JPH0826784A - Intermediate film for laminated glass and laminated glass - Google Patents

Abstract

PURPOSE:To provide the intermediate film having good humidity resistance, excellent adhesion and superior transparency and also to provide laminated glass using this intermediate film. CONSTITUTION:This intermediate film is obtained by forming a coating layer comprising a water-retaining agent on at least one surface of a resin film which consists of a resin composition composed of a polyvinylacetal resin, a plasticizer and a silane coupling agent and/or a compound contg. an epoxy group. The laminated glass using the intermediate film is also provided.

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 using the interlayer film.

[0002]

2. Description of the Related Art Conventionally, laminated glass has been widely used for construction and for windshields of automobiles. As a typical example of this laminated glass, there is one in which an interlayer film made of a plasticized polyvinyl acetal resin composition is interposed and bonded between a pair of glass plates. In such a laminated glass, the glass portion is damaged when an external impact is applied, but the interlayer film interposed between the glass plates is not easily damaged, and the damaged glass plate adheres to the interlayer film. As a result, glass fragments are less likely to scatter. Therefore, it is possible to prevent the human body in the transportation system or the building from being damaged by the glass fragments.

In the above laminated glass, when the adhesive force between the glass plate and the intermediate film is small, the glass fragments are peeled off from the intermediate film and scattered by an external impact. On the other hand, when the adhesive strength is large, the glass plate and the intermediate film are simultaneously broken. Therefore, it is necessary to adjust the adhesive force between the interlayer film and the glass plate in order to absorb the shock when the driver and the passenger collide with the glass and prevent the penetration in the case of a car accident. In the case of construction,
It is necessary to prevent the glass plate from penetrating foreign objects coming from the outside and to prevent the scattering of glass fragments.

[0004] Therefore, in order to set the adhesive force between the intermediate film and the glass plate within a predetermined range, various adhesive force adjusting additives for the intermediate film have been conventionally studied. Japanese Patent Publication 58-3
Japanese Patent No. 9178 discloses a technique of using a silane compound as an adhesive force adjusting agent, but it was difficult to skillfully reduce the adhesive force with glass. Nowadays, as disclosed in Japanese Patent Publication No. 47-1305, etc., a metal salt of a carboxylic acid is mainly used as an adhesion control agent. When the metal salt of a carboxylic acid is contained in the interlayer film, the metal salt of the carboxylic acid bleeds from the interlayer film at the high temperature in an autoclave or the like used especially when forming the interlayer film and when pressure-bonding with a glass plate, so that the interlayer surface is bleeded. Many gather. Then, the metal salt of the carboxylic acid and the water coordinated with the metal salt of the carboxylic acid inhibit hydrogen bonding between the hydroxyl groups of the acetal resin in the interlayer film and the hydroxyl groups of the glass plate, so that the adhesive strength is lowered. Therefore, the adhesiveness adjusting effect of the metal salt of carboxylic acid is adjusted by changing the distribution state of the metal salt of carboxylic acid in the interlayer film and the surface of the interlayer film or by changing the amount of water in the interlayer film. .

Under the present circumstances, the distribution of the metal salt of carboxylic acid is kept constant under a predetermined kneading condition, and the water content is 0.4-.
The content of the metal salt of carboxylic acid is determined so that the adhesive force between the glass plate and the intermediate film falls within a suitable range while the concentration is kept constant at about 0.5% by weight. However, it has been found that when an interlayer film containing a metal salt of carboxylic acid is used for laminated glass, there is a problem in moisture resistance. That is, when placed in a high-humidity atmosphere, since the interlayer film is in direct contact with air in the peripheral portion of the laminated glass, the interlayer film is whitened depending on the amount of the carboxylic acid metal salt. was there.

Further, when the laminated glass is used under high humidity, there is a problem that peeling gradually occurs from the peripheral portion. In order to prevent peeling of the peripheral portion, JP-A-2-24
Japanese Patent No. 8348 discloses a technique in which it is effective to introduce an epoxy group to strengthen the adhesive force between the glass and the film, but there is a problem that it is impossible to suppress whitening due to water absorption of the intermediate film.

[0007]

SUMMARY OF THE INVENTION In view of the above, it is an object of the present invention to provide an interlayer film for laminated glass and a laminated glass which have good moisture resistance and excellent adhesive strength and transparency.

[0008]

Means for Solving the Problems The gist of the present invention is to provide a polyvinyl acetal resin, a plasticizer, and at least one surface of a resin film made of a resin composition containing a silane coupling agent and / or an epoxy group-containing compound, An interlayer film for laminated glass and a laminated glass having a coating layer made of a water retention agent formed thereon.

The polyvinyl acetal resin used in the present invention may be a resin of the type conventionally used for interlayer films for laminated glass. Specifically, the butyralization degree is 60.
Polyvinyl butyral having a degree of polymerization of 70 mol% and a degree of polymerization of 1000 to 2000 is preferably used.

The plasticizer used in the present invention is not particularly limited, and examples thereof include ethylene glycol di-2-ethylbutyrate, 1,3-propylene glycol di-2-ethylbutyrate and 1,4-propylene glycol. J-2
-Ethyl butyrate, 1,4-butylene glycol di-
2-ethyl butyrate, 1,2-butylene glycol di-2-ethyl butyrate, diethylene glycol di-2
-Ethyl butyrate, diethylene glycol di-2-ethyl hexoate, dipropylene glycol di-2-ethyl butyrate, triethylene glycol di-2-ethyl pentate, triethylene glycol di-2-ethyl hexoate, tetra Examples thereof include ethylene glycol di-2-ethylbutyrate, diethylene glycol dicapryate, and triethylene glycol dicapryate. The content of the plasticizer is preferably in the range of 20 to 60 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin.

Examples of the water retention agent used in the present invention include acrylic acid, vinyl alcohol copolymer, sodium acrylate polymer and the like. The water retention agent is used by being applied to the interlayer film for laminated glass or the glass surface,
It is preferable that it is applied to the inside of the surfaces excluding the peripheral portion of the mating surfaces. Further, it is preferable that the water retention agent is applied at a slight distance from the peripheral portion of the mating surface between the interlayer film for laminated glass and the glass, because the water absorption effect is further enhanced. The amount of the water retention agent applied is preferably 0.001 to 10 parts by weight, and more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the polyvinyl acetal resin.

The silane coupling agent used in the present invention is preferably bifunctional having a group that reacts with the glass surface and a group that reacts with the resin sheet. As such, for example, vinyltrichlorosilane,
Vinyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, 3-glycidoxypropyldimethylethoxysilane, etc. Can be mentioned. The silane coupling agent may be contained in the intermediate film or may be applied to the surface of the intermediate film, but is preferably applied. The amount of the silane coupling agent used is preferably 0.001 to 10 parts by weight based on 100 parts by weight of the polyvinyl acetal resin. If it is less than 0.001 part by weight, peripheral peeling after moisture absorption may not be suppressed, and if it exceeds 10 parts by weight, the adhesive strength may be too strong. When it is applied, it is preferably 0.02 to 5 parts by weight, and when it is contained, it is preferably 0.2 to 8 parts by weight.

Examples of the epoxy group-containing compound used in the present invention include resins having an epoxy group, adhesives made of them, and modified silicone oil. The epoxy group-containing compound can be cured with, for example, amines, organic acids, acid anhydrides, phenol resins, urea resins, polyamide resins and the like. The epoxy group-containing compound may be contained in the intermediate film or may be coated on the surface of the intermediate film, but is preferably coated. The amount of the epoxy group-containing compound used is 0.00 based on 100 parts by weight of the polyvinyl acetal resin.
1 to 10 parts by weight is preferable. If it is less than 0.001 part by weight, peeling around the edges after moisture absorption may not be suppressed, and 1
If it exceeds 0 parts by weight, the adhesive strength may be too strong. When it is applied, it is preferably 0.02 to 5 parts by weight, and when it is contained, it is preferably 0.2 to 8 parts by weight. When the silane coupling agent and / or the epoxy group-containing compound is coated and used, the order of the obtained coating layer 1 and the coating layer 2 made of a water retention agent is not particularly limited.

The resin composition may contain an ultraviolet absorber, an antioxidant and the like, and conventionally known ones are used as these.

The interlayer film for laminated glass of the present invention is obtained by molding the above resin composition into a sheet and then adjusting the water content for adjusting the adhesive strength. This water content is 0.4
~ 0.5 wt% is preferable, 0.2-2.0 wt%
It can be used to a certain degree. The interlayer film for laminated glass may be embossed on the surface in order to improve the degassing property. A conventionally known adhesive strength adjusting agent is optionally used to adjust the adhesive strength.

The laminated glass of the present invention is produced by inserting the above-mentioned interlayer film for laminated glass between a pair of ordinary glass plates or between a glass plate and a resin sheet. A metal oxide layer or a metal layer may be formed on the inner surface of the glass plate or the resin sheet. The glass plate may be formed of normal inorganic glass or organic glass.

[0017]

When a coating layer made of a water retention agent is formed between the interlayer film and the glass plate as in the present invention, the water retention agent at the interface absorbs water, which impedes the penetration of water into the film. , Whitening is suppressed. Furthermore, the silane coupling agent or the epoxy group-containing compound improves the binding force between the glass plate or resin sheet and the intermediate film, and prevents the glass plate or resin sheet and the intermediate film from peeling off.

[0018]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 As a polyvinyl acetal resin, a butyralization degree of 65 mol%, an acetylation degree of 1 mol%, and a residual vinyl alcohol 3
100 parts by weight of polyvinyl butyral resin having a polymerization degree of 1700 at 4 mol%, 40 parts by weight of triethylene glycol di-2-ethylbutyrate as a plasticizer, 0.048 parts by weight of magnesium acetate as an adhesive strength adjusting agent, and a silane coupling agent 0.5 parts by weight of γ-aminopropyltriethoxysilane was mixed, and the mixture was well kneaded with a two-roll roller heated at 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 heated and pressed by a press at a temperature of 150 ° C. to obtain a sheet having a uniform thickness. Then, the water content was adjusted to 0.4 to 0.5% by weight in a constant temperature and humidity chamber to obtain an interlayer film. Then, on the glass side, 0.01 part by weight of acrylic acid / vinyl alcohol copolymer as a water retention agent was applied to the inside of the mating surface excluding the peripheral portion of 3 mm and dried. The thus obtained interlayer film was sandwiched between the above glass plates, prebonded by a roll method, and then pressure-bonded at a pressure of 13 kg / cm ^{2 in} an autoclave at 140 ° C. to obtain a laminated glass. The following tests were performed on the obtained laminated glass, and the results are shown in Table 1.

Moisture resistance Based on the moisture resistance test of JIS R 3212, the obtained laminated glass was kept in a constant temperature and humidity chamber at 50 ± 2 ° C. and 95 ± 4% relative humidity for 6 weeks, and the interlayer whitening distance And the peeled distance was measured from the end.
Further, the obtained laminated glass was immersed in warm water of 80 ° C. for 200 hours and the same test was conducted.

Example 2 As a polyvinyl acetal resin, the butyralization degree is 65 mol%, the acetylation degree is 1 mol%, and the residual vinyl alcohol 3 is used.
100 parts by weight of polyvinyl butyral resin having a degree of polymerization of 1700 at 4 mol%, 40 parts by weight of triethylene glycol di-2-ethylbutyrate as a plasticizer, and 0.048 parts by weight of magnesium acetate as an adhesion control agent were mixed, and the mixture was mixed. The resin film having a thickness of about 0.8 mm was well kneaded with a two roll heated to 80 ° C. This resin film has a thickness of 0.
The resin film was regulated by a 76 mm spacer and heated and pressed by a press at a temperature of 150 ° C. to obtain a resin film having a uniform thickness. 10 ml of a water retaining agent, acrylic acid, vinyl alcohol copolymer, prepared in advance on this resin film was applied to the inside of the mating surfaces excluding the peripheral portion 3 mm (0.01 parts by weight application) and dried,
n of γ-methacryloxypropyltrimethoxysilane
-Apply 10 ml of hexane solution (0.1 mol / liter) on the entire surface (0.221 parts by weight application), and adjust the water content to 0.4 to 0.5% by weight in a constant temperature and humidity chamber. To obtain an intermediate film. The obtained interlayer film was sandwiched between glass plates, prebonded by a roll method, and then pressure-bonded at a pressure of 13 kg / cm ^{2 in} an autoclave at 140 ° C. to obtain a laminated glass. The same test as in Example 1 was performed on the obtained laminated glass. As a result, whitening was observed only in the part where the water retention agent was not applied, that is, in the part within 3 mm from the periphery. The results obtained are shown in Table 1.

Example 3 As a polyvinyl acetal resin, a butyralization degree of 65 mol%, an acetylation degree of 1 mol%, and residual vinyl alcohol 3
100 parts by weight of polyvinyl butyral resin having a degree of polymerization of 1700 at 4 mol%, 40 parts by weight of triethylene glycol di-2-ethylbutyrate as a plasticizer, and 0.048 parts by weight of magnesium acetate as an adhesion control agent were mixed, and the mixture was mixed. The resin film having a thickness of about 0.8 mm was well kneaded with a two roll heated to 80 ° C. This resin film has a thickness of 0.
The resin film was regulated by a 76 mm spacer and heated and pressed by a press at a temperature of 150 ° C. to obtain a resin film having a uniform thickness. Then, the water content was adjusted to 0.4 to 0.5% by weight in a constant temperature and humidity chamber. Then, on the glass side, 0.01 part by weight of acrylic acid / vinyl alcohol copolymer as a water retention agent was applied to the inside of the mating surface excluding the peripheral portion of 3 mm and dried. Thus, 0.2 part by weight of a mixture of an epoxy resin adhesive and a curing agent was applied to the obtained resin film, the resin film was sandwiched between the above glass plates, pre-bonded by a roll method, and then an autoclave at 140 ° C. 13 kg / cm
^It pressure-bonded by the pressure of ² and obtained the laminated glass. The obtained laminated glass was subjected to the same moisture resistance test as in Example 1, and the laminated glass was immersed in hot water at 80 ° C. for 200 hours to conduct the same test. The results are shown in Table 1.

Example 4 A resin film was obtained in the same manner as in Example 2. The resin film was regulated by a spacer having a thickness of 0.76 mm and heated and pressed by a press at a temperature of 150 ° C. to obtain a resin film having a uniform thickness. A water retention agent prepared in advance, 10 ml of acrylic acid / vinyl alcohol copolymer, was applied to the inside of the mating surface excluding the peripheral portion of 5 mm (0.01 part by weight), and dried and then kept at constant temperature and humidity. In the chamber, adjust the water content to 0.4 to 0.5% by weight, apply 0.2 parts by weight of a mixture of epoxy resin adhesive and curing agent to the obtained resin film, and sandwich it between glass plates. , Pre-bond with roll method, then 140 ℃
Crimped with a pressure of 13 kg / cm ^{2 in} the autoclave of
A laminated glass was obtained. About the obtained laminated glass,
The same test as in Example 3 was performed, and the results are shown in Table 1.

Example 5 The same results were obtained as in Example 1 except that the water retention agent was applied to the entire mating surfaces, and the results obtained are shown in Table 1.

Comparative Example 1 A laminated glass was obtained in the same manner as in Example 1 except that the water retention agent was not applied to the glass and the silane coupling agent was not contained in the film. The same tests as in Example 1 were performed on the obtained laminated glass, and the results are shown in Table 1.

Comparative Example 2 A laminated glass was obtained in the same manner as in Example 2 except that the silane coupling agent was not applied. The same tests as in Example 1 were performed on the obtained laminated glass, and the results are shown in Table 1.

Comparative Example 3 A laminated glass was obtained in the same manner as in Example 2 except that the water retention agent was not applied. The same tests as in Example 1 were performed on the obtained laminated glass, and the results are shown in Table 1.

Comparative Example 4 A laminated glass was obtained in the same manner as in Example 3 except that the water retention agent was not used. The same test as in Example 3 was performed on the obtained laminated glass, and the results are shown in Table 1.

[0029]

[Table 1]

[0030]

The intermediate film for laminated glass and the laminated glass of the present invention are at least a resin film comprising a polyvinyl acetal resin, a plasticizer, and a resin composition containing a silane coupling agent and / or an epoxy group-containing compound. By forming a coating layer made of a water retention agent on one surface, moisture resistance, adhesive strength and transparency are remarkably improved.

Claims (4)

[Claims] 1. A coating layer made of a water retention agent is formed on at least one surface of a resin film made of a resin composition containing a polyvinyl acetal resin, a plasticizer, and a silane coupling agent and / or an epoxy group-containing compound. An interlayer film for laminated glass, which is characterized in that 2. A coating layer 1 made of a silane coupling agent and / or an epoxy group-containing compound and a coating made of a water retention agent on at least one surface of a resin film made of a resin composition containing a polyvinyl acetal resin and a plasticizer. An interlayer film for laminated glass, characterized in that the layer 2 is formed. 3. A water retention agent, a silane coupling agent, and / or 100 parts by weight of a polyvinyl acetal resin.
Or, the epoxy group-containing compound is 0.001-10, respectively.
A weight part is used, The claim 1 or 2 characterized by the above-mentioned.
The interlayer film for laminated glass described. 4. A laminated glass, wherein the interlayer film for laminated glass according to claim 1, 2 or 3 is interposed between the glass plate or sheet and the glass plate.