JPS608059A - Laminated glass - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a laminated glass in which an inorganic glass plate and an organic glass plate are laminated with a novel thermoplastic polyurethane interlayer interposed therebetween.

In recent years, there has been an increase in the danger to humans caused by broken window glass in car accidents, etc., as well as from broken window glass in high-rise buildings during earthquakes, gas explosions, bombings, etc. There is a strong desire for highly safe glass that is resistant to breaking even in such accidents. on the other hand,
Recently, organic glasses (acrylic resin plates and polycarbonate plates) have been used in some applications to reduce the weight of automobiles, vehicles, etc., and as the above-mentioned hard-to-break glass. However, these organic glasses have a major drawback in that their surfaces are easily scratched (inferior surface hardness) compared to inorganic glasses.

Therefore, a combination of inorganic glass and organic glass (laminate)
The idea is to leverage each other's strengths and compensate for each other's weaknesses, but it is still at the development stage, and of course has not yet been put into practical use. One of the major technical reasons that makes this practical application difficult is that an interlayer film that can absorb the difference in thermal expansion coefficient between two completely different materials, inorganic and organic materials, has not been developed. There is a problem.

An object of the present invention is to provide a laminated glass that is hardly cracked or peeled off at the interface between the interlayer film and the inorganic or organic glass, not only at room temperature but also at extremely low temperatures. A laminated glass characterized by being laminated with a plastic polyurethane interlayer interposed therebetween.

The inorganic glass used in the present invention is Na2O-CaO-
It is a general term for glass that has an inorganic composition such as 5i02 series and is used for windshield glass of vehicles such as automobiles, aircraft, etc., or window glass of buildings. Examples of such glass include ordinary plate glass, polished plate glass, float glass, tempered glass, colored glass, heat-absorbing glass, wired glass, and the like. The thickness of these glass plates is not particularly limited, but if it is too thin, it will easily break during transportation or other handling, and if it is too thick, weight reduction will not be achieved, so it is usually 0.5 to 10%, preferably 1 to 5%. .

On the other hand, organic glass refers to plate-like materials with good transparency, a certain degree of rigidity, and an organic composition with good impact strength, such as polycarbonate resin and acrylic resin, and vinyl chloride resin and styrene resin. This also includes the following. Among these, the polycarbonate resin used is a general polymer compound produced by a reaction between a dihydroxy compound such as bisphenol A and phosgene, or a transesterification reaction between a dihydroxy compound and a carbonic acid diester. This may also be a copolymer with other reactive monomers.

Acrylic resin generally refers to addition polymers of methacrylic esters, such as polymethyl methacrylate (P
MMA) is most preferably used. It may also be a copolymer with other polymerizable monomers. Further, these organic glasses may contain stabilizers, colorants, ultraviolet absorbers, and other additives. The thickness of organic glass should be 0.1 to 10% because if it is too thin, it will increase and easily cause various deformations and cracks during handling, and if it is too thick, the shrinkage stress at low temperatures will be large and cause the inorganic glass to break. It is preferable that

In the present invention, the above (1) and (2) regarding the elastic modulus are
) A thermoplastic polyurethane that satisfies the following conditions is used as the interlayer film.

The tensile modulus of polycrethane at low temperatures largely depends on the composition and molecular weight of the polyol used as the raw material, the chain extender, the type of isocyanate, etc.

=5= Among the polyols used in the production of the thermoplastic polycrethane, preferred examples of polyester polyols include dibasic acids having 4 or more carbon atoms, preferably 6 or more carbon atoms, such as adipic acid and sepacanoic acid, and hexanediol. Branched diols such as 6 or more carbon atoms such as 1.27' propylene glycol neopentyl glycol, or diol condensates having an ether bond such as diethylene glycol and dipropylene glycol with a number average molecular weight of 100 or more can be mentioned. These dibasic acids and diols may be used in appropriate combinations.

For example, polyester polyols prepared by reacting adipic acid or sebacic acid with two types of diols are preferably used.

For polyol vita, polyester polyol,
Number average molecule! Preferred examples include polyoxy-1,2-propylene glycol having a molecular weight of 1,500 or more and polyoxytetramethylene glycol having a number average molecular weight of 2,000 or more.

6- As a chain extender, a diol having 6 or more carbon atoms such as hexanediol, or a branched diol such as 1,2 propylene glycol or neopentyl glycol.

Diols having an ether bond such as diethylene glycol and diethylene glycol, and alicyclic diols such as nocrohexyl diol are preferably used.

Further preferred examples of isocyanates include ethylene diiso7anate, hexamethylene diino7anate, 1-
Isonoanato 3-isocyanatomethyl-3,3,5-
Examples include aliphatic iso/anates such as trimethyl/chlorohexane (manufactured by Huls, product name Inholo/diisonoanate) 9 and the like.

To produce the thermoplastic polycrethane used in the present invention, an excess cap of the diisonoanate is reacted with the diol to form the corresponding prepolymer containing terminal iso/anate groups, and these prepolymers are subsequently chained with a chain extender. It is preferable to extend it.

For example, for 1 mole of the above diol, 2 diiso/anate
．． 0 to 2.10 mol is added, and the reaction temperature is maintained at 80 to 140° C. for 10 hours or more while stirring in the absence of a catalyst to obtain an incyanate prepolymer.

Diptyltin laurate as a catalyst is added to this prepolymer in an amount of 0.01 to 0.05% by weight based on the prepolymer, and a chain extender is added at 1 mol per 1 mol of the prepolymer.
Raise the temperature to 55°C and stir until uniformly mixed. As soon as the temperature inside the reaction system rises to 65°C due to reaction heat, stirring is stopped and the mixture is poured into a container. The urethane polymer obtained in this way was heated in an open oven at 60 to 160°C for 20 to 30 minutes.
The reaction was completed by heating for 100 hours.

The thickness of such a thermoplastic polyurethane interlayer film is not particularly limited, but if it is too thin, it will be difficult to uniformly laminate it with inorganic glass and organic glass.
It is estimated to be 1.03 to 2%.

In order to bond the above-mentioned inorganic glass and organic glass via a polyurethane interlayer, the interlayer is inserted between the former two and heated in an autoclave at a temperature below 110°C, preferably below 110°C.

The laminated glass of the present invention has the above-mentioned configuration example, and since inorganic glass and organic glass are laminated via a thermoplastic polyurethane interlayer that satisfies the conditions (1) and (2) above regarding the elastic modulus, it can be used at low temperatures. The interlayer film absorbs and alleviates the strain stress of the organic glass that occurs in the low temperature range due to the difference in thermal expansion coefficient between the inorganic glass and the organic glass in the low temperature range. There is almost no possibility of peeling at the interface with inorganic glass or organic glass.

Further, the laminated glass of the present invention has the advantage of being safe due to its excellent impact strength, being lightweight and having excellent transparency.

Examples of the present invention are shown below.

Parts simply refer to parts by weight.

9- The physical properties of the interlayer film etc. were determined by the following method.

(1) Tensile elastic modulus Measured at a frequency of 1 OHZ using a viscoelasticity spectrometer.

(2) Cooling and heating cycle test A After leaving the laminated glass in an atmosphere of 60°C for 3 hours, it was cooled to -20°C at a constant temperature gradient for 2 hours.
The test was carried out for 10 cycles by holding the temperature at 0°C for 3 hours and increasing the temperature to 60°C over a period of 2 hours at a constant temperature gradient.

(3) Cooling and heating cycle test B After leaving the laminated glass in an atmosphere of 80°C for 3 hours, it was cooled to -40°C at a constant temperature gradient for 3 hours.
The test was carried out for 10 cycles by holding the sample at ℃ for 3 hours and increasing the temperature to 80 ℃ over 3 hours at a constant temperature gradient.

Example 1 Productivity: 10- A layered glass was obtained.

1-Isonoanato-3-inkanatomethin, -3
,3,5-to! 100 parts of polyethylene/butylene (50150) adipate glycol (manufactured by Nippon Polyurethane Co., Ltd., product name Niraporan 4042) was added to 22.2 parts of J methylcyclohexane (manufactured by Hüls Co., Ltd., product name: isophorone cyclohexanate) as a polyester glycol. Stir dropwise at 100'C for 14 hours after dropping.
A prepolymer was synthesized by a time reaction. Next, the reaction system is
While maintaining the temperature at 5° C., 5.0 parts of neopentyl glycol was added to the previously synthesized prepolymer with stirring. The reaction mixture was poured into molds.

The resin heated at 100° C. for 2 days was pressed into a 0.76% thick film. The tensile modulus of this membrane was as shown in FIG. This film was sandwiched between a 300 x 300 x 2.5% inorganic glass plate and a 300 x 300 x 2% polycarbonate plate (Mitsubishi Gas Chemical Exhibition, #! Product name: Kneepilon) and placed in an autoclave at 120°C x 13 atm x 1 hour. Laminated glass was obtained by laminating and bonding. Cold/heat cyclic test A,
The results of B were consistent with Table 1.

Example 2 Polyester glycol in Example 1.

Niraporan 40420 series also contains polypropylene/neobethylene (so/) which is a polyester glycol.
s O) An interlayer film having a thickness of 0.76% was obtained in the same manner as in Example 1 except that adipate glycol (manufactured by Nippon Polyurethane Co., Ltd., Mn: 2000) was used. The elastic modulus was as shown in Table 1. This film is 300 x 300 x
2.5 bait inorganic glass plate and 300 x 300 x
2 txm between polycarbonate plates at 120℃
Lamination and adhesion were carried out in an autoclave at 13 atmospheres for 1 hour.

The results of the repeated heating and cooling test are shown in Table 1.

Example 3 A laminated glass was obtained using polyether polyurethane.

11.1 parts of isophorontsquanate and hydrogenated xylene diiso/anate (manufactured by Shikinichi Yakuhin Co., Ltd.).

100 parts of polyoxytetramethylene glycol having a number average molecular weight of 2000 was added dropwise to 9.7 parts of the mixed liquid (product name: Takenate 600K) and stirred at 100°C. After finishing dropping 1
The mixture was stirred at 00°C for 4 hours to synthesize a prepolymer.

Next, 8 parts of the dipropylene glycol isomer mixture were added to the previously synthesized prepolymer with stirring, and the reaction mixture was cast into a mold and pressurized at 100° C. for 2 days.

The resulting resin was pressed into a 0.76 m thick film.

This interlayer film was sandwiched between a 300 x 300 x 2.5 m inorganic glass plate and a 300 x 300 x 2 m polycarbonate plate, and laminated and bonded in an autoclave at 120°C x 13 atm x 1 hour at atmospheric pressure.

Each physical property value was as shown in Table 1.

Example 4 Everything was as in Example 3 except that polypropylene glycol (number average molecular t1500) was used as the polyether diol instead of polyoxy/tetraethylene glycol in Example 3. 13- Intermediate film and laminated glass were treated in the same manner as in Example 3. Obtained.

Example 5 In Example I, the thickness of the inorganic glass plate was set to 2.5 to 0.3.
A laminated glass was obtained in exactly the same manner except that the percentage was changed.

Each physical property was as shown in Table 1.

Example 6 A laminated glass was obtained in exactly the same manner as in Example 1 except that the thickness of the interlayer film was 0.76 m for three glasses.

Each physical property was as shown in Table 1.

Example 7 A laminated glass was obtained in exactly the same manner as in Example 11c except that the thickness of the polycarbonate g2.0 fin was changed to 16%.

Each physical property was as shown in Table 1.

14- Table 1 Comparative Example 1 262 parts of the 4.4'-1f renbis(cyclohexyliso7anate) isomer mixture contains -142,000 number average molecules.
100 parts of polyester glycol (polybutanediol-adipate glycol, manufactured by Nippon Polyurethane Co., Ltd., trade name Nipporan 4010) was added dropwise and stirred at 100°C, and after the addition was completed, the reaction was carried out at 100°C for 14 hours to synthesize a prepolymer. The reaction system was kept at 55°C and then 4.5 parts of 1.4
- 0.76% of the prepolybutanediol synthesized first
It was applied to a film with a thickness of am. This interlayer film was heated at 300
300X 2.5 fin glass plate and 300X300X
Sandwiched between 2+W polycarbonate plates at 120℃ x 13
Lamination and adhesion were carried out in an autoclave under atmospheric pressure for 1 hour.

Each physical property value was as shown in Table 2.

Comparative Example 2 Tuborane N was added to the polyester glycol in Comparative Example 1.
4010), a polyester polyol (Nippon Boliu Vtan N406) which is also a polyester glycol but is a condensate of ethylene glycol and adipic acid.
An interlayer film having a thickness of 0.76 m was obtained in the same manner as in Comparative Example 1, except that a material having a number average molecular weight of 2,000 was used. This interlayer film was sandwiched between a 300 x 30' OX 2.5 fl glass plate and a 300 x 300 x 2% polycarbonate plate, and bonded in one layer under pressure at 120°C x 13 atm x 1 hour.

Nitsuboin 4009 (number average molecule 'IIL
An interlayer film was synthesized by carrying out the same experiment as in Comparative Example 1, except that IOOO, a condensate of adipic acid and ethylene glycol) was used. Each physical property was as shown in Table 2.

17- Table 2 *E represents tensile modulus (dyne/c+d) 1-1
Patent applicant Sekisui Chemical Co., Ltd. Representative Mototoshi Fujinuma-18=

Claims (1)

[Claims] 1. The inorganic glass and the organic glass have (1) a tensile modulus of elasticity at -40°C of 1 x 10 to 5 x 109 dyne;
/d, and (2) the tensile modulus at 0°C is I×1
1. A laminated glass characterized by being laminated with a thermoplastic polyurethane interlayer having a density of 0 to 5 x 10 dyne/m interposed therebetween. 2. The laminated glass according to item 1, wherein the thermoplastic polyurethane interlayer is a thermoplastic polyester poly9 urethane interlayer. 3. The laminated glass according to item 1 or 2, wherein the organic glass is an acrylic resin or a polycarbonate resin. 4. The laminated glass according to any one of the first to third top sides, wherein the interlayer film has a thickness of 0.03 to 2%. 5. The laminated glass according to any one of the first to fourth top sides, wherein the organic glass has a thickness of 0.1 to 10%. 6. The laminated glass according to any one of the first to fifth top sides, wherein the inorganic glass has a thickness of 0.5 to 10%.