KR102223184B1 - Laminate film for bonding and light transmitting layered product comprising of the same - Google Patents

Abstract

The laminated film for bonding of the present invention, a light-transmitting laminate including the same, provides a laminated film with improved optical properties while having sound insulation performance. The laminated film for bonding can substantially prevent traces such as melt fractures of the core layer, which may be formed in the extrusion process by applying a metal salt additive to the core layer, remaining after glass bonding, and has sufficient sound insulation properties. It can substantially prevent the occurrence of optical defects while maintaining the temperature, and provides a laminated film with stable physical properties that suppresses haze and refractive index changes even in a moisture-resistant environment by applying a high refractive index thermal stabilizer as a aging change inhibitor. do.

Description

Laminated film for bonding and light-transmitting laminate containing the same {LAMINATE FILM FOR BONDING AND LIGHT TRANSMITTING LAYERED PRODUCT COMPRISING OF THE SAME}

The present invention is to provide a laminated film in which optical properties are improved and change with time is suppressed while having sound insulation performance, and a light-transmitting laminate that can be used as a windshield of a moving means, including the same.

Polyvinyl acetal film is used as an intermediate layer of laminated glass (safety glass) or a light-transmitting laminate. Laminated glass is mainly used for windows, exterior materials of buildings, and automobile window glass, and its debris does not scatter even when damaged, and it does not allow penetration even with a certain strength of blow. Loss can be secured with stability to minimize damage or injury.

The main function of laminated glass is to minimize damage or injury to objects or persons within the transparent barrier by absorbing the energy caused by hitting, while not allowing penetration through the laminated glass (penetration resistance) (impact resistance). . In addition, to be applied to transparent glass, it should have excellent optical properties, do not cause double-image phenomenon or optical distortion, and should have strong properties in environments such as humidity (optical properties, moisture resistance). In addition, the interlayer sheet applied to the laminated glass may impart additional functionality to the laminated glass, such as weakening acoustic noise and reducing UV and/or IR light transmission. A sound insulation film, which is a film having a function of reducing acoustic noise, is usually composed of three or more layers.

KR 2016-0019927 A, 2014.06.10 KR 2017-0093221 A, 2015.12.04

An object of the present invention is to provide a laminated film with improved optical properties and suppressed change over time while having sound insulation performance, and a light-transmitting laminate that can be used as a windshield of a moving means, including the same.

In order to achieve the above object, the laminated film for bonding according to an embodiment disclosed in the present specification includes a skin layer including a first polyvinyl acetal resin and a first plasticizer, and a second polyvinyl acetal resin and a second plasticizer. The core layer includes a high refractive index metal salt having a refractive index higher than that of the second plasticizer, and a high refractive index additive including a high refractive index thermal stabilizer having a refractive index higher than that of the second plasticizer, and , The difference in refractive index between the skin layer and the core layer is 0.0060 or less.

The high refractive index thermal stabilizer may be a hindered phenolic thermal stabilizer having a refractive index greater than or equal to 0.080 than that of the second plasticizer.

The core layer may include the high refractive index metal salt and the high refractive index thermal stabilizer in a weight ratio of 1: 1.5 to 8.

The high refractive index additive may be included in an amount of 0.005 to 1.0% by weight based on the entire core layer.

The core layer may have a refractive index measured at 532 nm of 1.4775 or higher.

The laminated film may have a whitening distance of 30 mil or less after being left for 2 weeks in an atmosphere of 65° C. and 95% relative humidity.

A laminated film for bonding according to another embodiment of the present specification includes a skin layer including a first polyvinyl acetal resin and a first plasticizer, and a core layer including a second polyvinyl acetal resin and a second plasticizer, The core layer includes a high refractive index additive including a high refractive index metal salt having a refractive index higher than that of the second plasticizer and a high refractive index thermal stabilizer having a refractive index higher than that of the second plasticizer, and the laminated film is 65°C And the refractive index change after leaving for 2 weeks in an atmosphere of 95% relative humidity is less than 0.001.

A laminated film for bonding according to another embodiment disclosed in the present specification includes a first skin layer including a first polyvinyl acetal resin and a first plasticizer; A core layer positioned on the first skin layer and including a second polyvinyl acetal resin and a second plasticizer; And a second skin layer positioned on the core layer and including the third polyvinyl acetal resin and the third plasticizer, wherein the core layer includes a high refractive index additive including a high refractive index metal salt and a high refractive index thermal stabilizer Including, wherein the high refractive index metal salt is a metal salt having a refractive index higher than that of the second plasticizer, and the high refractive index thermal stabilizer is a thermal stabilizer having a refractive index higher than that of the second plasticizer.

The whitening distance after leaving the laminated film for 2 weeks in an atmosphere of 65° C. and 95% relative humidity may be 30 mils or less.

The core layer includes a high refractive index metal salt or chlorine containing chlorine in a molecule, and the content of chlorine may be 0.0001 to 0.1% by weight based on the entire core layer.

The core layer may include a high refractive index metal salt or sulfur containing sulfur in a molecule, and the content of sulfur may be 0.0001 to 0.1% by weight based on the entire core layer.

A light-transmitting laminate according to another embodiment disclosed in the present specification includes: a first light-transmitting layer; A laminated film for bonding described above positioned on one surface of the first light-transmitting layer; And a second light-transmitting layer positioned on the laminated film for bonding.

The light-transmitting laminate may have a loss factor value of 0.34 or more.

The light-transmitting laminate may be a windshield.

The moving means according to another embodiment disclosed in the present specification includes the light-transmitting laminate described above.

The laminated film for bonding of the present invention, a light-transmitting laminate including the same, provides a laminated film with improved optical properties while having sound insulation performance. The laminated film for bonding may substantially prevent traces such as melt fractures of the core layer, which may be formed during the extrusion process, remaining after glass bonding by a method such as applying a metal salt additive to the core layer. In addition, the laminated film for bonding can substantially prevent the occurrence of optical defects while maintaining sufficient sound insulation properties, and at the same time, moisture resistance or haze characteristics over time by applying a high refractive index thermal stabilizer. , It is possible to provide a laminated film for bonding and the like having more excellent physical properties by suppressing changes in optical properties such as interlayer refractive index difference properties.

1 is a conceptual diagram illustrating the structure of a laminated film for bonding according to an embodiment of the present invention in cross section.
2 is a conceptual diagram illustrating a structure of a light-transmitting laminate according to another embodiment of the present invention in cross section.
3 is a conceptual diagram illustrating another moving means according to another embodiment of the present invention.
4 is a photograph showing the result of the optical defect of the sample observed in the laboratory example of the present specification (A is the result of Comparative Example 1 and B is the result of Example 3)
5 is a diagram illustrating a method of measuring a whitening distance measured in an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art may easily implement the present invention. However, the present invention may be implemented in a number of different forms and is not limited to the embodiments described herein. Like reference numerals are attached to similar parts throughout the specification.

As used herein, the terms "about", "substantially" and the like are used at or close to the numerical value when manufacturing and material tolerances specific to the stated meaning are presented, and are used in the sense of the present invention. To assist, accurate or absolute numerical values are used to prevent unreasonable use of the stated disclosure by unscrupulous infringers.

Throughout this specification, the term "combination of these" included in the expression of the Makushi format refers to one or more mixtures or combinations selected from the group consisting of the components described in the expression of the Makushi format, and the constituent elements It means to include one or more selected from the group consisting of.

Throughout this specification, the description of “A and/or B” means “A, B, or A and B”.

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

In the present specification, the meaning that B is located on A means that B is located on A or that B is located on A while another layer is located between them, and B is located in contact with the surface of A. It is limited to that and is not interpreted.

In the present specification, the singular expression is interpreted as meaning including the singular or plural, which is interpreted in context, unless otherwise specified.

In the present specification, the size of each component in the drawings may be exaggerated for the purpose of describing the invention, and may be different from the size that is actually applied.

The evaluation of the amount of hydroxyl groups in the present specification was evaluated by measuring the amount of ethylene groups to which the hydroxyl groups of the polyvinyl acetal resin are bound in a method in accordance with JIS K6728.

In the case of the sound insulation film, a larger amount of plasticizer is applied to the core layer than the skin layer, and the difference in the amount of the plasticizer used may cause a difference in refractive index between the skin layer and the core layer. During the film manufacturing process, a melt fracture is likely to be formed on the surface of the core layer, which is related to the difference in refractive index between the two layers, and may cause a visually identifiable erroneous phenomenon at the interface between the skin layer and the core layer.

The inventors of the present invention remarkably reduce the occurrence of optical defects such as the above-mentioned fringing phenomenon while reducing the difference in refractive index between the skin layer and the core layer by applying a high refractive index additive containing a metal salt to the core layer. After confirming that it can be reduced, the present invention was completed. In addition, in order to suppress changes over time such as changes in haze and change in refractive index that may occur depending on the amount of additives applied and the application environment, etc., a high refractive index thermal stabilizer is applied together as a time change inhibitor. Completed the present invention.

1 is a conceptual diagram illustrating the structure of a laminated film 100 for bonding according to an embodiment of the present invention in cross section, and FIG. 2 is a cross-sectional view of the structure of a light-transmitting laminate 800 according to another embodiment of the present invention. It is a conceptual diagram described as, and FIG. 3 is a conceptual diagram illustrating another moving means 900 according to another embodiment of the present invention. Hereinafter, each exemplary embodiment disclosed in the present specification will be described in more detail with reference to FIGS. 1 to 3.

In order to achieve the above object, the laminated film 100 for bonding according to an embodiment of the present invention includes a skin layer 300 and a core layer 200, and the difference in refractive index between the skin layer and the core layer is 0.0060 Below.

The skin layer 300 includes a first polyvinyl acetal resin and a first plasticizer, and the core layer 200 includes a second polyvinyl acetal resin and a second plasticizer.

The difference in refractive index between the skin layer 300 and the core layer 200 is controlled by including a high refractive index additive having a refractive index higher than that of the second plasticizer in the core layer 200.

The high refractive index additive includes a high refractive index metal salt and a high refractive index thermal stabilizer, the high refractive index metal salt is a metal salt having a refractive index higher than that of the second plasticizer, and the high refractive index thermal stabilizer is higher than the refractive index of the second plasticizer. It is a heat stabilizer with a high refractive index.

Specifically, the difference in refractive index between the skin layer 300 and the core layer 200 may be 0.0060 or less, 0.0059 or less, and 0.0058 or less. The difference in refractive index may be 0 or more, and may be 0.0001 or more. When there is such a difference in refractive index, the difference in refractive index between the skin layer and the core layer becomes insignificant, so that optical distortion caused by the difference in refractive index does not substantially occur. Even if there are circumstances such as the formation of the optical defects observed with the naked eye after being bonded with the light-transmitting laminate 800, the optical defects may be minimal.

The high refractive index metal salt and/or the high refractive index thermal stabilizer alleviates the difference in refractive index between the core layer and the skin layer due to the difference in refractive index and content of the polyvinyl acetal resin and the plasticizer, and those having a larger refractive index than the plasticizer may be applied. .

As for the high refractive index metal salt, 0.005 or more may be applied based on the refractive index of the plasticizer, 0.010 or more may be applied, 0.020 or more may be applied, and 2.000 or less may be applied. When such a high refractive index metal salt is applied to the core layer, it is possible to provide a laminated film substantially free of optical defects while substantially no change in sound insulation properties, etc. The plasticizer is based on triethylene glycol bis 2-ethylhexanoate (3G8, refractive index: 1.447) applied in the examples presented herein.

The high refractive index metal salt may have a large refractive index of 0.01 or more based on magnesium acetate (MgAc, Magnesium acetate, refractive index: 1.358), may have a large refractive index of 0.02 or more, and may have a large refractive index of 0.04 or more, It may have a refractive index greater than or equal to 0.07. In addition, the high refractive index metal salt may have a refractive index difference of 2.00 or less based on magnesium acetate. When the high refractive index metal salt having such a refractive index value is applied to the core layer, the physical properties of the laminated film are maintained at a certain level or higher, and excellent optical defect reduction effect can be obtained.

The high refractive index thermal stabilizer may be applied with a value greater than or equal to 0.080 based on the refractive index of the plasticizer, a greater than or equal to 0.090 may be applied, a greater than or equal to 0.10 may be applied, and a greater than or equal to 2.0 may be applied. When such a high refractive index thermal stabilizer is applied to the core layer, it is possible to provide a laminated film having excellent moisture resistance and substantially no optical defects without substantial change in sound insulation properties. The plasticizer is based on triethylene glycol bis 2-ethylhexanoate (3G8, refractive index: 1.447) applied in the examples presented herein.

As the high refractive index thermal stabilizer, a hindered phenolic antioxidant may be applied, and in this case, it is possible to induce a stable effect of suppressing changes over time while minimizing the influence on other physical properties of the laminated film.

The high refractive index thermal stabilizer is specifically, a group consisting of Iganox 1035 (irganox, refractive index: 1.575), Iganox 1330 (irganox 1330, refractive index: 1.58), Iganox 1010 (irganox 1010, refractive index: 1.54), and combinations thereof It may be any one selected from.

The high refractive index metal salt may be a compound represented by Formula 1 below. Specifically, the high refractive index metal salt may be included in the form of a salt (including a hydrate) or a derivative thereof containing the compound in the core layer.

[Formula 1]

In Chemical Formula 1, M is Mg, Ca, Na or K, X is COOH, Cl, SO ₄ , or NO ₃ , and n and m are integers of 1 or 2, respectively.

Specifically, when M is Mg or Ca, and X is Cl or NO ₃ , n is 1 and m is 2.

Specifically, when M is Mg or Ca, and X is SO ₄ , n is 1 and m is 1.

Specifically, when M is Na or K, and X is COOH, Cl, or NO ₃ , n is 1 and m is 1.

Specifically, when M is Na or K, and X is SO ₄ , n is 2 and m is 1.

More specifically, the high refractive index metal salt may be any one selected from the group consisting _{of KCOOH, NaCOOH, MgCl 2} , CaCl ₂ , NaCl, CaSO _{4 and combinations thereof.}

When such a high-refractive-index metal salt is applied to the core layer 200, sound insulation properties are maintained at a certain level or more throughout the laminated film, and an excellent optical defect control effect can be obtained.

The high refractive index additive may be included in an amount of 0.005 to 1.0% by weight based on the entire core layer, and may be included in an amount of 0.01 to 0.7% by weight. If the high refractive index metal salt is included in an amount of less than 0.005% by weight based on the entire core layer, the refractive index control effect may be insignificant. Symptoms may occur.

The core layer may include the high refractive index metal salt and the high refractive index thermal stabilizer in a weight ratio of 1: 1.5 to 8, and may include a weight ratio of 1: 2 to 5, and a weight ratio of 1: 2.1 to 4 can do. In this case, the effect of suppressing optical distortion and the effect of suppressing change over time can be obtained more stably at the same time.

The high refractive index metal salt may be included in an amount of 0.001 to 0.21% by weight based on the entire core layer, and may be included in an amount of 0.0015 to 0.14% by weight.

The high refractive index thermal stabilizer may be included in an amount of 0.004 to 0.79% by weight based on the entire core layer, and may be included in an amount of 0.0035 to 0.56% by weight.

When the high-refractive-index metal salt and the high-refractive-index thermal stabilizer are included in such a content ratio, the difference in refractive index between the core layer and the skin layer is slightly adjusted, and more stable film properties can be obtained even with a change with time.

The high refractive index metal salt may be dispersed or hydrolyzed in a solvent such as distilled water during the manufacturing process and mixed with a resin or plasticizer, and in the bonding film, metal ions and Cl ions, SO ₄ ions, or NO ₃ ions or their It can be detected in the form of a derivative. Specifically, the high refractive index metal salt may be detected and calculated based on the content of Cl, S, or N in the bonding film. The content of Cl, S, or N, which is a standard for detection, may be 0.0001 to 0.1% by weight based on the entire core layer.

That is, the core layer 200 may include Cl, SO ₄ , or NO ₃ in an amount of 0.0001 to 0.1% by weight based on the entire core layer.

The content of Cl, S, or N may be detected and quantified by an appropriate combustion ion chromatography method. For example, after injecting a sample of an appropriate amount (between 10 and 50 mg) into a furnace having an inlet and an outlet through a sample boat and heat-treating at 900° C., the compounds to be detected are burned by _{Ar/O 2 gas and H After separating the ions generated by absorption in the 2} O ₂ solution by the ion exchange column of the Ion Chromatograph, qualitative and quantitative analysis is performed through a suppressor-detector. At this time, a pressure of 5.49 MPa, a flow of 1.000 ml/min may be applied, and a recording time of 19.0 min may be applied.

When the high refractive index additive is applied to the core layer 200, melt fractures that may occur on the surface of the core layer during extrusion are improved by improving the fluidity of the core layer in the manufacturing process of the laminated film 100 that proceeds through the coextrusion process. By mitigating, it is possible to bring about an effect of improving optical distortion that may occur at the skin layer-core layer interface of the laminated film.

The core layer 200 may have a refractive index measured at 24° C. and a wavelength of 532 nm of 1.4775 or higher, 1.4780 or higher, and 1.4783 or higher. The core layer 200 may have a refractive index of less than 1.5 measured at 24° C. and a wavelength of 532 nm. The core layer having such a refractive index has a relatively small difference in refractive index from the skin layer, and thus has excellent optical properties in which optical defects such as visual appearance are not observed when manufacturing laminated glass.

The difference in the hydroxyl content of the first polyvinyl acetal resin and the second polyvinyl acetal resin may be 20 mol% or more, 24 mol% or more, and 26 mol% or more. In addition, the difference in the hydroxyl group content may be 32 mol% or less. When the first polyvinyl acetal resin and the second polyvinyl acetal resin are applied to the skin layer 300 and the core layer 200, respectively, so as to have such a difference in the hydroxyl group content, the plasticizer moves while having better sound insulation properties. It is possible to obtain a laminated film having substantially no development and excellent in moisture resistance.

The first polyvinyl acetal resin has a butyral group content of 50 mol% or more, and 50 to 60 mol%. The first polyvinyl acetal resin may have a hydroxyl content of 35 mol% or more, 40 mol% or more, and less than 49.5 mol%. When the first polyvinyl acetal resin having such characteristics is applied to the skin layer 300, the skin layer can have appropriate mechanical properties while being excellently bonded to a substrate such as glass, and excellent sound insulation properties together with the core layer. I can have it.

The first polyvinyl acetal resin may be a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol having a polymerization degree of 1,600 to 3,000 with aldehyde, and a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol having a polymerization degree of 1,700 to 2,500 with aldehyde. It may be an acetal resin. When such a polyvinyl acetal resin is applied, mechanical properties such as penetration resistance can be sufficiently improved.

The first polyvinyl acetal resin may be a synthesis of polyvinyl alcohol and an aldehyde, and the type of the aldehyde is not limited. Specifically, the aldehyde may be any one selected from the group consisting of n-butyl aldehyde, isobutyl aldehyde, n-barrel aldehyde, 2-ethyl butyl aldehyde, n-hexyl aldehyde, and blend resins thereof. When the n-butyl aldehyde is applied as the aldehyde, the prepared polyvinyl acetal resin may have a refractive index characteristic with a small difference from the refractive index of glass, and excellent adhesion to glass.

The first plasticizer is triethylene glycol bis 2-ethylhexanoate (3G8), tetraethylene glycol diheptanoate (4G7), triethylene glycol bis 2-ethyl butyrate (3GH), triethylene glycol bis 2-heptanoate (3G7), dibutoxyethoxyethyl adipate (DBEA), butyl carbitol adipate (DBEEA), dibutyl sebacate (DBS), bis 2-hexyl adipate (DHA) and combinations thereof Any one may be applied, specifically in the group consisting of triethylene glycol di-2-ethyl butyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol di-n-heptanoate, and combinations thereof Any one selected may be included, and more specifically, triethylene glycol bis 2-ethylhexanoate (3G8) may be applied.

The skin layer 300 may include 60 to 76% by weight of the first polyvinyl acetal resin, 70 to 76% by weight, and 71 to 74% by weight. When the polyvinyl acetal resin is included in this range, relatively excellent mechanical properties may be provided to the laminated film 100.

The skin layer 300 may contain the first plasticizer in an amount of 24 to 40% by weight, 24 to 30% by weight, and 26 to 29% by weight. When the skin layer includes the plasticizer in such a range, it is good in terms of imparting appropriate bonding strength and impact resistance to the laminated film for bonding.

The description of the first polyvinyl acetal resin and the first plasticizer applied to the skin layer 300 may be equally applied to the third polyvinyl acetal resin and the third plasticizer applied to the second skin layer 320. . Specifically, the same resin may be applied to the first polyvinyl acetal resin and the third polyvinyl acetal resin, and other resins having the characteristics described above may be applied. It is good to apply. Specifically, the first plasticizer and the third plasticizer may be applied with the same type and amount of plasticizer, may be applied in different amounts, and may be applied in different types and contents.

The second polyvinyl acetal resin applied to the core layer 200 may have a butyral group content of 60 mol% or more, and may be 60 to 72 mol%. The second polyvinyl acetal resin may have a hydroxyl group content of 20 mol% or less, 18 mol% or less, and may exceed 5 mol%. When the second polyvinyl acetal resin having such characteristics is applied to the core layer, the core layer may have excellent optical characteristics while imparting excellent sound insulation characteristics to the laminated film.

The second polyvinyl acetal resin is a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol having a polymerization degree of 1,600 to 3,000 with an aldehyde, and may be obtained by synthesizing polyvinyl alcohol and aldehyde. A detailed description thereof is duplicated with that described for the first polyvinyl acetal resin above, and thus detailed description thereof will be omitted.

Since the description of the specific type of plasticizer applicable to the second plasticizer is redundant with the description of the first plasticizer above, detailed description thereof will be omitted.

The core layer 200 may include 58 to 68% by weight of the second polyvinyl acetal resin based on the entire core layer, and may include 63 to 68% by weight. When the second polyvinyl acetal resin is included in this range, it is possible to impart an appropriate level of mechanical strength to the laminated film 100 and at the same time provide relatively excellent sound insulation properties.

The core layer 200 may contain 31 to 41% by weight of the second plasticizer based on the entire core layer, and may include 31 to 36% by weight. When the plasticizer is included in such a range, it is good in that it can impart appropriate sound insulation performance and mechanical properties to the laminated film for bonding.

The skin layer 300 and/or the core layer 200 may further include an additive to be described later. The additive may be any one selected from the group consisting of a heat stabilizer (limited to the skin layer), a UV absorber, a UV stabilizer, an IR absorber, a glass adhesion modifier, and a combination thereof.

As the thermal stabilizer, a phosphite-based thermal stabilizer may be used. For example, BASF's IRGAFOS 168 may be used, but is not limited thereto.

As the UV absorber, Chemisorb 12, Chemisolve 79, Chemisolve 74, Chemisolve 102, BASF's Tinuvin 328, Tinuvin 329, Tinuvin 326, etc. may be used as the UV absorber. The UV stabilizer may be used, such as BASF's Tinuvin.

ITO, ATO, AZO, etc. may be used as the IR absorber, and a metal salt such as Mg, K, Na, etc., an epoxy-based modified Si oil, or a mixture thereof may be used as the glass adhesion modifier applied to the skin layer. The present invention is not limited thereto.

The laminated film 100 may include a skin layer 300 and a core layer 200, and includes a core layer 200 positioned between the first skin layer 300 and the second skin layer 320 Can include.

The laminated film 100 may have a three-layer structure, and may have a four- or five-layer structure further including an additional functional layer (eg, hud, color, shade band, infrared blocking/reflection, etc.).

The laminated film 100 may further include a buffer layer (not shown) between the skin layer and the core layer, and the buffer layer has the same or different characteristics as described above as having a function of inhibiting movement of the plasticizer of the core layer. Different types of resins such as polyvinyl acetal resin or TPU (Thermoplastic PolyUrethane) can be applied.

The laminated film 100 has a sound insulation function, and may have a loss factor value of 0.34 or more.

The laminated film 100 has excellent stability over time, and may have a whitening distance of 30 mils or less after performing a moisture resistance test in which it is left for 2 weeks in an atmosphere of 65° C. and 95% relative humidity.

The laminated film 100 has excellent aging stability and may have a refractive index change of less than 0.001 before and after the moisture resistance test, which is left for 2 weeks in an atmosphere of 65° C. and 95% relative humidity.

The laminated film 100 may have a total thickness of 400 um or more, specifically 400 to 1600 um, 500 to 1200 um, and 600 to 900 um. Since the laminated film is applied to the manufacture of light-transmitting laminates such as laminated glass, the thicker the thickness, the better the mechanical strength or sound insulation performance, etc., but when considering the minimum legal performance, cost, weight reduction, etc., the above thickness range may vary. It is possible to manufacture a film that satisfies the conditions.

The thicknesses of the first skin layer 300 and the second skin layer 320 may each independently be 20 to 600 um, and may be 200 to 400 um.

The thickness of the core layer 200 may be 60 to 600 um, 70 to 300 um, and 70 to 200 um.

A laminated film including each layer having such a thickness range can provide a light-transmitting laminate having excellent optical properties and sound insulation properties along with appropriate mechanical properties.

The laminated film 100 for bonding according to another embodiment disclosed in the present specification includes a skin layer 300 and a core layer 200, and is left for 2 weeks in an atmosphere of 65° C. and 95% relative humidity. The refractive index change before and after is less than 0.001.

The first skin layer 300, the second skin layer 320, the core layer 200, and the types and contents of resins, plasticizers, additives, etc. contained in each of them, and their characteristics, are overlapped with the above description. Detailed description is omitted.

A laminated film 100 for bonding according to another embodiment disclosed in the present specification includes a first skin layer 300 including a first polyvinyl acetal resin and a first plasticizer; A core layer 200 positioned on the first skin layer and including a second polyvinyl acetal resin and a second plasticizer; And a second skin layer 320 positioned on the core layer and including the third polyvinyl acetal resin and the third plasticizer.

The core layer 200 contains a high refractive index additive including a high refractive index metal salt and a high refractive index thermal stabilizer. The high refractive index metal salt is a metal salt having a refractive index higher than that of the second plasticizer, and the high refractive index thermal stabilizer is a thermal stabilizer having a refractive index higher than that of the second plasticizer.

In the core layer 200, the content of Cl, S, or N in the core layer may be 0.0001 to 0.1% by weight based on the entire core layer. The CIC analysis method can be applied to the analysis of this content, and the detailed description thereof is omitted because it overlaps with that described above.

The first skin layer 300, the second skin layer 320, the core layer 200, and the types and contents of resins, plasticizers, additives, etc. contained in each of them, and their characteristics, are overlapped with the above description. Detailed description is omitted.

The light-transmitting laminate 800 according to another embodiment disclosed in the present specification includes a first light-transmitting layer 820; The laminated film 100 for bonding described above positioned on one surface of the first light-transmitting layer; And a second light-transmitting layer 840 positioned on the laminated film for bonding.

The first light-transmitting layer 820 and the second light-transmitting layer 840 may each independently be made of light-transmitting glass or light-transmitting plastic.

Since the detailed description of the laminated film 100 for bonding is duplicated with the above description, the description thereof will be omitted.

The light-transmitting layered body 800 maintains the light-transmitting properties of the first light-transmitting layer 820 and the second light-transmitting layer 840 at almost the same level, while the laminated film 100 for bonding The light-transmitting layers on both sides are bonded to each other and can have the properties necessary for safety glass, such as impact resistance and penetration resistance.

The light-transmitting laminate 800 may satisfy impact resistance characteristics based on KS L 2007:2008.

The light-transmitting laminate 800 may satisfy penetration resistance characteristics based on KS L 2007.

The light-transmitting laminate 800 has excellent functionality when applied to automobile glass (including a windshield), a building material, and the like. In particular, it is possible to provide a laminated film 100 for bonding and a light-transmitting laminate 800 including the same while having a relatively thin thickness when applied to the windshield of an automobile and having both penetration resistance, sound insulation properties, and double-image prevention functions. have.

The moving means 900 according to another embodiment disclosed in the present specification includes the light-transmitting laminate 800 described above as a windshield.

The moving means 900 may be applied as long as it is a moving means to which a windshield is applied. Typically, the moving means may be a vehicle, and the body, the drive, the driving wheel, the connecting device, etc. are usually applied to a vehicle. If it is, it can be applied without limitation.

The moving means 900 includes a body part forming a main body of the moving means, a driving part (engine, etc.) mounted on the body part, a driving wheel (wheel, etc.) rotatably mounted on the body part, the driving wheel and the A connecting device connecting the driving unit; And a windshield, which is a light-transmitting laminate that is mounted on a part of the body and blocks wind from the outside.

Hereinafter, the present invention will be described in more detail through specific examples. The following examples are only examples to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

Manufacturing example

Each component used in the following Examples and Comparative Examples is as follows.

Preparation of resins and additives

Method for producing polyvinyl butyral resin (A):

By synthesizing n-butylaldehyde in a polyvinyl alcohol resin having an average polymerization degree of 1700 and a saponification degree of 99, a polyvinyl butyral resin (A) having a butyral group of 56.2 mol% and a hydroxyl group of 42.9 mol% was obtained.

Method for producing polyvinyl butyral resin (B):

A polyvinyl butyral resin (B) having 68.5 mol% of butyral group and 16.5 mol% of hydroxyl group was obtained by synthesizing n-butylaldehyde in a polyvinyl alcohol resin having an average polymerization degree of 2400 and a saponification degree of 88.

Preparation of additives for skin layer:

0.3 parts by weight of an additive for a skin layer was prepared by mixing 0.15 parts by weight of Tinuvin-328 as a UV additive, 0.1 parts by weight of dibutyl hydroxy toluene (H-BHT) as an antioxidant, and 0.05 parts by weight of an adhesion modifier.

Preparation of additives for the core layer:

CA-1: sodium chloride (NaCl, refractive index 1.5442) and irgafos 168 as a heat stabilizer were mixed in a ratio of 30:70 to prepare an additive for adjusting the refractive index.

CA-2: Sodium chloride (NaCl, refractive index 1.5442) and irganox 1010 as a heat stabilizer were mixed in a ratio of 30:70 to prepare an additive for adjusting the refractive index.

CA-3: magnesium sulfate (MgSO ₄ , refractive index 1.523) and irganox 1010 as a heat stabilizer were mixed in a ratio of 30:70 to prepare an additive for adjusting the refractive index.

CA-4: calcium sulfate (CaSO ₄ , refractive index 1.530) and irganox 1010 as a heat stabilizer were mixed in a ratio of 30:70 to prepare an additive for adjusting the refractive index.

CA-5: potassium sulfate (K ₂ SO ₄ , refractive index 1.495) and irganox 1010 as a heat stabilizer were mixed in a ratio of 30:70 to prepare an additive for adjusting the refractive index.

CA-6: Magnesium acetate (Mg Ac, refractive index 1.358) was prepared as an additive for adjusting the refractive index.

CA-7: Magnesium acetate (Mg Ac, refractive index 1.358) and irgafos 168 as a heat stabilizer were mixed in a ratio of 30:70 to prepare an additive for adjusting the refractive index.

# The refractive index of the refractive index modifier is the literature value.

Preparation of laminated film for bonding

Polyvinyl butyral resin (A) 27.5 parts by weight of 3G8 as a plasticizer and 0.3 parts by weight of skin layer additive are added to 72.2 parts by weight of polyvinyl butyral resin (A), and then sufficiently kneaded in a twin-screw extruder A (skin layer resin), and polyvinyl buty. Ral resin (B) 67 parts by weight of plasticizer 3G8 32.5 parts by weight, core layer additive (refer to the core layer composition in Table 1 below) 0.5 parts by weight of a twin-screw extruder B and sufficiently kneaded melted resin for the core layer (skin layer) Sample films having a total thickness of 780 μm, each consisting of a thickness of 330 μm/120 μm/330 μm, were prepared by coextrusion in the structure of /(core layer)/(skin layer).

Evaluation of physical properties

(1) Optical defect (preparation and evaluation of DISTORTION evaluation samples)

The prepared sample films were cut into a size of 10 cm in length and 10 cm in width, and sandwiched between two sheets of transparent glass (10 cm in length, 10 cm in width, 2.1 cm in thickness) and vacuum in a laminator at 110°C and 1 atmosphere for 30 seconds. After the laminated glass was pre-pressed by performing lamination, the laminated glass pre-pressed at a temperature of 140° C. and a pressure of 1.2 MPa in an autoclave was pressed for 20 minutes to obtain laminated glass samples. The obtained samples were erected at a distance of 10 cm from the wall, and then a led light was illuminated from 30 cm back at an angle of 20 degrees, and it was confirmed that optical distortion was observed in the shadow reflected on the wall. The results are shown in Table 1 below, and a real photograph is shown in FIG. 4. 4 is a photograph showing the result of the optical defect observed in the laboratory example of the present specification, A is the result of Comparative Example 1 and B is the result of Example 3.

(2) How to measure sound insulation performance (L/F)

The prepared sample films were cut into a size of 30 cm in length and 2.5 cm in width, and sandwiched between two sheets of transparent glass (30 cm in length, 2.5 cm in width, 2.1 cm in thickness) and vacuumed in a laminator at 110°C and 1 atmosphere for 30 seconds. After the laminated glass was pre-pressed by performing lamination, the laminated glass pre-pressed at a temperature of 140° C. and a pressure of 1.2 MPa in an autoclave was squeezed for 20 minutes to obtain laminated glass samples used for sound insulation measurement.

The conjugated samples were stored for 2 weeks in a constant temperature and humidity chamber at 20°C and 20RH% (Relative Humidity) for stabilization, and then the sound insulation performance was measured.

The measurement of sound insulation performance was carried out as follows.

Vibration is applied to the laminated glass sample by a vibration generator for a damp (DAMP) test, and the resulting vibration characteristics are amplified with a mechanical impedance measuring device, and the vibration spectrum is analyzed by an FFT spectrum analyzer, and then calculated by 1dB method and L/F ( loss factor). If the sound insulation performance is 0.34 or more, it is evaluated as pass, and if it is less than 0.34, it is evaluated as fail, and is shown in Table 1 below.

(3) Method of measuring the refractive index of the film

The refractive index of the prepared film was measured in an offset mode using a prism coupler (model 2010M) manufactured by Metricon in the United States. All of the measured values were measured with the relative refractive index at 24° C. and 532 nm wavelength, and are shown in Table 1 below.

(4) Moisture resistance evaluation

Preparation of Sample: Preparation of Sample: A laminated film left for 1 week at 20°C and 25%RH was cut into a size of 100mm*100mm horizontally*height, and two sheets of 2.1T (mm, hereinafter the same) transparent glass were placed on both sides. It was placed in a laminated structure of 2.1T glass-film-2.1T glass, and preliminary bonding was performed for 20 seconds at 120'C and 1 atmosphere in a vacuum laminator. Thereafter, the pre-laminated glass-film-glass laminate was subjected to main bonding in an autoclave to obtain a laminated glass sample. The conditions of the main bonding were applied with a heating time of 25 minutes from room temperature to 140'C and a holding time of 25 minutes at 140'C.

Haze evaluation of change over time: The laminated glass sample 100 prepared above was left in a constant temperature and humidity chamber at 65℃ 95%rh for 2 weeks, and then taken out and haze occurred from the center of the four sides (area where whitening phenomenon appeared, 10) Was visually checked, and the distance was measured with a ruler (see FIG. 5), and the average value of the values of the four sides was calculated according to Equation (1) below, and expressed as whitening distance (mm).

Equation (1) Average whitening distance = (d1+ d2+ d3+ d4)÷ 4

In Equation (1), the distances at which the whitening phenomenon, measured from the center of the first to fourth sides, is indicated are respectively d1 to d4 (unit is mil).

If the average whitening distance was less than 30 mil, it was evaluated as Pass, and if it exceeded 30 mil, it was evaluated as Fail.

Refractive index evaluation with time change: Compare the refractive index measurement value of the laminated glass before the moisture resistance evaluation above and the refractive index measurement value of the laminated glass after the evaluation is completed.If the difference is less than 0.001, PASS or more, FAIL is indicated in Table 1 below. I did.

Core layer composition Type of additive Metal salt (wt%) Heat stabilizer (wt%) Additive sum (wt%)* Example 1 CA-1 Na Cl 0.15 irgafos 168 0.35 0.5 Example 2 CA-2 Na Cl 0.15 irganox 1010 0.35 0.5 Example 3 CA-3 Mg SO4 0.15 irganox 1330 0.35 0.5 Example 4 CA-4 Ca SO4 0.15 irganox 1330 0.35 0.5 Example 5 CA-5 K2 SO4 0.15 irganox 1330 0.35 0.5 Comparative Example 1 CA-6 Mg Ac 0.5 - - 0.5 Comparative Example 2 CA-7 Mg Ac 0.15 irgafos 168 0.35 0.5 Refractive index measurement result Laminated glass evaluation result Sound insulation layer refractive index Refractive index difference* DISTORTION Change over time (invasion) Sound insulation performance Haze (%) Refractive index change (L/F) Example 1 1.4782 0.0059 Pass Pass Pass Pass Example 2 1.4783 0.0058 Pass Pass Pass Pass Example 3 1.4784 0.0057 Pass Pass Pass Pass Example 4 1.4784 0.0057 Pass Pass Pass Pass Example 5 1.4784 0.0057 Pass Pass Pass Pass Comparative Example 1 1.4774 0.0067 Fail Fail Fail Pass Comparative Example 2 1.4779 0.0062 Fail Fail Pass Pass

* The wt% of the additive is based on the entire core layer.

* The difference in refractive index refers to the value of (skin layer refractive index-sound insulation layer refractive index).

* "-" means do not apply.

Referring to Table 1, in the case of Comparative Example 1 and Comparative Example 2, although a metal salt was applied, it was confirmed that optical distortion occurred, and it was also confirmed that the difference in refractive index between the core layer and the skin layer was relatively large. In the case of both Comparative Example 1 and Comparative Example 2, a change in haze or a change in refractive index occurred in the moisture resistance test, and when a heat stabilizer was applied in Comparative Example 2, the change in the refractive index was suppressed, but the change in haze was not suppressed, so that the moisture resistance characteristics were deteriorated. I could confirm.

In the case of Examples 1 to 5, there are some differences in the metal salt material to be applied, but all of them showed excellent results in the results of evaluating the difference in refractive index or occurrence of a fringing phenomenon. Excellent results were shown in both the haze value and the refractive index change.

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 by those skilled in the art using the basic concept of the present invention defined in the following claims are also present. It belongs to the scope of rights of

100: laminated film for bonding, laminated film 200: core layer
300: skin layer, first skin layer 320: second skin layer
800: light-transmitting laminate 820: first light-transmitting layer
840: second light-transmitting layer 900: moving means
10: the area where the whitening phenomenon appears 20: the area where the whitening phenomenon does not appear
d1: whitening distance at the first side d2: whitening distance at the second side
d3: whitening distance at the third side d4: whitening distance at the fourth side

Claims (14)

A skin layer including a first polyvinyl acetal resin and a first plasticizer, and a core layer including a second polyvinyl acetal resin and a second plasticizer,
The core layer includes a high refractive index additive including a high refractive index metal salt having a refractive index higher than that of the second plasticizer and a high refractive index thermal stabilizer having a refractive index higher than that of the second plasticizer,
The difference in refractive index between the skin layer and the core layer is 0.0060 or less,
The high refractive index thermal stabilizer has a refractive index greater than the refractive index of the second plasticizer by 0.080 or more,
Laminated film for bonding.
The method of claim 1,
The high refractive index thermal stabilizer is a hindered phenolic thermal stabilizer, a laminated film for bonding.
The method of claim 1,
The core layer includes the high refractive index metal salt and the high refractive index thermal stabilizer in a weight ratio of 1: 1.5 to 8, a laminated film for bonding.
The method of claim 1,
The high refractive index additive is contained in an amount of 0.005 to 1.0% by weight based on the entire core layer, a laminated film for bonding.
The method of claim 1,
The core layer has a refractive index measured at 532 nm of 1.4775 or more, a laminated film for bonding.
The method of claim 1,
The laminated film for bonding, having a whitening distance of 30 mil or less after leaving the laminated film in an atmosphere of 65° C. and 95% relative humidity for 2 weeks.
A skin layer including a first polyvinyl acetal resin and a first plasticizer, and a core layer including a second polyvinyl acetal resin and a second plasticizer,
The core layer includes a high refractive index additive including a high refractive index metal salt having a refractive index higher than that of the second plasticizer and a high refractive index thermal stabilizer having a refractive index higher than that of the second plasticizer,
The refractive index change before and after leaving for 2 weeks in an atmosphere of 65° C. and 95% relative humidity is less than 0.001,
The high refractive index thermal stabilizer has a refractive index greater than the refractive index of the second plasticizer by 0.080 or more,
Laminated film for bonding.
A first skin layer comprising a first polyvinyl acetal resin and a first plasticizer;
A core layer positioned on the first skin layer and including a second polyvinyl acetal resin and a second plasticizer; And
Including; a second skin layer positioned on the core layer and including a third polyvinyl acetal resin and a third plasticizer,
The core layer includes a high refractive index additive including a high refractive index metal salt and a high refractive index thermal stabilizer,
The high refractive index metal salt is a metal salt having a refractive index higher than that of the second plasticizer, and the high refractive index thermal stabilizer is a thermal stabilizer having a refractive index higher than that of the second plasticizer,
The high refractive index thermal stabilizer has a refractive index greater than the refractive index of the second plasticizer by 0.080 or more,
Laminated film for bonding.
The method of claim 8,
The laminated film for bonding, having a whitening distance of 30 mil or less after leaving the laminated film in an atmosphere of 65° C. and 95% relative humidity for 2 weeks.
The method of claim 8,
The core layer contains a high refractive index metal salt or chlorine containing chlorine in the molecule, and the content of the chlorine is 0.0001 to 0.1% by weight based on the entire core layer, a laminated film for bonding.
The method of claim 8,
The core layer includes a high refractive index metal salt or sulfur containing sulfur in a molecule, and the content of sulfur is 0.0001 to 0.1% by weight based on the entire core layer, a laminated film for bonding.
A first light-transmitting layer; The laminated film for bonding according to claim 1 or 8 positioned on one surface of the first light-transmitting layer; And a second light-transmitting layer positioned on the laminated film for bonding.
The method of claim 12,
Light-transmitting laminate, which is a windshield with a loss factor of 0.34 or more.
A moving means comprising the light-transmitting laminate according to claim 12.

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