JPH05330864A - Intermediate film for laminated glass - Google Patents

Abstract

PURPOSE:To produce a laminated glass having excellent sound insulating property for a wide temp. range. CONSTITUTION:This intermediate film for laminated glass consists of polynornornene resin film (A) interposed between two polyvinylacetal resin films (B). The polynorbornene resin film (A) consists of polynorbornene resin having 50000 to 5000000 number average mol.wt and plasticizer, and has -20 to 30 deg.C glass transition temp., (TgA). The polyvinylacetal resin (B) consists of polyvinylacetal resin having 4-10 carbon numbere of acetal groups and plasticizer and has -10 to 30o glass transition temp. (TgB0. These glass transition temps. (TgA) and (TgB) satisfy the relation of TgA+5 deg.C<TgB<TgA+18 deg.C or TgA-18 deg.C<TgB<TgA-5 deg.C.

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 used for producing laminated glass capable of exhibiting excellent sound insulation over a wide temperature range.

[0002]

2. Description of the Related Art Recently, there has been a strong demand for a glass plate which is intended to improve the environment of a house and which is capable of preventing the scattering of fragments such as window glass to ensure safety and exhibiting excellent sound insulation.

Generally, the sound insulation performance is shown as a transmission loss amount according to a change in frequency, and the transmission loss amount is JIS.
In A4708, as indicated by the solid line in FIG.
Above 0 Hz, it is regulated by a constant value according to the sound insulation class. By the way, the sound insulation of the glass single plate is significantly reduced by the coincidence effect in the frequency region around 2000 Hz as shown by the broken line in FIG. 1 (the valley portion of the broken line in FIG. 1 shows the sound insulation performance by the coincidence effect). Corresponding to the decrease, indicating that the prescribed sound insulation performance is not maintained). Here, the coincidence effect is defined by the rigidity and inertia of the glass plate when a sound wave enters the glass plate.
Transverse waves are conducted on the glass surface and the transverse waves resonate with the incident sound,
As a result, the phenomenon of sound transmission occurs.

In order to improve the sound insulation performance of glass, the coincidence effect as described above is alleviated, and the minimum portion of the transmission loss amount caused by the coincidence effect (hereinafter, the transmission loss amount of this minimum portion is referred to as TL value. (See) should be prevented.

Conventionally, various measures such as increasing the mass of glass and subdividing the glass area have been proposed as means for preventing a decrease in the TL value. However, none of them bring a sufficiently satisfactory effect, and in addition to the cost, the price is not reasonable for practical use.

Recently, the demand for sound insulation performance has been increasing,
For example, as a window glass for a building, it has been demanded that a window glass that always exhibits excellent sound insulation performance without being affected by the change in the outside air temperature every season.

Therefore, sound-insulating laminated glass constituted by laminating two sheet glasses through an intermediate film made of a synthetic resin typified by plasticized polyvinyl butyral resin is considered to be an effective means.

The conventional laminated glass is excellent in terms of preventing scattering of fragments, but is 2000 Hz in terms of sound insulation.
In the frequency region centered on, the decrease in sound insulation due to the coincidence effect is unavoidable, and improvement of this point is required.

The principle of sound insulation by laminated glass is mainly due to the viscoelasticity of the interlayer film. Viscoelasticity is a property peculiar to a polymer that has both elasticity for accumulating energy from the outside and viscosity for releasing energy as heat. That is, the compressional wave energy of air generated when sound is transmitted to the outside is partially converted into heat energy by viscoelasticity of the intermediate film, and the sound transmitted to the inside is reduced.

Therefore, the greater the efficiency of conversion of the interlayer film into heat energy, the more advantageous the sound insulation performance. This conversion efficiency is measured by dynamic viscoelasticity, and the dynamic loss coefficient (hereinafter tan
(denoted by δ). Usually, this tan δ has a maximum value in the vicinity of the glass transition temperature of the polymer compound (hereinafter referred to as Tg), so it is necessary to set Tg of the interlayer film to room temperature and maximize tan δ in the vicinity of room temperature. This is an important measure for improving sound insulation performance.

[0011]

2. Description of the Related Art The prior art of an interlayer film intended to improve the sound insulation performance of laminated glass is, for example, as follows.

Japanese Examined Patent Publication No. 46-5830 describes an intermediate film made of a resin having a fluidity about 3 times higher than that of a normal intermediate film, for example, plasticized polyvinyl butyral.

Japanese Patent Laid-Open No. 60-27630 proposes an intermediate film composed of a vinyl chloride-ethylene-glycidyl methacrylate terpolymer as a measure for improving the sound insulation in the initial stage.

[0014]

All of these prior art interlayer films for sound-insulating laminated glass have a TL value higher than that of a glass single plate, but each resin has a limit in tan δ. There is a big problem that the desired TL value cannot be obtained and the absolute value of sound insulation is low.

Therefore, in order to improve the sound insulation performance of the laminated glass using the intermediate film, the tan δ value in the vicinity of Tg as the intermediate film is as high as possible (specifically, 1.5 or more), and the Tg is low. It is desirable to use a resin near room temperature.

By the way, in general, polynorbornene has T
When tan δ near g is about 1 Hz, for example, about 2.
5 is very high. Polynorbornene is a polymer resin compound obtained by ring-opening polymerization of norbornene produced by Diels-Alder reaction of cyclopentadiene and ethylene and having a structure in which double bonds and five-membered rings are alternately bonded. The Tg of this resin alone is 4
Although it is around 0 ° C., it has a good compatibility with the plasticizer, so that its Tg can be easily lowered to around room temperature.
Therefore, when this is blended with the base resin of the interlayer film for laminated glass, it is expected to exhibit excellent sound insulation performance. Moreover, polynorbornene is excellent in mechanical strength, and transparency is improved by adding a specific plasticizer.

However, ordinary polynorbornene has a very narrow glass transition temperature range of about 10 ° C. Therefore, the maximum value of tan δ near Tg is about 2.5, but when the temperature shifts by 1 to 2 ° C., the tan δ value becomes around 1.0, which is not so high. Therefore, the laminated glass using the interlayer film containing polynorbornene exhibits excellent sound insulation performance at a certain temperature, but it is expected that the sound insulation performance will be significantly reduced if the temperature of the outside air changes even a little. Therefore, conventionally, using polynorbornene in a laminated glass for the purpose of sound insulation,
It was considered to be practically difficult.

The present invention has been made in view of the above circumstances, and an object thereof is to take advantage of the excellent characteristics of polynorbornene, to eliminate the above-mentioned drawbacks, and to provide excellent sound insulation over a wide temperature range. An object of the present invention is to provide an interlayer film for laminated glass that can exhibit the above-mentioned effects.

[0019]

The interlayer film for laminated glass according to the present invention has been devised to achieve the above-mentioned object, and the polynorbornene resin film (A) has two polyvinyl acetal resin films (B). The polynorbornene resin film (A) is a laminated film sandwiched by
Consisting of 1,000,000 to 5,000,000 polynorbornene resin and plasticizer, and glass transition temperature (Tg _A ) of -20 to 30 ° C
On the other hand, the polyvinyl acetal resin film (B) is composed of a polyvinyl acetal resin having an acetal group having 4 to 10 carbon atoms and a plasticizer, and has a glass transition temperature (Tg _{B of} −10 to 30 ° C.). ), And the glass transition temperature (T
g _A ) and (Tg _B ) are Tg _A + 5 ° C. <Tg _B <Tg
_A + 18 ℃, or Tg _A -18 ℃ <Tg _B <Tg _A
It is characterized by having a relationship of -5 ° C.

First, the polynorbornene resin film (A) will be described.

As polynorbornene, 50,000 to 500
Those having a number average molecular weight of 10,000, preferably 500,000 to 1,000,000 are used. If the number average molecular weight is less than 50,000, it is not preferable because it is difficult to form a film and the elastic modulus is drastically lowered in the temperature range of Tg or higher. Further, if the number average molecular weight is more than 5,000,000, the fluidity at high temperature deteriorates, and as a result, it becomes difficult to manufacture a laminated glass, which is not preferable. As a typical example of the high molecular weight polynorbornene having a number average molecular weight of about 3,000,000, "NOSOLEX" manufactured by Nippon Zeon Co., Ltd. can be mentioned.

Polymerization of polynorbornene is ring-opening polymerization. At that time, a transition metal type is used as a polymerization catalyst. For example, tungsten, titanium, vanadium, molybdenum,
Compounds of metals such as ruthenium, rhenium, osmium, iridium and tantalum are preferable, and specifically, tungsten hexachloride, titanium tetrachloride, molybdenum pentachloride, iridium trichloride, osmium trichloride, ruthenium trichloride,
Examples are rhenium pentachloride and tantalum pentachloride. Further, a compound such as aluminum or tin may be used as a cocatalyst component in combination with the above compound, and as the aluminum compound for the cocatalyst, trimethylaluminum,
Examples include aluminum trioxide and dichloroethylaluminum, and examples of the tin compound include tetraphenyl tin and tetramethyl tin.

The glass transition temperature (Tg _A ) of the polynorbornene resin film (A) is -20 to 30 depending on the addition of the plasticizer.
C., more preferably -10 to 25.degree. When the glass transition temperature (Tg _A ) deviates from the temperature range of −20 to 30 ° C., good sound insulation performance near room temperature cannot be obtained.

The plasticizer blended with polynorbornene has good compatibility with the polynorbornene and has a pour point of -5.
It is preferable to have 0 to 30 ° C. Pour point is -50 to 3
The reason for using a plasticizer having a temperature of 0 ° C. is that the polynorbornene alone has a Tg of about 40 ° C., and the tan δ peak has a frequency of 1
Since it appears at 50 ° C. in the vicinity of Hz, a plasticizer having good compatibility with hydrogenated polynorbornene and a pour point of −50 to 30 ° C. is added within the above range, so that its peak is −10 to 20 ° C. This is because it can be lowered to the range, and as a result, the sound insulation performance near room temperature can be improved. Pour point is JI
Based on SK2265 petroleum product pour point test method.

The plasticizer used is preferably a colorless and transparent liquid. This is because if the film is colored due to the inclusion of the plasticizer, it cannot be used as a laminated glass that requires transparency. As such a plasticizer, 1 ring, 2 which is used as a petroleum-based softening agent for rubber,
Ring and tricyclic aromatic hydrocarbon oils and naphthenic oils are preferred. Aromatic oils include, for example, tetradecylbenzene, 2
-Methylnaphthalene, 4,5-dihydro-6H-cyclohexaacephenanthrene and the like, specifically, alkene 200P (pour point; -50 ° C, sold by Nippon Petrochemical Co., Ltd.), Nisseki-Highsol-SAS-LH ( Pour point: -5
℃, the same company), Nisseki-Highsol-SAS-296 (pour point; -50 ℃, the same company), Diana process oil AH-
58 (pour point; 10 ° C., Idemitsu Kosan Co., Ltd.) and the like.
The naphthenic oil is, for example, perhydronaphthalene, perhydrophenanthrene, or the like, and specifically, Sunthene 4
50 (pour point; 5 ° C, Sun Oil), Sunthene 424
0 (pour point: 10 ° C., SunOil) and the like.

The compounding amount of the plasticizer is polynorbornene 100.
The amount is preferably 50 to 500 parts by weight, more preferably 100 to 300 parts by weight, based on parts by weight. If the compounding amount of the plasticizer is less than 50 parts by weight, Tg cannot be lowered to around room temperature, so that the obtained laminated glass does not have high sound insulation performance around room temperature, and further, the above resin composition is formed into a film. It is not preferable because the workability when doing is poor. Further, if the amount of the plasticizer compounded exceeds 500 parts by weight, bleeding of the plasticizer may occur, which is not preferable.

Next, the polyvinyl acetal resin film (B) will be described.

The polyvinyl acetal resin is obtained by acetalizing polyvinyl alcohol with an aldehyde, and usually has an acetal group, an acetyl group and a hydroxyl group in the ethylene group of the main chain.

The average degree of polymerization of polyvinyl alcohol, which is a raw material for producing the polyvinyl acetal resin, is preferably 8
It is from 00 to 3,000. When the degree of polymerization is less than 800, the mechanical strength becomes weak, which is not preferable in terms of safety as a laminated glass. When the degree of polymerization is 3,000 or more, the viscosity of the resin at the time of melting is high, and thus the melting at the time of producing laminated glass is not sufficient, which is not preferable. The more preferable degree of polymerization is 1000 to 2,200. The degree of saponification of polyvinyl alcohol is preferably 95 mol or more,
It is more preferably at least 98.5 mol. Saponification degree 95
If it is less than the molar amount, there is a problem in long-term durability such as weather resistance as a laminated glass.

4 carbon atoms used to obtain a polyvinyl acetal resin having an acetal group having 4 to 10 carbon atoms
Aldehydes of 10 include n-butyraldehyde,
Isobutyraldehyde, valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, 2-ethylhexylaldehyde, n-
Examples include decylaldehyde, cinnamaldehyde, benzaldehyde, phenylacetaldehyde, etc., which may be used alone or in appropriate combination. When the aldehyde has less than 4 carbon atoms, the glass transition temperature of the polyvinyl acetal resin is -10 to 10 even if a plasticizer is added to the polyvinyl acetal resin.
It does not fall within the range of 40 ° C. When the carbon number exceeds 10,
The obtained polyvinyl acetal is poor in rigidity, and the penetration resistance of the laminated glass is not sufficient. As more preferable aldehydes, n-butyraldehyde, isobutyraldehyde, and n-hexylaldehyde are used alone or in combination. The degree of acetalization of polyvinyl acetal is preferably 55 to 85 mol%, more preferably 60 to 75 mol%. Acetalization degree is 55
When it is at most mol%, the polyvinyl acetal impairs the compatibility with the plasticizer and it becomes impossible to add the plasticizer in an amount necessary for ensuring penetration resistance. The degree of acetalization is 8
When it is 5 mol% or more, the rigidity at a high temperature (around 40 ° C.) required for the penetration resistance of the laminated glass is significantly lowered, which is not preferable.

As a method for obtaining a polyvinyl acetal resin, for example, polyvinyl alcohol is dissolved in hot water,
After maintaining the obtained aqueous solution of polyvinyl alcohol at a predetermined temperature, the aldehyde and the catalyst are added to this to proceed the acetalization reaction, and then the reaction solution is kept at a high temperature at a predetermined temperature, followed by neutralization, washing with water and drying. There is a method of obtaining a resin powder through the steps.

The glass transition temperature (Tg _B ) of the polyvinyl acetal resin film (B) is -20 to 20 depending on the addition of the plasticizer.
The temperature is adjusted to 30 ° C, more preferably -10 to 25 ° C. When the glass transition temperature (Tg _B ) deviates from the temperature range of −20 to 30 ° C., good sound insulation performance cannot be obtained in a wide temperature range around room temperature, and penetration resistance as a laminated glass can be secured. Can not. Therefore, the addition amount of the plasticizer is preferably 20 to 60 parts by weight with respect to 100 parts by weight of the resin. If the amount of plasticizer added is less than 20 parts by weight,
The polyvinyl acetal resin film (B) at a low temperature is poor in flexibility and the penetration resistance is lowered, which is not preferable. If the amount of the plasticizer added exceeds 60 parts by weight, bleeding of the plasticizer may occur, which is not preferable.

Examples of the plasticizer added to the polyvinyl acetal resin include organic plasticizers such as monobasic acid esters and polybasic acid esters, and phosphoric acid plasticizers such as organic phosphoric acid-based and organic phosphorous acid-based plasticizers. Used.

Among the monobasic acid esters, triethylene glycol, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptanoic acid, n-octylic acid, 2-ethylhexylic acid, and pelargonic acid (n-nonylic acid). A glycol-based ester obtained by a reaction with an organic acid such as decyl acid is preferable. In addition, esters of tetraethylene glycol and tripropylene glycol with the above organic acids can also be used.

As the polybasic acid ester, adipic acid,
An ester of an organic acid such as sebacic acid or azelaic acid and a linear or branched alcohol having 4 to 8 carbon atoms is preferable.

As the phosphoric acid type plasticizer, tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphite and the like are preferable.

More preferred examples of the monobasic acid ester include triethylene glycol-di-2-ethylbutyrate, triethylene glycol-di-2-ethylhexoate, triethylene glycol-dicapronate and triethylene glycol. -Di-n-octoate and the like, dibasic acid ester, dibutyl phthalate,
Examples thereof include dibutyl sebacate, dioctyl azelate and dibutyl carbitol adipate.

Additives usually used for adjusting the adhesive strength between the resin film and the glass plate, stabilizers for preventing the deterioration of the resin, antioxidants, ultraviolet absorbers, etc. At the time of mixing with the agent or during the resin manufacturing process,
It can be used as needed.

As the additives, metal salts of carboxylic acids, for example, potassium metal such as octylic acid, hexylic acid, butyric acid, acetic acid and formic acid, alkali metal salts such as sodium, alkaline earth metal salts such as calcium and magnesium, zinc. , Cobalt salts, etc. are used.

As the stabilizer, a surfactant such as sodium lauryl sulfate or alkylbenzene sulfonic acid is used.

Antioxidants include 2,6-di-t-butyl-4-methylphenol (BHT), butylated hydroxyanisole (BHA), pentaerythrityl-tetrakis (3- (3,5-butyl). -4-hydroxyphenyl) propionate), 2,6-di-t-butyl-4
-Ethylphenol, stearyl-β- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate,
“Irganox 1010” manufactured by Ciba-Gaiki, etc. is used.

Examples of ultraviolet absorbers include benzotriazole type and hindered amine type.

In the benzotriazole type, for example, as a benzotriazole type ultraviolet absorber in which at least one of hydrogens at the 4th to 7th positions in the benzotriazole ring is substituted with chlorine, 2- (3-t-butyl-) is used. 5-methyl-
2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole and the like are exemplified, and 4 to 7 of the benzotriazole ring are exemplified. As a benzotriazole-based ultraviolet absorber having no substituent at the position,
2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl) -2H-benzotriazole, 2- (3,5- Di-t-butyl-2-
Hydroxyphenyl) benzotriazole, 2- (3,
5-di-t-amyl-2-hydroxyphenyl) benzotriazole, methyl-3- (3-t-butyl-5-
Examples thereof include (2H-benzotriazol-2-yl) -4-hydroxyphenyl) propionate-polyethylene glycol condensate.

In the hindered amine system, bis (2,2,2
6,6-tetramethyl-4-piperidyl) sebacate,
Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, Sanol LS-770, Sanol LS-7
65, Sanol LS-2626, Chimasso
b944LD, Thinuvin manufactured by Ciba Geigy
-662, Thinvin-622LD, Mark
LA-57, Mark LA-77, MarkLA-6
2, Mark LA-67, Mark LA-63, M
ark LA-68, Mark LA-82, Mark
LA-87, Goodrite UV-3404, etc. are illustrated.

The thickness of the polynorbornene resin film (A) is 0.
2 to 1.0 mm is preferable. If it is less than 0.2 mm, the sound insulation effect is not recognized, and if it exceeds 1.0 mm, it is not preferable in terms of cost. On the other hand, polyvinyl acetal resin film
The thickness of (B) is preferably 0.05 to 0.3 mm. 0.0
If it is less than 5 mm, good weatherability and penetration resistance cannot be exhibited. Considering the weather resistance and penetration resistance of the laminated glass, the upper limit of the thickness of the resin film (B) is 0.3 m.
m is sufficient.

The glass transition temperature (Tg _A ) of the polynorbornene resin film (A) and the glass transition temperature (Tg _B ) of the polyvinyl acetal resin film ( _B ) are Tg _A + 5 ° C. <Tg _B <
It is necessary that Tg _A + 18 ° C. or Tg _A −18 ° C. <Tg _B <Tg _A −5 ° C. be satisfied. Glass transition temperature (T
g _A ) and the glass transition temperature (Tg _B ) are more preferably Tg _A + 8 ° C. <Tg _B <Tg _A + 12 ° C., or T
There is a relationship of g _A −12 ° C. <Tg _B <Tg _A −8 ° C.
If the difference between the two is wider than 18 ° C., the respective temperatures exhibiting good sound insulation performance are too far apart to cover a wide temperature range. Also, when the difference between the two becomes narrower than 5 ° C,
These temperatures are too close to cover a wide temperature range. For example, a polynorbornene resin film (A) having Tg _A = 10 ° C., a polyvinyl acetal resin film (B) having Tg _B = 0 and Tg _B = 20 ° C., a polynorbornene resin film (A) having Tg _A = 20 ° C. and Tg _A = 20 ° C. _B = 10 ° C. of the polyvinyl acetal resin film _{(B), Tg a = 0} ℃ polynorbornene resin film (a) and Tg _B = 10 ° C. of the polyvinyl acetal resin film (B), and the like.

The film forming method is a method in which a mixture of a resin and a plasticizer is kneaded by a mixing roller to be made into an elastomer, which is produced by press hot pressing using a spacer having a predetermined thickness.

As a laminating method, a polynorbornene resin film (A) and a polyvinyl acetal resin film (B) are laminated so that one resin film (A) is sandwiched by two resin films (B). After stacking them, a method of melt-pressing them with a thermocompression press is generally used.

The intermediate film according to the present invention has a laminated structure in which the polynorbornene resin film (A) is sandwiched between two polyvinyl acetal resin films (B) or includes this structure, and the following examples are given. ..

(1) Three-layer laminated structure of layer (B) / layer (A) / layer (B) (2) layer (B) / layer (A) / layer (B) / layer (A) / layer ( B) etc. 5
Layer stacking structure.

In the multi-layered structure of three or more layers, the laminated structure may be an asymmetrical structure such as layer (B) / layer (B) / layer (A) / layer (B).

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

Further, the intermediate film may be sandwiched by a transparent body other than glass, for example, a transparent body such as a polycarbonate resin.

[0054]

EXAMPLES Some examples of the present invention and comparative examples to be compared with the examples will be given below, and the performance of the obtained laminated glass will be shown.

The degree of acetalization of the polyvinyl acetal resin was measured by the following NMR method and titration method.

NMR Method The proton nuclear magnetic resonance spectrum of the product was measured by the following method.

A 2 wt% deuterated chloroform solution of polyvinyl acetal resin was prepared, a small amount of tetramethylsilane [(CH ₃ ) ₄ Si] was added as a standard substance, and spectrum measurement was performed at a temperature of 23 ° C.

Titration method JIS “Polyvinyl acetal test method” (K-672
The degree of acetalization was measured by the hydroxylamine hydrochloride method in accordance with the test method for "vinyl acetal" in the section of composition analysis in 8-1977).

The amount of acetyl groups of the polyvinyl acetal resin (mol% of ethylene groups to which acetyl groups are bonded relative to the total ethylene groups of the main chain) is determined by the above-mentioned JIS "Polyvinyl acetal test method" (K-6728-197).
It was measured according to the test method of "vinyl acetal" in the section of composition analysis in 7).

Example 1 a) Preparation of polynorbornene resin film (A) 10 mol (941 g) of purified norbornene was dissolved in 6 liters of purified toluene to prepare a monomer solution. A cocatalyst system of tungsten hexachloride (WCl ₆ ) and tetraphenyltin (Ph ₄ Sn) was used as a catalyst. The amount of catalyst added was 1/100 mol (WCl ₆ ; 3
9.6 g, Ph ₄ Sn; 42.7 g), which were dissolved in 4 liters of purified toluene to prepare a catalyst solution. These solutions were aged at 40 ° C. for 15 minutes, then the monomer solution was added to the catalyst solution, and polymerization was carried out at 40 ° C. for 4 hours. The termination of the polymerization was performed by adding an appropriate amount of toluene / isobutyl alcohol (4/1) to the polymerization solution. After termination, the polymerization solution was precipitated with methanol, the precipitate was filtered and then dried. Thus, a polynorbornene resin was prepared.

The weight average molecular weight of this polymer was 1,200,000 in terms of polystyrene as a result of determination by the light scattering gel permeation chromatography (GPC) method.

A plasticizer Nisseki-Hi having a pour point of 5 ° C. was added to 50 g of the polynorbornene resin obtained by the above polymerization.
150 g of ghsol-SAS-LH was added and mixed at room temperature for about 1 hour, and the resulting mixture was mixed with a mixing roller for 10 hours.
The mixture was thoroughly kneaded at 0 ° C. for about 20 minutes to prepare an elastomeric sheet. Then, using a stainless steel spacer having a thickness of 0.8 mm, a predetermined amount of the above sheet was held at 130 ° C. for 10 minutes with a press molding machine to obtain a thickness of about 0.8.
mm film was prepared. The glass transition temperature (T
g _A ) was 11 ° C. as a result of differential scanning calorimetry with “DSC220C” manufactured by Seiko Denshi KK

B) Preparation of polyvinyl acetal resin film (B) To 2910 g of pure water, 190 g of polyvinyl alcohol having a polymerization degree of 1700 and a saponification degree of 99.2 mol% was added and dissolved by heating. The temperature of the reaction system was adjusted to 12 ° C., and 35 wt% hydrochloric acid 2
Polyvinyl acetal was precipitated by adding 01 g and 124 g of n-butyraldehyde. Then, the reaction system was kept at a temperature of 50 ° C. for 4 hours to complete the reaction. Unreacted aldehyde was washed away by washing with excess water, the hydrochloric acid catalyst was neutralized, the salt was removed, and the product was dried to obtain a white powder polymer. Thus, a polyvinyl acetal resin was prepared.

The degree of acetalization of this polyvinyl acetal resin was 66.3 mol% as measured by the proton NMR method. The amount of acetyl groups in this polyvinyl acetal resin was 0.9 mol%.

50 g of this polyvinyl acetal resin was sampled, 20 g of triethylene glycol-di-2-ethylbutyrate as a plasticizer was added thereto, and this mixture was sufficiently kneaded with a mixing roll to give an elastomer. Then, using a stainless steel spacer having a thickness of 0.2 mm, a predetermined amount of the elastomeric material was held at 150 ° C. for 20 minutes with a press molding machine to give a thickness of about 0.2.
mm film was prepared. The glass transition temperature (T
g _B ) was 22 ° C. as a result of differential scanning calorimetry measurement by “DSC220C” manufactured by Seiko Instruments Inc.

C) Preparation of laminated glass One resin film (A) obtained from polynorbornene resin
And two resin films (B) obtained from a polyvinyl acetal resin are laminated so that the laminated structure is layer (B) / layer (A) / layer (B), and a laminated interlayer film is obtained. It was

This interlayer film was sandwiched from both sides with two float glass sheets each having a side length of 30 cm and a thickness of 3 mm, and the unpressed sandwich body was placed in a rubber bag and deaerated at a vacuum degree of 20 torr for 20 minutes. Then, it was transferred to an oven at 90 ° C. in the degassed state and kept at this temperature for 30 minutes. The sandwich thus temporarily adhered by deaeration was then thermocompression-bonded at a pressure of 12 kg / cm ² and a temperature of 135 ° C. in an autoclave to produce a transparent laminated glass.

Example 2 In the production of the polynorbornene resin film (A), the glass transition temperature (T
g _A ) was 18 ° C.

In the preparation of the polyvinyl acetal resin, the resin was prepared in the same manner as in Example 1 except that n-hexylaldehyde was used as the aldehyde used. The degree of acetalization of the obtained polyvinyl acetal resin is 6
9.3 mol% and glass transition temperature (Tg _B ) is 7 ° C.
Met.

A laminated glass was produced in the same manner as in Example 1 except for the above points.

Example 3 In the preparation of a polynorbornene resin, 0.5 M of ethyl acrylate as a chain transfer agent was added to the polymerization system to prepare a resin having a number average molecular weight of 700,000.

In the production of the polynorbornene resin film (A), Nisseki-Highsol-SAS-2 was used as a plasticizer.
80 parts by weight of 96 (pour point: -50 ° C) was added, and its glass transition temperature (Tg _A ) was set to -12 ° C.

Further, in the preparation of the polyvinyl acetal resin, the resin was prepared in the same manner as in Example 1 except that the aldehyde used was replaced with n-octylaldehyde and the addition amount of the plasticizer was 20 parts. The degree of acetalization of the obtained polyvinyl acetal resin is 64.6 mol%,
The glass transition temperature (Tg _B ) was 3 ° C.

A laminated glass was produced in the same manner as in Example 1 except for the above points.

Comparative Example 1 A laminated glass was produced by using a polynorbornene resin film (A) having a thickness of about 1.2 mm and using only this film as an intermediate film.

Comparative Example 2 The thickness of the polyvinyl acetal resin film (B) was about 1.2 mm.
Then, a laminated glass was produced using only this film.

Comparative Example 3 In the production of the polynorbornene resin film (A), Nisseki-Highsol-SAS-LH (pour point: -5) was used as a plasticizer.
80 parts by weight, and its glass transition temperature (T
_A laminated glass was produced in the same manner as in Example 1 except that g _A ) was changed to 45 ° C.

Comparative Example 4 Acetaldehyde was used as the aldehyde used in the preparation of the polyvinyl acetal resin. The degree of acetalization of the obtained polyvinyl acetal resin is 73.5 mol%.
And the glass transition temperature (Tg _B ) was 62 ° C.

A laminated glass was produced in the same manner as in Example 1 except for the above points.

<Measurement of Sound Insulation> The sound insulation of each laminated glass of the above-mentioned Examples and Comparative Examples was measured by the following method.

A vibration generator for damping test of laminated glass (vibrating machine manufactured by Shinken Co., Ltd., “G21-005”).
D ”), and the vibration characteristics obtained therefrom are mechanical impedance amplifiers (“ XG- manufactured by Rion Co., Ltd. ”).
81 "), and the vibration spectrum was analyzed by an FFT analyzer (" FFT spectrum analyzer HP 3582A "manufactured by Yokogawa Hewlett-Packard Co.). The transmission loss was calculated from the loss coefficient thus obtained and the ratio of the resonance frequency with the glass (measurement temperature: 20).
C). Based on this result, the minimum transmission loss amount around the frequency of 2000 Hz was taken as the TL value. The measurement temperature was set at three points of 10 ° C, 20 ° C and 30 ° C. The results of these measurements are shown in Table 1.

[0082]

[Table 1] As is clear from Table 1, it is recognized that the laminated glass of the example exhibits excellent sound insulation over a wider temperature range than that of the comparative example.

[0083]

Since the interlayer film for laminated glass according to the present invention is configured as described above, it is possible to produce a laminated glass exhibiting excellent sound insulation over a wide temperature range.

[Brief description of drawings]

FIG. 1 is a graph showing sound insulation characteristics of laminated glass as a transmission loss amount with respect to frequency.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08L 29/14 LHA 6904-4J

Claims (1)

[Claims] 1. A polynorbornene resin film (A) having two sheets
The product sandwiched between the vinyl acetal resin membranes (B)
The layer film, the polynorbornene resin film (A) is a number average
Polynorbornene resin having a molecular weight of 50,000 to 5,000,000 and a plasticizer
And a glass transition temperature of −20 to 30 ° C.
(Tg_A), On the other hand, a polyvinyl acetal resin film
(B) is a polyvinyl chloride having an acetal group with 4 to 10 carbon atoms.
Consisting of a nilacetal resin and a plasticizer, and -10
Glass transition temperature (Tg of -30 ° C) _B) Has a glass
Transfer temperature (Tg_A) And (Tg_B) Is Tg_A+ 5 ° C <T
g _B<Tg_A+ 18 ℃ or Tg_A-18 ° C <Tg
_B<Tg_AA combination characterized by a relationship of -5 ° C
Intermediate film for glass.