JP3255203B2 - Polycarbonate laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic polycarbonate (PC) / polyvinyl butyral (PVB) laminate structure, and more particularly, to a high quality PC / PVB / glass laminate without clouding or craze on the laminated PC. The present invention relates to a laminate such as a body or a glass / PVB / PC / PVB / glass laminate.

[0002]

2. Description of the Related Art Aromatic polycarbonate has impact resistance,
It is widely used as an engineering plastic having excellent transparency and dimensional stability. For example, it is well known that a PC sheet is used mainly in the field of glazing as one of its uses. Among them, in recent years, attempts have been made to use the PC sheet as an intermediate film in order to further improve the impact resistance of the laminated glass.

However, when a PC sheet is used as an intermediate film, there is a problem that cloudiness or craze occurs due to PVB used for an adhesive layer. Therefore, many studies have been made to obtain a laminated glass in which whitening of polycarbonate is prevented.

For example, there has been proposed a method of using a plasticizer having low opacity of polycarbonate as a plasticizer for polyvinyl butyral as an adhesive layer, including sulfonamide (Japanese Patent Publication No. 46-35156) and phosphate (USP).
JP-A-3406086), ethylene oxide adducts of monohydric alcohols (JP-A-59-111954),
Multiesters of higher unsaturated fatty acids (JP-A-60-64)
848) and propylene oxide oligomers (JP-B-63-33455). Also, a method of forming an intermediate layer between the adhesive layer and the polycarbonate layer to prevent clouding has been studied. For example, a thermosetting paint layer (Japanese Patent Application Laid-Open No. 53-1292) is used as the intermediate layer.
No. 0) or an acrylic resin layer (Japanese Utility Model Publication No. 62-18452).
Publication) is being studied.

[0005] However, the former has the problems that the plasticizer must be decomposed during the production of the PVB sheet, and that a special plasticizer must be used. There is a problem that the manufacturing process is complicated by the need for the layer.

Therefore, the inventors of the present invention have repeatedly conducted research focusing on the molecular weight of a PC sheet, which has not been neglected in the past, and as a result, have found that by using a PC sheet having a higher molecular weight than before, it is possible to prevent clouding and craze due to PVB. Filed in (JP-A-3-251448, JP-A-4-298
No. 44). However, even in the PC / PVB laminate produced by this method, when a PC sheet having a weight-average molecular weight of about 50,000 is used, there is a problem that slight turbidity occurs when used at a high temperature. Was revealed.

[0007]

As described above, a PC / PVB laminate which can be easily produced without using a special plasticizer and has no clouding or craze even after long-term use at a high temperature is still provided. It was not done, and its appearance was desired.

[0008] The inventors of the present invention used a general-purpose plasticizer for PVB. However, an ester-based plasticizer which could not be used due to clouding or craze when laminated with a conventional PC sheet was used.
As a plasticizer, as a result of intensive research to obtain a laminate that has achieved the above-mentioned object, surprisingly, when laminated with PVB plasticized with phthalic diesters and a PC sheet having a specific molecular weight or more. Only, it has been found that it is possible to provide a PC / PVB laminate which does not cause cloudiness or craze and does not cause cloudiness or craze even when used at a high temperature.
The present invention has been reached.

[0009]

That is, the present invention relates to an aromatic polycarbonate sheet having a weight average molecular weight of 35,000 or more , di-2-ethylhexyl phthalate,
Selected from octyl phthalate and diisononyl phthalate
And a polyvinyl butyral sheet plasticized by at least one plasticizer . The polycarbonate resin used in the present invention is a polycarbonate resin having a main chain composed of a repeating unit represented by the following general formula (1).

[0010]

Embedded image (In the formula, Ar is a divalent aromatic residue, for example, phenylene, naphthylene, biphenylene, pyridylene,
Examples include those represented by the following general formula (2). )

[0011]

Embedded image (Wherein, Ar ¹ and Ar ² are each an arylene group, for example, a group such as phenylene, naphthylene, biphenylene, pyridylene, and Y is a group represented by the following general formulas (3) to (3))
An alkylene group or a substituted alkylene group represented by (5). )

[0012]

Embedded image [Wherein R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group,
An aralkyl group, which may be optionally substituted with a halogen atom or an alkoxy group, k is an integer of 3 to 11, and a hydrogen atom of the general formula (4) is a lower alkyl group, an aryl group, a halogen, May be replaced by )〕Also,
A divalent aromatic residue represented by the general formula (6) may be contained as a copolymer component.

[0013]

Embedded image [Wherein, Ar ¹ and Ar ² are the same as those described above, and Z is a mere bond or —O—, —CO—, —S—, —SO _{2
-, - CO 2 -, -} CON (R 1) -, a divalent group such as (R ¹ is same as defined above). Examples of these divalent aromatic residues include those represented by the following general formulas (7) to (27).

[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 ₁
-C ₁₀ cycloalkyl or phenyl, m
And n is an integer of 1 to 4, and when m is 2 to 4, each R ⁵
May be the same or different, or when n is 2 to 4, each R ⁶ may be the same or different. Among them, one represented by the following general formula (28) is a preferable example.

[0017]

Embedded image

In particular, those containing 85 mol% or more of a repeating unit represented by the general formula (28) as Ar are preferable. The polycarbonate resin of the present invention may contain a trivalent or higher aromatic residue as a copolymer component.
Although the molecular structure of the polymer terminal is not particularly limited, one or more terminal groups selected from a hydroxyl group, an aryl carbonate group, and an alkyl carbonate group can be bonded. The aryl carbonate terminal group has the following general formula (29)

[0019]

Embedded image (In the formula, Ar ³ is a monovalent aromatic residue, and the aromatic ring may be substituted.) Specific examples thereof include, for example, general formulas (30) to (35)

[0020]

Embedded image And the like. The alkyl carbonate terminal group is represented by the following general formula (36)

[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, the following general formulas (37) to (39)

[0022]

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

The weight average molecular weight (Mw) of the aromatic polycarbonate used in the present invention must be 35,000 or more. If the weight average molecular weight is less than 35,000, whitening and craze occur during bonding with PVB and subsequent use, which is not preferable. The upper limit of the weight average molecular weight is not particularly limited, but may be about 30.
If it is larger than about 000, the melt viscosity becomes too high and the extrudability decreases. Preferably, it is in the range of 40,000 to 100,000, and more preferably in the range of 40,000 to 80,000. In particular, a weight average molecular weight in the range of 45,000 to 65,000 is 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 constitution curve of a standard monodisperse polystyrene using a reduced molecular weight calibration curve according to the following formula (1).

[0025]

[Number 1] ^{_{M PC = 0.3591M PS 1.0388 ...... (}} 1) (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 (JP-A-1-158033, JP-A-1-158033).
271426, 3-68627 and the like). Among them, the solid-phase polymerization method can easily produce a high-molecular-weight polycarbonate, and can obtain a polycarbonate substantially free of methylene chloride, a chlorine compound, and a sodium compound, and has properties such as heat resistance and color. Is preferred 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-based stabilizers described in JP-A-163160 and JP-A-3-163161 is preferably used.

The polyvinyl butyral (PVB) that constitutes the other part of the laminate of the present invention is not particularly limited.
Polyvinyl butyral of the following general formula (40) having a molar ratio of hydroxyl group (q): acetyl group (p): butyral group (o) in VB of about 10 to 50: 1 to 5:40 to 85 can be preferably used. .

[0029]

Embedded image

The degree of polymerization is not particularly limited as long as it can maintain the performance as an intermediate film. PV
B may contain a heat stabilizer, an ultraviolet absorber, a coloring agent, an anti-stick agent, an antistatic agent, an anti-fogging agent, a flame retardant, a fluorescent agent and the like.

As the plasticizer for PVB used in the laminate of the present invention, phthalic acid diesters are particularly preferred.
Di-2-ethylhexyl phthalate, dioctyl phthalate
It is essential to use a plasticizer selected from the group consisting of a salt and diisononyl phthalate . Only by using the plasticizer, the laminate without whitening of the present invention is completed.

The mixing ratio of the plasticizer to PVB is not particularly limited, but is usually in the range of 10 to 70% by weight, and particularly preferably in the range of 20 to 60% by weight. In the present invention, the above plasticizer is used as a main plasticizer, and a small amount of other plasticizers within a range that does not cause whitening or craze of PC,
For example, a plasticizer such as a phosphate ester type, a fatty acid ester type, or a glycol derivative type can be used in combination.

The laminate of the present invention basically comprises a P sheet containing the above PC sheet and the above aliphatic phthalic acid diester as a plasticizer.
Any laminate comprising two layers of VB sheets and including this laminate structure is included in the present invention. Such examples include:
For example, PC / PVB / PC, PC / PVB / glass,
Hard coat layer / PC / PVB / glass, glass / PV
Laminated materials such as B / PC / PVB / glass, PC / PVB / other resins, etc., and are used for window glasses and show windows of buildings requiring high impact resistance, window glasses of vehicles and aircraft, railways and roads, etc. It can be widely used for transparent sound insulation boards and the like. In particular, since the (hard coat layer) / PC / PVB / glass laminate is a PC having one side more flexible than glass, it is particularly safe in the event of a collision, such as a window glass for a vehicle or a window glass of a public institution such as a gymnasium. It is highly useful as a safety glass that emphasizes surface. In addition, glass / PVB / PC / PVB / glass laminate is
It has higher utility value than conventional laminated glass as a glass requiring more impact resistance and security. Further, the thickness of each layer in the laminate of the present invention, the overall thickness of the laminate, and the like are not particularly limited.

The laminate of the present invention has about 8
It can be easily manufactured by laminating each layer under pressure at a temperature of 0 ° C. or higher. For example, after laminating each layer in the form of a sheet, place it under reduced pressure to remove air between the layers sufficiently, then bond by heating and pressing, or coat PVB previously diluted with a solvent on the surface of glass etc. and dry Later PC
There is a method of applying heat and pressure to the sheet and bonding it together. Also,
It can also be manufactured by a method in which PVB diluted with a solvent that does not attack PC (for example, isopropyl alcohol or the like) is coated on a PC sheet and dried.

[0035]

EXAMPLES The present invention will be described below in detail with reference to Examples, but it should not be construed that the invention is limited thereto.

Examples 1 to 5, Comparative Example 1 The o: p: q ratio in the PVB of the general formula (40) was 6
5: 2: 33 100 parts by weight of PVB and plasticizer di-
40 parts by weight of 2-ethylhexyl phthalate (DOP) was kneaded at 70 ° C. for 5 minutes using a mixing roll, and then press-molded at 110 ° C. and 150 kg / cm ² for 5 minutes to form a 100 × 100 × 0.5 mm. A PVB sheet was obtained.

On the other hand, diphenyl carbonate and 2,2-
Polycarbonate produced from bis (4-hydroxyphenyl) propane by the method of JP-A-3-68627 (weight average molecular weight = 28,000, 43,00)
0, 56,000, 62,000, 75,000
0, 98,000) and melt extrusion using 100 ×
A 100 × 1 mm PC sheet was obtained.

These sheets are stacked in the order of PC / PVB / PC, the whole is put in a vacuum bag, the inside of the vacuum bag is evacuated, and the vacuum bag is sealed. Then
The entire vacuum bag is sandwiched between a Teflon plate and an iron plate, with a pressure of 10 kg.
The laminate was pressed by pressing at 120 ° C./cm ² for about 20 minutes to obtain a laminate. Table 1 shows the appearance evaluation of the obtained laminate.

Comparative Examples 2 and 3 A PVB sheet was obtained in the same manner as in Example 1, except that 40 parts by weight of triethylene glycol di-2-ethylbutyrate (3GH) was used as a plasticizer. Next, a laminate was obtained in the same manner as in Example 1, except that the PC sheets used had the weight average molecular weights of 43,000 and 62,000 of Example 1. Table 1 shows the appearance evaluation of the obtained laminate.
Shown in

Examples 6, 7, 8 Di-n-octyl phthalate (DNO
P), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) and a weight average molecular weight of 6
A laminate was obtained in the same manner as in Example 1 except that 2,000 PC sheets were used. Table 1 shows the appearance evaluation of the obtained laminate.
Shown in

Examples 9 and 10 The PVB sheet prepared in Example 1 and a weight average molecular weight of 6
A PC / PVB / glass laminate and a glass / PVB / PC / PVB / glass laminate were produced in the same manner as in Example 1 using 2,000 PC sheets and 2.6 mm-thick plate glass. The obtained laminate was transparent, and no change was observed in the heat resistance test (50 ° C. × 100 hours).

[0042]

[Table 1]

[0043]

As described above, as shown in the examples, the laminate of the present invention does not cause white turbidity or craze during lamination or when used at high temperatures. Therefore, it can be suitably used for various laminates having the laminate of the present invention as a basic structure. For example, a laminated body with glass is transparent, excellent in impact resistance, excellent in scattering resistance of glass, lightweight, and excellent in heat insulation, and has great value as safety glass and energy saving glass. Therefore, it can be suitably used as window glass for buildings, show windows and doors, particularly glass for high-rise buildings having a large glass area, and as 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.

Claims (1)

(57) [Claims] 1. An aromatic polycarbonate sheet having a weight average molecular weight of 35,000 or more, and di-2-ethylhexyl
Ruphthalate, dioctyl phthalate, diisononyl phthalate
A laminate comprising a two-layer structure consisting of a polyvinyl butyral sheet plasticized with at least one plasticizer selected from tarates .