JPH0781983A - Intermediate film for laminated glass - Google Patents

Abstract

(57) [Summary] [Object] To provide a resin-based interlayer film for laminated glass, which has excellent sound insulation properties and does not require addition of a plasticizer. [Structure] The main raw material of the interlayer film for laminated glass is an amorphous polyester resin composed of a polyvalent carboxylic acid and an aliphatic dihydric alcohol. The amorphous polyester resin has a glass transition temperature of -20 ° C to + 40 ° C and a melting start temperature of 100 ° C or lower. In particular, 0.1 to 3 mol% of all constituent monomers of the amorphous polyester resin is an aromatic dihydric alcohol represented by the following formula [I] or an aromatic divalent carboxylic acid represented by the following formula [II]. At least one of. (In the formula, n is 3 or 4, R ¹ and R ² are each independently an alkylene group, and l and m are each independently 0 or an integer of 1 or more.) (In the formula, p represents 3 or 4.)

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 that exhibits excellent sound insulation performance over a wide temperature range for a long period of time, and the glass that can be laminated from both sides can be widely used such as inorganic glass and organic glass. The present invention relates to an interlayer film for laminated glass.

[0002]

2. Description of the Related Art Conventionally, a laminated glass in which an interlayer film typified by a polyvinyl butyral film plasticized by adding a plasticizer is laminated between glass plates is well known. Since this laminated glass has excellent anti-scattering properties,
For example, it is widely used for applications such as window glass of transportation vehicles such as automobiles and window glass of buildings.

The significance of laminated glass with respect to single-plate glass lies in the properties of the interlayer film. That is, a 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 essential as a safety glass.
However, in recent years, not only is there a demand for safe window glass for buildings that does not scatter when damaged,
Excellent sound insulation and decorative properties are required.

In the frequency range centered on 2 kHz to 4 kHz, the glass plate has a reduced sound insulation due to the coincidence effect. The coincidence effect is a phenomenon in which when a sound wave is incident on the glass, the glass and the incident sound resonate with each other, and as a result, the sound is transmitted. It is known from the equal loudness curve 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 the deterioration of the sound insulation performance due to the coincidence effect is effective for the window glass, the wall, etc. It can be said that it is very important for sound insulation.

That is, the problem that the sound insulation performance is deteriorated by the coincidence effect is at the minimum portion of the transmission loss (hereinafter, the db value of the transmission loss at the minimum portion is referred to as "TL value") which is caused by the coincidence effect. Therefore, in order to improve the sound insulation performance, it is necessary to mitigate the coincidence effect, and specifically, it is necessary to prevent the TL value from decreasing.

[0006] Conventional laminated glass using polyvinyl butyral is excellent in terms of preventing scattering, but a decrease in sound insulation due to the coincidence effect is unavoidable, and
The sound insulation performance was not sufficient because the sound insulation performance changed significantly with changes in temperature.

[0007] In general, Japanese Patent Publication No. 46-5830, it has been 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 cannot be exhibited in a wide temperature range, and it cannot be practically used as sound insulation glass.

Further, conventionally, in the plasticized butyral system,
Since the plasticizer bleeds, the surface of the organic glass is attacked when the organic glass is used, resulting in opacity. Regarding this, a proposal that it can be improved by selecting a ricinoleic acid ester plasticizer species is made in JP-A-53-139684, but there is a problem that the stability of transparency for a long period of time cannot be endured. . Further, the intermediate film may be used for bonding other functional films, but in this case also, the dye printed on the decorative PET film causes migration, causing a problem such as bleeding of printing. .

Further, Japanese Patent Laid-Open No. 60-226436 proposes a laminated glass obtained by interposing an organic resin film (polyester film) between the intermediate films, but the sound insulation performance is not preferable.

In order to solve such a problem, in JP-A-60-27630, vinyl chloride / ethylene /
Proposals for glycidyl methacrylate type have been made,
Although the sound insulation has been improved, there is a similar problem from the viewpoint of improving with a plasticizer.

As other materials, Japanese Examined Patent Publication No. 47-210
In JP-A-3, an ethylene-vinyl acetate copolymer resin is also proposed as an intermediate film. Regarding this, it has the required flexibility and toughness as an interlayer film for laminated glass without a plasticizer, but has the drawback of low sound insulation.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin-based interlayer film for laminated glass which has a sound insulation property superior to the conventional one and does not require addition of a plasticizer. . Another object of the present invention is the required function as a laminated glass, excellent transparency in the initial and aging,
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 in order to achieve the above objects. As a result, an amorphous polyester resin composed of a polyvalent carboxylic acid and an aliphatic dihydric alcohol, which has a glass transition temperature of −20 ° C. to + 40 ° C. and a melting start temperature of 100 ° C. or less as a main raw material We have completed the sound insulating interlayer film for laminated glass.

The glass transition temperature of the amorphous polyester resin is -20 ° C to + 40 ° C in order to adjust the sound insulation of the interlayer film to a practical temperature range in which the laminated glass is used. Further, in the case of using laminated glass, in order to have higher sound insulation, the glass transition temperature is −10 ° C. to +3.
It is preferably 0 ° C. All of these glass transition temperatures are limited in order to obtain high sound insulation performance at room temperature.

The reason why the amorphous polyester resin of the present invention has such a high sound insulating property has not been completely clarified yet, but in the molecular structure of polyester, a polyvalent carboxylic acid is esterified by a dihydric alcohol. The converted part and the carboxylic acid skeleton part form the soft segment part and the hard segment part, respectively, and bring about a pseudo internal friction effect at the time of vibration due to sound energy, and efficiently convert sound energy into heat energy. It seems to bring about the effect.

As the polyester of the present invention, an amorphous one is used to maintain the transparency when the laminated glass is prepared. When the polyester has crystallinity, the transparency (haze) is impaired and it cannot be used as a laminated glass. Here, the term "amorphous" means that the resin has no endothermic peak indicating melting of crystals when the resin is measured by a differential scanning calorimeter (hereinafter abbreviated as "DSC").

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

The main constituent of the polyester of the present invention is an aromatic and / or aliphatic polycarboxylic acid,
And aliphatic dihydric alcohols.

Examples of the aromatic divalent 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'-dicarboxydiphenyl sulfone, 3,3'-dicarboxybenzophenone, 4,4'-dicarboxybenzophenone, 1,2-bis (4-Carboxyphenoxy) ethane, 1,4-dicarboxynaphthalene, 2,6-dicarboxynaphthalene and the like are preferably used.

As the above-mentioned aliphatic divalent carboxylic acid, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, etc. are preferably used.

Examples of the above-mentioned trivalent or higher carboxylic acids include hemamellitic acid, trimellitic acid, trimesic acid,
Pyromellitic acid, 1,1,2,2-ethanetetracarboxylic acid, 1,1,2-ethanetricarboxylic acid, 1,3,5
-Pentane tricarboxylic acid, 1,2,3,4-cyclopentane tetracarboxylic acid and the like.

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

The aliphatic dihydric alcohol is preferably one or more diols selected from the group consisting of glycols and polyalkylene oxides.

The 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, 1, 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 kinds.

Examples of the polyalkylene oxide include polyethylene oxide, polypropylene oxide,
Examples thereof include polytetramethylene oxide and polyhexamethylene oxide, which may be used alone,
Two or more kinds may be used in combination. If the number average molecular weight of these polyalkylene oxides is too small, the ability to impart flexibility to the resulting polyester is reduced, and if it is too large, the physical properties such as thermal stability of the resulting polyester are reduced, so that It is preferably 20,000, more preferably 500 to 5,000.

A polyester is obtained by subjecting the above polyvalent carboxylic acid and an aliphatic dihydric alcohol to a condensation reaction, but all of the amorphousness, the glass transition temperature of -20 to + 40 ° C., and the melting start temperature of 100 ° C. or less are all required. In order to satisfy the above condition, it is desirable to synthesize using several kinds of polycarboxylic acid and / or several kinds of dihydric alcohol.

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

Examples of the aromatic dihydric alcohol include hydroquinone, resorcin, chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4,4'-dihydroxybiphenyl, 4,4'-.
Dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, 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 ′ ″-dihydroxy-p-quaterphenyl and the like can be mentioned.

Examples of the aromatic hydroxycarboxylic acid include parahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid and 4-hydroxy-4'-carboxybiphenyl.

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

In the second aspect of the present invention, in order to maintain a glass transition point suitable for sound insulation and to maintain a good film-forming property at around room temperature, all constituent monomers of the amorphous polyester are used. 0.1 to 3 mol% of the formula [I]
And at least one of the rigid dicarboxylic acid represented by the following formula [II].

As described above, the glass transition temperature of the amorphous polyester is −20 to 40 ° C. in order to obtain high sound insulation performance at room temperature. Further, in order to obtain high sound insulation performance even in winter, it is preferable that the glass transition temperature is 10 ° C. or lower, and in order to obtain high sound insulation performance even when used under low temperature, the glass transition temperature is 0 ° C. or lower. Preferably there is.

By the way, as the glass transition temperature of the amorphous polyester becomes lower than room temperature, the amorphous polyester tends to become viscous at room temperature. That is, when an intermediate film is produced from an amorphous polyester having a glass transition temperature of 10 ° C. or lower and higher than 0 ° C., the surface becomes sticky in the normal temperature range and the handleability is poor. Further, when an interlayer film is made of an amorphous polyester having a glass transition temperature of 0 ° C. or less, the strength of the interlayer film is insufficient at room temperature, which makes it extremely difficult to process the film, and further the surface becomes sticky. As a result, the interlayer films adhere to each other, and the handling property and the processability for laminated glass are remarkably poor.

The compound [I] and the compound [II] are compounds having a polyparaphenylene skeleton, and it is known that the polyparaphenylene skeleton is effective as a mesogen of a liquid crystal molecule. As described in JP-A-2-276817, when the [I] compound is incorporated into the polymer chain or at the polymer terminal, a segment based on the [I] compound is obtained due to the strong cohesive force based on the liquid crystallinity of the [I] compound. Has been found to act effectively as a physical crosslink.

As a result of diligent studies in making the present invention, 0.1 to 3 of all the constituent monomers of the amorphous polyester is obtained.
When the amorphous polyester has a glass transition temperature of 10 ° C. or lower, as well as when the amorphous polyester has a low glass transition temperature of 0 ° C. or lower, [I] It was clarified that the segment based on the compound effectively acts as a physical crosslink, so that a film which is strong and has a non-sticky surface can be formed at room temperature.

[0036]

[Chemical 3] (In the formula, n is 3 or 4, R ¹ and R ² are each independently an alkylene group, and l and m are each independently 0 or an integer of 1 or more.)

[0037]

[Chemical 4] (In the formula, p represents 3 or 4.)

Examples of the compound [I] are 4,4 ″ -dihydroxy-p-terphenyl, 4,4 ″ -dihydroxyethoxy-p-terphenyl and 4,4 ″ ′-dihydroxy-p-quaterphenyl. , 4,4 ″ ′-dihydroxyethoxy-p-quaterphenyl is preferably used.

As the compound [II], 4,4 ″ -p-
Terphenyldicarboxylic acid and 4,4 ′ ″-p-quaterphenyldicarboxylic acid are preferably used.

When the content of either the [I] compound or the [II] compound in all the constituent monomers of the amorphous polyester resin is more than 3 mol%, the density of physical crosslinking increases and the sound insulation decreases. Or the melting start temperature rises. The content of either the [I] compound or the [II] compound is 0.1 m.
When it is less than ol%, stickiness on the film surface cannot be suppressed.

Next, the method for producing the polyester of the present invention will be described. As the method for producing the polyester of the present invention, any generally known polycondensation method can be adopted. For example, the following method may be mentioned.

A method of directly reacting a polyvalent carboxylic acid and a dihydric alcohol component. A method of reacting a lower ester of a polyvalent carboxylic acid with a dihydric alcohol component by transesterification. A method of reacting a halide of a polycarboxylic acid with a dihydric alcohol in a suitable solvent such as pyridine. A method of reacting a metal alcoholate of a dihydric alcohol component with a halide of a polyvalent carboxylic acid. A method of reacting an acetylated product of a dihydric alcohol component and a polyvalent carboxylic acid using transesterification.

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

In the polycondensation, a catalyst generally used in producing polyester may be used. As this catalyst, 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, organometallic compounds thereof, organic acid salts, metal alkoxides, metal oxides and the like can be mentioned. .

Particularly preferred catalysts are calcium acetate, diacyl stannous tin, tetraacyl stannic tin, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate,
Tin dioctanoate, tin tetraacetate, lithoisobutyl aluminum, tetrabutyl titanate, germanium dioxide and antimony trioxide. Two or more kinds of these catalysts may be used in combination. Further, in order to efficiently distill off water, alcohol, glycol and the like produced as a by-product during the polymerization and obtain a high molecular weight polymer, it is preferable to reduce the pressure of the reaction system to 1 mmHg or less in the latter stage of the polymerization.

During or after the production of the polyester of the present invention, the following additives may be added within a range not impairing the practicality. That is, triphenyl phosphite, trilauryl phosphite, trisnonyl phenyl phosphite, 2-tert-butyl-α- (3-te
A heat stabilizer such as rt-butyl-4-hydroxyphenol) -p-cumenylbis (p-nonylphenyl) phosphite, a flame retardant such as tris- (2,3-dichloropropyl) phosphate, pentabromophenylallyl ether, p. -Tert-butylphenyl salicylate, 2-
UV absorbers such as hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and 2,4,5-trihydroxybutyrophenone, butylhydroxyanisole, butylhydroxytoluene, distearylthiodipropionate ,
An antioxidant such as dilauryl thiodipropionate and hindered phenols may be added.

An intermediate film having a thickness of 0.4 mm has a thickness of 3 mm.
The haze of the laminated glass when sandwiched between the float glass is preferably 2 or less. When the haze is 2 or more, the transparency is remarkably impaired, which is not preferable in practical use. However, even if the haze is 2 or more, an intermediate film having a haze of 2 or more may be used as long as there is no problem in use.

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

As the constitution of the laminated glass, the following modes are appropriately selected. Glass plate / intermediate film / glass plate, glass plate / intermediate film / glass / intermediate film / glass plate Glass plate / intermediate film / PET film or film with decoration on PET film / intermediate film / glass plate

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

In order to produce laminated glass by laminating it between glass plates, a method used in ordinary production of laminated glass is adopted. For example, it is a method of producing a laminated glass by sandwiching an intermediate film from both sides and performing a hot press.

In the present invention, the glass includes not only inorganic glass such as alkali glass but also laminated glass using glass called organic glass such as polycarbonate and PMMA resin. In a system in which a conventional polyvinyl butyral resin system is plasticized with a plasticizer, a whitening phenomenon is caused by the plasticizer attacking the organic glass, but the present invention does not have such a problem.

[0053]

EXAMPLES Examples of the sound insulating interlayer film for laminated glass and the laminated glass using the same according to the present invention will be described below. In the examples and comparative examples, “part” means part by weight.

(Crystallinity) Crystallinity was confirmed by DSC. The case where no crystal peak appeared was regarded as amorphous. DSC
The measurement was performed using "DSC220C" manufactured by Seiko Instruments Inc. at a temperature rising rate of 10 ° C / min.

(Glass Transition Temperature) The glass transition temperature is measured by a viscoelasticity spectrometer (“VES-F-II” manufactured by Iwamoto Seisakusho).
I "), temperature rising rate 3 ° C / min, temperature range -50
The measurement was performed under the conditions of -100 ° 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).
It was measured at a temperature rising rate of 6 ° C./min, a load of 100 kg / cm ² , a die size of 1 mmφ × 10 mm, and a preheating temperature of 150 seconds.

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

(Measurement of Transparency) According to JIS K6714 “Methacrylic resin plate for aircraft” parallel line transmittance and haze value, a 0.4 mm thick sample was manufactured by Tokyo Denshoku Co., Ltd. The total light transmittance and the haze value were evaluated using a "total meter".

(Impact resistance test) The impact resistance test is JISR3.
It carried out according to 205. That is, temperature 23 ℃, humidity 5
Laminated glass held at 0% for 4 hours was held vertically by a support frame, and an attacking body with a weight of 45 kg and a maximum diameter of 75 mm was used for 30 hours.
It 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 portion was marked with x, and the case where it was not formed was marked with o.
Note that n = 4 was used.

(Plastic Lamination Property) Two 3 mm thick polymethylmethacrylate plates, which are organic glass, were interleaved with an interlayer film to prepare a laminated glass, and then 40 weeks for one week.
The haze was measured by standing at 0 ° C.

(Decorative Alignment Property) Two intermediate films and two PET films were inserted between two 3 mm-thick float glasses to prepare a laminated glass and then left at 40 ° C. for 1 week to measure haze. .

(A) Polyester Synthesis For Examples 1 to 11, polyesters were synthesized as shown below.

[Example 1] 63.3 g (0.4 mo) of dimethyl terephthalate was placed in a glass flask having an internal volume of 11 equipped with a stirrer, a thermometer, a gas blowing port and a distillation port.
l), dimethyl isophthalate 63.3 g (0.4 mo
l), 209 g (1.2 mol) of dimethyl adipate,
273 g (4.4 mol) of ethylene glycol, 4,
4 '''-dihydroxy-p-quaterphenyl 3.
4 g (0.01 mol), 0.2 g of calcium acetate and 0.2 g of germanium dioxide as a catalyst were added. After replacing the inside of the flask with nitrogen, raise the temperature inside the flask to 1
The reaction was carried out at 90 ° C for 2 hours. With the reaction, methanol was distilled from the flask. The flask was further heated to 250 ° C. and reacted in this state for 1 hour. Next, the distillation port was connected to a vacuum device, and the reaction was carried out for 1 hour while the pressure inside the flask was reduced to 1 mmHg or less. Excess ethylene glycol was distilled off along with the reaction, and the resulting polyester was taken out after cooling. It was confirmed to be amorphous by DSC. The physical properties are shown in Table 1.

Example 2 In a flask similar to that of Example 1, 97 g (0.5 mol) of dimethyl terephthalate, 97 g (0.5 mol) of dimethyl isophthalate, 174 g (1.0 mol) of dimethyl adipate, trimellitic acid. Trimethyl 2.5 g (10 mmol), ethylene glycol 273 g (4.4 mol), 4,4 ′ ″-dihydroxy-p-quaterphenyl 6.8 g (0.02 m)
ol; 0.5 mol%), and 0.2 g of calcium acetate and 0.2 g of germanium dioxide as a catalyst were added. Polyester was obtained by the same polymerization operation as in Example 1. DS
It was confirmed to be amorphous by C. The physical properties are shown in Table 1.

Example 3 In a flask similar to that of Example 1, 63.3 g (0.4 mo) of dimethyl terephthalate was added.
l), dimethyl isophthalate 63.3 g (0.4 mo
l), 209 g (1.2 mol) of dimethyl adipate,
2.5 g (10 mmol) of trimethyl trimellitate,
273 g (4.4 mol) of ethylene glycol, 4,
4 '''-dihydroxy-p-quaterphenyl 6.
8 g (0.02 mol; 1 mol%), 0.2 g of calcium acetate and 0.2 g of germanium dioxide as a catalyst were added. Polyester was obtained by the same polymerization operation as in Example 1. It was confirmed to be amorphous by DSC. Table 1
Showed physical properties.

Example 4 In a flask similar to that of Example 1, 63.3 g (0.4 mo) of dimethyl terephthalate was added.
l), dimethyl isophthalate 63.3 g (0.4 mo
l), 209 g (1.2 mol) of dimethyl adipate,
2.5 g (10 mmol) of trimethyl trimellitate,
Ethylene glycol 87g (1.4mol), butylene glycol 126g (1.4mol), 4,4 '''-
Dihydroxyethoxy-p-quaterphenyl 17g
(0.04 mol; 2 mol%), and a small amount of tetrabutyl titanate as a catalyst was added. Polyester was obtained by the same polymerization operation as in Example 1. It was confirmed to be amorphous by DSC. The physical properties are shown in Table 1.

Example 5 In the same flask as in Example 1, 97 g (0.5 mol) of dimethyl terephthalate, 29.6 g (0.3 mol) of dimethyl isophthalate, 276 g (1.2 mol) of dimethyl sebacate, and ethylene. Glycol 87 g (1.4 mol), neopentyl glycol 146 g (1.4 mol), 4,4 ″ -dihydroxy-p-terphenyl 15.7 g (0.06 mol;
3 mol%), and calcium acetate as a catalyst and a small amount of antimony trioxide. Polyester was obtained by the same polymerization operation as in Example 1. It was confirmed to be amorphous by DSC. The physical properties are shown in Table 1.

Example 6 In a flask similar to that of Example 1, 47.4 g (0.3 mo) of dimethyl terephthalate was added.
l), 47.4 g of dimethyl isophthalate (0.3 mo
l), 244 g (1.4 mol) of dimethyl adipate,
2.5 g (10 mmol) of trimethyl trimellitate,
273 g (4.4 mol) of ethylene glycol, 4,
4 '''-p-quaterphenyl dicarboxylic acid isobutyl ester 30.4 g (0.06 mol; 3 mol
%), And 0.2 g of calcium acetate and 0.2 g of germanium dioxide as a catalyst were added. Polyester was obtained by the same polymerization operation as in Example 1. It was confirmed to be amorphous by DSC. The physical properties are shown in Table 1.

Example 7 In a flask similar to that of Example 1, 63.3 g (0.4 mo) of dimethyl terephthalate was added.
l), dimethyl isophthalate 63.3 g (0.4 mo
l), 209 g (1.2 mol) of dimethyl adipate,
2.5 g (10 mmol) of trimethyl trimellitate,
273 g (4.4 mol) of ethylene glycol, 4,
4 '''-dihydroxy-p-quarterphenyl 34
g (0.1 mol; 5 mol%), 0.2 g of calcium acetate and 0.2 g of germanium dioxide as a catalyst were added. Polyester was obtained by the same polymerization operation as in Example 1. It was confirmed to be amorphous by DSC. The physical properties are shown in Table 1.

[Embodiment 8] A flask similar to that used in Embodiment 1 was charged with 63.3 g (0.4 mo) of dimethyl terephthalate.
l), dimethyl isophthalate 63.3 g (0.4 mo
l), 209 g (1.2 mol) of dimethyl adipate,
2.5 g (10 mmol) of trimethyl trimellitate,
273 g (4.4 mol) of ethylene glycol, 4,
4 '''-dihydroxy-p-quaterphenyl 0.
34 g (0.001 mol; 0.05 mol%), 0.2 g of calcium acetate and 0.2 g of germanium dioxide as a catalyst were added. Polyester was obtained by the same polymerization operation as in Example 1. It was confirmed to be amorphous by DSC. The physical properties are shown in Table 1.

[0071]

[Table 1]

[Example 9] In a flask similar to that of Example 1, 63.3 g (0.4 mo) of dimethyl terephthalate was added.
l), dimethyl isophthalate 63.3 g (0.4 mo
l), 209 g (1.2 mol) of dimethyl adipate,
As a catalyst, 0.2 g of calcium acetate and 0.2 g of germanium dioxide were added. After replacing the inside of the flask with nitrogen, the inside of the flask was heated and reacted at 180 ° C. for 2 hours.
With the reaction, methanol was distilled from the flask. The flask was further heated to 240 ° C. and reacted in this state for 2 hours. Next, the distillation port was connected to a vacuum device, and the reaction was carried out for 1 hour while the pressure inside the flask was reduced to 1 mmHg or less.
Excess ethylene glycol was distilled off along with the reaction, and the resulting polyester was taken out after cooling. It was confirmed to be amorphous by DSC. The physical properties are shown in Table 2.

Example 10 In a flask similar to that of Example 1, 63.3 g (0.4 mo) of dimethyl terephthalate was added.
l), dimethyl isophthalate 95 g (0.6 mol),
Dimethyl adipate 174 g (1.0 mol), trimethyl trimellitate 2.5 g (10 mmol), ethylene glycol 273 g (4.4 mol), calcium acetate 0.2 g and germanium dioxide 0.2 g as catalysts.
Was added. Polyester was obtained by the same polymerization operation as in Example 1. It was confirmed to be amorphous by DSC. The physical properties are shown in Table 2.

Example 11 In a flask similar to that of Example 1, 95 g (0.6 mol) of dimethyl terephthalate, 95 g (0.6 mol) of dimethyl isophthalate, 139 g (0.8 mol) of dimethyl adipate, trimellitic acid were added. 2.5 g (10 mmol) of trimethyl, 273 g (4.4 mol) of ethylene glycol, 0.2 g of calcium acetate as a catalyst and 0.2 g of germanium dioxide were added. Polyester was obtained by the same polymerization operation as in Example 1. It was confirmed to be amorphous by DSC. The physical properties are shown in Table 2.

[0075]

[Table 2]

(B) Preparation of laminated glass Using the polyesters of Examples 1 to 11 obtained as described above, laminated glass was prepared by the following method.

First, by holding at 150 ° C. for 2 minutes with a press molding machine, an intermediate film having a thickness of 0.40 mm was obtained. In Examples 1 to 7 and Example 11, the interlayer films of any composition were tough, the surface was not sticky, and the handleability was good. On the other hand, the intermediate films having the compositions of Examples 8 and 9 were viscous at room temperature and had a sticky surface and were difficult to handle. The intermediate films having the composition of Example 10 had a slightly sticky surface at room temperature. The process was carried out.

The interlayer film is 30 cm square from both sides and has a thickness of 3 m.
It is sandwiched between 2 pieces of float glass of m, put in a rubber bag, deaerated in a vacuum of 20 torr for 20 minutes, and then 90 ° C.
Degas in an oven for another 30 minutes, 90
Vacuum pressing was performed while maintaining the temperature. The laminated glass body temporarily adhered from the bag was set at a pressure of 12 kg / cm ² and a temperature of 1.
A transparent laminated glass was prepared in an autoclave at 00 ° 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, 200 g of 35% hydrochloric acid and 170 g of butyraldehyde were added to precipitate polyvinyl acetal, and the mixture was kept at 45 ° C. for 6 hours to complete the reaction to obtain a white powder of polyvinyl acetal. 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 sampled, and an amount of plasticizer (triethylene glycol-di-2-ethylbutyrate) corresponding to 45 parts with respect to 100 parts of this resin and 2- (2 ') as an ultraviolet absorber. -Hydroxy-
5'-methylphenyl) -benzotriazole was added to 0.1
Parts and BHT as an antioxidant in an amount of 0.1 part were added and kneaded sufficiently with a mixing roll.
By holding for 1 minute, an interlayer film having a thickness of 0.40 mm was obtained. Table 3 shows the physical properties.

(B) Preparation of laminated glass The interlayer film obtained above was 30 cm square from both sides and had a thickness of 3 mm.
Sandwich it with two pieces of float glass and put it in a rubber bag
And degassed in a vacuum of 20 torr for 20 minutes, then at 90 ° C.
Degas in an oven for another 30 minutes, 90
Vacuum pressing was performed while maintaining the temperature. Temporarily bonded from the bag
The laminated glass body, pressure 12kg / cm ², Temperature 13
Preparation of transparent laminated glass in an autoclave at 0 ° C
did.

(A) Synthesis of Polyester The polyesters of Comparative Examples 2 and 3 were synthesized as follows.

[Comparative Example 2] In a flask similar to that used in Example 1, 388 g (2.0 mol) of dimethyl terephthalate,
174 g (2.8 mol) of ethylene glycol, 0.2 g of calcium acetate and 0.2 g of germanium dioxide as a catalyst were added. Polyester was obtained by the same polymerization operation as in Example 1. Absorption of a melting point showing crystallinity at 253 ° C. was confirmed by DSC. Table 3 shows the physical properties.

[Comparative Example 3] In a flask similar to that of Example 1, 194 g (1.0 mol) of dimethyl terephthalate,
230 g (1.0 mol) of dimethyl sebacate, neobenthyl 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 were added. Polyester was obtained by the same polymerization operation as in Example 1. It was confirmed to be amorphous by DSC. Table 3 shows the physical properties.

[0085]

[Table 3]

(B) Preparation of laminated glass Using the polyesters of Comparative Examples 2 and 3 obtained as described above, laminated glass was prepared in the same manner as in Examples 1-11.

The laminated glass of each example obtained as described above is superior in sound insulation and transparency to the laminated glass of each comparative example and has excellent impact energy absorption.

[0088]

INDUSTRIAL APPLICABILITY The laminated glass using the sound insulating interlayer film for laminated glass of the present invention has transparency and safety which are the basic characteristics of laminated glass, and is effective in converting sound energy into heat energy. The effect of coincidence is mitigated in order to convert to, and the sound insulation is excellent near room 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 long-term transparency during plastic matching and decorative matching is stable and good.

Claims (2)

[Claims] 1. A resin having a glass transition temperature of −20 ° C. to + 40 ° C. and a melting start temperature of 100 ° C. or lower, which comprises an amorphous polyester resin composed of a polycarboxylic acid and an aliphatic dihydric alcohol as a main raw material. An interlayer film for laminated glass, which is characterized in that 2. The aromatic dihydric alcohol represented by the following formula [I] or the aromatic dihydric alcohol represented by the following formula [II] is 0.1 to 3 mol% of all the constituent monomers of the amorphous polyester resin. The interlayer film for laminated glass according to claim 1, which is at least one of divalent carboxylic acids. [Chemical 1] (In the formula, n is 3 or 4, R ¹ and R ² are each independently an alkylene group, and l and m are each independently 0 or an integer of 1 or more.) (In the formula, p represents 3 or 4.)