JPH10139496A - Safety glass interlayer and safety glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a safety glass interlayer free from whitening trouble by moisture absorption and provide a safety glass produced by using the interlayer. SOLUTION: This safety glass interlayer is composed of 100 pts.wt. of a polyvinyl butyral resin having a butyralation degree of 60-75mol% and a metallic ion content of <=10ppm, 20-60 pts.wt. of a diester compound composed of a dicarboxylic acid and an alcohol, 0.01-0.1 pt.wt. of a monocarboxylic acid or dicarboxylic acid alkali metal salt or alkaline earth metal salt and 0.01-0.2 pt.wt. of a modified silicone oil. The safety glass is produced by using the safety glass interlayer.

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 in 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 intermediate film made of the above-mentioned plasticized polyvinyl butyral resin easily absorbs moisture, and due to this property, the moisture content of the film increases, and the peripheral portion of the laminated glass becomes whitened. There was a problem.

To solve the above-mentioned problems, Japanese Patent Publication No. 53-18207 discloses that an alkali metal salt or an alkaline earth metal salt of a monocarboxylic acid or a dicarboxylic acid and a modified silicone oil are contained. There is disclosed a laminated glass in which at least two sheets of glass are bonded together by an intermediate film made of an attached plasticized polyvinyl acetal resin.

However, since the polyvinyl butyral resin used in the interlayer film for laminated glass contains a large amount of neutralizing agent used in the neutralization step in the form of metal ions, whitening due to long-term moisture absorption is prevented. From a prevention point of view, it was not perfect.

[0007]

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.

[0008]

According to the present invention, there is provided a polyvinyl butyral resin having a butyralization degree of 60 to 75 mol% and a metal ion content of 10 ppm or less.
Parts by weight, 20 to 60 parts by weight of a diester compound composed of a dicarboxylic acid and an alcohol, an alkali metal salt or an alkaline earth metal salt of a monocarboxylic acid or a dicarboxylic acid.
0.1 to 0.1 parts by weight, and modified silicone oil 0.1.
It is an interlayer film for laminated glass consisting of 01 to 0.2 parts by weight. Hereinafter, the present invention will be described in detail.

The polyvinyl butyral resin used in the present invention has a butyralization degree of 60 to 75 mol%. 6
If the amount is less than 0 mol%, the water absorption is improved and whitening is likely to occur. If the amount exceeds 75 mol%, the mechanical strength of the interlayer film is reduced, so that it is limited to the above range. Preferably,
It is 64 to 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 production of the polyvinyl butyral resin, if an aqueous solution of a metal salt such as sodium bicarbonate or sodium carbonate is used in the neutralization step, a large amount of metal ions will remain in the resin. It is preferable to use an aqueous solution of ammonium oxide.

The polyvinyl butyral resin used in the present invention has a metal ion content of 10 ppm or less.
If the content exceeds 10 ppm, when the resin absorbs moisture, problems such as promoting aggregation of water and increasing the degree of whitening may occur. In addition, if there is an excessive amount of metal ions in the resin, these may be used as nuclei. Since the metal salt of a carboxylic acid, which is an adhesive force modifier added later, may agglomerate with time and cause problems such as an increase in the degree of whitening during moisture absorption, the content is limited to the above range. Examples of the metal ions include alkali metal ions such as lithium ion, sodium ion, and potassium ion; and alkaline earth metal ions such as beryllium ion, magnesium ion, and calcium ion.

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

The polyvinyl alcohol is obtained by saponifying polyvinyl acetate, and the degree of saponification is determined by the transparency, heat resistance, and the like of the obtained interlayer film for laminated glass.
In order to improve the light resistance, the content is preferably 95 mol% or more.

The diester compound comprising a dicarboxylic acid and an alcohol used in the present invention is not particularly restricted but includes, for example, di-n-hexyl adipate, di-2-
Ethylhexyl adipate, diisodecyl adipate,
Octyl decyl adipate, heptyl nonyl adipate, diisooctyl adipate, di-n-octyl adipate, didecyl adipate, dibutyl sebacate, di-2-ethylhexyl sebacate, diisooctyl sebacate, butyl benzyl sebacate, di-2 -Ethylhexyl azelate, dihexyl azelate, diisooctyl azelate, dibutyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, dicapryl phthalate, dilauryl phthalate and the like. These are those generally used as plasticizers. 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. If the amount is too large, the transparency of the laminated glass obtained by bleed-out and the adhesive force with the glass are reduced, so that the range is limited to the above range. Preferably, 30
５５55 parts by weight.

The alkali metal salt or alkaline earth metal salt of a monocarboxylic acid or dicarboxylic acid used in the present invention is not particularly limited, and examples thereof include magnesium acetate, potassium acetate, magnesium octanoate, magnesium 2-ethylhexylate, and the like. And potassium octoate. These may be used alone or in combination of two or more.

In the present invention, these metal salts exist in the form of a salt without being ionized in the film, and by attracting water molecules, it becomes possible to suppress the adhesive force between the intermediate film and the glass. It is considered that this makes it possible to improve the penetration resistance of the obtained laminated glass.

The amount of the alkali metal salt or alkaline earth metal salt of the above monocarboxylic acid or dicarboxylic acid is 0.01 to 100 parts by weight of the polyvinyl butyral resin.
0.1 parts by weight. If the amount is too small, the effect of reducing the adhesive force will be insufficient, and if it is too large, the compatibility with the resin will be poor and the transparency will be reduced, so that the content is limited to the above range. Preferably, it is 0.02 to 0.06 parts by weight.

The modified silicone oil used in the present invention 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 modified silicone oil has a molecular weight of 8
00-5000 is preferable. If it is too small, localization on the film surface is reduced, and if it is too large, compatibility with the resin becomes poor, and bleed out to the film surface and the adhesive strength to glass may be reduced. More preferably, 1500 to 40
00.

The modified silicone oil is added in an amount of 0.01 to 100 parts by weight of the polyvinyl butyral resin.
０．２0.2 parts by weight. If it is too small, the effect of preventing whitening due to moisture absorption will be insufficient, and if it is too large, compatibility with the resin will be poor and bleed out to the film surface, and the adhesive strength with glass will be reduced, so it is limited to the above range. You. Preferably, it is 0.03 to 0.1 part by weight.

The interlayer film for laminated glass of the present invention may further contain, if necessary, a stabilizer for preventing deterioration of the polyvinyl butyral resin, an antioxidant, an ultraviolet absorber and the like. Examples of the stabilizer include surfactants such as sodium lauryl sulfate and alkylbenzene sulfonic 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) and the like. No.

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); and hindered amines such as LA-57, manufactured by Adeka Argus Co. No.

The interlayer film for laminated glass of the present invention can be produced, for example, by the following method. The polyvinyl butyral resin, the diester compound, the alkali metal salt or alkaline earth metal salt of the monocarboxylic acid or dicarboxylic acid and the modified silicone oil are supplied to a mixing roll, and the kneaded product obtained by kneading is obtained. It is molded into a sheet by a press molding machine, calender roll, extruder, etc. to produce a resin film.

The present invention 2 is a laminated glass using the interlayer film for a laminated glass of the present invention 1. 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, a conventionally used method can be used. For example, two layers of the interlayer film for a laminated glass of the present invention 1 can be used. The sandwich is placed in a float glass, and the sandwich is placed in a vacuum bag, kept in a vacuum at 90 ° C. for 30 minutes in an oven, and the sandwich taken out of the vacuum bag is subjected to a pressure of 12 kg / h in an autoclave. cm ^2, and hot pressing at a temperature of 135 ° C., include a method such as to obtain a laminated glass transparency is.

[0027]

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 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 196 parts by weight (1.9 mol) of hydrochloric acid and 135 parts by weight (1.9 mol) of n-butyraldehyde, the liquid temperature was lowered to 2 ° C., and this temperature was maintained to precipitate the polyvinyl butyral resin. Then, the liquid temperature was raised to 30 ° C. and maintained for 5 hours. After the holding, 147 parts by weight (1.7 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%. The content of metal ions (sodium ions and potassium ions) in the obtained resin was 5 ppm.

Preparation of resin film 100 parts by weight of the obtained polyvinyl butyral resin, 30 parts by weight of dihexyl adipate, 0.04% of magnesium acetate
4 parts by weight and the modified silicone oil shown in Table 1
05 parts by weight was supplied to a mixing roll, and the kneaded product obtained by kneading was mixed at 150 ° C. and 120 kg with a press molding machine.
/ M ² for 30 minutes, 0.8m thick
m was obtained.

Preparation of Laminated Glass The resin film obtained above was sandwiched between two pieces of float glass having a size of 30 cm square and a thickness of 2.5 mm, and the sandwiched body was placed in a vacuum bag at a degree of vacuum of 20 torr. Hold for 90 minutes at 90 ° C. in an oven with vacuum applied.
The sandwich taken out of the vacuum bag was hot-pressed in an autoclave at a pressure of 13 kg / cm ² and a temperature of 140 ° C. to obtain a laminated glass.

Preparation of Adhesive Force Measurement Sample A laminated glass (2 × 10 cm) was prepared from one side glass and one side polyethylene terephthalate. Matching conditions are the same as above

Evaluation (1) Moisture whitening resistance test A resin film (one immediately after film formation and one month after film formation) was cut into a size of 4 × 4 cm, and was cut at 50 ° C. and 95%
The sample was allowed to stand in an atmosphere of RH for 24 hours, and then the haze was measured by an integral turbidimeter manufactured by Tokyo Denshoku Co., Ltd.

(2) Measurement of Initial Adhesive Strength One-sided glass, laminated glass made of one-sided polyethylene terephthalate were cut into a size of 2 × 10 cm, and a 90 ° peel at a pulling speed of 500 mm / min using Tensilon UCE500 manufactured by Orientec. The strength was measured.

(3) Penetration Resistance Test The penetration resistance test was carried out in accordance with JIS R 3212 “Test method for safety glass for automobiles”. That is, the edge of the laminated glass was fixed to a support frame and held horizontally, and a steel ball weighing 2.26 kg was dropped freely from the height of 4 m to the center of the laminated glass. Regarding the six sheets of laminated glass, if the steel ball did not penetrate within 5 seconds after the impact, the steel sheet was judged as acceptable. Furthermore, the height at which the steel ball is dropped is changed in units of 0.5 m,
The test was repeated at the same height. The height at which the penetration of the steel ball was hindered in 50% of the number of laminated glasses was determined, and the distance between the steel ball and the glass plate surface at this time was defined as "average penetration height". Accordingly, the larger the numerical value of the average penetration height, the greater the penetration resistance. In addition,
This test was performed while maintaining the temperature of the laminated glass at 23 ° C. Table 2 shows the results of these evaluations.

Example 2 A resin film was prepared in the same manner as in Example 1 using the components shown in Table 1, and a laminated glass and a sample for measuring adhesive strength were prepared using the resin film. Physical properties were measured. The results are shown in Table 2. Example 3 A resin film was prepared in the same manner as in Example 1 using the components shown in Table 1, and a laminated glass and a sample for measuring the adhesive strength were prepared using the resin film. Each physical property was measured in the same manner as in Example 1. did. The results are shown in Table 2.

Example 4 Synthesis of polyvinyl butyral resin 2900 parts by weight of ion-exchanged water, 198 parts by weight of polyvinyl alcohol having an average degree of polymerization of 1700 and a saponification degree of 99.2 mol% (equivalent to 4.5 mol of vinyl alcohol) were equipped with a stirrer. The mixture was supplied to a reactor and heated to 95 ° C. with stirring to dissolve. The solution was cooled to 30 ° C., and 35% by weight hydrochloric acid 2
08 parts by weight (2.1 mol) and n-butyraldehyde 15
2 parts by weight (2.1 mol) was added, and then the liquid temperature was lowered 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. After the holding, 156 parts by weight (1.8 mol) of sodium hydrogencarbonate was added to neutralize, washed with water and dried repeatedly to obtain a polyvinyl butyral resin having a butyralization degree of 69 mol%. Using the obtained resin, a resin film was prepared in the same manner as in Example 1 using the components shown in Table 1, and a laminated glass and a sample for measuring the adhesive force were prepared using the resin film. Each physical property was measured. The results are shown in Table 2.

Comparative Example 1 A resin film was prepared using the components shown in Table 1 in the same manner as in Example 1, and a laminated glass and a sample for measuring adhesive strength were prepared using the resin film. Physical properties were measured. The results are shown in Table 2. Comparative Example 2 A resin film was prepared in the same manner as in Example 1 using the components shown in Table 1, and a laminated glass and a sample for measuring adhesive strength were prepared using the resin film. Each physical property was measured in the same manner as in Example 1. did. The results are shown in Table 2. Comparative Example 3 A resin film was prepared in the same manner as in Example 1 using the components shown in Table 1, and a laminated glass and a sample for measuring adhesive strength were prepared using the resin film, and each physical property was measured in the same manner as in Example 1. did. The results are shown in Table 2.

[0038]

[Table 1]

In Table 1, chemical formulas (1) to (5) represent chemical structural formulas represented by the following formulas (1) to (5), respectively.

[0040]

Embedded image

[0041]

[Table 2]

[0042]

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.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // (C08L 29/14 83:04)

Claims (2)

[Claims] 1. A polybutyral resin having a degree of butyralization of 60 to 75 mol% and a metal ion content of 10 ppm or less, 100 parts by weight, and a diester compound comprising a dicarboxylic acid and an alcohol, 20 to 60 parts by weight. A laminated glass comprising: 0.01 to 0.1 part by weight of an alkali metal salt or an alkaline earth metal salt of a monocarboxylic acid or a dicarboxylic acid; and 0.01 to 0.2 part by weight of a modified silicone oil. For intermediate film. 2. A laminated glass using the interlayer film for laminated glass according to claim 1.