JPS59111954A - Laminated glass - Google Patents

Abstract

PURPOSE:Laminated glass useful as window glass, etc. having improved transparency, durability, etc., obtained by laminating two sheets of plate glass with putting a film of a polyvinyl butyral resin containing an adduct of a monohydric alcohol with ehtylene oxide. CONSTITUTION:(A) 100pts.wt. polyvinyl butyral resin is blended with (B) 15- 60pts.wt. adduct shown by the formula (R is 1-24C alkyl, or 0-18C alkyl group-substituted aryl; n is 1-10) (e.g., an adduct of butyl alcohol with ehylene oxide) of a monohydric alcohol with ethylene oxide as a plasticizer. The plasticized polyvinyl butyral resin is molded into a film. Two sheets of inorganic plate glass or inorganic plate glass and organic plate glass (glass made of polycarbonate) are laminated, to give the desired laminated glass.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to laminated glass. More specifically, it relates to reinforced, lightweight laminated glass that is useful as window glass for automobiles, aviation aircraft, etc., show windows and showcase glass, and window glass for skyscrapers.

In general, so-called laminated glass is made by laminating two glass plates, and in particular, laminated glass made of inorganic glass and organic glass such as polycarbonate or polymethyl methacrylate has good impact resistance and It has the advantage of being lightweight, and its disadvantage of being easily scratched is compensated for by the use of inorganic glass.

In these laminated glasses, because different materials such as inorganic glass and organic glass are bonded together, and because the laminated glass is used for various purposes and uses, the adhesive material is required to have divine performance.

Liquid and film adhesives are generally known as such adhesives depending on their usage. Thermosetting adhesives such as silicone and epoxy adhesives and photosensitive adhesives are known as liquid adhesives, but these liquid adhesives are difficult to bond when the glass area is large. However, it is difficult to maintain a constant thickness of the adhesive layer, and perspective distortion is likely to occur.

On the other hand, polyvinyl butyral film is known as a film-like adhesive and is used practically for laminating inorganic glasses together.This film-like adhesive does not have the problem of perspective distortion as described above. , workability is also good,
Widely used for automobile windshields, etc. However, this film has the disadvantage of poor adhesion to organic glass, and is also susceptible to the effects of the plasticizers used, such as glycol fats, which can cause damage to organic glass, especially organic glass made of polycarbonate or polymethyl methacrylate. The drawback was that the glass became cloudy and cracked, making it unusable.

In order to solve this problem, various plasticizers for polyvinyl butyral resin have been examined, including sulfonamide (see Japanese Patent Publication No. 46-35156), alcohol having 2 to 4 hydroxyl groups, and acid having one hydroxyl group per molecule. Partial esters produced by reaction with CI6-C20-unsaturated fatty acids bound to (JP-A-53-1396
84), propion oxide oligomer (see Publication No. 84), propion oxide oligomer (
%) has been proposed. Although these compounds are effective in solving the problem of clouding of organic glass, they have the disadvantage that they do not satisfy optical standards in terms of adhesion, durability, etc. Furthermore, when the sulfonamide described in the above-mentioned Japanese Patent Publication No. 46-35156 is blended with polyvinyl butyral resin, there is no problem when it is formed into a sheet by a solvent casting method, but it is formed into a sheet by a processing method that applies heat such as extrusion molding. There was a problem in that when it did so, it decomposed and ceased to play its role as a plasticizer.

The present inventors solved the above problems and improved the various performances of laminated glass, namely transparency, adhesion, impact force absorption, durability, and
The present invention was completed as a result of extensive research into a plasticizer for polyvinyl butyral resin that satisfies weather resistance, perspective distortion, etc., and does not cause clouding or cracking even in organic glass.

An object of the present invention is to provide a laminated glass that does not produce cloudiness or cracks and has various performances such as excellent transparency and good durability.

The memorandum of the present invention is “Polyvinyl butyral resin 10
At least two films of polyvinyl butyral containing 15 to 60 parts by weight of an ethylene oxide adduct of a monohydric alcohol represented by the following general formula [I] are inserted into the 0-type assembly part. This is achieved by laminated glass, which is characterized by laminating glass plates.

General formula [1] RO-(CH2C'H20)n H [wherein, R is an alkyl group having 1 to 24 carbon atoms or an alkyl group-substituted aryl group having 0 to 18 carbon atoms, and n is the average The value is 1 to 1o. ] The film-like material used in the present invention is a film sheet produced from plasticized polyvinyl butyral resin using a known molding method.

The above-mentioned polyvinyl butyral resin is obtained by acetalizing polyvinyl alcohol with butyraldehyde, and preferably has a vinyl butyral monolayer unit of 60 to 80% by weight (degree of butylation).

The degree of polymerization is preferably 600 to 2,000.

The above general formula [1] which acts as a plasticizer in the present invention
The ethylene oxide adduct of monohydric alcohol represented by is contained in an amount of 15 to 60 parts by weight, preferably 20 to 50 parts by weight, based on 100 parts by weight of the polyvinyl butyral resin. If the amount is less than 15N parts, there will be no plasticizing effect on polyvinyl butyral resin, and the adhesive property will be poor.
If the amount exceeds the vehicle weight, the plasticizer will bleed onto the surface of the film when it is processed into a film, resulting in poor adhesion and poor adhesion workability.

the ethylene oxide adduct of the -hydric alcohol;
An average of 1 to 10 moles of ethylene oxide is added to 1 mole of the alcohol. This value indicates the value of n in the general formula [I], and the expression "as an average value" means that all molecules participate in the addition reaction in an amount equivalent to the number of moles of ethylene oxide charged. This is because there is no In the above values, less than 1 mol and 10
If the amount exceeds the molar amount, the compatibility with polyvinyl butyral is poor, and it bleeds onto the film surface over time, resulting in poor adhesion between the film and inorganic glass and organic glass.

Examples of the -hydric alcohol include aliphatic alcohols having 1 to 24 hydrogen atoms and alkyl-substituted phenols having 0 to 18 hydrogen atoms, and particularly preferred compounds include butyl alcohol, hexyl alcohol, Aliphatic alcohols with 4 to 18 carbon atoms, such as octyl alcohol, tesyl alcohol, lauryl alcohol, stearyl alcohol, oleyl alcohol, 2-ethylhexyl alcohol, and phenol, cresol, ethylphenol, phthylphenol, octylphenol, nonylphenol, laurylphenol number of carbon atoms such as 0
-12 alkyl group-substituted phenols.

As a method for adding ethylene oxide to a monohydric alcohol, a known method can be applied. For example, 150-200°C in the presence of an alkali catalyst.

O~5 Kg/rrli G for gas-liquid or liquid-
This can be done by liquid reaction.

The film-like material used in the present invention is prepared by adding stabilizers, antioxidants, ultraviolet absorbers, colorants, adhesion modifiers, etc. as necessary to the ethylene oxide adduct of polyvinyl butyral and monohydric alcohol. Manufactured by kneading and extrusion. The thickness of such a film-like material is not limited, but is usually between 0.1 and 5.0 mm, preferably 0.3 mm.
Hu ~ 2, θ Shu.

In the laminated glass 7 of the present invention, ml of the above film-like material is sandwiched between two sheets of glass to form a laminate, and this laminate is heated to a temperature of around 100°C to perform a defoaming treatment. rear,
It is produced by autoclaving for 10 to 60 minutes at a temperature of 90 to 150C and a pressure of 5 to 15/rrl. The method for manufacturing laminated glass is not limited to the above, but it can also be manufactured by, for example, bonding the laminate using a heat furnace and a pressure roll.

The glass plate that can be used in the present invention is made of inorganic glasses such as silicate glass, borate glass, and phosphate glass, and/or organic glasses such as polycarbonate and polymethyl methacrylate.

The laminated glass of the present invention uses the general formula [1] as an adhesive as an adhesive.
] Since we use a film of polyvinylbutylene containing an ethylene oxide adduct of monohydric alcohol represented by It has good transparency and excellent durability, and is suitable for use as window glass for automobiles, aircraft, etc., show windows, showcase glass, and high-rise building window glass. Good results were obtained, with no clouding or cracking, even when the material was wet.

Examples of the present invention will be described below.

[Example 1] Polyvinyl butyral resin consisting of a composition containing 40 parts by weight of an ethylene oxide adduct of lauryl alcohol (i=2) as a plasticizer based on 100 parts by weight of powdered polyvinyl butyral resin with a degree of butylation of 70% by weight. A film having a thickness of 0.76 mm was produced from the 2-L resin using an extruder at a temperature of 190°C. A polycarbonate plate of the same size and thickness of 3.0 mm was placed between two inorganic glass plates of size 300 m x 300 mm and thickness of 2.0 mm, and the two films were cut to the same size as the glass and sandwiched between the three plates. I did. This laminated carcass was first subjected to a defoaming treatment at a temperature of 110C, and then autoclaved at a temperature of 120C and a pressure of 11~/tri for 30 minutes to obtain a laminated glass of the present invention.

When this laminated glass was visually inspected,
There were no adhesion defects such as cloudiness or bubbles, and the transparency was good.

Next, to check the durability, a thermal cycle test (conditions;
The 20-cycle line now has one cycle in the temperature range of 50℃ to -200℃ in 24 hours. ) and humidity resistance test (conditions: left in an atmosphere with a temperature of 55°C and a relative humidity of 95 parts), but there was little change in appearance, no problems such as peeling, and no decrease in strength was observedf'L There wasn't. An impact test was also conducted in which a 5 pound steel ball was dropped from a height of 4 crn, but no penetration occurred.

[Example 2] To 100 parts by weight of powdered polyvinyl butyral resin with a degree of butylation of 65% by weight, an ethylene oxide adduct of lauryl alcohol (n=5) t45-l resin was added at a temperature of 19%.
A film having a thickness of 0.6 mm was produced using an extruder at 0°C.

Using these two films, two inorganic glass plates as in Example 1 and one 0.5 tone polycarbonate plate were laminated together under the same conditions as in Example 1 to make glass.

This laminated glass was subjected to various tests under the same conditions as in Example 1, and no problems were found in terms of appearance, durability, and impact resistance.

[Example 3] A film was produced in the same manner as in Example 1 except that 35 parts by weight of p-cresol ethylene oxide adduct (n = 2) was used in place of the plasticizer in Example 1. A laminated glass was produced in the same manner.

This laminated glass was subjected to various tests under the same conditions as in Example 1, and no problems were found in terms of appearance, durability, and impact resistance.

Example 4 A polyvinyl butyral film was produced in the same manner as in Example 1 except that 30 parts by weight of an ethylene oxide adduct of p-cresol (n=10) was used in place of the plasticizer in Example 1, A laminated glass was produced in the same manner as in Example 1.

This laminated glass was subjected to various tests under the same conditions as in Example 1, and no problems were found in terms of appearance, durability, and impact resistance.

[Example 5] A laminate was made using a polymethyl methacrylate plate instead of the polycarbonate plate of Example 1, and a defoaming treatment was performed at a temperature of 90°C, followed by a temperature of 100°C and a pressure of 11 Ky/
A laminated glass was produced by autoclaving at aJ for 35 minutes.

This laminated glass was tested under the same conditions as in Example 1, and no problems were found in terms of appearance, durability, and impact resistance.

[Comparative Example 1] To 100 parts by weight of powdered polyvinyl butyral resin with a degree of butylation of 70 weight range, triethylene glycol di-2-ethyl butyrate (3GF()e40 A film was prepared in the same manner as in Example 1 by adding part by weight.

A laminated glass was produced using this film in the same manner as in Example 1, but it became cloudy and devitrified after being taken out of the oven.

[Comparative Example 2] A film was produced in the same manner as in Example 1 except that the number of moles of plasticizer added in Example 1 was n=12, and a laminated glass was produced. The result was that the plasticizer bladed onto the surface of the film, resulting in poor adhesion and poor transparency.

[Comparative Example 3] Example 1 except that the content of plasticizer was 12 parts by weight per 100 parts by weight of polyvinyl butyral resin.
When a film was produced under the same conditions as in Example 1 and an attempt was made to produce a laminated glass, there was no plasticizing effect on the polyvinyl butyral resin and the adhesiveness was poor.

[Comparative Example 4] A film was produced 1-1 under the same conditions as in Example 1, except that the content of the plasticizer in Example 1 was 65 parts by weight per 100 parts by weight of polyvinyl butyral resin. When attempting to produce laminated glass, the plasticizer bled onto the film surface, resulting in poor adhesion and poor adhesion workability.

Patent applicant Mitsui Toatsu Chemical Co., Ltd. Central Glass Co., Ltd. agent Patent attorney Suzuki Sakaguchi (and 1 other person) 271-

Claims (1)

[Scope of Claims] (υ Polyvinyl butyral containing 15 to 60 parts by weight of an ethylene oxide adduct of a monohydric alcohol represented by the following general formula [I, 1] per 100 parts by weight of polyvinyl butyral resin. A laminated glass characterized by laminating at least two glass plates with a film-like material sandwiched between them.General formula [1] (2) At least one of the glass plates is an organic glass. (3) The laminated glass according to claim 2, characterized in that the organic glass is made of polycarbonate. (4) The laminated glass according to claim 2, characterized in that it is made of organic gas ζ polymethyl methacrylate.