KR20190114671A - Multilayer polyvinyl acetal film having improved sound insulation and laminated glass comprising the same - Google Patents

Abstract

The present invention relates to a multilayer sound insulation film having excellent sound insulation performance within a wide temperature range and not showing foaming phenomena on laminated glass, and laminated glass comprising the same. The multilayer sound insulation film comprises: a first skin layer comprising a first polyvinyl acetal and a plasticizer; a first buffer layer positioned on the first skin layer and including a second polyvinyl acetal and the plasticizer; a core layer positioned on the first buffer layer and including a third polyvinyl acetal and the plasticizer; a second buffer layer positioned on the core layer and including the second polyvinyl acetal and the plasticizer; and a second skin layer positioned on the second buffer layer and including the first polyvinyl acetal and the plasticizer.

Description

Multi-layered sound insulating film and laminated glass including the same {MULTILAYER POLYVINYL ACETAL FILM HAVING IMPROVED SOUND INSULATION AND LAMINATED GLASS COMPRISING THE SAME}

The present invention relates to a multilayer sound insulating film having excellent sound insulation performance in a wide temperature range and no foaming phenomenon in the laminated glass and a laminated glass including the same.

Plasticized polyvinyl acetals are used in the manufacture of films applied as intermediate layers in light-transmitting laminates such as laminated glass (tempered glass, safety glass), polymer laminates, and the like.

Laminated glass refers to a transparent laminate produced by placing a polyvinyl butyral sheet between two sheets of glass. Laminated glass is mainly used to provide transparent barriers in building railings, exterior materials and automotive windshields.

The main function of laminated glass is to minimize the damage or injury to objects or people in the transparent barrier by absorbing the energy caused by the blow without allowing penetration through the laminated glass (penetration resistance) (impact resistance). . In addition, interlayer sheets applied to laminated glass may impart additional functionality to the laminated glass, such as reducing acoustic noise and reducing UV and / or IR light transmission.

In particular, the film used for glass of automobiles, buildings, and the like has a great demand for improving sound insulation. The sound insulation can be evaluated as the transmission loss according to the frequency change, and especially the range of 1,000 to 6,000 Hz, which falls within the range of the loudness curve, has a high sensitivity in human hearing, so it is above the sound insulation performance in other areas. Sound insulation performance is important.

The laminated glass using the conventional interlayer film has sufficient anti-scattering effect, but it is difficult to sufficiently reduce the coincidence effect, which is a resonance effect of the glass plate around 2,000 Hz, and thus has insufficient sound insulation performance.

For example, Japanese Patent No. 3,335,436 discloses a laminated glass exhibiting scattering prevention performance and sound insulation performance by interposing an interlayer film between a pair of glass plates. However, since the interlayer film interposed between the laminated glass is specialized in sound insulation performance only at room temperature, the effect of sound insulation performance is limited in the actual field (FIELD) where temperature change occurs by morning / evening or season.

Japanese Patent No. 3,224,436 Domestic Patent No. 10-1354439

An object of the present invention is to provide a multi-layer sound insulating film and a laminated glass comprising the same excellent in sound insulation performance in a wide temperature range does not appear foaming phenomenon in the laminated glass.

In order to achieve the above object, the multilayer sound insulating film according to an embodiment of the present invention, the first skin layer comprising a first polyvinyl acetal resin and a plasticizer; A first buffer layer on the first skin layer and including a second polyvinyl acetal resin and a plasticizer; A core layer on the first buffer layer and including a third polyvinyl acetal resin and a plasticizer; A second buffer layer on the core layer and including a second polyvinyl acetal resin and a plasticizer; And a second skin layer on the second buffer layer and including a first polyvinyl acetal resin and a plasticizer.

In the multilayer sound insulating film, the amount of hydroxyl groups of the second polyvinyl acetal resin has a value between the amount of hydroxyl groups of the first polyvinyl acetal resin and the amount of hydroxyl groups of the third polyvinyl acetal resin.

The HD2 value, which is the amount of hydroxyl groups of the second polyvinyl acetal resin, may satisfy Equation 1 below.

[Equation 1]

HD2 = HD3 + (HD1-HD3) * N

In Formula 1, HD1 is the amount of hydroxyl groups of the first polyvinyl acetal resin, HD2 is the amount of hydroxyl groups of the second polyvinyl acetal resin, HD3 is the amount of hydroxyl groups of the third polyvinyl acetal resin, and N is It is a real number from 0.1 to 1.0.

The first polyvinyl acetal resin may be one in which the amount of hydroxyl group HD1 is greater than 17.5 wt%.

In the third polyvinyl acetal resin, the amount of hydroxyl group HD3 may be less than 9.3 wt%.

The first skin layer and the second skin layer may each include 70 to 76 parts by weight of the first polyvinyl acetal resin, and 24 to 30 parts by weight of the plasticizer.

Each of the first buffer layer and the second buffer layer may include 58 to 68 parts by weight of the second polyvinyl acetal resin, and 32 to 42 parts by weight of the plasticizer.

The core layer may include 58 to 68 parts by weight of the third polyvinyl acetal resin, and 32 to 42 parts by weight of the plasticizer.

The first polyvinyl acetal resin may be an acetyl group containing 0.1 to 3% by weight.

The third polyvinyl acetal resin may include 3 to 15 wt% of an acetyl group.

In order to achieve the above object, the multilayer sound insulating film according to an embodiment of the present invention, the first skin layer comprising a first polyvinyl acetal resin and a plasticizer; A first buffer layer on the first skin layer and including a resin mixture and a plasticizer; A core layer on the first buffer layer and including a third polyvinyl acetal resin and a plasticizer; A second buffer layer on the core layer and comprising a resin mixture and a plasticizer; And a second skin layer on the second buffer layer, the second skin layer comprising a first polyvinyl acetal resin and a plasticizer, wherein the resin mixture includes a second polyvinyl acetal resin and a second polyvinyl acetal resin having different amounts of hydroxyl groups. It contains -2 polyvinyl acetal resin.

The amount of hydroxyl groups of the resin mixture has a value between the amount of hydroxyl groups of the first polyvinyl acetal resin and the amount of hydroxyl groups of the third polyvinyl acetal resin.

The 2-1 polyvinyl acetal resin has a hydroxyl content of HD2-1 and is included in a content ratio based on the resin mixture 1, and the 2-2 polyvinyl acetal resin has a hydroxyl content of HD2-2. It may be included in the b content ratio based on the resin mixture 1.

When the amount of hydroxyl groups of the first polyvinyl acetal resin is HD1, the amount of hydroxyl groups of the third polyvinyl acetal resin is HD3, and the amount of hydroxyl groups of the mixed resin is HD2, the value of HD2 is represented by Equations 1 and 2 below. Can be satisfied.

[Equation 1]

HD2 = HD3 + (HD1-HD3) * N

[Equation 2]

HD2 = HD2-1 * a + HD2-2 * b

In Formula 1 and Formula 2, the amount of hydroxyl groups of the first polyvinyl acetal resin, the HD2 is the amount of hydroxyl groups of the polyvinyl acetal resin applied to the buffer layer, the HD3 is the amount of hydroxyl groups of the third polyvinyl acetal resin, the HD2 -1 is the amount of hydroxyl groups of the 2-1 polyvinyl acetal resin, HD2-2 is the amount of hydroxyl groups of the 2-2 polyvinyl acetal resin, and a is based on the resin mixture 1 contained in the buffer layer. The content ratio of 2-1 polyvinyl acetal resin, b is the content ratio of 2-2 polyvinyl acetal resin based on the resin mixture 1 contained in the buffer layer and a and b are each greater than 0 and less than 1 Is a real number, the sum of a and b does not exceed 1, and N is a real number of 0.1 to 1.0.

The first polyvinyl acetal resin may be one in which the amount of hydroxyl group HD1 is greater than 17.5 wt%.

The third polyvinyl acetal resin may be that the amount of hydroxyl group HD3 is less than 9.3% by weight.

The first skin layer and the second skin layer may each include 70 to 76 parts by weight of the first polyvinyl acetal resin, and 24 to 30 parts by weight of the plasticizer.

Each of the first buffer layer and the second buffer layer may include 58 to 68 parts by weight of the second polyvinyl acetal resin, and 32 to 42 parts by weight of the plasticizer.

The core layer may include 58 to 68 parts by weight of the third polyvinyl acetal resin, and 32 to 42 parts by weight of the plasticizer.

The first polyvinyl acetal resin may be an acetyl group containing 0.1 to 3% by weight.

The third polyvinyl acetal resin may include 3 to 15 wt% of an acetyl group.

Laminated glass according to another embodiment of the present invention includes a laminate in which the first glass layer and the second glass layer are laminated with the multilayer sound insulating film according to the embodiment of the present invention described above.

The laminated glass is a multilayer sound insulating film having the same thickness, and the loss coefficient measured at 30 ° C. compared with the case of applying a three-layer film including the first skin layer, the core layer, and the second skin layer. (loss factor) value may be increased by more than 0.02.

The laminated glass is a multilayer sound insulating film having the same thickness, and a loss coefficient measured at 10 ° C. compared with the case where a three-layer film including the first skin layer, the core layer, and the second skin layer is applied ( loss factor) may increase by more than 0.02.

Multilayered sound insulation film and laminated glass of the present invention has excellent sound resistance and impact resistance even at a thin thickness below a certain level and at the same time excellent sound insulation over a wide temperature range, it occurs after the glass bonding which is a problem of conventional sound insulation film It is possible to provide a multi-layered sound insulating film and laminated glass in which the foaming phenomenon does not occur or the generation is insignificant to the naked eye.

1 (a) is a conceptual diagram illustrating a cross section of a multilayer sound insulation film according to an embodiment of the present invention, (b) is a cross-sectional view of a multilayer sound insulation film described in the prior art (or comparative example) in the present invention. It is a conceptual diagram.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. Like parts are designated by like reference numerals throughout the specification.

As used herein, the terms "about", "substantially", and the like, are used at, or in close proximity to, numerical values when manufacturing and material tolerances inherent in the meanings indicated are intended to aid the understanding of the invention. Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers.

Throughout this specification, the term "combination of these" included in the expression of the makushi form means one or more mixtures or combinations selected from the group consisting of constituents described in the expression of the makushi form, wherein the constituents It means to include one or more selected from the group consisting of.

Throughout this specification, description of "A and / or B" means "A, B, or A and B".

Throughout this specification, terms such as “first”, “second” or “A”, “B” are used to distinguish the same terms from each other unless otherwise specified.

As used herein, B being located on A means that B is located on A, or that B may be located on A while another layer is located therebetween and B is in contact with the surface of A. It is limited to doing so and is not interpreted.

In the present specification, the singular forms “a,” “an” and “the” are intended to be interpreted in the context of the singular or plural forms unless the context describes them.

In the present specification, the size of each component in the drawings may be exaggerated for explanation of the invention, and may differ from the size actually applied.

In this invention, evaluation of the amount of hydroxyl groups measured and evaluated the amount of ethylene groups which the hydroxyl group of the said polyvinyl acetal resin couple | bonded with the method based on JISK6728.

The inventors of the present invention confirmed that the foaming phenomenon may occur more easily when the multilayer film with improved sound insulation is produced in laminated glass, and during the research for developing a film without such a foaming phenomenon, When the buffer layer is inserted between the skin layer and the core layer, it was confirmed that foaming does not appear while having excellent sound insulation in a wide temperature range, and completed the present invention.

In order to achieve the above object, the multilayer sound insulating film 500 according to an embodiment of the present invention, the first skin layer 100 including a first polyvinyl acetal resin and a plasticizer; A first buffer layer 200 disposed on the first skin layer and including a second polyvinyl acetal resin and a plasticizer; A core layer 300 disposed on the first buffer layer and including a third polyvinyl acetal resin and a plasticizer; A second buffer layer 200 disposed on the core layer and including a second polyvinyl acetal resin and a plasticizer; And a second skin layer 100 disposed on the second buffer layer and including a first polyvinyl acetal resin and a plasticizer.

The multilayer sound insulating film of the present invention further includes a buffer layer 200 between the skin layer 100 and the core layer 300. That is, the multilayer sound insulation film 500 may include a five-layer structure in which a core layer 300 is positioned between two skin layers 100 and a buffer layer 200 is inserted between each skin layer and the core layer. Can be.

The skin layer 100 may have sufficient bonding strength with a bonding surface such as glass, and may impart physical properties necessary for tempered glass, such as impact resistance and penetration resistance, to the laminated glass.

The core layer 300 may contribute to improving sound insulation performance.

However, when the skin layer 100 and the core layer 300 are applied to a layer having a large difference in relative physical properties, foaming may occur more easily, resulting in poor quality, and improved sound insulation performance in a wider temperature range. It can be difficult.

Therefore, in the present invention, the skin layer 100 and the core layer 300 of the multilayer sound insulation film 500, while applying a layer having a large difference in relative physical properties, the buffer layer 200 is inserted therebetween so that the layers do not directly contact each other. Introduce the way.

Therefore, the multilayer sound insulation film 500 of the present invention is different from the case of the conventional multilayer sound insulation film in which the buffer layer 200 alternately stacks two or three layers having different physical properties. It has a lamination structure of the buffer layer 200-the core layer 300-the buffer layer 200-the skin layer 100, and is made of polyvinyl acetal resin between the skin layer 100-the buffer layer 200-the core layer 300. Make a step difference in the characteristics.

Specifically, the multilayer sound insulation film 500 of the present invention introduces a step difference between each layer in the amount of hydroxyl groups, the amount of hydroxyl groups of the second polyvinyl acetal resin is the amount of hydroxyl groups of the first polyvinyl acetal resin and the first It has a value between the amount of hydroxyl groups of 3 polyvinyl acetal resin. At this time, the amount of hydroxyl groups of each polyvinyl acetal resin may be calculated by weight or mol%.

HD2 value of the hydroxyl group amount of the second polyvinyl acetal resin included in the multilayer sound insulation film 500 of the present invention may satisfy the following Equation 1.

[Equation 1]

HD2 = HD3 + (HD1-HD3) * N

In Formula 1, HD1 is the amount of hydroxyl groups of the first polyvinyl acetal resin, HD2 is the amount of hydroxyl groups of the second polyvinyl acetal resin, HD3 is the amount of hydroxyl groups of the third polyvinyl acetal resin, and N is It is a real number from 0.1 to 1. When the resin satisfying the N value condition is applied to the multilayer sound insulation film, it is possible to manufacture a multilayer sound insulation film having improved foaming properties.

In Formula 1, N may have a value of 0.15 to 0.95, may have a value of 0.2 to 0.85, and may have a value of 0.4 to 0.85. In this case, while satisfying the foaming conditions it may have a better sound insulation characteristics in a wider temperature range.

In Equation 1, N may have a value of 0.15 or more and less than 0.5 and may have a value of 0.2 to 0.48. In this case, it may have excellent sound insulation characteristics even at a higher temperature.

In Formula 1, N may have a value of 0.5 or more and 1.0 or less. In this case, it may have excellent sound insulation characteristics at lower temperatures, and exhibit stable sound insulation performance in a wider temperature range.

In the first polyvinyl acetal resin, the amount of hydroxyl group HD1 may be greater than 17.5 wt%. When the HD1 value of the first polyvinyl acetal resin is greater than 17.5 wt%, the film may have sufficient sound insulation performance while providing sufficient bonding strength and strength to the film.

Specifically, the first polyvinyl acetal resin may have a hydroxyl value greater than 17.5 wt% and less than 40 wt%, a hydroxyl value may be 18 to 25 wt%, and 20 to 23 wt%. In this case, it is advantageous to stack the buffer layer and the core layer together to provide excellent sound insulation characteristics over a wide temperature range.

Specifically, the first polyvinyl acetal resin may have a hydroxyl value of 17.5 to 40% by weight, and an acetyl group value of 0.1 to 3% by weight.

The first polyvinyl acetal resin may have a hydroxyl value of 18 to 30% by weight and an acetyl group value of 0.1 to 3% by weight.

The first polyvinyl acetal resin may have a hydroxyl value of 18 to 25% by weight and an acetyl group value of 0.1 to 3% by weight.

When the first polyvinyl acetal resin is applied to the skin layer, it is possible to impart sufficient mechanical properties to the laminated glass while having sufficient heat of bonding with the glass and miscibility with the plasticizer.

The third polyvinyl acetal resin may be less than 9.3 wt% HD3 value of the hydroxyl value. The third polyvinyl acetal resin may impart excellent sound insulation performance to the film when the amount of hydroxyl group value HD3 is less than 9.3% by weight.

Specifically, the third polyvinyl acetal resin may have a hydroxyl value of 1 wt% or more and less than 9.3 wt%, 3 to 9 wt%, and 6 to 9 wt%. In this case, better sound insulation performance can be given to the multilayer sound insulation film.

Specifically, the third polyvinyl acetal resin may have a hydroxyl value of 1 to 9.3 wt%, an acetyl group value of 3 to 15 wt%.

The third polyvinyl acetal resin may have a hydroxyl value of 3 to 9 wt%, an acetyl group value of 6 to 15 wt%.

The third polyvinyl acetal resin may have a hydroxyl value of 6 to 9 wt% and an acetyl group value of 7 to 15 wt%.

When the third polyvinyl acetal resin is applied to the core layer, excellent sound insulation performance can be given to the laminated glass while having sufficient compatibility with the plasticizer.

The second polyvinyl acetal resin may have a hydroxyl value of less than 11.1 wt% to less than 18.9 wt%, but the hydroxyl value of the second polyvinyl acetal resin is greater than the hydroxyl value of the first polyvinyl acetal resin. not big.

The second polyvinyl acetal resin may have a hydroxyl value of less than 13.5 wt% to 18.9 wt%, but the hydroxyl value of the second polyvinyl acetal resin is greater than the hydroxyl value of the first polyvinyl acetal resin. not big.

The second polyvinyl acetal resin may have a hydroxyl value of less than 14.7 wt% to 18.9 wt%, but the hydroxyl value of the second polyvinyl acetal resin is greater than the hydroxyl value of the first polyvinyl acetal resin. not big.

The second polyvinyl acetal resin may have a hydroxyl value of less than 15.8 wt% to 18.4 wt%, but the hydroxyl value of the second polyvinyl acetal resin is greater than the hydroxyl value of the first polyvinyl acetal resin. not big.

Specifically, the second polyvinyl acetal resin may have a hydroxyl value of 11.1 to 18.9 wt%, an acetyl group value of 3 to 15 wt%.

The second polyvinyl acetal resin may have a hydroxyl value of 13.5 to 18.9 wt% and an acetyl group of 3 to 15 wt%.

The second polyvinyl acetal resin may have a hydroxyl value of 14.7 to 18.9 wt% and an acetyl group value of 3 to 15 wt%.

The second polyvinyl acetal resin may have a hydroxyl value of 15.8 to 18.4 wt% and an acetyl group of 3 to 12 wt%.

When the second polyvinyl acetal resin is applied to the buffer layer, the foaming phenomenon is suppressed and the sound insulation performance is improved at low temperature, high temperature, or both low temperature and high temperature, thereby providing a film having improved sound insulation characteristics in a wider range. Can be.

The first skin layer 100 and the second skin layer 100 may each include 70 to 76 parts by weight of the first polyvinyl acetal resin, and 24 to 30 parts by weight of the plasticizer. In this case, it is possible to satisfy the penetration resistance, impact resistance, etc., with improved bonding characteristics to the film to which the skin layer 100 is applied.

The first buffer layer 200 and the second buffer layer 200 may each include 58 to 68 parts by weight of the second polyvinyl acetal resin, and 32 to 42 parts by weight of the plasticizer. In this case, the film may be provided with sound insulation characteristics in a wider temperature range.

The core layer 300 may include 58 to 68 parts by weight of the third polyvinyl acetal resin, and 32 to 42 parts by weight of the plasticizer. In this case, the sound insulating properties may be better provided to the film.

The multilayer sound insulation film 500 of the present invention may further contain additives selected from the group consisting of antioxidants, heat stabilizers, UV absorbers, UV stabilizers, IR absorbers, glass bonding force regulators, and combinations thereof, as necessary. have.

The antioxidant may be used hindered amine or hindered phenol (hindered phenol). Specifically, a hindered phenolic antioxidant is more preferable in polyvinyl butyral (PVB) manufacturing process requiring a process temperature of 150 ° C or higher. Hindered phenolic antioxidants can be used, for example, ISFANOX 1076, 1010, etc. of BASF.

The thermal stabilizer may be a phosphite-based thermal stabilizer when considering compatibility with the antioxidant. For example, IRSF's IRGAFOS 168 may be used.

The UV absorber may be Chemisorb 12 (Cemisorb) 12, Chemi Sol 79, Chemi Sol 74, Chemi Sol 102, Tinuvin 328, Tinuvin 329, Tinuvin 326, etc. of BASF. The UV stabilizer may be used such as BASF Tinuvin. ITO, ATO, AZO, etc. may be used as the IR absorber, and the glass bonding force modifier may be a metal salt such as Mg, K, Na, epoxy-modified Si oil, or a mixture thereof, but the present invention is limited thereto. It doesn't happen.

Multilayer sound insulating film 500 according to another embodiment of the present invention includes a first skin layer 100 including a first polyvinyl acetal resin and a plasticizer; A first buffer layer 200 disposed on the first skin layer and including a resin mixture and a plasticizer; A core layer 300 disposed on the first buffer layer and including a third polyvinyl acetal resin and a plasticizer; A second buffer layer 200 disposed on the core layer and including a resin mixture and a plasticizer; And a second skin layer 100 disposed on the second buffer layer and including a first polyvinyl acetal resin and a plasticizer, wherein the resin mixture is a 2-1 polyvinyl acetal resin having a different amount of hydroxyl groups. And 2-2 polyvinyl acetal resin.

The amount of hydroxyl groups of the resin mixture has a value between the amount of hydroxyl groups of the first polyvinyl acetal resin and the amount of hydroxyl groups of the third polyvinyl acetal resin.

When the resin mixture having such a property is applied as the buffer layer, the multilayer sound insulating film of the present invention introduces a step difference between the layers in the amount of hydroxyl groups, that is, the amount of hydroxyl groups in the resin mixture layer is the first polyvinyl. By having a value between the amount of hydroxyl groups of acetal resin and the amount of hydroxyl groups of said third polyvinyl acetal resin, foaming does not occur while said multilayer sound insulating film has sound insulation characteristics.

The 2-1 polyvinyl acetal resin may be included in a content ratio (0 <a <1, where a is a real number) based on the resin mixture 1, wherein the amount of hydroxyl groups is HD2-1.

The 2-2 polyvinyl acetal resin has a hydroxyl content of HD2-2, and based on the resin mixture 1, the b content ratio (0 <b <1, where b is a real number and the sum of a and b is 1 May not be exceeded).

The content ratio is calculated by weight ratio of the content of the 2-1 polyvinyl acetal resin or the 2-2 polyvinyl acetal resin with respect to the entire resin mixture.

When the amount of hydroxyl groups of the first polyvinyl acetal resin is HD1, the amount of hydroxyl groups of the third polyvinyl acetal resin is HD3, and the amount of hydroxyl groups of the mixed resin is HD2, the value of HD2 is expressed by Equation 1 below and The two may be satisfied.

[Equation 1]

HD2 = HD3 + (HD1-HD3) * N

[Equation 2]

HD2 = HD2-1 * a + HD2-2 * b

In Formula 1 and Formula 2, HD1 is the amount of hydroxyl groups of the first polyvinyl acetal resin, HD2 is the amount of hydroxyl groups of the polyvinyl acetal resin applied to the buffer layer, and HD3 is the amount of hydroxyl groups of the third polyvinyl acetal resin. , HD2-1 is the amount of hydroxyl groups of the 2-1 polyvinyl acetal resin, HD2-2 is the amount of hydroxyl groups of the 2-2 polyvinyl acetal resin, and a is a resin mixture 1 contained in the buffer layer. Based on the content ratio of the 2-1 polyvinyl acetal resin, b is the content ratio of the 2-2 polyvinyl acetal resin based on the resin mixture 1 contained in the buffer layer and a and b are each greater than 0 1 It is a real number with a value less than, and the sum of a and b does not exceed 1. N is as defined in the description above.

The skin layer 100, the core layer 300, the composition of each layer, the properties of the first polyvinyl acetal resin, the properties of the third polyvinyl acetal resin, the amount of plasticizer applied in each layer, etc. Since the description is duplicated, the description thereof is omitted.

In the buffer layer 200 to which the resin mixture is applied, the description of the buffer layer to which the second polyvinyl acetal resin is applied above is omitted, and the description of the second polyvinyl acetal resin is omitted. It can be applied to the content of resin mixture.

The resin mixture contains a 2-1 polyvinyl acetal resin and a 2-2 polyvinyl acetal resin having different amounts of hydroxyl groups, wherein the 2-1 polyvinyl acetal resin includes the first polyvinyl acetal resin or The third polyvinyl acytal resin may be applied.

In addition, the resin mixture may include a second polyvinyl acetal resin described in the multilayer sound insulating film according to an embodiment of the present invention.

The resin mixture is advantageous in that the hydroxyl group content of the entire resin mixture can be controlled by physical mixing rather than chemical synthesis, and through this, the hydroxyl group content of the buffer layer of the multilayer sound insulation film can be controlled.

Specifically, when the entirety of the 2-1 polyvinyl acetal resin and the resin mixture included in the resin mixture is 1, it may be applied in an amount ratio of 0.1 to 0.9, an amount ratio of 0.2 to 0.8, or an amount ratio of 0.3 to 0.7. . In addition, the 2-2 polyvinyl acetal resin may be applied in a content ratio of 0.1 to 0.9, a content ratio of 0.2 to 0.8, or a content ratio of 0.3 to 0.7 when the entire resin mixture is 1.

When the resin mixture is mixed and applied, HD2, which is the amount of hydroxyl groups in the buffer layer described above, satisfies the above N range, it is possible to provide a multilayer sound insulation film 500 having no foaming characteristics or having a good sound insulating property in a relatively wide temperature range. have.

Laminated glass according to another embodiment of the present invention is a first glass layer (not shown) and the second glass layer (not shown) with a multilayer sound insulating film 500 according to an embodiment of the present invention described above. This laminated body is included.

Detailed description of the multilayer sound insulating film 500 is omitted because it is overlapped with the above.

The glass of the first glass layer and the second glass layer is applied without limitation as long as the glass is applied to the glass, building interior material or exterior material applied to the opening of the automobile, and is not particularly limited in kind. In addition, instead of the glass layer, a material applicable to ordinary glass, such as light-transmissive plastic, may be applied.

The laminated glass including the multilayer sound insulation film 500 according to the embodiment of the present invention is a multilayer sound insulation film 600 having the same thickness, and includes the first skin layer, the core layer, and the second skin layer. The loss factor value measured at 30 ° C. may be increased by 0.02 or more as compared with the case of applying the three-layer film including.

In this case, while the loss factor value measured at 20 ° C. is maintained at an equivalent level or higher, the loss factor value measured at 30 ° C. may be increased, and thus may have improved sound insulation characteristics in a wide temperature range of room temperature to high temperature as a whole. have.

The laminated glass including the multilayer sound insulation film 500 according to the embodiment of the present invention is a multilayer sound insulation film 600 having the same thickness, and includes the first skin layer, the core layer, and the second skin layer. The loss factor value measured at 10 ° C. may be increased by 0.02 or more as compared with the case of applying the three-layer film including.

In this case, while the loss factor value measured at 20 ° C. is maintained at an equivalent level or higher, the loss factor value measured at 10 ° C. may be increased to have better sound insulation characteristics in a wider temperature range of low temperature to room temperature. have.

The difference in the loss coefficient value was evaluated based on a film having a total thickness of 800 um, and a 3 layer film of 340-120-340 um without a buffer layer and 300-50-100-50-300 um with a buffer layer. It evaluated based on the result measured using the layer film.

Hereinafter, exemplary experimental examples of the present invention will be described in more detail.

Manufacturing method of multilayer sound insulation film

The following first to fourth polyvinyl acetal resins were obtained by butyrating a polyvinyl alcohol resin having a degree of polymerization of 1700 and 2400 from n-butylaldehyde:

First polyvinyl acetal resin (skin layer): average degree of polymerization of polyvinyl alcohol of 1700, acetalization degree of 78.2% by weight, hydroxyl group amount of 20.6% (45.3 mol%), acetyl group amount of 1.2% by weight,

Second polyvinyl acetal resin A (buffer layer): average degree of polymerization of polyvinyl alcohol 2400, acetalization degree 79.4% by weight, hydroxyl group amount 11.9% by weight (29.1 mol%), acetyl group amount 8.7% by weight,

Second polyvinyl acetal resin B (buffer layer): average degree of polymerization of polyvinyl alcohol 2400, acetalization degree 75.1 wt%, hydroxyl group amount 14.3 wt% (33.3 mol%), acetyl group amount 10.6 wt%,

Third polyvinyl acetal resin (core layer): average degree of polymerization of polyvinyl alcohol 2400, acetalization degree 82.2% by weight, hydroxyl group amount 8.8% by weight (22.6 mol%), acetyl group amount 9.0% by weight,

Mixed resin (buffer layer): A mixture of a first polyvinyl acetal resin and a second polyvinyl acetal resin B in a weight ratio of 50:50, and an arithmetic average of hydroxyl groups: 17.45% by weight (39.3 mol%).

The polyvinyl acetal resin and the plasticizer triethylene glycol di-2-ethylhexanoate (3G8, obtainable from PROVIRON, PROVIST 1766) are each added in the amounts shown in Table 1 below, and kneaded with a mixing roll sufficiently to form a resin composition for each layer. Got.

By co-extrusion with an extruder using the obtained resin composition for each layer, a five-layered multilayer sound insulating film laminated in the order of the first skin layer, the first buffer layer, the core layer, the second buffer layer, and the second skin layer (total thickness approx. 800 um) was produced. In addition, a three-layer constitution (first skin layer-core layer-second skin layer, total thickness of about 800 um) was prepared as a sample of a comparative example with the same thickness.

Multilayer
Configuration Polyvinyl acetal
Resin type Hydroxyl content
(weight%) N * Plasticizer Content (parts by weight **) Example 1 Skin layer First Polyvinyl Acetal Resin 20.6 0.26 27 Core layer Tertiary polyvinyl acetal resin 8.8 37 Buffer layer Second Polyvinyl Acetal Resin A 11.9 34 Example 2 Skin layer First Polyvinyl Acetal Resin 20.6 0.26 27 Core layer Tertiary polyvinyl acetal resin 8.8 40 Buffer layer Second Polyvinyl Acetal Resin A 11.9 34 Example 3 Skin layer First Polyvinyl Acetal Resin 20.6 0.26 27 Core layer Tertiary polyvinyl acetal resin 8.8 34 Buffer layer Second Polyvinyl Acetal Resin A 11.9 40 Example 4 Skin layer First Polyvinyl Acetal Resin 20.6 0.47 27 Core layer Tertiary polyvinyl acetal resin 8.8 34 Buffer layer Second Polyvinyl Acetal Resin B 14.3 37 Example 5 Skin layer First Polyvinyl Acetal Resin 20.6 0.47 27 Core layer Tertiary polyvinyl acetal resin 8.8 37 Buffer layer Second Polyvinyl Acetal Resin B 14.3 37 Example 6 Skin layer First Polyvinyl Acetal Resin 20.6 0.73 27 Core layer Tertiary polyvinyl acetal resin 8.8 34 Buffer layer Mixed resin
(First Polyvinyl Acetal Resin + Second Polyvinyl Acetal Resin B) 17.45 37 Example 7 Skin layer First Polyvinyl Acetal Resin 20.6 0.73 27 Core layer Tertiary polyvinyl acetal resin 8.8 34 Buffer layer Mixed resin
(First Polyvinyl Acetal Resin + Second Polyvinyl Acetal Resin B) 17.45 40 Comparative Example 1 Skin layer First Polyvinyl Acetal Resin 20.6 - 27 Core layer Tertiary polyvinyl acetal resin 8.8 37

* N means the value of N in Equation 1 as described above.

[Formula 1] HD2 = HD3 + (HD1-HD3) * N

** The plasticizer content represents the content of the plasticizer contained in parts by weight when the sum of the polyvinyl acetal resin and the plasticizer content is 100 parts by weight.

Evaluation of physical properties

(Sound insulation evaluation)

Each of the 5-layer multilayer sound insulation film and the 3-layer film of the comparative example were cut to a size of 30 cm in length and 2.5 cm in width, and sandwiched between two transparent float glasses (30 cm in length, 2.5 cm in width and 2.1 cm in thickness). Got it. The laminate was placed in a rubber bag and degassed for 20 minutes with a vacuum of 2.6 KPa. The laminate was then degassed and placed in an oven for 30 minutes at 90 ° C. to preliminarily press the laminate with a vacuum press. The laminated body preliminarily crimped in the autoclave at the temperature of 140 degreeC and the pressure conditions of 1.2 MPa was crimped for 20 minutes, and the laminated glass used for sound insulation measurement was obtained.

The laminated glass was subjected to vibration by a vibration generator for dumping test, and the vibration characteristics obtained therefrom were amplified by a mechanical impedance measuring device, and the vibration spectrum was analyzed by an FFT spectrum analyzer to obtain L / F (loss factor) values. Indicated.

(Evaluation degree of foaming)

Five laminated glass used for the foaming test were produced for each multilayer sound insulating film. Specifically, except for laminating a multi-layer sound insulation film of the same size and each of the three-layer film of the comparative example between two sheets of transparent float glass (10 cm wide, 10 cm long, 2.1 cm thick), and used for the sound insulation test above. The laminated glass used for foaming test was obtained by the same method as laminated glass.

The laminated glass thus prepared was left in a 50 ° C. oven for 100 hours, and then visually observed whether foaming occurred in the laminated glass. From the observation result, the state of foaming was determined by the following criteria.

The foaming size generated in the five pieces of laminated glass was approximated to an ellipse in plan view, and its elliptical area was made into the foaming area. The average value of the elliptic area observed in the five laminated glass was obtained, and the ratio (percentage) of the average value (foamed area) of the elliptic area to the area of the laminated glass (10 cm wide and 10 cm long) was obtained. Table 2 shows.

○ ○: No foaming was observed on all 5 laminated glass

(Circle): The ratio of the average value (foam area) of an ellipse area is less than 5%.

(Triangle | delta): The ratio of the average value (foam area) of an ellipse area is 5% or more and less than 10%.

X: The ratio of the average value (foam area) of an ellipse area is 10% or more.

Penetration Assessment

The penetration resistance of the laminated glass was evaluated based on KS L 2007.

2.1 mm thick glass of 300 mm × 300 mm and each of the Examples and Comparative Films were prepared in a laminated structure of glass-film-glass, and were pre-bonded by vacuum to degas and edge sealing. Thereafter, the specimens were prepared by main bonding at 150 ° C. for 2 hours using an autoclave. Thereafter, a steel ball of 2.26 kg was dropped on the specimen, and the height (MBH) through which the specimen was penetrated was measured. In this case, when penetrating at a height of less than 4 m, it is marked as fail, and when penetrating at a height of more than 4 m, it is marked as pass.

(Impact resistance evaluation)

Based on KS L 2007: 2008, the absence or absence of the laminated glass in which the polyvinyl acetal film was laminated was evaluated.

The process of manufacturing and bonding each of the 2.1 cm thick glass and the Examples and Comparative Films into a laminated structure of glass-film-glass proceeded in the same manner as the above penetration resistance evaluation.

The low temperature test was to drop 227 g of steel balls at a temperature of minus 20 ° C for 4 hours and then drop them at 9 m height, fail if the impacted specimens were broken and the glass was scattered or the amount of glass falling from the sheet was more than 15 g. When the received specimen is not broken or the glass is scattered and the amount of glass falling from the sheet is less than 15 g, it is marked as pass.

The room temperature evaluation is a failure of the glass when it is stored at 40 ° C for 4 hours and then impacted at 10 m. If the amount of glass falling from the sheet which is not broken or the glass is scattered is less than 15 g, it is marked as pass.

In the case of evaluating the pass in both the low temperature evaluation and the room temperature evaluation, it is indicated as pass in Table 2 below.

L / F 20 ℃ L / F 30 ℃ Foam evaluation Penetration Tolerance Impact resistance Example 1 0.33 0.24 ○○ pass pass Example 2 0.33 0.24 ○○ pass pass Example 3 0.33 0.22 ○○ pass pass Example 4 0.34 0.2 ○○ pass pass Example 5 0.32 0.2 ○○ pass pass Example 6 0.32 0.17 ○○ pass pass Example 7 0.32 0.16 ○○ pass pass Comparative Example 1 0.32 0.16 X pass pass

Referring to Table 2, it can be confirmed that the foaming phenomenon does not appear in the evaluation evaluation while maintaining the basic physical properties of the penetration resistance and impact resistance of the samples. This was evaluated as a superior characteristic over the comparative example with the same film thickness. In addition, in the samples of Examples 1 to 7, it was confirmed that the sound insulation performance at the high temperature sound insulation evaluation temperature 30 ° C as well as the reference temperature of the sound insulation evaluation was improved at 20 ° C. It was confirmed that the performance has a wider range.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.

500: multilayer sound insulation film (example)
100: skin layer, the first skin layer, the second skin layer
200: buffer layer, first buffer layer, second buffer layer
300: core layer
600: multilayer sound insulation film (comparative example)

Claims (12)

A first skin layer comprising a first polyvinyl acetal resin and a plasticizer; A first buffer layer on the first skin layer and including a second polyvinyl acetal resin and a plasticizer; A core layer on the first buffer layer and including a third polyvinyl acetal resin and a plasticizer; A second buffer layer on the core layer and including a second polyvinyl acetal resin and a plasticizer; And a second skin layer on the second buffer layer and including a first polyvinyl acetal resin and a plasticizer.
The amount of hydroxyl groups of the second polyvinyl acetal resin has a value between the amount of hydroxyl groups of the first polyvinyl acetal resin and the amount of hydroxyl groups of the third polyvinyl acetal resin. The method of claim 1,
HD2 value of the hydroxyl group amount of the second polyvinyl acetal resin is to satisfy the following formula 1, multilayer sound insulation film;
[Equation 1]
HD2 = HD3 + (HD1-HD3) * N
In Formula 1,
HD1 is the amount of hydroxyl groups of the first polyvinyl acetal resin,
HD2 is the amount of hydroxyl groups of the second polyvinyl acetal resin,
HD3 is the amount of hydroxyl groups of the third polyvinyl acetal resin,
N is a real number of 0.1 to 1.0. The method of claim 1,
The first polyvinyl acetal resin is a hydroxyl-based HD1 value is more than 17.5% by weight, multilayer sound insulation film. The method of claim 1,
Wherein the third polyvinyl acetal resin is a hydroxyl group HD3 value is less than 9.3% by weight, multilayer sound insulation film. The method of claim 1,
The first skin layer and the second skin layer is a multilayer sound insulating film, each of which comprises 70 to 76 parts by weight of the first polyvinyl acetal resin, and 24 to 30 parts by weight of the plasticizer. The method of claim 1,
The first buffer layer and the second buffer layer is a multi-layer sound insulating film, each containing 58 to 68 parts by weight of the second polyvinyl acetal resin, and 32 to 42 parts by weight of the plasticizer. The method of claim 1,
The core layer is a multilayer sound insulating film comprising 58 to 68 parts by weight of the third polyvinyl acetal resin, and 32 to 42 parts by weight of the plasticizer. The method of claim 1,
Wherein the first polyvinyl acetal resin is 0.1 to 3% by weight of an acetyl group, multilayer sound insulating film. The method of claim 1,
The third polyvinyl acetal resin is 3 to 15% by weight of an acetyl group, multilayer sound insulating film. A laminated glass comprising a laminate in which a first glass layer and a second glass layer are laminated with a multilayer sound insulating film according to claim 1 interposed therebetween. The method of claim 10,
The laminated glass is a multilayer sound insulating film having the same thickness, and the loss coefficient measured at 30 ° C. compared with the case where the three-layer film including the first skin layer, the core layer, and the second skin layer is applied ( loss Factor) Laminated glass, the value is increased by 0.02 or more. The method of claim 10,
The laminated glass is a multilayer sound insulating film having the same thickness, and a loss coefficient measured at 10 ° C. compared with the case where a three-layer film including the first skin layer, the core layer, and the second skin layer is applied ( loss Factor) Laminated glass, the value is increased by 0.02 or more.

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