JP3333013B2 - Interlayer for laminated glass - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an interlayer film for laminated glass which exhibits excellent sound insulation performance in a wide temperature range for a long period of time, and can be used widely, such as inorganic glass and organic glass, which can be bonded from both sides. It relates to a laminated interlayer film.

[0002]

2. Description of the Related Art A laminated glass in which an intermediate film typified by a polyvinyl butyral film plasticized by adding a plasticizer is laminated between glass plates has been well known. Because this laminated glass has excellent shatterproof properties,
For example, it is widely used for applications such as window glasses of traffic vehicles such as automobiles and window glasses of buildings.

[0003] The significance of laminated glass to single-pane glass lies in the properties of the interlayer film. That is, the polyvinyl butyral film has been used for many years as a windshield for automobiles as an intermediate film having both excellent adhesiveness to the glass and high transparency which is essential as a safety glass.
However, in recent years, as a window glass of a building, not only is it required to be safe so as not to scatter when damaged,
Excellent sound insulation and decorativeness have been required.

[0004] In a frequency range centered on 2 kHz to 4 kHz, the sound insulation of the glass plate is reduced due to the coincidence effect. The coincidence effect is a phenomenon in which when sound waves enter glass, the glass and the incident sound resonate, and as a result, sound transmission occurs. From the equal loudness curve, it is known that human hearing has a very high sensitivity in the range of 1000 Hz to 6000 Hz as compared with other frequency regions, and eliminating a drop in sound insulation performance due to the coincidence effect can be achieved by using a window glass, a wall, or the like. It is very important for sound insulation.

That is, the problem of the deterioration of the sound insulation performance due to the coincidence effect becomes a problem at the minimum portion of the transmission loss caused by the coincidence effect (hereinafter, the dB value of the transmission loss at the minimum portion is referred to as "TL value"). In order to improve the sound insulation performance, it is necessary to reduce the coincidence effect. Specifically, it is necessary to prevent the TL value from decreasing.

[0006] Laminated glass using conventional polyvinyl butyral is excellent in scattering prevention, but inevitably suffers from a decrease in sound insulation due to a coincidence effect.
Since the sound insulation performance greatly changes with the temperature change, the sound insulation performance was not sufficient.

[0007] Starting with Japanese Patent Publication No. 46-5830, it has been generally proposed that polyvinyl butyral can impart a sound insulating effect to laminated glass for vehicles. However, with regard to sound insulation, high sound insulation performance could not be exhibited in a wide temperature range, and practically it could not be used as sound insulation glass.

Further, conventionally, in the plasticized butyral system,
When the organic glass is used, the plasticizer bleeds, so that the organic glass surface is eroded. Regarding this, a proposal has been made in JP-A-53-139684 that it can be improved by selecting a ricinoleate plasticizer type.
There is a problem that it cannot withstand long-term transparency stability.
Further, the intermediate film may be used for bonding other functional films, but even in this case, PET for decoration is used.
The dye printed on the film causes migration,
This causes problems such as blurred printing.

Japanese Unexamined Patent Publication (Kokai) No. 60-226436 proposes a laminated glass obtained by interposing an organic resin film (polyester film) between interlayers, but has a poor sound insulation performance.

In order to solve such a problem, Japanese Patent Application Laid-Open No. 60-27630 discloses a vinyl chloride / ethylene /
Although glycidyl methacrylate has been proposed,
Although the sound insulation has been improved, there is a similar problem from the viewpoint of trying to improve with a plasticizer.

As another material, Japanese Patent Publication No. 47-210
In Japanese Patent Publication No. 3 (1999), an ethylene-vinyl acetate copolymer resin is also proposed as an intermediate film. As for this, although it has the necessary flexibility and toughness as an interlayer film for laminated glass without a plasticizer, it has a drawback that its sound insulation performance is low.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin-based interlayer film for a laminated glass which has excellent sound insulation properties and does not require the addition of a plasticizer. . Another object of the present invention is a function required as a laminated glass, excellent transparency at initial and over time,
An object of the present invention is to provide an interlayer film for laminated glass which has excellent impact energy absorption and the like.

[0013]

Means for Solving the Problems The present inventors have studied various resins to achieve the above object. As a result, non-crystalline resins containing a polyester oligomer and a polyvalent isocyanate as constituents and having a glass transition temperature (Tg) of −20 ° C. to + 40 ° C. and a melting onset temperature of 100 ° C. or lower are mainly used. We have completed a sound-insulating interlayer film for laminated glass as a raw material.

First, the present inventors have found that an amorphous polyester resin has high sound insulation. Although the reason why the polyester resin has high sound insulation properties has not yet been completely elucidated, in the molecular structure of the polyester, a portion where the polycarboxylic acid is esterified by the dihydric alcohol and a skeleton portion of the carboxylic acid are: It is considered that the soft segment portion and the hard segment portion respectively form a pseudo internal friction effect when vibrating due to sound energy, and have an effect of efficiently converting sound energy into heat energy.

Further, in order to maintain transparency when a laminated glass is produced, it is necessary that the resin is amorphous. When the resin has crystallinity, transparency (haze) is impaired, and the resin cannot be used as a laminated glass. Here, the term "amorphous" is defined as having no endothermic peak indicating melting of a crystal when a resin is measured by a differential scanning calorimeter (hereinafter abbreviated as "DSC"). As mentioned above,
Amorphous polyester is promising as a raw material for sound-insulating interlayer films for laminated glass.

By the way, in order to adapt the sound insulation of the interlayer film to a practical temperature range where laminated glass is used,
The glass transition temperature of the amorphous polyester is from -20 ° C to +
The temperature of 40 ° C. is necessary in that the laminated glass has higher sound insulation. This limitation of the glass transition temperature is for obtaining high sound insulation performance in a normal temperature range.

Further, in order to obtain high sound insulation performance even in winter, the glass transition temperature is preferably from -20 to + 10 ° C. The temperature is preferably -20 to 0C. However, as the glass transition temperature of the amorphous polyester becomes lower than room temperature, the amorphous polyester generally tends to become viscous in a normal temperature range.

That is, when an interlayer is prepared from an amorphous polyester having a glass transition temperature of 10 ° C. or lower and higher than 0 ° C., the surface becomes sticky in a normal temperature range and the handleability is poor. In addition, when an interlayer is prepared from an amorphous polyester having a glass transition temperature of 0 ° C. or lower, the strength of the interlayer at room temperature is insufficient, so that processing into a film is extremely difficult, and the surface becomes sticky. The interlayers coalesce to increase,
The handleability and workability into laminated glass are remarkably poor.

Therefore, as a result of intensive studies, the present inventors have found that an amorphous resin obtained by reacting a polyester oligomer with a polyvalent isocyanate and having a glass transition temperature of -20 ° C. to + 40 ° C. The present inventors have found that an amorphous resin has an appropriate glass transition temperature for obtaining sound insulation performance, and that it is possible to produce an intermediate film that is durable in a normal temperature range and has less sticky surface from the amorphous resin.

That is, the urethane group generated by the reaction between the polyester oligomer and the polyvalent isocyanate acts as a weak constraining component, and even when the glass transition temperature is lower than room temperature, unlike the case of the amorphous polyester alone, it is durable. It is thought that it became possible to produce an intermediate film with less sticky surface.

The glass transition temperature of the amorphous resin is preferably -20 to + 10 ° C. in order to obtain a high sound insulation performance even in winter, and in order to obtain a high sound insulation performance when used at a low temperature. The glass transition temperature is preferably -20 to 0C.

The introduction of a urethane group is also effective for improving the transparency and impact resistance of the interlayer. In other words, a crystalline polyester that is not transparent to crystallize alone becomes amorphous by introducing a urethane group,
It was found that the transparency was improved. It was also found that the impact resistance was improved by introducing a urethane group into the polyester.

Further, the amorphous resin of the present invention needs to have a melting start temperature of 100 ° C. or lower so that it can be processed together with an inorganic or organic glass as an intermediate film. If the melting start temperature is higher than that, the adhesion and transparency will be poor during the laminating process, so that it cannot be used for the purpose of the present invention.

The polyester oligomer which is a component of the amorphous resin of the present invention is preferably a polyester having a molecular weight of 300 to 10,000 having a divalent or higher valent hydroxyl group in the molecular chain, and having two hydroxyl groups at both ends of the molecule. Having a molecular weight of 5
Polyesters of 00 to 5,000 are particularly preferred.

The molecular weight of the polyester oligomer is 300
If it is smaller than the above, the density of urethane groups of the amorphous resin to be formed increases, so that the fluidity becomes poor. Further, when the molecular weight of the polyester oligomer is larger than 10,000, it is difficult to use the polyester oligomer due to poor reactivity with the polyvalent isocyanate.

The glass transition temperature of the polyester oligomer is -20 to +4.
The temperature is preferably from -80 ° C to 20 ° C in order to make the range of 0 ° C. More preferably, it is -60 to 10C.

The above-mentioned polyester oligomer comprises an aromatic and / or aliphatic polycarboxylic acid and an aliphatic dihydric alcohol as main components and is obtained by polycondensation thereof.

Examples of the aromatic dihydric alcohol carboxylic acid include terephthalic acid, isophthalic acid, metal salts of 5-sulfoisophthalic acid, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether,
4,4′-dicarboxydiphenyl sulfide, 4,
4'-dicarboxydiphenylsulfone, 3,3'-dicarboxybenzophenone, 4,4'-dicarboxybenzophenone, 1,2-bis (4-carboxyphenoxy) ethane, 1,4-dicarboxynaphthalene, or 2, 6-Dicarboxynaphthalene and the like are preferably used.

As the aliphatic dihydric carboxylic acid, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid and the like are preferably used.

These may be used alone or in combination of two or more.

The aliphatic dihydric alcohol is preferably at least one diol selected from the group consisting of glycols and polyalkylene oxides.

The above glycol has 2 to 1 carbon atoms.
0 is preferable, for example, ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, Cyclohexane-
Examples thereof include 1,3-diol, cyclohexane-1,4-diol, and cyclohexane-1,4-dimethanol, and these may be used alone or in combination of two or more.

Examples of the polyalkylene oxide include polyethylene oxide, polypropylene oxide,
Polytetramethylene oxide, polyhexamethylene oxide and the like, which may be used alone,
Two or more kinds may be used in combination. The number average molecular weight of these polyalkylene oxides is preferably 20,000 or less, more preferably 5,000 or less.

Polyester is obtained by polycondensation of the above-mentioned dihydric carboxylic acid and aliphatic dihydric alcohol. The polyester has a sound insulating property, an amorphous property, a glass transition temperature of -20 to + 40 ° C, and a melting start of 100 ° C or less. In order to satisfy all the conditions of temperature, it is desirable to synthesize using several kinds of dihydric carboxylic acids and / or several kinds of dihydric alcohols.

The polyester of the present invention may contain an aromatic dihydric alcohol, aromatic hydroxycarboxylic acid, or lactone other than the above as a constituent.

Examples of the aromatic dihydric alcohol include hydroquinone, resorcin, chlorohydroquinone,
Bromohydroquinone, methylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4,4'-dihydroxybiphenyl, 4,4 '
-Dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane,
Bisphenol A, 1,1-di (4-hydroxyphenyl) cyclohexane, 1,2-bis (4-hydroxyphenoxy) ethane, 1,4-dihydroxynaphthalene,
2,6-dihydroxynaphthalene, 4,4 ″ -dihydroxy-p-terphenyl, 4,4 ″ -dihydroxyethoxy-p-terphenyl, 4,4 ′ ″-dihydroxy-p-quarterphenyl, 4, 4 ′ ″-dihydroxyethoxy-p-quarterphenyl and the like.

Examples of the aromatic hydroxycarboxylic acid include parahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid and 4-hydroxy-4′-carboxybiphenyl, 4,4 ″ -p-terphenyldicarboxylic acid,
4,4 ′ ″-p-quarterphenyldicarboxylic acid,
And the like.

Examples of the lactone include ε-caprolactone, δ-valerolactone, and γ-butyrolactone.

As a method for producing the polyester oligomer, any generally known polycondensation method can be employed. For example, the following method can be mentioned. A method of directly reacting a dihydric carboxylic acid with a dihydric alcohol component. A method in which a lower ester of a dihydric carboxylic acid is reacted with a dihydric alcohol component by utilizing transesterification. A method in which a halide of a dihydric carboxylic acid and a dihydric alcohol component are reacted in a suitable solvent such as pyridine. A method of reacting a metal alcoholate of a dihydric alcohol component with a halide of a dihydric carboxylic acid. A method in which an acetylated product of a dihydric alcohol component is reacted with a divalent carboxylic acid by utilizing transesterification.

By reacting a dihydric alcohol with a dihydric carboxylic acid in excess, a polyester having hydroxyl groups at both ends can be synthesized.

As a form of the condensation reaction, a bulk reaction method is usually employed, but a solution reaction method or the like can also be employed. The reaction temperature is usually set appropriately in the range of 150 to 350 ° C. The reaction pressure is usually normal pressure, but can be reduced or increased. Reaction time is 1 minute to 7 days,
Preferably, it is 30 minutes to 24 hours.

In the polycondensation, a catalyst generally used for producing a polyester may be used. Examples of the catalyst include lithium, sodium, potassium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, and manganese. The organic metal compound, the organic acid salt, the metal alkoxide, the metal oxide and the like can be mentioned.

Particularly preferred catalysts are calcium acetate, stannous diacyl, stannous tetraacyl, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate,
Tin dioctanoate, tin tetraacetate, triisobutylaluminum, tetrabutyltitanate, germanium dioxide, and antimony trioxide. Two or more of these catalysts may be used in combination. In order to efficiently distill out water, alcohol, glycol, and the like produced as a by-product of the polymerization and obtain a high-molecular-weight polymer, the pressure of the reaction system is preferably reduced to 1 mmHg or less in the latter stage of the polymerization.

Further, as the polyester oligomer, a polylactone obtained by ring-opening polymerization of lactones may be used. Ε-caprolactone and δ- as monomers
It is synthesized using valerolactone and γ-butyrolactone. These may be used alone or in combination of two or more.

By using a dihydric alcohol as an initiator, a polylactone having hydroxyl groups at both ends can be synthesized.

As a reaction form of the ring-opening polymerization, a bulk reaction method is usually employed, but a solution reaction method or the like can also be employed. The reaction temperature is usually set appropriately in the range of 50 to 250 ° C. The reaction pressure is usually normal pressure, but can be reduced or increased. Reaction time is 1 minute to 7 days,
Preferably, it is 30 minutes to 24 hours.

In the polycondensation, a catalyst generally used for producing polylactone may be used. This catalyst includes lithium, sodium, potassium, cesium, magnesium, calcium, barium,
Metals such as strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, and manganese, and organic metal compounds, organic acid salts, metal alkoxides, and metal oxides thereof .

Particularly preferred catalysts are calcium acetate, stannous diacyl, stannous tetraacyl, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate,
Tin dioctanoate, tin tetraacetate, triisobutylaluminum, tetrabutyltitanate, germanium dioxide, and antimony trioxide. Two or more of these catalysts may be used in combination.

The polyvalent isocyanate which is a constituent component of the amorphous resin of the present invention is preferably a divalent isocyanate. The polyvalent isocyanate is preferably a trivalent or more polyvalent isocyanate as long as the fluidity and sound insulation of the resulting amorphous resin are not reduced practically. May be used.

As the divalent isocyanate, any of an aromatic diisocyanate and an aliphatic diisocyanate can be used.

The aromatic diisocyanate includes:
4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and the like.

As the aliphatic diisocyanate, 1,
2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butylene diisocyanate,
Examples include 1,6-hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, and isophorone diisocyanate.

The method for producing an amorphous resin according to the present invention comprises reacting a hydroxyl group of a polyester oligomer with an isocyanate group of a polyvalent isocyanate by a polyaddition reaction from a polyester oligomer and a polyvalent isocyanate, and conducting a chain extension reaction by a urethane group. Can be manufactured.

As a reaction mode, a bulk reaction method or a solution reaction method is usually used. The reaction temperature is usually 5
In the range of 0 to 250 ° C, preferably 100 ° C to 200 ° C
Is appropriately set within the range. The reaction time is 1 minute to 7 days, preferably 30 minutes to 24 hours. In order to prevent decomposition, the reaction is preferably performed under a stream of an inert gas such as nitrogen.

The hydroxyl group of the polyester oligomer and the isocyanate group of the polyvalent isocyanate are usually preferably equimolar in order to produce a high-molecular-weight amorphous polyester, but any one of the functional groups may be added in excess of about 20%. A reaction may be performed. Alternatively, the reaction may be carried out by adding an excessive amount of a polyvalent isocyanate and adding a dihydric alcohol as a chain extender such that the amount of all hydroxyl groups and the amount of isocyanate groups are substantially equivalent. As the dihydric alcohol, those described above can be used, butylene glycol is particularly preferred.

The glass transition temperature of the resulting amorphous resin is
It can be arbitrarily set depending on the glass transition temperature, molecular weight, and amount of polyvalent isocyanate of the polyester oligomer. That is, the glass transition temperature of the polyester oligomer is fundamental, and the temperature rises by about 10 to 80 ° C. depending on the amount of the introduced urethane group. That is, increasing the molecular weight of the polyester oligomer reduces the amount of equimolar isocyanate,
The increase in the glass transition temperature is small because the density of the urethane group is also small, but when the molecular weight of the polyester oligomer is reduced, the amount of isocyanate in an equimolar amount increases, and the increase in the density of the urethane group causes a large increase in the glass transition temperature. Become.

In the polycondensation, a catalyst may be used. Examples of the catalyst include lithium, sodium, potassium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, and manganese. The organic metal compound, the organic acid salt, the metal alkoxide, the metal oxide and the like can be mentioned.

Particularly preferred catalysts are calcium acetate, stannous diacyl, stannous tetraacyl, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate,
Tin dioctanoate, tin tetraacetate, triisobutylaluminum, tetrabutyltitanate, germanium dioxide, and antimony trioxide. Two or more of these catalysts may be used in combination.

During or after the production of the amorphous resin of the present invention, the following additives may be added as long as the practicality is not impaired.

That is, triphenyl phosphite, trilauryl phosphite, trisnonyl phenyl phosphite, 2-tert-butyl-α- (3-tert-
Heat stabilizers such as butyl-4-hydroxyphenol) -p-cumenylbis (p-nonylphenyl) phosphite,
Tris- (2,3-dichloropropyl) phosphate,
Flame retardants such as pentabromophenyl allyl ether;
tert-butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4
-Methoxy-2'-carboxybenzophenone, 2,
Examples include ultraviolet absorbers such as 4,5-trihydroxybutyrophenone, antioxidants such as butylhydroxyanisole, butylhydroxytoluene, distearylthiodipropionate, dilaurylthiodipropionate, and hindered phenol-based antioxidants.

Incidentally, an intermediate film having a thickness of 0.4 mm
It is preferable that the haze of the laminated glass when sandwiched between the above float glasses is 2 or less. If the haze is 2 or more, the transparency is significantly impaired, which is not practically preferable. However, an intermediate film having a haze of 2 or more may be used as long as the haze is 2 or more and there is no problem in use.

The total light transmittance of the laminated glass when the intermediate film having the thickness of 0.4 mm is sandwiched between the float glasses having the thickness of 3 mm is preferably 80% or more. It is more preferably at least 83%.

As the structure of the laminated glass, the following modes are appropriately selected. A configuration in which glass of glass plate / interlayer / glass plate is composed of two sheets. Glass plate / interlayer / glass / interlayer / glass plate etc. composed of three or more glasses. Decorative laminated glass such as glass plate / intermediate film / PET film or PET film or decorative film / intermediate film / glass plate.

In order to obtain the necessary penetration resistance and sound insulation performance required for an interlayer for laminated glass, the thickness of the interlayer is 0.1 mm.
To 1.6 mm is preferred. In particular, from 0.2 mm to 1.
A 0 mm interlayer is preferably used.

In order to produce a laminated glass by laminating between glass plates, a method used in the production of ordinary laminated glass is employed. For example, a method of sandwiching a film from both sides thereof and manufacturing a laminated glass by a hot press.

In the present invention, the glass includes not only an inorganic glass such as an alkali glass but also an embodiment of a laminated glass using a glass called an organic glass such as a polycarbonate or a PMMA resin. In a system in which a conventionally used polyvinyl butyral resin system is plasticized with a plasticizer, the plasticizer attacks the organic glass to cause a whitening phenomenon, but the present invention does not have such a problem.

[0067]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of a sound insulating interlayer for laminated glass and a laminated glass using the same according to the present invention will be described. In the examples and comparative examples, “parts” means parts by weight.

<Crystallinity> Crystallinity was confirmed by DSC. The case where no crystal peak appeared was regarded as amorphous. DSC
The measurement was performed at a heating rate of 10 ° C./min using “DSC220C” manufactured by Seiko Instruments Inc.

<Glass Transition Temperature> The glass transition temperature was measured using a viscoelastic spectrometer (“VES-F-II” manufactured by Iwamoto Seisakusho).
I ”), at a heating rate of 3 ° C./min, and in a temperature range of −50.
The measurement was performed under conditions of １００100 ° C. and a measurement frequency of 100 Hz.

<Melting Start Temperature> The melting start temperature was measured using a flow tester (“CFT-500C” manufactured by Shimadzu Corporation).
The measurement was performed at a heating rate of 6 ° C./min, a load of 100 kg / cm ² , a die size of 1 mmφ × 10 mm, and a preheating time of 150 seconds.

<Method of Measuring Sound Insulation Performance> The sound insulation was measured by using a laminated glass with a vibration generator (“G2” manufactured by Shinken Co., Ltd.) for a dumping test.
1-005D)) and vibrating characteristics obtained therefrom are measured by a mechanical impedance amplifier (Rion XG-8).
11)), and the vibration spectrum was analyzed by an FFT analyzer (FFT spectrum analyzer “HP-3582A” manufactured by Yokogawa Hewlett-Packard).
From the loss coefficient thus obtained and the ratio of the resonance frequency of the glass, the transmission loss was calculated (measured temperature: 10 to 40).
° C). Based on this result, the TL value was defined as the minimum transmission loss amount near the frequency of 2000 Hz.

<Measurement of Transparency> A 0.4 mm-thick sample was subjected to “integration turbidity” manufactured by Tokyo Denshoku Co., Ltd. in accordance with the terms of parallel line transmittance and haze value of JIS K6714 “Methacrylic resin plate for aircraft”. The total light transmittance and the haze value were evaluated using a “total meter”.

<Impact resistance test> The impact resistance test was conducted according to JISR3
205. That is, temperature 23 ° C, humidity 5
The laminated glass held at 0% for 4 hours is held vertically by a support frame, and a striker having a weight of 45 kg and a maximum diameter of 75 mm is placed on the support frame.
The glass was dropped from the height of cm to the center of the laminated glass in a pendulum manner. The case where an opening through which a sphere having a diameter of 75 mm can freely pass was formed in the broken part, and the case where it did not occur was evaluated as O.
Note that the measurement was performed with n = 4.

<Plastic Lamination Properties> An interlayer was interposed between two 3 mm-thick polymethyl methacrylate plates of organic glass to form a laminated glass.
The haze was measured by allowing the sample to stand at ℃.

<Decoration Characteristics> Two interlayer films and a PET film were interposed between two float glasses having a thickness of 3 mm, and laminated glass was formed. After that, the laminate was allowed to stand at 40 ° C. for one week to measure haze. .

(A) Synthesis of Amorphous Resin [Example 1] (Synthesis of Polyethylene Oligomer) Dimethyl terephthalate was placed in a glass flask having an internal volume of 11 equipped with a stirrer, a thermometer, a gas injection port and a distillation port. 58g (0.3mo
l), 8 g (0.3 mol) of dimethyl isophthalate, 244 g (1.4 mol) of dimethyl adipate, 249 g (4.0 mol) of ethylene glycol, 0.2 g of calcium acetate and 0.2 g of germanium dioxide as a catalyst were added. After the inside of the flask was replaced with nitrogen, the inside of the flask was heated and reacted at 180 ° C. for 2 hours. With the reaction, methanol was distilled out of the flask. Add 24 more flasks
The temperature was raised to 0 ° C., and the reaction was carried out for 10 minutes in this state. next,
The distillation port was connected to a vacuum, and the reaction was carried out for 30 minutes while the pressure in the flask was reduced to 10 mmHg. Ethylene glycol was distilled off along with the reaction, and the resulting polyester was allowed to cool, and then the produced polyester was taken out. The resulting polyester has a glass transition temperature of -8.0 ° C and a gel permeation chromatograph (G
Majority average molecular weight (PC equivalent)
Was 3,300.

(Synthesis of Amorphous Resin) 165 g of the above polyethylene oligomer was placed in a glass flask having an internal volume of 11 provided with a stirrer, a thermometer, a gas injection port and a distillation port.
(0.05 mol), 12.6 g (0.05 mol) of 4,4'-diphenylmethane diisocyanate, and 200 ml of dimethylformamide as a solvent were added to form a mixture of 120
The reaction was performed at a temperature of 1 ° C for 1 hour. The dimethylformamide was removed under reduced pressure to give a clear solid. DSC confirmed that it was amorphous. Table 1 shows the physical properties.

Example 2 200 g (0.1 m 2) of a polylactone oligomer having a number average molecular weight of 2,000 (“TONE0240” from UCC) was placed in the same flask as in Example 1.
ol), 2,7.6 g (0.11 mol) of 4,4'-diphenylmethane diisocyanate and 200 mol of dimethylformamide as a solvent were added and reacted at 120 ° C. for 1 hour. The dimethylformamide was removed under reduced pressure to give a clear solid. DSC confirmed that it was amorphous. Table 1 shows the physical properties.

Example 3 (Synthesis of Polyester Oligomer) In the same flask as in Example 1, 348 g of dimethyl adipate (2.0 mol
l), butylene glycol 270 g (3.0 mol),
A small amount of tetrabutyl titanate was added as a catalyst. After replacing the inside of the flask with nitrogen, the inside of the flask was heated to 18
The reaction was performed at 0 ° C. for 1 hour. With the reaction, methanol was distilled out of the flask. The temperature of the flask was further raised to 220 ° C., and the reaction was performed for 10 minutes in this state. After cooling, the produced polyester was taken out. The glass transition temperature of the produced polyester was −52.3 ° C., and the number average molecular weight (in terms of polyester) measured by gel permeation chromatography (GPC) was 850.

(Synthesis of Amorphous Resin) In the same flask as in Example 1, 170 g of the above-mentioned polyester oligomer (0.
2 mol) and 29 g of tolylene diisocyanate (0.2
mol) and dimethylformamide 200 as solvent
Then, a small amount of dibutyltin dilaurylate was added as a catalyst and reacted at 120 ° C. for 1 hour. The dimethylformamide was removed under reduced pressure to give a clear solid. DSC confirmed that it was amorphous. Table 1 shows the physical properties.

Example 4 33 g (0.01 mol) of the polyester oligomer synthesized in Example 1 and 4,4′-
3.5 g of diphenylmethane diisocyanate (0.01
4 mol) and butylene glycol 0.36 g (0.00
4 mol) was kneaded at 160 ° C. for 10 minutes under a nitrogen stream using a plastograph manufactured by Toyo Seiki Co., Ltd. A clear solid was obtained. DSC confirmed that it was amorphous. Table 1 shows the physical properties.

[0082]

[Table 1]

(B) Preparation of Laminated Glass A laminated glass was prepared by the following method using the amorphous resins of Examples 1 to 4 obtained as described above.

By maintaining the press molding machine at 150 ° C. for 2 minutes, an intermediate film having a thickness of 0.40 mm was obtained. The interlayer film is sandwiched between two float glass pieces of 30 cm square and 3 mm in thickness from both sides, and this is put into a rubber bag, and the torso is put at 20 torr.
After degassing to a vacuum of 20 minutes, transfer to a 90 ° C. oven while degassing, and further maintain 90 ° C. for 30 minutes,
Vacuum pressed. The laminated glass body temporarily mounted from the bag was prepared into a transparent laminated glass in an autoclave at a pressure of 12 kg / cm ² and a temperature of 100 ° C.

Comparative Example 1 (a) Preparation of Intermediate Film To 2890 g of pure water, 190 g of polyvinyl alcohol having a polymerization degree of 1700 was added and dissolved by heating. The temperature of the reaction system was adjusted, and 200 g of 35% hydrochloric acid and 170 g of butyraldehyde were added to precipitate polyvinyl acetal. The reaction was completed at 45 ° C. for 6 hours to complete the reaction, and a white powder of polyvinyl acetal was obtained. The degree of acetalization was 62.3 mol%, the amount of acetyl groups was 12.3 mol%, and the viscosity was 590 cps.

50 g of this polyvinyl acetal was collected, and a plasticizer (triethylene glycol-di-2-ethylbutyrate) in an amount corresponding to 45 parts per 100 parts of the resin and 2- (2 ′) as an ultraviolet absorber. -Hydroxy-
(5′-methylphenyl) benzotriazole in an amount corresponding to 0.1 part, and BHT as an antioxidant in 0.1 part.
An amount corresponding to one part was added, and the mixture was sufficiently kneaded with a mixing roll, and the predetermined amount was held at 150 ° C. for 30 minutes by a press molding machine to obtain an intermediate film having a thickness of 0.40 mm.

(B) Preparation of Laminated Glass The above-obtained interlayer film was 30 cm square from both sides and 3 mm thick.
And put it in a rubber bag, evacuated it to a vacuum of 20 torr for 20 minutes,
Degassed and transferred to an oven for another 30 minutes.
Vacuum pressing was performed while maintaining the temperature. The laminated glass body temporarily bonded from the bag was pressed at a pressure of 12 kg / cm 2 and a temperature of 1
The resultant was autoclaved at 30 ° C. to prepare a transparent laminated glass.

(A) Synthesis of Polyester [Comparative Example 2] In a flask similar to that of Example 1, 388 g (2.0 mol) of dimethyl terephthalate, 174 g (2.8 mol) of ethylene glycol, 0.2 g of calcium acetate as a catalyst and 0.2 g of germanium dioxide was added. A polyester was obtained by the same polymerization operation as in Example 1. By DSC, absorption of a melting point showing crystallinity at 253 ° C. was confirmed. Table 2 shows the physical properties.

Comparative Example 3 In the same flask as in Example 1, 194 g (1.0 mol) of dimethyl terephthalate was placed.
Dimethyl sebacate 230 g (1.0 mol), neopentyl glycol 146 (1.4 mol), ethylene glycol 50 g (0.8 mol), hydroquinone 66 g
(0.6 mol), 0.2 g of calcium acetate as a catalyst
And 0.2 g of germanium dioxide. A polyester was obtained by the same polymerization operation as in Example 1. DSC confirmed that it was amorphous. Table 2 shows the physical properties.

Comparative Example 4 The polyester obtained in Example 3 was used as it was. By DSC, absorption of a melting point showing crystallinity at 52% was confirmed. Table 2 shows the physical properties.

[0091]

[Table 2]

(B) Preparation of Laminated Glass Laminated glass was prepared in the same manner as in Examples 1 to 3, using the polyesters of Comparative Examples 1 to 4.

The laminated glass of each example obtained as described above has excellent sound insulation and transparency, and has excellent impact energy absorption as compared with the laminated glass of each comparative example. .

[0094]

According to the laminated glass using the interlayer film for sound insulating laminated glass of the present invention, the transparency and safety, which are the basic characteristics of the laminated glass, are maintained, and sound energy is effectively used as heat energy. Because of this, the coincidence effect is reduced, and the sound insulation is excellent near normal temperature.
Furthermore, since the interlayer film for laminated glass of the present invention does not contain a plasticizer, the plasticizer does not bleed, and the transparency is stable and good for a long period of time during plastic or decorative bonding.

Claims (1)

(57) [Claims] 1. An amorphous resin having a glass transition temperature of -20 ° C. to + 40 ° C. and a melting start temperature of 100 ° C. or lower, and an amorphous resin containing a polyester oligomer and a polyvalent isocyanate as main components. An interlayer film for laminated glass.