JPH10182195A - Laminated glass and interlayer therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent a whitening phenomenon due to moisture absorption by forming an interlayer from a resin composition containing a polyvinyl butyral resin, a diester-based compound, an Mg halide and a modified silicone oil. SOLUTION: This interlayer for a laminated glass is formed of a resin composition having detailed composition of components of 100 pts.wt. polyvinyl butyral resin having 60-75mol% butyralization degree, 20-60 pts.wt. diester composed of a dicarboxylic acid and a monohydric alcohol or a monocarboxylic acid and a dihydric alcohol, 0.002-0.1 pt.wt. Mg halide and 0.01-0.2 pt.wt. modified silicone oil. Thereby, the transparency, light and heat resistances, adhesion, etc., which are fundamental characteristics required by the laminated glass can be improved to improve moisture resistance. The whitening due to moisture absorption can be prevented for a long period.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an interlayer film for laminated glass and a laminated glass.

[0002]

2. Description of the Related Art Conventionally, laminated glass having an interlayer film sandwiched between glass plates is safe without breaking glass fragments when it is damaged by an external impact. Widely used for window glass etc.
Among the interlayer films used for such laminated glass, a polyvinyl butyral resin interlayer film plasticized by a plasticizer has excellent adhesion to glass, strong tensile strength, and high transparency. It is suitably used as a window glass.

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

[0004] To solve the above problems, for example, Japanese Patent Publication No. 53-18207 discloses an interlayer film. The polyvinyl butyral resin used for the interlayer film is subject to long-term moisture absorption. The whitening phenomenon that occurred could not be completely prevented.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object the purpose of laminated glass such as transparency, light resistance, weather resistance, impact resistance, and adhesion. It is an object of the present invention to provide an interlayer film for laminated glass capable of preventing the whitening phenomenon due to moisture absorption without impairing basic characteristics and a laminated glass using the same.

[0006]

The interlayer film for laminated glass of the present invention comprises 100 parts by weight of a polyvinyl butyral resin having a degree of butyralization of 60 to 75 mol%, a dicarboxylic acid and a monohydric alcohol or a monocarboxylic acid. Formed from a resin composition containing 20 to 60 parts by weight of a diester compound composed of a dihydric alcohol, 0.01 to 0.1 part by weight of a magnesium halide, and 0.01 to 0.2 part by weight of a modified silicone oil. Is done.

The interlayer film for a laminated glass of the present invention is formed from a resin composition containing a polyvinyl butyral resin, a diester compound, a halide of magnesium and a modified silicone oil.

The degree of butyralization of the above polyvinyl butyral resin is limited to 60 to 75 mol%, because if it decreases, water absorption increases and whitening tends to occur, and if it increases, the mechanical strength of the interlayer decreases. Is 64-7
1 mol%.

As the method for producing the polyvinyl butyral resin, known methods can be employed. For example, polyvinyl alcohol is dissolved in hot water, and the resulting aqueous solution is dissolved in hot water.
-20 ° C, butyraldehyde and an acid catalyst were added to advance the acetalization reaction.
After the temperature is raised and maintained, neutralization, washing and drying are performed to obtain a polyvinyl butyral resin powder.

When the degree of polymerization of the polyvinyl alcohol is small, the penetration resistance of the obtained interlayer film for laminated glass may decrease, and when the degree of polymerization is large, the strength may be high and the impact resistance may be too high. Those having an average degree of polymerization of 800 to 3000 are preferred.

The above-mentioned polyvinyl alcohol can be obtained by saponifying polyvinyl acetate, and the degree of saponification is 95 mol in order to improve the transparency, heat resistance and light resistance of the obtained interlayer film for laminated glass. % Is preferable.

The diester compound comprising a dicarboxylic acid and a monohydric alcohol or a monocarboxylic acid and a dihydric alcohol includes, for example, di-n-hexyl adipate, di-2-ethylhexyl adipate, diisodecyl adipate, and octyl. Decyl adipate, heptyl nonyl adipate, diisooctyl adipate, di-n-
Octyl adipate, didecyl adipate, dibutyl sebacate, di-2-ethylhexyl sebacate, diisooctyl sebacate, butylbenzyl sebacate, di-
2-ethylhexyl azelate, dihexyl azelate, diisooctyl azelate, dibutyl phthalate,
Dioctyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, dicapryl phthalate, dilauryl phthalate, triethylene glycol di-2-ethyl butyrate, diethylene glycol di-2
-Ethyl butyrate, tetraethylene glycol di-2
-Ethyl butyrate, diethylene glycol dipentylate, diethylene glycol dihexylate and the like. These compounds may be used alone,
More than one species may be used in combination.

When the amount of the diester compound is reduced, the penetration resistance of the obtained laminated glass decreases,
If the amount increases, the transparency of the laminated glass obtained by bleed-out and the adhesive strength with the glass decrease, so that the content is 20 to 60 parts by weight, preferably 30 to 55 parts by weight, based on 100 parts by weight of the polyvinyl butyral resin. is there.

As the magnesium halide, for example, magnesium fluoride, magnesium chloride,
Examples thereof include magnesium bromide and magnesium iodide. These compounds may be used alone or in combination of two or more.

The magnesium halide exists in the form of a salt without being ionized in the film, and by attracting water molecules, the adhesive force between the intermediate film and the glass can be suppressed. Thus, the resulting laminated glass can have good penetration resistance.

Further, since the above-mentioned halide is distributed at a high concentration on the film surface without agglomerating in the film, a small amount of the halide exhibits an adhesive force adjusting effect. Also, excessive whitening during moisture absorption does not occur. The whitening resistance does not deteriorate even after a lapse of time after film formation.

When the amount of the above-mentioned magnesium halide is small, the effect of adjusting the adhesive force is reduced, so that the penetration resistance of the intermediate film is reduced. When the amount is large, the transparency of the laminated glass obtained by bleed-out and the interlayer film are reduced. Since the adhesive strength between the resin and the glass is excessively reduced, the amount is 0.002 to 0.1 part by weight, preferably 0.005 to 0.05 part by weight, based on 100 parts by weight of the polyvinyl butyral resin.

Examples of the modified silicone oil include epoxy-modified silicone oil, ether-modified silicone oil, ester-modified silicone oil, carboxyl-modified silicone oil, and amine-modified silicone oil. These silicone oils can be used alone. Or two or more of them may be used in combination. These modified silicone oils are generally liquids obtained by reacting a compound to be modified with polysiloxane.

When the molecular weight of the silicone oil is small, the localization on the surface of the film is reduced. When the molecular weight is large, the compatibility with the resin is extremely poor, and the silicone oil bleeds out to the surface of the film to reduce the adhesive force with glass. Because
It is preferably from 800 to 5,000, more preferably from 1,5.
00 to 4,000.

If the amount of the silicone oil is too small, the effect of preventing whitening due to moisture absorption is insufficient, and if the amount is too large, the compatibility with the resin is poor and bleed out to the film surface, and the adhesive strength between the interlayer and the glass is reduced. To 100 parts by weight of polyvinyl butyral resin,
To 0.2 parts by weight, preferably 0.03 to 0.1 parts 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 alkylbenzenesulfonic acid. As the antioxidant, for example,
t-butylhydroxytoluene (BHT), tetrakis- [methylene-3- (3'-5'-di-t-butyl-
4'-Hydroxyphenyl) propionate] methane (Ciba-Geigy, trade name; Irganox 101)
0) and the like.

As the above-mentioned ultraviolet absorber, for example, 2-
(2'-hydroxy-5'-methylphenyl) benzotriazole (manufactured by Ciba-Geigy, trade name; Tinuvin P), 2- (2'-hydroxy-3 ', 5'-di-t-)
Butylphenyl) benzotriazole (trade name; Tinuvin 320, manufactured by Ciba Geigy), 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5
Chlorobenzotriazole (Ciba Geigy, trade name; Tinuvin 326), 2- (2′-hydroxy-
Benzotriazoles such as 3 ′, 5′-di-amylphenyl) benzotriazole (manufactured by Ciba Geigy, trade name: Tinuvin 328) and hindered amines such as LA-57 manufactured by Adeka Argus Co., Ltd. No.

The intermediate film of the present invention can be manufactured, for example, as follows. A resin composition (kneaded product) obtained by supplying and kneading a polyvinyl butyral resin and an additive to a mixing roll is supplied to a press molding machine, a calender roll, an extruder, etc., and formed into a sheet to form a resin film. Can be obtained as

As a method for producing a laminated glass using the interlayer film for laminated glass of the present invention, a conventionally used method can be adopted. For example, an interlayer film for laminated glass is sandwiched between float glasses, and The sandwich was placed in a vacuum bag, kept in an oven at 90 ° C. for 30 minutes while maintaining a vacuum, and the sandwich taken out of the vacuum bag was heated in an autoclave at a pressure of 12 kg / cm ² and a temperature of 135 ° C. A method of obtaining a transparent laminated glass by pressing under pressure.

[0026]

Next, embodiments of the present invention will be described.

Example 1 (Synthesis of polyvinyl butyral resin) Ion-exchanged water 29
00 parts by weight, 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) are supplied to a reactor equipped with a stirrer, and heated to 95 ° C. while stirring. And dissolved. The solution was cooled to 30 ° C. and 196 parts by weight of 35% by weight hydrochloric acid (1.
9 mol) and 135 parts by weight of n-butyraldehyde (1.9)
Mol) was added, and then the liquid temperature was lowered to 2 ° C. and maintained at this temperature. After the polyvinyl butyral resin was deposited, 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%.

(Preparation of resin film) 100 parts by weight of the obtained polyvinyl butyral resin, 30 parts by weight of triethylene glycol di-2-ethyl butyrate as a diester compound, 0.02 parts by weight of magnesium chloride as a halide of magnesium, Further, 0.05 parts by weight of a modified silicone oil [the structural formula is represented by the following formula (1)] is supplied to a mixing roll and kneaded, and the kneaded product obtained is kneaded with a press molding machine at 150 ° C. and 120 kg / cm ^2. 3 under the condition
Press molding was performed for 0 minutes to obtain a resin film (intermediate film for laminated glass) having a thickness of 0.8 mm.

(Examples 2 and 3) A diester compound, a halide of magnesium and a modified silicone oil having the components and the compounding amounts shown in Table 1 [structures represented by the following formula (2):
A laminated glass was produced after obtaining a resin film in the same manner as in Example 1 except that the formula (3) was used.

Example 4 A reactor equipped with a stirrer was charged with 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). And heated to 95 ° C. with stirring to dissolve. Add this solution to 30
C., and 208 parts by weight (2.1 mol) of 35% by weight hydrochloric acid and 152 parts by weight (2.1 mol) of n-butyraldehyde were added. Then, the liquid temperature was lowered to 2 ° C., and this temperature was maintained. After the polyvinyl butyral resin is deposited, the liquid temperature is adjusted to 3
The temperature was raised to 0 ° C. and maintained for 5 hours. Further, 156 parts by weight (1.8 mol) of sodium hydrogencarbonate was added to neutralize, washed with water and dried to obtain a polyvinyl butyral resin having a butyralization degree of 69 mol%. Example 1 was repeated except that the obtained polyvinyl butyral resin was used with the diester compound, the halide of magnesium, and the modified silicone oil [shown by the following formula (4)] in the components and amounts shown in Table 1 After obtaining a resin film in the same manner as described above, a laminated glass was produced.

(Comparative Examples 1 to 3) Except that diester compounds, halides of magnesium and modified silicone oils (the structural formula is shown by the following (1)) were used in the components and amounts shown in Table 1, As in Example 1,
After obtaining the resin film, a laminated glass was produced.

[0032]

[Table 1]

The structural formulas of the modified silicone oils used in the above Examples and Comparative Examples are shown below.

[0034]

Embedded image

With respect to the resin film obtained above, performance evaluation of the following items was performed, and the results are shown in Table 2. (1) Moisture Whitening Resistance Test The resin film was cut into a size of 4 cm × 4 cm, immersed in ion-exchanged water at normal temperature, and the haze after 24 hours was measured.
In addition, it measured about the resin film immediately after film-formation and after leaving for one month.

(2) Initial adhesion test A laminated glass produced by sandwiching a resin film between the glass and the polyethylene terephthalate film was subjected to 2c
The film was cut into a size of mx 10 cm, and the polyethylene terephthalate film was peeled off and attached to "Tensilon UCE500" manufactured by Orientec Co., Ltd., and the 90 degree peel strength was measured at a tensile speed of 500 mm / min. still,
The production of the laminated glass was performed by the following method.

The resin film obtained above is sandwiched between a float glass of 30 cm square and a thickness of 2.5 mm and a polyethylene terephthalate film (0.1 mm thickness) of the same size, and the sandwich is vacuum-backed. 20 torr in vacuum
r for 20 minutes and in an oven under vacuum for 90 minutes.
C. for 30 minutes. Next, the sandwiched body taken out of the vacuum bag was subjected to a pressure of 13 kg / cm in an autoclave.
^2. Hot pressed at a temperature of 140 ° C. to obtain a laminated glass.

(3) Penetration Resistance Test The penetration resistance test was carried out in accordance with JIS-R3212 “Test method for automotive safety glass”. In other words, the edge of the laminated glass is fixed to the support frame and held horizontally,
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.

Further, the height at which the steel ball is dropped is 0.5 m.
The test was repeated at the same height while changing the unit. 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". Therefore, the larger the numerical value of the average penetration height, the greater the penetration resistance. In each test, the temperature of the laminated glass was 23 ° C.
And carried out.

The above laminated glass was produced by the following method. The resin film obtained above is sandwiched between two pieces of float glass of 30 cm square and 2.5 mm in thickness, and the sandwich is placed in a vacuum bag and held at a degree of vacuum of 20 torr for 20 minutes. 30 in the oven at 90 ° C
Hold for minutes. Next, the sandwiched body 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.

[0041]

[Table 2]

[0042]

The interlayer film for laminated glass and the laminated glass of the present invention have the above-mentioned constitution, and have excellent basic physical properties as an interlayer film and excellent moisture resistance, so that whitening after moisture absorption does not occur. And since its moisture resistance is maintained for a long period of time, it is suitably used as an interlayer film for laminated glass and laminated glass for buildings and vehicles.

Claims (2)

[Claims] 1. 100 parts by weight of a polyvinyl butyral resin having a degree of butyralization of 60 to 75 mol%, 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.
An interlayer film for laminated glass, comprising a resin composition containing 0.002 to 0.1 parts by weight of a halide of magnesium and 0.01 to 0.2 parts by weight of a modified silicone oil. 2. A laminated glass comprising the interlayer film for laminated glass according to claim 1.