JP2001261384A - Interlayer for laminated glass, and laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both an interlayer for laminated glass having excellent antistatic property, excellent humidity resistance, transparency, penetration resistance and scattering prevention of glass, and a laminated glass. SOLUTION: This interlayer for laminated glass comprises a plasticized polyvinyl butyral resin having 62-72 mol% butyralation degree and 0.05-3 pts.wt. of a compound of general formula (1) R-O-(CH2CH2O)nH (R is a 1-25C hydrocarbon group; n is an integer of 1-20)...(1), 0.05-3 pts.wt. of a compound of general formula (2) R-O-(CH2CH2CH2O)nH (R is a 1-25C hydrocarbon group; n is an integer of 1-20)...(2) and 0.05-3 pts.wt. of a compound of general formula (3) R-O-(CH2CH2CH2CH2O)nH (R is a 1-25C hydrocarbon group; n is an integer of 1-20)...(3) based on 100 pts.wt. of the butyral resin. This laminated glass is obtained by using the 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 and a laminated glass having excellent antistatic properties.

[0002]

2. Description of the Related Art Laminated glass in which a resin interlayer is sandwiched between at least two glass plates is hard to penetrate when subjected to an impact from an object, and is safe because glass fragments are not scattered. Widely used for window glass of automobiles, aircraft, buildings, etc.

[0003] Among resin interlayers used for this kind of laminated glass, an interlayer made of plasticized polyvinyl butyral resin has excellent adhesion to glass, and has both tough tensile strength and high transparency. It is suitable as a window glass of a vehicle.

However, an intermediate film made of the plasticized polyvinyl butyral resin is a resin towards the surface resistance is difficult to generally charged at 10 ¹³ Ω / cm ² or so, and since the use is sandwiched between glass plates, in particular Less consideration was given to antistatic performance.

[0005] In recent years, requirements for quality have become strict, and adhesion of dust and foreign matter due to static electricity has become a problem, and an interlayer film for laminated glass having excellent antistatic performance has been demanded.

Therefore, it is conceivable to include an antistatic agent, which is widely used in conventional transparent plastics, in the intermediate film. However, an intermediate film made of a plasticized polyvinyl butyral resin containing such an antistatic agent is considered. In the case of a film, the adhesion to glass, transparency, durability and the like are impaired, and thus, no suitable combination of antistatic agents has been found.

For example, Japanese Patent Application Laid-Open No. 7-223849 discloses an interlayer made of a plasticized polyvinyl butyral resin containing a nonionic antistatic agent such as polyoxyethylene alkyl ether. The adhesiveness to glass and moisture resistance are not sufficiently satisfactory, and there is room for improvement.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to provide an excellent antistatic property and even when placed in a humid atmosphere. In order to provide an interlayer film and a laminated glass for laminated glass, which are less likely to peel or whiten at the periphery of the laminated glass, have excellent moisture resistance, and have excellent transparency, penetration resistance and glass scattering prevention. is there.

[0009]

An object of the present invention is to provide an interlayer film for laminated glass comprising a plasticized polyvinyl butyral resin having a degree of butyralization of 62 to 72 mol%, based on 100 parts by weight of polyvinyl butyral resin. 0.05 to 3 parts by weight of a compound represented by the following general formula (1), 0.05 to 3 parts by weight of a compound represented by the following general formula (2) and represented by the following general formula (3) It can be achieved by an interlayer film for laminated glass characterized by containing 0.05 to 3 parts by weight of a compound and a laminated glass using the same. _{R-O- (CH 2 CH 2} O) n H ...... (1) (R is a hydrocarbon group having 1 to 25 carbon atoms, n represents an integer of 1 to _{20) R-O- (CH 2 CH} 2 CH 2 O) n H ...... (2) (R is a hydrocarbon group having 1 to 25 carbon atoms, n represents an integer of 1 to _{20) R-O- (CH 2 CH} 2 CH 2 CH 2 O) n H ...... ( 3) (R is a hydrocarbon group having 1 to 25 carbon atoms, n is an integer of 1 to 20)

In the present invention, a polyvinyl butyral resin used in a conventional interlayer film for laminated glass is used as a resin constituting the interlayer film. When the butyralization degree of this polyvinyl butyral resin is low, it becomes easy to absorb moisture and whitening easily occurs at the periphery of the laminated glass. Conversely, when it is high, the mechanical strength of the interlayer film is reduced. Preferably 63.5-70.
0 mol%. The amount of residual acetyl groups is preferably 5 mol or less from the viewpoint of transparency, heat resistance and weather resistance of the interlayer.

On the other hand, when the average degree of polymerization of the polyvinyl butyral resin is too small, the resulting intermediate film has poor penetration resistance, and when it is too large, the resulting intermediate film has too high impact resistance. Preferably, one is used.

Such a polyvinyl butyral resin is produced by a known synthesis method. For example, an average degree of polymerization of 100
0 to 2500 polyvinyl alcohol is dissolved in hot water,
The obtained aqueous solution is kept at 0 to 50 ° C., butyraldehyde and an acid catalyst are added thereto to proceed the butyralization reaction, and then the temperature of the reaction system is raised to ripen the reaction, thereby completing the reaction. It can be produced by a method of obtaining polyvinyl butyral resin powder through neutralization, washing and drying.

The above polyvinyl alcohol is obtained by saponifying polyvinyl acetate.
In order to improve the transparency, heat resistance and weather resistance of the obtained intermediate film, it is preferably at least 95 mol%. In addition, it is preferable to use the thing whose average polymerization degree is 1000-2500.

The polyvinyl butyral resin thus obtained contains a plasticizer to give a plasticized polyvinyl butyral resin. Examples of the plasticizer include triethylene glycol di-2-ethyl butyrate, triethylene glycol di-2-ethylhexanosoate, triethylene glycol dicaprylate, tetraethylene glycol di-2-ethylhexoate, and tetraethylene glycol di-2-ethylhexoate. Preference is given to ethylene glycol diheptanoate, tetraethylene glycol dicaprylate and the like.

Among them, triethylene glycol di-
The interlayer film made of polyvinyl butyral resin containing 2-ethylhexanoate has good low-temperature flexibility, excellent pre-compression bonding properties, and is excellent in work environment and trim-cutting properties during laminating. These plasticizers are generally preferably used in an amount of 30 to 50 parts by weight based on 100 parts by weight of the polyvinyl butyral resin.

Thus, in the present invention, 0.05 to 3 parts by weight of the compound represented by the above general formula (1) and 100 parts by weight of the above polyvinyl butyral resin, 0.05 to 3 parts by weight of the compound represented by the formula (1) and 0.05 to 3 parts by weight of the compound represented by the formula (3) are contained.

The compound represented by the general formula (1) has an effect of dispersing and conducting static electricity (charge) in a film to prevent chargeability. Here, when the carbon number of the hydrocarbon group R increases, bleeding to the film surface occurs, which adversely affects the adhesion to glass, and the antistatic performance decreases,
Limited to 1 to 25. Further, the value of n is limited to 1 to 20 because the moisture resistance of the film decreases as the value increases.

The compound represented by the general formula (1) includes
For example, dodecyloxydiethylene glycol, dodecyloxytriethylene glycol, methoxytetraethylene glycol, pentoxyhexaethylene glycol,
3,3-dipropylbutoxytetraethylene glycol, 2,2-diethylbutoxytetraethylene glycol, phenoxyhexaethylene glycol, 1,5-diethylphenoxyoctaethylene glycol, and the like. These compounds may be used alone or in combination of two or more.

When the content of the compound represented by the general formula (1) decreases, the antistatic performance of the film decreases, and when it increases, the moisture resistance of the film decreases. And 0.05 to 3 parts by weight.

The compound represented by the general formula (2) has a role of interacting with the compound represented by the general formula (1) to improve the antistatic performance. Here, the carbon number of the hydrocarbon group R is limited to 1 to 25 since an increase in the number of carbon atoms causes bleeding to the film surface, adversely affecting the adhesion to glass and lowering the antistatic performance. Further, the value of n is limited to 1 to 20 because the moisture resistance of the film decreases as the value increases.

The compound represented by the general formula (2) includes
For example, dodecyloxytripropylene glycol, methoxytetrapropylene glycol, pentoxyhexapropyleneglycol, 3,3-dipropylbutoxytetrapropyleneglycol, 2,2-diethylbutoxytetrapropyleneglycol, phenoxyhexapropyleneglycol, 1,5- And diethylphenoxyoctapropylene glycol. These compounds may be used alone or in combination of two or more.

When the content of the compound represented by the general formula (2) decreases, the antistatic performance of the film decreases, and when it increases, the moisture resistance of the film decreases. And 0.05 to 3 parts by weight.

The compound represented by the general formula (3) is
It interacts with the compound represented by the general formula (1) and plays a role in improving its antistatic performance. Here, the carbon number of the hydrocarbon group R is limited to 1 to 25 since an increase in the number of carbon atoms causes bleeding to the film surface, adversely affecting the adhesion to glass and lowering the antistatic performance. Further, the value of n is limited to 1 to 20 because the moisture resistance of the film decreases as the value increases.

The compound represented by the general formula (3) includes
For example, dodecyloxytetrabutylene glycol, methoxytetrabutylene glycol, pentyloxyhexabutylene glycol, 3,3-dipropylbutoxytetrabutylene glycol, 2,2-diethylbutoxytetrabutylene glycol, phenoxyhexabutylene glycol, 1,5- And diethylphenoxyoctabutylene glycol. These compounds may be used alone or in combination of two or more.

When the content of the compound represented by the general formula (3) decreases, the antistatic performance of the film decreases, and when the content increases, the moisture resistance of the film decreases. Therefore, based on 100 parts by weight of the polyvinyl butyral resin, And 0.05 to 3 parts by weight.

Thus, the interlayer film for laminated glass of the present invention is obtained. The intermediate film may contain various known additives, such as an adhesive force regulator, an ultraviolet absorber, an antioxidant, and a light stabilizer, in an appropriate amount, if necessary.

In particular, in order to appropriately adjust the adhesion to glass, an adhesion regulator is often included. As such an adhesion regulator, generally used are alkali metal salts or alkaline earth metal salts of monocarboxylic acids or dicarboxylic acids such as potassium acetate, magnesium acetate, and magnesium 2-ethylbutyrate. Such an adhesion regulator is generally contained in the range of 0.01 to 1 part by weight.

The interlayer film for laminated glass of the present invention is manufactured by a method similar to the conventional method. For example, a predetermined amount of a plasticizer is added to a polyvinyl butyral resin, and general formulas (1), (2),
(3) a compound represented by the formula, if necessary, an adhesion regulator;
Other known additives are mixed, the mixture is supplied to a mixing roll, and the kneaded material obtained by kneading is extruded.
It is manufactured by forming into a sheet shape using a calender roll, a press forming machine, or the like. The thickness of the intermediate film is substantially the same as that of a conventional intermediate film, and is, for example, 0.2 to 3 mm.

In order to produce a laminated glass using the interlayer film of the present invention, an ordinary method for producing a laminated glass is employed.
For example, an interlayer is sandwiched between at least two transparent glass plates, the laminate is placed in a rubber bag, a rubber bag is connected to an exhaust system, and the pressure is reduced by suction or pressure-bonded by a roll, and pre-adhesion is performed. It is manufactured by performing actual bonding using an autoclave or using a press.

As the above glass plate, not only an inorganic glass plate but also an organic glass plate such as a polycarbonate plate and a polymethyl methacrylate plate can be used. The laminated structure of the laminated glass may be not only a three-layer structure of a glass plate / interlayer / glass plate, but also a multilayer structure such as a glass plate / interlayer / glass plate / interlayer / glass plate. it can.

[0031]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Examples and comparative examples of the present invention are shown below. (Examples 1 to 3 and Comparative Examples 1 to 7) <Synthesis of polyvinyl butyral resin> In a reactor equipped with a stirrer, 2900 parts by weight of ion-exchanged water and an average degree of polymerization of 17 were added.
Then, 198 parts by weight of polyvinyl alcohol having a saponification degree of 99.2 mol% was supplied, and heated to 95 ° C. with stirring to dissolve. The aqueous solution was cooled to 30 ° C.
After adding 208 parts by weight of hydrochloric acid and 152 parts by weight of n-butyraldehyde, the liquid temperature was lowered to 2 ° C., and the reaction was allowed to proceed while maintaining this temperature. After the polyvinyl butyral resin was precipitated, the liquid temperature was raised to 30 ° C. Warm and hold for 5 hours to ripen.
Thereafter, 156 parts by weight of sodium bicarbonate was added to neutralize, washed with water and dried to obtain a powdery polyvinyl butyral resin used in Example 1 (butyralization degree: 69 mol%, residual acetyl group: 0.8 mol%, Average degree of polymerization 170
0) was obtained. In a similar manner, as shown in Tables 1 and 2,
Powdered polyvinyl butyral resins used in Examples 2 and 3 and Comparative Examples 1 to 7 were obtained.

<Preparation of interlayer film for laminated glass> 39 parts by weight of a plasticizer (triethylene glycol di-2-ethylhexanoate or tetraethylene glycol diheptanoate) was added to 100 parts by weight of each of the above polyvinyl butyral resins. Compounds represented by the general formulas (1), (2) and (3) and an adhesion regulator (magnesium 2-ethylbutyrate, magnesium acetate and potassium acetate) are blended in the proportions shown in Table 1 and mixed with a mixing roll. And the kneaded product obtained by kneading is subjected to press molding at 150 ° C. and 9.8 Mpa.
(100 kgf / cm < ² >) was press-molded for 30 minutes, and ten types (Examples 1-3 and Comparative Examples 1-7) of interlayer films (thickness 0.8 mm) for laminated glass were produced.

[0033]

[Table 1]

[0034]

[Table 2]

<Preparation of Laminated Glass> Each of the interlayer films for laminated glass was cut into a length of 300 mm × width 300 mm, and this was sandwiched between two pieces of float glass 300 mm × 300 mm × 2.5 mm thick. This sandwich was placed in a vacuum bag and held at a degree of vacuum of 20 Torr (20 mmHg) for 20 minutes, and then kept at 90 ° C. for 30 minutes in an oven while keeping the vacuum. Take out from the vacuum bag and put it in an autoclave at 150 ° C., 1.27 Mpa (13 kgf / c
m ² ) and hot pressed under 10 conditions (Examples 1 to 3)
And the transparent laminated glass of Comparative Examples 1-7) was obtained.

Each of the laminated glasses was subjected to a Pummel test, a moisture resistance test and a measurement of surface resistance by the following methods. The results are shown in Tables 3 and 4.

[0037]

[Table 3]

[0038]

[Table 4]

(1) Pummel test (Sekisui method) The laminated glass was adjusted to a temperature of −18 ° C. ± 0.6 ° C. for 16 hours, and the center of the laminated glass (length 150 mm × width 1).
(50 mm portion) was hit with a 0.45 kg hammer on the head and crushed until the particle size of the glass became 6 mm or less. Method). The initial value and the value after standing at 50 ° C. for 4 weeks are shown.

[0040]

[Table 5]

A laminated glass having a Pummel value in the range of 3.5 to 5 is most preferable because it has excellent penetration resistance and glass scattering prevention properties. When the Pummel value is 3 or less, the adhesive strength is low, and the scattering of glass by impact or the like is reduced. Conversely, if the Pummel value is 6 or more, the adhesive strength increases, and the penetration resistance of the laminated glass due to impact or the like decreases.

(2) Moisture resistance test The laminated glass was subjected to a temperature of 80 ° C. and a relative humidity of 95%.
Store for a week, then immediately take out the laminated glass,
The whitening distance (mm) from the edge was measured.

(3) Surface Specific Resistance The interlayer film for laminated glass was dried in a desiccator for 24 hours, and then immediately after the laminated glass was taken out, using a surface resistance measuring device (DSM-8103 manufactured by Toa Denpa Kogyo Co., Ltd.). And the surface specific resistance was measured.

[0044]

As described above, the degree of butyralization is 62 to 72.
An interlayer film for laminated glass composed of mol% of a plasticized polyvinyl butyral resin, wherein 0.05 to 3 parts by weight of the compound represented by the general formula (1) is added to 100 parts by weight of the polyvinyl butyral resin. 0.05 to 3 parts by weight of the compound represented by the general formula (2) and the aforementioned general formula (3)
By containing 0.05 to 3 parts by weight of the compound represented by the formula, an interlayer film for laminated glass and a laminated glass having excellent antistatic properties can be obtained.

In addition, even when the laminated glass is placed in a high humidity atmosphere, peeling and whitening of the peripheral portion of the laminated glass are less likely to occur, and the laminated glass is excellent in moisture resistance. Furthermore, it is excellent in transparency, penetration resistance and glass scattering prevention. Therefore, the laminated glass obtained by the present invention can be used without any problem even in an environment with high moisture or humidity.

Claims (2)

[Claims] 1. An interlayer for laminated glass comprising a plasticized polyvinyl butyral resin having a degree of butyralization of 62 to 72 mol%, which is represented by the following general formula (1) with respect to 100 parts by weight of the polyvinyl butyral resin. Compound 0.0
It contains 5 to 3 parts by weight, 0.05 to 3 parts by weight of a compound represented by the following general formula (2), and 0.05 to 3 parts by weight of a compound represented by the following general formula (3). An interlayer for laminated glass, characterized in that: _{R-O- (CH 2 CH 2} O) n H ...... (1) (R is a hydrocarbon group having 1 to 25 carbon atoms, n represents an integer of 1 to _{20) R-O- (CH 2 CH} 2 CH 2 O) n H ...... (2) (R is a hydrocarbon group having 1 to 25 carbon atoms, n represents an integer of 1 to _{20) R-O- (CH 2 CH} 2 CH 2 CH 2 O) n H ...... ( 3) (R is a hydrocarbon group having 1 to 25 carbon atoms, n is an integer of 1 to 20) 2. A laminated glass, wherein the interlayer film for laminated glass according to claim 1 is sandwiched between at least two glass plates.