JPS6096551A - Sandwich glass - Google Patents

Abstract

PURPOSE:To manufacture a sandwich glass having high impact resitance and excellent transparency, by laminating an inorganic glass plate with an inorganic or organic glass plate interposing a specific thermoplastic polyurethane interlayer therebetween. CONSTITUTION:An inorganic glass plate is laminated with an inorganic or organic glass plate using thermoplastic polyurethane interlayer produced by reacting (A) 1.0mol of a polymeric diol having a number-average mol.wt. of 800-5,000 with (B) 0.5-3.0mol of a low molecular diol containing >=10wt% alicyclic diol or heterocyclic spiro diol and (C) and alicyclic diisocyanate or an aliphatic diisocyanate. The molar amount of the component C is selected to be equal to the sum of the componets A and B. The heterocyclic spiro diol is preferably 3,9-bis(1,1-bismethyl-2-oxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a laminated glass using thermoplastic polyflex as an interlayer film.

Conventionally, it has been known to use thermoplastic polyurethane obtained from the reaction pressure of diol and diisocyanate, for example, as a media membrane for laminated glass that reduces the scattering of glass fragments and prevents the penetration of impact objects when subjected to impact. It is being However, polyurethanes obtained using aromatic isocyanates tend to become colored over time, and polyurethanes obtained using aliphatic diols tend to have poor impact energy absorption, and furthermore, both become white and opaque at low temperatures. The major drawback was that it was easy to become

The present invention was made with the aim of providing a laminated glass that uses a polyflex interlayer film and has high impact resistance and good transparency, especially transparency at low temperatures. (2) Low molecular weight diols Q5 to Kame O containing 10% by weight or more of alicyclic diol or heterocyclic Spi U type diol per 10 moles of high molecular weight diol having a number average molecular weight of 800 to 5000.
mol, and (3) via a thermoplastic polyurethane interlayer obtained by reacting an alicyclic diisocyanate or an aliphatic diisocyanate in an amount substantially equal to the total number of moles of the high molecular weight diol and the low molecular weight diol. , a transparent laminated glass characterized by being formed by laminating an inorganic glass and an inorganic glass or an organic glass.

As the high molecular weight diol for obtaining the above-mentioned polyurethane, polyether diol and polyester diol are preferably used, but it is necessary that the number average molecular weight is 1j800 to 5000.

This is because if the molecular weight is too large, the transparency of the polyurethane obtained tends to decrease, and if the molecular weight is too small, the elasticity of the polyurethane obtained tends to decrease.

Specific examples of polyether diols include polyoxytetramethylene glycol, polyoxy-1,2-propylene glycol, and oxy-1,2-propylene glycol/oxy-1,2-propylene glycol copolymer. Specific examples of polyester diols include dibasic acids such as adipic acid, succinic acid, and sebacic acid, ethylene glycol, 1.2 propanediol, 1.310 panediol, 1.4 butane diol, and l.
.

Obtained by ring-opening condensation of caprolactone or polycondensation reaction products with aliphatic alcohols such as 6-hexanediol and neopentyl alcohol, or alicyclic alcohols such as 1.4-cyclohexane dimetatool and 1,4-cyclohexanediol. Examples include polycaprodictone diol.

Next, as the paper molecular weight diol, in addition to alicyclic diols and heterocyclic spiro diols, for example, aliphatic diols can also be used. Proportion of the formula spiro diol 1jl
0% by weight or more, preferably 30 to 100% by weight. By adjusting the content of alicyclic diol or heterocyclic spiro diol in the low molecular weight diol to the above ratio,
The resulting polyurethane has increased impact energy absorption and maintains the same transparency even at low temperatures as at room temperature, improving the impact resistance of the laminated glass of the present invention and maintaining good transparency at low temperatures. It is estimated that

If the amount of the low molecular weight diol is too large relative to the high molecular weight diol, the transparency of the obtained polyurethane at low temperatures tends to decrease, and if the amount is too small, the mechanical strength tends to decrease. /LO mole, a low molecular weight diol (15 to 0 moles is used. From this condition and the amount of diincyanate used, which will be described later), the NCO proportion in the total amount of diols and diincyanate
The amount will normally be kept in the range 3-12% by weight.

Among specific examples of low molecular weight diols, aliphatic diols include ethylene glycol, 1,4-butanediol, 1.2
Pro/propanediol, 1.3 propanediol, 1.6
Examples of the alicyclic diol include hexanediol and neopentyl glycol. Examples of the alicyclic diol include 1.4 cyclohexane diol, 1.4 cyclohexane dimetatool, i13 cyclohexane diol, and the use of alicyclic spiro diol. It is possible. Further, as the heterocyclic spiro diol, those having oxygen as a hetero δζ atom are often used, and diols represented by the general formula (where Rt1 represents a hydrocarbon group having 1 to 6 carbon atoms, particularly an alkylene group) are preferably used, especially 3゜9-bis(l,1-bismethyl-2-oxyethyl)-2,4
, 8,10-tetraoxaspiro[5,5]kundecane is preferred.

The molecular weight of these low molecular weight diols is not particularly limited, but is generally 500 or less.

As the diisocyanate used in the production of polyclecne described in K 11Q, l-insyanate-3,3,5
-Trimethyl-5-incyanate methylcyclohexane (manufactured by Hulles, product name Inphorone diisocyanate), l-methyl-2,4-diisocyanate cyclohexane (also known as water #*2,.4 tolylene diisocyanate), 1-methyl -2,6-diisocyanatecyclohexane (hydrogenated 2.6-tolylene diisocyanate)),
Alicyclic diisocyanates such as Is'-diisocyanate methylcyclohexane (hydrogenated xylylene diinocyanate) are particularly preferred because of their good weather resistance, and ethylene diisocyanate, butylene diisocyanate, hexamethylene diinocyanate, and dodecamethylene Aliphatic isocyanates such as diisocyanates may be used.

The thermoplastic polyclecne used in the present invention is obtained by reacting the diisocyanate in an amount substantially equal to the total number of moles of the high molecular weight diol and the low molecular weight diol with the diol. Generally, the amount of the diisocyanate is added in excess of the amount of the diol. Specifically, known methods such as a one-shot method, a half-prepolymer method, and a full-prepolymer method are employed. For example, in the one-shot process, a high molecular weight diol, low molecular weight diol, and incyanate are mixed together and reacted simultaneously; in the all-prepolymer process, incyanate is reacted with a high molecular weight diol to form terminal isocyanate groups. These prepolymers are then reacted with low molecular weight diols. At this time, a catalyst such as an organic tin compound may be used if necessary.

In order to obtain the polyflex interlayer film used in the present invention,
Continuously introduce each of the above raw materials and prepolymers into the extruder,
The polyurethane obtained by the Funshicott, semi- or full prepolymer method may be continuously extruded into a film, or the polyurethane obtained in a separate reactor may be heated and pressurized using a press.

The obtained interlayer film is preferably embossed to prevent blocking.

The laminated glass of the present invention is formed by laminating inorganic glasses or an inorganic glass and an organic glass with the above-mentioned thermoplastic polyurethane interlayer interposed therebetween.

Here, 1 inorganic glass is Na20-CaO-8iO.

It is a general term for glass that has an inorganic composition such as, and is used for windshield glass of vehicles such as automobiles, aircraft, etc., or window glass of buildings, etc. Examples of such materials include plain glass, polished glass, float glass, tempered glass, colored glass, heat-absorbing glass, wired glass, and the like.

On the other hand, organic glass refers to plate-like materials such as polycarbonate resin and acrylic resin, which have good transparency, a certain degree of rigidity, and a fine organic composition with good impact strength. This also includes the following. Among these, as the polycarbonate tree 1Pri, a polymer compound generally 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 is used. This may also be a copolymer with other reactive monomers.

Acrylic resin is generally added polymer III of meccrylic acid ester, 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.

A thermoplastic polyclecne obtained by reacting a similar molecular weight diol o, 5 to &0 mol containing a specific amount of an all-or-heteroheterohetero-spiro-thread diol, and the alicyclic diincyanate or aliphatic isocyanate of (3) above. is used as a medium-sized film, so it has great impact resistance, transparency,
Particularly good transparency at low source.

Examples of the present invention are shown below.

Parts simply refer to parts by weight.

Incidentally, the impact resistance, etc. of the laminated glass was measured by the following method.

Impact resistance (falling ball height) B8-thick polyflex medium FIRWl with a thickness of 25 m
, Two inorganic glass plates of 30a +
The laminated glass a was obtained by heating and pressurizing for 5 minutes. After storing this laminated glass at the specified temperature for more than 8 hours, the outer frame becomes 31a+
X31g, inner frame is 26 asi X 26 (III,
Place it horizontally on a mass-shaped iron frame with a height of 20 cm and λ268
A Q (5 bond) steel ball was dropped from a specified height onto the center of the laminated glass.

The height at which the φ ratio at which the steel ball penetrates the laminated glass a is 50% is expressed in m.

Also, instead of the inorganic glass plate of the laminated glass 1, a thickness of 15
Laminated glass b obtained using polycarbonate plate m
Measurements were also made in the same manner.

Transparency above combination of txa,b(30csX30aI&)-
Stored in an atmosphere at 40°C for 30 days and visually inspected the IJ.
The I character was determined.

A is the same as the translucency at room temperature, B1 is partially translucent (cloudy), and B1 is partially white (
The one in which the entire surface of C1 became white was designated as D.

This test serves as a guideline for determining the usability of laminated glass in winter.

Example 1 100 parts of a polyester diol (number average molecular weight 19615, manufactured by Nippon Polyurethane Co., Ltd., Nilaboran 4070) obtained by reacting adipic acid, 1.6 hexene diol and neopentyl glycol (equal moles of the latter two) was added. 2:&3 parts of inphorone diisocyanate and 04 parts of diptyltin crater were added and mixed and stirred. Further [3゜9-bis(1,l-bismethyA/-2-oxyethyl)-2
Add 84 parts of 14-butanedio-sy to 456 parts of 4,8,10-tetoquaxaspiro(5,5) kundacan (hereinafter referred to as spirodiol) and dissolve it uniformly. Add the solution to the above mixture and stir thoroughly. A polyurethane resin was obtained by reacting at 80° C. for 100 hours. Note that the ratio of each raw material used was 1 mole of low molecular weight diol per 1 mole of polyester diol, and equivalent moles of incyanate were reacted with a total of 2 moles of these.

The obtained polyurethane resin was heated at 100℃2 by heat pressing.
It was molded under 0 atmospheric pressure conditions, and the film was adjusted to a thickness of L8sm.

This film is sandwiched between two pieces of float glass or one piece of 70-glass and a polycarbonate plate to form a laminated glass a.
, b were obtained, and the impact resistance and transparency of each were measured. The results were as shown in Table 1.

Example 2 Polyurethane was obtained in the same manner as in Example 1 except that 5.91 parts of 1,4 cyclohexane dimetatool was used instead of 1.4 butanediol and 84 parts in Example 1, and laminated glass a, I got b.

These physical properties were as shown in Table 1.

Example 3 Inphorone diisocyanate in Example 1) 23.
Polyurethane was obtained by pressing in the same manner as in Example 1, except that 20.3 parts of 1,4-diincyanate methylcyclohexane was used instead of 3 parts, and a laminated glass was obtained.

Their physical properties are shown in Table 1.

A polyurethane was obtained and a laminated glass was obtained in the same manner as in Example 1 except that 7.34 parts of Kl and 4-cyclohegysan dimethanol were used instead of 3.84 parts of 1.4 pukundiol.

ξTheir physical properties #f#i were as shown in Table 1.

Example 5 A polyurethane was obtained and a laminated glass was obtained in the same manner as in Example 1 except that 79.0 parts of polyoxytetramethylene glycol having a number average molecular weight of 1550 was used in place of Nilaborane 4070.

Their physical properties are shown in Table 1.

Example 6 A polyester diol obtained by reacting adipic acid with II6 hexanediol and 1°4 butanediol (ODX2103, Dainippon Ink Chemical, number average molecular weight 2
956) 1.4 cyclohexanedimethanol-1 was added to 100 parts, 9.74 ff1 (twice the mole of polyester diol), and 2 parts of inphorone diincyanate was added. Polyurethane was obtained in the same manner, and laminated glass was obtained.

These physical properties were as shown in Table 1 of Todosha.

Example 7 To 100 parts of polyester diol obtained by reacting adipic acid and 1.4 gutanediol (manufactured by Nippon Polyflexen Co., Ltd., Niboran 4060, number average molecular weight 1955),
1 & 2 parts of an isomer mixture of l-methyl-2,6-diisocyanate cyclohexane and 1-methyl-2,4-diisocyanate cyclohexane were added as incyanate, and 0.04 part of diptyltin acetate was added as a catalyst, and 3 parts were heated at 80°C. A prepolymer was synthesized by performing a time-varying reaction. To 100 parts of this prepolymer were added 2 parts of 1.4 cyclohexane dimetatriol as a low molecular weight diol and 130 parts of ethylene glycol and mixed uniformly at 80°C.
The mixture was reacted for 48 hours to obtain polyurethane in the same manner as in Example 1, and a laminated glass was obtained.

These physical properties were as shown in Table 1.

Below is the blank space No. 1 (Table 1) Molar hostility to 1 mole of high molecular weight diol) The impact resistance of laminated glass b was 8 m or more in all cases.

Comparative Example 1 A polyurethane was obtained and a laminated glass was obtained in the same manner as in Example 1 except that 4.6 parts of 1°4 pukundiol was used as the low molecular weight diol in Example I.

Their physical properties are shown in Table 2.

Comparative Example 2 Polyflex was obtained in the same manner as in Example 1 except that 3.16 parts of ethylene glycol was used as the low molecular weight diol, and WIN Gax fr: was obtained.

Their physical properties are shown in Table 2.

Comparative Example 3 Polyurethane was obtained in the same manner as in Example 3 except that 4.6% of 1°4-butanediol was used as the low molecular weight diol, and Ii'I layer galame glass was obtained.

These physical properties were as shown in Table 2 of Todosha.

Comparative Example 4 All Example 5 and 1T except that 3.16 parts of ethylene glycol was used as the low molecular weight diol in Example 5.
Polyurethane was obtained in a manner similar to No. 11, and laminated glass 1 was obtained.

These physical properties were in accordance with Table V52.

l as the low molecular weight diol in Example 6.

Polyflex was obtained in the same manner as in Example 6, except that 3.87 parts of 2Pro/Runnediol was used, and a laminated glass was obtained.

λ Their physical properties were as shown in Table 1.

Comparative Example 6 After synthesizing a prepolymer in the same manner as in Example 7, only ethylene glycol was added as a low molecular weight diol to 1 to 260
The lath was laminated in the same manner as in Example 7, except that a portion of the lath was added.

Comparative Example 7 Polynate 21 having a number average molecular weight of 600 in Example 1
Polyflex was obtained in exactly the same manner as in Example 1 except that 3 parts were used, and a laminated glass was obtained. The results were as shown in Table 2.

Comparative Example 8 Polyflex was obtained in exactly the same manner as in Example 1, except that 18.4111S of 4-butanediol and 59.0 parts of isophorone diisocyanate were used, and a laminated glass was obtained. As a result, the meeting was as shown in Table 2.

Table 2 (Table 2) The impact resistance of laminated glass b for 1 mol of high molecular weight diol was 8 m or more in all cases.

Claims (1)

[Claims] L lr) A high molecular weight diol having a number average molecular weight of 800 to 5000, (2) A low molecular weight diol containing 10% by weight or more of an alicyclic diol or a heterocyclic spiro diol. Diol Q5~3
．． 0 mol, and (3) via a thermoplastic polyflexion interlayer film obtained by reacting an alicyclic diisocyanate or an aliphatic diisocyanate in an amount substantially equal to the total number of moles of the high molecular weight diol and low molecular weight diol. , a transparent laminated glass characterized by being formed by laminating an inorganic glass and an inorganic glass or an organic glass. λ The laminated glass according to item 1, wherein the low molecular weight diol is a heterocyclic spiro diol. Tortoise The laminated glass according to Item II1 or Company Item 2, wherein the alicyclic diol is 1,4-cyclohequinane dimethanol. The heterocyclic spiro diol is 3,9-bis(1,1
-bismethyl-2-oxyethyl sr) 2゜4.8.
The laminated glass according to any one of Items 1 to 3m Xi, which is 10-tetraoxaspiro(5e5)kundecane. The laminated glass according to any one of Items 1 to 4, wherein the content of the alicyclic diol or heterocyclic spiro diol in the low molecular weight diol is 30 to 100% by weight. Tortoise Cycloaliphatic diisocyanate is 1-incyane)'-
At least the following: 3,3,5-)dimethyl-5-inocyanatemethylcyclohexane, 1-methyl-2゜4-diisocyanatecyclohexane, l-methyl-2,6-diisocyanatecyclohexane, and 1,4-diisocyanatemethylcyclohexane. No. 1311, which is type 1
The laminated glass according to any one of Items 11i4 to 4s5.