KR100192528B1 - An interlayer film for laminated glass - Google Patents

Abstract

At least one layer comprising a polyvinyl acetal resin (A) having 4 to 6 carbon atoms in the acetal group and a molar fraction of 8 to 30 mol% of the main chain of the average value of the ethylene group to which the acetyl group is bonded, and a plasticizer At least a polyvinyl acetal resin (B) having a carbon number of 3 to 4 carbon atoms of the acetal group and 4 mol% or less of the average of the ethylene group to which the acetyl group is bonded to the entire ethylene group of the main chain; It is an interlayer film for laminated glass in which one layer (B) is laminated.

Sound energy is effectively converted to and absorbed by thermal energy, and in particular, the deterioration of sound insulation performance due to the coincidence effect is effectively prevented in the mid- and high-pitched regions around 2000 Hz.

Description

Interlayer for Laminated Glass

1 is a graph showing the sound insulation characteristics of laminated glass in terms of transmission loss with respect to frequency.

[Industrial use]

The present invention relates to an interlayer film for laminated glass having excellent sound insulation.

[Background of invention]

In general, laminated glass formed by sandwiching a resin film between a pair of glass plates is excellent in safety because it does not scatter fragments upon breakage and is excellent in safety. Therefore, the laminated glass is widely used for window glass of traffic vehicles such as automobiles and window glass of buildings.

Among the interlayer films for laminated glass, the polyvinyl butyral resin film plasticized by the addition of a plasticizer has excellent adhesion with glass, strong tensile strength, high transparency, and the like. It is suitable as.

In general, the sound insulation performance is expressed as the transmission loss amount according to the change of frequency, and the transmission loss amount is prescribed by the sound insulation class at 500 kHz or more according to the sound insulation class as indicated by the solid line in FIG. 1 in JIS A 4708.

By the way, as shown by the broken line in a 1st degree, the sound insulation of a glass plate falls remarkably by the coincidence effect in the frequency range centering on 2000 Hz (The valley part of the broken line in 1st degree is coincidence. It corresponds to the reduction of the sound insulation performance by an effect, and it does not hold | maintain predetermined sound insulation performance. Herein, the coincidence effect refers to a phenomenon in which when the sound wave is incident on the glass plate, the transverse wave is conducted on the glass surface due to the rigidity and inertia of the glass plate, so that the transverse wave and incident sound resonate, resulting in sound transmission.

Although conventional laminated glass is excellent in preventing scattering of debris, in the frequency range centered on 2000 Hz in terms of sound insulation, a decrease in sound insulation due to the coincidence effect is unavoidable and improvement of advantages. This is required.

On the other hand, human hearing is known to exhibit very high sensitivity compared to other frequency ranges in the range of 1000 to 6000 Hz in an isoluminance curve, and the sound insulation performance is deteriorated by the coincidence effect. It can be seen that solving the problem is extremely important for sound insulation. In order to improve the sound insulation performance of laminated glass, the coincidence effect is alleviated as described above, so that the smallest part of the transmission loss caused by the coincidence effect (hereinafter referred to as TL, see FIG. 1). It is necessary to prevent the drop.

Conventionally, as a means of preventing the fall of TL value, various measures, such as the increase of the mass of laminated glass, the multilayer of glass, the refinement of a glass area, and the improvement of a glass plate support means, are proposed. However, they do not produce a satisfactory effect on either of them, and they are not a reasonable price for practical use in terms of cost.

In recent years, the demand for sound insulation performance is increasing, for example, in the building window glass is required excellent sound insulation near room temperature. That is, the temperature (sound insulation performance maximum temperature = TLmax temperature) with the best sound insulation performance obtained by plotting transmission loss (TL value) with respect to temperature is near room temperature, and the maximum sound insulation performance (maximum sound insulation performance value = TLmax value) itself is Excellent sound insulation which is large is calculated | required. However, the laminated glass for windshields of automobiles using conventional plasticized polyvinyl butyral resin film has a problem that the maximum sound insulation performance is higher than room temperature, and the sound insulation performance is not good near room temperature.

[Prior art and problem to be solved]

As a prior art of an interlayer film for the purpose of improving the sound insulating performance of laminated glass, for example, Japanese Unexamined Patent Publication No. 46-5830 discloses a resin having a fluidity about 3 times higher than that of a conventional interlayer film, for example, poly Interlayers made of vinyl butyral are described. However, this has a serious problem that the absolute value of sound insulation of laminated glass is low.

Japanese Laid-Open Patent Publication No. 2-229742 discloses an intermediate film made of a laminate of a polymer film having a glass transition temperature of 15 ° C. or less, for example, a vinyl chloride-ethylene-glycidyl methacrylate copolymer film and a plasticized polyvinyl acetal film. It is described. However, it does not exhibit sound insulation exceeding the Ts-35 grade in the sound insulation grade according to JIS A 4706, but the temperature range indicating sound insulation is limited and it is not possible to exhibit good sound insulation in a wide temperature range.

Japanese Laid-Open Patent Publication No. 62-37148 discloses a laminate made of two or more types of viscoelastic materials having different acoustic resistances, for example, poly, for the purpose of preventing a decrease in sound insulation performance in the coincidence region of a rigid plate (glass plate). There is proposed an intermediate film made of a laminate of a methyl methacrylate film and a vinyl chloride-ethylene-glycidyl methacrylate copolymer film. However, this is a problem that the sound insulation is not satisfactory in the initial performance, the performance is also degraded in long-term durability. The reason for this is that these resins cause mass transfer by the diffusion action at the interface, and the constrained layer effect at the interface is blurred.

Japanese Laid-Open Patent Publication No. 60-27630 proposes an interlayer film containing a plasticizer in a polyvinyl chloride resin as a measure for improving sound insulation at an early stage. In this interlayer film, the initial sound insulation is slightly improved, but in the laminated glass processing, the processing conditions need to be changed under the conditions of the polyvinyl butyral interlayer film. The polyvinyl butyral interlayer is still the mainstream of the material for laminated glass interlayer, and the preliminary bonding conditions of the joining process are set to the conditions of the polyvinyl butyral interlayer.

Japanese Laid-Open Patent Publication No. 62-278148 proposes an interlayer film for low-adhesion laminated glass comprising a polyvinyl acetal resin having 6 to 10 carbon atoms of an acetal group and a plasticizer. However, the sound insulation of this interlayer is not enough.

Japanese Laid-Open Patent Publication No. 51-106190 proposes to obtain a structure having vibration damping properties in a wide temperature range by laminating two or more kinds of resins having different glass transition temperatures. In this structure, it is recognized that the vibration damping property is improved in a wide temperature range. However, this publication does not describe the sound insulation, transparency, etc. required for laminated glass, and this structure does not satisfy the requirements of high impact energy absorption required for safety glass and scattering prevention at the time of glass breakage.

Japanese Unexamined Patent Publication No. 62-10106 proposes a polyvinyl butyral crosslinked to a low degree by intermolecular bonding. However, in the laminated glass using the interlayer film which adds a plasticizer to this resin, only about 30 dB of sound insulation performance can be obtained near room temperature. Japanese Laid-Open Patent Publication No. 3-124441 discloses an interlayer film comprising a laminate of two or more layers of polyvinyl butyral containing a plasticizer and varying the degree of polymerization. However, the desired sound insulation performance is hardly obtained only by stacking two or more layers of polyvinyl butyral having different degrees of polymerization.

Japanese Patent Laid-Open No. 62-9928 discloses an extruded sheet composed of a polyvinyl butyral resin and a plasticizer crosslinked to a low degree by stable intermolecular bonding. However, this cannot clear the JIS 30 grade near room temperature, and the sound insulation performance is too low.

Japanese Unexamined Patent Publication No. 4-254444 proposes an interlayer film in which a film made of polyvinyl acetal having 6 to 10 carbon atoms of acetal group and a plasticizer and a film made of polyvinyl acetal having 1 to 4 carbon atoms of acetal group and a plasticizer are laminated. have. In this interlayer film, the improvement effect of sound insulation performance is certainly recognized, and the sound insulation performance by temperature change does not change greatly, but the effect thereof is not enough yet.

In the interlayer film of Japanese Patent Laid-Open No. 4-254444, an interlayer film in which both surfaces of a polyvinyl acetal having 6 to 8 carbon atoms of acetal group and a plasticizer are laminated with a film made of polyvinyl butyral and a plasticizer has cleared the JIS 35 grade. In this regard, the effect of improving sound insulation performance is recognized. However, it does not have good sound insulation in a wide temperature range, which is an important requirement as a sound insulating interlayer.

As described above, in the interlayer film of the prior art, laminated glass exhibiting excellent sound insulation performance over a long period of time especially in a wide temperature range cannot be constituted.

In view of the above, the present invention prevents the lowering of the TL value by the mildness of the coincidence effect without impairing the basic properties required for laminated glass such as transparency, weather resistance, impact energy absorption, and adhesion to glass, and It is an object of the present invention to provide an interlayer film for sound insulating laminated glass that can stably exhibit excellent sound insulation performance over a wide temperature range.

[Means for solving the problem]

MEANS TO SOLVE THE PROBLEM In the point which the film | membrane which consists of polyvinyl acetal plasticized by the plasticizer used as the interlayer film for laminated glass is balanced in various characteristics, such as transparency, weather resistance, impact energy absorption, adhesiveness with glass, and the like. In view of this, in order to improve sound insulation without damaging such a desirable characteristic, improvement of the intermediate film which uses polyvinyl acetal as a resin component was earnestly examined.

As a result, at least one polyvinyl acetal film composed of a polyvinyl acetal resin having a specific acetyl group and a plasticizer, obtained by aldehyde acetalization of polyvinyl alcohol, is laminated at least one each, and the laminate is stacked on two glass plates. It was found that the coincidence effect was alleviated at or near room temperature by sandwiching, thereby completing the present invention.

That is, in the first interlayer film for laminated glass according to the present invention, the acetal group has 4 to 6 carbon atoms, and the molar fraction (ie, the amount of remaining acetyl groups in the total amount of ethylene groups in the main chain) of the average value of the ethylene groups to which the acetyl group is bonded. Backbone of the average value of the amount of ethylene groups to which the carbon number of the at least one layer (A) which consists of 8-30 mol% of polyvinyl acetal resin (A) and a plasticizer, and an acetal group is 3-4, and an acetyl group couple | bonds At least one layer (B) made of a polyvinyl acetal resin (B) and a plasticizer having a mole fraction of 4 mol% or less with respect to the total amount of ethylene groups is laminated.

In the second interlayer film for laminated glass according to the present invention, in the first interlayer film, the polyvinyl acetal resin (A) is a resin in which the standard deviation σ of the amount of ethylene groups bonded to the acetyl group is 0.8 or less.

In the third interlayer film for laminated glass according to the present invention, in the first interlayer film, the standard deviation? Of the amount of ethylene groups to which the acetyl group is bonded to the polyvinyl acetal resin (A) is 2.5 to 8.

In the interlayer film for fourth laminated glass according to the present invention, the molecular weight distribution ratio (weight average molecular weight Mw / number average molecular weight Mn) of the polyvinyl acetal resin (A) is 1.01 to 1.50 in the first interlayer film.

In the 5th interlayer film for laminated glass by this invention, the molecular weight distribution ratio (weight average molecular weight Mw / number average molecular weight Mn) of polyvinyl acetal resin (A) is 3.5-20 in a 1st interlayer film.

As for the 6th interlayer film for laminated glass which concerns on this invention, in the 1st interlayer film, the outermost layer of the side which needs at least weather resistance among the multiple layers laminated | stacked absorbs the ultraviolet absorber whose effective ultraviolet absorption wavelength is 300-340 nm. It consists of the layer (B) containing so that coefficient X might become 0.01 or more.

In the seventh interlayer film for laminated glass according to the present invention, in the first interlayer film, the degree of block formation Y of the following definition of the ethylene group to which the acetyl group of the polyvinyl acetal resin (A) is bonded is 0.15 to 0.40.

In the eighth interlayer film for laminated glass according to the present invention, in the first interlayer film, the blockage degree Y of the following definition of the ethylene group to which the acetyl group of the polyvinyl acetal resin (A) is bonded is 0.55 to 0.90.

Block degree Y = 0.5 × S / (T × U)

Here, S, T and U in the formula are -CH (OH) -CH _2- (OCOCH ₃ ) CH-, the amount of methylene group in the structure (S), the amount of hydroxyl group (T), the amount of acetyl group (U) is shown.

Polyvinyl acetal resin is obtained by aldehyde acetalization of polyvinyl alcohol, and usually has an acetal group, an acetyl group, and a hydroxyl group in the ethylene group of a principal chain.

The average degree of polymerization of polyvinyl alcohol which is a raw material for polyvinyl acetal resin is preferably 500 to 3000. This is because when the polymerization degree is less than 500, the penetration resistance of the laminated glass is inferior, and when the polymerization degree exceeds 3000, the strength becomes too large and cannot normally be used as safety glass. More preferable degree of polymerization is 1000-2500.

As the aldehyde having 4 to 6 carbon atoms used to obtain the polyvinyl acetal resin (A) having 4 to 6 carbon atoms of the acetal group, n-butyl aldehyde, isobutyl aldehyde, barrel aldehyde, n-hexyl aldehyde, 2-ethylbutyl aldehyde Etc. are used alone or in combination as appropriate. If the aldehyde contains less than 4 carbon atoms, sufficient sound insulation performance cannot be obtained. Aldehydes having more than 6 carbon atoms are remarkably lacking in the reactivity of acetalization, and the obtained interlayer film cannot sufficiently exhibit sound insulation performance near room temperature. As a more preferable aldehyde, n-butyl aldehyde, isobutyl aldehyde, n-hexyl aldehyde is used individually or in combination.

In addition, propionaldehyde, n-butylaldehyde, isobutylaldehyde, etc. may be used alone or in combination of two or more kinds of the aldehyde having 3 to 4 carbon atoms used to obtain the polyvinyl acetal resin (B) having 3 to 4 carbon atoms. .

In polyvinyl acetal resin (A), the average value of the amount of residual acetyl groups is limited to 8-30 mol%. The reason is that if the amount is 8 mol% or less, the initial performance is not sufficiently exhibited, and at 30 mol% or more, the reaction rate of the aldehyde remarkably decreases. In the polyvinyl acetal resin (A), the more preferable value is 10-24 mol% than the average value of the acetyl group amount.

In polyvinyl acetal resin (B), the average value of the amount of residual acetyl groups is limited to 4 mol% or less. The reason is that, when the amount is 4 mol% or more, the difference from the average value of the amount of residual acetyl groups in the polyvinyl acetal resin (A) is small, and good sound insulation performance is not exhibited. In polyvinyl acetal resin (B), the more preferable value of the average value of an acetyl group amount is 0-2 mol%.

As polyvinyl acetal resins (A) and (B), it is particularly preferable to use n-butylaldehyde. By using n-butylaldehyde, the adhesive strength between the layers constituting the laminated film is made stronger, and polyvinyl acetal resin can be obtained in the same manner as in the conventional synthesis method of butyral resin.

As polyvinyl acetal resins (A) and (B), even if a mixture of two or more kinds of polyvinyl acetal resins obtained by polyvinyl alcohol obtained by aldehyde acetalization, respectively, is more than 30% by weight relative to the total acetal portion. Even if the polyvinyl acetal resin obtained by performing acetalization using aldehydes other than the said aldehyde together in the range which does not use, it does not deviate from the scope of the present invention.

It is preferable that the acetalization degree of polyvinyl acetal resin (A) is 40 mol% or more. This is because when the acetalization degree is less than 40 mol%, compatibility with the plasticizer is poor, and it is difficult to add the plasticizer in an amount necessary to exhibit sound insulation performance. More preferable acetalization degree is 50 mol% or more.

It is preferable that the acetalization degree of polyvinyl acetal resin (B) is 50 mol% or more. This is because when the acetalization degree is less than 50 mol%, compatibility with the plasticizer is poor, and it is difficult to add the plasticizer in an amount necessary for securing the penetration resistance.

In the present invention, as a method of obtaining the polyvinyl acetal resins (A) and (B), for example, polyvinyl alcohol is dissolved in hot water, and the obtained polyvinyl alcohol aqueous solution is maintained at a predetermined temperature. Thereafter, acetalization reaction is carried out, and then, the reaction solution is maintained at a high temperature at a predetermined temperature, and thereafter, a resin powder is obtained through a supplying well of neutralization, washing with water, and drying.

In the second interlayer film, the average value of the amount of acetyl groups in the polyvinyl acetal resin (A) relative to the total amount of ethylene groups in the main chain, that is, the average value of the amount of remaining acetyl groups is also 8 to 30 mol%. If the average value of the amount of residual acetyl groups is less than 8 mol%, the sound insulation performance is good in the temperature range higher than room temperature, but the sound insulation performance may not be obtained in the vicinity of room temperature. On the contrary, when the average value of the amount of residual acetyl groups exceeds 30 mol%, the sound insulation performance is good at low temperatures, but it is difficult to obtain good sound insulation performance near normal temperatures. The average value of the amount of remaining acetyl groups is particularly preferably 12 to 24 mol%.

The standard deviation? Of the component fraction of the ethylene group to which the acetyl group in the polyvinyl acetal resin (A) is bonded is 0.8 or less. When this standard deviation (sigma) exceeds 0.8, the sound insulation performance maximum may fall. The range with especially preferable standard deviation (sigma) of the component fraction of the ethylene group which the acetyl group couple | bonds is 0.5 or less.

The average value of the amount of remaining acetyl groups in the polyvinyl acetal resin (A) in the third interlayer is also 8 to 30 mol%. The range with especially preferable said mole fraction of polyvinyl acetal resin (A) is 12-22 mol%.

The standard deviation? Of the component fraction of the ethylene group to which the acetyl group in the polyvinyl acetal resin (A) is bound is 2.5 to 8. If the standard deviation σ is less than 2.5, good sound insulation performance may not be obtained over a wide temperature range. Conversely, when this standard deviation (sigma) exceeds 8, the sound insulation performance maximum may fall. The range with especially preferable standard deviation (sigma) of the component fraction of the ethylene group which the acetyl group couple | bonds is 3-6.

The polyvinyl acetal resin having the above standard deviation sigma of 2.5 to 8 is, for example, a method of acetalizing a polyvinyl alcohol obtained by dividing the polyvinyl acetate in several steps, and a mixture of a plurality of polyvinyl alcohols having different degrees of saponification. It is obtained by the method of acetal and the method of mixing several polyvinyl acetal of the amount of an acetyl group. The most economically preferred method is to adjust the distribution of the ethylene group to which the acetyl group is bound by the step of polyvinyl alcohol and to acetal this polyvinyl alcohol.

The standard deviation? Of the component fraction of the ethylene group to which the acetyl group in the polyvinyl acetal resin (B) is bonded in the second and third interlayer films is not particularly limited in terms of improving the sound insulation performance.

By the use of polyvinyl acetal resin (A) having a molecular weight distribution ratio (Mw / Mn) of 1.01 to 1.50 in the fourth interlayer, the coincidence effect is remarkably alleviated near room temperature, and the sound insulation according to JIS A 4706 is reduced. Excellent sound insulation in grades above Ts-35 is obtained.

It is difficult to synthesize | combine resin whose molecular weight distribution ratio (Mw / Mn) is less than 1.01, and when this ratio exceeds 1.50, TL value will fall.

The polyvinyl acetal resin having a narrow molecular weight distribution in this manner is obtained by fractionating from a known polyvinyl acetal using, for example, preparative chromatography.

In the fifth interlayer film, the use of the polyvinyl acetal resin (A) having a molecular weight distribution ratio (Mw / Mn) of 3.5 to 20 significantly relieves the coincidence effect over a wide temperature range and obtains good sound insulation.

When the molecular weight distribution ratio (Mw / Mn) is less than 3.5, the temperature range in which the coincidence effect is alleviated becomes narrow and good sound insulation may not be obtained in a wide temperature range. If the molecular weight distribution ratio (Mw / Mn) exceeds 20, the sound insulation performance exceeding the Ts-35 grade is difficult to obtain.

Thus, the polyvinyl acetal resin having a wide range of molecular weight distribution is, for example, by mixing a plurality of polyvinyl alcohols having different molecular weight, followed by acetal reaction or a method of mixing a plurality of polyvinyl acetals having different molecular weights. Obtained.

The number average molecular weight Mn of the polyvinyl acetal resin in the fourth and fifth interlayers is preferably 27,000 to 270,000, more preferably 45,000 to 235,000. If Mn of polyvinyl acetal resin is less than 27,000, the obtained laminated glass will be inferior in penetration resistance, and if Mn exceeds 270,000, the strength of the obtained laminated glass will become too large and it may not be usable as a safety glass.

In the sixth interlayer film, at least the outermost layer on the side where weather resistance is required is composed of a layer (B) containing an ultraviolet absorber having an effective ultraviolet absorption wavelength of 300 to 340 nm so that the ultraviolet absorption coefficient X is 0.01 or more.

Here, the ultraviolet absorption coefficient X is a value defined by {pressure t (mm) x {number of UV absorber addition parts u (parts by weight) of the film of the layer (B) to be used for the outermost layer requiring weather resistance). In the seventh interlayer, polyvinyl acetal resin having a blocking degree of 0.15 to 0.40 of the ethylene group to which the acetyl group is bonded is obtained by acetalization of polyvinyl alcohol having a blocking degree of 0.15 to 0.40 of the ethylene group to which the acetal group is bonded. Obtained. By using polyvinyl alcohol having such high blockability, a polyvinyl acetal resin having a low temperature dependency of the mechanical loss tangent curve in viscoelasticity is obtained. By using it as a polyvinyl acetal resin (A) in these 1st intermediate | middle films, the outstanding sound insulation intermediate film which can convert sound energy into thermal energy effectively in a wide temperature range is obtained. Thus, the synthesis | combining method of polyvinyl alcohol which has high block property is described, for example in Unexamined-Japanese-Patent No. 37-17385.

When the said degree of blocking is less than 0.15, TL value in each temperature may fall remarkably, and when the degree of blocking is larger than 0.40, good sound insulation may not be obtained in a wide temperature range. More preferably, the degree of blocking is in the range of 0.20 to 0.35.

The polyvinyl acetal resin having a blocking degree of 0.55 to 0.90 of the ethylene group bonded to the acetyl group in the eighth interlayer is obtained by acetalization of polyvinyl alcohol having a blocking degree of 0.55 to 0.90 of the ethylene group bonded to the acetyl group. Lose. Thus, polyvinyl acetal with a low glass transition temperature is obtained by using polyvinyl alcohol which has high randomness. By using this as the polyvinyl acetal resin (A) in the first interlayer, an excellent sound insulating interlayer is obtained which has good fluidity and can convert sound energy into heat energy more effectively. Such a method of synthesizing polyvinyl alcohol having high randomness is described, for example, in Japanese Patent Laid-Open No. 2-255806.

If the block degree is smaller than 0.55, excellent sound insulation may not be obtained. If the block degree is larger than 0.90, the acetalization degree is lowered, so that impact resistance, which is a basic characteristic as an interlayer film, may be lowered. The block degree is more preferably in the range of 0.65 to 0.80.

Definition of the Blocking Degrees of the Interlayers 7 and 8 At Y = 0.5 × S / (T × U), S, T and U in the formulas are each -CH (OH) -CH ₂ -obtained by the measurement of ¹³ C-NMR. The amount (S) of the methylene group in the (OCOCH ₃ ) CH-structure, the amount (T) of the hydroxyl group, and the amount (U) of the acetyl group are shown.

In the interlayer film of the present invention, as the polyvinyl acetal (A), the viscosity of a solution dissolved in 10% by weight in a mixed solvent of ethanol and toluene (weight ratio 1: 1) is 200 to 1000 centipoise (cP) by measurement with a BM viscometer. A crosslinked polyvinyl acetal resin such as) is preferably used.

By using the cross-linked polyvinyl acetal resin as described above, the sound insulation performance is excellent near room temperature, and the effective temperature range for converting sound energy into heat energy is expanded, and the sound insulation performance is excellent in a wide temperature range near room temperature. You can get an interlayer.

If the viscosity is less than 200 cP, good sound insulation performance in a wide range may not be obtained, and if it exceeds 1000 cP, the change in temperature of the sound insulation performance is small, but the absolute value of the sound insulation performance is lowered, and the production or film formation of the resin It may become difficult. The range of viscosity which shows a more preferable crosslinking degree is 300-800 cP.

As one of the methods for producing a polyvinyl acetal resin having an intermolecular crosslink as described above, as shown in Japanese Patent Application Laid-Open No. 39-24711, the acetalization reaction between molecules and the intermolecular crosslinking between molecules are carried out by precipitation method. It is a way to produce.

On the other hand, polyvinyl having cross-molecular crosslinking is obtained by using an amount of aldehyde during acetalization reaction of polyvinyl alcohol in an amount of 10 to 200 mol% excess of acetalization degree of polyvinyl acetal resin obtained or adding an acid catalyst more than usual. It is also possible to obtain acetal resin easily.

When the excess amount of aldehyde is 10 mol% or less, crosslinking reaction hardly progresses between molecules, and the improvement of sound insulation performance in a wide range may not be expected. On the other hand, in the case of 200 mol% or more, gelation occurs at the stage of the synthesis of the polyvinyl acetal resin, the reaction rate of the aldehyde is lowered, or the treatment of unreacted aldehyde is often undesirable. More preferably, 15 to 50 mol% of aldehydes are used in excess of acetalization degree.

Moreover, the method of making intermolecular crosslinking by adding a small amount of polyfunctional aldehydes is also used preferably. As the polyfunctional aldehyde, glutaraldehyde, 4,4 '-(ethylenedioxy) dibenzaldehyde, 2-hydroxyhexanediar, and the like are suitably used. It is preferable that the addition amount of polyfunctional aldehyde is 0.001-1.0 mol% with respect to mol% of the hydroxyl group of polyvinyl alcohol, More preferably, it is 0.01-0.5 mol%.

In the interlayer film of the present invention, the polyvinyl acetal resin (A) also has a narrow acetalization distribution, for example, 90% or more of the distribution of acetalization degree is -2 mol% and +2 mol% of the average value of acetalization degree. Polyvinyl acetal resins present in the range of? Are preferably used.

By using a polyvinyl acetal resin having a narrow acetalization degree distribution in this way, it is possible to obtain an interlayer film which is much better in sound insulation performance than a conventional sound insulation interlayer in a certain temperature range. This interlayer film can pass JIS sound insulation grade Ts-40 grade.

The polyvinyl acetal resin having a narrow acetalization distribution as described above is obtained by setting the temperature when the aldehyde and the catalyst are added to the polyvinyl alcohol aqueous solution to a low temperature, preferably 5 ° C. or lower. It is also effective to reduce the original amount of the catalyst used up to 60% by weight, for example. In some cases, the remaining catalyst may be added slowly in small amounts, for example, over 30 minutes to 3 hours.

Other types of solvents having different polarities may be used to separate and extract a narrow synthetic polyvinyl acetal resin having acetalization degree for each acetalization degree.

In the interlayer film of the present invention, the polyvinyl acetal resin (A) further has a wide acetalization degree distribution, for example, 10 to 30% of the acetalization degree distribution is -10 mol% or less of the average value of acetalization degree and +10. Polyvinyl acetal resin which exists in the range with mol% or more is used preferably.

Thus, the intermediate film which consists of polyvinyl acetal resin which has a wide acetalization fraction can pass JIS sound insulation grade Ts-30 grade in the range of -10 degreeC-80 degreeC.

The polyvinyl acetal resin having a wide acetalization distribution as described above dissolves polyvinyl alcohol with hot water and maintains this aqueous solution at an appropriate temperature, for example, 20 ° C. or higher, and then adds an aldehyde and a catalyst to the acetal reaction. Obtained by advancing. As another method, the amount of aldehyde added to the aqueous polyvinyl alcohol solution is initially 40% by weight or less of the total amount, followed by maintaining the reaction solution at the required temperature, and then gradually removing the remaining aldehyde in small amounts. For example, it can be added over 30 minutes to 3 hours. Moreover, the method of mixing the two or more types of polyvinyl acetal resins of average acetalization degree, which increases the usage-amount of a catalyst, and the temperature increase rate after addition of an aldehyde and a catalyst very much may be effective.

The acetalization degree distribution of polyvinyl acetal resin can be measured by methods, such as a liquid chromatography and thin layer chromatography.

Next, the plasticizer added to polyvinyl acetal resin (A) (B) is demonstrated.

In the present invention, as the plasticizer, organic plasticizers such as monobasic acid esters and polybasic acid esters, and phosphoric acid plasticizers such as organic phosphoric acid and organic phosphorous acid are used.

Among the monobasic acid esters, triethylene glycol, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptanoic acid, n-octylic acid, 2-ethylhexyl acid, pelagonic acid (n-nonylic acid), decyl acid, etc. Preference is given to glycol esters obtained by reaction with an organic acid. In addition, esters of other tetraethylene glycol, tripropylene glycol and the above organic acid are also used.

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

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

As a more suitable example, as a monobasic acid ester, triethylene glycol-di-2-ethyl butyrate, triethylene glycol-di-2-ethylhexate, triethylene glycol dicapronate, and triethylene glycol di n-octate Examples of the dibasic acid ester include dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, and the like.

It is preferable that the addition amount of the plasticizer of a layer (A) is 30-70 weight part with respect to 100 weight part of polyvinyl acetal resins (A). If the addition amount of the plasticizer is less than 30 parts by weight, the sound insulation performance cannot be sufficiently obtained. If the amount of the plasticizer is more than 70 parts by weight, the plasticizer may bleed out and the transparency of the laminated glass and the adhesion between the interlayer film and the glass plate may be impaired. Especially preferable addition amount is 35-65 weight part.

It is preferable that the addition amount of the plasticizer of a layer (B) is 25-55 5 weight part with respect to 100 weight part of polyvinyl acetal resins (B). If the added amount of the plasticizer is less than 25 parts by weight, the penetration resistance decreases. On the contrary, if it exceeds 55 parts by weight, the plasticizer may bleed out and the transparency of the laminated glass and the adhesion between the interlayer film and the glass plate may be impaired. Especially preferable addition amount is 30-45 weight part.

In the interlayer film according to the present invention, a UV absorber (i) which is commonly used to improve the weather resistance of each polyvinyl acetal resin layer, an additive (ii) which is usually used to adjust the adhesion between the resin film and the glass plate, and polyvinyl acetal Stabilizers to prevent deterioration (iii), UV stabilizers to improve the stability of the resin layer against ultraviolet rays (iv), antioxidants to improve the thermal stability of the resin layer (v), and the like mixed with polyvinyl acetal and a plasticizer In the preparation of poetry or polyvinyl acetal, it is appropriately added depending on the dinosaur.

In the sixth intermediate film, in order to improve the weather resistance of the polyvinyl acetal resin layer of the layer (A), the outermost layer on the side of the layer constituting the laminated film, which requires at least weather resistance, has an effective ultraviolet absorption wavelength of 300 to 340 nm. It consists of the layer (B) which contained the phosphorus ultraviolet absorber so that ultraviolet-ray absorption coefficient X may be 0.01 or more.

In the ultraviolet absorbent whose upper limit of the effective ultraviolet absorption wavelength is 340 nm or less, sufficient weather resistance cannot be obtained, and such an ultraviolet absorber is not preferable.

(i) Ultraviolet absorbers are classified into benzotriazole type, benzophenone type, cyanoacrylate type and the like.

As a benzotriazole type ultraviolet absorber, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2 '-Hydroxy-3', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole , 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t- Amylphenyl) benzotriazole, 2- [2'-hydroxy-3 '-(3' ', 4' ', 5' ', 6' '-tetrahydrophthalamidemethyl) -5'-methylphenyl] benzotria Slumber is illustrated.

As a benzophenone type ultraviolet absorber, 2, 4- dihydroxy benzophenone, 2-hydroxy-4- methoxy benzophenone, 2-hydroxy-4- octokishi benzophenone, 2-hydroxy-4- dodecyl Oxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5 Sulfur benzophenone etc. are illustrated.

As a cyanoacrylate type ultraviolet absorber, 2-ethylhexyl-2-cyano-3,3'- diphenyl acrylate, ethyl-2-cyano-3,3'- diphenyl acrylate, etc. are illustrated.

The amount of the ultraviolet absorber added is 0.01 (the weight of ultraviolet absorption coefficient X defined by the film pressure t (mm) x {ultraviolet absorber addition number u (part by weight)} of the layer (B) used for the outermost layer on the side where weather resistance is required). It is preferable that the value is equal to or larger than the number of mm. However, in the sixth interlayer film, the amount of the ultraviolet absorber added must be such that the ultraviolet absorption coefficient X in the above definition is 0.01 (parts by weight. Mm) or more.

If the ultraviolet absorption coefficient X is less than 0.01 (mm. Parts), sufficient weather resistance may not be obtained. The amount of the ultraviolet absorber added is more preferably a value when the ultraviolet absorption coefficient X is 0.02 or more. Moreover, it is preferable that the addition amount of a ultraviolet absorber is 0.01-5 weight part with respect to 100 weight part of polyvinyl acetal resins. If this addition amount is less than 0.01 part by weight, sufficient weather resistance may not be obtained, and if it is 5 parts by weight or more, a decrease in the strength of the interlayer film and a decrease in the total light transmittance of the laminated glass may occur. Function may be impaired.

(ii) As the additive, metal salts of carboxylic acids such as alkali metal salts such as potassium, sodium such as octylic acid, hexyl acid, butyric acid, acetic acid and formic acid, alkali earth metal salts such as calcium and magnesium, zinc and cobalt salts are used. do.

(iii) As stabilizers, surfactants such as sodium lauryl sulfate, alkylbenzenesulfonic acid and the like are used.

(iv) As a ultraviolet stabilizer, the ultraviolet stabilizer of a handadamine type | system | group or a metal complex salt type is used suitably.

In the handadamine amine system, bis (2,2,6,6-tetramethyl-4-piperidyl) sebagate and tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1, 2,3,4-butanetetracarboxylate, Sanol LS-770, Sanol LS-765, Sanol LS-2626, Chimassob 944LD, Thinuvin-622 LD, Mark LA-57, Mark LA-77, Mark LA-62, Mark LA-67, Mark LA-63, Mark LA-68, Mark-82, Mark LA-87, Goodrite UV-3404, etc. are illustrated.

Examples of the metal stabilizer UV stabilizer include nickel [2,2] -thiobis (4-t-octyl) phenolate] -n-butylamine, nickel dibutyldithio carbamate, nickel bis [0-ethyl-3, 5- (di-t-butyl-4-hydroxybenzyl)] phosphate, cobaltdicyclohexyldithiophosphate, [1-phenyl-3-methyl-4-decanonyl-pyrazolate (5) ₂ ] nickel Etc. are illustrated.

It is preferable to use 0.01-3 weight part of addition amounts of an ultraviolet stabilizer. If this addition amount is 0.01 weight part or less, sufficient stabilization effect cannot be acquired, and in 3 weight part or more, the fall of the total light transmittance of a laminated glass, the physical property of an intermediate film, etc. may arise. Especially preferable addition amount of an ultraviolet stabilizer is 0.1-1.5 weight part.

(v) As antioxidant, a phenol type, a sulfur type, phosphorus type etc. are mentioned. Especially 2,6-di-t-butyl-p-cresol (BHT), butylated hydroxy niazole (BHA), 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylene-bis- (4-methyl-6-butylphenone), 2,2'-methylene-bis (4- Ethyl-6-t-butylphenol), 4,4'-thiobis- (3-methyl-6-t-butylphenol), 4,4'-butylidene-bis- (3-methyl-6-t -Butylphenol), 1,1,3-tris- (2-methyl-hydroxy-5-t-butylphenyl) butane, tetrakis [methylene-3- (3 ', 5'-butyl-4'-hydride Oxyphenyl) propionate] methane, 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenol) butane, 1,3,5-trimethyl-2,4,6- Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (3,3'-bis- (4'-hydroxy-3'-t-butylphenol) butyric acid) glycol ester Etc. are used as appropriate.

It is preferable to add 0.05-3 weight part of antioxidant. If the added amount of the antioxidant is less than 0.05 part by weight, sufficient antioxidant capacity cannot be obtained. If the amount of the antioxidant is added, more than 3 parts by weight may cause a decrease in the total light transmittance and the physical properties of the interlayer film. Especially preferable addition amount of antioxidant is 0.2-1.5 weight part.

Next, the laminated structure of the intermediate film by this invention is demonstrated.

Examples of the laminated structure include the following.

(1) Two-layer laminated structure of layer (A) / layer (B)

(2) Three-layer lamination structure such as layer (A) / layer (B) / layer (A), layer (B) / layer (A) / layer (B)

(3) 4-layer lamination structure such as layer (B) / layer (A) / layer (B) / layer (A)

In the multilayer structure of the above three layers, the laminated structure may be an asymmetrical structure such as / layer (A) / layer (B) / layer (B).

Moreover, the interlayer film by this invention laminated | stacked the layer (C) in which the characteristic as an interlayer film for adhesive glasses is not impaired by the transition of a plasticizer, for example, the lamination | stacking or the decoration-decorated polystyrene phthalate film laminated | stacked. It may be. Examples of the laminated structure of such an interlayer film include the following.

(4) 3-layer lamination structure such as layer (A) / layer (C) / layer (B)

(5) 4-layer lamination structure such as layer (B) / layer (C) / layer (B) / layer (A), layer (B) / layer (A) / layer (C) / layer (A)

It is preferable that the outermost layer of at least both sides among the layers which comprise the interlayer film for laminated glass is comprised from the layer (B). By this arrangement, the conventional technique can be used as it is in the bonding processing between the glass plate and the intermediate film.

When weather resistance from one direction is desired, for example, in the interlayer film of laminated glass used for windshields of automobiles or windows of buildings, the outermost layer on the side where weather resistance is required has an effective ultraviolet absorption wavelength of 300 to 340 nm. It is preferable to comprise the layer (B) which contained the phosphorus ultraviolet absorber so that ultraviolet-ray absorption coefficient X may be 0.01 or more.

In the sixth interlayer film, however, the outermost layer on the side where weather resistance is required needs to be composed of the layer B containing the ultraviolet absorber having the effective ultraviolet absorption wavelength such that the ultraviolet absorption coefficient X is 0.01 or more.

About the thickness of layer (A) and layer (B), the thickness of the sum total of layer (A) is preferably 0.05 mm or more. If it is less than 0.05 mm, it is not enough to exhibit initial performance.

As for the thickness of the whole interlayer film, 0.3-1.6 mm which is thickness as a normal interlayer film for laminated glass is preferable.

The larger the thickness is, the more excellent the sound insulation is, but it is preferable to determine the thickness in consideration of the penetration resistance required as the laminated glass, and the range of the above-mentioned thickness is practically suitable.

As the film forming method, for example, various molding methods may be applied, such as a method of forming a laminate separately and then laminating them between glass plates, and a method of integrally forming each layer using a multilayer molding machine.

In order to manufacture laminated glass by sandwiching an intermediate film between glass plates, the method used for manufacture of a normal laminated glass is employ | adopted. For example, the method of manufacturing laminated glass by thermopress press is carried out by inserting a film | membrane into the glass plate at the both sides.

Further, sandwiching the interlayer film of the present invention with a transparent body having a higher rigidity than the present polyvinyl acetal plasticizer such as a polycarbonate resin such as a polycarbonate resin does not depart from the scope of the present patent.

EXAMPLE

Hereinafter, the performance of the obtained laminated glass which shows the Example of this invention and the comparative example which should be compared with this is shown.

The acetalization degree of polyvinyl acetal resin is prepared by preparing a 2 wt% heavy water-benzene solution of resin and adding a small amount of tetramethylsilane [(CH ₃ ) ₄ Si] as a reference material and proton of polyvinyl acetal resin at a temperature of 23 ° C. It was measured by taking the nuclear magnetic resonance spectrum.

The average value of the acetal group content of polyvinyl acetal resin was measured based on the test method of "vinyl acetal" of the term of composition analysis in said JIS [polyvinyl acetal test method] (K-6728-1977). Distribution of the ethylene group which the acetyl group couple | bonded was calculated | required by the following method. First, hydrochloric acid hydroxyamine is acted on the polyvinyl acetal resin to desorb the acetal group, and then, the obtained polyvinyl alcohol is fractionated according to the amount of acetyl group, and the amount of the fraction is determined by weight ratio. Vinyl Acetal Test Method] (K-6728-1977) was measured according to the test method of [Vinyl Acetal] in the item of composition analysis.

The weight average molecular weight Mw, the number average molecular weight Mn, and the molecular weight distribution ratio (Mw / Mn) were determined by light scattering gel permeation chromatography chromatography (PCO-LS-8000 system, column: Showa Denko Zepolystyrene gel KF-802, KF -803, KF-804, internal diameter 8mm, length 300mm, and a solvent: hexafluoroisopropanol) were calculated | required.

Fractionation of the polymer was performed using the above-described GPC (LS-8000 system) as preparative chromatography, using a HFIP preparative column made by Showa Denko as a column, and hexafluoroisopropanol as a solvent.

The sound insulation of the laminated glass was measured by the following method. That is, at a predetermined temperature, the laminated glass is excited by a vibration generator for dumping test (exciter manufactured by Shikensha Co., Ltd., [G21-005D]), and the vibration characteristics obtained here are obtained by a mechanical impedance amplifier manufactured by Lion Co., Ltd. [XG-81]), and the vibration spectrum was analyzed by an FFT analyzer ([FFT Spectrum Analyzer HP 3582A] manufactured by Yokogawa Hewlett Pakkaadsha). The transmission loss was calculated from the ratio of the loss coefficient thus obtained to the resonance frequency of the glass. As a result, the TL value was set as the minimum transmission loss around 2000 Hz.

Weatherability evaluation of the laminated glass was performed at the black panel temperature of 63 degreeC using the sunshine weatherability tester (by JIS 1415). The transmittance (by JSR 3212 visible light transmittance) and yellowness (by JIK 7103) were measured. Furthermore, the yellowness was measured by reflection type, C light source, and 2 degree field of view.

For the sound insulation performance maximum temperature = TLmax temperature and the sound insulation performance maximum value = TLmax value, the transmission loss is measured at a temperature interval of 10 ° C. The minimum transmission loss is plotted against the temperature at a frequency of about 2000 Hz, and the maximum value of the TL value is measured. It was set as TLmax, and the temperature at that time was made into TLmax temperature.

Example 1

[(Preparation of Resin (A)]

To 2890 g of pure water, 191 g of polyvinyl alcohol having a degree of polymerization of 1700 was added and heated and dissolved. The reaction system was temperature-controlled at 12 degreeC, 201 g of 35 weight% hydrochloric acid, and 130 g of butylaldehydes were added, and polyvinyl acetal was deposited. The reaction system was then kept at a temperature of 50 ° C. for 5 hours to complete the reaction. After washing with excess water, the unreacted aldehyde was washed out, the hydrochloric acid catalyst was neutralized and the salt was removed, and then dried to obtain a white powder of polyvinyl acetal resin (A).

The acetalization degree of this polyvinyl acetal resin (A) was 60.2 mol%, and the acetyl group content was 11.9 mol%.

[Preparation of film A]

50 g of the polyvinyl acetal (A) was collected, and 25 g of triethylglycol-di-2-ethylbutylate as a plasticizer and tetrakis [methylene-3- (3 ', 5'-butyl-4') as an antioxidant. -Hydroxyphenyl) propionate] 0.15 g of methane was added and the blend was sufficiently kneaded with a mixing roll to maintain a predetermined amount of the kneaded product at 150 DEG C for 30 minutes with a press molding machine. In this way, a 0.20 mm thick film A was produced.

[Preparation of Resin (B)]

190 g of polyvinyl alcohol having a degree of polymerization of 1700 was added to 2910 g of pure water to dissolve it by heating. The reaction system was temperature-controlled at 12 degreeC, and polyvinyl acetal was precipitated by adding 201g of 35weight% hydrochloric acid and 124g of butylaldehydes. The reaction was then held at a temperature of 50 ° C. for 4 hours to complete the reaction. After washing with excess water, the unreacted aldehyde was washed out, the hydrochloric acid catalyst was neutralized, the salt was removed, and the white powder of polyvinyl acetal resin (B) was obtained via drying.

The acetalization degree of this polyvinyl acetal resin (B) was 65.9 mol%, and the acetyl group content was 0.9 mol%.

[Preparation of film (B)]

50 g of the polyvinyl acetal resin (B) was collected, which was triethylene glycol-di-2-ethylbutylate (20 g) as a plasticizer and 2- (2'-hydroxy-5'-methylphenyl) bezo as an ultraviolet absorber. 0.1 g of triazole was added, and the blend was sufficiently kneaded with a mixing roller, and a predetermined amount of the kneaded product was maintained at 150 DEG C for 30 minutes by a press molding machine. In this way, a film having a thickness of 0.20 mm was produced.

[Production of Laminated Glass]

The single film obtained from the polyvinyl acetal resin (A) and the two films obtained from the polyvinyl acetal resin (B) are laminated (layer) (B) / layer (A) / layer (B). The layers were stacked to obtain a three-layer laminated intermediate film. The interlayer is sandwiched from two sides with two float glass, each with a thickness of 30 mm of 30 cm on one side, and the uncompressed sandwich is placed in a rubber bag and degassed for 20 minutes under a vacuum of 20 torr. Transfer to an oven at 90 ° C. and hold this temperature for 30 minutes. Thus, the sandwich agent temporarily bonded by the vacuum press was thermo-compression-processed at the pressure of 12 kg / cm <2>, and the temperature of 135 degreeC in an autoclave, and the transparent adhesive glass was produced.

EXAMPLES 2-7

As shown in Table 1, an intermediate film was prepared by changing the acetalization degree and the acetyl group amount, the amount of plasticizer added, the layer thickness, and the lamination structure of the polyvinyl acetal resin (A) and the polyvinyl acetal resin (B) within the scope of the present invention. And the laminated glass was produced using this.

[Comparative Examples 1-4]

[Measurement of Sound Insulation]

About each laminated glass of the said Examples 1-7 and Comparative Examples 1-4, the sound insulation property was measured in temperature of 20 degreeC.

The measurement results are shown in Table 1 together.

As is apparent from Table 1, it is recognized that the laminated glass according to the embodiment of the present invention has excellent sound insulation performance.

Example 8

[Preparation of Resin (A)]

180 g of polyvinyl alcohol (manufactured by Nippon Kosei Chemical Co., Ltd.) having a degree of polymerization of 1700 and a standard deviation of 0.5 and a degree of polymerization of 1700 were added to 2890 g of pure water and an average value of 12. mol% of an acetyl group was added. The reaction system was temperature-controlled at 12 degreeC, the polyvinyl acetal was deposited by adding 200 g of 35 weight% hydrochloric acid and 135 g of butylaldehydes. The reaction system was then maintained at a temperature of 45 ° C. for 4 hours to complete the reaction. By washing with excess water, the unreacted aldehyde was washed out, the hydrochloric acid catalyst was neutralized and the salt was removed, followed by drying to obtain a white powder of polyvinyl acetal resin (A).

The acetalization degree of this polyvinyl acetal resin (A) was 64.3 mol%, the amount of acetyl groups was 12.3 mol%, and the standard deviation (sigma) of the amount of ethylene groups which the acetyl group couple | bonded was 0.5.

[Preparation of film A]

50 g of the polyvinyl acetal (A) was collected and 25 g of triethylene glycol-di-2-ethylbutylate as a plasticizer and 0.05 g of 2- (2'-hydroxy-5'-methylphenyl) benzotriazole as a ultraviolet absorber. And 0.05 g of BHT was added as an antioxidant, and the blend was sufficiently kneaded with a mixing roller, and a predetermined amount of the kneaded product was maintained at 150 ° C. for 30 minutes by a press molding machine. This produced the film A with a thickness of 0.40 mm.

[Preparation of Resin (B)]

The standard deviation sigma of 66.3 mol% of acetalization degree, 0.9 mol% of acetyl group, and the amount of ethylene groups which the acetyl group couple | bonded by operation similar to preparation of resin (B) of Example 1 is white of polyvinyl acetal resin (B) of 0.3 A powder was obtained.

[Preparation of film (B)]

The polyvinyl acetal (B) was produced by the same operation as the preparation of the film (B) of Example 1, and a film (B) having a thickness of 0.10 mm was produced.

[Production of Laminated Glass]

The transparent laminated glass was produced by operation similar to the manufacture of the laminated glass of Example 1.

[Examples 9-11]

As shown in Table 2, Kariki shows the amount of acetalization and acetyl group, standard deviation sigma, addition amount of plasticizer, layer thickness and lamination structure of polyvinyl acetal resin (A) and polyvinyl acetal resin (B) within the scope of the present invention. Modified to prepare an interlayer, and used to produce a laminated glass.

[Comparative Examples 5-6]

As shown in Table 2, the interlayer film which does not belong to the scope of the present invention was prepared, respectively, and the laminated glass was produced using this.

[Measurement of Sound Insulation]

About each laminated glass of the said Examples 8-11 and Comparative Examples 5-6, sound insulation was measured at predetermined temperature.

The measurement result was put together in Table 2 and shown.

As is apparent from Table 2, it is recognized that the laminated glass according to the embodiment of the present invention has excellent sound insulation performance in the vicinity of room temperature.

Example 12

[Preparation of Resin (A)]

1890 g of pure polyvinyl alcohol (manufactured by Nippon Kosei Chemical Co., Ltd.) having a degree of polymerization of 1700 and a polymerization degree of 1700 was added to 2890 g of pure water, an average value of 11.8 mol% of an acetyl group, an atylene group to which an acetyl group was bonded, and warmed and dissolved. The reaction system was temperature controlled to 12 ° C., and polyvinyl acetal was precipitated by adding 201 g of 35% by weight hydrochloric acid and 130 g of butylaldehyde. The reaction system was then maintained at a temperature of 45 ° C. for 4 hours to complete the reaction. By washing with excess water, the unreacted aldehyde was washed out, the hydrochloric acid catalyst was neutralized, the salt was removed, and dried to obtain a white powder of polyvinyl acetal resin (A).

The acetalization degree of this polyvinyl acetal resin (A) was 61.3 mol%, the amount of acetyl groups was 11.8 mol%, and the standard deviation (sigma) of the amount of ethylene groups which the acetyl group couple | bonded was 3.4.

[Preparation of film A]

50 g of the polyvinyl acetal (A) was collected, and 22.5 g of triethylene glycol-di-2-ethylbutylate as a plasticizer and 2- (2'-hydroxy-5'-methylphenyl) benzotriazole 0.05 as a ultraviolet absorber were added. g and 0.05 g of BHT as an antioxidant were added, and the blend was sufficiently kneaded with a mixing roll, and a predetermined amount of the kneaded material was held at a press molding machine for 30 minutes. Thus, a film A having a thickness of 0.15 mm was produced.

[Preparation of Resin (B)]

The polyvinyl acetal resin (B) having a standard deviation sigma 0.3 of the amount of acetalization of 66.3 mol%, the amount of acetyl groups and the amount of ethylene groups bonded to the acetyl group by the same operation as in the preparation of the resin (B) of Example 1 White powder was obtained.

[Preparation of film (B)]

By the same operation as the preparation of the film (B) of Example 1, the polyvinyl acetal (B) was formed into a film to produce a film (B) having a thickness of 0.10 mm.

[Production of Laminated Glass]

By the same operation as the production of the laminated glass of Example 1, a transparent laminated glass was produced.

[Examples 13-16]

As shown in Table 3, within the scope of the present invention, the acetalization degree and the acetyl group amount, the standard deviation σ, the amount of plasticizer added, the layer thickness, and the lamination structure of the polyvinyl acetal resin (A) and the polyvinyl acetal resin (B) are changed. To prepare an interlayer film, and manufactured laminated glass using the same.

[Comparative Examples 7-8]

As shown in Table 3, the interlayer film which does not belong to the scope of the present invention was prepared, respectively, and the laminated glass was produced using this.

[Measurement of Sound Insulation]

For each laminated glass of Examples 12 to 16 and Comparative Examples 7 to 8, sound insulation was measured at a predetermined temperature.

The measurement results are collectively shown in Table 3.

As is apparent from Table 3, it is recognized that the laminated glass according to the embodiment of the present invention has excellent sound insulation performance over a wide temperature range.

Example 17

[Preparation of Resin (A)]

The white powder of the polyvinyl acetal resin (A) of 60.2 mol% of acetalization degree and 11.9 mol% of acetyl groups was obtained by operation similar to the preparation of resin (A) of Example 1.

This polymer was dissolved in 2 liters of hexafluoroisopropanol, and fractionated using the GPC (LS-8000 system), and the polyvinyl acetal resin having a number average molecular weight Mn of 160,000 and a molecular weight distribution ratio (Mw / Mn) of 1.02. (A) was obtained.

[Preparation of film A]

The said polyvinyl acetal (A) was formed into a film by operation similar to the preparation of the film (A) of Example 1, and the film A was produced with a thickness of 0.20 mm.

[Preparation of Resin (B)]

The white powder of the polyvinyl acetal resin (B) of 65.9 mol% of acetalization degree and 0.9 mol% of acetal groups was obtained by operation similar to the preparation of resin (B) of Example 1.

[Preparation of film (B)]

The said polyvinyl acetal (B) was formed into a film by operation similar to the preparation of the film (B) of Example 1, and the film (B) of thickness 0.20mm was produced.

[Production of Laminated Glass]

The transparent laminated glass was produced by operation similar to the manufacture of the laminated glass of Example 1.

[Examples 18-23]

As shown in Table 4, within the scope of the present invention, the acetalization degree and the acetyl group amount, the number average molecular weight Mn and the molecular weight distribution ratio (Mw / Mn) of the polyvinyl acetal resin (A) and the polyvinyl acetal resin (B), The interlayer film was prepared by changing the amount of plasticizer added, the layer thickness, and the lamination structure, to prepare laminated glass using the same.

[Comparative Examples 9-11]

As shown in Table 4, the interlayer film which does not belong to the scope of the present invention was prepared, respectively, and the laminated glass was produced using this.

[Measurement of Sound Insulation]

About each laminated glass of the said Examples 17-23 and Comparative Examples 9-11, the sound insulation was measured at predetermined temperature.

The measurement results are collectively shown in Tables 4a and 4b.

As apparent from Table 4, it is recognized that the laminated glass according to the embodiment of the present invention has excellent sound insulation performance in the vicinity of room temperature.

Example 24

[Preparation of Resin (A)]

Acetal was carried out in the same manner as in the preparation of the resin (A) of Example 1, except that a mixed product (mixing ratio 1: 1) of polyvinyl alcohol having a polymerization degree of 500 and polyvinyl alcohol having a polymerization degree of 3000 was used as polyvinyl alcohol. A white powder of polyvinyl acetal resin (A) having a degree of fluorescence of 59.9 mol% and an acetyl group content of 12.1 mol% was obtained.

The number average molecular weight Mn of this polymer was 36,400, and the molecular weight distribution ratio (Mw / Mn) was 6.71.

[Preparation of film A]

The said polyvinyl acetal (A) was formed into a film by operation similar to the preparation of the film (A) of Example 1, and the film (A) of thickness 0.20mm was produced.

[Preparation of Resin (B)]

The white powder of the polyvinyl acetal resin (B) of 65.9 mol% acetalization degree and 0.9 mol% of acetyl groups was obtained by operation similar to the preparation of resin (B) of Example 1.

[Preparation of film (B)]

By the same operation as the preparation of the film B of Example 1, the polyvinyl acetal B was formed into a film to prepare a film B having a thickness of 0.20 mm.

[Production of Laminated Glass]

The transparent laminated glass was produced by operation similar to the manufacture of the laminated glass of Example 1.

[Examples 25-30]

As shown in Table 5, in the range of the present invention, the degree of acetalization and the acetyl group, the number average molecular weight Mn and the molecular weight distribution ratio (Mw / Mn) of the polyvinyl acetal resin (A) and the polyvinyl acetal resin (B) The interlayer film was prepared by changing the addition amount, layer thickness and lamination configuration of the plasticizer, and the laminated glass was prepared using the same.

[Comparative Examples 12-14]

As shown in Table 5, the interlayer film which does not belong to the scope of the present invention was prepared, respectively, and the laminated glass was produced using this.

[Measurement of Sound Insulation]

For each laminated glass of Examples 24 to 30 and Comparative Examples 12 to 14, sound insulation was measured at a predetermined temperature.

The measurement results are collectively shown in Table 5.

As is apparent from Table 5, it is recognized that the laminated glass according to the embodiment of the present invention has excellent sound insulation performance over a wide temperature range.

Example 31

[Preparation of Resin (A)]

The white powder of the polyvinyl acetal resin (A) of 60.2 mol% of acetalization degree and 11.9 mol% of acetyl groups was obtained by operation similar to the preparation of resin (A) of Example 1.

[Preparation of film A]

The said polyvinyl acetal (A) was formed into a film by operation similar to the preparation of the film (A) of Example 1, and the film (A) of thickness 0.20mm was produced.

[Preparation of Resin (B)]

The white powder of the polyvinyl acetal resin (B) of 65.9 mol% of acetalization degree and 0.9 mol% of acetal groups was obtained by operation similar to the preparation of resin (B) of Example 1.

[Preparation of film (B)]

By the same operation as the preparation of the film B of Example 1, the polyvinyl acetal B was formed into a film to prepare a film B having a thickness of 0.20 mm.

[Production of Laminated Glass]

By the same operation as the manufacture of the laminated glass of Example 1, the transparent laminated glass in which the outermost outer layer consisted of layer (B) was produced.

[Examples 32-33]

As shown in Table 6, the degree of acetalization and acetyl group of the polyvinyl acetal resin (A) and the polyvinyl acetal resin (B), the amount of plasticizer added, the layer thickness, the laminated structure, and the amount of the ultraviolet absorber are changed. To prepare an interlayer film and manufactured laminated glass using the same.

[Comparative Examples 15-17]

As shown in Table 6, the interlayer film which does not belong to the scope of this invention was prepared, respectively, and the laminated glass was produced using these.

[Measurement of Sound Insulation]

For each of the laminated glass of Examples 31 to 33 and Comparative Examples 15 to 17, sound insulation was measured at a predetermined temperature, and weather resistance was measured.

The measurement results are collectively shown in Table 6.

As is apparent from Table 6, it is recognized that the laminated glass according to the embodiment of the present invention has excellent sound insulation performance near room temperature and excellent weather resistance.

Example 34

[Preparation of Resin (A)]

To 2890 g of pure water, 191 g of polyvinyl alcohol having a degree of polymerization of 0.24 and a degree of block of ethylene group having an acetyl group bonded thereto was added and warmed and dissolved. The reaction system was temperature-controlled at 12 degreeC, 201 g of 35 weight% hydrochloric acid, and 130 g of butylaldehydes were added, and polyvinyl acetal was deposited. Thereafter, the reaction system was maintained at a temperature of 50 ° C. for 5 hours to complete the reaction. After washing with excess water, the unreacted aldehyde was washed out, the hydrochloric acid catalyst was neutralized, the salt was removed, and dried to obtain a white powder of polyvinyl acetal resin (A).

The acetalization degree of this polyvinyl acetal (A) was 60.2 mol%, and the acetyl group content was 11.5 mol%.

In addition, in the definition of block degree, Y = 5.0 × S / (T × U), S, T, and U in the formula represent polyvinyl alcohol. It was calculated | required as follows from C-NMR charat. Three peaks derived from methylene groups appear at 42.5 ppm. Each of these three peaks has a methylene group (methylene 1) and a -CH (OH) -CH- (OCOCHCH- structure in the -CH (OCOCH) -CH- (OCOCH) CH-structure on the high magnetic side, respectively. It is a peak derived from the methylene group (methylene 2,) and the methylene group (methylene 3) in -CH (OH) -CH- (OH) CH- structure.

The peak area ratio was calculated from the integration curve, and the amount (S) (mole fraction) of the methylene group in the -CH (OH) -CH- (OCOCH) CH- structure was calculated from this.

The amount (T) (mole fraction) of the hydroxyl group and the amount (U) (mole fraction) of the acetyl group were determined by the following equation. T = (amount of methylene 3) + (amount of methylene 2) / 2, U = 1-T

[Preparation of film A]

The said polyvinyl acetal (A) was formed into a film by operation similar to the preparation of the film (A) of Example 1, and the film (A) of thickness 0.20mm was produced.

[Preparation of Resin (B)]

The white powder of the polyvinyl acetal resin (B) of 65.9 mol% of acetalization degree and 0.7 mol% of acetyl groups was obtained by operation similar to the preparation of resin (B) of Example 1.

[Preparation of film (B)]

By the same operation as the preparation of the film (B) of Example 1, the polyvinyl acetal (B) was formed into a film to prepare a film (B) having a thickness of 0.240 mm.

[Production of Laminated Glass]

The transparent laminated glass was produced by operation similar to the manufacture of the laminated glass of Example 1.

[Examples 35-40]

As shown in Table 7, the acetalization degree and the acetyl group amount of the polyvinyl acetal resin (A) and the polyvinyl acetal resin (B), the amount of plasticizer added, the layer thickness, the lamination structure, and the amount of the ultraviolet absorber are changed. To prepare an interlayer and to produce a laminated glass using the same.

[Comparative Examples 18 ~ 19]

As shown in Table 7, the interlayer film which does not belong to the scope of this invention was prepared, respectively, and the laminated glass was produced using these.

[Measurement of Sound Insulation]

For each laminated glass of Examples 34 to 40 and Comparative Examples 18 to 19, sound insulation was measured at a predetermined temperature.

The measurement results are shown in Table 7 together.

As is apparent from Table 7, it is recognized that the laminated glass according to the embodiment of the present invention has excellent sound insulation performance over a wide temperature range.

Example 41

[Preparation of Resin (A)]

To 2890 g of pure water, 191 g of polyvinyl alcohol having a polymerization degree of 1,700 and a degree of blocking of ethylene group having an acetyl group bonded thereto was added thereto, followed by heating and melting. The reaction system was temperature-controlled at 12 degreeC, 201 g of 35 weight% hydrochloric acid, and 130 g of butylaldehydes were added, and polyvinyl acetal was deposited. Thereafter, the reaction system was maintained at a temperature of 50 ° C. for 5 hours to complete the reaction. After washing with excess water, the unreacted aldehyde was washed out, the hydrochloric acid catalyst was neutralized, the salt was removed, and the white powder of polyvinyl acetal resin (A) was obtained via drying.

The acetalization degree of this polyvinyl acetal (A) was 60.2 mol%, and the acetyl group content was 12.5 mol%.

In addition, in the definition Y of 0.5 x S / (T x U), S, T and U in the formula are polyvinyl alcohol. It was calculated | required by the method similar to Example 34 from C-NMR charat.

[Preparation of film A]

50 g of the polyvinyl acetal (A) was collected, 25 g of triethylene glycol-di-2-ethylbutylate as a plasticizer and 0.15 g of BHT as an antioxidant were added thereto, and the mixture was sufficiently kneaded with a mixing roll to obtain a predetermined amount of the kneaded product. Was maintained at 150 ° C. for 30 minutes with a press molding machine. Thus, a film A having a thickness of 0.20 mm was produced.

[Preparation of Resin (B)]

By the same operation as in the preparation of the resin (B) of Example 1, acetalization degree of 65.9 mol%, an acetyl group content of 0.9 mol%, and a white powder of polyvinyl acetal resin (B) were obtained.

[Preparation of film (B)]

By the same operation as the preparation of the film B of Example 1, the polyvinyl acetal B was constrained to prepare a film B having a thickness of 0.240 mm.

[Production of Laminated Glass]

The transparent laminated glass was produced by operation similar to the manufacture of the laminated glass of Example 1.

EXAMPLES 42-47

As shown in Table 8, within the scope of the present invention, the acetalization degree and the acetyl group amount of the polyvinyl acetal resin (A) and the polyvinyl acetal resin (B), the amount of the plasticizer added, the layer thickness, the laminated structure, and the amount of the ultraviolet absorber By changing the interlayer to prepare a laminated glass using the same.

[Comparative Example 20]

As shown in Table 8, the interlayer film which does not belong to the scope of this invention was prepared, respectively, and the laminated glass was produced using this.

[Measurement of Sound Insulation]

For each laminated glass of Examples 41 to 47 and Comparative Example 20, sound insulation was measured at a predetermined temperature. The measurement results are shown in Table 8 together.

As is apparent from Table 8, it is confirmed that the laminated glass according to the embodiment of the present invention has excellent sound insulation performance in the vicinity of room temperature.

Example 48

[Preparation of Resin (A)]

190 g of polyvinyl alcohol having a degree of polymerization of 1700 was added to 2890 g of pure water to dissolve it by heating. The reaction system was temperature-controlled at 12 ° C, 200 g of 35% by weight hydrochloric acid and 170 g of butylaldehyde were added to precipitate polyvinyl acetal. Thereafter, the reaction system was maintained at a temperature of 45 ° C. for 6 hours to complete the reaction. After washing with excess water, the unreacted aldehyde was washed out, the hydrochloric acid catalyst was neutralized and the salt was removed, followed by drying to obtain a white powder of polyvinyl acetal resin (A).

The acetalization degree of this polyvinyl acetal resin (A) was 62.3 mol%, the amount of acetyl groups was 12.3 mol%, and the viscosity was 590 cP.

Furthermore, the measurement of the viscosity of polyvinyl acetal resin was performed as follows.

150 ml of a mixed solvent of ethanol / toluene (weight ratio 1: 1) was taken in a Erlenmeyer flask, and a sample weighed thereto was added, the resin concentration was adjusted to 10 ± 0.1 wt%, and shaken in a constant temperature room at 20 ° C. for at least 3 hours. Dissolution was performed. Next, this solution was injected into a 43 ± 2 mm inner diameter measuring tube, the temperature was maintained at 20 ± 0.2 ° C., and the viscosity was measured using a BM viscometer.

[Preparation of film A]

50 g of the polyvinyl acetal (A) was collected, and 25 g of triethylene glycol-di-2-ethylbutylate was used as a plasticizer and 2- (2'-hydroxy-5'-methylphenyl) benzotriazole was used as a ultraviolet absorber. 0.05 g of BHT as an antioxidant and g were added, and this compound was kneaded enough by a mixing roller, and the predetermined amount of kneaded material was hold | maintained at 150 degreeC by the press molding machine for 30 minutes. Thus, the film A of thickness 0.38 mm was produced.

[Preparation of Resin (B)]

The white powder of the polyvinyl acetal resin (B) of 66.3 mol% of acetalization degree and 0.9 mol% of acetyl groups was obtained by operation similar to the preparation of resin (B) of Example 1.

[Preparation of film (B)]

By the same operation as the preparation of the film B of Example 1, the polyvinyl acetal B was formed into a film, and a film B having a thickness of 0.30 mm and 0.40 mm was produced.

[Production of Laminated Glass]

The transparent laminated glass was produced by operation similar to the manufacture of the laminated glass of Example 1.

[Examples 49-50]

As shown in Table 9, within the scope of the present invention, the acetalization degree and the acetyl group amount of the polyvinyl acetal resin (A) and the polyvinyl acetal resin (B), the amount of the plasticizer added, the layer thickness, the laminated structure and the amount of the ultraviolet absorber Was prepared to prepare an interlayer film, and the laminated glass was manufactured using the interlayer film.

[Comparative Examples 21-25]

As shown in Table 9, the interlayer film which does not belong to the scope of this invention was prepared, respectively, and the laminated glass was produced using this.

[Measurement of Sound Insulation]

For each laminated glass of Examples 48 to 50 and Comparative Examples 21 to 25, sound insulation was measured at a predetermined temperature.

The measurement results are summarized in Table 9 and displayed.

As is apparent from Table 9, it is recognized that the laminated glass according to the embodiment of the present invention has excellent sound insulation performance in a wide temperature range.

[Production example]

Examples of the preparation of polyvinyl acetal resins in which 90% or more of the acetalization degree exists in the range of -2 mol% and +2 mol% of the average value of the acetalization degrees will be described with Reference Examples 1 and 2. In addition, the manufacture examples of the polyvinyl acetal resin in which 10-30% distribution of acetalization degree exists in the range of -10 mol% or less and +10 mol% or more of the average value of acetalization degree are demonstrated with reference examples 3 and 4.

Reference Example 1

To 2900 g of pure water, 193 g of polyvinyl alcohol having a degree of polymerization of 1700 and a degree of saponification of 98.9 mol% was added and dissolved in a mixture. The reaction system was temperature-controlled at 5 ° C, 201 g of 35% by weight hydrochloric acid and 192 g of n-hexylaldehyde were added to precipitate polyvinyl acetal. Thereafter, the reaction system was maintained at a temperature of 35 ° C. for 5 hours to complete the reaction. By washing with excess water, the unreacted aldehyde was washed out, the hydrochloric acid catalyst was neutralized to remove the salt, and dried to obtain a white powder of polyvinyl acetal resin.

The polyvinyl acetal resin was 64.0 mol% of acetalization degree and 94% of distribution of acetalization degree in the range of -2 mol% and +2 mol% of the average value of acetalization degree.

Furthermore, the acetalization degree distribution of polyvinyl acetal resin was performed as follows using liquid chromatography.

First, a polar liquid (for example, water) is allowed to flow through the column as an eluent. Subsequently, when polyvinyl acetal resin is safely dissolved in a solvent such as ethanol and injected into a column, only a highly polar resin portion (low acetalization portion) is leaked out. Thereafter, the polarity of the eluent is gradually lowered (for example, water → ethanol → ethyl acetate → .....), whereby the lower polarity portion (higher acetylation degree portion) can be sequentially discharged and detected. Finally, non-polar liquids (for example, toluene) are allowed to flow, so that all of the resin parts with low polarity (high acetalization degree) can be leaked out and the acetalization degree distribution can be obtained from the fractions obtained in this order.

Reference Example 2

Polyvinyl alcohol was changed to 1700 degree of polymerization degree and 87.8 mol% of saponification degree, n-hexyl aldehyde was changed to n-butylaldehyde, and the white powder of polyvinyl acetal resin was obtained by operation similar to the reference example 1. This polyvinyl acetal resin was 57.2 mol% of acetalization degrees and 92% of acetalization degrees exist in the range of -2 mol% and +2 mol% of the average value of acetalization degree.

Reference Example 3

To 2900 g of pure water, 193 g of polyvinyl alcohol having a degree of polymerization of 1700 and a degree of saponification of 98.9 mol% was added and dissolved in a mixture. The reaction system was temperature controlled to 32 ° C, and 201 g of 35% by weight hydrochloric acid and 192 g of n-hexylaldehyde were added to precipitate polyvinyl acetal. Thereafter, the reaction system was maintained at a temperature of 35 ° C. for 5 hours to complete the reaction. After washing with excess water, the unreacted aldehyde was washed out, the hydrochloric acid catalyst was neutralized and the salt was removed, followed by drying to obtain a white powder of polyvinyl acetal resin.

In this polyvinyl acetal resin, acetalization degree is 62.9 mol%, 19% distribution of acetalization degree exists below -10 mol% of the average value of acetalization degree, 12% of distribution of acetalization degree is 10 mol of the average value of acetalization degree It was present in more than%.

Reference Example 4

The polyvinyl alcohol was changed to one having a polymerization degree of 1700 and a saponification degree of 87.8 mol%, the n-hexyl aldehyde was changed to n-butylaldehyde, the reaction system was temperature-controlled at 40 ° C, and polyvinyl acetal was carried out by the same operation as in Reference Example 1. White powder of resin was obtained.

Acetylation degree of acetalization is 56.9 mol%, 20% distribution of acetalization degree is -10 mol% or less of average value of acetalization degree, 10% distribution of acetalization degree is 10 mol% or more of average value of acetalization degree It was to exist.

[Effects of the Invention]

The first interlayer film for laminated glass according to the present invention comprises at least one layer composed of a plasticized polyvinyl acetal resin (A) having 4 to 6 carbon atoms in the acetal group and 8 to 30 mol% of the remaining acetyl group ( Since A) and the acetal group have a carbon number of 3 to 4 and at least one layer (B) made of a plasticized polyvinyl acetal resin (B) having 4 mol% or less of the amount of the remaining acetyl group, negative energy effectively heat energy. The sound absorption performance is effectively prevented from being absorbed by the coincidence effect, especially in the mid-range of the midrange of 2000 Hz. Therefore, the TL value is increased by mitigating the coincidence effect without impairing the basic performance required for laminated glass such as transparency, weather resistance, impact energy absorption, adhesion at the resin layer interface, and contact with the glass plate, thereby providing excellent sound insulation. Can exhibit performance.

In the second interlayer film for laminated glass according to the present invention, the polyvinyl acetal resin (A) is a resin having a standard deviation σ of 0.8 or less of the amount of ethylene groups bonded to an acetyl group, and has a maximum sound insulation performance temperature near room temperature and is large. The interlayer film for laminated glass having a maximum sound insulation performance can be obtained.

In the third interlayer film for laminated glass according to the present invention, the polyvinyl acetal resin (A) is a resin having a standard deviation sigma of 2.5 to 8 of the amount of ethylene groups bonded to an acetyl group, and has a maximum sound insulation performance in a wide temperature range. The interlayer film for laminated glass having a large sound insulation performance maximum value roll can be obtained.

Since the interlayer film for fourth laminated glass according to the present invention has a molecular weight distribution ratio (weight average molecular weight Mw / number average molecular weight Mn) of the polyvinyl acetal resin (A) of 1.01 to 1.50, the sound insulating grade Ts according to JIS A4706 is used. It is possible to obtain an interlayer film for laminated glass that exhibits excellent sound insulation properties of more than -35 grade.

The fifth interlayer film for laminated glass according to the present invention exhibits good sound insulation in a wide temperature range because the molecular weight distribution ratio (weight average molecular weight Mw / number average molecular weight Mn) of the polyvinyl acetal resin (A) is 3.5 to 20. The interlayer film for laminated glass can be obtained.

In the sixth intermediate film according to the present invention, at least the outermost layer on the side of the layer constituting the laminated film contains a ultraviolet absorber having an effective ultraviolet absorption wavelength of 300 to 340 nm so that the ultraviolet absorption coefficient X is 0.01 or more. (B), the interlayer film is excellent in weatherability, and the bonding processability of the interlayer film can be made equivalent to that of the conventional polyvinyl butyral series interlayer film.

In the seventh interlayer film according to the present invention, since the polyvinyl acetal resin (A) is a polyvinyl acetal resin having a high blocking property, an excellent sound insulating interlayer can be obtained which can effectively convert negative energy into thermal energy over a wide temperature range. Lose.

In the eighth interlayer film according to the present invention, since the polyvinyl acetal resin (A) is a polyvinyl acetal resin having a high randomness, an excellent sound insulating interlayer that has good fluidity and can convert sound energy into heat energy more effectively. Obtained.

Claims (8)

At least one consisting of a polyvinyl acetal resin (A) having 4 to 6 carbon atoms in the acetal group, and a molar fraction of 8 to 30 mol% relative to the total amount of ethylene groups in the main chain of the average amount of ethylene groups bonded to the acetyl group. Layer (A), polyvinyl acetal resin (B) and a plasticizer having 3 to 4 carbon atoms in the acetal group and a mole fraction of 4 mol% or less relative to the total amount of ethylene groups in the main chain of the average amount of ethylene groups bonded to the acetyl group. At least one layer (B) which consists of is laminated | stacked, The interlayer film for laminated glass characterized by the above-mentioned. The interlayer film for laminated glass according to claim 1, wherein the polyvinyl acetal resin (A) is a resin having a standard deviation σ of 0.8 or less of the amount of ethylene groups bonded to the acetyl group. The interlayer film for laminated glass according to claim 1, wherein the polyvinyl acetal resin (A) has a standard deviation sigma of 2.5 to 8 of the amount of ethylene groups bonded to the acetyl group. The interlayer film for laminated glass according to claim 1, wherein the polyvinyl acetal resin (A) has a molecular weight distribution ratio (weight average molecular weight Mw / number average molecular weight Mn) of 1.01 to 1.50. The interlayer film for laminated glass according to claim 1, wherein the polyvinyl acetal resin (A) has a molecular weight distribution ratio (weight average molecular weight Mw / number average molecular weight Mn) 3.5 to 20. The outermost layer of the side which needs at least weather resistance among the several layer laminated | stacked is comprised by the layer (B) which contains the ultraviolet absorber whose effective ultraviolet absorption wavelength is 300-340 nm so that ultraviolet-ray absorption coefficient X may be 0.01 or more. Interlayer film for laminated glass, characterized in that the The polyvinyl acetal resin (A) according to claim 1, wherein the polyvinyl acetal resin (A) is an interlayer film for laminated glass, characterized in that the blocking degree Y of the following definition of the ethylene group to which the acetyl group is bonded is 0.15 to 0.40; Blocking degree Y = 0.5 × S / (T × U) where S, T and U in the formula are the amounts of methylene groups (S) in the -CH (OH) -CH _2- (OCOCH ₃ ) CH- structure, The amount (T) of hydroxyl group and the amount (U) of acetyl group are shown. 2. The interlayer film for laminated glass according to claim 1, wherein the polyvinyl acetal resin (A) has a block degree Y of 0.55 to 0.90 as defined below for the ethylene group to which the acetyl group is bonded; Blocking degree Y = 0.5xS / (TxU) where S, T and U in the formula are the amounts of methylene groups in the -CH (OH) -CH _2- (OCOCH ₃ ) CH-structure (S), The amount (T) of hydroxyl group and the amount (U) of acetyl group are shown.