JPH07237942A - Intermediate film for laminated glass and laminated glass - Google Patents

Abstract

PURPOSE:To obtain an intermediate film for laminated glass, excellent in adhesiveness and moisture resistance and improved in both of release and whitening in the peripheral part of laminated glass even in the case kept in an atmosphere having high moisture and a laminated glass. CONSTITUTION:This intermediate film for laminated glass is obtained by kneading an organic acid and a silane coupling agent into a plasticized polyvinyl acetal resin film or applying the organic acid and the silane coupling agent to the film. A 0.01-10 pts.wt. of the organic acid and 0.01-10 pts.wt. of the silane coupling agent based on 100 pts.wt. of the resin constituting the resin film are preferably used. This laminated glass is obtained by putting the intermediate film for laminated glass between two glass plates or a glass plate and a sheet.

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 laminated glass.

[0002]

2. Description of the Related Art Laminated glass is widely used for construction and windshields of automobiles. As a typical example of this laminated glass, there is known one in which a plasticized polyvinyl acetal resin intermediate film is adhered between two glass plates.

In such a laminated glass, the glass portion is damaged when an external impact is applied, but the interlayer film bonded between the glass plates is not easily damaged, and the damaged glass plate is bonded to the interlayer film. Since it is in a broken state, the glass fragments are less likely to scatter. In this way, it is possible to prevent the human body from being injured by broken glass in an automobile or a building.

In order to satisfy such a function as a laminated glass, it is necessary to adjust the adhesive force between the glass plate and the intermediate film within a predetermined range. In a laminated glass having a small adhesive force between the glass plate and the intermediate film, glass fragments are peeled off from the intermediate film and scattered by an external impact, and conversely, when the adhesive force is large, the intermediate film is broken together with the glass plate.

Therefore, adjusting the adhesive force between the glass plate and the interlayer film within a predetermined range can absorb the impact when the driver and passenger collide with the laminated glass in the case of a car accident or the like. , It is necessary to prevent the penetration of laminated glass, and in the case of buildings, it is necessary to prevent the penetration of laminated glass against flying objects from the outside and to prevent the scattering of glass fragments. is there.

[0006] Therefore, conventionally, various adhesive force adjusting agents have been studied so that the adhesive force between the glass plate and the intermediate film can be set within a predetermined range.
Carboxylic acid metal salts, in particular, carboxylic acid metal salts having a small number of carbon atoms that change little over time are exclusively used (for example,
(See Japanese Patent Publication No. 46-4270).

When this kind of carboxylic acid metal salt is contained in the intermediate film, the carboxylic acid metal salt bleeds from the intermediate film to form an intermediate film, especially during film formation of the intermediate film and thermocompression bonding with a glass plate. Many gather on the surface of the membrane. Further, due to the water absorption property of the carboxylic acid metal salt, a large amount of water is retained at the interface between the glass plate and the intermediate film, so that the adhesive force between the glass plate and the intermediate film is reduced.

In this case, the effect of adjusting the adhesive force by the carboxylic acid metal salt is adjusted by changing the distribution state of the carboxylic acid metal salt in the film and the film surface or by changing the amount of water in the film. It Under the present circumstances, the distribution of the metal carboxylate is kept constant under a predetermined kneading condition and the water content is also kept constant at about 0.4 to 0.5% by weight so that the adhesive force between the glass plate and the interlayer film is kept at a predetermined level. The content of the carboxylic acid metal salt is determined so as to fall within the range.

However, when an interlayer film containing a carboxylic acid metal salt is used for laminated glass, there is a problem in moisture resistance. That is, when placed in an atmosphere of high humidity, the interlayer film at the peripheral edge of the laminated glass is in direct contact with air, so that the interlayer film at the peripheral edge of the laminated glass is exposed to air in the air depending on the amount of the carboxylic acid metal salt. It absorbs water, which causes the interlayer film around the laminated glass to whiten.

In order to reduce the whitening of the peripheral portion of the laminated glass, it is most effective to reduce the amount of the carboxylic acid metal salt. However, when the amount of the carboxylic acid metal salt is reduced, the adhesion between the glass plate and the interlayer film is reduced. There is a problem that the laminated glass is likely to penetrate due to the impact because the force becomes too high.

Therefore, as a method for reducing the whitening of the peripheral portion of the laminated glass while maintaining the adhesive force between the glass plate and the intermediate film within a predetermined range, Japanese Patent Laid-Open No. 5-186250 discloses a carboxylic acid metal salt and an organic compound. A method in which an acid is used in combination has been proposed. In this method, even if the content of the carboxylic acid metal salt is smaller than in the conventional case, the adhesive strength between the glass plate and the intermediate film can be adjusted within a predetermined range, so that the whitening of the peripheral portion of the laminated glass is reduced. be able to.

[0012] However, in the method proposed above, the whitening of the peripheral portion of the laminated glass is reduced only by the reduction of the carboxylic acid metal salt, and when the organic acid is used in a too large amount, the intermediate film on the peripheral portion of the laminated glass absorbs moisture. Then, there is a problem that peeling is likely to occur between the glass plate at the peripheral portion of the laminated glass and the intermediate film.

As an adhesive strength adjusting agent, Japanese Patent Publication Sho 58-
Japanese Patent No. 39178 proposes a method using a silane compound such as a silane coupling agent. However, in this method, it is difficult to actually adjust the adhesive force within a predetermined range, and it is not possible to improve both peeling and whitening of the peripheral portion of the laminated glass, and it has not been put to practical use yet.

[0014]

SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned problems, and its object is to achieve excellent adhesion and moisture resistance, and even when placed in a high-humidity atmosphere. An object of the present invention is to provide an interlayer film for laminated glass and a laminated glass in which both peeling and whitening of the glass peripheral portion are improved.

[0015]

The above-mentioned object is defined in claim 1.
An interlayer film for laminated glass according to claim 2 or 3, and
It can be achieved by the laminated glass described in.

That is, the interlayer film for laminated glass according to claim 1 is characterized in that a plasticized polyvinyl acetal resin film is kneaded or coated with an organic acid and a silane coupling agent.

The interlayer film for laminated glass according to claim 2 is the interlayer film for laminated glass according to claim 1, wherein
Resin 10 constituting a plasticized polyvinyl acetal resin film
It is characterized in that 0.01 to 10 parts by weight of an organic acid and 0.01 to 10 parts by weight of a silane coupling agent are used with respect to 0 part by weight.

Further, the laminated glass according to claim 3 is
The interlayer film for laminated glass according to claim 1 or 2 is sandwiched between two glass plates or between a glass plate and a sheet.

In the present invention, the plasticized polyvinyl acetal resin film is a resin film similar to that used as a conventional interlayer film for laminated glass, for example, a resin obtained by adding a plasticizer to a polyvinyl acetal resin. Membranes are used.

As the polyvinyl acetal resin, a resin obtained by acetalizing polyvinyl alcohol with an aldehyde having 1 to 10 carbon atoms is generally used. Among them, polyvinyl butyral resins obtained by acetalizing polyvinyl alcohol with n-butyraldehyde and having a butyralization degree of 60 to 70 mol% and a polymerization degree of 1000 to 2000 are various properties such as transparency, adhesiveness, weather resistance and toughness. It is preferable because it has excellent performance.

Examples of the plasticizer include ethylene glycol-di-2-ethylbutyrate, 1,3-propylene glycol-di-2-ethylbutyrate, 1,4-propyleneglycol-di-2-ethylbutyrate, 1,4-butylene glycol-di-2-ethylbutyrate, 1,2
-Butylene glycol-di-2-ethylbutyrate, diethyleneglycol-di-2-ethylbutyrate, diethyleneglycol-di-2-ethylhexoate, dipropyleneglycol-di-2-ethylbutyrate, triethyleneglycol-di -2-ethylbutyrate, triethylene glycol-di-2-ethylpentoate,
Examples thereof include triethylene glycol-di-2-ethylhexoate, tetraethylene glycol-di-2-ethylbutyrate, diethylene glycol-di-capryate and triethylene glycol-di-capryate.

These plasticizers may be used alone or 2
You may use it, combining two or more types suitably. The content of these plasticizers is preferably 20 to 60 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin. When the content of the plasticizer is less than 20 parts by weight, flexibility and the like are insufficient, and conversely 6
If it exceeds 0 parts by weight, bleeding occurs and the transparency and adhesiveness are impaired.

In the present invention, the plasticized polyvinyl acetal resin film is kneaded or coated with an organic acid and a silane coupling agent. Specifically, (1) the resin film When both the organic acid and the silane coupling agent are kneaded, (2) When both the organic acid and the silane coupling agent are applied to both surfaces of the resin film, (3) the resin film is applied. In some cases, one of the organic acid and the silane coupling agent is kneaded, and the other is applied to both surfaces of the resin film.

Examples of the organic acid include propionic acid, butanoic acid, 2-ethylbutyric acid, hexanoic acid, 2-ethylhexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid and erucic acid. Is used. Particularly, an organic acid having 4 or more carbon atoms is preferable. These organic acids may be used alone or in appropriate combination of two or more kinds.

These organic acids are used in an amount of 0.01 to 100 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin constituting the above resin film in both the kneading method and the double-sided coating method.
It is preferably used in the range of 10 parts by weight, more preferably 0.02 to 1 part by weight. The amount of organic acid used is 0.0
If the amount is less than 1 part by weight, the whitening-suppressing effect is small. On the contrary, if the amount is more than 10 parts by weight, not only the resin is deteriorated by the organic acid but also foaming may occur when the temperature is relatively high. is there.

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, γ-aminopropyltriethoxysilane,
γ-methacryloxypropyltrimethoxysilane, γ
-Glycidyloxypropyltrimethoxysilane, γ-
Glycidoxypropylmethyldimethoxysilane or the like is used. These silane coupling agents may be used alone or in appropriate combination of two or more kinds.

These silane coupling agents are used in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin constituting the resin film, regardless of the kneading method or the double-sided coating method. It is preferably used, and more preferably 0.2 to 8 parts by weight for the kneading method and 0.02 to 5 parts by weight for the double-sided coating method. If the amount of the silane coupling agent used is less than 0.01 parts by weight, the adhesive force cannot be sufficiently maintained, and the peripheral peeling may not be suppressed when placed in a relatively high humidity. Yes, and conversely, if more than 10 parts by weight,
The adhesion may be too strong.

If necessary, conventionally used additives such as an adhesiveness adjusting agent composed of a carboxylic acid metal salt such as potassium acetate or magnesium acetate, an ultraviolet absorber, an antioxidant, etc. may be added to the resin film. , May be contained within the range in which the object of the present invention is achieved.

For example, when the adhesive force adjusting agent comprising the carboxylic acid metal salt is contained, it is added in an amount of 0.01 to 100 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin constituting the resin film.
The amount is preferably 0.5 part by weight, more preferably 0.02 to 0.2 part by weight. If the content of the adhesive strength adjusting agent is less than 0.01 parts by weight, the effect of adjusting the adhesive strength is hardly obtained, and conversely, if it exceeds 0.5 parts by weight,
The adhesive strength becomes too low, the moisture resistance decreases, and the transparency of the interlayer film is lost.

To produce the interlayer film for laminated glass of the present invention by the kneading method, for example, the polyvinyl acetal resin, the plasticizer, the organic acid, and the silane coupling agent are mixed in a predetermined amount, and the mixture is mixed with an extruder or an extruder. A method of melting and kneading with a roll to form a film is adopted.

To produce the interlayer film for laminated glass of the present invention by a coating method, for example, the polyvinyl acetal resin and a plasticizer are blended in a predetermined amount, and the mixture is melt-kneaded by an extruder or a roll to form a film. A method is employed in which the resin film is molded into a shape, and a predetermined amount of a solution of an organic acid and a silane coupling agent is applied to both surfaces of the resin film by a spray method, a dipping method, a roll method, a brush method, or the like and dried.

When applying a solution of an organic acid and a silane coupling agent, a method of applying a mixed solution of an organic acid and a silane coupling agent is preferably adopted. You may make it apply | coat one of the single solutions of a silane coupling agent, and apply the remaining other single solution on it.

Thus, the interlayer film for laminated glass of the present invention is obtained. In order to manufacture laminated glass using the interlayer film for laminated glass of the present invention, the following known methods are adopted, for example. The surface of this intermediate film may be embossed by using a roll having an emboss in the film forming step in order to improve the deaerating property during the laminating process.

First, the water content of the interlayer film for laminated glass is adjusted. The water content of this interlayer is generally between 0.4 and
It is desirable to adjust to about 0.5% by weight, but 0.2 to
It can be used even at about 2.0% by weight. Next, the above-mentioned intermediate film is sandwiched between two transparent glass plates, which is put in a rubber bag and pre-bonded at about 70 to 110 ° C. under vacuum suction, and then about 120 by using an autoclave or a press. It is manufactured by carrying out the main bonding at a temperature of about 150 ° C. and a pressure of about 10 to 15 kg / cm ² .

As the glass plate, not only an inorganic glass plate such as a float glass but also an organic glass plate made of a transparent synthetic resin such as polycarbonate, methyl methacrylate, amorphous polyamide can be used. Also,
As the sheet, a sheet made of the above-mentioned transparent synthetic resin is used. In addition, a metal oxide layer or a metal layer may be formed on at least one inner surface of the glass plate or sheet to impart functions such as transparent conductivity and light selective transmission that does not transmit heat rays.

[0036]

When a laminated glass is prepared by using an interlayer film for laminated glass in which an organic acid and a silane coupling agent are kneaded or applied to a plasticized polyvinyl acetal resin film as in the present invention, a glass plate is obtained. Adhesiveness and moisture resistance to the interlayer film are improved, and both peeling and whitening of the peripheral portion of the laminated glass are improved even when placed in a high-humidity atmosphere.

The reason is presumed to be as follows. When the laminated glass is placed in an atmosphere with high humidity, the water that has entered the inner film from the peripheral edge of the laminated glass (the part where the film is in contact with air) is mainly kneaded into the intermediate film. Attracted to organic acids that are rare or applied,
Without being aggregated around this organic acid, it is uniformly dispersed inside (in the case of kneading) or on the surface (in the case of coating) the intermediate film at the peripheral portion of the laminated glass. Therefore, it is presumed that the scattering of light due to the aggregation of water does not occur and the whitening of the interlayer film is improved.

[0038] In the prior art, an adhesiveness adjusting agent composed of a carboxylic acid metal salt is exclusively used. However, such a carboxylic acid metal salt easily absorbs water, and the carboxylic acid metal salt is changed depending on its content. It exists as a minute crystal in the film, and water concentrates around this as a center to scatter light, so that whitening progresses from the peripheral edge of the laminated glass to the inner peripheral part. When the amount of metal carboxylate is small, whitening is unlikely to occur because there are few parts where water agglomerates.

As described above, when the organic acid is present in the interlayer film of the laminated glass, the adhesive force between the glass plate and the interlayer film is reduced and the film is easily peeled off. However, the silane coupling agent is kneaded into the interlayer film. When it is diluted or applied, the adhesive action of the silane coupling agent compensates for the decrease in the adhesive force between the glass plate and the intermediate film, and therefore the glass plate and the intermediate film in the peripheral portion of the laminated glass are It is presumed that peeling is prevented.

[0040]

EXAMPLES Examples and comparative examples of the present invention will be shown below. Example 1 Polyvinyl acetal resin (polyvinyl butyral resin, polymerization degree 1700, butyralization degree 65 mol%, acetylation degree 1 mol%, residual vinyl alcohol 34 mol%)
100 parts by weight, 40 parts by weight of plasticizer (triethylene glycol-di-2-ethylbutyrate), 0.5 parts by weight of organic acid (octanoic acid), and silane coupling agent (γ-
Glycidoxypropylmethyldimethoxysilane) 0.5
Parts by weight and adhesive strength modifier (magnesium acetate) 0.04
8 parts by weight were mixed.

This mixture was well kneaded with a two roll heated to 80 ° C. to obtain a resin film having a thickness of about 0.8 mm. The resin film was regulated by a spacer having a thickness of 0.76 mm and press-molded at 150 ° C. to produce a transparent interlayer film for laminated glass having a thickness of 0.76 mm.

The interlayer film for laminated glass was adjusted in a constant temperature and humidity chamber so that the water content was 0.4 to 0.5% by weight, and this was used as two transparent float glass plates (length 30 cm × width 30 cm).
× thickness 0.3 cm) and pre-bonded with a sandwich roll. Then, in an autoclave at 140 ° C, 13 kg / cm ²
The main pressure bonding was performed under the pressure of 1 to produce a transparent laminated glass.

The laminated glass was evaluated for adhesion and moisture resistance by the following methods. The results are summarized in Table 1.

Adhesion test Based on the Panmel test method, the laminated glass was placed at -18 ° C.
Leave it at ± 0.5 ° C for 16 hours, place it on a steel block inclined at 45 °, and hit it with a 0.45 kg flat-head hammer until the glass particle size is 6 mm or less. Smash. Then, the degree of exposure of the film after the glass was partially peeled off was measured, and as shown in Table 2, it was judged by a limit sample pre-graded.

This test is for judging whether the adhesive force between the glass plate and the intermediate film is within a predetermined range.
It is preferable that the numerical value (total Panmel value) is within the range of 3 to 7. When the Panmel value is less than 3, the shatterproof property of glass fragments is reduced, and when the Panmel value exceeds 7, the penetration resistance is reduced. .

At the same time, the number of mm from the peripheral edge of the portion where the interlayer film was completely peeled off from the glass plate and was 100% exposed (Pummel value 0) was measured, and the average value was taken as the peeling distance (mm ).

Moisture resistance test Based on JIS R3212, laminated glass is
Leave for 2 weeks in a constant temperature and humidity room at ℃ ± 2 ℃, relative humidity 95% ± 4%, and then measure how many mm whitening of the interlayer film is from the edge, and take the average value as the whitening distance (mm). Indicated.

Example 2 Polyvinyl acetal resin (polyvinyl butyral resin, degree of polymerization 1700, degree of butyralization 65 mol%, degree of acetylation 1 mol%, residual vinyl alcohol 34 mol%)
100 parts by weight, 40 parts by weight of a plasticizer (triethylene glycol-di-2-ethylbutyrate), and 0.048 parts by weight of an adhesive strength modifier (magnesium acetate) were mixed.

This mixture was well kneaded with a two roll heated to 80 ° C. to obtain a resin film having a thickness of about 0.8 mm. This resin film was regulated by a spacer having a thickness of 0.76 mm and press-molded at 150 ° C. to produce a transparent resin film for laminated glass having a thickness of 0.76 mm.

An acetone solution of an organic acid (2-ethylhexanoic acid) was evenly applied to both surfaces of the resin film for laminated glass, dried, and then silane coupling agent (γ-glycidoxy) was applied to both surfaces. An n-hexane solution of propylmethyldimethoxysilane) was applied and dried to prepare a transparent interlayer film for laminated glass.

The organic acid is 0.146 parts by weight in total on both sides with respect to 100 parts by weight of the resin, and the silane coupling agent is 0.221 in total on both sides with respect to 100 parts by weight of the resin. It was part by weight.

A transparent laminated glass was prepared in the same manner as in Example 1 except that the obtained interlayer film for laminated glass was used, and its adhesiveness and moisture resistance were evaluated. The results are summarized in Table 1.

Example 3 An acetone solution of n-undecanoic acid was applied in place of the acetone solution of 2-ethylhexanoic acid (this organic acid was added in an amount of 0.186 parts by weight based on 100 parts by weight of the resin on both sides in total). Was also used), and also an adhesion control agent (magnesium acetate)
A laminated glass was produced in the same manner as in Example 2 except that 0.048 parts by weight was not mixed, and the adhesiveness and the moisture resistance were evaluated. The results are summarized in Table 1.

Comparative Example 1 Except that 0.5 part by weight of an organic acid (octanoic acid) and 0.5 part by weight of a silane coupling agent (γ-glycidoxypropylmethyldimethoxysilane) were not mixed. A laminated glass was prepared in the same manner as in Example 1 and evaluated for adhesiveness and moisture resistance. The results are summarized in Table 1.

Comparative Example 2 A laminated glass was prepared in the same manner as in Example 2 except that an acetone solution of an organic acid (2-ethylhexanoic acid) was not applied, and its adhesiveness and moisture resistance were evaluated. The results are summarized in Table 1.

Comparative Example 3 A laminated glass was prepared in the same manner as in Example 2 except that the n-hexane solution of the silane coupling agent (γ-glycidoxypropylmethyldimethoxysilane) was not applied, and the adhesiveness was improved. And moisture resistance were evaluated. The results are shown in Table 1.
Are shown together.

Comparative Example 4 A laminated glass was prepared in the same manner as in Example 3 except that the acetone solution of n-undecanoic acid was not applied.
Adhesion and moisture resistance were evaluated. The results are summarized in Table 1.

Comparative Example 5 Instead of 0.146 parts by weight of 2-ethylhexanoic acid, n
-A laminated glass was prepared in the same manner as in Example 2 except that 0.186 parts by weight of undecanoic acid was used and the n-hexane solution of the silane coupling agent (γ-glycidoxypropylmethyldimethoxysilane) was not applied. It was produced and evaluated for adhesiveness and moisture resistance. The results are summarized in Table 1.

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

As described above, in the interlayer film for laminated glass of the present invention, the plasticized polyvinyl acetal resin film is kneaded or coated with the organic acid and the silane coupling agent, and preferably the resin film is formed. An organic acid of 0.01 to 10 parts by weight and a silane coupling agent of 0.01 to 10 parts by weight are used with respect to 100 parts by weight of the resin constituting the laminated glass using the interlayer film.
Even when placed in a high-humidity atmosphere, the adhesiveness and moisture resistance are excellent, and both peeling and whitening of the peripheral portion of the laminated glass are improved, which is a remarkable effect.

Further, the interlayer film for laminated glass and the laminated glass of the present invention are excellent in transparency, and moreover, the adhesive force between the pair of glass plates or the interlayer film between the sheet and the glass plate is adjusted to a desired value. It's also easy.

Claims (3)

[Claims] 1. A plasticized polyvinyl acetal resin film,
An interlayer film for laminated glass, characterized in that an organic acid and a silane coupling agent are kneaded or applied. 2. An organic acid of 0.01 to 1 is added to 100 parts by weight of a resin constituting the plasticized polyvinyl acetal resin film.
The interlayer film for laminated glass according to claim 1, wherein 0 part by weight and 0.01 to 10 parts by weight of the silane coupling agent are used. 3. A laminated glass, characterized in that the interlayer film for laminated glass according to claim 1 is sandwiched between two glass plates or between a glass plate and a sheet.