JPH09255376A - Laminated glass with excellent fire resistance and method for producing the same - Google Patents

Abstract

(57) [Abstract] [Problem] When a laminated glass is damaged by a disaster such as a fire caused by heat, the adhesive and film inside melt and flow out to the outside. At that time, smoke and ignition due to thermal decomposition products occur. Prevent. SOLUTION: Silicon-based adhesive layers 2, 2'are formed on each inner surface of two glass plates 1, 1 ', and an organic compound is formed on the surfaces of the silicon-based adhesive layers 2, 2'of the glass plates. An intermediate layer composed of an adhesive layer 4, films 5, and an organic compound adhesive layer 4'is laminated so as to be sandwiched, and a silicon-based adhesive layer and an organic compound are bonded by a treatment such as heating, pressurization, and depressurization. Laminated glass is used in which mixed layers 3, 3'with both adhesives are formed between the layers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a window used for an opening or an internal partition provided in a civil engineering structure or a building structure for the purpose of entrance / exit, ventilation opening, daylighting, etc. The present invention relates to a laminated glass that is particularly excellent in fireproofing among laminated glass that constitutes one member of a partitioning material such as a door, and a manufacturing method thereof.

[0002]

2. Description of the Related Art Laminated glass has a structure in which an inner layer of at least two glass plates holds an intermediate layer composed of at least two organic compound adhesive layers and at least one film. By adhering the film to the glass plate, the structure has improved penetration resistance, which was conventionally lacking in glass.

[0003]

By such means for improvement, the laminated glass has been reinforced with respect to penetration resistance to have excellent crime prevention property, and in addition, if the glass is scattered little even in case of breakage. Since it also has the so-called safety, it has come to be used as a member of the entrance door of a detached house in recent years.

However, since both the adhesive and the film forming the intermediate layer sandwiched between the glass plates are organic compounds and have a common point that they are inferior in heat resistance, when they encounter a disaster accompanied by heat such as fire. It is known that when the intermediate layer held by the glass plate is melted and the glass is broken, it flows out to the outside and ignites depending on the damaged portion.

On the other hand, glass as a single item has excellent fireproofing properties, but is inferior in terms of crime prevention due to its low penetration resistance. Except for small holes such as crime prevention eyeglasses (door scopes), the entrance of an apartment house, etc. The plate-shaped single glass or laminated glass is not used as a door member, but a steel door made of metal, which is particularly excellent in terms of fire protection and crime prevention, is used instead.

However, in an apartment house or the like using a metal entrance door, the interior of the entrance is dark even in the daytime due to the lack of daylighting of the doors, and it is used as security glasses (door scope) with a narrow view of visitors. There are problems such as having to rely on it,
It is usual to use lighting and a door chain to open and close the door as well as at night.

For this reason, the appearance of a glass member that can be incorporated into the metal door by providing a lighting property without impairing both the fireproof property and the crime preventive property of the metal door is an apartment house which is obliged to be fireproof. Although the long-awaited development research has been done by the people involved in the construction of a multi-tenant building, the laminated glass with sufficient fire protection has not yet been developed.

[0008] Summarizing the contents of many applications relating to laminated glass, heat insulation, sound insulation, penetration resistance, whitening prevention, heat retention, adhesiveness, decorativeness, safety, light diffusion, etc. are limited. 6-2111548, JP-A-6-21154
9, JP-A-6-256043, JP-A-6-3294.
In No. 46, the abstract of the application is as follows.

Japanese Unexamined Patent Publication (Kokai) No. 6-212548 uses a plasticized polyvinyl acetal resin for a film of an intermediate layer, and a silane coupling agent and a modified silicone oil for a sealing layer and an adhesive force adjusting layer, respectively, and uses them in a peripheral portion of a laminated glass. Prevents whitening and improves penetration resistance and glass scattering prevention.

In Japanese Unexamined Patent Publication (Kokai) No. 6-211549, a metal layer is formed on the glass inner surface on one side, a plasticized polyvinyl acetal resin is used for the intermediate layer film, and polar or non-polar modified silicone oil is used for the adhesion adjusting layer. , Weather resistance and heat reflection, penetration resistance and glass shatterproof are improved.

According to Japanese Patent Laid-Open No. 6-256043, a metal layer is formed on the inner surface of one side of the glass, a plasticized polyvinyl acetal resin is formed on the intermediate layer film, and a polar or non-polar modified silicone oil is formed depending on the position of the adhesion adjusting layer. Are used separately to prevent whitening and improve weather resistance, heat reflection, penetration resistance, and glass scattering prevention.

Japanese Unexamined Patent Publication (Kokai) No. 6-329446 describes an intermediate layer formed by laminating a resin layer (A) and a resin layer (B) which does not require a manufacturing process of high temperature pressurization when making a laminated glass. Although the adhesion to glass, impact resistance and transparency have been improved, none of the examples is able to find any description relating to improvement of fireproofness.

[0013]

[Means for Solving the Problems] At least two adhesive layers and at least one film are laminated on the inner surface of at least two glass plates, and the glass plate is an intermediate layer composed of the adhesive layer and the films. The structure sandwiching the layers is (A) applying a silicone adhesive on the surfaces of two glass plates and drying,
(B) On one silicon adhesive layer surface of the glass plate,
The organic compound adhesive, the films, and the organic compound adhesive are sequentially layered in this order, and the remaining one glass is placed so as to come into contact with the uppermost organic compound adhesive layer in (C) step (B). A laminate is formed by stacking the plates so that their silicon adhesive layer surfaces face each other, and (D) the laminate is heated, preferably under pressure under reduced pressure, to heat the silicone adhesive layer and the organic compound adhesive. A laminated glass excellent in fireproofing, characterized by being manufactured through each step of forming a layer and a mixed layer thereof, and a method for manufacturing the same.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION As a result of various investigations to solve the problems, the present inventor provided a silicon-based adhesive layer and an organic compound adhesive layer in an adhesive layer, and formed the both adhesive layers between the both layers. It has been found that by forming a mixed layer, it can be used as a laminated glass having excellent fire resistance without impairing the function of the conventional laminated glass.

As described above, when a disaster involving heat such as fire is encountered, the conventional laminated glass melts because the adhesive layer and the film are organic compounds, and flows out from the damaged portion of the laminated glass to the outside. The problem of ignition due to thermal decomposition occurs during the outflow, and an ignition phenomenon of the product due to the thermal decomposition is recognized in the fire prevention test.

[0016] As a result of studying in consideration of the above, the present inventor found that between the silicon-based substance having an adhesive function and the conventional organic compound adhesive layer formed on the laminated glass surface,
It has been discovered that by providing a mixed layer composed of a silicon-based material and an organic compound adhesive, the amount of decomposition products generated can be suppressed even if the organic compound adhesive layer is melted by heat.

As a result, it is possible to suppress the ignition phenomenon, but this has an influence on the adhesiveness and adhesiveness between the adhesive layer and the glass surface or between the adhesive layer and the film surface, which the adhesive originally requires. Instead, we have completed a laminated glass that has excellent fire resistance in addition to physical properties that are the same as those of conventional laminated glass.

As long as the glass itself constituting the laminated glass according to the present invention is a glass used as a material for ordinary civil engineering or construction, the glass may be of any kind (see Table 1) and the combinations may be the same. Alternatively, they can be used in a configuration of different types (see Table 2).

[0019]

The glass is cut according to the specifications and the glass surface (adhesive surface) is washed. The washing method may be a glass washing machine or hand washing, and the washing agent is not limited. Instead, they may be used alone or in combination selected from water, an organic solvent system, a surfactant system, etc. depending on the stain.

[0021]

After the glass surface is dried, a silicone adhesive is applied. As the silicone adhesive to be treated, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropylmethyldiethoxysilane, mercaptoethyltriene is used. Silane compounds such as methoxysilane, mercaptoethyltrietomethoxysilane, polymethylsiloxane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane and glycidoxypropyltrimethoxysilane, silane compound derivatives thereof, and these silane compounds A commercially available product such as a mixture of silane compounds, a mixture of these silane compound derivatives, a mixture of these silane compounds and these silane compound derivatives can be used, but the liquid form of the silicon-based adhesive is preferable, and a film is preferable. The use of solid powder such is not preferred to difficult to form a mixed layer of an organic compound adhesive.

The means for applying the silicon-based adhesive to the surface of the glass plate is selected from among the usual methods such as brush coating for applying a liquid substance, spraying, screen printing, roll coating, etc., depending on the viscosity of the silicon-based adhesive used. It may be selected and determined in consideration of the conditions such as the coating amount on the glass surface.

Next, the heating condition of the silicon adhesive applied to the surface of the glass plate is preferably such that the silicon adhesive can form a mixed layer with the organic compound adhesive. The temperature for is, of course, different depending on the type of the silicon-based adhesive, but is usually in the range of room temperature to 250 ° C, preferably room temperature to 200 ° C, more preferably 50 to 150 ° C. It is good to do in the range.

The heating is usually carried out for 10 to 60 minutes, preferably 10 to 40 minutes, more preferably 15 to 30 minutes, and if it exceeds a predetermined temperature and time frame. Not only does the silicone-based adhesive dry completely and does not form a mixed layer, but the original functions (penetration resistance, etc.) of the laminated glass itself are also reduced.

The thickness of the layer formed of the silicone adhesive naturally varies depending on the physical properties or concentration of the silicone adhesive used, and is usually in the range of 50 to 500 μm, preferably in the dry state. Is 100 to 50
The range is 0 μm, preferably 200 to 400 μm.

However, in order to secure the mixed layer formed with the organic compound adhesive layered on the silicon adhesive layer, if the thickness of the silicon adhesive layer is less than the above range. Since the effect of suppressing the generation of thermal decomposition products due to heat melting of the organic compound adhesive layer due to fire, etc. is reduced and the fire resistance is deteriorated, the thickness of the organic compound adhesive layer before heating is calculated as the thickness of the mixed layer. On the other hand, it is usually in the range of 30 to 90%, preferably in the range of 40 to 80%, and more preferably in the range of 40 to 70%.

After the silicon-based adhesive on the glass plate surface is heat-treated, an organic compound adhesive is sequentially formed on the silicon-based adhesive layer,
Films, organic compound adhesive, and finally another glass plate coated with a silicon adhesive in the same manner as the glass plate and heat-treated is laminated with the silicon adhesive layer facing the organic compound adhesive layer, and under reduced pressure. The organic compound adhesive is heated and melted.

In this depressurizing operation, a laminated body composed of a glass plate, an adhesive layer held by the glass plate, and an intermediate layer composed of a film is preferably used, including the pressurization by the own weight of the laminated body itself. The outer surface of the plate is depressurized while being kept pressurizable so that the layers of the laminate are degassed to ensure sufficient adhesion between the layers.

The depressurizing operation is usually -600 to -760 mmH.
g, preferably in the range of -650 to -760 mmHg, more preferably in the range of -700 to -760 mmHg, and the pressing operation is usually 2 to 1.1 kg / cm.
The range is preferably ² G, preferably ^{2 to} 1.3 kg / cm ² G, more preferably ^{2 to} 1.5 kg / cm ² G. It is preferable that the present invention is implemented in equipment having a means capable of setting and controlling in combination with time in the range of simultaneous operation.

Suitable organic compound adhesives to be used are thermoplastic organic compounds, thermosetting organic compounds, and the like. Vinyl ester copolymers, ethylene-vinyl acetate copolymers and their saponified products, polyvinyls. Examples thereof include butyral, vinyl chloride copolymer, polyvinyl butyl ether, polyvinyl acetal, ethylene-acrylic acid ester copolymer, and the like. These are unstretched with or without processing such as uniaxial stretching or biaxial stretching. It is also possible to use a material such as a film or fine powder of the above, and these organic compound adhesives are uniform when heated except in an environment where manufacturing conditions such as insufficient degassing cannot be satisfied. Melt to.

The film, which is one of the constituents of the intermediate layer, is
It may be molded from a solid material having an arbitrary shape or may be used as a fine powder, and the material includes resin, paper, cloth, metal, or those obtained by performing various processes such as printing (hereinafter referred to as films) It can be used alone or in plural as long as it does not deteriorate fire and crime prevention performance.

In particular, when the film is an organic polymer material such as polyethylene terephthalate, polypropylene, polybutylene terephthalate, etc., which is a resin, it is a non-stretched material which has or has not undergone processing such as uniaxial stretching or biaxial stretching. It can also be used, and includes those obtained by adding an inorganic salt such as calcium carbonate to the resin to make the film opaque.

The thickness of the organic compound adhesive layer is not particularly limited, but in consideration of fire resistance, penetration resistance, and adhesion between films and a glass plate, the thickness of the organic compound adhesive layer is dry. In the state, it is usually in the range of 20 to 250 μm, preferably in the range of 50 to 200 μm, and more preferably 50.
It is preferable that the thickness is in the range of to 150 μm.

Next, the thickness of the films usually depends on the physical properties such as heat resistance and penetration resistance of the films themselves, and also on the thickness and type of the adhesive layer formed on both sides of the films. Is in the range of 50 to 400 μm, preferably 50 to 30
It is good to be in the range of 0 μm, more preferably in the range of 100 to 250 μm.

The glass plate, the adhesive, and the films are stacked in a predetermined order, and then heated to melt the organic compound adhesive and laminate the layers. The heating means is used to melt the organic compound adhesive to be used. Any method may be used as long as it can stably supply and control a sufficient temperature and amount of heat.

For example, in the case of an organic compound adhesive that melts at a heating temperature of 100 ° C. or lower, water or an aqueous solution in which an inorganic salt or organic compound and its salt are added to water to raise the boiling point is used as a heat source. By doing so, the object can be achieved, and at 100 ° C or higher, city gas, propane, heavy oil or electricity can be used as a heat source.

The heating is performed in order to melt the organic compound adhesive and to bond the glass plates, the adhesive, and the laminates of films to each other to form a silicon-based adhesive, an organic compound adhesive, and a mixed layer thereof. And the time are determined in consideration of the type and heating temperature of the silicone adhesive, the melting temperature of the organic compound adhesive, the thickness of the formed mixed layer, the heat resistance of the films, and the like.

Therefore, if the heating temperature is low and the heating time is short, the above-mentioned mixed layer is not sufficiently formed and the fire resistance and crime prevention are deteriorated, and conversely, if the heating temperature is high and the heating time is long, the glass plate is held. The resulting intermediate layer is thermally deformed or deteriorated, resulting in deterioration of fire resistance, crime prevention and decorativeness, which are the original functions of the laminated glass.

For this reason, the heating temperature is usually 9
The temperature is preferably in the range of 0 to 200 ° C, preferably in the range of 90 to 150 ° C, more preferably in the range of 100 to 150 ° C, and the heating time is usually in the range of 10 to 60 minutes, preferably 10 to 40 minutes. Minutes, more preferably 15 to 30 minutes.

The function of the laminated glass of the present invention is J
ISA1311 ^-1994 "fire test method of construction for the fire door"
As a result of performing the impact test specified in the Ministry of Construction Notification No. 1125 in 1990, using the heating furnace specified in No. 1 for the heating grade of 1 hour, the condition as a class A fire door listed in the test piece was obtained. Adapted.

Examples and comparative examples according to the present invention will be described in the following paragraphs, and when the explanations of both examples overlap, the fact that the latter example is omitted is noted and the latter example is omitted. See the description of. Further, FIG. 1 is a conceptual diagram of the present invention.

[0043]

Example 1 The test piece used in the example will be described with reference to FIG. 1. Two float plate glasses 1, 1 ′ each having a test surface of 300 mm × 300 mm and a thickness of 3 mm.
Of each of the glass plates, layers 2 and 2'made of a thermosetting silicone adhesive (trade name: SC100: made by Cemedine Co., Ltd.) are applied on a roll coater to a thickness of about 350 μm, and then heated by a heating device. A semi-cured state was obtained by heating at 100 ° C for about 30 minutes.

After cooling, layers 4 and 4'consisting of two film-like thermoplastic organic compound adhesives (trade name: Dumiran: Takeda Seisaku Kogyo Co., Ltd.) on the above-mentioned two glass plates 1 and 1 '. Hold one sheet of polyester film 5 with
Put it in a vacuum bag and evacuate it to -760 mmHg, and then reduce it to 110
After heating at 50 ° C for 15 minutes, cooling to about 70 ° C, releasing the reduced pressure over about 5 minutes, there is a mixed layer 3,3 'consisting of a thermosetting silicone adhesive and a thermoplastic organic compound adhesive. A laminated glass was obtained.

[0045] Thus, laminated glass that has been produced, in 1990 the Ministry of Construction notice fire performance test method defined in No. 1125 and JISA1311 ^-1994 fire resistance of the test according to the "fire test method of construction for the fire door", That is, the heating furnace defined in JIS Chapter 3 was used, and heating was performed for 1 hour in accordance with Appendix 2 defined in Chapter 4, Heating Grade 2.

After heating, the laminated glass dropped a sand bag of 3 kg in weight, which was hung with a rope on the back side of the heated surface, from a height of 50 cm in vertical distance. No flame or smoke was generated from the back side of the heated surface under the acceptable conditions, cracks reaching the back side of the heated surface or cracks due to heating, and destruction, peeling, or dropping when the sand bag was dropped were not observed.

[0047]

[Comparative Example 1] The specimens used in the comparative examples were the laminated glass according to the present invention (the same specifications as those of the examples), ordinary laminated glass as a building material, and single-plate glass (float plate glass, mesh-type plate glass, wire-cored). figured glass, made from reinforced plate glass) and was tested in both the method of falling ball test and shot bags test specified in JISR3205 ^-1989.

In the falling ball test, the above-mentioned test piece was 610 mm × 6.
Cut out into 10 mm square, 4 hours until the test, 23 ± 2 °
Maintained at room temperature of C and fixed to an iron frame, diameter 63.5 mm
A steel ball having a mass of 1,040 g was naturally dropped from a height of 120 cm to observe the cracked state of the specimen. The test results are shown in Table 3.

[0049]

The shot bag test was carried out using the above-mentioned test piece 19
Cut out into a 30 mm × 864 mm square, keep it at room temperature of 23 ± 5 ° C for 4 hours and fix it to a predetermined frame until just before the test, and attach an attacker with a mass of 45 ± 0.1 kg to a height of 50 cm and 100
The result of the test is shown in Table 4 for observing the cracked state of the test piece by free fall in a pendulum manner from cm.

Regarding the thickness of the glass plate used for the test piece, the product of the present invention and the ordinary laminated glass are 3 mm in the float plate glass, and the single plate glass is 6 mm in the float plate glass and the tempered plate glass in the net-inserted plate glass and the wire-inserted plate glass. 6.8 mm
However, the laminated glass of the present invention had a penetration resistance comparable to that of ordinary laminated glass.

[0052] Symbol Description ○: Not broken or cracked but not penetrated. X: Penetration or dropout. -: No test was conducted.

[0053]

[Comparative Example 2] As a test piece of this comparative example, a laminated glass according to the present invention (same specifications as in the example) (1) was dried at a temperature of 200 ° C for 2 hours under a heating condition of a silicon-based adhesive,
A laminated glass in which no mixed layer was present with the organic compound adhesive was selected as (2), and a laminated glass excluding the silicon-based adhesive was selected as (3).

The difference between the above-mentioned specimens is that the laminated glass (1) according to the present invention is different from the laminated glass (2) in the drying condition of the silicon-based adhesive and the laminated glass (3) is the silicon-based adhesive. Since the application of the adhesive and the heating or drying step associated therewith are omitted, the other configurations and conditions are the same.

The dimensions of the test piece and the test method were carried out in accordance with the explanations given in Examples and Comparative Example 1, respectively, and the fireproofness, falling ball test and shot bag test (however, the height of free fall of the attacking body was Is limited to 100 cm), and the results of examining the difference in performance are shown in Table 5.

[0056] Explanation of symbols ○: No problem. Δ: Poor adhesion, one glass scatters. ×: Not usable

As shown in Table 5, the laminated glass (1) according to the present invention is superior to the ordinary laminated glass (3) in terms of fire resistance and has the same performance in both the drop ball and shot bag tests. On the other hand, the laminated glass (2) having a sufficiently dried silicon layer had no fire resistance and the results of both the falling ball and shot bag tests were insufficient.

[0058]

The laminated glass according to the present invention has an integrated structure in which two glass plates are sandwiched with a silicon adhesive layer, an organic compound adhesive layer, a mixed layer of these adhesives and films. Therefore, not only excellent fire resistance but also many functions such as decorativeness, heat ray reflection, and ultraviolet ray removal could be added depending on the type and processing of the films.

[Brief description of drawings]

FIG. 1 shows a conceptual diagram according to the present invention.

[Explanation of symbols]

 1,1 'Glass plate 2,2' Silicon adhesive layer 3,3 'Mixed layer 4,4' Organic compound adhesive layer 5 Films

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kengo Hase 89-6 Yamashita-cho, Naka-ku, Yokohama-shi, Kanagawa Pref. Toyoco RIKEN Co., Ltd. ) Inventor Toshikazu Koshiki 136-1 Calm Sakai A-509, 2-6-1 Mihocho, Sakai-shi, Osaka

Claims (3)

[Claims] 1. At least two glass plates (1,1 ')
At least two adhesive layers and at least one film are laminated on the inner surface of the glass, and a glass plate (1, 1 ') is sandwiched between the adhesive layer and the intermediate layer consisting of the films to prevent fire. Laminated glass with excellent properties. 2. The constitution of the adhesive layer comprises a silicon-based adhesive layer (2, 2 ′), an organic compound adhesive layer (4, 4 ′) and a mixed layer (3, 3 ′) thereof. The laminated glass excellent in fireproofness according to claim 1. 3. At least two adhesive layers and at least one film are laminated on the inner surface of at least two glass plates, and the glass plate sandwiches an intermediate layer consisting of the adhesive layer and the films. The composition is (A) two glass plates (1,
1 ') surface is coated with a silicone adhesive (2, 2') and dried, and (B) one glass adhesive layer (2) of the glass plate (1) is organically coated on the surface. The compound adhesive (4), the films (5), and the organic compound adhesive (4 ′) are arranged in layers in this order, and the organic compound adhesive layer (4 ′) at the top of the step (C) (B) is arranged. The remaining one glass plate (1 ') is laminated so that its silicon adhesive layer surface (2') faces each other so as to be in contact with each other to form a laminate, and (D) preferably under pressure under reduced pressure. The fireproof property, characterized in that the laminate is heated to form a silicon-based adhesive layer, an organic compound adhesive layer, and a mixed layer (3, 3 ') thereof Excellent manufacturing method for laminated glass.