JPH10273344A - Interlayer for laminated glass and laminated glass using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject interlayer excellent in transparency, light resistance, weathering resistance, shock resistance and adhesiveness, etc., and prevented from whitening due to moisture-absorption by including a polyvinyl butyral resin with a specific butyralization degree, diester-based compound, magnesium salt of carboxylic acid or dicarboxylic acid and modified silicone oil. SOLUTION: This interlayer is obtained by preparing such a composition which is produced by blending 100 pts.wt. polyvinyl butyral resin having a butyralization degree of 60 to 75 mol.% and an average degree of polymerization of 800 to 3000, with 20 to 60 pts.wt. diester-based compound prepared from a dicarboxylic acid and monohydric alcohol or from a monocarboxylic acid and dihydric alcohol, 0.01 to 0.1 pt.wt. magnesium salt of 3-7C carboxylic acid or dicarboxylic acid, and 0.01 to 0.2 pt.wt. modified silicone oil of 800 to 5,000 in molecular weight, followed by supplying the resultant composition to a mixing roll for kneading and then forming the kneaded product into a sheetlike form by using a press molding machine, calendaring roll or extruder, etc.

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, the present invention has the basic physical properties necessary for an intermediate film such as transparency, light resistance, weather resistance, impact resistance, and adhesion, and causes whitening due to moisture absorption. It is an object of the present invention to provide an interlayer film for laminated glass which does not have a laminated glass and a laminated glass using the same.

[0009]

According to the present invention, there is provided a polyvinyl butyral resin having a butyralization degree of 60 to 75 mol%, comprising 100 parts by weight of a dicarboxylic acid and a monohydric alcohol or a monocarboxylic acid and a dihydric alcohol. 20 to 60 parts by weight of a diester compound comprising a carboxylic acid having 3 to 7 carbon atoms or a magnesium salt of dicarboxylic acid 0.01 to
0.1 parts by weight, and modified silicone oil 0.01 to
It is an interlayer film for laminated glass consisting of 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%. When the degree of butyralization is less than 60 mol%, water absorption is increased and whitening is likely to occur, and when it exceeds 75 mol%, the mechanical strength of the interlayer film is reduced, so that the range 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.

The above polyvinyl alcohol preferably has an average degree of polymerization of 800 to 3000. Average degree of polymerization is 80
When it is less than 0, the penetration resistance of the obtained laminated glass may be inferior. When it exceeds 3000, 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 95% in order to improve the transparency, heat resistance and light resistance of the obtained interlayer film for laminated glass. It is preferably at least 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 is not particularly restricted but includes, for example, di-n-hexyl adipate and diester. -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, triethylene glycol di-2-ethyl butyrate , Diethylene glycol di-2-ethyl butyrate, tetraethylene glycol di-2-ethyl butyrate, diethylene glycol dipentylate, diethylene glycol di Kishireto, and the like. These compounds are generally used as plasticizers for resins. These may be used alone or in combination of two or more.

The amount of the diester compound comprising the dicarboxylic acid and the monohydric alcohol or the monocarboxylic acid and the dihydric alcohol is 20 to 60 parts by weight based on 100 parts by weight of the polyvinyl butyral resin. When the addition amount is less than 20 parts by weight, the penetration resistance of the obtained laminated glass decreases, and when the addition amount exceeds 60 parts by weight, the transparency of the laminated glass obtained by bleed out is impaired, and the interlayer film and the glass are removed. Therefore, the adhesive strength is limited to the above range. Preferably, it is 30 to 55 parts by weight.

The magnesium salt of a carboxylic acid or dicarboxylic acid having 3 to 7 carbon atoms used in the present invention is not particularly limited. Examples thereof include magnesium propionate, magnesium butyrate, magnesium 2-ethylbutyrate, magnesium valerate, and hexane. Magnesium acrylate, magnesium heptanoate, magnesium malonate, magnesium succinate, magnesium glutarate, magnesium adipate and the like. These may be used alone or in combination of two or more.

In the present invention, the magnesium salt of a carboxylic acid or dicarboxylic acid having 3 to 7 carbon atoms exists in the form of a salt without being ionized in the film, and attracts water molecules to form the intermediate film and the glass. It is considered possible to suppress the adhesive force between the laminated glasses, and it is presumed that this can improve the penetration resistance of the obtained laminated glass.

The magnesium salt of a carboxylic acid or dicarboxylic acid having 3 to 7 carbon atoms is distributed at a high concentration on the surface of the film without agglomeration in the film, so that a small amount of the magnesium salt exhibits the effect of adjusting the adhesive force. Also, excessive whitening during moisture absorption does not occur.

In the present invention, the magnesium salt of a carboxylic acid or dicarboxylic acid having 3 to 7 carbon atoms preferably has the same structure as the acid component of the diester compound. By having a structure similar to the diester compound used as a plasticizer, because it can be stably and uniformly dispersed in the film,
Does not change over time.

The addition amount of the magnesium salt of carboxylic acid or dicarboxylic acid having 3 to 7 carbon atoms is 0.01 to 0.1 part by weight based on 100 parts by weight of the polyvinyl butyral resin. If the amount is less than 0.01, the effect of adjusting the adhesive strength is lost, and the penetration resistance of the obtained laminated glass is reduced. If it exceeds 0.1 part by weight, the transparency of the laminated glass obtained by bleed out is reduced. In addition to impairing the properties, the adhesive strength between the interlayer film and the glass is excessively reduced, so that it is limited to the above range. Preferably, it is 0.03 to 0.08 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 molecular weight of the modified silicone oil is 8
00-5000 is preferable. When the molecular weight is less than 800, localization on the interlayer film surface may be reduced,
If it exceeds 00, the compatibility with the resin becomes poor, bleeds out to the surface of the intermediate film, and the adhesive strength between the intermediate film and the glass may decrease. More preferably, 1500 to 40
00.

The amount of the modified silicone oil added is 0.01 to 100 parts by weight of the polyvinyl butyral resin.
０．２0.2 parts by weight. When the addition amount is less than 0.01 part by weight, the effect of preventing whitening due to moisture absorption becomes insufficient,
If the amount exceeds 0.2 parts by weight, the compatibility with the resin becomes poor, bleeds out to the surface of the intermediate film, and the adhesive strength between the intermediate film and the glass decreases, so that it is limited to the above range. 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. As the above stabilizer, for example,
Surfactants such as sodium lauryl sulfate and alkylbenzene sulfonic acid are included. Examples of the antioxidant include t-butylhydroxytoluene (BH
T), tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane (Irganox 10 manufactured by Ciba-Geigy)
10) and the like.

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 can be produced, for example, by the following method. The polyvinyl butyral resin, the dicarboxylic acid and a monoester alcohol or a diester compound composed of a monocarboxylic acid and a dihydric alcohol, the C3 to C7 carboxylic acid or a magnesium salt of a dicarboxylic acid, and
The modified silicone oil is supplied to a mixing roll and kneaded, and the kneaded product 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).

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, and also has excellent moisture resistance. ,
No whitening after moisture absorption and no change with time.

The laminated glass of the present invention (hereinafter referred to as present invention 2) is a laminated glass using the interlayer film for laminated glass of the present invention (hereinafter referred to as 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.

The laminated glass of the present invention 2 is excellent in transparency, light resistance, weather resistance, impact resistance, adhesiveness and moisture resistance. The laminated glass of the second aspect of the present invention can be suitably used for construction and vehicles.

[0030]

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 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 hydrogencarbonate was added to neutralize, washed with water and dried to obtain a polyvinyl butyral resin having a butyralization degree of 69 mol%.

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-ethylbutyrate, 0.04 parts by weight of magnesium 2-ethylbutyrate, and Table 1 Is supplied to a mixing roll, and the kneaded product obtained by kneading is press-formed at 150 ° C. and 120 kg / cm ² for 30 minutes using a press-forming machine. A 0.8 mm resin film (intermediate film) was obtained.

Preparation of Laminated Glass The resin film (intermediate film) obtained above was sandwiched between two float glass sheets of 30 cm square and 2.5 mm thickness, and the sandwich was placed in a vacuum bag and vacuumed. The temperature was kept at 20 torr for 20 minutes, and then kept in an oven at 90 ° C. for 30 minutes while keeping the vacuum. 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.

Production of Adhesive Force Measurement Sample Adhesive force measurement sample (2 × 10 cm) was produced from one-sided glass and one-sided polyethylene terephthalate. The matching conditions are the same as above.

Evaluation (1) Moisture whitening resistance test A resin film (intermediate film) was cut into a size of 4 × 4 cm, and was cut in an atmosphere at a temperature of 50 ° C. and a humidity of 95% RH for 24 hours (h).
r) After standing, haze was measured with an integral turbidimeter manufactured by Tokyo Denshoku Co., Ltd. In addition, one month after film formation,
Measured similarly.

(2) Measurement of Adhesive Force A sample for measuring an adhesive force made of one-sided glass and one-sided polyethylene terephthalate was cut into a size of 2 × 10 cm, and a tensile speed of 500 mm / min was obtained using Tensilon UCE500 manufactured by Orientec. The peel strength was measured. In addition, the same measurement was performed for the product one month after the film formation.

(3) Penetration Resistance Test The penetration resistance test was carried out in accordance with JIS R 3212 “Testing method for automotive safety glass”. 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 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.,
96 parts by weight (1.9 mol) and n-butyraldehyde 13
5 parts by weight (1.9 mol) were 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 holding, 147 parts by weight of sodium bicarbonate (1.7
Mol) and neutralized, washed with water and dried to obtain a polyvinyl butyral resin having a butyralization degree of 65 mol%. Using the obtained resin, a resin film (intermediate film) was produced 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 produced using the resin film. 1
Each physical property was measured in the same manner as described above. The results are shown in Table 2.

Examples 3 to 7 A resin film (intermediate 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. The results are shown in Table 2.

Comparative Examples 1 to 3 A resin film (intermediate 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. The results are shown in Table 2.

[0041]

[Table 1]

In Table 1, Formulas (1) to (3) represent chemical structural formulas represented by the following Formulas (1) to (3), respectively.

[0043]

Embedded image

[0044]

[Table 2]

[0045]

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. A polyvinyl butyral resin having a degree of butyralization of 60 to 75 mol%, 100 parts by weight of a diester compound comprising a dicarboxylic acid and a monohydric alcohol or a diester compound comprising a monocarboxylic acid and a dihydric alcohol.
A combination comprising 0 parts by weight, 0.01 to 0.1 parts by weight of a magnesium salt of a carboxylic acid or dicarboxylic acid having 3 to 7 carbon atoms, and 0.01 to 0.2 parts by weight of a modified silicone oil. Interlayer for glass. 2. The magnesium salt of a carboxylic acid or dicarboxylic acid having 3 to 7 carbon atoms is the same as an acid component of a diester compound comprising a dicarboxylic acid and a monohydric alcohol or a monocarboxylic acid and a dihydric alcohol. The interlayer film for laminated glass according to claim 1, wherein the interlayer film has a structure. 3. A laminated glass comprising the interlayer film for laminated glass according to claim 1 or 2.