JP2000203899A - Interlayer for laminated glass and laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an interlayer exhibiting excellent whitening resistance and cut resistance in a highly humid atmosphere by including a polyvinyl acetal resin, a plasticizer such as an oligoethylene glycol di-2-ethylhexanoate, a magnesium salt of a mono or dicarboxylic acid and a silicone oil having a specific molecular weight. SOLUTION: The objective composition for interlayer contains 100 pts.wt. of a polyvinyl acetal resin, 20-60 pts.wt. of a plasticizer such as oligoethylene glycol di-2-ethylhexanoate, 0.01-0.2 pt.wt. of a 3-10C monocarboxylic acid or dicarboxylic acid magnesium salt and 0.03-0.1 pt.wt. of a silicone oil expressed by formula ((m) and (n) are each 8-15; 0.5<m/n<3.5) and having a molecular weight of 800-5,000. If necessary, the composition is further compounded with a stabilizer, an antioxidant, a UV-absorber, etc. The polyvinyl acetal resin has an acetalization degree of 66-72 mol% and an average polymerization degree of 1,000-2,500 and is preferably a polyvinyl butyral resin, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an interlayer for laminated glass and a laminated glass using the same.

[0002]

2. Description of the Related Art Conventionally, a laminated glass in which an interlayer film is sandwiched between transparent glass plates is safe because fragments of the glass plate are not scattered even if it is damaged by an external impact. Widely used for aircraft, windows of buildings, etc. Among the interlayer films used for such laminated glass, a polyvinyl butyral resin interlayer film plasticized by a plasticizer has excellent adhesiveness to glass, tough tensile strength, and high transparency. In particular, it is suitably used as a window glass for vehicles.

However, in the laminated glass comprising the plasticized polyvinyl butyral resin interlayer, there is a problem that the moisture content of the interlayer increases due to moisture absorption, and the peripheral portion of the laminated glass is whitened.

An intermediate film for solving the above problem is disclosed in Japanese Patent Publication No. 53-18207. However, the polyvinyl butyral resin used for this interlayer film is white-resistant due to long-term moisture absorption.
There was still room for improvement. Further, when the modified silicone oil disclosed in the above-mentioned patent publication is used for a certain kind of metal salt, there is a problem that the adhesive force changes with time.

As the above plasticizer, dihexyl adipate, triethylene glycol di-2-ethylbutyrate and the like are generally used. However, since these plasticizers have a low boiling point, fire may occur during autoclave treatment. ,
Edge cut (trim) of interlayer after autoclaving
Therefore, use of a plasticizer having a higher boiling point is desired.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a laminated glass in a humid atmosphere without impairing the basic properties required for laminated glass, such as transparency, light resistance, weather resistance, impact resistance and adhesiveness. To provide an interlayer film for laminated glass and a laminated glass using the same, in which whitening is less likely to occur in the peripheral portion of the laminated glass even in the case of being fired, and there is no danger of fire during autoclaving, and the edge cut property is improved. It is in.

[0007]

The interlayer film for laminated glass of the present invention comprises 100 parts by weight of a polyvinyl acetal resin having a degree of acetalization of 66 to 72 mol%, and oligoethylene glycol di-2-ethylhexanoate as a plasticizer. 2
0 to 60 parts by weight, 0.01 to 0.1 part by weight of a magnesium salt of a carboxylic acid or dicarboxylic acid having 3 to 10 carbon atoms, and a molecular weight of 800 to 5,000 represented by the general formula (1)
Of silicone oil of 0.01 to 0.2 parts by weight.

As a method for producing the above-mentioned polyvinyl acetal resin, a known method is employed. For example, polyvinyl alcohol is dissolved in hot water, and the resulting aqueous solution is dissolved in 10 to 2 times.
A method of obtaining an acetalization reaction by adding an alkyl aldehyde and an acid catalyst while maintaining the temperature at 0 ° C., and then raising the temperature to 70 ° C., performing neutralization, washing and drying to obtain a polyvinyl acetal resin powder. No.

The degree of acetalization of the polyvinyl acetal resin is preferably 66 to 72 mol%, because the smaller the degree of acetalization, the higher the water absorption and the more likely the whitening to occur, and the higher the degree, the lower the mechanical strength of the interlayer film. 67.
5 to 70 mol%.

[0010] Among the above polyvinyl acetal resins,
Particularly, polyvinyl butyral resin is preferable.

The polyvinyl alcohol used for the polyvinyl acetal resin has an average degree of polymerization of 1,000.
0 to 2,500 is preferred. When the average degree of polymerization is less than 1,000, the penetration resistance may be reduced when laminated glass is used, and when it exceeds 2,500, the strength of the interlayer film may be too strong and the impact strength may be too high. It is not preferable because there is.

The polyvinyl alcohol is obtained by saponifying polyvinyl acetate. If the degree of saponification is low, the transparency, heat resistance and light resistance of the intermediate film may be reduced. % Or more is preferable.

Oligoethylene glycol di-2-ethylhexanoate (hereinafter referred to as N) used as the plasticizer
GO) and oligoethylene glycol and 2-
It can be produced by reacting with ethylhexanoic acid.

When the amount of the NGO compounded is too small, the penetration resistance of the laminated glass obtained is reduced, and when it is too large, the transparency of the laminated glass obtained by bleed-out and the adhesive strength to the glass plate are reduced. 20 to 60 parts by weight based on 100 parts by weight of the acetal resin.

Examples of the magnesium salt of a carboxylic acid or dicarboxylic acid having 3 to 10 carbon atoms include magnesium propionate, magnesium butyrate, magnesium 2-ethylbutyrate, magnesium valerate, magnesium hexanoate, magnesium heptanoate, and malonic acid. Magnesium, magnesium succinate, magnesium glutarate,
Magnesium adipate and the like may be mentioned, and these may be used alone or in combination of two or more.

The magnesium salt of carboxylic acid or dicarboxylic acid exists in the form of a salt without being ionized in the intermediate film, and attracts water molecules to suppress the adhesive force between the intermediate film and the glass plate. It is considered possible to improve the penetration resistance of the obtained laminated glass.

Further, the magnesium salt of the carboxylic acid or dicarboxylic acid does not aggregate in the intermediate film,
Since it is distributed at a high concentration on the surface of the intermediate film, the effect of adjusting the adhesive force is exhibited with a small amount. In addition, excessive whitening does not occur during moisture absorption.

When the amount of the magnesium salt of the carboxylic acid or the dicarboxylic acid is too small, the effect of adjusting the adhesive force is lost, so that the penetration resistance is lowered. When the amount is too large, the transparency of the laminated glass obtained by bleed-out and the glass plate are reduced. Is excessively reduced, so that the amount is 0.01 to 0.1 part by weight, preferably 0.03 to 0.08 part by weight, per 100 parts by weight of the polyvinyl acetal resin.

The silicone oil is represented by the general formula (1) and has an appropriate hydrophilicity and hydrophobicity, and may prevent the function of the above-mentioned magnesium salt of carboxylic acid or dicarboxylic acid in the interlayer. Therefore, a stable adhesive force can be developed on the intermediate film.

[0020]

Embedded image

In the formula, m and n are each in the range of 8 to 15 and represent an integer satisfying 0.5 <m / n <3.5, and a represents an integer of 4 to 10.

As the above-mentioned silicone oil, a liquid obtained by reacting a compound to be modified with polysiloxane is generally used. The silicone oil may be used alone or in combination of two or more. When the molecular weight of the silicone oil is small, localization on the surface is reduced, and when the molecular weight is large, the silicone oil bleeds out to the surface of the intermediate film and the adhesion to the glass plate is reduced.
It is limited to 0, preferably 1,500 to 4,500.

When the amount of the silicone oil is too small, the effect of preventing whitening due to moisture absorption becomes insufficient, and when the amount is too large, the compatibility with the polyvinyl acetal resin is reduced and bleed out to the surface of the intermediate film, and the amount of the silicone oil is reduced. Since the adhesiveness is reduced, the amount is 0.01 to 0.2 part by weight, preferably 0.03 to 0.1 part by weight, based on 100 parts by weight of the polyvinyl acetal resin.

In order to prevent the polyvinyl acetal resin from deteriorating, additives such as a stabilizer, an antioxidant and an ultraviolet absorber may be added.

Examples of the stabilizer include surfactants such as sodium lauryl sulfate and alkylbenzene sulfonic acid; examples of the antioxidant include t-butylhydroxytoluene (BHT) and tetrakis- [methylene-3- ( 3'-5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane (manufactured by Ciba Geigy, trade name: Irganox 1010); Examples of the ultraviolet absorber include 2- (2'-hydroxy -5 '
-Methylphenyl) benzotriazole (trade name: Tinuvin P, manufactured by Ciba Geigy), 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole (trade name: Tinuvin, manufactured by Ciba Geigy) 32
0), 2- (2'-hydroxy-3'-t-butyl-
5'-methylphenyl) -5-chlorobenzotriazole (manufactured by Ciba Geigy, trade name: Tinuvin 326), 2
-(2'-hydroxy-3 ', 5'-di-amylphenyl) benzotriazole (trade name, manufactured by Ciba-Geigy);
Benzotriazole-based compounds such as tinuvin 328); and hindered amine-based compounds such as ADK STAB LA-57 manufactured by Asahi Denka Co., Ltd., respectively.

The intermediate film of the present invention is prepared by, for example, supplying the above-mentioned polyvinyl acetal resin and additives to a mixing roll and kneading the mixture, and forming the kneaded product into a sheet by a molding device such as a press molding machine, a calender roll, or an extruder. It is manufactured by molding.

In the case of manufacturing a laminated glass using the above-mentioned intermediate film, a conventionally known method can be adopted. Specifically, for example, the intermediate film is sandwiched by float glass, and the sandwiched body is placed in a vacuum bag and kept at 90 ° C.
After holding in the oven for 30 minutes, the sandwich was taken out of the vacuum bag, and then the pressure was set to 13 k in an autoclave.
It is hot pressed at 140 ° C. and g / cm ² to obtain a transparent laminated glass.

[0028]

Next, embodiments of the present invention will be described.

(Example 1) Polyvinyl butyral resin
2900 parts by weight of synthetic ion-exchanged water and an average degree of polymerization of 1,7
198 parts by weight of polyvinyl alcohol having a saponification degree of 99.2 mol% (equivalent to 4.5 mol of vinyl alcohol) were supplied to a reactor equipped with a stirrer, and heated to 95 ° C. with stirring to dissolve. The resulting solution was cooled to 30 ° C and 35
208 parts by weight of hydrochloric acid (2.1 mol) and 152 parts by weight of n-butyraldehyde (2.1 mol) were added. The temperature of the solution is then reduced to 2 ° C. and maintained at this temperature,
After the polyvinyl butyral resin was precipitated, the liquid temperature was raised to 30 ° C. and maintained for 5 hours. Further, the mixture was neutralized by adding 156 parts by weight (1.8 mol) of sodium hydrogen carbonate, washed with water and dried to obtain a polyvinyl butyral resin having a butyralization degree of 69 mol%.

Preparation of Intermediate Film 100 parts by weight of polyvinyl butyral resin, NGO as a plasticizer (oligoethylene glycol part: average polymerization degree of ethylene glycol: 4.8, ethylene glycol unit content: 3 to 9; 96%) , NGO-1) 3
9 parts by weight, 0.04 parts by weight of magnesium 2-ethylbutyrate, and 0.05 parts by weight of the silicone oil described in Table 1 were supplied to a mixing roll and kneaded, and the obtained kneaded product was pressed by a press molding machine. 150 ° C, 100 kg / cm ²
Under the conditions described above for 30 minutes to obtain an interlayer film having a thickness of 0.8 mm.

Preparation of Laminated Glass The obtained interlayer film was sandwiched between two float glass plates of 2.5 mm thickness and 30 cm square, and the obtained sandwich was put in a vacuum bag and placed at a vacuum degree of 20 torr. After holding for a minute,
It was kept in a 90 ° C. oven for 30 minutes while maintaining the vacuum. Next, the sandwich was taken out of the vacuum bag and placed in an autoclave, and the pressure was 13 kg / cm ² and the temperature was 150 ° C.
The resultant was hot-pressed at ℃ to obtain a transparent laminated glass.

(Examples 2 and 3, Comparative Examples 1 to 3) 100 parts by weight of a polyvinyl butyral resin, a predetermined amount of a plasticizer, a magnesium salt of carboxylic acid, and silicone oil described in Table 1 were supplied to a mixing roll. And the resulting kneaded material was pressed at 150 ° C., 100 kg /
Press molding under the condition of cm ² for 30 minutes, thickness 0.08
mm was obtained. Using the above intermediate film, a transparent laminated glass was produced in the same manner as in Example 1. In Example 3, NGO (oligoethylene glycol part: average degree of polymerization of ethylene glycol: 5.6, ethylene glycol unit content: 3 to 9: 95%) as a plasticizer (described as NGO-2 in the table) In Comparative Example 1, dihexyl adipate was used as a plasticizer.

[0033]

[Table 1]

With respect to the interlayer film and the laminated glass obtained above, the following items were evaluated for performance. The results are shown in Table 3. (1) Pummel value The obtained laminated glass was heated at a temperature of −18 ± 0.6 ° C. for 1 hour.
After adjusting by leaving it for 6 hours, the head is 0.45kg.
And crushed until the particle size of the glass fragments became 6 mm or less. The degree of exposure of the interlayer film after the glass was partially peeled was determined by a sample graded in advance, and the result was determined according to the Pummel value described in Table 2.
The greater the Pummel value, the greater the adhesion to glass, and the lower the Pummel value, the lower the adhesion.

[0035]

[Table 2]

(2) Moisture resistance (whitening resistance) test The obtained laminated glass was left in an atmosphere at 80 ° C. and a relative humidity of 95% for 2 weeks, taken out, and immediately measured the whitening distance from the edge.

(3) Volatility test of the plasticizer in the intermediate film After leaving the obtained intermediate film in an oven at 150 ° C. for 1 hour, the weight loss due to heating was determined from the weight difference before and after heating, and the volatilization amount of the plasticizer was determined. Calculated.

[0038]

[Table 3]

[0039]

The interlayer film for laminated glass of the present invention has the above-mentioned structure, and has excellent basic performances required for laminated glass such as transparency, light resistance, weather resistance, impact resistance, and adhesiveness.
Even when placed in a humid atmosphere, there is little whitening around the laminated glass, and there is also very little volatilization of the plasticizer, so there is no danger of fire during autoclave processing and excellent edge cutability. . Therefore, a laminated glass using the interlayer film for a laminated glass of the present invention is suitably used as a window glass for a building or a vehicle.

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Claims (3)

[Claims] 1. 100 parts by weight of a polyvinyl acetal resin having an acetalization degree of 66 to 72 mol%, 20 to 60 parts by weight of oligoethylene glycol di-2-ethylhexanoate as a plasticizer, and a carboxylic acid having 3 to 10 carbon atoms Or 0.01 to 0.1 part by weight of a magnesium salt of dicarboxylic acid, and a molecular weight of 800 to 5, represented by the general formula (1).
An interlayer film for laminated glass, comprising 0.01 to 0.2 parts by weight of silicone oil. Embedded image (Where m and n are each in the range of 8 to 15,
An integer satisfying 0.5 <m / n <3.5, and a is 4
Represents an integer from 10 to 10) 2. The interlayer film for laminated glass according to claim 1, wherein the polyvinyl acetal resin is a polyvinyl butyral resin. 3. A laminated glass comprising the interlayer film for laminated glass according to claim 1 or 2.