JPH11157886A - Intermediate film for laminated glass and laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an intermediate film for a laminated glass which does not cause whitening due to moisture absorption for a long time without decreasing the basic clgracteristics such as transparency, light resistance, weatherability, shock resistance and adhesion property required for a laminated glass, and to provide a laminated glass using the film. SOLUTION: This intermediate film for a laminated glass consists of 100 pts.wt. of a polyvinylbutyral resin having 60 to 75 mol.% butyration degree prepared by using a sodium salt neutralizer, 20 to 60 pts.wt. of diester compds. comprising dicarboxylic acids and univalent alcohols or comprising monocarboxylic acids and bivalent alcohols, 0.02 to 2 pts.wt. of carboxylic acids having 4 to 14 carbon atoms, and 0.005 to 0.1 pt.wt. of magnesium salts of carboxylic acids having 4 to 14 carbon atoms. The laminated glass is produced by using the intermediate film.

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 which does not cause whitening and a laminated glass.

[0002]

2. Description of the Related Art A laminated glass comprises an interlayer film sandwiched between glass plates. Laminated glass is safe because it does not scatter glass fragments even if it is damaged by an impact, and thus is widely used for window glass of vehicles, aircraft, buildings, and the like.

[0003] Among the interlayer films used for such laminated glass, an interlayer film made of polyvinyl butyral resin plasticized with a plasticizer has excellent adhesiveness to glass,
It has strong tensile strength and high transparency,
Particularly, it is suitably used for a window glass of a vehicle.

However, a laminated glass using an interlayer film made of the plasticized polyvinyl butyral resin easily absorbs moisture, and due to this property, the water content of the interlayer film increases,
There were problems such as whitening of the periphery of the laminated glass.

To solve the above-mentioned problems, Japanese Patent Publication No. 53-18207 discloses a plasticized polyvinyl acetal resin containing an alkali metal salt or an alkaline earth metal salt of a monocarboxylic acid or a dicarboxylic acid and a modified silicone oil. Discloses a laminated glass in which at least two glasses are laminated by an intermediate film containing or adhering to the glass.

Japanese Patent Application Laid-Open No. Sho 60-210551 discloses that a plasticized polyvinyl acetal resin (100 parts by weight) contains potassium monocarboxylate having 1 to 6 carbon atoms in an amount of 0.02 to 0.
40 parts by weight and modified silicone oil 0.01 to 0.2
A laminated glass is disclosed in which at least two sheets of glass are laminated by an interlayer film containing or adhering to 6 parts by weight.

However, depending on the kind of metal salt used, these metal salts are hardened into particles in the interlayer film and cause whitening, so that the whitening due to long-term moisture absorption is prevented. From then on, it was not perfect.

[0008]

SUMMARY OF THE INVENTION In view of the above, an object of the present invention is to provide an interlayer film for laminated glass which does not cause whitening due to moisture absorption, and a laminated glass using the same.

[0009]

The invention according to claim 1 (hereinafter referred to as "the present invention 1") provides a polyvinyl butyral having a degree of butyralization of 60 to 75 mol% obtained by using a sodium salt-based neutralizing agent. 100 parts by weight of butyral resin, 20 to 60 parts by weight of a diester compound comprising a dicarboxylic acid and a monohydric alcohol or a monocarboxylic acid and a dihydric alcohol, 0.02 to 2 parts by weight of a carboxylic acid having 4 to 14 carbon atoms And an interlayer for laminated glass comprising 0.005 to 0.1 parts by weight of a magnesium salt of a carboxylic acid having 4 to 14 carbon atoms. The invention according to claim 2 (hereinafter referred to as the present invention 2) An interlayer having a carbon number of 4 to 14 is further added to the interlayer film for laminated glass of the first aspect. The invention according to claim 3 (hereinafter referred to as invention 3)
It is a laminated glass using the interlayer film for laminated glass of the present invention 1 or 2. Hereinafter, the present invention 1 will be described in detail.

The polyvinyl butyral resin used in the present invention 1 has a butyralization degree of 60 to 75 mol%.
If it is less than 60 mol%, the water absorption is increased and whitening is likely to occur, and if it is more than 75 mol%, the mechanical strength of the interlayer film is reduced, so that it is limited to the above range. Preferably, it is 64-71 mol%.

For the production of the polyvinyl butyral resin, a known method can be used. For example, polyvinyl alcohol is dissolved in hot water, and the obtained aqueous solution is dissolved in 10 to 10 wt.
While maintaining the temperature at 20 ° C., the acetalization reaction was allowed to proceed by adding butyraldehyde and an acid catalyst. Then, the temperature was raised to 70 ° C., and the polyvinyl butyral resin powder was neutralized, washed with water, and dried. And the like. In the neutralization step, an aqueous solution of a metal salt such as sodium hydroxide or sodium hydrogen carbonate is used, so that sodium remains in the obtained polyvinyl butyral resin.
The residual sodium promotes aggregation of water when the polyvinyl butyral resin absorbs moisture, and increases the degree of whitening of the polyvinyl butyral resin.

The above polyvinyl alcohol preferably has an average degree of polymerization of 800 to 3000. If the average degree of polymerization is too small, the penetration resistance of the obtained interlayer film for laminated glass may be inferior. If it is too large, the strength of the obtained laminated glass may be too high and the impact strength may be too high.

The polyvinyl alcohol is obtained by saponifying polyvinyl acetate. The degree of saponification is determined in order to improve the transparency, heat resistance and light resistance of the obtained interlayer film for laminated glass. It is preferably at least 95 mol%.

The diester compound comprising a dicarboxylic acid and a monohydric alcohol or a monocarboxylic acid and a dihydric alcohol used in the present invention includes, for example, di-n-
Hexyl adipate, di-2-ethylhexyl adipate, diisodecyl adipate, octyldecyl adipate, heptyl nonyl adipate, diisooctyl adipate, di-n-octyl adipate, didecyl adipate, dibutyl sebacate, di-2-ethylhexyl sebacate, di-2-ethylhexyl adipate Isooctyl sebacate, butyl benzyl sebacate, di-2-ethylhexyl azelate, dihexyl azelate, diisooctyl azelate, dibutyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, dicapryl phthalate, dicaprylate Lauryl phthalate, triethylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl butyrate, tetraethylene glycol di- - ethyl butyrate, diethylene glycol pentylate, diethylene glycol Hye carboxylates like. These may be used alone or in combination of two or more.

The amount of the diester compound is 20 to 60 parts by weight based on 100 parts by weight of the polyvinyl butyral resin.
Parts by weight. If the amount is too small, the penetration resistance of the obtained laminated glass is reduced, and if the amount is too large, the transparency of the laminated glass obtained by bleed-out and the adhesive strength between the glass and the interlayer are reduced, so that it is limited to the above range. You. Preferably, it is 30 to 55 parts by weight.

The carboxylic acid having 4 to 14 carbon atoms used in the present invention includes, for example, butyric acid, isobutyric acid,
-Ethylbutyric acid, valeric acid, isovaleric acid, n-hexanoic acid,
n-heptanoic acid, n-octanoic acid, 2-ethylhexylic acid, lauric acid, myristic acid, oxalic acid, malonic acid,
Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, acrylic acid, propiolic acid, methacrylic acid, crotonic acid, isocrotonic acid, fumaric acid, maleic acid, benzoic acid, toluic acid, naphthoic acid And the like. These may be used alone or in combination of two or more.

The addition amount of the carboxylic acid is 0.02 to 2 parts by weight based on 100 parts by weight of the polyvinyl butyral resin. If the amount is too small, the effect of preventing whitening due to moisture absorption is reduced. If the amount is too large, the transparency of the laminated glass obtained by bleed-out and the adhesive strength between the glass and the interlayer are reduced, so that the content is limited to the above range. Preferably, 0.1 to 1
Parts by weight.

In the present invention 1, when the residual sodium in the polyvinyl butyral resin becomes an aggregate having a large particle size, the carboxylic acid is adsorbed on the surface of the sodium particles, and the particles are reduced to a small particle size. It is thought to have the function of dispersing, thereby suppressing aggregation of water when absorbing moisture,
It is estimated that the whitening resistance of the polyvinyl butyral resin interlayer can be improved.

The magnesium salt of a carboxylic acid having 4 to 14 carbon atoms used in the present invention includes, for example, magnesium butyrate, magnesium isobutyrate, magnesium 2-ethylbutyrate, magnesium valerate, magnesium isovalerate, n -Magnesium hexanoate, magnesium n-heptanoate, magnesium n-octanoate, magnesium 2-ethylhexylate, magnesium laurate,
Magnesium myristate, magnesium oxalate, magnesium malonate, magnesium succinate, magnesium glutarate, magnesium adipate, magnesium pimerate, magnesium suberate, magnesium azelate, magnesium sebacate, magnesium acrylate, magnesium propiolate, methacrylic acid Examples include magnesium, magnesium crotonate, magnesium isocrotonate, magnesium fumarate, magnesium maleate, magnesium benzoate, magnesium toluate, magnesium naphthoate, and the like. These may be used alone or in combination of two or more.

The magnesium salt is added in an amount of 0.005 to 100 parts by weight of the polyvinyl butyral resin.
0.1 parts by weight. If the amount is too small, the effect of preventing whitening due to moisture absorption is reduced. If the amount is too large, the transparency of the laminated glass obtained by bleed-out and the adhesive strength between the glass and the interlayer are reduced, so that the content is limited to the above range. Preferably, it is 0.01 to 0.05 parts by weight.

In the present invention 1, it is considered that the magnesium salt is uniformly dispersed in the polyvinyl butyral resin interlayer. Therefore, it is presumed that the water at the time of moisture absorption gathers around the magnesium salt as a nucleus and becomes a large number of extremely fine water droplets, and the degree of whitening of the polyvinyl butyral resin interlayer is reduced.

The interlayer film for laminated glass of the present invention 1 may further contain, if necessary, a modified silicone oil, a stabilizer, an antioxidant, an ultraviolet absorber and the like.

The modified silicone oil is not particularly restricted but includes, for example, epoxy-modified silicone oil, ether-modified silicone oil, ester-modified silicone oil, carboxyl-modified silicone oil, amine-modified silicone oil and the like. These modified silicone oils are generally liquids obtained by reacting a compound to be modified with polysiloxane. These may be used alone or in combination of two or more.

The amount of the modified silicone oil added is 0.01 to 100 parts by weight of the polyvinyl butyral resin.
~ 0.2 parts by weight is preferred. If the addition amount is too small, the effect of preventing whitening due to moisture absorption will be insufficient, and if it is too large,
The compatibility with the resin becomes poor and bleeds out to the surface of the interlayer, and the adhesive strength between the glass and the interlayer is reduced. More preferably, it is 0.03 to 0.1 part by weight.

Examples of the stabilizer include surfactants such as sodium lauryl sulfate and alkylbenzenesulfonic acid. As the antioxidant, for example,
t-butylhydroxytoluene (BHT), tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-
4'-hydroxyphenyl) propionate] methane (Irganox 1010, manufactured by Ciba Geigy).

As the above-mentioned ultraviolet absorber, for example, 2-
(2'-hydroxy-5'-methylphenyl) benzotriazole (Ciba Geigy, Tinuvin P), 2-
(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole (manufactured by Ciba Geigy, Tinuvin 320), 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) ) -5-chlorobenzotriazole (Ciba Geigy, Tinuvin 326), 2-
Benzotriazoles, such as (2'-hydroxy-3 ', 5'-di-amylphenyl) benzotriazole (Ciba Geigy, Tinuvin 328); hindered amines, such as LA-57, manufactured by Adeka Argus Is mentioned.

The interlayer film for laminated glass of the present invention 1 can be produced, for example, by the following method. The polyvinyl butyral resin, the diester compound, the carboxylic acid having 4 to 14 carbon atoms and the carbon number of 4 to 14
The magnesium salt of carboxylic acid 14 is supplied to a mixing roll, and the kneaded product obtained by kneading is formed into a sheet by a press molding machine, a calender roll, an extruder, or the like to produce a resin film (intermediate film). .

Next, the present invention 2 will be described. The interlayer film for a laminated glass according to the second aspect of the invention is obtained by further adding an alcohol having 4 to 14 carbon atoms to the interlayer film for a laminated glass. Examples of the alcohol include butanol, pentanol, hexanol, heptanol, dodecanol, tridecanol, tetradecanol, 1-methylpropanol, ethylene glycol, propylene glycol, glycerin, 1,1-dimethylpropanol, and 2-
Ethyl-2-butene-1,4-diol, 2-cyclohexen-1-ol, benzyl alcohol, 2-phenylethanol and the like. These may be used alone or in combination of two or more.

The amount of the alcohol to be added is 0.05 to 0.5 part by weight based on 100 parts by weight of the polyvinyl butyral resin. If the amount is too small, the effect of preventing whitening due to moisture absorption is reduced. If the amount is too large, the transparency of the laminated glass obtained by bleed-out and the adhesive strength between the glass and the interlayer are reduced, so that the content is limited to the above range. Preferably, 0.1
０．３0.3 parts by weight.

The laminated glass of the present invention 3 is a laminated glass using the interlayer film for laminated glass of the present invention 1 or 2. In order to manufacture the laminated glass of the present invention 2 using the interlayer film for a laminated glass of the present invention 1 or 2, a conventionally used method can be used. The sandwich was placed in a glass, and the sandwich was placed in a vacuum bag, kept in an oven at 90 ° C. for 30 minutes while keeping the vacuum, and the sandwich taken out of the vacuum bag was placed in an autoclave at a pressure of 12 kg / cm 2. Hot press at a temperature of 135 ° C. to obtain a transparent laminated glass.

[0031]

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

Example 1 Synthesis of polyvinyl butyral resin 2900 parts by weight of ion-exchanged water and an average degree of polymerization of 170
Polyvinyl alcohol 1 having a saponification degree of 99.2 mol% at 0
98 parts by weight (equivalent to 4.5 mol of vinyl alcohol) was supplied to a reactor equipped with a stirrer, and heated to 95 ° C. with stirring to dissolve. The solution was cooled to 30 ° C. and 35% by weight
After adding 208 parts by weight (2.1 mol) of hydrochloric acid and 152 parts by weight (2.1 mol) of n-butyraldehyde, the temperature of the solution was lowered to 2 ° C. and maintained at this temperature, and the polyvinyl butyral resin was precipitated. Then, the liquid temperature was raised to 30 ° C. and maintained for 5 hours. After the holding, 156 parts by weight (1.8 mol) of sodium hydrogen carbonate was added to neutralize, washed with water and dried to obtain a polyvinyl butyral resin having a butyralization degree of 65 mol%. As a result of quantifying the sodium content of the resin by ICP emission analysis, it was 50 ppm. In the ICP emission analysis, a sample was heated and decomposed with sulfuric acid and nitric acid, and the decomposed product was made to have a constant volume with ultrapure water. Then, an ICP-AES apparatus (“ICAP-575” manufactured by Nippon Jarrell Ash) was used. And quantification by the ICP-AER method.

Preparation of Resin Film (Intermediate Film) 100 parts by weight of the obtained polyvinyl butyral resin, 40 parts by weight of triethylene glycol di-2-ethyl butyrate, 0.05 parts by weight of ethylenediaminetetraacetic acid, and 0% by weight of magnesium 2-ethylbutyrate 0.04 parts by weight and 0.05 parts by weight of the modified silicone oil represented by the following formula are supplied to a mixing roll, and the resulting mixture is kneaded at 150 ° C. and 120 kg / cm 2 using a press molding machine. Press molding was performed for 30 minutes to obtain a resin film (intermediate film) having a thickness of 0.8 mm. A wet whitening resistance test was performed using the obtained resin film (intermediate film), and the results are shown in Table 1.

Embedded image

Moisture Whitening Resistance Test The resin film (intermediate film) was cut into a size of 4 × 4 cm, left in ion-exchanged water for 8 hours, and then the haze was measured with an integral turbidity meter manufactured by Tokyo Denshoku Co., Ltd.

Examples 1 to 8 and Comparative Examples 1 to 4 Modified silicone oil was added to the components shown in Table 1 in the same manner as in Example 1, and a resin film (intermediate film) was prepared in the same manner as in Example 1. A wet whitening resistance test was performed in the same manner as in Example 1. Table 1 shows the results.

[0036]

[Table 1]

[0037]

As described above, the interlayer film for laminated glass of the present invention has basic physical properties required as an interlayer film such as transparency, light resistance, weather resistance, impact resistance, and adhesiveness. Furthermore, it has excellent moisture resistance, has no whitening after moisture absorption, and does not change with time. The laminated glass using the interlayer film for laminated glass of the present invention can be suitably used for construction and vehicles.

Claims (3)

[Claims] 1. 100 parts by weight of a polyvinyl butyral resin having a butyralization degree of 60 to 75 mol%, obtained using a sodium salt-based neutralizing agent, dicarboxylic acid and monohydric alcohol, or monocarboxylic acid and dihydric acid 20 to 60 parts by weight of a diester compound composed of alcohol and having 4 carbon atoms
0.02 to 2 parts by weight of a carboxylic acid having a carbon number of 14 to 14, and 0.02 parts by weight of a magnesium salt of a carboxylic acid having a carbon number of 4 to 14.
An interlayer for laminated glass, comprising 0.5 to 0.1 parts by weight. 2. An alcohol having 4 to 14 carbon atoms.
2. The interlayer film for laminated glass according to claim 1, wherein 0.05 to 0.5 parts by weight of the glass is added. 3. A laminated glass comprising the interlayer film for laminated glass according to claim 1 or 2.