JPH1036146A - Sound-insulating laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To increase the sound insulating properties without adverse effect on the basic performance excellent in transparency, whether resistance and adhesion by placing a specific interlayer between 2 or more glass sheets and restricting the dissipation factor within a certain frequencies. SOLUTION: A polyvinyl alcohol with an average polymerization degree of 500-5,000 is dissolved in warm water and held at a prescribed temperature, for example, at 0-95 deg.C. Then, an acid catalyst and an aldehyde are added to proceed the acetalization with stirring. Then, the temperature is raised to complete the reaction, the reaction mixture is neutralized, washed with water and dried to give a powder of polyvinyl alcohol. In order to reduce the polyvinyl acetate component lower than 30mol.%, the polyvinyl alcohol to be used has a saponification degree of >=70mol%. The aldehyde to be used for preparing an interlayer containing at least one of resin layer has 3-10 carbon atoms, a prescribed amount of a plasticizer is formulated to form an interlayer. The interlayer is placed between 2 or more glass plates to give a laminated glass sheet with a dissipation factor of >=0.1 in the frequency range of 1,000-3,000Hz at 10-40 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sound insulating laminated glass using an intermediate film made of a plasticized polyvinyl acetal resin film.

[0002]

2. Description of the Related Art A laminated glass in which an intermediate film made of plasticized polyvinyl butyral is sandwiched between at least two glass plates has good transparency, weather resistance and adhesiveness, good penetration resistance, and glass shards. Has the basic performance required for laminated glass, such as hardly scattering, and is widely used, for example, for window glasses of automobiles and buildings.

[0003] Laminated glass of this kind has good basic performance as described above and is excellent in safety, but is inferior in sound insulation. Especially,
In the middle and high frequency range around the frequency of 2000 Hz, the sound transmission loss value 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, and sound transmission occurs.

[0004] The demand for sound insulating properties has been increasing more and more recently. In particular, in the case of architectural window glasses, in addition to the above-mentioned basic performance, which is excellent in safety, there is a demand for sound insulating laminated glass exhibiting excellent sound insulating performance. Have been.

Japanese Unexamined Patent Publication (Kokai) No. 5-310450 discloses a laminated glass using an intermediate film made of a plasticized polyvinyl butyral resin film or a plasticized vinyl chloride resin film. Sound insulating laminated glass (automobile window glass) controlled to maintain the interlayer film in a temperature range of 10 to 50 ° C by means or cooling means.
Has been proposed.

[0006]

However, in the sound insulating laminated glass proposed above, an appropriate heating means such as a transparent conductive film or a fine wire element is provided on the surface of the interlayer film or the glass surface in contact with the interlayer film. Since the cooling means must be provided, the cost increases accordingly.

Further, when an ordinary plasticized polyvinyl butyral resin film is used as the intermediate film, a laminated glass having good transparency, weather resistance and adhesiveness, good penetration resistance, and little scattering of glass fragments is used. However, sufficient sound insulation performance cannot be obtained in a relatively low temperature range, particularly in a temperature range of 10 to 20 ° C.

When an intermediate film made of a normal plasticized vinyl chloride resin film is used as the intermediate film, good sound insulation performance can be obtained in a relatively wide temperature range, for example, in a temperature range of 10 to 40 ° C. However, there is a problem in the above basic performance, particularly in weather resistance and adhesiveness.

The present invention solves the above-mentioned problems, and the object of the present invention is to improve transparency, weather resistance and adhesiveness, as well as penetration resistance, and to prevent glass fragments from scattering. It is an object of the present invention to provide a sound insulating laminated glass exhibiting excellent sound insulating properties in a relatively wide temperature range without impairing the basic performance required for glass.

[0010]

SUMMARY OF THE INVENTION The present inventor has focused on plasticized polyvinyl acetal resin films such as a plasticized polyvinyl butyral resin film having excellent basic performance as described above, and improved the sound insulation of such a resin film. Various studies were conducted to improve the situation.

As a result, the loss factor of the laminated glass in which the intermediate film made of the plasticized polyvinyl acetal resin film is sandwiched is kept at a specific value or more under a specific frequency range and temperature range. It has been found that by producing glass, it is possible to exhibit excellent sound insulation over a relatively wide temperature range without impairing the basic performance as described above.

[0012] That is, the invention according to claim 1 of the present application is a laminated glass in which an intermediate film made of a plasticized polyvinyl acetal resin film is sandwiched between at least two glass plates, and has a frequency of 1000 to 3000 Hz. It is characterized in that the loss coefficients are all kept at 0.1 or more in a temperature range of at least 10 to 40 ° C.

According to a second aspect of the present invention, in the sound insulating laminated glass according to the first aspect, the intermediate film is obtained by acetalizing polyvinyl alcohol with an aldehyde having 4 to 10 carbon atoms. It is characterized by including a resin film composed of an acetal resin and a plasticizer.

The invention described in claim 3 of the present application is claim 1
In the sound insulating laminated glass according to the above, the intermediate film is a laminated resin film of at least two layers consisting of two types of plasticized polyvinyl acetal resin films A and B, wherein the resin film A
Is obtained by acetalizing polyvinyl alcohol with an aldehyde having 4 to 6 carbon atoms, and the vinyl acetate component is 8
The resin film B is obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or 4 carbon atoms, and the vinyl acetate component has a vinyl acetate component of 4 mol% or less. It is characterized by comprising a polyvinyl acetal resin (b) and a plasticizer.

The invention described in claim 4 of the present application is claim 1
In the sound-insulating laminated glass according to any one of the above-described items 3, the intermediate film has at least two layers of a plasticized polyvinyl acetal resin film laminated thereon, and has an average degree of polymerization of the polyvinyl acetal resin used for each adjacent layer. 30 difference
It is not less than 0 and not more than 4500.

Further, the invention described in claim 5 of the present application is
The sound insulating laminated glass according to any one of claims 1 to 4, wherein the intermediate film is formed by laminating at least two layers of a plasticized polyvinyl acetal resin film, and the plasticizer content (resin 100) of each adjacent layer is laminated. A difference of 5 parts by weight or more and 50 parts by weight or less.

Hereinafter, the present invention will be described in more detail.

In the invention according to claim 1 of the present application, the frequency is set to 1000 to 3000 Hz for the following reason. That is, the sound transmission loss (dB) of the laminated glass is reduced by the coincidence effect, and the sound insulation is reduced. Since this phenomenon occurs especially in the middle and high frequency range around the frequency of 2000 Hz, it is intended for the frequency range of 1000 to 3000 Hz. The reason for setting the temperature range to at least 10 to 40 ° C. is that the environment in which the laminated glass is used is mainly in the temperature range of 10 to 40 ° C.

Under these conditions, the loss coefficient of the laminated glass and the sound transmission loss (dB) as an index of sound insulation were examined. As a result, the loss coefficient at a frequency of 1000 to 3000 Hz was at least 10 to 40 ° C. If all are kept at 0.1 or more in the temperature range, excellent sound insulation is surely obtained. If even one place is less than 0.1 in this range, excellent sound insulation is ensured. It turned out that it could not be obtained.

The loss coefficient of the laminated glass is measured by using a resonance method based on central vibration. This means that the mechanical impedance at the excitation point at the center of the sample is detected, and the frequency (f) showing the peak of the mechanical impedance curve (vertical axis: mechanical impedance, horizontal axis: frequency) in each vibration mode
1) and the half value width (the width of the frequency that gives an impedance 3 dB smaller than the peak value) (Δf1), the loss coefficient (Δf
1 / f1).

Next, as a method for preparing a polyvinyl acetal resin constituting a plasticized polyvinyl acetal resin film as an intermediate film, for example, polyvinyl alcohol is dissolved in warm water, and the obtained aqueous solution is heated to a predetermined temperature, for example, 0 to 0.
While maintaining the temperature at 95 ° C., the required acid catalyst and aldehyde were added, the acetalization reaction was allowed to proceed with stirring, and then the reaction temperature was raised to ripen and complete the reaction.
A method of performing neutralization, washing and drying to obtain a polyvinyl acetal resin powder is employed.

In the above method for preparing a polyvinyl acetal resin, the polyvinyl alcohol preferably has an average degree of polymerization of 500 to 5,000, and has an average degree of polymerization of 100 to 5,000.
Those having 0 to 2500 are more preferred. If the average degree of polymerization is less than 500, the penetration resistance of the laminated glass decreases. Conversely, if the average degree of polymerization exceeds 5000, molding of the resin film becomes difficult, and the strength of the resin film becomes too strong, which is not suitable.

Further, the vinyl acetate component of the obtained resin is preferably set to 30 mol% or less, and therefore, a polyvinyl alcohol having a saponification degree of 70 mol% or more is suitably used. When the degree of saponification of polyvinyl alcohol is lower than 70 mol%, the transparency and heat resistance of the resin are reduced, and the reactivity is also reduced. Here, the average degree of polymerization and the degree of saponification of polyvinyl alcohol are, for example, JI
It can be measured based on SK6726 “Polyvinyl alcohol test method”.

The intermediate film may be any one of an intermediate film including at least one resin film as described in claim 2, and an intermediate film including at least two laminated resin films as described in claim 3 to 5. It may be.

In the invention described in claim 2 of the present application, an aldehyde having 3 to 10 carbon atoms is used as an aldehyde used to obtain an intermediate film including at least one resin film.

Examples of such aldehydes include n-propyl aldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, n-hexyl aldehyde, 2-ethyl butyraldehyde, n-heptyl aldehyde, n-octyl aldehyde, n-nonyl Aliphatic, aromatic and alicyclic aldehydes such as aldehyde, n-decylaldehyde, benzaldehyde and cinnamaldehyde may be used alone or in combination of two or more.

When the carbon number of the aldehyde is 2 or less, sufficient sound insulation may not be obtained. Conversely, if the carbon number of the aldehyde is 11 or more, the reactivity of acetalization decreases, and further, resin blocks are easily generated during the reaction, and the rigidity of the film also decreases, resulting in a decrease in sound insulation. More preferably, a single or a combination of two or more of n-butyraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde and n-octylaldehyde having 4 to 8 carbon atoms of the aldehyde is used.

In the third aspect of the present invention, the intermediate film comprising at least two laminated resin films is obtained by acetalizing polyvinyl alcohol with an aldehyde having 4 to 6 carbon atoms as one resin film A. A resin film comprising a polyvinyl acetal resin (a) having a vinyl acetate component of 8 to 30 mol% and a plasticizer is used. Also,
As the other resin film B, a resin film obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or 4 carbon atoms and comprising a polyvinyl acetal resin (b) having a vinyl acetate component of 4 mol% or less and a plasticizer is used. .

In the preparation of the resin (a), if the carbon number of the aldehyde is 3 or less, sufficient sound insulation cannot be obtained. On the other hand, when the aldehyde has 7 or more carbon atoms, the reactivity of acetalization decreases, and sound insulation near room temperature is not sufficiently exhibited. In particular, n-butyraldehyde, isobutyraldehyde, and n-hexylaldehyde alone or in combination of two or three are preferred.

In the preparation of the resin (b), if the number of carbon atoms of the aldehyde is 2 or less, the moldability of the resin film becomes insufficient, and if the number of carbon atoms of the aldehyde is 5 or more, the reactivity of acetalization decreases. Moreover, sound insulation near room temperature is not sufficiently exhibited. Particularly, n-butyraldehyde and isobutyraldehyde alone or in combination of two kinds are preferable.

In particular, the above resin (a) and resin (b)
In any case, those obtained by acetalization with n-butyraldehyde having 4 carbon atoms are preferable. By using the resin acetalized with n-butyraldehyde, the adhesive strength of each resin film is increased, the weather resistance is excellent, and the production of the resin is facilitated.

The polyvinyl acetal resin thus obtained is 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 K6728 “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. be able to.

When the content of the vinyl acetate component of the resin (a) is less than 8 mol%, the sound insulation performance is not sufficiently exhibited. Conversely, when the content of the vinyl acetate component exceeds 30 mol%, blocking occurs during the production of the resin. And the production is difficult. Particularly, the content of the vinyl acetate component is preferably from 10 to 19 mol%.

When the content of the vinyl acetate component of the resin (b) exceeds 4 mol%, the viscoelastic properties of the resin films A and B become similar, and the sound insulation performance in a wide temperature range is insufficient. Is not exhibited. In particular, the content of the vinyl acetate component is preferably from 0 to 2 mol%.

Further, the average degree of acetalization of the above-mentioned various polyvinyl acetal resins is generally 40 to 75 mol%.
Is preferred. If the average degree of acetalization of the resin is less than 40 mol%, the compatibility with the plasticizer deteriorates, and it becomes difficult to mix the plasticizer in an amount necessary for ensuring sound insulation and penetration resistance. vice versa,
A long reaction time is required to obtain a resin having an average acetalization degree exceeding 75 mol%, which is not preferable in terms of process.
In the present invention, by changing the production conditions of the polyvinyl acetal resin constituting the intermediate film, for example, the type of aldehyde used, the average acetalization degree and the distribution of the acetalization degree, the loss factor of the laminated glass is reduced. Can be adjusted.

Next, in the invention according to claim 4, as a method for preparing the polyvinyl acetal resin constituting the plasticized polyvinyl acetal resin film, for example, polyvinyl alcohol is dissolved in warm water, and the obtained aqueous solution is subjected to a predetermined process. While maintaining the temperature at, 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 the reaction, thereby completing the reaction. , Washing with water and drying to obtain a polyvinyl acetal resin powder. Examples of the aldehyde used include aldehydes having 3 to 10 carbon atoms, and preferably butyl aldehyde having 4 carbon atoms.

The difference in the average degree of polymerization of the polyvinyl acetal resin used in each of the adjacent layers of the intermediate film is 300 or more.
It must be less than 500. Average polymerization degree difference of 300
If it is less than 3, the viscoelastic properties of the adjacent layers are close to each other, so that the effect of converting sound energy into heat energy due to the internal friction effect at the interface becomes small, and sufficient sound insulation cannot be obtained. On the other hand, the average degree of polymerization of the polyvinyl acetal resin used for each layer is preferably from 500 to 5,000. If the average degree of polymerization is less than 500, the rigidity of the resin film is remarkably reduced, so that the penetration resistance of the laminated glass is reduced.
Conversely, if the average degree of polymerization exceeds 5,000, the film formability is poor. Therefore, the difference in the average degree of polymerization of the polyvinyl acetal resin used for each adjacent layer is 4500 or less. A more preferable range of the difference in the average degree of polymerization is 500 to 3,500.

In order to obtain an intermediate film used in the present invention, a predetermined amount of a plasticizer is blended with each of the above-mentioned resins, and this is formed into a sheet by extrusion, calendering, pressing or the like to form a resin film. It is molded and used as an intermediate film.

More specifically, according to the second aspect of the present invention, a predetermined amount of a plasticizer is blended with a polyvinyl acetal resin, and the resultant is formed into a sheet to form a resin film. The film is used as an intermediate film, or this resin film and another film are laminated to form an intermediate film. In the third aspect of the present invention, the polyvinyl acetal resin (a) and the polyvinyl acetal resin (b) are each blended with a predetermined amount of a plasticizer and formed into a sheet to form a resin film A. And a resin film B, which is used as an intermediate film, or
A predetermined amount of a plasticizer is mixed with each of the resin (a) and the resin (b), and the resulting mixture is integrally molded by a multilayer extrusion method to obtain an intermediate film. Further, in the invention according to claim 4, a predetermined amount of a plasticizer is blended into each polyvinyl acetal resin, and the resulting mixture is formed into a sheet to form each resin film. Alternatively, a predetermined amount of a plasticizer is mixed into each of the above resin films, and these are integrally molded by a multilayer extrusion method to obtain an intermediate film.

Examples of the plasticizer used in the present invention include known plasticizers used in this type of interlayer, for example, organic plasticizers such as monobasic acid esters and polybasic acid esters, and the like.
A phosphoric acid plasticizer such as an organic phosphoric acid or an organic phosphorous acid 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 or azelaic acid with 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-ethylhexoate, triethylene glycol dicaprylate, triethylene glycol di-n-octoate, triethylene glycol di-n -Heptoate, tetraethylene glycol di-n-heptate, other dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate are preferably used.

The amount of the plasticizer incorporated in the polyvinyl acetal resin (including the polyvinyl butyral resin) is 2 parts per 100 parts by weight of the polyvinyl acetal resin.
0 to 70 parts by weight is preferred. If the amount of the plasticizer is less than 20 parts by weight, sufficient sound insulation cannot be obtained, and the penetration resistance decreases. Conversely, if the amount of the plasticizer exceeds 70 parts by weight, sufficient sound insulation cannot be obtained. In some cases, the plasticizer bleeds to increase the optical distortion and decrease the transparency and adhesiveness of the resin film. Particularly, the amount of the plasticizer is preferably 40 to 60 parts by weight.

Further, in the invention according to claim 5, the intermediate film is formed by laminating at least two layers of a plasticized polyvinyl butyral resin film, and the plasticizer content of each adjacent layer (the plasticizer content relative to 100 parts by weight of the resin). (Parts by weight of the agent) should be 5 parts by weight or more and 50 parts by weight or less. When the difference between the plasticizer contents of the adjacent layers is less than 5 parts by weight,
Since the viscoelastic properties of the adjacent layers are close to each other, the effect of converting sound energy due to internal friction at the interface into heat energy is reduced, and excellent sound insulation cannot be obtained. on the other hand,
The plasticizer content of each layer is preferably from 20 to 70 parts by weight. If the plasticizer content is less than 20 parts by weight, the rigidity of the resin film is too high, and the penetration resistance of the laminated glass is reduced.
Conversely, if the content of the plasticizer exceeds 70 parts by weight, bleeding of the plasticizer occurs, which has an adverse effect on the adhesiveness of the laminated glass. Therefore, the difference between the plasticizer contents of the adjacent layers must be 50 parts by weight or less.

To these polyvinyl acetal resins, known additives such as an ultraviolet absorber, a light stabilizer, an antioxidant, an adhesion regulator, a surfactant, and a coloring agent, which are used in an interlayer film for laminated glass, are used. An agent can be compounded.

As the ultraviolet absorber, benzotriazole-based ones, for example, Tinuvin P manufactured by Ciba-Geigy, Inc.
(Trade name), Tinuvin 320 (trade name), Tinuvin 32
6 (trade name) and Tinuvin 328 (trade name). As the light stabilizer, a hindered amine-based stabilizer such as ADK STAB LA-57 (trade name) manufactured by Asahi Denka Co., Ltd.
And the like.

Examples of the antioxidant include phenol-based ones, for example, SUMIRIDER BHT (trade name) manufactured by Sumitomo Chemical Co., Ltd., and Irganox 1010 (trade name) manufactured by Ciba Geigy Co., Ltd.

Examples of the adhesion regulator include metal salts of carboxylic acids, for example, potassium salts and sodium salts of octylic acid, hexyl acid, butyric acid, acetic acid, formic acid and the like. Also,
Examples of the surfactant include sodium lauryl sulfate and alkylbenzene sulfonic acid.

In order to produce the sound-insulating laminated glass of the present invention, an ordinary method for producing laminated glass is employed. For example, an intermediate film made of the resin film formed by the above-described method is sandwiched between two transparent glass plates, and this is put into a rubber bag, and pre-adhered at about 70 to 110 ° C. while suctioning under reduced pressure.
Then, using an autoclave or a press, at about 120 to 150 ° C., about 10 to 15 kg / cm ²
It is manufactured by performing main bonding at a pressure of:

Although the overall thickness of the intermediate film is better as the thickness of the intermediate film is higher, the sound insulation is better. However, in consideration of the minimum penetration resistance and weather resistance required for a laminated glass, a practically used intermediate film for laminated glass is practically used. As with the thickness of the film, it is generally 0.3-1.
A range of 6 mm is preferred. As the glass plate, not only an inorganic transparent glass plate but also an organic transparent glass plate such as a polycarbonate plate and a polymethyl methacrylate plate can be used.

[0053]

EXAMPLES Examples of the present invention will be described below together with comparative examples.

Example 1 Production of Intermediate Film A polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with n-octylaldehyde (polymerization degree: 1700, acetalization degree: 63 mol%, vinyl acetate component: 0.9 mol%) 100 parts by weight and triethylene glycol di-2-ethyl butyrate 40 as a plasticizer
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 an intermediate film having a thickness of 0.38 mm.

Production of Laminated Glass The above-mentioned interlayer film was sandwiched between transparent float glasses (length 30 cm × width 30 cm × thickness 3 mm) from both sides, placed in a rubber bag, and degassed for 20 minutes at a vacuum of 20 torr. Then, it was transferred to a 90 ° C. oven while being degassed, and further vacuum-pressed while being kept at 80 ° C. for 30 minutes.

The laminated glass thus preliminarily bonded is placed in a pneumatic autoclave at a pressure of 12 kg / cm.
^{2. The} main bonding was performed at a temperature of 135 ° C. for 20 minutes to obtain a transparent laminated glass having a single-layer structure of an intermediate film.

Example 2 Production of Intermediate Film A polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with n-butyraldehyde (polymerization degree 1700, acetalization degree 50 mol%, vinyl acetate component 28 mol%) 100 weight Part, and 40 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer were mixed and sufficiently melt-kneaded with a mixing roll, and then press-formed at 150 ° C. for 30 minutes using a press forming machine. An intermediate film having a thickness of 0.38 mm was obtained.

Production of Laminated Glass Using this interlayer film, the other steps were carried out in the same manner as in Example 1 to obtain a transparent laminated glass having a single-layer interlayer film.

Example 3 Production of Intermediate Film Polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with n-hexylaldehyde (degree of polymerization: 1700, degree of acetalization: 65 mol%, vinyl acetate component: 0.9 mol%) 100 parts by weight and triethylene glycol di-2-ethyl butyrate 40 as a plasticizer
After the mixture was sufficiently melt-kneaded with a mixing roll, the mixture was press-formed at 150 ° C. for 30 minutes using a press-forming machine to obtain a resin film A having a thickness of 0.12 mm.

Also, 100 parts by weight of a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with n-butyraldehyde (polymerization degree: 1700, acetalization degree: 66 mol%, vinyl acetate component: 0.9 mol%), and a plasticizer Was mixed with 40 parts by weight of triethylene glycol di-2-ethyl butyrate, and the mixture was sufficiently melted and kneaded with a mixing roll.
Press molding was performed at 30 ° C. for 30 minutes to obtain a resin film B having a thickness of 0.13 mm.

Production of Laminated Glass The resin film A and the resin film B were laminated as B / A / B, and the other steps were the same as in Example 1, except that the intermediate film was B / A / B.
A transparent laminated glass having an A / B laminated structure was obtained.

Example 4 Production of Intermediate Film Polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with n-butyraldehyde (polymerization degree 1700, acetalization degree 58 mol%, vinyl acetate component 12 mol%) 100 weight Part, and 40 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer were mixed and sufficiently melt-kneaded with a mixing roll, and then press-formed at 150 ° C. for 30 minutes using a press forming machine. A resin film A having a thickness of 0.12 mm was obtained.

Further, 100 parts by weight of a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with n-butyraldehyde (degree of polymerization: 1700, degree of acetalization: 66 mol%, vinyl acetate component: 0.9 mol%), and a plasticizer Was mixed with 40 parts by weight of triethylene glycol di-2-ethyl butyrate, and the mixture was sufficiently melted and kneaded with a mixing roll.
Press molding was performed at 30 ° C. for 30 minutes to obtain a resin film B having a thickness of 0.13 mm.

Production of Laminated Glass The resin film A and the resin film B were laminated as B / A / B, and the other steps were the same as in Example 1, except that the intermediate film was B / A / B.
A transparent laminated glass having an A / B laminated structure was obtained.

Example 5 Production of Intermediate Film A polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with n-hexylaldehyde (polymerization degree: 1700, acetalization degree: 67 mol%, vinyl acetate component: 12 mol%), 100 wt. Part, and 40 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer were mixed and sufficiently melt-kneaded with a mixing roll, and then press-formed at 150 ° C. for 30 minutes using a press forming machine. A resin film A having a thickness of 0.38 mm was obtained.

Further, 100 parts by weight of a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with n-butyraldehyde (degree of polymerization: 1700, degree of acetalization: 66 mol%, vinyl acetate component: 0.9 mol%), and a plasticizer Was mixed with 40 parts by weight of triethylene glycol di-2-ethyl butyrate, and the mixture was sufficiently melted and kneaded with a mixing roll.
Press molding was performed at 30 ° C. for 30 minutes to obtain a resin film B having a thickness of 0.38 mm.

Production of Laminated Glass The resin film A and the resin film B were laminated like A / B, and the other steps were the same as in Example 1, except that the intermediate film had a laminated structure of A / B. A transparent laminated glass was obtained.

Example 6 Production of Intermediate Film A polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with n-butyraldehyde (polymerization degree: 1700, acetalization degree: 50 mol%, vinyl acetate component: 28 mol%) Part, and 40 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer were mixed and sufficiently melt-kneaded with a mixing roll, and then press-formed at 150 ° C. for 30 minutes using a press forming machine. A resin film A having a thickness of 0.12 mm was obtained.

Also, 100 parts by weight of a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with n-butyraldehyde (degree of polymerization 1700, degree of acetalization 66 mol%, vinyl acetate component 0.9 mol%), and a plasticizer Was mixed with 40 parts by weight of triethylene glycol di-2-ethyl butyrate, and the mixture was sufficiently melted and kneaded with a mixing roll.
Press molding was performed at 30 ° C. for 30 minutes to obtain a resin film B having a thickness of 0.13 mm.

Production of Laminated Glass The resin film A and the resin film B were laminated as B / A / B, and the other steps were the same as in Example 1, except that the intermediate film was B / A / B.
A transparent laminated glass having an A / B laminated structure was obtained.

Example 7 Production of Intermediate Film Polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with n-hexyl aldehyde (polymerization degree: 1700, acetalization degree: 65 mol%, vinyl acetate component: 9 mol%), 100 wt. And 50 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer, and after sufficiently melting and kneading the mixture with a mixing roll, press molding at 150 ° C. for 30 minutes using a press molding machine. A resin film A having a thickness of 0.19 mm was obtained.

Further, 100 parts by weight of a polyvinyl acetal resin (polymerization degree: 1700, degree of acetalization: 66 mol%, vinyl acetate component: 3 mol%) obtained by acetalizing polyvinyl alcohol with n-propyl aldehyde, and tri as a plasticizer Ethylene glycol di-2-ethyl butyrate was mixed with 40 parts by weight, and the mixture was sufficiently melt-kneaded with a mixing roll.
Press molding was performed at 30 ° C. for 30 minutes to obtain a resin film B having a thickness of 0.13 mm.

Production of Laminated Glass The resin film A and the resin film B were laminated as B / A / B / A / B, and the other steps were the same as in Example 1, except that the intermediate film was B / A. A transparent laminated glass having a laminated structure of / B / A / B was obtained.

(Comparative Example 1) Production of Intermediate Film Polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with n-butyraldehyde (polymerization degree: 1700, acetalization degree: 67 mol%, vinyl acetate component: 0.9 mol%) After 100 parts by weight and 40 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer were mixed and sufficiently melt-kneaded with a mixing roll, the mixture was press-formed at 150 ° C. for 30 minutes by a press-forming machine. Thus, an interlayer having a thickness of 0.38 mm was obtained.

Production of Laminated Glass Using this interlayer film, the other steps were carried out in the same manner as in Example 1 to obtain a transparent laminated glass having a single-layer interlayer film.

Comparative Example 2 Production of Interlayer PVC resin (vinyl chloride-ethylene-glycidyl methacrylate copolymer, degree of polymerization 800, vinyl chloride component 9)
3% by weight, ethylene component 5% by weight, glycidyl methacrylate component 2% by weight), 100 parts by weight, triethylene glycol di-2-ethylbutyrate 40 parts by weight as a plasticizer, and an organic tin heat stabilizer 3 parts by weight. After mixing and sufficiently kneading the mixture with a mixing roll, the mixture is press-formed at 160 ° C. for 5 minutes with a press-forming machine to have a thickness of 0.38 m.
m of intermediate film was obtained.

Production of laminated glass Using this interlayer film, the temperature of the final bonding in an air-type autoclave was changed to 150 ° C., and otherwise the same procedure as in Example 1 was carried out. A laminated glass was obtained.

Comparative Example 3 Production of Intermediate Film EVA resin (ethylene-vinyl acetate copolymer, ethylene component 81% by weight, vinyl acetate component 19% by weight, MI:
2.5) Adhesion with 100 parts by weight, 3 parts by weight of triallyl isocyanurate as a crosslinking agent, and 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane 1 as a crosslinking initiator 0.3 parts by weight of γ-methacryloxypropyltrimethoxysilane as a force regulator was supplied to a roll mill and melt-kneaded at 100 ° C., and this was press-molded at 100 ° C. and 120 kg / cm ² with a press molding machine. An intermediate film having a thickness of 0.38 mm was obtained.

Production of Laminated Glass The above intermediate film was sandwiched between two transparent float glass plates (300 mm × 300 mm) having a thickness of 3 mm, and this three-layer laminate was placed in a rubber bag and placed under a vacuum of 10 torr for 20 minutes.
After degassing for a minute, the sample was transferred to an oven at 100 ° C. in a degassed state, and kept at this temperature for 30 minutes. Next, thermocompression bonding was performed in an autoclave at a temperature of 135 ° C. and a pressure of 12 kg / cm ² to obtain a transparent laminated glass having a single-layer interlayer.

With respect to the laminated glass obtained in each of the above Examples and Comparative Examples, the loss coefficient was measured by the following method while changing the frequency and the temperature. Regarding the sound insulation of the laminated glass, the sound transmission loss (TL
Value) was measured and evaluated based on this value. Further, the weather resistance was evaluated by the following method. The results are shown in Tables 1 to 3.

(Measurement of Loss Coefficient) A sample (width 25 mm × length 300 mm) was cut out from each laminated glass, and the sample was shaken in a constant-temperature bath using a vibration generator (a shaker manufactured by Shinken Co., Ltd.). G21-005D ”), and the vibration characteristics obtained therefrom are amplified by a mechanical impedance amplifier (“ XG-81 ”manufactured by Rion) and the vibration spectrum is analyzed by an FFT spectrum analyzer (Yokogawa Hewlett-Packard). "FFT Analyzer HP
3582A ") to determine the loss factor.

(Evaluation of sound insulation) From the ratio between the loss coefficient obtained by the above method and the resonance frequency with glass, the frequency (H
A graph showing the relationship between z) and the sound transmission loss (dB) was created, the minimum sound transmission loss (TL value) near a frequency of 2000 Hz was obtained, and the sound insulation at a predetermined temperature was evaluated using the TL value. The higher the TL value, the better the sound insulation.

(Evaluation of weather resistance) The above laminated glass was subjected to a black panel temperature of 63 ° C. using a sunshine weatherometer in accordance with JIS A1415.
Irradiated for 0 hours. About the laminated glass after irradiation, JI
The total light transmittance (%) was measured based on SK7105. In addition, about the laminated glass before and after irradiation,
The degree of yellowness (YI) was measured based on JIS K7105, and the degree of yellowing (ΔYI) was determined.

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

[Table 3]

Example 8 Production of Intermediate Film Polyvinyl butyral resin (PVB resin: polymerization degree 170)
0, vinyl acetate component 1 mol%, butyralization degree 6
6 mol%), and 100 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer were mixed with 40 parts by weight, and the mixture was sufficiently melt-kneaded with a mixing roll, followed by press molding with a press molding machine. Average thickness 0.13m
m of the resin film C was obtained.

Further, polyvinyl butyral resin (PVB)
Resin: 100 parts by weight of polymerization degree 2200, vinyl acetate component 1 mol%, butyralization degree 65 mol%) and 40 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer are mixed and mixed. After sufficient melting and kneading, press molding with a press molding machine,
A resin film D having an average thickness of 0.12 mm was obtained.

Production of Laminated Glass The above-mentioned resin film C and resin film D are laminated as in C / D / C, and otherwise the same as in Example 1, except that the intermediate film is C / D / C.
A transparent laminated glass having a D / C laminated structure was obtained.

Example 9 Production of Intermediate Film Polyvinyl butyral resin (PVB resin: polymerization degree 500)
0, 1 mol% of residual acetyl group, degree of butyralization of 66 mol%), and 40 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer,
This was sufficiently melt-kneaded with a mixing roll, and then press-formed with a press-forming machine to obtain a resin film C having an average film thickness of 0.19 mm.

Further, polyvinyl butyral resin (PVB)
Resin: 100 parts by weight of polymerization degree: 1000, vinyl acetate component: 1 mol%, butyralization degree: 65 mol%) and 40 parts by weight of triethylene glycol di-2-ethylbutyrate as a plasticizer are mixed and mixed. After sufficient melting and kneading, press molding with a press molding machine,
A resin film D having an average thickness of 0.38 mm was obtained.

Production of Laminated Glass The above-mentioned resin film C and resin film D are laminated like C / D / C, and otherwise the same as in Example 1, except that the intermediate film is C / D / C.
A transparent laminated glass having a D / C laminated structure was obtained.

Example 10 Production of Intermediate Film Polyvinyl butyral resin (PVB resin: polymerization degree 170)
0, vinyl acetate component 1 mol%, butyralization degree 6
6 mol%), and 100 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer were mixed with 40 parts by weight, and the mixture was sufficiently melt-kneaded with a mixing roll, followed by press molding with a press molding machine. Average thickness 0.20m
m of the resin film C was obtained.

Further, polyvinyl butyral resin (PVB)
Resin: polymerization degree 500, 1 mol% of vinyl acetate component,
100 parts by weight of butyralization degree) and 40 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer are mixed, sufficiently mixed and kneaded with a mixing roll, and then pressed by a press molding machine. By molding, a resin film D having an average thickness of 0.18 mm was obtained.

Further, polyvinyl butyral resin (PV
B resin: 100 parts by weight of a polymerization degree of 4000, a vinyl acetate component of 1 mol%, butyralization degree of 66 mol%) and 40 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer are mixed and mixed. After sufficiently melt-kneading with rolls, press-molding with a press molding machine,
A resin film E having an average thickness of 0.18 mm was obtained.

Production of Laminated Glass The above-mentioned resin film C, resin film D and resin film E are combined with C / D / E
/ C, and the other steps were performed in the same manner as in Example 1 to obtain a transparent laminated glass in which the intermediate film had a laminated structure of C / D / E / C.

Example 11 Production of Intermediate Film Polyvinyl butyral resin (PVB resin: polymerization degree 150)
0, vinyl acetate component 1 mol%, butyralization degree 6
6 mol%), and 100 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer were mixed with 40 parts by weight, and the mixture was sufficiently melt-kneaded with a mixing roll, followed by press molding with a press molding machine. Average thickness 0.19m
m of the resin film C was obtained.

Further, polyvinyl butyral resin (PVB)
Resin: 100 parts by weight of polymerization degree 2500, 1 mol% of vinyl acetate component, degree of butyralization of 66 mol%) and 40 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer are mixed and mixed. After sufficient melting and kneading, press molding with a press molding machine,
A resin film D having an average thickness of 0.19 mm was obtained.

Production of Laminated Glass The above resin film C and resin film D are laminated like C / D,
Other than that, it carried out similarly to Example 1 and obtained the transparent laminated glass whose intermediate | middle film had the laminated structure of C / D.

With respect to the laminated glass obtained in each of the above Examples, the loss coefficient was measured and the sound insulation and weather resistance were evaluated by the above-described method. Tables 4 and 5 show the results.
Shown in

[0101]

[Table 4]

[0102]

[Table 5]

Example 12 Production of Intermediate Film Polyvinyl butyral resin (PVB resin: polymerization degree 170)
0, vinyl acetate component 1 mol%, butyralization degree 6
6 mol%), and 100 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer were mixed with 40 parts by weight, and the mixture was sufficiently melt-kneaded with a mixing roll, followed by press molding with a press molding machine. Average thickness 0.13m
m of the resin film F was obtained.

Further, polyvinyl butyral resin (PVB)
Resin: 100 parts by weight of polymerization degree 1700, vinyl acetate component 1 mol%, butyralization degree 65 mol%) and 55 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer are mixed, and the mixture is mixed. After sufficient melting and kneading, press molding with a press molding machine,
A resin film G having an average thickness of 0.12 mm was obtained.

Production of Laminated Glass The above-mentioned resin film F and resin film G are laminated as F / G / F, and otherwise the same as in Example 1, except that the intermediate film is
A transparent laminated glass having a laminated structure of G / F was obtained.

Example 13 Production of Intermediate Film Polyvinyl butyral resin (PVB resin: polymerization degree 170)
0, vinyl acetate component 1 mol%, butyralization degree 6
6 mol%), and 100 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer were mixed with 40 parts by weight, and the mixture was sufficiently melt-kneaded with a mixing roll, followed by press molding with a press molding machine. Average thickness 0.19m
m of the resin film F was obtained.

Further, polyvinyl butyral resin (PVB)
Resin: 100 parts by weight of polymerization degree 1700, vinyl acetate component 1 mol%, butyralization degree 65 mol%) and 45 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer are mixed and mixed. After sufficient melting and kneading, press molding with a press molding machine,
A resin film G having an average thickness of 0.38 mm was obtained.

Production of Laminated Glass The above-mentioned resin film F and resin film G are laminated like F / G / F, and otherwise the same as in Example 1, except that the intermediate film
A transparent laminated glass having a laminated structure of G / F was obtained.

Example 14 Production of Intermediate Film Polyvinyl butyral resin (PVB resin: polymerization degree 170)
0, vinyl acetate component 1 mol%, butyralization degree 6
6 mol%), and 40 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer were mixed and sufficiently melt-kneaded with a mixing roll, followed by press molding with a press molding machine. Average thickness 0.21m
m of the resin film F was obtained.

Further, polyvinyl butyral resin (PVB)
Resin: 100 parts by weight of polymerization degree 1700, 1 mol% of vinyl acetate component, degree of butyralization of 65 mol%) and 70 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer are mixed and mixed. After sufficient melting and kneading, press molding with a press molding machine,
A resin film G having an average thickness of 0.17 mm was obtained.

Further, polyvinyl butyral resin (PV
B resin: 100 parts by weight of polymerization degree 1700, vinyl acetate component 1 mol%, butyralization degree 66 mol%) and 25 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer are mixed and mixed. After sufficiently melt-kneading with a roll, press molding was performed with a press molding machine to obtain a resin film H having an average film thickness of 0.17 mm.

Production of Laminated Glass The above-mentioned resin film F, resin film G and resin film H were combined with F / G / H /
By laminating as in F, the other steps were carried out in the same manner as in Example 1 to obtain a transparent laminated glass having an intermediate film having a laminated structure of F / G / H / F.

Example 15 Production of Intermediate Film Polyvinyl butyral resin (PVB resin: polymerization degree 170)
0, vinyl acetate component 1 mol%, butyralization degree 6
6 mol%) and 100 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer were mixed with 35 parts by weight, and the mixture was sufficiently melt-kneaded with a mixing roll, followed by press molding with a press molding machine. Average thickness 0.19m
m of the resin film F was obtained.

Further, polyvinyl butyral resin (PVB)
Resin: 100 parts by weight of polymerization degree 1700, vinyl acetate component 1 mol%, butyralization degree 66 mol%) and 55 parts by weight of triethylene glycol di-2-ethyl butyrate as a plasticizer are mixed and mixed. After sufficient melting and kneading, press molding with a press molding machine,
A resin film G having an average thickness of 0.19 mm was obtained.

Production of Laminated Glass The above resin film F and resin film G are laminated as F / G,
Otherwise, the same operation as in Example 1 was performed, and the intermediate film was formed of F / G
A transparent laminated glass having a laminated structure of was obtained.

With respect to the laminated glass obtained in each of the above Examples, the loss coefficient was measured and the sound insulation and weather resistance were evaluated by the above-described method. Tables 6 and 7 show the results.
Shown in

[0117]

[Table 6]

[0118]

[Table 7]

[0119]

As described above, the sound insulating laminated glass of the present invention uses the same polyvinyl acetal resin as in the prior art, so that it has good transparency, weather resistance, adhesion, and penetration resistance. It has the basic performance required for laminated glass, such that glass fragments are not easily scattered. Moreover, the loss coefficient at a frequency of 1000 to 3000 Hz is maintained at 0.1 or more in at least a temperature range of 10 to 40 ° C., thereby exhibiting excellent sound insulation over a relatively wide temperature range.

Further, according to the sound-insulating laminated glass of the present invention, a suitable heating means or cooling means such as a transparent conductive film or a thin linear element is formed on the surface of the intermediate film or the glass surface in contact with the intermediate film as in the prior art. To provide an intermediate film of 10 to 50
There is no need to control the temperature to be maintained in the temperature range of ° C., and the device can be obtained at low cost.

Therefore, the sound-insulating laminated glass of the present invention is particularly suitable for window glasses of buildings requiring particularly high sound-insulating performance.

Claims (5)

[Claims] 1. A laminated glass comprising an intermediate film made of a plasticized polyvinyl acetal resin film sandwiched between at least two glass plates, the laminated glass having a frequency of 1000 to 30.
The loss coefficient at 00 Hz is at least 10 to 40 ° C.
Characterized in that they are all kept at 0.1 or higher in the above temperature range. 2. The method according to claim 1, wherein the intermediate film includes a resin film comprising a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 to 10 carbon atoms and a plasticizer. Sound insulating laminated glass. 3. The intermediate film is 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 is formed by converting polyvinyl alcohol to an aldehyde having 4 to 6 carbon atoms. And a vinyl acetate component comprising 8 to 30 mol% of a polyvinyl acetal resin (a) and a plasticizer. The resin film B is obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or 4 carbon atoms. The sound insulating laminated glass according to claim 1, wherein the obtained vinyl acetate component comprises 4 mol% or less of a polyvinyl acetal resin (b) and a plasticizer. 4. An intermediate film comprising a laminate of at least two layers of a plasticized polyvinyl acetal resin film, wherein the difference in the average degree of polymerization of the polyvinyl acetal resin used for each adjacent layer is 300 or more and 4500 or less. The sound insulating laminated glass according to any one of claims 1 to 3. 5. The intermediate film is formed by laminating at least two layers of a plasticized polyvinyl acetal resin film, and the difference in the plasticizer content between adjacent layers (parts by weight of plasticizer with respect to 100 parts by weight of resin) is 5 parts by weight. The sound insulating laminated glass according to any one of claims 1 to 4, wherein the amount is not less than 50 parts by weight and not more than 50 parts by weight.