JPH07232937A - Laminated glass and intermediate film therefor - Google Patents

Abstract

PURPOSE:To produce an intermediate film excellent in resistance to penetration, scatter preventing property of glass, etc., by constituting the intermediate film held and adhered between a transparent plate forming a metallic (oxide) layer on at least inside surface side and a glass plate with plural specified layers. CONSTITUTION:In this laminated glass, the intermediate film 20 is composed of a base layer 22 formed from a resin composition consisting essentially of a polyvinyl acetal resin having 60-75mol.% acetalization degree and the resin composition consisting essentially of the polyvinyl acetal resin having 80-95mol.% degree acetalization, and a layer 21 having high acetalization degree whose surface is provided on a side to be abutted on the metallic (oxide) layer 11 of the transparent plate out of the surface of the base layer 22 and an adhesion control layer 23 consisting of >=1 modified silicone oil (e.g. polyether modified silicone oil) selected from a (non)polar modified silicon oil and other kind functional group-modified silicone oil having (non) polar modified group in a molecule and whose surface is provided on the side to be abutted to a glass plate 10 out of the surface of the base layer 22.

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 which are used for laminated glass having excellent penetration resistance and glass scattering prevention and high functions such as heat ray reflection.

[0002]

2. Description of the Related Art Hitherto, laminated safety glass has been widely used for construction and windshields of automobiles. As a typical example of this laminated safety glass, there is one in which an interlayer film made of a plasticized polyvinyl acetal resin composition is sandwiched and bonded between a pair of glass plates. In such laminated safety glass, the glass part is damaged when an impact is applied from the outside, but the interlayer film sandwiched between the glasses is not easily damaged, and the glass is stuck to the interlayer film. Since it is in the open state, even if it breaks, glass fragments are unlikely to scatter. Therefore, it is possible to prevent a person in a transportation system or a building from being injured by the broken glass.

In order to satisfy such a function as a safety glass, it is necessary to adjust the adhesive force between the interlayer film and the glass within a certain range. In the case of laminated glass where the adhesion between the glass plate and the interlayer film is too small, the glass fragments will be peeled off and scattered from the interlayer film due to an external impact, and conversely the adhesion between the glass plate and the interlayer film. This is because if the laminated glass is too strong, the glass plate and the intermediate film both crack and penetrate due to an external impact.

Therefore, in order to properly adjust the adhesive force between the glass plate and the intermediate film, it is usual to knead and include an adhesive force adjusting agent (sometimes called an impact strength increasing agent) in the intermediate film. Alternatively, a method in which an adhesiveness modifier is attached to the surface of the interlayer film is adopted, and the water content in the interlayer film is also adjusted.

As the above-mentioned adhesion control agent, an alkali metal salt or an alkaline earth metal salt of carboxylic acid, a modified silicone oil or the like is generally used (for example, JP-B-45).
-32071, Japanese Patent Publication No. 55-29950,
Etc.).

By the way, in recent years, there has been proposed a laminated glass in which a layer having a high function is provided on the inner surface of a glass plate to impart a high function such as selective light transmittance and transparent conductivity. For example, heat-reflecting glass, dew condensation-preventing conductive glass, and the like, and these special laminated glasses have begun to be used in buildings and automobiles. These characteristics are mainly obtained by forming a highly functional thin film on the glass surface by a vacuum deposition method, a sputtering method, or the like.

As for the structure of the layer having a high function, for example, in the heat ray reflective glass for construction, in many cases, a metal oxide layer (heat ray reflective layer) is provided on the inner surface of the glass plate. On the other hand, in many heat ray reflective glasses for automobiles, a layer (heat ray reflection layer) in which a metal layer such as silver is sandwiched between metal oxides is provided on the inner surface of a glass plate. In many cases, other layers having high functions are also formed of a metal oxide layer or a metal layer.

Laminated glass using these metal oxide layers or metal layers (heat ray reflective layer) is mainly composed of glass plate / heat ray reflective layer / intermediate film / glass sheet, glass plate / intermediate film / heat ray reflective sheet / intermediate. A high-performance layer (heat-reflecting layer) that is a film / glass plate and is provided on the glass plate or sheet.
Is placed inside the laminated glass to protect it. Therefore, the metal oxide layer or the metal layer comes into contact with the intermediate film.

[0009]

Even in a laminated glass having such a metal oxide layer or a metal layer, a high degree of penetration resistance and glass scattering prevention properties are required, and these properties are imparted. In order to do so, it is necessary to appropriately adjust the adhesive force between the metal oxide layer or the metal layer and the intermediate film.

However, the one prepared by kneading the adhesiveness adjusting agent comprising a carboxylic acid metal salt into the intermediate film or coating it on the surface of the intermediate film is different from ordinary laminated glass having no metal oxide layer or metal layer. However, there has been a problem that the adhesive strength between the two tends to decrease over time due to outdoor exposure or ultraviolet irradiation, and the glass plate is likely to peel off from the interlayer film due to impact or the like.

In the case where the adhesive strength adjusting agent made of modified silicone oil is kneaded into the interlayer film, the change with time due to outdoor exposure or ultraviolet irradiation is small, but the change with time in the adhesive strength is large, and impact etc. Therefore, there is a problem that the glass plate is more likely to be peeled off than the intermediate film. This decrease in adhesive strength is caused by bleeding out gradually at the interface between the metal oxide layer or the metal layer and the intermediate film because the modified silicone oil is a liquid and is not completely compatible with the resin and the plasticizer. It is thought to be for the sake of saving.

The present invention is intended to solve the above problems, and its object is to prevent the adhesive strength from being deteriorated with time due to outdoor exposure, ultraviolet irradiation, temperature, etc. It is an object of the present invention to provide an interlayer film for laminated glass and a laminated glass which are used for laminated glass having excellent properties of preventing glass from scattering and having high functionality such as heat ray reflectivity.

[0013]

An intermediate film for laminated glass according to the present invention is sandwiched between a transparent plate having a metal oxide layer or a metal layer formed on at least the inner surface side thereof and a glass plate. An interlayer film for laminated glass to be attached, which comprises a base layer made of a resin composition containing a polyvinyl acetal resin having an acetalization degree of 60 to 75 mol% as a main component, and an acetalization degree of 80 to 95 mol%. It is formed of a resin composition containing a polyvinyl acetal resin as a main component, and is provided on the surface of the base layer which is in contact with the surface of the transparent plate on which the metal oxide layer or the metal layer is formed. It is selected from the group consisting of an acetalization degree layer, a nonpolar modified silicone oil, a polar modified silicone oil, and a heterofunctional group-modified silicone oil having a nonpolar modified group and a polar modified group in one molecule. It consists of one or more modified silicone oil, consisting of the adhesive force adjusting layer provided on the surface on the side that is in contact with the glass plate of the surface of the base layer.

The base layer in the interlayer film for laminated glass according to the first aspect of the present invention comprises a plasticized polyvinyl acetal resin obtained by adding a plasticizer to a polyvinyl acetal resin having an acetalization degree of 60 to 75 mol%. It is formed from a resin composition. When the degree of acetalization is low, the compatibility between the polyvinyl acetal resin and the plasticizer decreases,
If it becomes higher, the penetration resistance of the obtained laminated glass will be lowered, so that it is limited to the range of 60 to 75 mol%.

As the polyvinyl acetal resin,
Resins that have been used for interlayer films for laminated glass,
For example, a resin or the like in which polyvinyl alcohol is acetalized with an aldehyde having 4 to 10 carbon atoms can be used.

The average degree of polymerization of the polyvinyl alcohol used to prepare the polyvinyl acetal resin is
When it becomes low, the penetration resistance of the obtained laminated glass decreases,
When it becomes higher, the adhesive force between the interlayer film for laminated glass and the glass plate becomes stronger and the safety is lowered.
Is preferred. If the saponification degree of the polyvinyl alcohol is low, the transparency, heat resistance, light resistance and the like of the laminated glass obtained may be lowered, so that it is preferably 95 mol% or more.

Examples of the plasticizer include ester plasticizers such as monobasic acid esters and polybasic acid esters, and phosphoric acid plasticizers such as organic phosphoric acid compounds and organic phosphorous acid compounds. As the monobasic acid ester, for example,
Triethylene glycol, tetraethylene glycol or tripropylene glycol and butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptanoic acid, n-octylic acid, 2-ethylhexylic acid, pelargonic acid (n-nonylic acid) or decyl acid Glycol-based ester obtained by reaction with an organic acid such as, and preferably triethylene glycol-di-2-ethylbutyrate, triethylene glycol-di-2-ethylhexoate,
It is a glycol-based ester of triethylene glycol and an organic acid such as triethylene glycol-di-capronate and triethylene glycol-di-n-octoate.

Examples of the polybasic acid ester include:
Organic acids such as adipic acid, sebacic acid, azelaic acid,
Examples thereof include esters with straight-chain or branched alcohols having 4 to 8 carbon atoms. Examples of the phosphoric acid plasticizer include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate, and the like.

When the content of the plasticizer is small, the resulting laminated glass may have low penetration resistance,
If the amount of the plasticizer increases, the transparency of the laminated glass obtained by bleeding out the plasticizer and the adhesion between the interlayer film for laminated glass and the glass plate may decrease. Parts are preferred.

The base layer of the interlayer film for laminated glass may contain known additives such as an ultraviolet absorber, a light stabilizer, an antioxidant and an antistatic agent. Further, an adhesive strength adjusting agent composed of a carboxylic acid metal salt, a modified silicone oil or the like may be contained in a small amount so that the adhesive strength with the glass plate is not lowered.

The thickness of the base layer in the interlayer film for laminated glass is preferably 0.1 to 2 mm, because the penetration resistance of the laminated glass obtained may decrease regardless of whether it is thin or thick. In addition, this base layer is obtained by blending a polyvinyl acetal resin with a required amount of a plasticizer, and further adding other additives as necessary, and melt-kneading the mixture with an extruder to form a sheet. To be Also,
It can also be obtained by melt-kneading with a roll and then pressing.

The high-acetalization layer in the interlayer film for laminated glass according to the first aspect of the invention is formed of a resin composition containing a polyvinyl acetal resin as a main component and a plasticizer. When the degree of acetalization of the polyvinyl acetal resin is low, the adhesive strength between the interlayer film for laminated glass and the glass plate is high and the penetration resistance of the laminated glass obtained is low, and when it is high, the interlayer film for laminated glass and glass are Since the number of hydroxyl groups that contribute to the adhesiveness to the plate is reduced and the required adhesive force cannot be obtained, the amount is limited to 80 to 95 mol%.

As the polyvinyl acetal resin,
Although there is a difference in the degree of acetalization, for example, a polyvinyl acetal resin of the type used for the base layer, that is,
Examples thereof include resins in which polyvinyl alcohol is acetalized with an aldehyde having 4 to 10 carbon atoms. As the method for preparing the polyvinyl acetal resin, for example, a method of synthesizing 30% by weight or more of dimethylsulfoxide (DMSO) in a solvent, a method of synthesizing a resin acetalized by 50 mol% or more in a nonpolar solvent, Etc.

The degree of saponification of the polyvinyl alcohol used in the polyvinyl acetal resin having an acetalization degree in the range of 80 to 95 mol%, the type and amount of the plasticizer contained, and the like are used in the base layer. Further, known additives such as an ultraviolet absorber, a light stabilizer, an antioxidant and an antistatic agent similar to those used in the above-mentioned base layer may be contained. The thickness of the high acetalization degree layer is not particularly limited, but is usually 0.1 to 2 mm in many cases.

The adhesion control layer in the interlayer film for laminated glass according to the first aspect of the present invention has a nonpolar modified silicone oil, a polar modified silicone oil, and a nonpolar modified group and a polar modified group in one molecule. It comprises one or more modified silicone oils selected from the group consisting of different functional group-modified silicone oils.

The modified silicone oil is a viscous liquid obtained by reacting polysiloxane with a compound to be modified, and the site where the modifying group is introduced is not particularly limited, and is a terminal part of the polysiloxane. It may be a side chain portion. Also, the rate of modification is not particularly limited.

Among the above modified silicone oils, examples of the nonpolar modified silicone oil include, for example, polyether modified silicone oil, α-methylstyrene modified silicone oil, α-olefin modified silicone oil, higher fatty acid modified silicone oil, carnauba modified silicone oil. Oil, etc. are mentioned. Examples of the polar modified silicone oil include carboxyl modified silicone oil, epoxy modified silicone oil, ester modified silicone oil, amino modified silicone oil, alcohol modified silicone oil, and the like. Examples of the different functional group-modified silicone oil having a non-polar modified group and a polar modified group in one molecule include a modified silicone oil having an amino group and an alkoxy group, a modified silicone oil having an epoxy group and a polyether group, and an amino group. And modified silicone oils having a polyether group.

As the modified silicone oil, two or more kinds of modified silicone oil belonging to the same category among nonpolar modified silicone oil, polar modified silicone oil, and different functional group modified silicone oil may be used. That is, two or more kinds of modified silicone oils belonging to non-polar modified silicone oils may be used, two or more kinds of modified silicone oils belonging to polar modified silicone oils may be used, and different functional group-modified silicone oils may be used. Two or more kinds of modified silicone oils belonging thereto may be used.

The above adhesive strength adjusting layer can be obtained by dissolving a modified silicone oil in a suitable solvent, applying it to the surface of the base layer prepared in advance, and drying it. When the coating amount of the modified silicone oil is small, it becomes difficult to obtain the effect of adjusting the adhesive force, and when the coating amount of the modified silicone oil is large, the adhesive force is excessively reduced, so that it is preferably 10 ^-7 to 10 ^-1 g / m ² , and more preferably It is 10 ⁻⁵ to 10 ⁻² g / m ² .

The above modified silicone oil may be applied, for example, by coating or spraying the surface of the base layer with the modified silicone oil as it is or by dissolving it in a solvent, by transferring or printing from the roll surface, or by the base layer. A method of immersing the above in a modified silicone oil or a solution thereof, and the like.

When embossing is applied to the film surface by using an embossing roll in the step of extruding the interlayer film for laminated glass for the purpose of improving the degassing property in the laminating process, the modified silicone oil or its modified silicone oil is applied to the surface of the embossing roll. By continuously applying the solution, the modified silicone oil can be applied to the surface of the interlayer film for laminated glass simultaneously with the embossing treatment. When embossing is applied to the surface of the laminated glass interlayer film, a solvent that does not dissolve the surface of the laminated glass interlayer film is used in order to prevent deformation of the embossed surface of the laminated glass interlayer film. A solvent that is compatible with the surface of the interlayer film for laminated glass may be used to some extent in order to make it compatible with the surface of the interlayer film for laminated glass.

The metal oxide layer or the metal layer formed on the inner surface side of the transparent plate is for imparting high functions such as transparent conductivity and heat ray reflectivity, and for imparting transparent conductivity. Is, for example, a mixture of indium oxide and tin oxide (I
TO), tin oxide, zinc oxide, gold, silver, copper, etc. are formed. For imparting heat ray reflectivity, for example, gold, silver,
Metal coatings of copper, tin, aluminum, nickel, palladium and alloys or mixtures thereof are formed.

The metal oxide layer or the metal layer may be directly formed on the inner surface side of the glass plate, or may be once formed in advance on a suitable sheet, and this sheet may be formed on the inner surface side of the glass plate by a suitable adhesive film ( It may be adhered via an intermediate film). The metal oxide layer or the metal layer may be formed not only on the inner surface side of the glass plate but also on both the inner surface side and the outer surface side of the glass plate.

The laminated glass of the invention described in claim 2 is a laminated glass obtained by using the interlayer film for laminated glass according to claim 1. To make the above laminated glass,
The interlayer film for laminated glass is sandwiched between a glass plate and a transparent plate having a metal oxide layer or a metal layer formed on the inner surface side. At that time, the high acetalization degree layer in the interlayer film for laminated glass contacts the metal oxide layer or the metal layer of the transparent plate,
The adhesion adjusting layer in the interlayer film for laminated glass is laminated so as to come into contact with the glass plate on which the metal oxide layer or the metal layer is not formed. The transparent plate refers to a glass plate on one surface of which a heat-reflecting layer made of a metal oxide layer or a metal layer is formed. As the glass plate, an inorganic or organic transparent glass plate is generally used.

Then, this laminate is heated and pressurized by a conventional method using an apparatus such as an autoclave. Thus, the laminated glass according to the second aspect of the invention is produced.
In this case, the adhesion between the transparent plate on which the metal oxide layer or the metal layer is formed and the interlayer film for laminated glass, and the adhesion between the glass plate on which the metal oxide layer or the metal layer is not formed and the interlayer film for laminated glass From the viewpoint of penetration resistance, it is preferable that the adhesive strength is almost the same. This adhesive force can be adjusted by changing the degree of acetalization of the interlayer film for laminated glass.

FIG. 1 is a schematic sectional view showing a typical example of the laminated glass of the invention according to claim 2. In FIG. 1, 10 is a glass plate, 11 is a metal oxide layer or a metal layer,
Reference numeral 20 is an interlayer film for laminated glass, 21 is a high acetalization layer in the interlayer film for laminated glass, 22 is a base layer in the interlayer film for laminated glass, 23 is an adhesive force adjusting layer in the interlayer film for laminated glass, and 30 is It is a laminated glass.

[0037]

In the interlayer film for laminated glass according to claim 1, the high acetalization degree layer is brought into contact with the surface of the transparent plate on which the metal oxide layer or the metal layer is formed, and the adhesion adjusting layer is glass. Abutted on the plate. As a result, the laminated glass according to claim 2, in which high functionality (heat ray reflectivity, etc.) is imparted by the metal oxide layer or the metal layer is obtained. The adhesive force on each of the abutting surfaces is appropriately adjusted so that there is no large difference.

The high acetalization degree layer is made of polyvinyl acetal resin having an acetalization degree in the range of 80 to 95 mol%, and has a usual acetalization degree of 60 to 75.
The water absorption is lower than that of the polyvinyl acetal resin in the range of mol%, and the moisture resistance is improved when used as an interlayer film for laminated glass.

Further, the adhesive force adjusting layer appropriately adjusts the adhesive force between the interlayer film for laminated glass and the glass plate. The modified silicone oil used in this adhesion control layer has better moisture resistance than carboxylic acid metal salts, and is not kneaded into the base layer in the interlayer film for laminated glass, but is coated on the surface to form a layer. And there is always a certain amount at the interface with the glass plate without bleeding out over time,
The change over time due to temperature is also prevented. Further, it is effective in a small amount as compared with the case of kneading.

[0040]

EXAMPLES Examples and comparative examples of the present invention will be described below. The term "part" means "part by weight". Example 1 (1) Preparation of Resin Film for Base Layer Polyvinyl butyral resin 1 having a polymerization degree of 1700, a saponification degree of 99.2% and an acetalization degree of 65 mol% was placed in a flask.
00 parts, triethylene glycol-di-2 as a plasticizer
-40 parts ethyl butyrate, 0.16 parts UV absorber,
0.16 parts of antioxidant was supplied and mixed. The obtained mixture was well kneaded by a two-roll heated at 80 ° C. to form a sheet having a thickness of 0.7 mm, which was heated and pressed at 150 ° C. by a press regulated by a spacer to a thickness of 0. 6m
m resin film for the base layer was obtained.

(2) Preparation of resin film for high-acetalization layer In a separable flask equipped with a stirrer and dropping funnel, polymerization degree 1700, saponification degree 99.2%, acetalization degree 65.
100 parts of mol% polyvinyl butyral resin and 2947 parts of xylene are supplied, and the mixture is stirred and dissolved at a temperature of 25 ° C., and 158 parts of n-butyraldehyde are supplied all at once.
Stir for 5 minutes to mix. Further, 25 parts of a 35% hydrochloric acid solution was added dropwise from the dropping funnel over 15 minutes and mixed. Thirty minutes after mixing, the reaction system was heated to 60 ° C. and kept at a constant temperature for 3 hours to complete the reaction, and a reaction product was obtained. A large excess of water / methanol solution (mixing ratio 1: 1) in which sodium bicarbonate was dissolved was added to the obtained reaction product and neutralized to obtain a neutralized product. The obtained neutralized product was dropped into a large excess of methanol to reprecipitate the resin, washed with water and dried to obtain a polyvinyl acetal resin having a high acetalization degree of 85%.

100 parts of the obtained polyvinyl butyral resin having a high degree of acetalization, 30 parts of triethylene glycol-di-2-ethylbutyrate as a plasticizer, 0.16 parts of an ultraviolet absorber, and 0.16 parts of an antioxidant. Was fed into a flask and mixed, and the resulting mixture was well kneaded with a two roll heated to 80 ° C. to form a sheet having a thickness of 0.2 mm, and this was pressed at 150 ° C. with a press regulated by a spacer.
By heating and pressurizing, a resin film for high acetalization layer having a thickness of 0.16 mm was obtained. The obtained resin film for high acetalization layer was allowed to stand in a constant temperature and constant humidity chamber and adjusted so that the water content was 0.4 to 0.5% by weight.

(3) Preparation of Adhesion Strength Adjustment Layer On one surface of the resin film for base layer obtained in the above (2), a solution prepared by dissolving a polyether-modified silicone oil represented by the following general formula (A) in acetone is prepared. Then, it was thinly applied with gauze and dried to form an adhesive strength adjusting layer. The resin film for a base layer having the adhesive strength adjusting layer formed on one surface was allowed to stand in a constant temperature and humidity chamber and adjusted so that the water content of the adhesive strength adjusting layer was 0.4 to 0.5% by weight. The amount of the polyether modified silicone oil applied was about 10 ⁻⁴ g / m ² . The contents of the high acetalization degree layer and the adhesive strength adjusting layer thus obtained are shown in Table 2.

[0044]

[Chemical 1] (In the formula, m and n represent a positive integer of 10 to 20, and x
Represents a positive integer of 2 to 8. )

(4) Production of laminated glass A resin film for a base layer and a resin film for a high-acetalization layer each having an adhesiveness adjusting layer formed on one surface thereof were formed in a length of 305 mm × width of 3
Glass plate / IT of the same size cut to a size of 05 mm
Between the conductive glass (thickness 2.5 mm) having a layered structure of O and the glass plate (thickness 2.5 mm), a glass plate / IT
It was sandwiched so as to have a layer structure of O / high acetalization degree layer / base layer / adhesive strength adjustment layer / glass plate, and pre-bonded with a roll. Then, in an autoclave at 130 ° C, 13 kg /
A laminated glass was produced by pressure bonding with a pressure of cm ² . Using the obtained laminated glass, a light resistance test was conducted and evaluated by the following method, and the obtained results are shown in Table 3.

Light resistance test According to the light resistance test of JIS R 3212, laminated glass was placed at a distance of 230 mm from a 750 W quartz glass mercury lamp (ultraviolet ray) and irradiated at 45 ° C. for 200 hours. The laminated glass before and after the ultraviolet irradiation was subjected to the Panmel test to measure the Panmel value.

Panmel test: The laminated glass before and after irradiation with ultraviolet rays was subjected to -18 ° C ±
The temperature was adjusted to 0.6 ° C for 16 hours, and the central portion of this laminated glass (150 mm in length × 150 mm in width) was adjusted to 0.4
The degree of exposure of the interlayer film for laminated glass after the glass was crushed by hammering with a hammer having a head of 5 kg until the particle diameter of the glass was 6 mm or less and the glass was partially peeled off was evaluated by the Panmel value according to Table 1.

[0048]

[Table 1]

In the present invention, the Panmel value is 3
A laminated glass having a range of up to 8 and a small difference in the Panmel value on both sides is preferable because it is excellent in penetration resistance and glass scattering prevention. If the Pummel value is less than 3, the adhesive strength will be low and the ability to prevent the glass from scattering due to impact or the like will deteriorate. On the other hand, when the Pammel value exceeds 8, the adhesive strength becomes high and the penetration resistance of the laminated glass due to impact or the like decreases.

Example 2 In the same manner as in Example 1, a resin film for base layer having an adhesive force adjusting layer formed on one surface thereof was obtained. The amount of polyether-modified silicone oil applied was about 10 ^-3 g / m ² . 163 parts of n-butyraldehyde, triethylene glycol-di-
The acetalization degree was 88% and the thickness was 0.16 mm in the same manner as in Example 1 except that 25 parts of 2-ethylbutyrate was used.
A resin film for high acetalization degree layer was obtained. Table 2 shows the contents of the obtained high acetalization degree layer and the adhesive strength adjusting layer.

Using the resin film for the base layer and the resin film for the high acetalization degree layer, each having the adhesiveness adjusting layer formed on one surface thereof,
As conductive glass (thickness 2.5 mm), glass plate / Z
Glass plate / ZnO was prepared in the same manner as in Example 1 except that the conductive glass having the layer structure of nO / Ag / ZnO was used.
A laminated glass having a layer structure of / Ag / ZnO / high-acetalization layer / base layer / adhesion control layer / glass plate was obtained. The obtained laminated glass was used for evaluation in the same manner as in Example 1, and the obtained results are shown in Table 3.

Example 3 In the same manner as in Example 1, a resin film for a base layer having an adhesiveness adjusting layer formed on one surface thereof was obtained. The amount of polyether modified silicone oil applied was about 10 ^-2 g / m ² . 168 parts of n-butyraldehyde, triethylene glycol-di-
The acetalization degree is 90 mol% and the thickness is 0.16 in the same manner as in Example 1 except that 18 parts of 2-ethylbutyrate is used.
A resin film for high acetalization layer having a thickness of mm was obtained. Table 2 shows the contents of the obtained high acetalization degree layer and the adhesive strength adjusting layer.

A laminated glass was obtained in the same manner as in Example 1 except that the resin film for the base layer and the resin film for the high acetalization degree layer having the adhesive strength adjusting layer formed on one surface thereof were used, and the obtained laminated glass was obtained. Evaluation was performed in the same manner as in Example 1 using glass,
The results obtained are shown in Table 3.

Example 4 In the same manner as in Example 1 except that an alkyl group-modified silicone oil represented by the following general formula (B) was applied instead of the polyether-modified silicone oil in an amount of about 10 ⁻⁴ g / m ^2. A laminated glass was obtained. The contents of the high acetalization degree layer and the adhesion control layer are shown in Table 2, the obtained laminated glass was used for evaluation in the same manner as in Example 1, and the obtained results are shown in Table 3.

[0055]

[Chemical 2] (In the formula, m and n represent a positive integer of 10 to 20, and x
Represents a positive integer of 2 to 8. )

Example 5 In the same manner as in Example 2 except that an alkyl group-modified silicone oil represented by the above general formula (B) was applied in an amount of about 10 ⁻³ g / m ² instead of the polyether-modified silicone oil. A laminated glass was obtained. The contents of the high acetalization degree layer and the adhesion control layer are shown in Table 2, the obtained laminated glass was used for evaluation in the same manner as in Example 1, and the obtained results are shown in Table 3.

Example 6 In the same manner as in Example 3 except that about 10 ^-1 g / m ^{2 of} a carboxyl group-modified silicone oil represented by the following general formula (C) was applied in place of the polyether modified silicone oil. A laminated glass was obtained. The contents of the high acetalization degree layer and the adhesion control layer are shown in Table 2, the obtained laminated glass was used for evaluation in the same manner as in Example 1, and the obtained results are shown in Table 3.
It was shown to.

[0058]

[Chemical 3] (In the formula, m represents a positive integer of 10 to 20, and n is 5
Represents a positive integer of -15, and x represents a positive integer of 2-8. )

Example 7 Example 6 except that about 10 ⁻⁵ g / m ² of a different functional group-modified silicone oil having a polyether-modified group and an epoxy-modified group in one molecule was applied instead of the polyether-modified silicone oil. A laminated glass was obtained in the same manner as in 1. Table 2 shows the contents of the high acetalization degree layer and the adhesion control layer,
The obtained laminated glass was used for evaluation in the same manner as in Example 1, and the obtained results are shown in Table 3.

Example 8 Polyether-modified silicone oil was added to the above general formula (C).
A mixture of carboxyl group-modified silicone oil represented by the formula (9) was added at a weight ratio of 9: 1 to about 10 ^-4 g / m ²
A laminated glass was obtained in the same manner as in Example 1 except that the coating was performed. Table 2 shows the contents of the high acetalization degree layer and the adhesion control layer.
And the obtained laminated glass was used for evaluation in the same manner as in Example 1, and the obtained results are shown in Table 3.

Example 9 To a polyether-modified silicone oil, a silicone oil having a heterofunctional group having a polyether-modified group and an epoxy-modified group in one molecule was added in a weight ratio of 1: 7, and a mixture was obtained. Example 2 except that 10 ⁻⁴ g / m ^{2 was} applied
A laminated glass was obtained in the same manner as in. The contents of the high acetalization degree layer and the adhesive strength adjusting layer are shown in Table 2, the obtained laminated glass was used for evaluation in the same manner as in Example 2, and the obtained results are shown in Table 3. The results are shown in Table 2.

Example 10 Instead of the polyether modified silicone oil, a heterofunctional group modified silicone oil having a polyether modified group and an amino modified group in one molecule and a carboxyl group modified represented by the above general formula (C). A laminated glass was obtained in the same manner as in Example 3 except that a mixture with silicon oil (weight ratio 5: 1) was applied at about 5 × 10 ⁻³ g / m ² . The contents of the high acetalization degree layer and the adhesion control layer are shown in Table 2, the obtained laminated glass was used for evaluation in the same manner as in Example 1, and the obtained results are shown in Table 3.

Example 11 Polyether-modified silicone oil, different functional group-modified silicone oil having a polyether-modified group and an epoxy-modified group in the above molecule, and a carboxyl-group-modified silicone represented by the above general formula (C). A laminated glass was obtained in the same manner as in Example 2 except that a mixture containing oil (weight ratio 4: 8: 1) was applied at about 5 × 10 ⁻³ g / m ² . Table 2 shows the contents of the high acetalization degree layer and the adhesion control layer,
The obtained laminated glass was used for evaluation in the same manner as in Example 1, and the obtained results are shown in Table 3.

Comparative Example 1 0.2 part of an ultraviolet absorber, 0.2 part of an antioxidant, 0.025 part of a polyether modified silicone oil represented by the above general formula (A), and 0 of magnesium acetate. A mixture was obtained in the same manner as in Example 1 except that 2 parts were used, and the obtained mixture was well kneaded with a two-roll to form a sheet having a thickness of 0.8 mm, which was pressed with a spacer. Was heated and pressurized to 150 ° C. to obtain a laminated glass interlayer film having a thickness of 0.76 mm. A laminated glass was obtained in the same manner as in Example 1 except that the obtained interlayer film for laminated glass was used. Table 2 shows the contents of the high acetalization degree layer and the adhesion control layer.
And the obtained laminated glass was used for evaluation in the same manner as in Example 1, and the obtained results are shown in Table 3.

Comparative Example 2 A laminated glass was obtained in the same manner as in Comparative Example 1 except that the alkyl group-modified silicone oil represented by the above general formula (B) was used instead of the polyether-modified silicone oil.
The contents of the high acetalization degree layer and the adhesion control layer are shown in Table 2, the obtained laminated glass was used for evaluation in the same manner as in Example 1, and the obtained results are shown in Table 3.

Comparative Example 3 The polyether-modified silicone oil represented by the above general formula (A) was applied to both surfaces of a 0.76 mm-thick interlayer film for laminated glass obtained in the same manner as in Comparative Example 1. The coating amount was about 10 ^-3 g / m ² on both sides. This interlayer film for laminated glass is allowed to stand in a constant temperature and humidity chamber and has a water content of 0.4 to
A laminated glass was obtained in the same manner as in Example 2 except that the interlayer film for laminated glass obtained by adjusting the amount to 0.5% by weight was used. The contents of the high acetalization degree layer and the adhesion control layer are shown in Table 2, the obtained laminated glass was used for evaluation in the same manner as in Example 1, and the obtained results are shown in Table 3.

Comparative Example 4 The alkyl group-modified silicone oil represented by the general formula (B) was used instead of the polyether-modified silicone oil, and a glass plate was used instead of the conductive glass having a glass plate / ITO layer structure. A laminated glass was obtained in the same manner as in Comparative Example 3 except that the conductive glass having the layer structure of / ZnO / Ag / ZnO was used. The contents of the high acetalization degree layer and the adhesion control layer are shown in Table 2, the obtained laminated glass was used for evaluation in the same manner as in Example 1, and the obtained results are shown in Table 3.

Comparative Example 5 A laminated glass was obtained in the same manner as in Comparative Example 3 except that the carboxyl group-modified silicone oil represented by the general formula (C) was used instead of the polyether-modified silicone oil. Table 2 shows the contents of the high acetalization degree layer and the adhesion control layer.
And the obtained laminated glass was used for evaluation in the same manner as in Example 1, and the obtained results are shown in Table 3.

Comparative Example 6 The coating amount of the carboxyl group-modified silicone oil was 3 × 10 5.
^A laminated glass was obtained in the same manner as in Comparative Example 5 except that ^-1 g / m ² was used. The contents of the high acetalization degree layer and the adhesion control layer are shown in Table 2, the obtained laminated glass was used for evaluation in the same manner as in Example 1, and the obtained results are shown in Table 3.

[0070]

[Table 2]

[0071]

[Table 3]

[0072]

EFFECT OF THE INVENTION Since the interlayer film for laminated glass and the laminated glass of the present invention are configured as described above, the laminated glass obtained by using the interlayer film for laminated glass of the present invention is a metal oxide layer or High functionality such as heat ray reflectivity is imparted by the metal layer, and in particular, a high acetalization degree layer formed from a resin composition containing a polyvinyl acetal resin as a main component and having a degree of acetalization in the range of 80 to 95 mol%. A non-polar modified silicone oil, a polar modified silicone oil, and a heterofunctional group-modified silicone oil having a non-polar modified group and a polar modified group in one molecule, showing appropriate adhesion on the surface of the metal oxide layer or the metal layer. 1 selected from the group consisting of
Adhesion adjustment layer consisting of more than one type of modified silicone oil,
Since it shows appropriate adhesiveness with the glass plate, it is adjusted appropriately without causing a large difference in adhesive strength on both sides of the interlayer film for laminated glass, and the adhesive strength with time varies depending on outdoor exposure, ultraviolet irradiation, temperature, etc. It is prevented from falling.

Therefore, according to the present invention, it is possible to obtain a laminated glass which is excellent in penetration resistance and glass scattering prevention property for a long period of time and has high functions such as heat ray reflectivity.
This laminated glass is suitably used for window glass for automobiles, aircraft, buildings and the like.

[Brief description of drawings]

FIG. 1 is a schematic view showing a cross section of a laminated glass using an interlayer film for laminated glass of the present invention.

[Explanation of symbols]

 10 Glass Plate 11 Metal Oxide Layer or Metal Layer 20 Intermediate Film for Laminated Glass 21 High Acetalization Layer in Intermediate Film for Laminated Glass 22 Base Layer in Intermediate Film for Laminated Glass 23 Adhesion Adjustment in Intermediate Film for Laminated Glass Layer 30 laminated glass

Claims (2)

[Claims] 1. An interlayer film for laminated glass, which is sandwiched between a transparent plate having a metal oxide layer or a metal layer formed on at least the inner surface side thereof and a glass plate, and having an acetalization degree of 60 to 60. A base layer formed of a resin composition containing 75 mol% of a polyvinyl acetal resin as a main component and a resin composition containing a polyvinyl acetal resin having an acetalization degree of 80 to 95 mol% as a main component, Of the surfaces, the high acetalization degree layer provided on the surface on the side where the metal oxide layer or the metal layer of the transparent plate is formed, and the non-polar modified silicone oil, the polar modified silicone oil, and One or more modified silicone oils selected from the group consisting of different functional group-modified silicone oils having a non-polar modified group and a polar modified group in one molecule. An interlayer film for laminated glass, comprising an adhesive force adjusting layer provided on a surface of the lath plate which is in contact with the lath plate. 2. A laminated glass in which an intermediate film for laminated glass is sandwiched between a glass plate and a transparent plate having a metal oxide layer or a metal layer formed on at least the inner surface side thereof. The interlayer film for laminated glass is the interlayer film for laminated glass according to claim 1, wherein the high acetalization degree layer in the interlayer film for laminated glass is in contact with the metal oxide layer or the metal layer of the transparent plate, Moreover, the laminated glass, wherein the adhesiveness adjusting layer in the interlayer film for laminated glass is in contact with a glass plate.