JP3125444B2 - New laminated glass - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in light weight, heat insulation and safety, which can be suitably used as glass for windows and doors of buildings having a glass surface and a central portion made of polycarbonate, and window glass for vehicles. Related to laminated glass.

[0002]

2. Description of the Related Art Transparency, rigidity, hardness, weather resistance,
Due to its excellent chemical resistance, it is currently used for window glass, show windows and doors for general buildings and high-rise buildings, automobiles,
It is widely used for transportation vehicles such as buses and railway vehicles, and window glasses for aircrafts and the like. However, glass is very brittle and easily broken, and thus has a problem in safety, and various improvements have been made. For example, tempered glass with increased strength of the glass itself by the quenching method, netted glass with increased security, impact resistance, and scattering resistance of broken glass by inserting a wire mesh, and polyvinyl butyral were cracked in the intermediate layer. There is a laminated glass or the like in which the scattering resistance of the glass is improved.

At present, these improved sheet glasses are used for buildings, particularly for high-rise buildings, but disasters caused by falling of broken glass are not interrupted, and impact resistance and broken glass are not affected. Further improvements in splash resistance are desired. In addition, with the increase in the glass area of a building, improvement in heat insulation and weight reduction of glass is also desired. In addition, laminated glass is mainly used in vehicle window glass from the viewpoint of safety. However, it is desired to reduce the weight of glass and improve heat insulation for improving fuel efficiency. On the other hand, polycarbonate is transparent and lightweight, and has excellent impact resistance.
It is processed into a sheet and is partially used as a substitute for glass.However, it cannot be used in these applications because it is colored by light, easily scratched, has poor solvent resistance, poor rigidity, etc. Was.

[0004]

SUMMARY OF THE INVENTION The present inventors would like to provide a laminated glass made of a polycarbonate having a light center and excellent impact resistance at the center and a glass having a surface having excellent rigidity, hardness, weather resistance and chemical resistance. We have been conducting research, considering that a window glass meeting the above requirements can be made. However,
When polyvinyl butyral is used for adhesion between glass and commonly used polycarbonate, there has been a problem that the polycarbonate is whitened and loses transparency. That
Laminated glass that prevents polycarbonate whitening
There have been many studies to get. For example, JP
-111954 and JP-A-60-64848
Has low opacity of polycarbonate as a plasticizer for the adhesive layer.
A method using no plasticizer is disclosed in JP-A-53-129.
In Japanese Patent Publication No. 20, the distance between the adhesive layer and the polycarbonate layer
A method for preventing whitening by providing an intermediate layer has been proposed.
You. However, the former uses a special plasticizer,
Widely used for automotive front glass as interlayer for laminated glass
Used polyvinyl butyral film can be used
Not in the latter, by requiring a new middle class
There is a problem that the manufacturing process becomes complicated. The present invention
It is an object of the present invention to overcome the whitening of polycarbonate and to complete a laminated glass excellent in impact resistance, scattering resistance of broken glass, light weight and heat resistance.

[0005]

The inventors of the present invention have conducted various studies to solve the above-mentioned problems. As a result, whitening can be prevented by using a polycarbonate having a weight-average molecular weight of 35,000 or more, and the above performance can be satisfied. The present inventors have found that a laminated glass can be obtained, and have reached the present invention. That is, the present invention relates to a laminated glass having at least a five-layer structure consisting essentially of glass / polyvinyl butyral / polycarbonate / polyvinyl butyral / glass,
A polycarbonate polycarbonate intermediate layer has a weight average molecular weight of 35,000 or more and該合
The specific gravity of frosted glass is 1.2 to 1.6 (g / cc), heat conduction
The rate is 4.5 × 10 ^{-4 to} 12 × 10 ^-4 (cal / cm · s
there is provided a thermal insulation case <br/> laminated glass, characterized in that the range of ec · deg).

[0006] The laminated glass of the present invention preferably contains 1 to 15% by weight of an ultraviolet absorber in the polyvinyl butyral layer. As the glass used in the present invention, glass generally used for plate glass or laminated glass can be used. For example, there are soda lime glass, phosphorus silicate glass, borosilicate glass, quartz glass, potassium lime glass, lead alkali glass, alumina silicate glass, barium glass, and the like. Of these, tempered glass, semi-tempered glass, partially tempered glass, Tempered glass or the like can be used, but is not particularly limited.

The polyvinyl butyral used in the present invention is not particularly limited as long as it is polyvinyl butyral, but a polyvinyl butyral film generally used as an interlayer for laminated glass can be used, and a hydroxyl group (n) in polyvinyl butyral: The molar ratio of acetyl group (m): butyral group (l) is 20 to 50: 1 to 5:40.
Polyvinyl butyral of the following general formula of about 70 can be suitably used.

[0008]

Embedded image

The performance of polyvinyl butyral varies depending on the degree of polymerization, the molar ratio of hydroxyl group / acetyl group / butyral group, plasticizer, heat stabilizer, etc., but is not particularly limited. Polyvinyl butyral, which is generally used as the interlayer film for laminated glass, can be preferably used.
Also, polyvinyl butyral has a plasticizer, a heat stabilizer,
An ultraviolet absorber, a coloring agent, and the like may be added. Examples of the plasticizer include a phthalate ester type, a phosphate ester type, a fatty acid ester type, and a glycol derivative type, and a fatty acid ester type and a glycol derivative type plasticizer are particularly preferably used. The polycarbonate used in the present invention is a polycarbonate having a main chain composed of a repeating unit represented by the following formula (1).

[0010]

Embedded image In the formula, Ar is a divalent aromatic residue, and examples thereof include phenylene, naphthylene, biphenylene, and pyridylene, and those represented by the formula (2).

[0011]

Embedded image -Ar ¹ -Y-Ar ² -Formula (2) wherein Ar ¹ and Ar ² are each an arylene group, for example, a group such as phenylene, naphthylene, biphenylene, pyridylene and the like; Is an alkylene group or a substituted alkylene group represented by the following formula 1. ]

[0012]

Embedded image Further, a divalent aromatic residue represented by the formula (3) may be contained as a copolymer component.

[0013]

-Ar ¹ -Z-Ar ² -Formula (3) [wherein, Ar ¹ and Ar ² are the same as above, and Z is a mere bond or -O-, -CO-, -S- , -SO _2- ,
-CO _2- , -CON (R ¹ ) (R ² )-, (R ¹ , R
² is the same as described above). Examples of these divalent aromatic residues include, for example,
And the like represented by Chemical Formula 8.

[0014]

Embedded image

[0015]

Embedded image

[0016]

Embedded image Wherein R ⁵ and R ⁶ are each hydrogen, halogen,
C ₁ -C ₁₀ alkyl group, C ₁ -C ₁₀ alkoxy group, C ₅
~ C ₁₀ cycloalkyl group or phenyl group, m and n are integers of 1 to 4, and when m is 2 to 4, each R ⁵ may be the same or different; Is 2
In the case of to 4, each R ⁶ may be the same or different. Among them, a compound represented by the following formula is a preferable example.

[0017]

Embedded image In particular, 85 repeating units in which Chemical Formula 9 is Ar
Those containing at least mol% are preferred.

The polycarbonate of the present invention may contain a trivalent or higher aromatic residue as a copolymer component. The molecular structure of the polymer terminal is not particularly limited,
At least one terminal group selected from a hydroxyl group, an aryl carbonate group, and an alkyl carbonate group can be bonded. Aryl carbonate group terminal is the following formula

[0019]

Embedded image [In the formula, Ar ³ is a monovalent aromatic residue. The aromatic ring may be substituted. ], As a specific example, for example,

[0020]

Embedded image And the like. The terminal of the alkyl carbonate group is represented by the following formula

[0021]

Embedded image [Wherein, R ⁷ is a linear or branched alkyl group having 1 to 20 carbon atoms], and specific examples include, for example,

[0022]

Embedded image And the like. Among these, a phenyl carbonate group, a pt-butylphenyl carbonate group, a p-cumylphenyl carbonate group, and the like are preferably used. The hydroxyl group terminal is preferably as small as possible to reduce heat resistance and hot water resistance.

The polycarbonate used in the present invention must have a weight average molecular weight (Mw) of 35,000 or more. If the weight average molecular weight is less than 35,000, whitening is not preferred during lamination with polyvinyl butyral or during subsequent use. This is presumably because the polycarbonate is soaked and whitened by the polyvinyl butyral body or an additive contained therein, such as a plasticizer. The upper limit of the weight average molecular weight is not particularly limited, but is about 300,000. If it is larger than this, the melt viscosity becomes too high and the extrudability is lowered. Preferably, 40,000 to 100,000
, More preferably from 40,000 to 80,
000 range. In particular, 45,000-65,000
Weight average molecular weights in the range of 0 are preferred.

The measurement of the weight average molecular weight (Mw) in the present invention is performed by using GPC, and the measurement conditions are as follows. Using a tetrahydrofuran solvent and a polystyrene gel, it was determined from a constitutive curve of a standard monodisperse polystyrene using a reduced molecular weight calibration curve according to the following equation.

[0025]

[Of 14] ^{_{M PC = 0.3591M PS 1.0388 (M}} PC is the molecular weight of the polycarbonate, M _PS molecular weight of polystyrene)

These polycarbonates can be produced by a known method. Specifically, a known method for reacting an aromatic dihydroxy compound with a carbonate precursor, for example, an interfacial polymerization method (phosgene method) in which an aromatic dihydroxy compound is reacted with phosgene in the presence of an aqueous sodium hydroxide solution and a methylene chloride solvent. , An ester exchange method (melting method) of reacting an aromatic dihydroxy compound with diphenyl carbonate, and a method of solid-phase polymerization of a crystallized carbonate prepolymer (Japanese Patent Application Laid-Open Nos. 1-158033 and 1-2)
71426, JP-A-3-68627, etc.). Among them, the solid-state polymerization method is easy to produce a high-molecular-weight polycarbonate, and the obtained polycarbonate is substantially free of methylene chloride, a chlorine compound, and a sodium compound, and has properties such as heat resistance and color. It is preferable because it is excellent.

The polycarbonate used in the present invention may contain a heat stabilizer, a releasing agent, a coloring agent, an ultraviolet absorber and the like. As the heat stabilizer, JP-A-Hei 3-
Use of phosphorus stabilizers described in JP-A-163160 and JP-A-3-163161 is preferably used. As the ultraviolet absorber, a benzophenone-based or benzotriazole-based ultraviolet absorber described later is preferably used. .

The laminated glass of the present invention has excellent weather resistance because the glass itself absorbs ultraviolet light.
For the purpose of further improving the weather resistance, an ultraviolet absorber may be added to each layer. In particular, a high concentration ultraviolet absorber may be added to the polyvinyl butyral layer for the purpose of improving the weather resistance of the borocarbonate by absorbing and cutting off the ultraviolet light in the polyvinyl butyral layer. In that case, the amount of the ultraviolet absorber used is preferably 1 to 15% by weight,
10% by weight is particularly preferred.

As the ultraviolet absorber to be used, for example, 2
-Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2,2'-
Dihydroxy-4-methoxybenzophenone, 2,2 ′
Benzophenones such as -dihydroxy-4,4'-dimethoxybenzophenone, 2- (2'-hydroxy-
5′-methylphenyl) benzotriazole, 2-
(2′-hydroxy-3′-t-butyl-5′-methylphenyl) 5-chlorobenzotriazole, 2- (2 ′
-Hydroxy-3 ', 5'-di-t-butylphenyl)
5-chlorobenzotriazole, 2- (3,5'-t-
Amylhydroxyphenyl) benzotriazole, 2-
(2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′,
5'-bis (α, α-dimethylbenzyl) phenyl)-
2H-benzotriazole, 2- (2′-hydroxy-
3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-lauryl-5'
Benzotriazoles such as -methylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4)
And hindered amines such as (piperidyl) sebacate.

The laminated glass of the present invention comprises the aforementioned glass,
The polyvinyl butyral and the polycarbonate basically have at least a five-layer structure of glass / polyvinyl butyral / polycarbonate / polyvinyl butyral / glass. The thickness of each layer is usually 0.1 to 10 mm for glass and 0.1 to 0.1 mm for polyvinyl butyral.
The thickness is 1.5 mm and the polycarbonate is in the range of 0.2 to 20 mm. For example, when used as bulletproof glass, the thickness of each layer is increased due to the ability of the bullet to prevent penetration, and may exceed this range.

The polyvinyl butyral layer has a function of absorbing the difference in the coefficient of thermal expansion between the glass layer and the polycarbonate layer, in addition to the role as the adhesive layer, and the thickness is determined by the thickness of each layer and the use conditions. . Further, each layer may have a multilayer structure. For example, a multilayer polycarbonate layer in which only the surface in contact with polyvinyl butyral has a polycarbonate having a weight average molecular weight of 35,000 or more and a polycarbonate of 35,000 or less may be used. In addition, by combining these, a structure of five or more layers, for example, a structure such as glass / polyvinyl butyral / polycarbonate / polyvinyl butyral / glass / polyvinyl butyral / glass, is also possible. It is also possible to attach an optical film or the like.

It is preferable that the total thickness of the front and back surfaces of the glass layer is smaller than the thickness of the polycarbonate layer, because the thermal conductivity and the specific gravity are smaller. The laminated glass of the present invention has a thermal conductivity of 4.5 × 10 ⁻⁴ to 15 × 10 ⁻⁴ [cal
/ Cm · sec · deg]. If it is smaller than this range, the thickness of the glass becomes small, making it difficult to manufacture. If it is larger than this range, the heat insulating effect becomes small. 4.5 × 10 ^{-4 to} 12 × 10 ^-4 [ca
l / cm · sec · deg], and more preferably 5 × 10 ⁻⁴ to 10 × 10 ⁻⁴ [cal / cm · sec · deg].
deg] is preferable.

The specific gravity is 1.2 to 2.0 [g / c
c]. If it is smaller than this range, the thickness of the glass becomes small, making it difficult to manufacture. If it is larger than this range, the weight increases and the handleability decreases. The range is more preferably from 1.2 to 1.8 [g / cc], and particularly preferably from 1.2 to 1.6 [g / cc].

Since the laminated glass of the present invention uses polyvinyl butyral as the adhesive layer, it can be easily manufactured by laminating under pressure at a temperature of 80 ° C. or more. For example, after laminating each layer, place it under reduced pressure, remove air between layers sufficiently, and bond by heating and pressing, or coat polyvinyl butyral diluted with a solvent on the glass surface in advance, dry and heat with polycarbonate. There is a method of pressing and bonding.

[0035]

Embodiments will be described in detail below with reference to embodiments. Further, in the examples, a planar laminated glass will be described for the purpose of clarifying the content of the present invention, but the present invention can be sufficiently applied to secondary and tertiary curved laminated glass. In the examples, the following layers were used as the layers constituting the present invention.

Glass: ordinary plate glass (unreinforced glass plate of soda-lime glass) Polyvinyl butyral A: Esrec film HI type manufactured by Sekisui Chemical Co., Ltd. Polyvinyl butyral B: 100% by weight of polyvinyl butyral resin (butyralization degree: 65 mol%) parts, ester plasticizer _{(C 4 H 9 O- (C} 2 H 4 O) 2 -COC 4 H
_{8 CO- (OC 2 H 4)} 2 -OC 4 H 9) 40 parts by weight,
UV absorber (2- (2'-hydroxy-3'-lauryl-5'-methylphenyl) benzotriazole) 14
Parts by weight kneading at 85 ° C. for 5 minutes using a biaxial kneader,
Then, a sheet polycarbonate obtained by press molding under the conditions of 110 ° C. and 150 kg / cm ² : a polycarbonate produced from diphenyl carbonate and 2,2-bis (4-hydroxyphenyl) propane by the method of JP-A-3-68627. (Weight average molecular weight = 28,000, 43,000, 5
6,000, 62,000 and 75,000) melt extruded sheets

Examples 1, 2, 3 and Comparative Example 1 1.1 mm thick glass plate, 0.38 mm thick polyvinyl butyral A sheet, 5 mm thick polycarbonate sheet (weight average molecular weight = 28,000, 43,000, 5
(6,000 and 75,000) Glass / polyvinyl butyral / polycarbonate / polyvinyl butyral / glass are stacked in this order, the whole is put in a vacuum pack bag, the inside of the vacuum pack bag is evacuated, and then the vacuum pack is sealed. Sandwiched between a Teflon plate and an iron plate, pressure 10 kg / cm ² ,
It was pressed at 120 ° C. for about 20 minutes and bonded. It was taken out of the press as it was and cooled slowly to obtain a laminated glass. Table 1 shows the results of the evaluation. The ball drop test is based on JIS
R3205, specific gravity is ASTM D792, thermal conductivity is AS
The measurement was performed according to the method described in TM C177.

Example 4 A 1 mm-thick glass plate, a 0.38 mm-thick polyvinyl butyral B sheet, and a 5 mm-thick polycarbonate sheet (weight average molecular weight = 56,000) were overlapped and bonded in the same manner as in Example 1. The laminated glass of the present invention was obtained.
Table 1 shows the evaluation results. The weather resistance was measured using a sunshine weather meter (xenon light source, 63 ° C. × 0.55 W).
/ M ² ) for 600 hours.

Example 5 As a polycarbonate sheet, 2 as an ultraviolet absorber
-(2'-hydroxy-5'-t-octylphenyl)
A laminated glass of the present invention was obtained in the same manner as in Example 1, except that a polycarbonate sheet containing 0.3% by weight of benzotriazole and having a weight average molecular weight of 56,000 was used. Table 1 shows the evaluation results.

Comparative Examples 2, 3 Plain glass (6 mm thickness = Comparative Example 2) and 2.5 m
A laminated glass (Comparative Example 3) in which a glass plate having a thickness of m and a polyvinyl butyral A sheet having a thickness of 0.38 mm and a glass plate having a thickness of 2.5 mm were bonded by the method shown in Example 1 was evaluated.
Table 1 shows the results.

Example 6 A glass plate having a thickness of 0.5 mm and a weight average molecular weight of 62,000
A laminated glass of the present invention was obtained in the same manner as in Example 1 except that the polycarbonate sheet was used. Table 1 shows the evaluation results.

Example 7 0.5 mm thick glass plate, 0.8 mm thick polyvinyl butyral A sheet, 10 mm thick, weight average molecular weight 6
2,000 polycarbonate sheets were adhered in the same manner as in Example 1 to obtain a laminated glass of the present invention. Table 1 shows the evaluation results.

[0043]

As described above, as shown in the examples, the laminated glass of the present invention is transparent, excellent in impact resistance, excellent in scattering resistance of glass, and excellent in measuring and heat insulating properties, safe glass, energy saving. Great evaluation as glass. Therefore, it can be suitably used as a window glass of a building, a show window or a door, particularly a glass of a high-rise building having a large glass area, or a glass for vehicles such as automobiles, buses, trucks, and railways. Furthermore, it can be suitably used as safety glass used for window glasses and doors of schools, gymnasiums, hospitals, and the like.

[0044]

[Table 1]

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-251448 (JP, A) JP-A-56-28421 (JP, U) JP-B-46-35156 (JP, B1) (58) Field (Int.Cl. ⁷ , DB name) B32B 1/00-35/00 C03C 27/12

Claims (1)

(57) [Claims] 1. A laminated glass having at least a five-layer structure consisting essentially of glass / polyvinyl butyral / polycarbonate / polyvinyl butyral / glass, wherein the polycarbonate of the intermediate layer is a polycarbonate having a weight average molecular weight of 35,000 or more ; And said
The specific gravity of the laminated glass is 1.2 to 1.6 (g / cc), heat
Conductivity of 4.5 × 10 ^{-4 to} 12 × 10 ^-4 (cal / cm
Thermal insulation, characterized in that in the range of · sec · deg)
Sex laminated glass.