (c) in the form of a white powder was stirred for 30 minutes with warm water of 60 ° C. (1,000 parts by weight of hot water with respect to 100 parts by weight of the resin), and after dehydration, washing and drying,
A final white powdery polyvinyl acetal resin (c) was obtained. This resin (c) had a degree of acetalization of 60.0 mol%, a vinyl acetate component of 12 mol%, and a residual vinyl alcohol of 28.0 mol%.

100 parts by weight of the resin (c), 50 parts by weight of triethylene glycol di-2-ethylbutyrate as a plasticizer, and Irganox 101 as an antioxidant.
0 (trade name) and 0.2 parts by weight of Ciba Geigy's Tinuvin P (trade name) as an ultraviolet absorber, and then sufficiently melt-kneaded with a mixing roll, followed by press molding. At 150 ° C. for 30 minutes to obtain a resin film C having a thickness of 0.20 mm.

<Preparation of Resin (d) and Resin Film D> 193 g of polyvinyl alcohol having an average polymerization degree of 1700 and a saponification degree of 98.9 mol% was added to 2900 g of pure water and dissolved by heating. The temperature of this solution was adjusted to 20 ° C., 201 g of a 35% hydrochloric acid catalyst and 124 g of n-butyraldehyde were added, the liquid temperature was lowered to 8 ° C., and this temperature was maintained to precipitate a reaction product.

Thereafter, the reaction system was maintained at 50 ° C. for 4 hours to complete the reaction, washed with excess water to wash away unreacted n-butyraldehyde, neutralized the hydrochloric acid catalyst, washed with water and dried. Thus, a white powdery polyvinyl acetal resin (d) was obtained. Further, this white powdery resin (d) was stirred for 30 minutes with warm water of 60 ° C. (1,000 parts by weight of warm water with respect to 100 parts by weight of resin), and after dehydration, washing and drying,
A final white powdery polyvinyl acetal resin (d) was obtained. The degree of acetalization of this resin (d) was 66.0 mol%, the vinyl acetate component was 1.1 mol%, and the residual vinyl alcohol was 32.9 mol%.

100 parts by weight of the resin (d), 40 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer, and Irganox 101 as an antioxidant.
0 (trade name) and 0.2 parts by weight of Ciba Geigy's Tinuvin P (trade name) as an ultraviolet absorber, and then sufficiently melt-kneaded with a mixing roll, followed by press molding. At 150 ° C. for 30 minutes to obtain a resin film D having a thickness of 0.20 mm.

<Preparation of Intermediate Film and Laminated Glass> Using the above resin films C and D, these resin films were adjusted in a constant temperature and high humidity chamber so that the water content was 0.4 to 0.5% by weight. This is superposed in the order of resin film D / resin film C / resin film D, and transparent float glass (30 cm × 30 cm) is applied from both sides.
× 3 mm thick) and put it in a rubber bag for 20 minutes.
After degassing for 20 minutes at a degree of vacuum of torr, the substrate was transferred to an oven at 90 ° C. while being degassed, and further vacuum-pressed while being kept at 90 ° C. for 30 minutes.

The laminated glass preliminarily bonded in this way was put in an air type autoclave at a pressure of 13 kg / cm ² .
The main bonding was performed at a temperature of 140 ° C. for 20 minutes, and the production of the interlayer film and the production of the laminated glass were simultaneously performed.

Example 4 In the preparation of the resin (c) and the resin (d), the temperature of the hot water in the washing step with hot water of 60 ° C. was changed to 50 ° C. Other than that, it carried out similarly to Example 3.

(Comparative Example 7) In the preparation of the resin (d),
The temperature of the hot water at the time of the washing process with hot water of 60 ° C. is set to 40 ° C.
Changed to Other than that, it carried out similarly to Example 3.

Comparative Example 8 In the preparation of resin (c),
The temperature of the hot water at the time of the washing process with hot water of 60 ° C. is set to 40 ° C.
Changed to Other than that, it carried out similarly to Example 3.

Comparative Example 9 In the preparation of the resin (c) and the resin (d), the temperature of the hot water in the washing step with the hot water of 60 ° C. was changed to 40 ° C. Other than that, it carried out similarly to Example 3.

Comparative Example 10 In the preparation of the resin (c), a washing step with hot water at 60 ° C. was not performed. Other than that, it carried out similarly to Example 3.

(Comparative Example 11) In the preparation of the resin (d), a washing step with hot water at 60 ° C was not performed. Other than that, it carried out similarly to Example 3.

(Comparative Example 12) In the preparation of the resin (c), the temperature of the hot water in the washing step with hot water of 60 ° C was 4
The temperature was changed to 0 ° C., and in the preparation of the resin (d), the temperature of the hot water in the washing step with hot water at 60 ° C. was changed to 50 ° C. Other than that, it carried out similarly to Example 3.

(Comparative Example 13) In the preparation of the resin (c), the temperature of hot water in the washing step with hot water of 60 ° C was 5
The temperature was changed to 0 ° C., and in the preparation of the resin (d), the temperature of the hot water in the washing step with hot water at 60 ° C. was changed to 40 ° C. Other than that, it carried out similarly to Example 3.

Example 5 <Preparation of Resin (e) and Resin Film E> 193 g of polyvinyl alcohol having an average degree of polymerization of 1700 and a saponification degree of 93.0 mol% was added to 2900 g of pure water and dissolved by heating. The solution was thermostatted at 28 ° C. and 3
201 g of 5% hydrochloric acid catalyst and 192 n-butyraldehyde
g was added thereto to lower the liquid temperature to 2 ° C., and the temperature was maintained to precipitate a reaction product.

Thereafter, the reaction system was maintained at 30 ° C. for 5 hours to complete the reaction, washed with excess water to wash away unreacted n-butyraldehyde, neutralized the hydrochloric acid catalyst, washed with water and dried. Thus, a white powdery polyvinyl acetal resin (e) was obtained. Further, this white powdery resin (e) was stirred for 30 minutes with warm water of 60 ° C. (1,000 parts by weight of hot water with respect to 100 parts by weight of resin), and after dehydration, washing and drying,
A final white powdery polyvinyl acetal resin (e) was obtained. The degree of acetalization of this resin (e) was 63.0 mol%, the vinyl acetate component was 7 mol%, and the residual vinyl alcohol was 30.0 mol%.

100 parts by weight of the resin (e), 40 parts by weight of triethylene glycol di-2-ethylbutyrate as a plasticizer, and Irganox 101 as an antioxidant.
0 (trade name) and 0.2 parts by weight of Ciba Geigy's Tinuvin P (trade name) as an ultraviolet absorber, and then sufficiently melt-kneaded with a mixing roll, followed by press molding. At 150 ° C. for 30 minutes to obtain a resin film E having a thickness of 0.20 mm.

<Preparation of Resin (f) and Resin Film F> 193 g of polyvinyl alcohol having an average degree of polymerization of 1700 and a saponification degree of 98.9 mol% was added to 2900 g of pure water and dissolved by heating. The temperature of the solution was adjusted to 20 ° C., 201 g of 35% hydrochloric acid catalyst and 124 g of n-butyraldehyde were added, the liquid temperature was lowered to 8 ° C., and this temperature was maintained to precipitate a reaction product.

Thereafter, the reaction system was maintained at 50 ° C. for 4 hours to complete the reaction, washed with excess water to wash away unreacted n-butyraldehyde, neutralized the hydrochloric acid catalyst, washed with water and dried. Thus, a white powdery polyvinyl acetal resin (f) was obtained. Further, the resin (f) in the form of a white powder is mixed with hot water at 60 ° C.
For 30 minutes, followed by dehydration, water washing and drying to obtain a final white powdery polyvinyl acetal resin (f).
The degree of acetalization of this resin (f) was 66.0 mol%, the vinyl acetate component was 1.1 mol%, and the residual vinyl alcohol was 32.9 mol%.

100 parts by weight of the resin (f), 40 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer, and Irganox 101 as an antioxidant.
0 (trade name) and 0.2 parts by weight of Ciba Geigy's Tinuvin P (trade name) as an ultraviolet absorber, and then sufficiently melt-kneaded with a mixing roll, followed by press molding. At 150 ° C. for 30 minutes to obtain a resin film F having a thickness of 0.20 mm.

<Preparation of Intermediate Film and Laminated Glass> Using the above resin films E and F, these resin films were adjusted in a constant temperature and high humidity chamber so that the water content was 0.4 to 0.5% by weight. This is overlaid in the order of resin film F / resin film E / resin film F, and transparent float glass (30 cm × 30 cm) is applied from both sides.
× 3 mm thick) and put it in a rubber bag for 20 minutes.
After degassing for 20 minutes at a degree of vacuum of torr, the substrate was transferred to an oven at 90 ° C. while being degassed, and further vacuum-pressed while being kept at 90 ° C. for 30 minutes.

The laminated glass preliminarily bonded in this manner was put in an air type autoclave at a pressure of 13 kg / cm ² .
The main bonding was performed at a temperature of 140 ° C. for 20 minutes, and the production of the interlayer film and the production of the laminated glass were simultaneously performed.

Example 6 In the preparation of the resin (e) and the resin (f), the temperature of the hot water in the washing step with the hot water of 60 ° C. was changed to 50 ° C. Other than that, it carried out similarly to Example 5.

(Comparative Example 14) In the preparation of the resin (f), the temperature of the hot water in the washing step with hot water of 60 ° C was 4
Changed to 0 ° C. Other than that, it carried out similarly to Example 5.

(Comparative Example 15) In the preparation of the resin (e), the temperature of the hot water in the washing step with hot water of 60 ° C was changed to 4
Changed to 0 ° C. Other than that, it carried out similarly to Example 5.

Comparative Example 16 Resin (e) and Resin (f)
Was prepared, the temperature of the hot water in the washing step with hot water of 60 ° C. was changed to 40 ° C. Other than that, it carried out similarly to Example 5.

(Comparative Example 17) In the preparation of the resin (e), a washing step with hot water at 60 ° C was not performed. Other than that, it carried out similarly to Example 5.

Comparative Example 18 In the preparation of the resin (f), the washing step with hot water at 60 ° C. was not performed. Other than that, it carried out similarly to Example 5.

(Comparative Example 19) In the preparation of the resin (e), the temperature of the hot water in the washing step with hot water of 60 ° C was 4
The temperature was changed to 0 ° C., and in the preparation of the resin (f), the temperature of the hot water in the washing step with 60 ° C. hot water was changed to 50 ° C. Other than that, it carried out similarly to Example 5.

(Comparative Example 20) In the preparation of the resin (c), the temperature of the hot water in the washing step with hot water of 60 ° C was 5
The temperature was changed to 0 ° C., and in the preparation of the resin (d), the temperature of the hot water in the washing step with hot water at 60 ° C. was changed to 40 ° C. Other than that, it carried out similarly to Example 5.

<Measurement of Sodium Concentration of Resin Film and Evaluation of Moisture Resistance of Intermediate Film> For each of the resin films A, B, C, D, E and F obtained in the above Examples and Comparative Examples, a resin film was used. Was determined by IPC emission elemental analysis. In the IPC emission elemental analysis, the sample was thermally decomposed with sulfuric acid and nitric acid, and the volume of the decomposed product was determined with ultrapure water.
The measurement was performed by an IPC-AES method using an AES emission element analyzer (ICAP-575, manufactured by Nippon Jarrell Ash Co., Ltd.). The results are shown in Tables 1 to 3.

In order to evaluate the moisture resistance of the interlayer films obtained in each of the above Examples and Comparative Examples, the laminated glass obtained in each of the Examples and Comparative Examples was subjected to a temperature of 80 ° C. and a relative humidity of 95%. %, And then the laminated glass was taken out and the whitening distance (mm) from the edge was measured. The results are shown in Tables 1 to 3.

[0081]

[Table 1]

[0082]

[Table 2]

[0083]

[Table 3]

[0084]

As described above, according to the laminated glass using the interlayer film for laminated glass of the present invention, the above-mentioned Japanese Patent Laid-Open No.
254444, JP-A-5-310449,
JP-A-10-36146 and JP-A-7-2064
As described in detail in Japanese Patent Publication No. 83, transparency, weather resistance and adhesion are good, and penetration resistance is good, and the basic performance required for laminated glass such as glass fragments are not easily scattered when broken. In addition, the sound insulation performance is improved.

Further, according to the laminated glass using the interlayer film for laminated glass of the present invention, the sodium concentration of the resin films A, C and E is 20 ppm or less, and the sodium concentration of the resin films B, D and F is 15 ppm or less. By doing so, the moisture resistance is excellent, the deterioration of the adhesive force between the glass plate and the interlayer over time is improved, and the whitening of the peripheral portion of the laminated glass can be reduced.

Accordingly, the interlayer film for laminated glass and the laminated glass of the present invention are suitably used particularly for window glasses of buildings where high sound insulation performance and moisture resistance are required.

Claims (4)

[Claims] 1. A laminated resin film of at least two layers composed of two types of plasticized polyvinyl acetal resin films A and B, wherein the resin film A comprises polyvinyl alcohol having 6 to 1 carbon atoms.
The resin film B is obtained by acetalization with an aldehyde of 0, 100 parts by weight of a polyvinyl acetal resin (a) having a vinyl acetate component of 4 mol% or less, and 30 to 60 parts by weight of a plasticizer. An interlayer for laminated glass comprising 100 parts by weight of a polyvinyl acetal resin (b) obtained by acetalization with an aldehyde of 3 or 4 and having a vinyl acetate component of 4 mol% or less and a plasticizer of 30 to 60 parts by weight; An interlayer for laminated glass, wherein the sodium concentration of the film A is 20 ppm or less, and the sodium concentration of the resin film B is 15 ppm or less. 2. A laminated resin film of at least two layers composed of two types of plasticized polyvinyl acetal resin films C and D, wherein the resin film C comprises polyvinyl alcohol having 4 to 6 carbon atoms.
Of vinyl acetal resin (c) having a vinyl acetate component of 8 to 30 mol% and a plasticizer. The resin film D is obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or 4 carbon atoms. In the interlayer film for a laminated glass, which is obtained by mixing a polyvinyl acetal resin (d) having a vinyl acetate component of 4 mol% or less and a plasticizer, the sodium concentration of the resin film C is 20 ppm or less. An interlayer for laminated glass, wherein the sodium concentration is 15 ppm or less. 3. A laminated resin film of at least two layers composed of two types of plasticized polyvinyl acetal resin films E and F, wherein the resin film E comprises polyvinyl alcohol having 4 to 6 carbon atoms.
Of vinyl acetal resin (e) containing 5 to 8 mol% of a vinyl acetate component and 55 to 70 parts by weight of a plasticizer. An intermediate film for laminated glass obtained by acetalizing with an aldehyde of 3 or 4 and comprising 100 parts by weight of a polyvinyl acetal resin (f) having a vinyl acetate component of 4 mol% or less and 25 to 55 parts by weight of a plasticizer; An interlayer for laminated glass, wherein the sodium concentration of the film E is 20 ppm or less, and the sodium concentration of the resin film F is 15 ppm or less. 4. A laminated glass characterized in that the interlayer film for laminated glass according to claim 1 is sandwiched between at least two transparent glass plates.